Composition, magnetic particle-containing cured product, magnetic particle-introduced substrate, and electronic material

Abstract

To provide a composition which enables formation of a cured product that is excellent in magnetic characteristics and filling suitability while being excellent in flowability, a magnetic particle-containing cured product formed using the composition, and a magnetic particle-introduced substrate containing the magnetic particle-containing cured product and an electronic material.SOLUTION: A composition contains magnetic particles, one or more kinds of components selected from the group consisting of a resin and a resin precursor, and a solvent, wherein the component contains two or more kinds of epoxy resins, a content of the magnetic particles having a primary particle diameter of 4 μm or more is 25 mass% or more with respect to the total mass of the magnetic particles, a content of the magnetic particles is 91 mass% or more with respect to the total solid content of the composition, and a content of the solvent is 3 to 24 mass% with respect to the total mass of the composition.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a composition, a magnetic particle-containing cured product, a magnetic particle-introduced substrate, and an electronic material. [Background technology]

[0002] As electronic devices become more compact and powerful, the integration of electronic circuits is increasing. Coating-type compositions containing magnetic particles are one of the materials that can improve integration. By using such compositions, magnetic bodies can be mounted in any shape, making it easier to realize smaller electronic devices with higher performance than the conventional method of placing individual pieces of magnetic bodies 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 resin composition is thermally cured to produce a cured product having 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 Summary of the Invention [Problem to be solved by the invention]

[0005] Recently, attempts have been made to produce a magnetic particle-introduced substrate by filling holes in a substrate with a magnetic material using a coating type composition containing magnetic particles.

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

[0007] Furthermore, from the viewpoints of application property and ease of filling work, excellent flowability is also required as a basic property of the composition. For example, Japanese Patent No. 6024927 discloses a solvent-free composition that does not contain a solvent and exhibits fluidity by using a resin component. However, in a solvent-free composition, in order to ensure a desired fluidity, there is a limit to the amount of magnetic particles that can be introduced into the solid content of the composition, which causes a problem that it is difficult to improve the magnetic properties (magnetic permeability) of the cured product.

[0008] Therefore, an object of the present invention is to provide a composition that is excellent in flowability and is capable of forming a cured product that is excellent in magnetic properties and filling suitability. Another object of the present invention is to provide a magnetic particle-containing cured product formed using the above composition. Another object of the present invention is to provide a magnetic particle-introduced substrate and an electronic material, which contain the above-mentioned magnetic particle-containing cured product. [Means for solving the problem]

[0009] As a result of intensive research into solving the above problems, the present inventors have found that the above problems can be solved by the following configuration.

[0010] [1] Magnetic particles; One or more components selected from the group consisting of resins and resin precursors; A composition comprising: The content of magnetic particles having a primary particle size of 4 μm or more is 25 mass% or more based on the total mass of the magnetic particles, The content of the magnetic particles is 91% by mass or more based on the total solid content of the composition, A composition, wherein the content of the solvent is 3 to 24% by mass based on 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 the content thereof is 3 mass% or more relative to the total mass of the composition. [6] The composition according to any one of [1] to [5], wherein the component includes at least one of an epoxy compound and an oxetane compound. [7] A magnetic particle-containing cured product formed using the composition according to any one of [1] to [6]. [8] A magnetic particle-introduced substrate comprising: a substrate having a hole formed therein; and the magnetic particle-containing cured material according to [7] disposed in the hole. [9] An electronic material comprising the magnetic particle-introduced substrate according to [8]. Effect of the Invention

[0011] According to the present invention, there is provided a composition capable of forming a cured product having excellent flowability, magnetic properties and filling suitability. Furthermore, according to the present invention, there is provided a magnetic particle-containing cured product formed using the above composition. Furthermore, according to the present invention, it is possible to provide a magnetic particle-introduced substrate and an electronic material, which contain the above-mentioned magnetic particle-containing cured product. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] The present invention will be described in detail below. The following description of the components may be based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment. In the present specification, the notation of groups (atomic groups) that does not indicate whether they are substituted or unsubstituted includes both unsubstituted and substituted groups, unless it is contrary to the spirit of the present invention. For example, an "alkyl group" includes not only an alkyl group that does not have a substituent (unsubstituted alkyl group), but also an alkyl group that has a substituent (substituted alkyl group). In addition, an "organic group" in the present specification refers to a group that contains at least one carbon atom.

[0013] In this specification, "actinic rays" or "radiation" refers to, for example, the bright line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV light: extreme ultraviolet), X-rays, and electron beams (EB), etc. In this specification, "light" refers to actinic rays or radiation. In this specification, unless otherwise specified, "exposure" includes not only exposure to the emission spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light, X-rays, EUV light, and the like, but also drawing with particle beams such as electron beams and ion beams.

[0014] In this specification, the symbol "to" is used to mean that the numerical values ​​before and after it are included as the lower limit and upper limit.

[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, the "solid content" of a composition means the components that form a magnetic particle-containing cured product (hereinafter sometimes abbreviated as "cured product"), and when the composition contains a solvent (organic solvent, water, etc.), it means all components excluding the solvent. In addition, liquid components that form a cured product are also considered to be solid contents.

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

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

[0019] In addition, in this specification, unless otherwise specified, each component may be used alone or in combination of two or more substances corresponding to each component. Here, when two or more substances are used in combination for each component, the content of the component refers to the total content of the substances used in combination, unless otherwise specified.

[0020] [Composition] The composition of the present invention comprises Magnetic particles; 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: The content of magnetic particles having a primary particle size of 4 μm or more is 25 mass% or more based on the total mass of the magnetic particles, The content of the magnetic particles is 91% by mass or more based on the total solid content of the composition, The content of the solvent is 3 to 24% by mass based on the total mass of the composition.

[0021] Compositions containing magnetic particles used as hole-filling compositions must not only exhibit excellent magnetic properties (magnetic permeability), but also must have sufficient fluidity in their liquid state from the standpoint of ease of application and filling work, and, after hardening, must suppress voids, cracks, and other gaps from the standpoint of strength (excellent filling suitability), as basic performance requirements. The present inventors have now, through extensive research, found that a composition having the above-described configuration exhibits excellent fluidity in a liquid state, and can form a cured product having excellent magnetic properties (magnetic permeability) and filling suitability. In addition, as described later, it has been confirmed that when the above solvent contains 3 mass% or more of a solvent having a boiling point of 160°C or higher, relative to the total mass of the composition, the filling suitability of the cured product formed from the composition is superior.

[0022] In the following, "the effects of the present invention are superior" may mean that the composition has superior fluidity, that the cured product formed from the composition has superior magnetic properties (magnetic permeability), and / or that the cured product formed from the composition has superior filling suitability.

[0023] Each component that may be included in the composition is described in detail below.

[0024] [Magnetic particles] The composition includes magnetic particles. The magnetic particles include metal atoms. As used herein, the metal atoms also include metalloid atoms such as boron, silicon, germanium, arsenic, antimony, and tellurium. The metal atoms may be contained in the magnetic particles as an alloy containing the 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 metal atoms relative to the total mass of the magnetic particles is preferably from 50 to 100 mass %, more preferably from 75 to 100 mass %, and even more preferably from 95 to 100 mass %.

[0025] The metal atom is not particularly limited, but preferably contains 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 (when multiple types are included, the total content) is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more, based on the total mass of metal atoms in the magnetic particles. The upper limit of the content is not particularly limited, and is, for example, 100% by mass or less, preferably 98% by mass or less, and more preferably 95% by mass or less.

[0026] The magnetic particles may contain materials other than Fe, Ni, and Co, specific examples of which 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. When the magnetic particles contain metal atoms other than Fe, Ni and Co, it is preferable that the metal atoms contain one or more types selected from the group consisting of Si, Cr, B and Mo.

[0027] Specific examples of magnetic particles include Fe-Co based alloys (preferably permendur), Fe-Ni based alloys (e.g. permalloy), Fe-Zr based alloys, Fe-Mn based alloys, Fe-Si based alloys, Fe-Al based alloys, Ni-Mo based alloys (preferably supermalloy), Fe-Ni-Co based alloys, Fe-Si-Cr based alloys, Fe-Si-B based alloys, Fe-Si-Al based alloys (preferably sendust), Fe-Si-BC based alloys, Fe-Si-B-Cr based alloys, Examples of the alloy 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, magnetoplumbite hexagonal ferrite). The alloys may be amorphous. As the magnetic particles, soft magnetic particles are preferable because they have lower loss. Examples of the soft magnetic particles include Fe-based amorphous alloys, Fe-Si-Cr-based alloys, Fe nanocrystalline alloys, Fe-Ni-Co-based alloys, Co-based amorphous alloys, Ni-Mo-based alloys, Ni ferrite, and Mn ferrite. The magnetic particles may be used alone or in combination of two or more types.

[0028] The magnetic particles may have a surface layer on the surface thereof, and by having the surface layer on the magnetic particles in this way, it is possible to impart a function to the magnetic particles according to the material of the surface layer. The surface layer may be an inorganic layer or an organic layer.

[0029] As the compound for forming the inorganic layer, metal oxides, metal nitrides, metal carbides, metal phosphate compounds, metal borate compounds, or silicate compounds (e.g., silicate esters such as tetraethyl orthosilicate, and silicates such as sodium silicate) are preferred, since they can form a surface layer excellent in at least one of insulation, 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 constituting the inorganic layer obtained using the compound for forming an inorganic layer include silicon oxide, germanium oxide, titanium oxide, aluminum oxide, zirconium oxide, and magnesium oxide, and the inorganic layer may be a layer containing two or more of these.

[0030] Examples of the organic layer-forming compound include acrylic monomers. Specific examples of the acrylic monomer include the compounds described in paragraphs 0022 to 0023 of JP2019-067960A. Examples of materials constituting the organic layer obtained by using the organic layer-forming compound include acrylic resins.

[0031] The thickness of the surface layer is not particularly limited, but is preferably from 3 to 1000 nm in order to better exhibit the function of the surface layer.

[0032] The lower limit of the average primary particle size 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 size 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 the primary particles of the magnetic particles can be measured, for example, by photographing the magnetic particles with a transmission electron microscope at a magnification of 100,000 times, printing the photograph on photographic paper to a total magnification of 500,000 times, tracing the outline of the particle (primary particle) with a digitizer, and calculating the diameter of a circle with the same area as the traced area (circular area diameter). Here, the primary particle refers to an independent particle without aggregation. The photographing using a transmission electron microscope is performed by a direct method using a transmission electron microscope at an acceleration voltage of 300 kV. The observation and measurement using a transmission electron microscope can be performed, for example, using a Hitachi transmission electron microscope H-9000 and Carl Zeiss image analysis software KS-400. In addition, when determining the average primary particle diameter, 1,000 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 to determine the arithmetic average primary particle diameter based on volume.

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

[0034] The content of magnetic particles having a primary particle diameter of 4 μm or more in the magnetic particles is 25% by mass or more relative to the total mass of the magnetic particles. When the content of magnetic particles having a primary particle diameter of 4 μm or more is 25% by mass or more relative to 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. The content of magnetic particles having a primary particle diameter of 4 μm or more in the magnetic particles is preferably 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 relative to the total mass of the magnetic particles. The upper limit is preferably 100% by mass or less. Among the magnetic particles, the content of magnetic particles having a primary particle diameter of 4 to 7 μm is preferably 55 mass% or more, more preferably 65 mass% or more, and even more preferably 70 mass% or more, based on the total mass of the magnetic particles, in terms of the superior effect of the present invention. The upper limit is not particularly limited, but is, for example, 100 mass% or less.

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

[0036] The magnetic particles may be used alone or in combination of two or more kinds. The content of magnetic particles in the composition (the total content when multiple types are included) is 91% by mass or more based on the total solid content of the composition. When the content of magnetic particles is 91% by mass or more based on the total solid content of the composition, the cured product formed from the composition has excellent magnetic properties. In particular, in terms of better effects of the present invention, the content of magnetic particles is preferably 92% by mass or more, more preferably 95% by mass or more, based on the total solid content of the composition. The upper limit of the content is not particularly limited, and is preferably 99% by mass or less.

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

[0038] An example of a composition using a resin itself is a composition containing magnetic particles, a solvent, and a resin dissolved in the solvent. When the solvent of this composition evaporates, the resin precipitates, and a composition in which the resin functions as a binder is obtained.

[0039] The resin precursor is a component that can form a resin by polymerization and / or crosslinking through a predetermined curing treatment using heat or light (ultraviolet light, etc.) The resin thus formed functions as a binder in the cured product. Specific examples of the resin precursor include a thermosetting compound and a photocurable compound. These compounds may be any of a monomer, an oligomer, and a polymer.

[0040] Specific examples of the binder component will be described below.

[0041] Examples of the binder component include (meth)acrylic resin, epoxy resin, enethiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, and phenoxy resin, etc. One of these resins may be used alone, or two or more may be mixed and used. As the cyclic olefin resin, norbornene resin is preferable from the viewpoint of improving heat resistance. Commercially available norbornene resins include, for example, the ARTON series (for example, ARTON F4520) manufactured by JSR Corporation. An example of a commercially available polyvinyl acetal resin is "KS-1" manufactured by Sekisui Chemical Co., Ltd. Moreover, a commercially available phenoxy resin product is, for example, "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-based epoxy resins, glycidyl amine-based epoxy resins, epoxy resins obtained by glycidylating halogenated phenols, condensates of silicon compounds having an epoxy group with other silicon compounds, and copolymers of polymerizable unsaturated compounds having an epoxy group with other polymerizable unsaturated compounds. Furthermore, as the epoxy resin, Marproof G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (manufactured by NOF Corporation, epoxy group-containing polymer), etc. may be used.

[0042] In addition, as the binder component, the resins described in the examples of WO 2016 / 088645 may be used. In addition, the binder component is also preferably a resin having an ethylenically unsaturated group (e.g., a (meth)acryloyl group) in a side chain, and in which the main chain and the ethylenically unsaturated group are bonded via a divalent linking group having an alicyclic structure.

[0043] The binder component is also preferably a resin or a resin precursor having a ring-polymerizable group such as an epoxy group or an oxetanyl group. Examples of resins or resin precursors having a ring-polymerizable group such as an epoxy group or an oxetanyl group include polymers having an epoxy group in a side chain, and polymerizable monomers or oligomers having two or more epoxy groups in the molecule. Specific examples thereof 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 products, or may be obtained by introducing an epoxy group into the side chain of a polymer. For commercially available products, see, for example, paragraph 0191 of JP 2012-155288 A, the contents of which are incorporated herein by reference. Other examples include ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, and EP-4011S (all manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, and EPPN-502 (all manufactured by ADEKA Corporation), and JER1031S. Specific examples of bisphenol A type epoxy resins and bisphenol F type epoxy resins include 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, examples of polymerizable monomers or oligomers having two or more epoxy groups in the molecule that can be used include ZX1658GS (liquid 1,4-glycidylcyclohexane type epoxy resin, manufactured by Nippon Steel Chemical & Materials 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 a polymer having an oxetanyl group in a side chain, and a polymerizable monomer or oligomer having two or more oxetanyl groups in the molecule described above include Aron Oxetane OXT-121, OXT-221, OX-SQ, and PNOX (all manufactured by Toagosei Co., Ltd.). When an epoxy group is introduced into a polymer side chain to synthesize a resin having an epoxy group, the introduction reaction can be carried out by reacting for a predetermined time at a reaction temperature of 50 to 150°C in an organic solvent using, for example, a tertiary amine such as triethylamine or benzylmethylamine, a quaternary ammonium salt such as dodecyltrimethylammonium chloride, tetramethylammonium chloride, or tetraethylammonium chloride, pyridine, or triphenylphosphine as a catalyst. The amount of the alicyclic epoxy unsaturated compound introduced can be controlled so that the acid value of the resulting resin is in the range of 5 to 200 KOH mg / g. The weight average molecular weight of the resin can be set to a range of 500 to 5,000,000 (preferably 1,000 to 500,000). Instead of the alicyclic epoxy unsaturated compound, compounds having a glycidyl group as an epoxy group such as glycidyl (meth)acrylate and allyl glycidyl ether can also be used. For such compounds, see, for example, paragraph 0045 of JP-A-2009-265518, the contents of which are incorporated herein by reference.

[0044] The binder component may also be a resin having an acid group, a basic group, or an amide group. Resins having an acid group, a basic group, or an amide group are suitable because they easily function as a dispersant for dispersing magnetic particles and provide superior effects of the present invention. Examples of the acid group include a carboxy group, a phosphate group, a sulfo group, and a phenolic hydroxyl group, and the carboxy group is preferred in terms of obtaining superior effects of the present invention. Examples of basic groups include amino groups (ammonia, a primary amine, or a secondary amine having one hydrogen atom removed therefrom) and imino groups. Among these, the resin preferably has a carboxy group or an amide group, since the effects of the present invention are more excellent.

[0045] When the resin has an acid group, the acid value of the resin is preferably from 10 to 500 mgKOH / g, and more preferably from 30 to 400 mgKOH / g, in terms of better effects of the present invention.

[0046] As the binder component, it is preferable to use a binder component having a solubility in the solvent of 10 g / L or more, and it is more preferable to use a binder component having a solubility in the solvent of 20 g / L or more, since this improves the dispersibility of the binder component in the composition and the effects of the present invention are more excellent. 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 means the amount (g) of the binder component that dissolves in 1 L of the solvent at 25°C.

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

[0048] <Resin having a repeating unit containing a graft chain (Resin A)> An example of the binder component is a resin having a repeating unit containing a graft chain (hereinafter, also referred to as "resin A"). Resin A can function as a dispersant for magnetic particles.

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

[0050] (Repeating unit including graft chain) In a repeating unit containing a graft chain, as the graft chain becomes longer, the steric repulsion effect increases, and the dispersibility of the magnetic particles improves. On the other hand, if the graft chain is too long, the adsorptive force to the magnetic particles decreases, and the dispersibility of the magnetic particles tends to decrease. For this reason, the graft chain preferably has an atomic number excluding hydrogen atoms of 40 to 10,000, more preferably an atomic number excluding hydrogen atoms of 50 to 2,000, and even more preferably an atomic number excluding hydrogen atoms of 60 to 500. Here, the graft chain refers to a chain extending from the root of the main chain (an atom attached to the main chain in a group branching from the main chain) to the end of the group branching from the main chain.

[0051] In addition, the graft chain preferably contains a polymer structure. Examples of such polymer structures include a poly(meth)acrylate structure (e.g., a poly(meth)acrylic structure), a polyester structure, a polyurethane structure, a polyurea structure, a polyamide structure, and a polyether structure. In order to improve the interaction between the graft chain and the solvent and thereby enhance the dispersibility of the magnetic particles, the graft chain is preferably a graft chain containing at least one structure selected from the group consisting of a polyester structure, a polyether structure, and a poly(meth)acrylate structure, and more preferably a graft chain containing at least one of a polyester structure and a polyether structure.

[0052] Resin A may be a resin obtained by using a macromonomer containing a graft chain (a monomer having a polymer structure and bonding to a main chain to form a graft chain). The macromonomer containing a graft chain (a monomer having a polymer structure and bonding to a main chain to form a graft chain) is not particularly limited, but a macromonomer containing a reactive double bond group can be preferably used.

[0053] Commercially available macromonomers corresponding to the repeating units containing the graft chain and suitable for use in the synthesis of resin A 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 Blenmer PP-100, Blenmer PP-500, Blenmer PP-800, Blenmer PP-1000, Blenmer 55-PET-800, Blenmer PME-4000, Blenmer PSE-400, Blenmer PSE-1300, and Blenmer 43PAPE-600B (all trade names, manufactured by NOF Corp.). Among these, AA-6, AA-10, AB-6, AS-6, AN-6, or Blenmer PME-4000 are preferred.

[0054] Resin A preferably contains at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and cyclic or linear polyester, more preferably contains at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and linear polyester, and further preferably contains at least one structure selected from the group consisting of polymethyl acrylate structure, polymethyl methacrylate structure, polycaprolactone structure, and polyvalerolactone structure. Resin A may contain one of the above structures alone, or may contain a plurality of these structures. Here, the polycaprolactone structure refers to a structure containing a ring-opened ε-caprolactone structure as a repeating unit, and the polyvalerolactone structure refers to a structure containing a ring-opened δ-valerolactone structure as a repeating unit.

[0055] When resin A contains repeating units in which j and k are 5 in formula (1) described below and formula (2) described below, the above-mentioned polycaprolactone structure can be introduced into resin A. Furthermore, when resin A contains repeating units in which j and k are 4 in formula (1) described below and formula (2) described below, the above-mentioned polyvalerolactone structure can be introduced into the resin. In addition, the resin A is X in the formula (4) described below. 5 is a hydrogen atom, and R 4 When the resin A contains a repeating unit in which is a methyl group, the above-mentioned polymethyl acrylate structure can be introduced into the resin A. In addition, the resin A is X in the formula (4) described below. 5 is a methyl group, and R 4 When the resin A contains a repeating unit in which is a methyl group, the above-mentioned polymethyl methacrylate structure can be introduced into the resin A. When resin A contains the formula (5) described below, and contains a repeating unit in which j in formula (5) is 5, the above-mentioned polycaprolactone structure can be introduced into resin A. Furthermore, when resin A contains the formula (5) described below and contains a repeating unit in which j in formula (5) is 4, the above-mentioned polyvalerolactone structure can be introduced into the resin.

[0056] Resin A preferably contains, as a repeating unit including a graft chain, a repeating unit represented by any one of the following formulae (1) to (4), and more preferably contains a repeating unit represented by any one of the following formulae (1A), (2A), (3A), (3B), and (4).

[0057] [ka]

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

[0059] In formulas (1) to (4), Y 1 , Y 2 , Y 3 , and Y 4 Each of Y independently represents a divalent linking group, and the linking group is not particularly limited in structure.1 , Y 2 , Y 3 , and Y 4 Specific examples of the divalent linking group represented by the formula include the following linking groups (Y-1) to (Y-21). In the structures shown below, A and B respectively represent the bonding sites with the left and right terminal groups in formulas (1) to (4). Among the structures shown below, (Y-2) or (Y-13) is more preferred from the viewpoint of ease of synthesis.

[0060] [ka]

[0061] In formulas (1) to (4), Z 1 , Z 2 , Z 3 , and Z 4 Each of Z independently represents a hydrogen atom or a monovalent substituent. The structure of the substituent is not particularly limited, but specific examples include an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, and an amino group. Among these, Z 1 , Z 2 , Z 3 , and Z 4 As the group represented by the formula (I), a group having a steric repulsion effect is preferable, particularly from the viewpoint of improving dispersibility, and each independently an alkyl group or alkoxy group having 5 to 24 carbon atoms is more preferable, and among these, each independently a branched alkyl group having 5 to 24 carbon atoms, a cyclic alkyl group having 5 to 24 carbon atoms, or an alkoxy group having 5 to 24 carbon atoms is even more preferable. The alkyl group contained in the alkoxy group may be any of linear, branched, and cyclic. Also, Z 1 , Z 2 , Z 3 , and Z 4The substituent represented by the formula (I) is preferably a group containing a curable group such as a (meth)acryloyl group, an epoxy group, and / or an oxetanyl group. Examples of the group containing a curable group include "-O-alkylene group-(-O-alkylene group-) AL -(meth)acryloyloxy group". AL represents an integer of 0 to 5, preferably 1. The above alkylene groups each independently preferably have 1 to 10 carbon atoms. When the above alkylene group has a substituent, the substituent is preferably a hydroxyl group. The above-mentioned substituent may be a group containing an onium structure. The onium structure-containing group is a group having an anion moiety and a cation moiety. The anion moiety is, for example, an oxygen anion (-O - ) containing partial structures. Among them, the oxygen anion (-O - ) is preferably directly bonded to the end of the repeating structure to which n, m, p, or q is added in the repeating units represented by formula (1) to (4), and is preferably bonded to the end of the repeating structure to which n is added in the repeating unit represented by formula (1) (i.e., -(-OC j H 2j -CO-) n It is more preferable that the aryl group is directly bonded to the aryl group (the right end in -). The cation of the cationic moiety of the group containing an onium structure can be, for example, an ammonium cation. When the cationic moiety is an ammonium cation, the cationic moiety is a cationic nitrogen atom (>N + It is a partial structure containing a cationic nitrogen atom (>N + <) 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 (preferably one) of the four substituents is a group containing a curable group such as a (meth)acryloyl group, an epoxy group, and / or an oxetanyl group. Examples of the group containing a curable group that the substituent may be include the above-mentioned "-O-alkylene group-(-O-alkylene group-)" as mentioned above. AL In addition to -(meth)acryloyloxy group, -alkylene group- (-O-alkylene group-)AL1 -(meth)acryloyloxy group". AL1 represents an integer of 1 to 5, preferably 1. The alkylene groups each independently preferably have 1 to 10 carbon atoms. When the alkylene group has a substituent, the substituent is preferably a hydroxyl group.

[0062] In the formulas (1) to (4), n, m, p, and q each independently represent an integer of 1 to 500. In the formulae (1) and (2), j and k each independently represent an integer of 2 to 8. In the formulae (1) and (2), j and k each preferably represent an integer of 4 to 6, and more preferably 5. In addition, 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 further preferably integers of 20 or more. In addition, when resin A contains a polycaprolactone structure and a polyvalerolactone structure, the sum of the repeat number of the polycaprolactone structure and the repeat number of the polyvalerolactone structure is preferably an integer of 10 or more, and more preferably an integer of 20 or more.

[0063] In formula (3), R 3 represents a branched or linear alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms. 3 may be the same or different from each other. 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 R is preferably a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, and more preferably a hydrogen atom or an alkyl group. 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 further preferably a linear alkyl group having 1 to 6 carbon atoms. In formula (4), when q is 2 to 500, a plurality of X present in the graft chain 5and R 4 may be the same or different from each other.

[0064] Resin A may contain repeating units having two or more different structures, including a graft chain. That is, the molecule of resin A may contain repeating units represented by formulas (1) to (4) having structures different from one another, and when n, m, p, and q in formulas (1) to (4) each represent an integer of 2 or more, in formulas (1) and (2), j and k may have structures different from one another in the side chain, and in formulas (3) and (4), R present in a plurality of units in the molecule may be present. 3 , R 4 , and X 5 may be the same or different from each other.

[0065] The repeating unit represented by formula (1) is more preferably a repeating unit represented by the following formula (1A). The repeating unit represented by formula (2) is more preferably a repeating unit represented by the following formula (2A).

[0066] [ka]

[0067] In formula (1A), X 1 , Y 1 , Z 1 , and n is X in formula (1). 1 , Y 1 , Z 1 In formula (2A), X has the same meaning as n, and the preferred range is also the same. 2 , Y 2 , Z 2 , and m is X in formula (2). 2 , Y 2 , Z 2 , and m have the same meaning and preferred range.

[0068] The repeating unit represented by formula (3) is more preferably a repeating unit represented by the following formula (3A) or (3B).

[0069] [ka]

[0070] In formula (3A) or (3B), X 3 , Y 3 , Z 3 , and p is X in formula (3). 3 , Y 3 , Z 3 , and p have the same meanings and preferred ranges.

[0071] Resin A more preferably contains a repeating unit represented by formula (1A) as a repeating unit including a graft chain.

[0072] When the resin A contains the repeating units represented by the above formulas (1) to (4), it also preferably contains a repeating unit represented by the following formula (5) as another repeating unit containing a graft chain.

[0073] [ka]

[0074] In formula (5), n represents an integer of 1 to 50, preferably an integer of 2 to 30, more preferably an integer of 2 to 10, and even more preferably an integer of 2 to 5. Furthermore, j represents an integer of 2 to 8, preferably an integer of 4 to 6, and more preferably 5. In addition, in formula (5), X 5 and Z 5 Each of them represents X in formula (1). 1 and Z 1 The same definition and preferred embodiments are also the same.

[0075] Resin A also preferably contains 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 polyalkyleneimine structure is a polymerized structure containing two or more identical or different alkyleneimine chains. Specific examples of the alkyleneimine chain include those represented by the following formula (4A) and (4B).

[0077] [ka]

[0078] In formula (4A), R X1 and R X2 each independently represents a hydrogen atom or an alkyl group. 1 represents an integer greater than or equal to 2. 1 represents a bonding position to a polyester chain, an adjacent alkyleneimine chain, or a hydrogen atom or a substituent.

[0079] [ka]

[0080] In formula (4B), R X3 and R X4 each independently represents a hydrogen atom or an alkyl group. 2 represents an integer of 2 or more. The alkyleneimine chain represented by formula (4B) is a polyester chain having an anionic group and a N + The anionic groups contained in the polyester chain form salt bridges, resulting in bonding.

[0081] * in formula (4A) and formula (4B), and * in formula (4B) 2each independently represents a position at which the group is bonded to an adjacent alkyleneimine chain, or a hydrogen atom or a substituent. In particular, the * in the formula (4A) and the formula (4B) preferably represents the position at which the alkyleneimine chain is bonded to the 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 alkyl group preferably has 1 to 6 carbon atoms, and more preferably has 1 to 3 carbon atoms. In formula (4A), R X1 and R X2 are preferably all hydrogen atoms. In formula (4B), R X3 and R X4 are preferably all hydrogen atoms.

[0083] a in formula (4A) 1 and a in formula (4B) 2 is not particularly limited as long as it is an integer of 2 or more. The upper limit is preferably 10 or less, more preferably 6 or less, even more preferably 4 or less, still more preferably 2 or 3, and particularly preferably 2.

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

[0085] The alkyleneimine chain represented by formula (4A) is the same as that described above. 1 Specifically, it is preferable that the carbonyl carbon in the polyester chain is linked to the polyester chain at the position of 1 It is preferred that the bond is at the position The polyester chain may be represented by the following formula (5A).

[0086] [ka]

[0087] When the alkyleneimine chain is an alkyleneimine chain represented by formula (4B), the polyester chain is anionic (preferably an oxygen anion O - ), and the anionic group and the N in formula (4B) + It is preferred that these form a salt bridge. An example of such a polyester chain is a polyester chain represented by the following formula (5B).

[0088] [ka]

[0089] L in formula (5A) X1 and L in formula (5B) X2 each independently represents a divalent linking group. The divalent linking group is preferably an alkylene group having 3 to 30 carbon atoms.

[0090] b in formula (5A) 11 and b in formula (5B) 21 each independently represents an integer of 2 or more, preferably an integer of 6 or more, and the upper limit thereof is, for example, 200 or less.

[0091] b in formula (5A) 12 and b in formula (5B) 22 each independently represents 0 or 1.

[0092] X in formula (5A) A and X in formula (5B) B each independently represents a hydrogen atom or a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a polyalkyleneoxyalkyl group, and an aryl group.

[0093] The number of carbon atoms in 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) can be 1 to 30, and preferably 1 to 10. The alkyl group may further have a substituent, and examples of the substituent include a hydroxyl group and a halogen atom (examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom).

[0094] Polyalkyleneoxyalkyl groups are R X6 (OR X7 ) p (O) q R is a substituent represented by the formula: X6 represents an alkyl group, R X7 represents an alkylene group, p represents an integer of 2 or more, and q represents 0 or 1. R X6 The alkyl group represented by X A In addition, R X7 The alkylene group represented by the formula: X A Examples of the alkyl group include those obtained by removing one hydrogen atom from the alkyl group represented by the following formula: p is an integer of 2 or more, and its upper limit is, for example, 10 or less, and preferably 5 or less.

[0095] The aryl group may be, for example, an aryl group having 6 to 24 carbon atoms (which may be either monocyclic or polycyclic). The aryl group may further have a substituent, and examples of the substituent include an alkyl group, a halogen atom, and a cyano group.

[0096] The polyester chain is preferably a structure obtained by ring-opening a lactone such as ε-caprolactone, δ-caprolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone, γ-valerolactone, enantholactone, β-butyrolactone, γ-hexanolactone, γ-octanolactone, δ-hexalanolactone, δ-octanolactone, δ-dodecanolactone, α-methyl-γ-butyrolactone, or lactide (which may be either L- or D-form), and more preferably a structure obtained by ring-opening ε-caprolactone or δ-valerolactone.

[0097] The repeating unit containing the polyalkyleneimine structure and the polyester structure can be synthesized according to the synthesis method described in Japanese Patent No. 5,923,557.

[0098] In the resin A, the content of the repeating unit containing a graft chain is, in mass terms, for example, 2 to 100 mass%, preferably 2 to 95 mass%, more preferably 2 to 90 mass%, and still more preferably 5 to 30 mass%, relative to the total mass of the resin A. When the repeating unit containing a graft chain is contained within this range, the effects of the present invention are more excellent.

[0099] (hydrophobic repeating unit) Resin A may also contain a hydrophobic repeating unit different from the repeating unit containing a graft chain (i.e., not corresponding to the repeating unit containing a graft chain). However, in this specification, a hydrophobic repeating unit is a repeating unit that does not have an acid group (e.g., a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phenolic hydroxyl group, etc.).

[0100] The hydrophobic repeating unit is preferably a repeating unit derived from (corresponding to) a compound (monomer) having a ClogP value of 1.2 or more, and more preferably a repeating unit derived from a compound having a ClogP value of 1.2 to 8. This makes it possible to more reliably exhibit the effects of the present invention.

[0101] The ClogP value is a value calculated by the program "CLOGP" available from Daylight Chemical Information System, Inc. This program provides a "calculated logP" value calculated by the fragment approach of Hansch and Leo (see the literature below). The fragment approach is based on the chemical structure of a compound, and divides the chemical structure into partial structures (fragments), and estimates the logP value of the compound by summing up the logP contributions assigned to the fragments. Details are described in the literature below. In this specification, the ClogP value calculated by the program CLOGP v4.82 is used. 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 stands for the common logarithm of the partition coefficient P, and is a physical property that quantitatively represents how an organic compound is distributed in equilibrium in a two-phase system of 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 water phase. As the logP value increases toward the positive side, around 0, the oil solubility increases, and as the absolute value increases toward the negative side, the water solubility increases. It has a negative correlation with the water solubility of organic compounds, and is widely used as a parameter to estimate the hydrophilicity or hydrophobicity of organic compounds.

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

[0104] [ka]

[0105] In the above formulas (i) to (iii), R 1 , R 2 , and R 3 each independently represents a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), or an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, etc.). 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 is more preferably a hydrogen atom. X represents an oxygen atom (-O-) or an imino group (-NH-), and is preferably an oxygen atom.

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

[0107] The divalent aliphatic group may have a cyclic structure or a 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 an unsaturated aliphatic group or a saturated aliphatic group, but a saturated aliphatic group is preferred. The aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group, and a heterocyclic group.

[0108] The number of carbon atoms in the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and further preferably 6 to 10. The aromatic group may have a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group, and a heterocyclic group.

[0109] The divalent heterocyclic group preferably contains a 5-membered or 6-membered ring as a heterocycle. The heterocycle may be condensed with another heterocycle, an aliphatic ring, or an aromatic ring. The heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an oxo group (=O), a thioxo group (=S), an imino group (=NH), a substituted imino group (=NR 32 , where R 32 is an aliphatic group, an aromatic group, or a heterocyclic group), an aliphatic group, an aromatic group, and a heterocyclic group.

[0110] L is preferably a single bond, an alkylene group, or a divalent linking group containing 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 repeated oxyalkylene structures. The polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure. The polyoxyethylene structure is represented by -(OCH2CH2)n-, where n is preferably an integer of 2 or more, more preferably an integer of 2 to 10.

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

[0112] The aliphatic group may have a cyclic structure or a 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 further includes a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group. Examples of the ring assembly hydrocarbon group include a bicyclohexyl group, a perhydronaphthalenyl group, a biphenyl group, and a 4-cyclohexylphenyl group. Examples of the bridged cyclic hydrocarbon ring include bicyclic hydrocarbon rings such as pinane, bornane, norpinane, norbornane, and bicyclooctane rings (such as bicyclo[2.2.2]octane ring and bicyclo[3.2.1]octane ring), homobredane, adamantane, and tricyclo[5.2.1.0]octane ring. 2,6 ]decane and tricyclo[4.3.1.1 2,5 ]undecane ring and other tricyclic hydrocarbon rings, as well as tetracyclo[4.4.0.1 2,5 .1 7,10 ]dodecane, and tetracyclic hydrocarbon rings such as perhydro-1,4-methano-5,8-methanonaphthalene ring. The bridged cyclic hydrocarbon ring also includes condensed rings in which multiple 5- to 8-membered cycloalkane rings are condensed, such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and perhydrophenalene rings. The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. The aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group, and a heterocyclic group. However, the aliphatic group does not have an acid group as a substituent.

[0113] The number of carbon atoms in the aromatic group is preferably 6 to 20, more preferably 6 to 15, and further preferably 6 to 10. The aromatic group may have a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group, and a heterocyclic group. However, the aromatic group does not have an acid group as a substituent.

[0114] The heterocyclic group preferably contains a 5- or 6-membered ring as a heterocycle. The heterocycle may be condensed with another heterocycle, an aliphatic ring, or an aromatic ring. The heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an oxo group (=O), a thioxo group (=S), an imino group (=NH), a substituted imino group (=NR 32 , where R 32 is an aliphatic group, an aromatic group, or a heterocyclic group), an aliphatic group, an aromatic group, and a heterocyclic group, provided that the heterocyclic group does not have an acid group as a substituent.

[0115] In the above formula (iii), R 4 , R 5 , and R 6 R each independently represents a hydrogen atom, a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group having 1 to 6 carbon atoms (e.g., a methyl group, an ethyl group, a propyl group, etc.), Z, or LZ, where L and Z are the same as the groups defined above. 4 , R 5 , and R 6 is preferably 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 3is a hydrogen atom or a methyl group, L is a single bond or a divalent linking group containing an alkylene group or an oxyalkylene structure, X is an oxygen atom or an imino group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group. In addition, as the monomer represented by the above formula (ii), R 1 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. 4 , R 5 , and R 6 is a hydrogen atom or a methyl group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group.

[0117] Representative examples of the compounds represented by formulas (i) to (iii) include radically polymerizable compounds selected from acrylic acid esters, methacrylic acid esters, styrenes, and the like. Representative examples of the compounds represented by formulas (i) to (iii) can be found in the compounds described in paragraphs 0089 to 0093 of JP-A No. 2013-249417, the contents of which are incorporated herein by reference.

[0118] In the resin A, the content of the hydrophobic repeating unit is preferably from 10 to 90 mass %, and more preferably from 20 to 80 mass %, based on the total mass of the resin A, in terms of mass.

[0119] (Functional group capable of forming an interaction with magnetic particles) Resin A may have a functional group capable of forming an interaction with the magnetic particles. It is preferable that resin A further contains a repeating unit containing a functional group capable of forming an interaction with the magnetic particles. Examples of functional groups capable of forming interactions with magnetic particles include acid groups, basic groups, coordinating groups, and reactive functional groups. When resin A contains an acid group, a basic group, a coordinating group, or a reactive functional group, it preferably contains a repeating unit containing an acid group, a repeating unit containing a basic group, a repeating unit containing a coordinating group, or a repeating unit having a reactive functional group, respectively.

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

[0121] Examples of the acid group, which is a functional group capable of forming an interaction with the magnetic particles, include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group, and at least one of the carboxylic acid group, the sulfonic acid group, and the phosphoric acid group is preferred, and the carboxylic acid group is more preferred. The carboxylic acid group has a good adsorption force to the magnetic particles and is highly dispersible. That is, it is preferable that resin A further contains a repeating unit containing at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.

[0122] Resin A may have one or more types of repeating units containing an acid group. When the resin A contains a repeating unit containing an acid group, the content thereof is preferably from 5 to 80 mass %, and more preferably from 10 to 60 mass %, based on the total mass of the resin A, in mass terms.

[0123] Examples of basic groups that are functional groups capable of forming interactions with magnetic particles include primary amino groups, secondary amino groups, tertiary amino groups, heterocycles containing N atoms, and amide groups, and a preferred basic group is a tertiary amino group because of its 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 from 0.01 to 50 mass %, and more preferably from 0.01 to 30 mass %, based on the total mass of the resin A, in mass conversion.

[0124] Examples of the coordinating group, which is a functional group capable of forming an interaction with the 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 preferred functional group is an acetylacetoxy group, which has good adsorption power to the magnetic particles and high dispersibility of the magnetic particles. Resin A may have one or more of these groups. When resin A contains a repeating unit containing a coordinating group or a repeating unit containing a reactive functional group, the content of these units, calculated on a mass basis, is preferably 10 to 80 mass % and more preferably 20 to 60 mass % based on the total mass of resin A.

[0125] When the resin A contains functional groups capable of forming interactions with magnetic particles other than the graft chains, it is sufficient that the resin A contains functional groups capable of forming interactions with the various magnetic particles, and there are no particular limitations on how these functional groups are introduced. For example, it is preferable that the resin contained in the composition contains one or more repeating units selected from repeating units derived from monomers represented by the following formulas (iv) to (vi).

[0126] [ka]

[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, a bromine atom, etc.), or an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, etc.). In formulas (iv) to (vi), R 11 , R 12 , and R 13In general formula (iv), 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. 12 and R 13 is more preferably a hydrogen atom.

[0128] X1 in formula (iv) represents an oxygen atom (-O-) or an imino group (-NH-), and is preferably an oxygen atom. In addition, Y in the formula (v) represents a methine group or a nitrogen atom.

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

[0130] L1 is preferably a single bond, an alkylene group, or a divalent linking group containing 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 repeated oxyalkylene structures. The polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure. The polyoxyethylene structure is -(OCH2CH2) n -, where n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.

[0131] In the formulae (iv) to (vi), Z1 represents a functional group capable of forming an interaction with the magnetic particles other than the graft chain, and is preferably a carboxylic acid group or a tertiary amino group, more preferably a carboxylic acid group.

[0132] In formula (vi), R 14 , R 15 , and R 16 R each independently represents a hydrogen atom, a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group having 1 to 6 carbon atoms (e.g., a methyl group, an ethyl group, a propyl group, etc.), -Z1, or L1-Z1. Here, L1 and Z1 have the same meanings as L1 and Z1 above, and preferred examples are also the same. R14 , R 15 , and R 16 is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.

[0133] As the monomer represented by formula (iv), R 11 , R 12 , and R 13 are each independently a hydrogen atom or a methyl group, L1 is an alkylene group or a divalent linking group containing an oxyalkylene structure, X1 is an oxygen atom or an imino group, and Z1 is a carboxylic acid group. In addition, as the monomer represented by formula (v), R 11 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. Further, as the monomer represented by formula (vi), R 14 , R 15 , and R 16 are each independently a hydrogen atom or a methyl group, and Z1 is a carboxylic acid group.

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

[0135] The content of the repeating unit containing a functional group capable of forming an interaction with the magnetic particles is, in terms of the interaction with the magnetic particles, stability over time, and permeability into the developer, preferably 0.05 to 90 mass %, more preferably 1.0 to 80 mass %, and even more preferably 10 to 70 mass %, relative to the total mass of resin A.

[0136] (ethylenically unsaturated group) Resin A may contain an ethylenically unsaturated group. The ethylenically unsaturated group is not particularly limited, but examples thereof include a (meth)acryloyl group, a vinyl group, and a styryl group, with a (meth)acryloyl group being preferred. Resin A preferably contains a repeating unit containing an ethylenically unsaturated group in the side chain, and more preferably contains a repeating unit containing an ethylenically unsaturated group in the side chain and derived from a (meth)acrylate (hereinafter also referred to as a "(meth)acrylic repeating unit containing an ethylenically unsaturated group in the side chain"). The (meth)acrylic repeating unit containing an ethylenically unsaturated group in the side chain can be obtained, for example, by subjecting an ethylenically unsaturated compound containing a glycidyl group or an alicyclic epoxy group to an addition reaction with the carboxylic acid group in the resin A containing a (meth)acrylic repeating unit containing a carboxylic acid group. By introducing in this manner, a (meth)acrylic repeating unit containing an ethylenically unsaturated group in the side chain can be obtained.

[0137] When the resin A contains a repeating unit containing an ethylenically unsaturated group, the content thereof is preferably from 30 to 70 mass %, and more preferably from 40 to 60 mass %, based on the total mass of the resin A in mass terms.

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

[0139] When the resin A contains a repeating unit containing another curable group, the content thereof is preferably from 5 to 50 mass %, and more preferably from 10 to 30 mass %, based on the total mass of the resin A, in mass conversion.

[0140] (Other repeating units) Furthermore, for the purpose of improving various properties such as film-forming ability, resin A may further contain other repeating units having various functions different from the repeating units described above, as long as the effects of the present invention are not impaired. Examples of such other repeating units include repeating units derived from radically polymerizable compounds selected from acrylonitriles and methacrylonitriles. Resin A may use one or more of these other repeating units, and the content thereof, calculated on a mass basis, is preferably from 0 to 80 mass %, more preferably from 10 to 60 mass %, based on the total mass of resin A.

[0141] (Physical properties of resin A) The acid value of resin A is not particularly limited, but is, for example, preferably 0 to 400 mgKOH / g, more preferably 10 to 350 mgKOH / g, further preferably 30 to 300 mgKOH / g, and particularly preferably in the range of 50 to 200 mgKOH / g. If the acid value of 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 a compound. Also, a resin having a desired acid value can be obtained by changing the content of repeating units containing an acid group in the resin.

[0143] The weight average molecular weight of the resin A is not particularly limited, but is preferably, for example, 3,000 or more, more preferably 4,000 or more, even more preferably 5,000 or more, and particularly preferably 6,000 or more. The upper limit is, for example, 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 a known method.

[0144] As specific examples of Resin A, reference can be made to the polymer compounds described in paragraphs 0127 to 0129 of JP-A No. 2013-249417, the contents of which are incorporated herein by reference.

[0145] Furthermore, as the resin A, the graft copolymers described in paragraphs 0037 to 0115 of JP 2010-106268 A (corresponding paragraphs 0075 to 0133 of US 2011 / 0124824) can also be used, the contents of which are incorporated herein by reference.

[0146] <Alkali-soluble resin> The binder component may contain an alkali-soluble resin. In this specification, the alkali-soluble resin refers to a resin that contains a group that promotes alkali solubility (alkali-soluble group, for example an acid group such as a carboxylic acid group), and refers to a resin different from the resin A described above.

[0147] Examples of the alkali-soluble resin include resins containing at least one alkali-soluble group in the 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 acid is not particularly limited, but examples thereof 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 acid anhydrides thereof; and polycarboxylic acid monoesters such as mono(2-(meth)acryloyloxyethyl)phthalate.

[0149] Examples of the copolymerizable ethylenically unsaturated compound include methyl (meth)acrylate, etc. Compounds described in paragraph 0027 of JP 2010-097210 A and paragraphs 0036-0037 of JP 2015-068893 A can also be used, and the contents of the above are incorporated herein by reference.

[0150] In addition, a copolymerizable ethylenically unsaturated compound having an ethylenically unsaturated group in a side chain may be used in combination. In other words, the alkali-soluble resin may contain a repeating unit having an ethylenically unsaturated group in a side chain. The ethylenically unsaturated group contained in the side chain is preferably a (meth)acrylic acid group. A repeating unit containing an ethylenically unsaturated group in a side chain can be obtained, for example, by subjecting a carboxylic acid group of a (meth)acrylic repeating unit containing a carboxylic acid group to an addition reaction with an ethylenically unsaturated compound containing a glycidyl group or an alicyclic epoxy group.

[0151] The alkali-soluble resin is also preferably an alkali-soluble resin containing a curable group. Examples of the curable group include, but are not limited to, ethylenically unsaturated groups (e.g., (meth)acryloyl groups, vinyl groups, styryl groups, etc.) and cyclic ether groups (e.g., epoxy groups, oxetanyl groups, etc.). Among these, the curable group is preferably an ethylenically unsaturated group, and more preferably a (meth)acryloyl group, in terms of the ability to control polymerization by radical reaction. The alkali-soluble resin containing a curable group is preferably an alkali-soluble resin having a curable group in a side chain, etc. Examples of the alkali-soluble resin containing a curable group include Dianaru 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 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series (e.g., ACA230AA), Plaxel CF200 series (all manufactured by Daicel Corporation), Ebecryl 3800 (manufactured by Daicel-Allnex Corporation), and Acricur RD-F8 (manufactured by Nippon Shokubai Co., Ltd.).

[0152] Examples of the alkali-soluble resin include radical polymers having a carboxylic acid group in the side chain described in JP-A-59-044615, JP-B-54-034327, JP-B-58-012577, JP-B-54-025957, JP-A-54-092723, JP-A-59-053836, and JP-A-59-071048; Examples of binders that can be used include acetal-modified polyvinyl alcohol-based binder resins containing an alkali-soluble group as described in JP 2001-318463 A; 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 WO 2008 / 123097 A.

[0153] As the alkali-soluble resin, for example, the compounds described in paragraphs 0225 to 0245 of JP-A-2016-075845 can also be used, the contents of which are incorporated herein by reference.

[0154] As the alkali-soluble resin, a polyimide precursor can also be used. The polyimide precursor refers to a resin obtained by subjecting a compound containing an acid anhydride group and a diamine compound to an addition polymerization reaction at 40 to 100°C. Specific examples of the polyimide precursor include compounds described in paragraphs 0011 to 0031 of JP 2008-106250 A, compounds described in paragraphs 0022 to 0039 of JP 2016-122101 A, compounds described in paragraphs 0061 to 0092 of JP 2016-068401 A, resins described in paragraph 0050 of JP 2014-137523 A, resins described in paragraph 0058 of JP 2015-187676 A, and resins described in paragraphs 0012 to 0013 of JP 2014-106326 A, the contents of which are incorporated herein by reference.

[0155] As the alkali-soluble resin, a copolymer of benzyl (meth)acrylate / (meth)acrylic acid / if necessary, other addition-polymerizable vinyl monomers and a copolymer of allyl (meth)acrylate / (meth)acrylic acid / if necessary, other addition-polymerizable vinyl monomers are preferred, as they have an excellent balance of film strength, sensitivity, and developability. The other addition-polymerizable vinyl monomers may be used alone or in combination of two or more kinds. The copolymer preferably contains a curable group, and more preferably contains an ethylenically unsaturated group such as a (meth)acryloyl group, in order to provide a cured film with better moisture resistance. For example, a curable group may be introduced into the copolymer by using a monomer having a curable group as the other addition polymerizable vinyl monomer. Also, a curable group (preferably an ethylenically unsaturated group such as a (meth)acryloyl group) may be introduced into a part or all of one or more of the units derived from (meth)acrylic acid and / or the other addition polymerizable vinyl monomer in the copolymer. Examples of the other addition-polymerizable vinyl monomers include methyl (meth)acrylate, styrene-based monomers (such as hydroxystyrene), and ether dimers. Examples of the ether dimer include a compound represented by the following general formula (ED1) and a compound represented by the following general formula (ED2).

[0156] [ka]

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

[0158] [ka]

[0159] In the general formula (ED2), R represents a hydrogen atom or an organic group having a carbon number of 1 to 30. Specific examples of the general formula (ED2) can be found in JP-A-2010-168539.

[0160] For specific examples of the ether dimer, see, for example, paragraph 0317 of JP 2013-029760 A, the contents of which are incorporated herein by reference. The ether dimer may be of only one type, or of two or more types.

[0161] The acid value of the alkali-soluble resin is not particularly limited, but in general, it is preferably from 30 to 500 mgKOH / g, and more preferably from 50 to 200 mgKOH / g or more.

[0162] When the composition contains an alkali-soluble resin, the content of the alkali-soluble resin is preferably 1 to 24 mass%, more preferably 1 to 15 mass%, even more preferably 1 to 12 mass%, particularly preferably 1 to 10 mass%, and most preferably 1 to 7 mass%, relative to the total mass of the composition. When the composition contains an alkali-soluble resin, the content of the alkali-soluble resin is preferably 0.8 to 24 mass%, more preferably 0.8 to 15 mass%, even more preferably 0.8 to 12 mass%, even more preferably 0.8 to 10 mass%, particularly preferably 0.8 to 8 mass%, and most preferably 0.8 to 7 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. The rheology control agent is a component that imparts thixotropic properties to the composition, ie, high viscosity when the shear stress (shear rate) is low and low viscosity when the shear stress (shear rate) is high. In this specification, the resin-type rheology control agent refers to a resin having the above-mentioned properties, and is different from the above-mentioned resin A.

[0164] Examples of the resin-type rheology control agent include compounds having one or more (preferably two or more) adsorptive groups and further having a steric repulsive structural group. The weight average molecular weight of the resin-type rheology control agent is preferably 2,000 or more, and is preferably in the range of 2,000 to 50,000. An example of a specific embodiment of the resin-type rheology control agent is a resin-type organic rheology control agent among the organic rheology control agents described below. 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 mass %, more preferably 1 to 15 mass %, even more preferably 1 to 12 mass %, particularly preferably 1 to 10 mass %, and most preferably 1 to 7 mass %, relative to the total mass of the composition. Furthermore, when 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 mass%, more preferably 0.8 to 15 mass%, even more preferably 0.8 to 12 mass%, even more preferably 0.8 to 10 mass%, particularly preferably 0.8 to 8 mass%, and most preferably 0.8 to 7 mass%, based on the total solid content of the composition.

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

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

[0167] (Compound containing a group containing an ethylenically unsaturated bond) Examples of the polymerizable compound include compounds that contain a group containing an ethylenically unsaturated bond (hereinafter, also simply referred to as an "ethylenically unsaturated group"). The polymerizable compound is preferably a compound containing one or more ethylenically unsaturated bonds, more preferably a compound containing two or more, even more preferably a compound containing three or more, and particularly preferably a compound containing five or more. The upper limit is, for example, 15 or less. Examples of the ethylenically unsaturated group include a vinyl group, a (meth)allyl group, and a (meth)acryloyl group.

[0168] As the polymerizable compound, for example, the compounds described in paragraph 0050 of JP-A-2008-260927 and paragraph 0040 of JP-A-2015-068893 can be used, the contents of which are incorporated herein by reference.

[0169] The polymerizable compound may be in any chemical form, such as a monomer, a prepolymer, an oligomer, a mixture thereof, or a polymer thereof. The polymerizable compound is preferably a 3- to 15-functional (meth)acrylate compound, more preferably a 3- to 6-functional (meth)acrylate compound.

[0170] As the polymerizable compound, a compound containing one or more ethylenically unsaturated groups and having a boiling point of 100° C. or more is also preferred. For example, the compounds described in paragraphs

[0227] of JP-A-2013-029760 and paragraphs

[0254] to

[0257] of JP-A-2008-292970 can be referred to, the contents of which are incorporated herein by reference.

[0171] As the polymerizable compound, dipentaerythritol triacrylate (commercially available product is KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available product is KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available product is KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available products are 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 is mediated by an ethylene glycol residue or a propylene glycol residue (for example, SR454, SR499, commercially available from Sartomer Co., Ltd.) are preferred. Oligomer types of these 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.), etc. may also be used.

[0172] The polymerizable compound may have an acid group such as a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group. As the polymerizable compound containing an acid group, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferable, and a polymerizable compound in which an acid group is provided by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride is more preferable, and in this ester, a compound in which the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol is even more preferable. Examples of commercially available products include Aronix TO-2349, M-305, M-510, and M-520 manufactured by Toagosei Co., Ltd.

[0173] The acid value of the polymerizable compound containing an acid group is preferably 0.1 to 40 mgKOH / g, more preferably 5 to 30 mgKOH / g. If the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the development dissolution property is good, and if it is 40 mgKOH / g or less, it is advantageous in terms of production and / or handling. Furthermore, the photopolymerization performance is good and the curing property is excellent.

[0174] As the polymerizable compound, a compound containing a caprolactone structure is also a preferred embodiment. The compound containing a caprolactone structure is not particularly limited as long as it contains a caprolactone structure in the molecule, and examples thereof 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 formula (Z-1), all of the six R's are groups represented by the following formula (Z-2), or 1 to 5 of the six R's are groups represented by the following formula (Z-2), and the remainder are groups represented by the following formula (Z-3).

[0177] [ka]

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

[0179] [ka]

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

[0181] As a polymerizable compound containing a caprolactone structure, for example, the KAYARAD DPCA series is commercially available from Nippon Kayaku, and DPCA-20 (wherein m=1 in the above formulas (Z-1) to (Z-3), the number of groups represented by formula (Z-2)=2, R 1 are all hydrogen atoms), DPCA-30 (same formula, m=1, the number of groups represented by formula (Z-2)=3, R 1 are all hydrogen atoms), DPCA-60 (same formula, m=1, the number of groups represented by formula (Z-2)=6, R 1 are all hydrogen atoms), and DPCA-120 (wherein m=2, the number of groups represented by formula (Z-2)=6, R 1 are all hydrogen atoms). In addition, a commercially available polymerizable compound containing a caprolactone structure includes M-350 (trade name) (trimethylolpropane triacrylate) manufactured by Toagosei Co., Ltd.

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

[0183] [ka]

[0184] In formulas (Z-4) and (Z-5), E is -((CH2) y CH2O)- or ((CH2) y CH(CH3)O)-, y represents an integer of 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 of 0 to 10; the sum of the m's is an integer of 0 to 40. In formula (Z-5), the total number of (meth)acryloyl groups is 5 or 6; n represents an integer of 0 to 10; and the sum of the n's is an integer of 0 to 60.

[0185] In formula (Z-4), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. The sum of the m's is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and further preferably an integer of 4 to 8. In the formula (Z-5), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. The sum of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and further preferably an integer of 6 to 12. In addition, -((CH2) y CH2O)- or ((CH2) y In the case of CH(CH3)O)-, the terminal on the oxygen atom side is preferably bonded to X.

[0186] The compound represented by formula (Z-4) or formula (Z-5) may be used alone or in combination of two or more. In particular, in formula (Z-5), the form in which all six Xs are acryloyl groups, and in formula (Z-5), the mixture of the compound in which all six Xs are acryloyl groups and the compound in which at least one of the six Xs is a hydrogen atom are preferred. With this configuration, the developability can be further improved.

[0187] The total content of the compound represented by formula (Z-4) or formula (Z-5) in the polymerizable compounds 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] The polymerizable compound may also contain a cardo skeleton. As the polymerizable compound containing a cardo skeleton, a polymerizable compound containing a 9,9-bisarylfluorene skeleton is preferable. Examples of the polymerizable compound containing a cardo skeleton include, but are not limited to, Oncoat EX series (manufactured by Nagase & Co., Ltd.) and OGSOL (manufactured by Osaka Gas Chemicals Co., Ltd.). The polymerizable compound is also preferably a compound containing an isocyanuric acid skeleton as a central core. An example of such a polymerizable compound is NK Ester A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.). The content of ethylenically unsaturated groups in the polymerizable compound (meaning the value obtained by dividing the number of ethylenically unsaturated groups in the polymerizable compound by the molecular weight (g / mol) of the polymerizable compound) is preferably 5.0 mmol / g or more. The upper limit is not particularly limited, but is generally 20.0 mmol / g or less.

[0189] (Compounds having an epoxy group and / or an oxetanyl group) 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 has 2 to 10 epoxy groups and / or oxetanyl groups. In the polymerizable compound, the epoxy group and / or oxetanyl group (preferably the epoxy group) may be condensed with a cyclic group (such as an alicyclic group). The cyclic group condensed with the epoxy group and / or oxetanyl group preferably has 5 to 15 carbon atoms. In the cyclic group, the portion other than the condensed epoxy group and / or oxetanyl group may be a monocyclic or polycyclic ring. Only one epoxy group or oxetanyl group may be condensed with one cyclic group, or two or more epoxy groups and / or oxetanyl groups may be condensed with one cyclic group.

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

[0191] The polymerizable compound may be a compound containing a caprolactone structure represented by the above formula (Z-1), in which the group represented by formula (Z-2) is changed to the following formula (Z-2E) 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 the number 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 "*" represents a bond.

[0194] The polymerizable compound may be a compound represented by formula (Z-4) above, modified so that X represents a group represented by formula (Z-3E) or a hydrogen atom. In the formula (Z-4) modified in this way, the total number of groups represented by formula (Z-3E) is 2 to 4.

[0195] The polymerizable compound may be a compound represented by formula (Z-5) above modified so that X represents a group represented by formula (Z-3E) or a hydrogen atom. In the formula (Z-5) modified 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 be a compound having a structure in which N (number of) cyclic groups condensed with an epoxy group and / or an oxetanyl group are bonded via a linking group. N is an integer of 2 or more, preferably an integer of 2 to 6, and more preferably 2. The total number of atoms other than hydrogen atoms in the linking group is preferably 1 to 20, and more preferably 2 to 6. When N is 2, examples of the linking group include an alkyleneoxycarbonyl group.

[0197] 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 Corp.). These are low-chlorine products, but not low-chlorine products such as EX-212, EX-214, EX-216, EX-321, EX-614, and EX-850 can also be used. In addition, a commercially available product such as Celloxide 2021P (manufactured by Daicel Corporation, a multifunctional epoxy monomer) can also be used. In addition, a commercially available product such as EHPE 3150 (manufactured by Daicel Corporation, a multifunctional epoxy / oxiranyl monomer) can also be used.

[0198] 〔solvent〕 The composition includes a solvent. The solvent includes 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, and from the viewpoint of obtaining superior effects of the present invention, is more preferably 80° C. or higher, further preferably 100° C. or higher, and particularly preferably 160° C. or higher. The upper limit of the boiling point of the solvent is not particularly limited, but 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), propylene glycol, Cholesterol 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 triacetate (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), gamma-butyrolactone (boiling point 204°C), ethyl acetate (boiling point 77.1°C), 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), but are not limited to these.

[0200] As a preferred embodiment of the solvent, an acetate-based solvent is also preferred in that the effects of the present invention are more excellent. The acetate solvent is intended to mean a solvent containing one or more acetate groups in the molecule. The number of acetate groups contained in the acetate solvent is preferably 2 or more, in terms of the superior effect of the present invention. The upper limit is not particularly limited, but is, for example, 6 or less. The acetate solvent preferably has a boiling point of 160°C or more.

[0201] An example of an acetate-based solvent containing two or more acetate groups in the molecule is a compound represented by the formula (1A). Formula (1A) M-(OC(=O)-CH3) m In formula (1A), M represents a linking group having a valence of m, and m represents an integer of 2 to 6.

[0202] Examples of M, which is a linking group having a valence of m (m=2 to 6), include linking groups represented by the following formulas (M-1) to (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 independently represents an organic group. X 11 , X 21 , X 31 , X 41 , and X 51Specific examples of the organic group represented by the formula (I) include a heteroatom (for example, a nitrogen atom, an oxygen atom, and a sulfur atom. In addition, examples of the heteroatom include -O-, -S-, -SO2-, -NR 1 The linking group may be in the form of -, -CO-, or a combination of two or more of these.) is preferably a hydrocarbon group formed from a hydrocarbon that may contain a heteroatom. Specifically, a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon ring group, an aromatic hydrocarbon ring group, a heterocyclic group, or a linking group that is a combination of two or more of these is preferred. In addition, the above X 11 The hydrocarbon group which may contain a heteroatom as an organic group represented by the formula (I) means a divalent group formed by removing two hydrogen atoms from the above-mentioned hydrocarbon which may contain a heteroatom, and the above-mentioned X 21 The hydrocarbon group which may contain a heteroatom as an organic group represented by the formula (I) means a trivalent group formed by removing three hydrogen atoms from the above-mentioned hydrocarbon which may contain a heteroatom, and the above-mentioned X 31 The hydrocarbon group which may contain a heteroatom as an organic group represented by the formula (I) means a tetravalent group formed by removing four hydrogen atoms from the above-mentioned hydrocarbon which may contain a heteroatom, and the above-mentioned X 41 The hydrocarbon group which may contain a heteroatom as an organic group represented by the formula (I) means a pentavalent group formed by removing five hydrogen atoms from the above-mentioned hydrocarbon which may contain a heteroatom, and the above-mentioned X 51 The hydrocarbon group which may contain a heteroatom as an organic group represented by the following formula (I) means a hexavalent group formed by removing six hydrogen atoms from the above-mentioned hydrocarbon which may contain a heteroatom.

[0205] Above R 1 represents a hydrogen atom or a substituent. The substituent is not particularly limited, but is preferably, for example, an alkyl group (preferably having 1 to 6 carbon atoms, which may be linear or branched).

[0206] The above-mentioned linear or branched aliphatic hydrocarbon group, aliphatic hydrocarbon ring group, aromatic hydrocarbon ring group, and heterocyclic group, which may contain a heteroatom, may further have a substituent.

[0207] The linear or branched aliphatic hydrocarbon group is not particularly limited in number of carbon atoms, but preferably has 1 to 12 carbon atoms, more preferably has 1 to 10 carbon atoms, and further preferably has 3 to 6 carbon atoms. The aliphatic hydrocarbon group includes an alkylene group.

[0208] The number of carbon atoms in the aliphatic hydrocarbon ring group (alicyclic group) is not particularly limited, but is preferably 3 to 30, more preferably 6 to 20, further preferably 6 to 15, and particularly preferably 6 to 12. The alicyclic group may be either monocyclic or polycyclic, or may be a spiro ring. Examples of the alicyclic ring constituting the monocyclic alicyclic group include monocyclic cycloalkanes such as cyclopentane, cyclohexane, and cyclooctane. Examples of the alicyclic ring constituting the 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 aromatic hydrocarbon ring group is not particularly limited, but is preferably 6 to 30, more preferably 6 to 20, further preferably 6 to 15, and particularly preferably 6 to 12. The aromatic hydrocarbon group may be monocyclic or polycyclic. Examples of the aromatic hydrocarbon ring include a benzene ring and a naphthalene ring.

[0210] The number of carbon atoms of the heterocyclic ring constituting 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 ring may be either monocyclic or polycyclic, and may be either an aromatic heterocyclic ring or an aliphatic heterocyclic ring. The heterocyclic ring may be a spiro ring. Examples of aromatic heterocyclic rings include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Examples of aliphatic heterocyclic rings include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring.

[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 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 the formula (I) is not particularly limited, but may be an alkylene group, -CO-, -CONR N It is preferably a divalent linking group consisting of one or more groups or a combination of two or more groups selected from the group consisting of -, -O-, and -S-. The alkylene group may be linear, branched, or cyclic. The alkylene group preferably has 1 to 10 carbon atoms, and more preferably has 1 to 4 carbon atoms. The alkylene group may further have a substituent. In addition, the above R Nrepresents a hydrogen atom or a substituent. The substituent is not particularly limited, but is preferably, for example, an alkyl group (preferably having 1 to 6 carbon atoms, which may be linear or branched).

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

[0213] One embodiment of M, which is a divalent linking group, is a substituted or unsubstituted alkylene group. The alkylene group is preferably linear or branched, and preferably has 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms, and further preferably 3 to 6 carbon atoms.

[0214] Moreover, one embodiment of M which is a trivalent linking group includes a group represented by the following formula (1a). Formula (1a) R A -C-(L 1 -*)3 In formula (1a), R A represents a hydrogen atom or a substituent. 1 represents a single bond or an alkylene group having 1 to 6 carbon atoms which may have a substituent. * represents the bonding position with the acetyl group ((OC(=O)-CH3)) shown in formula (1A). In addition, there are three L 1 may be the same or different from each other. R A The substituent represented by is not particularly limited, and examples thereof include monovalent organic groups, preferably alkyl groups having 1 to 6 carbon atoms which may have a substituent, and more preferably alkyl groups having 1 to 3 carbon atoms which may have a substituent. The substituent is not particularly limited, and examples thereof include a hydroxyl group. R A is preferably a hydrogen atom. L 1The alkylene group having 1 to 6 carbon atoms, which may have a substituent, is preferably an alkyl group having 1 to 3 carbon atoms, which may have a substituent. The substituent is not particularly limited, and examples thereof include a hydroxyl group.

[0215] Specific examples of the compound represented by formula (1A) include 1,4-BDDA, 1,6-HDDA, 1,3-BGDA, PGDA, and glycerol triacetate.

[0216] The solvent may be used alone or in combination of two or more kinds. The content of the solvent in the composition (the total content when multiple types are contained) is 3 to 24% by mass, based on the total mass of the composition. When the content of the solvent is 3% by mass or more, based on the total mass of the composition, the composition has excellent fluidity. On the other hand, when the content of the solvent is 24% by mass or less, based on the total mass of the composition, the cured product formed from the composition has excellent filling suitability. In particular, in terms of better effects of the present invention, the upper limit of the content is preferably 15% by mass or less, and more preferably 8% by mass or less.

[0217] In the composition, the content of the solvent having a boiling point of 160° C. or more is preferably 3% by mass or more based on the total mass of the composition. When the content of the solvent having a boiling point of 160° C. or more is 3% by mass or more, the shrinkage during curing during film formation is unlikely to occur, and the occurrence of voids and cracks can be suppressed. As a result, the cured product formed from the composition has excellent filling suitability. The upper limit of the content of the solvent having 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, based on the total mass of the composition.

[0218] [Rheology control agent] The composition may also include a rheology control agent. The rheology control agent is a component that imparts thixotropic properties to the composition, ie, high viscosity when the shear stress (shear rate) is low and low viscosity when the shear stress (shear rate) is high. The content of the rheology control agent is preferably 1 to 24 mass%, more preferably 1 to 15 mass%, even more preferably 1 to 12 mass%, particularly preferably 1 to 10 mass%, and most preferably 1 to 7 mass%, relative to the total mass of the composition. The content of the rheology control agent is preferably 0.8 to 24 mass%, more preferably 0.8 to 15 mass%, even more preferably 0.8 to 12 mass%, even more preferably 0.8 to 10 mass%, particularly preferably 0.8 to 8 mass%, and most preferably 0.8 to 7 mass%, based on the total solid content of the composition. The content of the rheology control agent mentioned above does not include the content of the resin-type rheology control agent, which corresponds to the resin that is the binder component mentioned above.

[0219] The rheology control agent may be an organic rheology control agent or an inorganic rheology control agent, with the organic rheology control agent being preferred. In addition,

[0220] <Organic rheology control agent> The content of the organic rheology control agent is preferably 1 to 24 mass%, more preferably 1 to 15 mass%, even more preferably 1 to 12 mass%, particularly preferably 1 to 10 mass%, and most preferably 1 to 7 mass%, relative to the total mass of the composition. The content of the organic rheology control agent is preferably 0.8 to 24 mass%, more preferably 0.8 to 15 mass%, even more preferably 0.8 to 12 mass%, even more preferably 0.8 to 10 mass%, particularly preferably 0.8 to 8 mass%, and most preferably 0.8 to 7 mass%, based on the total solid content of the composition. The content of the organic rheology control agent does not include the content of the resin-type rheology control agent, which corresponds to the resin that is the binder component described above. The organic rheology control agents may be used alone or in combination of two or more kinds.

[0221] Examples of the organic rheology control agent include compounds having one or more (preferably two or more) adsorptive groups and further having a steric repulsive structural group. The adsorptive groups interact with the surface of the magnetic particles to cause the organic rheology control agent to be adsorbed to the surface of the magnetic particles. Examples of the adsorptive group include an acid group, a basic group, and an amide group. Examples of the acid group include a carboxy group, a phosphate group, a sulfo group, a phenolic hydroxyl group, and an acid anhydride group thereof (such as an acid anhydride group of a carboxy group), and the carboxy group is preferred in terms of providing better effects of the present invention. Examples of basic groups include amino groups (groups in which one hydrogen atom has been removed from ammonia, primary amines, or secondary amines) and imino groups. Of these, the adsorptive group is preferably a carboxy group or an amide group, and more preferably a carboxy group. The steric repulsive structural group has a three-dimensionally bulky structure, and thus 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 the steric repulsive structural group, for example, a chain group is preferable, a long-chain fatty acid group is more preferable, and a long-chain alkyl group is even more preferable. The organic rheology control agent also preferably has a hydrogen bonding unit. The hydrogen-bonding unit is a partial structure that functions to construct a hydrogen-bonding network between organic rheology control agents, and between an organic rheology control agent and another component. The organic rheology control agent that contributes to the formation of the network may or may not be adsorbed to the surface of the magnetic particle. The hydrogen-bonding unit may be the same as or different from the above-mentioned adsorptive group. When the hydrogen-bonding unit is the same as the above-mentioned adsorptive group, a part of the adsorptive group binds to the surface of the magnetic particle, and another part functions as the hydrogen-bonding unit. The hydrogen-bonding unit is preferably a carboxy group or an amide group. The carboxy group as the hydrogen-bonding unit is preferred because it is easily incorporated in the curing reaction when preparing a cured product, and the amide group is preferred because the composition has better stability over time.

[0222] When the organic rheology control agent is a resin, the organic rheology control agent may have a repeating unit containing the above-mentioned graft chain, or may not have substantially any of the above-mentioned repeating units containing the graft chain. When the organic rheology control agent is a resin and does not substantially have any of the above-mentioned repeating units containing the graft chain, the content of the repeating unit containing the above-mentioned graft chain relative to the total mass of the 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 carboxy groups), polycarboxylic anhydrides (compounds having two or more acid anhydride groups consisting of carboxy groups), and amide waxes. These may be resins or materials other than resins. These may also correspond to an aggregation control agent and / or an aggregation dispersant, which will be described later.

[0224] Examples of organic rheology control agents include modified urea, urea modified polyamide, fatty acid amide, polyurethane, polyamide amide, polymeric urea derivatives, and salts thereof (such as carboxylates). The modified urea is a reaction product of an isocyanate monomer or its adduct with an organic amine. The modified urea is modified with polyoxyalkylene polyol (polyoxyethylene polyol, polyoxypropylene polyol, etc.) and / or alkyd chain, etc. The urea modified polyamide is, for example, a compound containing a urea bond and a compound having a medium polarity group or a low polarity group introduced at the end of the compound. Examples of the medium polarity group or low polarity group include polyoxyalkylene polyol (polyoxyethylene polyol, polyoxypropylene polyol, etc.) and an alkyd chain. The fatty acid amide is a compound having a long chain fatty acid group and an amide group in the molecule. These may be resins or non-resins. These may also correspond to an aggregation control agent and / or an aggregation dispersant, which will be described later.

[0225] The molecular weight of the organic rheology control agent (weight average molecular weight when the agent has a molecular weight distribution) is preferably in the range of 200 to 50,000. When the organic rheology control agent has an acid value, the acid value is preferably from 5 to 400 mgKOH / g. When the organic rheology control agent has an amine acid value, the amine value is preferably from 5 to 300 mgKOH / g.

[0226] (Aggregation control agent) Organic rheology control agents also include aggregation control agents, which may be resins or other substances. The aggregation control agent has the function of binding to relatively dense aggregates such as magnetic particles, and further dispersing components such as a resin precursor in the composition, thereby enabling the production of bulky aggregates. When the composition contains an aggregation control agent, the magnetic particles in the composition are prevented from forming a hard cake, and bulkier aggregates are formed, which can improve redispersibility.

[0227] The aggregation control agent may, for example, be a cellulose derivative. Examples of the cellulose derivatives include carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxypropyl ethyl cellulose, and salts thereof.

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

[0229] (Aggregation and dispersant) The organic rheology control agent also includes a flocculating dispersant. The flocculating dispersant may be a resin or may be something other than a resin. The aggregating dispersant has the function of adsorbing to the surface of the magnetic particles, separating the magnetic particles from each other, while maintaining the distance between the magnetic particles at a certain level or more through the interaction between the dispersants, thereby preventing the magnetic particles from aggregating directly with each other. As a result, the aggregation of the magnetic particles is suppressed, and even if an aggregate is formed, the aggregate has a relatively low density. Furthermore, components such as a resin precursor can be dispersed in the composition to create a bulky aggregate, which can improve redispersibility.

[0230] As the flocculating dispersant, an alkylol ammonium salt of a polybasic acid is preferred. The polybasic acid may have two or more acid groups, and examples thereof include acidic polymers containing repeating units having an acid group (e.g., polyacrylic acid, polymethacrylic acid, polyvinylsulfonic acid, polyphosphoric acid, etc.). Other examples of polybasic acids include polymers obtained by polymerizing unsaturated fatty acids such as crotonic acid. Alkylolammonium salts of polybasic acids can be obtained by reacting these polybasic acids with alkylolammonium. The salts obtained by such reactions usually contain the following partial structure: -C(=O)-N(-R 1 )(-R 2 -OH) Here, R 1 is an alkyl group, R 2 is an alkylene group. The alkylol ammonium salt of a polybasic acid is preferably a polymer containing a plurality of the above partial structures. When the alkylol ammonium salt of a polybasic acid is a polymer, the weight average molecular weight is preferably 1,000 to 100,000, more preferably 5,000 to 20,000. The polymer of the alkylol ammonium salt of a polybasic acid is bonded to the surface of the magnetic particles and is also hydrogen bonded to other flocculating dispersant molecules, so that the main chain structure of the polymer can penetrate between the magnetic particles and separate the magnetic particles from each other.

[0231] One of the preferred embodiments of the flocculating dispersant is amide wax, which is a dehydration condensation product of at least any acid selected from (a) saturated aliphatic monocarboxylic acids and hydroxyl group-containing aliphatic monocarboxylic acids, and (b) polybasic acids, and (c) at least any amine selected from diamines and tetraamines. The above (a) to (c) are preferably used in such a manner that the molar ratio of (a):(b):(c)=1-3:0-5:1-6.

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

[0233] The polybasic acids are preferably dibasic or higher carboxylic acids having 2 to 12 carbon atoms, and more preferably dicarboxylic acids. 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 alone or in combination.

[0234] The diamines preferably have a carbon number of 2 to 14. Specific 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. The tetraamines preferably have a carbon number of 2 to 14. Specific examples include butane-1,1,4,4-tetraamine and pyrimidine-2,4,5,6-tetraamine. These diamines and tetraamines may be used alone or in combination.

[0235] The amount of diamines and tetraamines is 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, when there are n moles (n=0-5) of aliphatic dicarboxylic acid, which is a polybasic acid, for 2 moles of aliphatic monocarboxylic acid, and the number of moles of diamines is (n+1), the acid and amine are equivalent.

[0236] The amide wax may be obtained as a mixture of a plurality of compounds having different molecular weights. The amide wax is preferably a compound represented by the following chemical formula (I). The amide wax may be a single compound or a mixture. AC-(BC) m -A···(I) In formula (I), A is a dehydroxylated residue of a saturated aliphatic monocarboxylic acid and / or a hydroxyl group-containing saturated aliphatic monocarboxylic acid, B is a dehydroxylated 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 aggregation dispersant is a compound represented by the following formula (II).

[0238] [ka]

[0239] In formula (II), R 1 represents a monovalent linear aliphatic hydrocarbon group having 10 to 25 carbon atoms, R 2 and R 3 each 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 represents a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, R 5 and R 6 each 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 independently represents an amide bond, L 1 and L 3 If -CONH-, then L 2 is -NHCO-, and L 1 and L 3 When is -NHCO-, L 2 is -CONH-.

[0240] R 1 is a monovalent linear aliphatic hydrocarbon group having 10 to 25 carbon atoms, and examples thereof include linear alkyl groups such as a decyl group, a lauryl group, a myristyl group, a pentadecyl group, a stearyl group, a palmityl group, a nonadecyl group, an eicosyl group, and a behenyl group; linear alkenyl groups such as a decenyl group, a pentadecenyl group, an oleyl group, and an eicosenyl group; and linear alkynyl groups such as a pentadecynyl group, an octadecynyl group, and a nonadecynyl group. Among them, R 1 is preferably a monovalent linear aliphatic hydrocarbon group having 14 to 25 carbon atoms, 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 the divalent aliphatic hydrocarbon group having 2, 4, 6 or 8 carbon atoms include an ethylene group, an n-butylene group, an n-hexylene group, and an n-octylene group. R 2 and R 3 Examples of the divalent alicyclic hydrocarbon group having 6 carbon atoms include a 1,4-cyclohexylene group, a 1,3-cyclohexylene group, and a 1,2-cyclohexylene group. R 2 and R 3 Examples of the divalent aromatic hydrocarbon group in include arylene groups having 6 to 10 carbon atoms, such as a 1,4-phenylene group, a 1,3-phenylene group, and a 1,2-phenylene group.

[0242] Among them, R 2 and R3 is preferably a divalent aliphatic hydrocarbon group having 2, 4, 6 or 8 carbon atoms, more preferably a divalent aliphatic hydrocarbon group having 2, 4 or 6 carbon atoms, still more preferably a divalent aliphatic hydrocarbon group having 2 or 4 carbon atoms, and still more preferably a divalent aliphatic hydrocarbon group having 2 carbon atoms. The divalent aliphatic hydrocarbon group is preferably a linear alkylene group.

[0243] R 4 represents a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, and among these, a linear or branched alkylene group is preferred, and a linear alkylene group is more preferred, in that it has an excellent thickening effect. Also, R 4 The divalent aliphatic hydrocarbon group in has 1 to 8 carbon atoms, and from the viewpoint of excellent thickening effect, it is preferably 1 to 7, more preferably 3 to 7, further preferably 3 to 6, and particularly preferably 3 to 5. Therefore, R 4 is preferably a linear or branched alkylene group having 1 to 8 carbon atoms, more preferably a linear alkylene group having 1 to 7 carbon atoms, still more preferably a linear alkylene group having 3 to 7 carbon atoms, particularly preferably a linear alkylene group having 3 to 6 carbon atoms, and most preferably a linear alkylene group having 3 to 5 carbon atoms.

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

[0245] R 5 and R 6 Examples of the hydroxyalkyl ether group in the formula (I) include mono- or di(hydroxy)C groups such as a 2-hydroxyethoxy group, a 2-hydroxypropoxy group, and a 2,3-dihydroxypropoxy group. 1-3Examples of such groups include alkyl ether groups.

[0246] Among them, R 5 and R 6 are each independently 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, still more preferably a linear alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group.

[0247] As the compound represented by formula (II), the compounds represented by the following formulae (II-1) to (II-9) are preferred.

[0248] [ka]

[0249] Examples of the flocculating dispersant 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 Disper 630 and 700 (all trade names, manufactured by Evonik Degussa Japan); TALENE VA-705B (trade name, manufactured by Kyoeisha Chemical Co., Ltd.); and FLOWNON RCM-300TL and RCM-230AF (trade names, manufactured by Kyoeisha Chemical Co., Ltd., Amide Wax).

[0250] When the composition contains an aggregating dispersant, the content of the aggregating dispersant is preferably 1 to 24 mass%, more preferably 1 to 15 mass%, even more preferably 1 to 12 mass%, particularly preferably 1 to 10 mass%, and most preferably 1 to 7 mass%, relative to the total mass of the composition. The content of the flocculating dispersant is preferably 0.8 to 24 mass%, more preferably 0.8 to 15 mass%, even more preferably 0.8 to 12 mass%, even more preferably 0.8 to 10 mass%, particularly preferably 0.8 to 8 mass%, and most preferably 0.8 to 7 mass%, based on the total solid content of the composition. The content of the aggregation dispersant does not include the content of the resin-type rheology control agent, which corresponds to the resin that is the binder component described above.

[0251] <Inorganic rheology control agent> Inorganic rheology control agents include, for example, bentonite, silica, calcium carbonate, and smectite.

[0252] [Hardening agent] The composition may also include a curing agent. In particular, when the composition contains a compound having an epoxy group and / or an oxetanyl group as a binder component, the composition preferably contains a curing agent. Examples of the curing agent 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 curing agent may be used alone or in combination of two or more kinds.

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

[0254] The acid anhydride curing agent includes a curing agent having one or more acid anhydride groups in one molecule. Specific examples of acid anhydride 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-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, and benzophenonetetracarboxylic dianhydride. Examples of acid anhydrides include anhydrides, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfonetetracarboxylic 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 polymeric acid anhydrides such as styrene-maleic acid resin, which is a copolymer of styrene and maleic acid. Commercially available acid anhydride curing agents include "HNA-100", "MH-700", "MTA-15", "DDSA", "HF-08", and "OSA" manufactured by New Japan Chemical Co., Ltd., "YH306" and "YH307" manufactured by Mitsubishi Chemical Corporation, "H-TMAn" manufactured by Mitsubishi Gas Chemical Company, Inc., and "HN-2200", "HN-2000", "HN-5500", and "MHAC-P" manufactured by Hitachi Chemical Co., Ltd.

[0255] As the active ester curing agent, a compound 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, is preferably used. As the active ester curing agent, an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and an active ester compound containing a benzoylated product of phenol novolac are preferred. Note that the "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 an acetylated product include "DC808" (manufactured by Mitsubishi Chemical Corporation); active ester compounds containing a benzoylated product of phenol novolac include "YLH1026" (manufactured by Mitsubishi Chemical Corporation); active ester-based hardeners which are acetylated products of phenol novolac include "DC808" (manufactured by Mitsubishi Chemical Corporation); and active ester-based hardeners which are benzoylated products of phenol novolac 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" manufactured by JFE Chemical Corporation; "HFB2006M" manufactured by Showa Polymer Co., Ltd.; and "Pd" and "Fa" manufactured by Shikoku Chemical Industry Co., Ltd.

[0258] Specific examples of cyanate ester-based curing agents include "PT30" and "PT60" (both of which are phenol novolac-type multifunctional cyanate ester resins), "BA230" and "BA230S75" (prepolymers in which part or all of bisphenol A dicyanate has been converted to triazine to form a trimer), all of which are manufactured by Lonza Japan.

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

[0260] Commercially available amine adduct curing agents include, for example, 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 the compound having an oxetanyl group) to the content of the curing agent is such that the equivalent ratio of the epoxy group (or the compound having an oxetanyl group) in the compound having an epoxy group to the reactive group (active hydrogen group such as a hydroxyl group in the curing agent) in the curing agent (the "number of epoxy groups (or the number of oxetanyl groups)" / "the number of reactive groups") is preferably 30 / 70 to 70 / 30, more preferably 40 / 60 to 60 / 40, and even more preferably 45 / 55 to 55 / 45. In addition, when the composition contains 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 compound having an epoxy group and an oxetanyl group in the compound having an epoxy group to the reactive groups in the curing agent ("the number of epoxy groups and the number of oxetanyl groups" / "the number of reactive groups") satisfies the above numerical range. The content of the curing agent is preferably from 0.001 to 3.5 mass %, and more preferably from 0.01 to 3.5 mass %, based on the total mass of the composition. The content of the curing agent is preferably from 0.001 to 3.5 mass %, more preferably from 0.01 to 3.5 mass %, based on the total solid content of the composition.

[0262] [Curing Accelerator] The composition may also include a cure accelerator. In particular, when the composition contains a compound having an epoxy group and / or an oxetanyl group as a binder component, the composition preferably contains a curing accelerator. Examples of the curing accelerator include triphenylphosphine, methyltributylphosphonium dimethylphosphate, tris-orthotolylphosphine, and boron trifluoride amine complex. Examples of commercially available phosphate curing accelerators include Hishicoline PX-4MP (manufactured by Nippon Chemical Industry Co., Ltd.). Other examples of hardening 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), 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'-undecylimidazole 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 isocyanuric acid adduct (trade name; 2MA-OK), 2-phenyl-4,5-dihydroxymethylimidazole (trade name; 2PHZ-PW), 2-phenyl-4-methyl-5-hydroxyimidazole (trade name; 2PHZ-PW), Examples of the imidazole-based curing accelerator include dimethylimidazole (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 Chemical Industry Co., Ltd.). In addition, examples of the triarylphosphine-based curing accelerator include the compounds described in paragraph 0052 of JP-A-2004-043405.Examples of phosphorus-based curing accelerators in which triphenylborane is added to triarylphosphine include the compounds described in paragraph 0024 of JP-A-2014-005382. The content of the curing accelerator is preferably from 0.0002 to 3 mass %, more preferably from 0.002 to 2 mass %, and even more preferably from 0.01 to 1 mass %, based on the total mass of the composition. The content of the curing accelerator is preferably from 0.0002 to 3 mass %, more preferably from 0.002 to 2 mass %, and even more preferably from 0.02 to 1 mass %, based on the total solid content of the composition.

[0263] [Polymerization initiator] The composition may include a polymerization initiator. In particular, when the composition contains a compound containing an ethylenically unsaturated group as a binder component, the composition preferably contains a polymerization initiator. The polymerization initiator is not particularly limited, and any known polymerization initiator can be used. Examples of the polymerization initiator include a photopolymerization initiator and a thermal polymerization initiator. When the composition contains a polymerization initiator, the content thereof is preferably from 0.5 to 10 mass %, more preferably from 0.5 to 5 mass %, and further preferably from 0.5 to 3 mass %, based on the total mass of the composition. When the composition contains a polymerization initiator, the content thereof is preferably from 0.8 to 5 mass %, more preferably from 0.8 to 4 mass %, and further preferably from 1.5 to 3 mass %, based on the total solid content of the composition.

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

[0265] <Photopolymerization initiator> The photopolymerization initiator is not particularly limited as long as it can initiate polymerization of the polymerizable compound, and a known photopolymerization initiator can be used. For example, the photopolymerization initiator is preferably a photopolymerization initiator having photosensitivity to the ultraviolet region to the visible light region. In addition, it may be an activator that generates an active radical by reacting with a photoexcited sensitizer, or an initiator that initiates cationic polymerization according to the type of polymerizable compound. The photopolymerization initiator preferably contains at least one compound having a molar absorption coefficient of at least 50 within a range of 300 to 800 nm (more preferably 330 to 500 nm).

[0266] Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (e.g., compounds containing a triazine skeleton, compounds containing an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxides, hexaarylbiimidazoles, oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, aminoacetophenone compounds, and hydroxyacetophenones. Specific examples of photopolymerization initiators can be found in, for example, paragraphs 0265 to 0268 of JP2013-029760A, the contents of which are incorporated herein by reference.

[0267] More specifically, for example, the aminoacetophenone-based initiators described in JP-A-10-291969 and the acylphosphine-based initiators described in Japanese Patent No. 4225898 can also be used as the photopolymerization initiator. As the hydroxyacetophenone compound, for example, Omnirad-184, Omnirad-1173, Omnirad-500, Omnirad-2959, and Omnirad-127 (trade names, all manufactured by IGM Resins BV) can be used. As the aminoacetophenone compound, for example, commercially available products Omnirad-907, Omnirad-369, and Omnirad-379EG (trade names, all manufactured by IGM Resins BV) can be used. As the aminoacetophenone compound, compounds described in JP-A-2009-191179, which have an absorption wavelength matching a long-wavelength light source such as a wavelength of 365 nm or 405 nm, can also be used. As the acylphosphine compound, commercially available products Omnirad-819 and Omnirad-TPO (trade names, both manufactured by IGM Resins BV) can be used.

[0268] As the photopolymerization initiator, an oxime ester-based polymerization initiator (oxime compound) is more preferable. In particular, an oxime compound is preferable because it has high sensitivity and high polymerization efficiency, and it is easy to design the content of the coloring material in the composition to be high. Specific examples of the oxime compound that can be used include the compounds described in JP-A-2001-233842, JP-A-2000-080068, and JP-A-2006-342166. Examples of the oxime compound include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one. Further examples include the compounds described in J.C.S. Perkin II (1979) pp.1653-1660, J.C.S. Perkin II (1979) pp.156-162, Journal of Photopolymer Science and Technology (1995) pp.202-232, JP-A No. 2000-066385, JP-A No. 2000-080068, JP-T No. 2004-534797, and JP-A No. 2006-342166. Commercially available products include IRGACURE-OXE01 (manufactured by BASF), IRGACURE-OXE02 (manufactured by BASF), IRGACURE-OXE03 (manufactured by BASF), and IRGACURE-OXE04 (manufactured by BASF). In addition, TR-PBG-304 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), Adeka Arcles NCI-831, Adeka Arcles NCI-930 (manufactured by ADEKA), and N-1919 (carbazole oxime ester skeleton-containing photoinitiator (manufactured by ADEKA)) can also be used.

[0269] In addition, as oxime compounds other than those described above, the compound described in JP-T-2009-519904 A in which an oxime is linked to the N-position of the carbazole; the compound described in U.S. Pat. No. 7,626,957 A in which a heterosubstituent is introduced at the benzophenone moiety; the compounds described in JP-A-2010-015025 A and U.S. Patent Publication No. 2009-292039 A in which a nitro group is introduced at the dye moiety; the ketoxime compounds described in WO-A-2009-131189; and the compound described in U.S. Pat. No. 7,556,910 which contains a triazine skeleton and an oxime skeleton in the same molecule; and the compound described in JP-A-2009-221114 A which has an absorption maximum at 405 nm and has good sensitivity to a g-line light source; etc. may be used. For example, see paragraphs 0274 to 0275 of JP 2013-029760 A, the contents of which are incorporated herein by reference. Specifically, the oxime compound is preferably a compound represented by the following formula (OX-1): The oxime compound may be an oxime compound in which the NO bond is an (E) form, an oxime compound in which the NO bond is an (Z) form, or a mixture of the (E) form and the (Z) form.

[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), the monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group. Examples of the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. These groups may have one or more substituents. The aforementioned substituents may be further substituted with other substituents. Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group. 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, and more preferably an aryl group or a heterocyclic group. These groups may have one or more substituents. Examples of the substituent include the above-mentioned substituents. In formula (OX-1), the divalent organic group represented by A is preferably an alkylene group, a cycloalkylene group, or an alkynylene group having 1 to 12 carbon atoms. These groups may have one or more substituents. Examples of the substituents include the above-mentioned substituents.

[0272] As the photopolymerization initiator, an oxime compound containing a fluorine atom can also be used. Specific examples of the oxime compound containing a fluorine atom include the compounds described in JP-A-2010-262028; compounds 24, 36 to 40 described in JP-T-2014-500852; and compound (C-3) described in JP-A-2013-164471. The contents of these compounds are incorporated herein by reference.

[0273] As the photopolymerization initiator, compounds represented by the following general formulas (1) to (4) can also be used.

[0274] [ka]

[0275] [ka]

[0276] In formula (1), R 1 and R 2 each 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; R 1 and R 2 When R is a phenyl group, the phenyl groups may be bonded to each other to form a fluorene group, 3 and R 4 each 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 formula (2), R 1 , R 2 , R 3 , and R 4 is R in formula (1). 1 , R 2 , R 3 , and R 4 is synonymous with R 5 -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, 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 of 0 to 4.

[0278] In formula (3), R 1 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; R 3 and R 4 each 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 formula (4), R 1 , R 3 , and R 4 is R in Eq. (3). 1 , R 3 , and R 4 is synonymous with R 5 -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, 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 of 0 to 4.

[0280] In the above formulas (1) and (2), R 1 and R 2 is preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclohexyl group, or a phenyl group. 3 R is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group, or a xylyl group. 4 R is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group. 5 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group, or a naphthyl group. X is preferably a direct bond. In addition, in the above formulas (3) and (4), R 1 is preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclohexyl group, or a phenyl group. 3 R is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group, or a xylyl group. 4 is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group. 5 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group, or a naphthyl group. X is preferably a direct bond. Specific examples of the compounds represented by formula (1) and formula (2) include the compounds described in paragraphs 0076 to 0079 of JP2014-137466A, the contents of which are incorporated herein by reference.

[0281] Specific examples of oxime compounds that can be 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. In addition, as the oxime compound, compounds described in Table 1 of International Publication No. 2015-036910 can also be used, the contents of which are incorporated herein by reference.

[0282] [ka]

[0283] [ka]

[0284] The oxime compound preferably has a maximum absorption wavelength in the wavelength region of 350 to 500 nm, more preferably has a maximum absorption wavelength in the wavelength region of 360 to 480 nm, and further preferably has high absorbance at wavelengths of 365 nm and 405 nm. The molar absorption coefficient of the oxime compound at 365 nm or 405 nm is preferably from 1,000 to 300,000, more preferably from 2,000 to 300,000, and even more preferably from 5,000 to 200,000, from the viewpoint of sensitivity. The molar absorption coefficient of a compound can be measured by a known method, but it is preferable to measure it, for example, using an ultraviolet-visible spectrophotometer (Varian Cary-5 spectrophotometer) using ethyl acetate at a concentration of 0.01 g / L. Two or more kinds of photopolymerization initiators may be used in combination, if necessary.

[0285] In addition, as the photopolymerization initiator, compounds described in paragraph 0052 of JP 2008-260927 A, paragraphs 0033 to 0037 of JP 2010-097210 A, and paragraph 0044 of JP 2015-068893 A can also be used, the contents of which are incorporated herein by reference. In addition, oxime initiators described in Korean Patent Publication No. 10-2016-0109444 can also be used.

[0286] [Polymerization inhibitor] The composition may also include a polymerization inhibitor. The polymerization inhibitor is not particularly limited, and known polymerization inhibitors can be used. Examples of the polymerization inhibitor include phenol-based 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-based polymerization inhibitors (e.g., hydroquinone, 2,6-di-tert-butylhydroquinone, etc.); quinone, etc.); quinone-based polymerization inhibitors (e.g., benzoquinone, etc.); free radical-based 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.); and the like. Among these, phenol-based polymerization inhibitors or free radical-based polymerization inhibitors are preferred.

[0287] The effect of the polymerization inhibitor is remarkable when it is used together with a resin containing a curable group. The content of the polymerization inhibitor in the composition is not particularly limited, but is preferably from 0.0001 to 0.5 mass %, more preferably from 0.0001 to 0.2 mass %, and even more preferably from 0.0001 to 0.05 mass %, based on the total mass of the composition. The content of the polymerization inhibitor is preferably from 0.0001 to 0.5 mass %, more preferably from 0.0001 to 0.2 mass %, and even more preferably from 0.0001 to 0.05 mass %, based on the total solid content of the composition.

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

[0289] Examples of the surfactant include a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant.

[0290] For example, if the composition contains a fluorine-based surfactant, the liquid properties (particularly, fluidity) of the composition are improved. That is, when a film is formed 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 to be coated, and improving the coatability to the surface to be coated. Therefore, even if a thin film of about several μm is formed with a small amount of liquid, it is effective in that a film of uniform thickness with little thickness unevenness can be more suitably formed.

[0291] The fluorine content in the fluorosurfactant is preferably 3 to 40 mass%, more preferably 5 to 30 mass%, and even more preferably 7 to 25 mass%. A fluorosurfactant having a fluorine content within this range is effective in terms of uniformity of the coating film thickness and / or liquid saving properties, and also has good solubility in the composition.

[0292] Examples of fluorine-based surfactants include those described in paragraphs 0060 to 0064 of JP 2014-041318 A (corresponding paragraphs 0060 to 0064 of WO 2014 / 017669 A), those described in paragraphs 0117 to 0132 of JP 2011-132503 A, and those described in JP 2020-008634 A, the contents of which are incorporated herein by reference. Commercially available fluorine-based surfactants include, for example, 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, and 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), Fluorard FC430, FC431, FC171 (all manufactured by Sumitomo 3M Limited), 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 Corporation), PolyFox Examples of such agents include PF636, PF656, PF6320, PF6520, and PF7002 (all manufactured by OMNOVA), and Ftergent 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, and 245F (all manufactured by NEOS Corporation). A block polymer can also be used as the fluorine-based surfactant, and specific examples include the compounds described in JP-A-2011-089090. Examples of silicone surfactants include KF6001 and KF6007 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0293] From the standpoint of environmental regulations, the use of perfluoroalkylsulfonic acids and their salts, and perfluoroalkylcarboxylic acids and their salts may be restricted. When the content of the above-mentioned compounds in the composition is reduced, the content of perfluoroalkylsulfonic acid (particularly perfluoroalkylsulfonic acid having 6 to 8 carbon atoms in the perfluoroalkyl group) and its salt, and perfluoroalkylcarboxylic acid (particularly perfluoroalkylcarboxylic acid having 6 to 8 carbon atoms in the perfluoroalkyl group) and its salt is preferably 0.01 to 1,000 ppb, more preferably 0.05 to 500 ppb, and even more preferably 0.1 to 300 ppb, based on the total solid content of the composition. In addition, the composition may be substantially free of perfluoroalkylsulfonic acid and its salt, and perfluoroalkylcarboxylic acid and its salt. For example, by using a compound that can be a substitute for perfluoroalkylsulfonic acid and its salt, and a compound that can be a substitute for perfluoroalkylcarboxylic acid and its salt, the composition may be substantially free of perfluoroalkylsulfonic acid and its salt, and perfluoroalkylcarboxylic acid and its salt. Examples of compounds that can be a substitute for regulated compounds include compounds that are excluded from the scope of regulation due to the difference in the number of carbon atoms in the perfluoroalkyl group. However, the above does not preclude the use of perfluoroalkylsulfonic acids and their salts, and perfluoroalkyl carboxylic acids and their salts. The composition may contain perfluoroalkylsulfonic acids and their salts, and perfluoroalkyl carboxylic acids and their salts within the maximum allowable range.

[0294] [Adhesion Aid] The composition also preferably contains a silane coupling agent as an adhesion aid. Specific examples of the silane coupling agent 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 (eg, KBM-573, KBM-103) manufactured by Shin-Etsu Chemical Co., Ltd. When the composition contains an adhesion aid, the content of the adhesion aid is preferably from 0.05 to 2 mass %, more preferably from 0.05 to 1 mass %, and even more preferably from 0.05 to 0.8 mass %, based on the total mass of the composition. The content of the adhesion aid is preferably from 0.05 to 2 mass %, more preferably from 0.05 to 1 mass %, and even more preferably from 0.05 to 0.8 mass %, based on the total solid content of the composition.

[0295] [Other optional ingredients] The composition may further contain optional components other than the above-mentioned components, such as a sensitizer, a co-sensitizer, a plasticizer, a diluent, a sensitizer, a filler, and a rubber component, and further, known additives such as auxiliaries (e.g., an antifoaming agent, a flame retardant, a leveling agent, a release agent, an antioxidant, a fragrance, a surface tension modifier, and a chain transfer agent) may be added as necessary.

[0296] [Physical Properties of Composition] When the shear rate is 0.1 (1 / s), 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, in view of superior sedimentation stability of the magnetic particles. When the shear rate is 1000 (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, in terms of superior sedimentation stability of the magnetic particles. When the shear rate is 1000 (1 / s), the lower limit is preferably 0.001 Pa s or more. Here, the viscosity of the composition at 23°C can be obtained by measuring at 23°C using MCR-102 (manufactured by Anton Paar) while increasing the speed from 0.1 / s to 1000 / s.

[0297] [Method of producing the composition] The composition can be prepared by mixing the above-mentioned components by a known mixing method (for example, a mixing method using a stirrer, a homogenizer, a high-pressure emulsifier, a wet grinder, or a wet disperser). When preparing the composition, each component may be mixed at once, or each component may be dissolved or dispersed in a solvent and then mixed successively. The order of addition and working conditions when mixing are not particularly limited. For example, when using multiple types of other resins, they may be mixed at once, or each type may be mixed in multiple batches.

[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, the composition preferably contains a resin precursor as a binder component, and more preferably contains an epoxy compound and / or an oxetanyl compound, in that the effects of the present invention are more excellent. When the composition contains an epoxy compound and / or an oxetanyl compound as a binder component, an example of a specific procedure for filling holes includes a method including the following steps 1 to 3. Step 1: A step of applying a composition onto a substrate having holes such as via holes or through holes by a known application method such as slit coating, inkjet coating, spin coating, casting coating, roll coating, or screen printing to fill the holes with the composition. Step 2: A step of curing the epoxy compound and / or oxetanyl compound in the composition by heating the composition on the substrate that has been subjected to step 1, for example, at about 120 to 180° C. for about 30 to 90 minutes. Step 3: The unnecessary parts of the cured material that protrude from the substrate surface are removed by physical polishing to create a flat surface.

[0299] When the composition contains a photocurable resin precursor as a binder component, it is preferable to change step 2 in the above procedure of steps 1 to 3 to a step including an exposure treatment of irradiating with actinic rays or radiation.

[0300] The composition is also preferably formed into a film. When the composition is cured, it is preferable that the composition contains a resin precursor as a binder component, and it is more preferable that the composition contains an epoxy compound and / or an oxetanyl compound, in that the effects of the present invention are more excellent. A film formed from the composition is suitably used as an electronic component such as an antenna or inductor mounted on an electronic communication device or the like. The thickness of the film formed from the composition is preferably from 1 to 10,000 μm, more preferably from 10 to 1,000 μm, and particularly preferably from 15 to 800 μm, in terms 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 above-mentioned composition of the present invention. The shape of the cured product of the present invention is not particularly limited, and for example, as described above, it may be a shape that matches the shape of the hole provided in the substrate, or may be a film.

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

[0303] The method for producing the cured product of the present invention will be described below by taking as an example a production method in which the cured product is in the form of a film. Note that the film-like cured product will be referred to as a magnetic particle-containing cured film hereinafter.

[0304] <Composition layer formation process> In the composition layer forming step, a composition layer (composition layer) is formed by applying the composition onto a substrate (support) etc. The substrate may be, for example, a wiring substrate having an antenna part or an inductor part.

[0305] The composition can be applied to a substrate by a variety of coating methods, including slit coating, inkjet, spin coating, casting, roll coating, and screen printing. The 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 applied to the substrate may be heated (prebaked), and the prebaking can be performed, for example, on a hot plate or in an oven at a temperature of 50 to 140° C. for 10 to 1,800 seconds. Prebaking is preferably performed when the composition contains a solvent.

[0306] <Curing process> The curing step is not particularly limited as long as it can cure the composition layer, and examples thereof include a heat treatment for heating the composition layer and an exposure treatment for irradiating the composition layer with actinic rays or radiation.

[0307] When the heat treatment is carried out, the heat treatment can be carried out continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation type dryer), or a high-frequency heater. The heating temperature in the heat treatment is preferably 120 to 260° C., more preferably 150 to 240° C. The heating time is not particularly limited, but is preferably 10 to 1800 seconds. The pre-baking in the composition layer forming step may also serve as the heat treatment in the curing step.

[0308] When exposure treatment is performed, the method of irradiating with actinic rays or radiation is not particularly limited, but it is preferable to irradiate through a photomask having openings in a pattern. The exposure is preferably carried out by irradiation with radiation. The radiation that can be used for exposure is preferably ultraviolet light such as g-rays, h-rays, or i-rays, and the light source is preferably a high-pressure mercury lamp. The irradiation intensity is 5 to 1500 mJ / cm. 2 is preferable, and 10 to 1000 mJ / cm 2 is more preferred. When the composition contains a thermal polymerization initiator, the composition layer may be heated in the exposure treatment. The heating temperature is not particularly limited, but is preferably 80 to 250° C. The heating time is not particularly limited, but is preferably 30 to 300 seconds. In addition, when the composition layer is heated in the exposure treatment, this may also serve as a post-heating step described later. In other words, when the composition layer is heated in the exposure treatment, the method for producing a magnetic particle-containing cured film does not need to include a post-heating step.

[0309] <Developing process> When an exposure treatment is performed in the curing step, a development step may be further included. The development step is a step of developing the composition layer after exposure to form a magnetic particle-containing cured film. By this step, the composition layer in the portion not irradiated with light in the exposure treatment is dissolved, and only the photocured portion remains, thereby obtaining a patterned magnetic particle-containing cured film. The type of developer used in the development step is not particularly limited, but an alkaline developer that does not damage circuits and the like is preferable. The development temperature is, for example, 20 to 30°C. The developing time is, for example, 20 to 90 seconds. In recent years, in order to remove residues more effectively, the developing time may be 120 to 180 seconds. Furthermore, in order to further improve the removability of residues, the process of shaking off the developing solution every 60 seconds and supplying new developing solution may be repeated several times.

[0310] The alkaline developer is preferably 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). 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 hydroxyl, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo[5.4.0]-7-undecene (among these, organic alkalis are preferred). When an alkaline developer is used, a washing treatment with water is generally carried out after development.

[0311] <Post bake> When an exposure treatment is performed in the curing step, it is preferable to perform a heat treatment (post-baking) after the curing step. Post-baking is a heat treatment for completing the curing. When a development step is performed, it is preferable to perform post-baking after the development step. The heating temperature is preferably 240° C. or less, more preferably 220° C. or less. There is no particular lower limit, but in consideration of efficient and effective processing, it is preferably 50° C. or more, more preferably 100° C. or more. In addition, the heating time is not particularly limited, but is preferably 10 to 1800 seconds. The post-baking can be carried out continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), or a high-frequency heater.

[0312] The post-baking is preferably carried out in an atmosphere with a low oxygen concentration. 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 a concentration of 10 ppm by volume or more is practical.

[0313] Moreover, instead of the post-baking by heating, the 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 a UV curing agent that can be cured at a wavelength shorter than 365 nm, which is the exposure wavelength of a polymerization initiator added for a lithography process using normal i-line exposure. An example of the UV curing agent is Chiba Ilgacure 2959 (trade name). In the case of performing UV irradiation, it is preferable that the composition layer is a material that is cured at a wavelength of 340 nm or less. There is no particular lower limit of the wavelength, but it is generally 220 nm or more. The exposure dose of 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-introduced substrate of the present invention comprises a substrate in which holes are formed, and the cured product of the present invention (magnetic particle-containing cured product) placed in the holes. The hole may be a through hole or a recess. Examples of the substrate having a hole include a wiring substrate having a via hole or a through hole. The method for forming the cured product of the present invention is as described above. The magnetic particle-introduced substrate can be applied to electronic materials such as inductors. EXAMPLES

[0315] The present invention will be described in more detail below based on examples. The materials, amounts, ratios, processing contents, processing procedures, etc. shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the following examples. In the following description, unless otherwise specified, "%" means "% by mass" and "parts" means "parts by mass".

[0316] [Various components used in the preparation of the composition] In preparing the composition, the components shown in Table 1 were prepared. The outline of each component shown in Table 1 is shown below.

[0317] [Magnetic particles] P-1: 80% Ni-4Mo PF-5F (Epson Atomics, solid content: 100% by mass, average primary particle size: 4 μm) P-2: 80% Ni-4Mo PF-15F (Epson Atomics, solid content: 100% by mass, average primary particle size: 8 μm) P-3: 80%Ni-4Mo WA13 (Epson Atomics, solid content: 100% by mass, average primary particle size: 12.5μm) P-4: KUAMET-CT5-25μm (Epson Atomics, solid content: 100% by mass, average primary particle size: 15μm) P-5: AW2-08 PF-3F (Epson Atomics, solid content: 100% by mass, average primary particle size: 3 μm) P-6: AW2-08 PF-8F (Epson Atomics, solid content: 100% by mass, average primary particle size: 5 μm) P-7: AW2-08 PF-20F (Epson Atomics, solid content: 100% by mass, average primary particle size: 10 μm) P-8: KUAMET6B2 (Epson Atomics, solid content: 100% by mass, average primary particle size: 24 μm) P-9: EA-SMP-10 PF-5F (Epson Atomics, solid content: 100% by mass, average primary particle size: 10 μm) P-10: KUAMETNC (Epson Atomics, solid content: 100% by mass, average primary particle size: 25 μm) P-11: BSN-125 (Toda Kogyo Co., Ltd., solid content: 100% by mass, average primary particle size: 8 μm) P-12: BSN-714 (Toda Kogyo Co., Ltd., solid content: 100% by mass, average primary particle size: 30 μm) P-13: BSN-828 (Toda Kogyo Co., Ltd., solid content: 100% by mass, average primary particle size: 66 μm) P-14: BSF-547 (Toda Kogyo Co., Ltd., solid content: 100% by mass, average primary particle size: 11 μm) P-15: KNS-415 (Toda Kogyo Co., Ltd., solid content: 100% by mass, average primary particle size: 4 μm) P-16: Particles prepared with reference to [Production Example 1] of JP2019-067960A, solid content concentration: 100% by mass, average primary particle diameter: 10 μm) P-17: M05S (Powder Tech Co., Ltd., solid content: 100% by mass, average primary particle size: 10 μm)

[0318] [Binder Component] B-1: Product name "BYK-P105" (polymer of low molecular weight unsaturated carboxylic acid, manufactured by BYK, solid content: 100% by mass) B-2: Product name "Tallen VA-705B" (higher fatty acid amide, manufactured by Kyoeisha Chemical Co., Ltd., solid content: 100% by mass) B-3: Product name "FLOWNON RCM-230AF" (higher fatty acid amide, manufactured by Kyoeisha Chemical Co., Ltd., solid content concentration: 10% by mass, dilution solvent: 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 10,000) (solid concentration: 30% by mass, dilution solvent: PGMEA (boiling point 146°C). The numbers attached to each repeating unit constituting the main chain represent the mass ratio, and the numbers 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 25,000) (solid concentration: 30% by mass, dilution solvent: PGMEA (boiling point 146°C). The numbers attached to each repeating unit constituting the main chain represent the mass ratio, and the numbers 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 10,000) (solid concentration: 30% by mass, dilution solvent: PGMEA (boiling point 146°C). The numbers attached to each repeating unit constituting the main chain represent the mass ratio, and the numbers 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. NOF Corporation, solid content: 100% by mass) B-8: Product name "EHPE 3150" (1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, manufactured by Daicel Chemical Industries, Ltd., solid content: 100% by mass) B-9: Product name "Acrylicure RD-F8" (alkali-soluble resin containing curable groups, manufactured by Nippon Shokubai Co., Ltd., solid content concentration: 40% by mass, dilution solvent: PGMEA (boiling point 146°C)) B-10: Product name "Celloxide 2021P" (3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, manufactured by Daicel Chemical Industries, Ltd., solid content: 100% by mass) B-11: Product name "Denacol EX-411" (pentaerythritol polyglycidyl ether, manufactured by Nagase ChemteX Corporation, solid content: 100% by mass) B-12: Product name "KAYARAD RP-1040" (the following compound, manufactured by Nippon Kayaku Co., Ltd., solid content: 100% by mass)

[0326] [ka]

[0327] B-13: Product name "A-TMMT" (polyfunctional acrylic monomer, manufactured by Toagosei Co., Ltd., solid content: 100% by mass) B-14: Product name "ZX1059" (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin, manufactured by Nippon Steel Chemical & Material Co., Ltd., solid content: 100% by mass) B-15: Product name "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin, manufactured by Nippon Steel Chemical & Material Co., Ltd., solid content: 100% by mass) B-16: Product name "HP-4700" (naphthalene-type tetrafunctional epoxy resin, manufactured by DIC Corporation, solid content: 100% by mass) B-17: Product name "YX7553BH30" (Phenoxy resin, manufactured by Mitsubishi Chemical Corporation, solid content: 30% by mass, dilution solvent: 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: 100% by mass) B-19: Product name "828US" (bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Corporation, solid content: 100% by mass) B-20: Product name "NC3000L" (biphenyl type epoxy resin, manufactured by Nippon Kayaku Co., Ltd., solid content: 100% by mass) B-21: Product name "HPC-4032" (Naphthalene type bifunctional epoxy resin, manufactured by DIC Corporation, solid content: 100% by mass)

[0328] [Additives] <Curing agent / curing accelerator> A-1: Product name: Hishicorin PX-4MP (phosphate-based epoxy curing accelerator, manufactured by Nippon Chemical Industry Co., Ltd., solid content: 100% by mass) A-2: Product name "2MZA-PW" (imidazole-based curing accelerator, manufactured by Shikoku Kasei Co., Ltd., solid content: 100% by mass) A-3: Product name "LA-7054" (Novolac type phenolic resin hardener, manufactured by DIC Corporation, solid content concentration: 60% by mass, dilution solvent: MEK (boiling point 80°C)) A-4: Product name "2E4MZ" (2-ethyl-4-methylimidazole (curing accelerator), manufactured by Shikoku Kasei Co., Ltd., solid content: 100% by mass) A-5: Product name "2PHZ-PW" (imidazole-based epoxy curing accelerator, manufactured by Shikoku Kasei Co., Ltd., solid content: 100% by mass) A-6: Product name "LA-3018-50P" (Novolac type phenolic resin hardener, manufactured by DIC Corporation, solid content concentration: 50% by mass, dilution solvent: 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, dilution solvent: toluene (boiling point 111°C)) A-8: Product name "V-03" (epoxy curing agent, manufactured by Nisshinbo Chemical Co., Ltd., solid content concentration: 50% by mass, dilution solvent: toluene (boiling point 111°C)) A-9: Product name "DMAP" (4-dimethylaminopyridine, Fujifilm Wako Pure Chemical Industries, Ltd., solid content: 100% by mass) A-10: Product name "PN-50" (amine adduct curing agent, manufactured by Ajinomoto Fine-Techno Co., Ltd., solid content: 100% by mass) A-16: Product name "HNA-100" (acid anhydride curing agent, manufactured by New Japan Chemical Co., Ltd., solid content: 100% by mass)

[0329] <Filler> A-11: Product name "SO-C2" (silica particles, manufactured by Admatechs, solid content: 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: 100% by mass) A-13: Product name "KBM-103" (phenyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., solid content: 100% by mass)

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

[0332] [Surfactant] Sur-1: Product name "MEGAFAC F-781F" (fluorosurfactant, manufactured by DIC, solid content: 100% by mass) Sur-2: Product name "KF-6001" (silicone surfactant, manufactured by Shin-Etsu Chemical Co., Ltd., solid content: 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 triacetate (boiling point 260°C, 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, Fujifilm Wako Pure Chemical Industries, Ltd.) S-8: Toluene (boiling point 110°C, Fujifilm Wako Pure Chemical Industries, Ltd.) S-9: 3-Methoxy-1-butanol (boiling point 161°C, Fujifilm Wako Pure Chemical Industries, Ltd.) S-10: Isopropyl acetate (boiling point 89°C, Fujifilm Wako Pure Chemical Industries, Ltd.) S-11: MEK (methyl ethyl ketone (boiling point 80°C), Fujifilm Wako Pure Chemical Industries, Ltd.) S-12: Ethanol (boiling point 78°C, Fujifilm Wako Pure Chemical Industries, Ltd.)

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

[0335] [evaluation] [Magnetic properties] <Preparation of sample substrate for measurement> A substrate was prepared by applying CT4000 (manufactured by FUJIFILM Electronic Materials Co., Ltd.) onto a 100 μm thick Si wafer. Onto the obtained substrate, each composition of the Examples and Comparative Examples was applied using an applicator with a gap of 100 μm to form a coating film. Next, when the applied composition did not contain a photopolymerization initiator, the obtained coating film was heated and dried under drying conditions of 100° C. for 120 seconds, and then further heated at 230° C. for 15 minutes to produce a substrate with a cured film. When the applied composition contained a photopolymerization initiator, the composition was exposed to 1000 mJ / cm 2 of light using a proximity exposure machine. 2 The exposure treatment was carried out under the above conditions, and then heating was carried out at 230° C. for 10 minutes to prepare a substrate with a cured film. Next, the obtained substrate with the cured film was cut into a size of 1 cm x 2.8 cm together with the substrate to prepare a sample substrate for measurement.

[0336] <Preparation of reference substrate for measurement> A measurement reference substrate was prepared in the same manner as the above-mentioned measurement sample substrate preparation method, except that the composition shown below (composition for preparing a measurement reference substrate) was used. In addition, in the composition for making measurement reference substrate, the magnetic particles used are the same as those used in each composition of the examples and comparative examples.In addition, when a plurality of magnetic particles are used in combination, they are mixed in the same ratio.That is, taking Example 17 as an example, in the preparation of the measurement reference substrate for the measurement sample substrate prepared using the composition of Example 17, the composition for making measurement reference substrate contains P-3 and P-1 as magnetic particles in a mass ratio of 1:1, similar to Example 17. In the composition for producing a measurement reference substrate, the binder component B-4 and the solvent S-1 are as described above.

[0337] (Composition for preparing a reference substrate for measurement) Magnetic particles (same type and mixing ratio as in each composition of the Examples and Comparative Examples): 85.8% by mass Binder component (B-4 used): 5.2% by mass Solvent (S-1 used): 9.0% by mass

[0338] Next, the magnetic properties (relative permeability μ′ at 100 MHz) of the films in each of the obtained measurement sample substrates and measurement reference substrates were measured using PER-01 (high frequency magnetic permeability measuring device, manufactured by Keycom). Based on the obtained relative magnetic permeability μ', the magnetic permeability ratio (Δμ') was calculated using the following formula (1), and an evaluation was performed based on the evaluation criteria described below. The larger the magnetic permeability ratio (Δμ') value, the better the formulation is at maintaining the inherent magnetic properties of the magnetic particles. In practice, a rating of "3" or higher is preferable, with a rating of "4" or higher being more preferable, and "5" being 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] The fluidity was evaluated based on whether or not application using an applicator was possible for the magnetic property evaluation. Specifically, the evaluation was performed based on the following evaluation criteria. <Evaluation criteria> "A": Applicable "B": The composition slides on the substrate and cannot be applied.

[0341] [Filling suitability] A 0.8 mm thick FR-4 board was prepared, and a through hole with a diameter of 0.4 mm was formed in it. Next, a process of embedding each composition of the Examples and Comparative Examples in the through-holes was carried out using DP-320 (Newlong Precision Industry Co., Ltd.). Next, when the composition did not contain a photopolymerization initiator, the substrate after embedding the obtained composition was heated at 160°C for 1 hour to harden the composition. When the composition contained a photopolymerization initiator, the composition was hardened by heating at 1000mJ / cm2 using a proximity exposure machine. 2 The composition was then cured by 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 with a SEM (Scanning Electron Microscope). Images were taken at n=30, and the void ratios calculated by Image J were averaged to provide an index of filling suitability. Evaluation was performed based on the value (Va) obtained by averaging, in accordance with the following evaluation criteria. The smaller the Va value, the fewer voids and cracks in the cured product, which is better. In practice, an evaluation of "3" or higher is preferable, with an evaluation of "4" or higher being more preferable, and "5" being 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 formulation of each composition and the results of the evaluation tests carried out on each composition. In Table 1, the units of values ​​shown in the "Amount" and "Total Amount" columns are "parts by mass." In addition, in Table 1, in the "Content (mass %) of solvents having a boiling point of 160°C or higher relative to the total mass of the composition," "N" indicates that the content of solvents having a boiling point of 160°C or higher is less than 3 mass % relative to the total mass of the composition, and "P" indicates that the content of solvents having a boiling point of 160°C or higher is 3 mass % or more relative to the total mass of the composition. In addition, in Table 1, "content (mass %) of magnetic particles having a primary particle diameter of 4 μm or more" refers to the content (mass %) of magnetic particles having 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 make clear that the composition of the present invention is capable of forming a cured product having excellent flowability and filling suitability as well as excellent magnetic properties. Furthermore, from the results of the Examples (e.g., comparison of Examples 1 to 16, etc.), it was confirmed that when the average primary particle size 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 the filling suitability is further improved in Example 15 because the magnetic particles are surface-coated particles. Furthermore, from the results of the examples (e.g., comparison of Examples 3, 24 to 27, etc.), it was confirmed that when the content of magnetic particles is 92 mass % or more (preferably 95 mass % or more) relative to the total solid content of the composition, the magnetic properties of the formed cured product are superior. Furthermore, from the results of the examples (e.g., comparison of Examples 3, 28 to 33, etc.), it was confirmed that the filling suitability of the composition is better when the solvent content is 15 mass% or less (preferably 8 mass% or less) relative to the total mass of the composition. Furthermore, from the results of the Examples (e.g., comparison of Examples 58 to 62, comparison of Examples 68 to 71, and comparison of Examples 78 to 80, etc.), it was confirmed that the filling suitability of the composition was superior when the composition contained an adhesion aid such as a silane coupling agent. In comparison of Examples 58 to 62, it is presumed that the fact that the composition contains an adhesion aid such as a silane coupling agent and that the content of the solvent is 8 mass% or less with respect to the total mass of the composition contributes to the improvement of the filling suitability of the composition (particularly, in Example 61, it is presumed that the fact that the magnetic particles in the composition are surface-coated also contributes to the improvement of the filling suitability of the composition). Furthermore, from the results of the examples (for example, comparison with Examples 83 to 96), it was confirmed that the filling suitability of the composition is superior when the composition contains a solvent having a boiling point of 160°C or higher and the content of the solvent is 3 mass% or more relative to the total mass of the composition. In Examples 24 to 33, the same results were obtained when the magnetic particles P-3 were replaced with P-2 or P-4.

[0349] On the other hand, the compositions of the comparative examples did not exhibit the desired effects. In addition, in the composition of Comparative Example 3, the content of the solvent in the composition was too small, so that the composition had poor fluidity and was difficult to apply with an applicator.

Claims

1. Magnetic particles; One or more components selected from the group consisting of resins and resin precursors; A composition comprising: The component contains two or more epoxy resins, The content of magnetic particles having a primary particle size of 4 μm or more is 25 mass% or more based on the total mass of the magnetic particles, The content of the magnetic particles is 91% by mass or more based on the total solid content of the composition; The content of the solvent is 3 to 24% by mass, based on the total mass of the composition.

2. The composition of claim 1 , wherein the components include three or more epoxy resins.

3. The composition according to claim 1 or 2, wherein the content of the component is 0.8 to 8 mass % based on the total solid content of the composition.

4. The composition according to any one of claims 1 to 3, further comprising a curing agent or a curing accelerator.

5. The composition according to any one of claims 1 to 4, wherein the magnetic particles are soft magnetic particles.

6. The composition according to any one of claims 1 to 5, wherein the solvent comprises a solvent having a boiling point of 80°C or higher.

7. The composition according to any one of claims 1 to 6, wherein the solvent comprises a solvent having a boiling point of 160°C or higher.

8. The composition according to any one of claims 1 to 7, wherein the solvent contains a solvent having a boiling point of 160°C or higher, and the content of the solvent is 3 mass% or more relative to the total mass of the composition.

9. A magnetic particle-containing cured product formed using the composition according to any one of claims 1 to 8.

10. A magnetic particle-introduced substrate comprising: a substrate having a hole formed therein; and the magnetic particle-containing cured material according to claim 9 disposed in the hole.

11. An electronic material comprising the magnetic particle-introduced substrate according to claim 10.

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