Magnetic particle-containing composition, magnetic particle-containing film, and electronic component

Abstract

To provide: a magnetic particle-containing composition that can form a magnetic particle-containing film having excellent magnetic permeability and is excellent in sedimentation stability; a magnetic particle-containing film that is formed of the magnetic particle-containing composition; and an electronic component that includes the magnetic particle-containing film.SOLUTION: A magnetic particle-containing composition contains: magnetic particles having a plurality of peak tops in a particle size distribution curve showing a volume-based frequency distribution; a resin; and a solvent. If Dmin represents a particle diameter at a peak top Pmin where a particle diameter is minimized and Dmax represents a particle diameter at a peak top Pmax where a particle diameter is maximized among the plurality of peak tops in the particle size distribution curve showing a volume-based frequency distribution, then the ratio of Dmax to Dmin is more than 2.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a magnetic particle-containing composition, a magnetic particle-containing film, and an electronic component.

Background Art

[0002] In electronic communication devices and the like, electronic components using a magnetic material are used from the viewpoints of noise reduction and energy efficiency improvement. Conventionally, an inductor obtained by winding a coil around a magnetic composite material obtained by filling a composition having soft magnetic metal powder and resin into a mold and curing it has been mounted on a printed wiring board. However, due to the recent demand for miniaturization of electronic components, a method of forming a coil by a conductor pattern of a printed wiring board and providing an inductor inside the printed wiring board may be adopted. In the manufacture of electronic components such as such inductors, for example, Patent Document 1 discloses using a paste composition (magnetic particle-containing composition) containing magnetic inorganic particles (magnetic particles), a compound having a function of dispersing the magnetic inorganic particles, a resin, and an organic solvent.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] The present inventors prepared a magnetic particle-containing composition containing magnetic particles, a resin, and a solvent with reference to Patent Document 1, and found that it is sometimes difficult to achieve both excellent sedimentation stability of the magnetic particles in the magnetic particle-containing composition (that is, the magnetic particles are difficult to sediment) and excellent magnetic permeability of the magnetic particle-containing film obtained using the magnetic particle-containing composition, and there is room for improvement.

[0005] Therefore, an object of the present invention is to provide a magnetic particle-containing composition capable of forming a magnetic particle-containing film excellent in magnetic permeability and having excellent sedimentation stability. Another object of the present invention is also to provide a magnetic particle-containing film formed using the magnetic particle-containing composition and an electronic component including the magnetic particle-containing film.

Means for Solving the Problems

[0006] As a result of intensive studies to solve the above problems, the present inventors have found that a magnetic particle-containing composition containing magnetic particles having a plurality of peak tops in a particle size distribution curve representing a frequency distribution based on volume, a resin, and a solvent is excellent in sedimentation stability, and the magnetic permeability of a magnetic particle-containing film formed using the composition is excellent, thereby completing the present invention. That is, the present inventors have found that the above problems can be solved by the following configuration.

[0007] [1] A magnetic particle-containing composition containing magnetic particles having a plurality of peak tops in a particle size distribution curve representing a frequency distribution based on volume, a resin, and a solvent. [2] When the particle size at the smallest peak top Pmin in the plurality of peak tops in the particle size distribution curve representing the frequency distribution based on volume is defined as Dmin and the particle size at the largest peak top Pmax is defined as Dmax, The magnetic particle-containing composition according to [1], wherein the ratio of Dmax to Dmin is more than 2. [3] When the particle size at the smallest peak top Pmin in the plurality of peak tops in the particle size distribution curve representing the frequency distribution based on volume is defined as Dmin, The Dmin is the particle size D when the frequency in the particle size distribution curve representing the cumulative distribution based on volume is 20%. 20 The magnetic particle-containing composition according to [1] or [2], wherein the Dmin is 1 to 10 μm or more. [4] The magnetic particle-containing composition according to [2] or [3], wherein the Dmin is 1 to 10 μm. [5] The magnetic particle-containing composition according to any one of [1] to [4], wherein the magnetic particles have two peak tops. [6] The magnetic particle-containing composition according to any one of [1] to [5], wherein the content of the magnetic particles is 60% by mass or more based on the total mass of the magnetic particle-containing composition. [7] The magnetic particle-containing composition according to any one of [1] to [6], wherein the resin has an acid group, a basic group or an amide group. [8] The magnetic particle-containing composition according to any one of [1] to [7], wherein the solubility of the resin in the solvent is 10 g / L or more. [9] A magnetic particle-containing film formed using the magnetic particle-containing composition according to any one of [1] to [8].

[10] An electronic component including the magnetic particle-containing film according to [9].

[11] The electronic component according to

[10] , which is used as an inductor.

[12] The electronic component according to

[10] , which is used as an antenna.

Advantages of the Invention

[0008] According to the present invention, it is possible to provide a magnetic particle-containing film excellent in magnetic permeability and a magnetic particle-containing composition excellent in sedimentation stability. Further, the present invention can also provide a magnetic particle-containing film formed using the magnetic particle-containing composition and an electronic component including the magnetic particle-containing film.

Brief Description of the Drawings

[0009]

Figure 1

Figure 2

Best Mode for Carrying Out the Invention

[0010] Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be made based on representative embodiments of the present invention, but the present invention is not limited to such embodiments. Regarding the notation of groups (atomic groups) in this specification, unless contrary to the gist of the present invention, notations that do not indicate substitution and unsubstitution include groups having substituents as well as groups having no substituents. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). Further, the “organic group” in this specification means a group containing at least one carbon atom.

[0011] The “actinic ray” or “radiation” in this specification means, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light: Extreme Ultraviolet), X-rays, and electron beams (EB: Electron Beam), etc. The “light” in this specification means actinic rays or radiation. The “exposure” in this specification, unless otherwise specified, includes not only exposure by the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays, X-rays, and EUV light, etc., but also drawing by particle beams such as electron beams and ion beams.

[0012] In this specification, “~” is used in the sense of including the numerical values described before and after it as the lower limit value and the upper limit value.

[0013] In this specification, (meth)acrylate represents acrylate and methacrylate, (meth)acrylic represents acrylic and methacrylic, and (meth)acryloyl represents acryloyl and methacryloyl.

[0014] In this specification, the "total solid content" of the magnetic particle-containing composition means the components that form the magnetic particle-containing film. When the magnetic particle-containing composition contains a solvent (organic solvent, water, etc.), it means all components excluding the solvent. Also, as long as it is a component that forms the magnetic particle-containing film, a liquid component is also regarded as a solid content.

[0015] In this specification, the weight average molecular weight (Mw) is a polystyrene equivalent value determined 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), with TSKgel SuperHZM-H, TSKgel SuperHZ4000, and TSKgel SuperHZ2000 (manufactured by Tosoh Corporation, 4.6 mm ID × 15 cm) as columns and THF (tetrahydrofuran) as the eluent.

[0016] In this specification, each component may be used alone as one kind of substance corresponding to each component, or two or more kinds may be used in combination. Here, when two or more kinds of substances are used in combination for each component, the content of that component refers to the total content of the combined substances, unless otherwise specified.

[0017] [Magnetic Particle-Containing Composition] The magnetic particle-containing composition of the present invention (hereinafter, also simply referred to as "composition") contains magnetic particles having a plurality of peak tops in a particle size distribution curve representing a frequency distribution based on volume, a resin, and a solvent. The magnetic particle-containing composition of the present invention can form a magnetic particle-containing film excellent in sedimentation stability and permeability. Although the details of the reason are not clear, it is generally estimated as follows.

[0018] If the average particle size of magnetic particles is not sufficiently large, it is known that the magnetic permeability of the magnetic particle-containing film obtained using the same becomes insufficient. However, the present inventors have found that simply using magnetic particles with a large average particle size cannot sufficiently increase the magnetic permeability because the gaps between the magnetic particles become large. The present inventors have found that the magnetic permeability can be improved by using magnetic particles having a plurality of peak tops in the particle size distribution curve representing the frequency distribution based on volume. This is presumably because the gaps between the magnetic particles in the magnetic particle-containing film are reduced by arranging magnetic particles with a small average particle size between magnetic particles with a large average particle size. On the other hand, there is a problem that magnetic particles with a large average particle size settle over time in the magnetic particle-containing composition. In response to this problem, it has been found that the sedimentation of magnetic particles can be suppressed by using a magnetic particle-containing composition containing magnetic particles having a plurality of peak tops in the particle size distribution curve representing the frequency distribution based on volume and a resin. This is presumably because the magnetic particles with a small average particle size are arranged by the action of the magnetic field existing between the magnetic particles with a large average particle size, and then, by the action of the resin, the magnetic particles are gently bound to each other, improving the static viscosity of the magnetic particle-containing composition and suppressing the sedimentation of the magnetic particles.

[0019] 〔Magnetic Particles〕 The composition contains magnetic particles having a plurality of peak tops in the particle size distribution curve representing the frequency distribution based on volume. The material constituting the magnetic particles preferably contains a metal element, and among them, it preferably contains at least one metal element selected from the group consisting of Fe, Ni, and Co. The above metal element 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 material constituting the magnetic particles may contain elements other than Fe, Ni, and Co. Specific examples thereof 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, and N.

[0020] Specific examples of the material constituting the magnetic particles include Fe-Co alloys (preferably, Permendur), Fe-Ni alloys (e.g., Permalloy), Fe-Zr alloys, Fe-Mn alloys, Fe-Si alloys, Fe-Al alloys, Ni-Mo alloys (preferably, Supermalloy), Fe-Ni-Co alloys, Fe-Si-Cr alloys, Fe-Si-B alloys, Fe-Si-Al alloys (preferably, Sendust), Fe-Si-B-C alloys, Fe-Si-B-Cr alloys, 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, and ferrites such as spinel ferrites (preferably, Ni-Zn ferrites, Mn-Zn ferrites) and hexagonal ferrites (preferably, barium ferrite, magnetoplumbite-type hexagonal ferrite represented by the following formula (F1)). The above alloys may be amorphous. Among them, alloys are preferable in terms of more excellent magnetic permeability of the magnetic particle-containing film, and Fe-based amorphous alloys, Fe-Si-Cr alloys, Fe nanocrystalline alloys, Fe-Ni-Co alloys, Co-based amorphous alloys, and Ni-Mo alloys are more preferable. Also, ferrites are preferable in terms of more excellent chemical stability of the magnetic particle-containing film, and spinel ferrites are more preferable. The material constituting the magnetic particles may be used alone or in combination of two or more.

[0021] Formula (F1) is as follows. AFe (12-X) Al X O 19 Formula (F1) In formula (F1), A represents at least one metal element selected from the group consisting of Sr, Ba, Ca, and Pb, and x satisfies 1.5 ≦ x ≦ 8.0.

[0022] In formula (F1), A may be any at least one metal element selected from the group consisting of Sr, Ba, Ca, and Pb, and the type and number of the metal elements are not particularly limited. For example, from the viewpoints of operability and handleability, A in formula (F1) is preferably at least one metal element selected from the group consisting of Sr, Ba, and Ca. In formula (F1), x satisfies 1.5 ≦ x ≦ 8.0, preferably satisfies 1.5 ≦ x ≦ 6.0, and more preferably satisfies 2.0 ≦ x ≦ 6.0. When x in formula (F1) is 1.5 or more, radio waves in a frequency band higher than 60 GHz can be absorbed. When x in formula (F1) is 8.0 or less, the magnetoplumbite-type hexagonal ferrite particles have magnetism.

[0023] Specific examples of the magnetoplumbite-type hexagonal ferrite represented by formula (F1) include SrFe (9.58) Al (2.42) O 19 、SrFe (9.37) Al (2.63) O 19 、SrFe (9.27) Al (2.73) O 19 、SrFe (9.85) Al (2.15) O 19 、SrFe (10.00) Al (2.00) O 19 、SrFe (9.74) Al (2.26) O 19 、SrFe (10.44) Al (1.56) O 19 、SrFe (9.79) Al (2.21) O 19 、SrFe (9.33) Al (2.67) O 19 、SrFe (7.88) Al (4.12)O 19 、 SrFe (7.04) Al (4.96) O 19 、 SrFe (7.37) Al (4.63) O 19 、 SrFe (6.25) Al (5.75) O 19 、 SrFe (7.71) Al (4.29) O 19 、 Sr (0.80) Ba (0.10) Ca (0.10) Fe (9.83) Al (2.17) O 19 、 BaFe (9.50) Al (2.50) O 19 、 CaFe (10.00) Al (2.00) O 19 、 PbFe (9.00) Al (3.00) O 19 include.

[0024] The composition of the magnetoplumbite-type hexagonal ferrite particles is confirmed by inductively coupled plasma (ICP) optical emission spectrometry. Specifically, a pressure-resistant container containing 12 mg of sample particles and 10 mL of a 4 mol / L (liter; the same hereinafter) hydrochloric acid aqueous solution is held in an oven at a set temperature of 120°C for 12 hours to obtain a dissolved solution. Next, 30 mL of pure water is added to the obtained dissolved solution, and then filtration is performed using a 0.1 μm membrane filter. Elemental analysis of the filtrate thus obtained is performed using an inductively coupled plasma (ICP) optical emission spectrometer. Based on the results of the obtained elemental analysis, the content of each metal atom with respect to 100 atomic% of iron atoms is determined. Based on the obtained content, the composition is confirmed. As the measuring device, for example, an inductively coupled plasma (ICP) optical emission spectrometer (model number: ICPS-8100) manufactured by Shimadzu Corporation can be preferably used. However, the measuring device is not limited to this.

[0025] The magnetoplumbite-type hexagonal ferrite represented by formula (F1) is preferably a magnetoplumbite-type hexagonal ferrite having a single crystal phase. In this specification, the case where "the crystal phase is a single phase" means that in powder X-ray diffraction (XRD) measurement, only one diffraction pattern showing the crystal structure of the magnetoplumbite-type hexagonal ferrite of any composition is observed. In other words, it means that there is no case where a plurality of magnetoplumbite-type hexagonal ferrites of any composition are mixed and two or more diffraction patterns are observed, or a diffraction pattern of a crystal other than the magnetoplumbite-type hexagonal ferrite is observed. For the attribution of the diffraction pattern, for example, the database of the International Centre for Diffraction Data (ICDD, registered trademark) can be referred to. For example, for the diffraction pattern of the magnetoplumbite-type hexagonal ferrite containing Sr, "00-033-1340" of the International Centre for Diffraction Data (ICDD) can be referred to. However, when a part of iron is replaced by aluminum, the peak position shifts.

[0026] The confirmation that the crystal phase of the magnetoplumbite-type hexagonal ferrite is a single phase can be performed, for example, by the X-ray diffraction (XRD) method. Specifically, a method of measuring using a powder X-ray diffractometer under the following conditions can be mentioned. As the measuring device, for example, the X'Pert Pro diffractometer of PANalytical can be preferably used. However, the measuring device is not limited to this.

[0027] - Conditions - X-ray source: CuKα ray 〔Wavelength: 1.54 Å (0.154 nm), Output: 40 mA, 45 kV〕 Scan range: 20° < 2θ < 70° Scan interval: 0.05° Scan speed: 0.75° / min

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

[0029] As the compound for forming the inorganic layer, from the viewpoint of being able to form a surface layer excellent in at least one of insulating properties, gas barrier properties, and chemical stability, metal oxides, metal nitrides, metal carbides, metal phosphate compounds, metal borate compounds, or silicate compounds (for example, silicate esters such as tetraethyl orthosilicate, and silicates such as sodium silicate) are preferable. Specific examples of the 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. Examples of the materials constituting the inorganic layer obtained using the compound for forming the 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 compound for forming the organic layer include acrylic monomers. Specific examples of the acrylic monomers include the compounds described in paragraphs 0022 to 0023 of JP-A-2019-67960. Examples of the materials constituting the organic layer obtained using the compound for forming the organic layer include acrylic resins.

[0031] The thickness of the surface layer is not particularly limited, but from the viewpoint of more effectively exhibiting the functions of the surface layer, 3 to 1000 nm is preferable.

[0032] The magnetic particles preferably contain a metal element having a standard oxidation-reduction potential of -0.3 V or more. Thereby, dissolution of the magnetic particles by an acid can be suppressed, so that the chemical stability of the magnetic permeability of the magnetic particle-containing film is more excellent. Specific examples of the metal element having a standard oxidation-reduction potential of -0.3 V or more include Ni and Co. The lower limit value of the standard redox potential of the metal element is preferably -0.3 V or more, and particularly preferably -0.27 V or more. The upper limit value of the standard redox potential of the metal element is preferably 1.5 V or less. From the viewpoint of more excellent magnetic permeability of the magnetic particle-containing film, the content of the metal element having a standard redox potential of -0.3 V or more is preferably 30% by mass or more, and particularly preferably 40% by mass or more, based on the total mass of the magnetic particles. The upper limit value of the content of the metal element having a standard redox potential of -0.3 V or more is preferably 100% by mass or less, and particularly preferably 95% by mass or less. The value of the standard redox potential in this specification adopts the value of the standard redox potential described in the Chemical Handbook (Fifth Edition).

[0033] From the viewpoint of more excellent magnetic permeability of the magnetic particle-containing film, the content of the magnetic particles is preferably 10% by mass or more, more preferably 25% by mass or more, further preferably 40% by mass or more, particularly preferably 50% by mass or more, and most preferably 60% by mass or more, based on the total mass of the composition. From the viewpoint of more excellent sedimentation stability of the magnetic particles, the content of the magnetic particles is preferably 95% by mass or less, and more preferably 90% by mass or less, based on the total mass of the composition. From the viewpoint of more excellent magnetic permeability of the magnetic particle-containing film, the content of the magnetic particles is preferably 10 to 99% by mass, and particularly preferably 40 to 97% by mass, based on the total solid content of the composition.

[0034] <Average primary particle diameter> The average primary particle diameter of the magnetic particles is preferably 0.001 to 100 μm, more preferably 0.01 to 50 μm, further preferably 0.1 to 30 μm, and particularly preferably 0.5 to 25 μm. " From the viewpoint that magnetic particles having a plurality of peak tops in the particle size distribution curve representing the frequency distribution based on volume can be easily obtained, it is preferable to use a combination of a plurality of particles having different average primary particle diameters as the magnetic particles.

[0035] The particle diameter of the primary particles of the magnetic particles is measured by taking a photograph of the magnetic particles at a magnification of 100,000 times using a transmission electron microscope, printing the photograph on a printing paper so that the total magnification becomes 500,000 times, tracing the contour of the particles (primary particles) with a digitizer on the obtained particle photograph, and calculating the diameter of a circle (equivalent circle diameter) having the same area as the traced region. Here, the primary particles refer to independent particles without aggregation. The photographing using a transmission electron microscope shall be performed by the direct method using a transmission electron microscope at an acceleration voltage of 300 kV. The transmission electron microscope observation and measurement can be performed, for example, using a Hitachi transmission electron microscope model H-9000 and Carl Zeiss image analysis software KS-400.

[0036] Regarding the shape of the magnetic particles, "plate-like" refers to a shape having two opposing plate surfaces. On the other hand, among the particle shapes without such plate surfaces, a shape with a distinction between a major axis and a minor axis is "elliptical". The major axis is determined as the axis (straight line) along which the length of the particle can be taken to be the longest. On the other hand, the minor axis is determined as the axis along which the length becomes the longest when the particle length is taken along a straight line orthogonal to the major axis. A shape without a distinction between the major axis and the minor axis, that is, a shape where the major axis length = minor axis length, is "spherical". A shape from which the major axis and the minor axis cannot be specified is called an amorphous shape. The photographing using a transmission electron microscope for specifying the above particle shape is performed without subjecting the particles to be photographed to an orientation treatment. The shape of the magnetic particles may be any of plate-like, elliptical, spherical, and amorphous.

[0037] Here, regarding the average primary particle diameter of the various particles described in this specification, when using a commercially available product, the catalog value is adopted. When there is no catalog value, the arithmetic mean of the values obtained for 500 randomly extracted particles is used using the particle photograph taken as described above.

[0038] <Particle size distribution> The magnetic particles contained in the composition have a plurality of peak tops in the particle size distribution curve representing the frequency distribution based on volume. In this specification, the particle size distribution curve representing the frequency distribution based on volume is also referred to as the "frequency distribution curve". FIG. 1 is a particle size distribution diagram showing an example of the frequency distribution curve of the magnetic particles contained in the composition of the present invention. As shown in FIG. 1, the frequency distribution curve is represented in a particle size distribution diagram with the horizontal axis being the particle diameter and the vertical axis being the frequency (%).

[0039] The frequency distribution curve in the present invention is obtained as follows. First, the composition is diluted with a main solvent as necessary, and ultrasonic dispersion is performed for 60 minutes to prepare a dispersion liquid. Note that the dilution of the composition is not performed when the content of the magnetic particles in the composition is 5% by mass or less, and when the content of the magnetic particles in the composition exceeds 5% by mass, the dilution is performed so that the content of the magnetic particles in the diluted dispersion liquid becomes 5% by mass. The main solvent means the solvent having the highest content among the solvents contained in the composition. Next, the dispersion liquid is measured by a laser diffraction / scattering particle size distribution measuring device (product name "LA960N", manufactured by Horiba, Ltd.) in a measurement range mode of 0.01 μm to 5000 μm to obtain a particle size distribution curve representing the volume-based frequency distribution of the magnetic particles contained in the composition.

[0040] The peak top in the frequency distribution curve means the maximum point in the frequency distribution curve. In the example of FIG. 1, the number of peak tops in the frequency distribution curve is two, namely the peak top Pmin with the smallest particle diameter and the peak top Pmax with the largest particle diameter, but the number of peak tops is not limited to this. The number of peak tops in the frequency distribution curve is plural (that is, two or more), preferably 2 to 5, more preferably 2 to 4, still more preferably 2 to 3, and particularly preferably 2 in terms of magnetic permeability and film formability.

[0041] Among the plurality of peak tops in the frequency distribution curve, when the particle diameter at the peak top Pmin with the smallest particle diameter is defined as Dmin and the particle diameter at the peak top Pmax with the largest particle diameter is defined as Dmax, from the viewpoint of more excellent effects of the present invention, the ratio of Dmax to Dmin (Dmax / Dmin) is preferably more than 2, more preferably 3 or more, and particularly preferably 4 or more. From the viewpoint of more excellent effects of the present invention, the upper limit of the above ratio (Dmax / Dmin) is preferably 150 or less, more preferably 100 or less, still more preferably 50 or less, and particularly preferably 10 or less. The above ratio (Dmax / Dmin) can be within the above value range, for example, by appropriately adjusting the blending ratios of a plurality of magnetic particles having different primary particle diameters.

[0042] FIG. 2 is a particle size distribution diagram showing an example of a particle size distribution curve representing the volume-based cumulative distribution of magnetic particles contained in the composition of the present invention. As shown in FIG. 2, the particle size distribution curve representing the volume-based cumulative distribution is represented in a particle size distribution diagram with the horizontal axis being the particle diameter and the vertical axis being the cumulative (%)). In the present specification, the particle size distribution curve representing the volume-based cumulative distribution is also referred to as a "cumulative distribution curve". The cumulative distribution curve is measured by the same method as the particle size distribution curve representing the volume-based frequency distribution. From the viewpoint of more excellent effects of the present invention, Dmin is the particle diameter D when the cumulative in the cumulative distribution curve is 80%. 80 It is preferably the following, and particularly preferably the particle diameter D when the cumulative in the cumulative distribution curve is 60%. 60 It is particularly preferably the following. From the viewpoint of more excellent effects of the present invention, Dmin is preferably the particle diameter D when the cumulative in the cumulative distribution curve is 10%. 10 It is preferably the above, and particularly preferably the particle diameter D when the cumulative in the cumulative distribution curve is 20%. 20 It is particularly preferably the above. From the viewpoint of more excellent effects of the present invention, Dmin is preferably 0.1 to 50 μm, more preferably 0.5 to 25 μm, and particularly preferably 1 to 10 μm.

[0043] From the viewpoint of more excellent effects of the present invention, Dmax is the particle diameter D when the cumulative in the cumulative distribution curve is 90%. 90 It is preferably the following, and particularly preferably the particle diameter D when the cumulative in the cumulative distribution curve is 80%. 80 It is particularly preferably the following. Dmax is preferably the particle size D at a cumulative 20% in the cumulative distribution curve, from the viewpoint of more excellent effects of the present invention. 20 More preferably, it is the particle size D at a cumulative 40% in the cumulative distribution curve. 40 Particularly preferably, it is the particle size D at a cumulative 40% in the cumulative distribution curve. From the viewpoint of more excellent effects of the present invention, Dmax is preferably 1 to 150 μm, more preferably 1 to 100 μm, still more preferably 5 to 75 μm, and particularly preferably 7.5 to 50 μm.

[0044] [Resin] The composition contains a resin. Examples of the resin include (meth)acrylic resin, epoxy resin, ene-thiol 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, phenoxy resin, and the like. One of these resins may be used alone, or two or more of them may be mixed and used. From the viewpoint of improving heat resistance, norbornene resin is preferable as the cyclic olefin resin. Examples of commercially available norbornene resins include the ARTON series (e.g., ARTON F4520) manufactured by JSR Corporation. Examples of the epoxy resin include epoxy resins that are glycidyl etherified products of phenolic compounds, epoxy resins that are glycidyl etherified products of various novolak 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 a silicon compound having an epoxy group and another silicon compound, copolymers of a polymerizable unsaturated compound having an epoxy group and another polymerizable unsaturated compound, and the like. In addition, 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), and the like can also be used. Further, as the resin, the resin described in the examples of International Publication No. 2016 / 088645 can also be used. Further, when the resin has an ethylenically unsaturated group, particularly a (meth)acryloyl group, in the side chain, it is also preferable that the main chain and the ethylenically unsaturated group are bonded via a divalent linking group having an alicyclic structure.

[0045] As one of the preferred embodiments of the resin, resins having polymerizable groups such as unsaturated double bonds (for example, ethylenically unsaturated double bonds), epoxy groups, or oxetanyl groups can be mentioned. When the polymerizable group reacts during the formation of the magnetic particle-containing film, a magnetic particle-containing film excellent in mechanical strength can be obtained. Examples of such resins include polymers having an epoxy group in the 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, aliphatic epoxy resins, and the like. These resins may be commercially available products, or may also be obtained by introducing an epoxy group into the side chain of the polymer. As commercially available products, for example, the descriptions in paragraph 0191 of JP-A-2012-155288 and the like can be referred to, and these contents are incorporated into the present specification. In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (manufactured by ADEKA Corporation), JER1031S, and the like can also be mentioned. Furthermore, as commercially available products of phenol novolac type epoxy resins, JER-157S65, JER-152, JER-154, JER-157S70 (manufactured by Mitsubishi Chemical Corporation), and the like can be mentioned. Specific examples of polymers having an oxetanyl group in the side chain and polymerizable monomers or oligomers having two or more oxetanyl groups in the molecule as described above include Aron Oxetane OXT-121, OXT-221, OX-SQ, PNOX (manufactured by Toagosei Co., Ltd.), which can be used. When synthesizing a resin having an epoxy group by introducing an epoxy group into a polymer side chain, the introduction reaction can be carried out, for example, in an organic solvent using a tertiary amine such as triethylamine or benzylmethylamine, a quaternary ammonium salt such as dodecyltrimethylammonium chloride, tetramethylammonium chloride or tetraethylammonium chloride, pyridine, triphenylphosphine, etc. as a catalyst, and reacting at a reaction temperature of 50 to 150 ° C for a predetermined time. The introduction amount of the alicyclic epoxy unsaturated compound can be controlled so that the acid value of the resulting polymer satisfies 5 to 200 KOH·mg / g. Further, the weight average molecular weight can be in the range of 500 to 5,000,000, preferably 1,000 to 500,000. Instead of the alicyclic epoxy unsaturated compound, those having a glycidyl group as an epoxy group such as glycidyl (meth)acrylate or allyl glycidyl ether can also be used. As such, for example, the description in paragraph 0045 of JP-A-2009-265518 can be referred to, and these contents are incorporated into the present specification.

[0046] One of the preferred embodiments of the resin includes a resin having an acid group, a basic group or an amide group. A resin having an acid group, a basic group or an amide group is likely to exhibit a function as a dispersant for dispersing magnetic particles, and is suitable from the viewpoint that the effects of the present invention are more excellent. Examples of the acid group include a carboxy group, a phosphoric acid group, a sulfo group, a phenolic hydroxyl group, etc. From the viewpoint that the effects of the present invention are more excellent, a carboxy group is preferred. Examples of the basic group include an amino group (a group obtained by removing one hydrogen atom from ammonia, a primary amine or a secondary amine), and an imino group. Among them, from the viewpoint that the effects of the present invention are more excellent, the resin preferably has a carboxy group or an amide group.

[0047] When the resin has an acid group, the acid value of the resin is preferably 10 to 500 mgKOH / g, particularly preferably 30 to 400 mgKOH / g or more, from the viewpoint that the effects of the present invention are more excellent.

[0048] As the resin, it is preferable to use a resin having a solubility in the solvent of 10 g / L or more, and it is more preferable to use a resin having a solubility in the solvent of 20 g / L or more, since this improves the dispersibility of the resin in the composition and makes the effects of the present invention more excellent. The upper limit of the solubility of the resin in the solvent is preferably 2000 g / L or less, particularly preferably 1000 g / L or less. The solubility of a resin in a solvent means the amount (g) of resin that dissolves in 1 L of solvent at 25°C.

[0049] The resin content is preferably 0.1 to 30 mass%, more preferably 1 to 20 mass%, even more preferably 2 to 15 mass%, and particularly preferably 2.5 to 10 mass%, relative to the total mass of the composition, in order to achieve better effects of the present invention.

[0050] <Resin that functions as a dispersant> One preferred embodiment of the resin is a resin that functions as a dispersant for dispersing magnetic particles in the composition (hereinafter also referred to as a "dispersion resin"). Use of a dispersion resin enhances the effects of the present invention. Suitable embodiments of the dispersing resin include a resin having a repeating unit containing a graft chain, an aggregation control agent, and an aggregation dispersant, which will be described later.

[0051] (Resin having repeating units containing graft chains) The dispersing resin may be a resin having a repeating unit containing a graft chain (hereinafter also referred to as "resin A"). However, resin A may also be used for purposes other than functioning as a dispersant.

[0052] When the composition contains resin A, the content of resin A is preferably 0.1 to 30 mass%, more preferably 0.5 to 20 mass%, and particularly preferably 1 to 10 mass%, relative to the total mass of the composition, in order to achieve better effects of the present invention.

[0053] Repeating units containing graft chains In the repeating unit containing the 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 adsorption force to the magnetic particles decreases, and the dispersibility of the magnetic particles tends to decrease. Therefore, the graft chain preferably has 40 to 10,000 atoms excluding hydrogen atoms, more preferably 50 to 2,000 atoms excluding hydrogen atoms, and even more preferably 60 to 500 atoms excluding hydrogen atoms. Here, the graft chain refers to the part from the root of the main chain (the atom bonded to the main chain in the group branched from the main chain) to the end of the group branched from the main chain.

[0054] Further, the graft chain preferably contains a polymer structure. Examples of such a polymer structure include a poly(meth)acrylate structure (for example, 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 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.

[0055] Resin A may be a resin obtained using a macromonomer containing a graft chain (a monomer having a polymer structure and bonded to the main chain to form a graft chain). The macromonomer containing a graft chain (a monomer having a polymer structure and bonded to the main chain to form a graft chain) is not particularly limited, but a macromonomer containing a reactive double bond group can be preferably used.

[0056] Commercially available macromonomers corresponding to the repeating unit containing the graft chain and suitably used for 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 are trade names, manufactured by Toagosei Co., Ltd.), and Brenmer PP-100, Brenmer PP-500, Brenmer PP-800, Brenmer PP-1000, Brenmer 55-PET-800, Brenmer PME-4000, Brenmer PSE-400, Brenmer PSE-1300, and Brenmer 43PAPE-600B (all are trade names, manufactured by NOF Corporation). Among these, AA-6, AA-10, AB-6, AS-6, AN-6, or Brenmer PME-4000 is preferred.

[0057] Resin A preferably contains at least one structure selected from the group consisting of methyl polyacrylate, methyl polymethacrylate, and cyclic or linear polyester, more preferably contains at least one structure selected from the group consisting of methyl polyacrylate, methyl polymethacrylate, and linear polyester, and particularly preferably contains at least one structure selected from the group consisting of methyl polyacrylate structure, methyl polymethacrylate structure, polycaprolactone structure, and polyvalerolactone structure. Resin A may contain one of the above structures alone or a plurality of these structures. Here, the polycaprolactone structure refers to a structure containing, as a repeating unit, a structure obtained by ring-opening ε-caprolactone. The polyvalerolactone structure refers to a structure containing, as a repeating unit, a structure obtained by ring-opening δ-valerolactone.

[0058] In addition, when Resin A contains a repeating unit in which j and k in the following formula (1) and the following formula (2) are 5, the above-described polycaprolactone structure can be introduced into Resin A. Also, when Resin A contains a repeating unit in which j and k in the following formula (1) and the following formula (2) are 4, the above-described polyvalerolactone structure can be introduced into the resin. In addition, when the resin A contains a repeating unit in which X in the following formula (4) is a hydrogen atom and R is a methyl group, the above-described polymethyl acrylate structure can be introduced into the resin A. 5 is a hydrogen atom, and R 4 is a methyl group, the above-described polymethyl acrylate structure can be introduced into the resin A. In addition, when the resin A contains a repeating unit in which X in the following formula (4) is a methyl group and R is a methyl group, the above-described polymethyl methacrylate structure can be introduced into the resin A. 5 is a methyl group, and R 4 is a methyl group, the above-described polymethyl methacrylate structure can be introduced into the resin A.

[0059] The resin A preferably contains a repeating unit represented by any one of the following formulas (1) to (4) as a repeating unit containing a graft chain, and more preferably contains a repeating unit represented by any one of the following formula (1A), the following formula (2A), the following formula (3A), the following formula (3B), and the following (4).

[0060]

Chemical formula

[0061] In formulas (1) to (4), W 1 , W 2 , W 3 , and W 4 each independently represents an oxygen atom or NH. W 1 , W 2 , W 3 , and W 4 are preferably oxygen atoms. In formulas (1) to (4), X 1 , X 2 , X 3 , X 4 , and X 5 each independently represents a hydrogen atom or a monovalent organic group. X 1 , X 2 , X 3 , X 4 , and X 5 are each independently preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms (number of carbon atoms) from the viewpoint of synthetic constraints, more preferably each independently a hydrogen atom or a methyl group, and even more preferably a methyl group.

[0062] In formulas (1) to (4), Y 1 , Y 2 , Y 3 , and Y 4 each independently represents a divalent linking group, and the linking group is not particularly restricted in structure. Y 1 , Y 2 , Y 3 , and Y 4 Examples of the divalent linking group represented by Y

[0063]

Chemical formula

[0064] In formulas (1) to (4), Z 1 , Z 2 , Z 3 , and Z 4 each independently represents a monovalent organic group. The structure of the organic group is not particularly limited, but specifically, 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, the organic groups represented by Z 1 , Z 2 , Z 3 , and Z 4 are preferably groups including a steric repulsion effect from the viewpoint of improving dispersibility, more preferably each independently an alkyl group or an alkoxy group having 5 to 24 carbon atoms, and among them, more preferably each independently a branched-chain 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. Note that the alkyl group contained in the alkoxy group may be linear, branched, or cyclic.

[0065] In formulas (1) to (4), n, m, p, and q are each independently an integer from 1 to 500. In addition, in formulas (1) and (2), j and k each independently represent an integer from 2 to 8. j and k in formulas (1) and (2) are preferably integers from 4 to 6, more preferably 5. In addition, in formulas (1) and (2), n and m are preferably integers of 10 or more, more preferably integers of 20 or more. When resin A contains a polycaprolactone structure and a polyvalerolactone structure, the sum of the number of repetitions of the polycaprolactone structure and the number of repetitions of polyvalerolactone is preferably an integer of 10 or more, more preferably an integer of 20 or more.

[0066] 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. When p is from 2 to 500, a plurality of R 3 may be the same as or different from each other. In formula (4), R 4 represents a hydrogen atom or a monovalent organic group, and the structure of this monovalent organic group is not particularly limited. As R 4 , a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group is preferable, and a hydrogen atom or an alkyl group is more preferable. When R 4 is an alkyl group, the alkyl group is preferably a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms, more preferably a linear alkyl group having 1 to 20 carbon atoms, and even more preferably a linear alkyl group having 1 to 6 carbon atoms. In formula (4), when q is from 2 to 500, a plurality of X 5 and R 4 in the graft chain may be the same as or different from each other.

[0067] In addition, resin A may contain repeating units including graft chains with two or more different structures. That is, the molecule of resin A may contain repeating units represented by formulas (1) to (4) having different structures from each other. Further, 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 in the side chain may contain structures different from each other, and in formulas (3) and (4), a plurality of R 3 , R 4 , and X 5 may be the same as or different from each other.

[0068] As the repeating unit represented by formula (1), a repeating unit represented by the following formula (1A) is more preferable. In addition, as the repeating unit represented by formula (2), a repeating unit represented by the following formula (2A) is more preferable.

[0069]

Chemical formula

[0070] In formula (1A), X 1 , Y 1 , Z 1 , and n have the same meanings as X 1 , Y 1 , Z 1 , and n in formula (1), and the preferable ranges are also the same. In formula (2A), X 2 , Y 2 , Z 2 , and m have the same meanings as X 2 , Y 2 , Z 2 , and m in formula (2), and the preferable ranges are also the same.

[0071] In addition, as the repeating unit represented by formula (3), a repeating unit represented by the following formula (3A) or formula (3B) is more preferable.

[0072]

Chemical formula

[0073] In formula (3A) or (3B), X 3 , Y 3 , Z 3 , and p are synonymous with X 3 , Y 3 , Z 3 , and p in formula (3), and the preferred ranges are also the same.

[0074] It is more preferable that resin A contains a repeating unit represented by formula (1A) as a repeating unit containing a graft chain.

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

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

[0077]

Chemical formula

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

[0079]

Chemical formula

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

[0081] The * in formula (4A) and formula (4B), and the * in formula (4B) 2 each independently represents a position where it binds to an adjacent alkyleneimine chain, or a hydrogen atom or a substituent. As the *, in formula (4A) and formula (4B), it is preferable to represent a position where it binds to an adjacent alkyleneimine chain.

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

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

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

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

[0086]

Chemical formula

[0087] When the alkyleneimine chain is an alkyleneimine chain represented by Formula (4B), the polyester chain contains anionic property (preferably oxygen anion O - ), and it is preferable that this anionic property and N in Formula (4B) + form a salt crosslinking group. Examples of such a polyester chain include a polyester chain represented by the following Formula (5B).

[0088]

Chemical formula

[0089] L in Formula (5A) X1 , and L in Formula (5B) X2 each independently represent a divalent linking group. Examples of the divalent linking group preferably include an alkylene group having 3 to 30 carbon atoms.

[0090] b in Formula (5A) 11 , and b in Formula (5B) 21each independently represents an integer of 2 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 carbon number of the above alkyl group (which may be linear, branched, or cyclic) and the alkyl group contained in the above alkoxy group (which may be linear, branched, or cyclic) is, for example, 1 to 30, preferably 1 to 10. Further, the above 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] The polyalkyleneoxyalkyl group is a substituent represented by R X6 (OR X7 ) p (O) q -. R 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 is synonymous with the alkyl group represented by X A . Further, examples of the alkylene group represented by R X7 include a group obtained by removing one hydrogen atom from the alkyl group represented by X A . p is an integer of 2 or more, and the upper limit value thereof is, for example, 10 or less, preferably 5 or less.

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

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

[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. 5923557.

[0098] In Resin A, the content of the repeating unit containing the graft chain is preferably 2 to 95% by mass, more preferably 2 to 90% by mass, and particularly preferably 5 to 30% by mass, in terms of mass, based on the total mass of Resin A. When the repeating unit containing the graft chain is included within this range, the effects of the present invention are more excellent.

[0099] · Hydrophobic repeating unit Further, Resin A may contain a hydrophobic repeating unit that is different from (i.e., does not correspond to) the repeating unit containing the graft chain. However, in this specification, the 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. Thereby, the effects of the present invention can be more surely exhibited.

[0101] The ClogP value is a value calculated by the program "CLOGP" available from Daylight Chemical Information System, Inc. This program provides the value of "calculated logP" calculated by the fragment approach of Hansch, Leo (see the following literature). The fragment approach is based on the chemical structure of the compound, divides the chemical structure into substructures (fragments), and estimates the logP value of the compound by summing the logP contributions assigned to the fragments. The details are described in the following literature. In this specification, the ClogP value calculated by the program CLOGP v4.82 is used. A. J. Leo, Comprehensive Medicinal Chemistry, Vol.4, C. Hansch, P. G. Sammnens, J. B. Taylor and C. A. Ramsden, Eds., p.295, Pergamon Press, 1990 C. Hansch & A. J. Leo. SUbstituent Constants For Correlation Analysis in Chemistry and Biology. John Wiley & Sons. A.J. Leo. Calculating logPoct from structure. Chem. Rev., 93, 1281-1306, 1993.

[0102] logP means the common logarithm of the partition coefficient P, and is a physical property value that quantitatively represents how an organic compound is distributed in the equilibrium of a two-phase system of oil (generally 1-octanol) and water, and is represented by the following formula. logP = log(Coil / Cwater) In the formula, Coil represents the molar concentration of the compound in the oil phase, and Cwater represents the molar concentration of the compound in the aqueous phase. When the value of logP is greater than 0 and increases positively, the oil solubility increases. When it is negative and the absolute value increases, the water solubility increases. There is a negative correlation with the water solubility of organic compounds, and it is widely used as a parameter for estimating the hydrophilic-lipophilic balance of organic compounds.

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

[0104]

Chemical formula

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

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

[0107] The divalent aliphatic group may have a cyclic structure or a branched structure. The number of carbon atoms of 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. Further, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group, and a heterocyclic group, etc.

[0108] The number of carbon atoms of the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and even more preferably 6 to 10. Further, 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, etc.

[0109] The divalent heterocyclic group preferably contains a 5-membered ring or a 6-membered ring as the heterocycle. Another heterocycle, an aliphatic ring, or an aromatic ring may be condensed with the heterocycle. Further, 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 (=N-R 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 divalent linking group including a single bond, an alkylene group or an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. Further, L may include a polyoxyalkylene structure in which the oxyalkylene structure is repeated two or more times. As the polyoxyalkylene structure, a polyoxyethylene structure or a polyoxypropylene structure is preferable. The polyoxyethylene structure is represented by -(OCH2CH2)n-, and n is preferably an integer of 2 or more, more preferably an integer of 2 to 10.

[0111] Examples of Z include 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 may include an oxygen atom (-O-), a sulfur atom (-S-), an imino group (-NH-), a substituted imino group (-NR 31 -, where R 31 is 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 of the aliphatic group is preferably 1 to 20, more preferably 1 to 15, still more preferably 1 to 10. The aliphatic group further includes a fused-ring hydrocarbon group and a bridged-ring hydrocarbon group. Examples of the fused-ring hydrocarbon group include a bicyclohexyl group, a perhydronaphthalenyl group, a biphenyl group, and a 4-cyclohexylphenyl group. Examples of the bridged-ring hydrocarbon ring include bicyclic hydrocarbon rings such as pinane, bornane, norpinane, norbornane, and bicyclooctane rings (bicyclo[2.2.2]octane ring and bicyclo[3.2.1]octane ring), tricyclic hydrocarbon rings such as homobredane, adamantane, tricyclo[5.2.1.0 2,6 decane, and tricyclo[4.3.1.1 2,5 undecane ring, and tetracyclic hydrocarbon rings such as tetracyclo[4.4.0.1 2,5 .1 7,10Examples include dodecane and 4-ring hydrocarbon rings such as perhydro-1,4-methano-5,8-methanonaphthalene ring. The bridged cyclic hydrocarbon ring also includes a condensed cyclic hydrocarbon ring, for example, a condensed ring formed by condensation of multiple 5- to 8-membered cycloalkane rings such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and perhydrophenalene rings. The saturated aliphatic group is more preferable than the 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 of the aromatic group is preferably 6 to 20, more preferably 6 to 15, and even more 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-membered ring or a 6-membered ring as the heterocyclic ring. Another heterocyclic ring, an aliphatic ring, or an aromatic ring may be condensed to the heterocyclic 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 (=N-R 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. However, 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 each independently represents a hydrogen atom, a halogen atom (e.g., a fluorine atom, a chlorine atom, and a bromine atom, etc.), an alkyl group having 1 to 6 carbon atoms (e.g., a methyl group, an ethyl group, and a propyl group, etc.), Z, or L-Z. Here, L and Z have the same meanings as the groups described above. R 4 , R5 and R 6 is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.

[0116] As the monomer represented by the above formula (i), R 1 R 2 and R 3 is 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. A compound is preferred. Further, 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. A compound is preferred. Further, as the monomer represented by the above formula (iii), R 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. A compound is preferred.

[0117] Examples of typical compounds represented by formulas (i) to (iii) include radical polymerizable compounds selected from acrylic esters, methacrylic esters, styrenes, and the like. In addition, as examples of typical compounds represented by formulas (i) to (iii), reference can be made to the compounds described in paragraphs 0089 to 0093 of JP-A-2013-249417, and the contents thereof are incorporated herein.

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

[0119] · Functional groups capable of forming an interaction with magnetic particles Resin A may have a functional group capable of forming an interaction with magnetic particles. Resin A preferably further contains a repeating unit containing a functional group capable of forming an interaction with magnetic particles. Examples of the functional group capable of forming an interaction with magnetic particles include an acidic group, a basic group, a coordinating group, and a reactive functional group. When Resin A contains an acidic group, a basic group, a coordinating group, or a reactive functional group, it preferably contains a repeating unit containing an acidic 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 alkali-soluble group as an acidic group may be the same repeating unit as the repeating unit containing the above graft chain or a different repeating unit, but the repeating unit containing an alkali-soluble group as an acidic group is a repeating unit different from the above hydrophobic repeating unit (that is, it does not correspond to the above hydrophobic repeating unit).

[0121] Examples of the acidic group as a functional group capable of forming an interaction with magnetic particles include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group, etc. At least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group is preferable, and a carboxylic acid group is more preferable. The carboxylic acid group has good adsorption force to magnetic particles and high dispersibility. That is, Resin A preferably 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 repeating units containing an acidic group. When Resin A contains a repeating unit containing an acidic group, its content is preferably 5 to 80% by mass, more preferably 10 to 60% by mass, based on the total mass of Resin A in terms of mass.

[0123] Examples of the basic group, which is a functional group capable of forming an interaction with magnetic particles, include a primary amino group, a secondary amino group, a tertiary amino group, a heterocyclic ring containing an N atom, and an amide group. A preferred basic group is a tertiary amino group in terms of good adsorption to magnetic particles and high dispersibility. Resin A may contain one or more of these basic groups. When Resin A contains a repeating unit containing a basic group, the content is preferably 0.01 to 50% by mass, more preferably 0.01 to 30% by mass, in terms of the total mass of Resin A in mass conversion.

[0124] Examples of the coordinating group, which is a functional group capable of forming an interaction with magnetic particles, and the reactive functional group include an acetylacetoxy group, a trialkoxysilyl group, an isocyanate group, an acid anhydride, and an acid chloride. A preferred functional group is an acetylacetoxy group in terms of good adsorption to magnetic particles and high dispersibility of 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 is preferably 10 to 80% by mass, more preferably 20 to 60% by mass, in terms of the total mass of Resin A in mass conversion.

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

[0126]

Chemical formula

[0127] In formulas (iv) to (vi), R 11 , R 12 , and R 13Each independently represents a hydrogen atom, a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, etc.), or an alkyl group having 1 to 6 carbon atoms (e.g., a methyl group, an ethyl group, a propyl group, etc.). In formulas (iv) to (vi), R 11 , R 12 , and R 13 are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group. In general formula (iv), R 12 and R 13 are even more preferably a hydrogen atom.

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

[0129] In formulas (iv) to (v), L1 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) described 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. Also, L1 may contain a polyoxyalkylene structure in which the oxyalkylene structure is repeated two or more times. As the polyoxyalkylene structure, a polyoxyethylene structure or a polyoxypropylene structure is preferred. The polyoxyethylene structure is represented by -(OCH2CH2)n-, and n is preferably an integer of 2 or more, more preferably an integer of 2 to 10.

[0131] In formulas (iv) to (vi), Z1 represents a functional group capable of forming an interaction with magnetic particles other than the graft chain, 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 16Each 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 the preferred examples are also the same. R 14 R 15 and R 16 are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, 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 a divalent linking group containing an alkylene group or an oxyalkylene structure, X1 is an oxygen atom or an imino group, and Z1 is a carboxylic acid group. Also, as the monomer represented by formula (v), a compound in which 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 is preferred. Furthermore, 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 (for example, 2-hydroxyethyl methacrylate) and succinic anhydride, a reaction product of a compound containing an addition-polymerizable double bond and a hydroxyl group in the molecule and phthalic anhydride, a reaction product of a compound containing an addition-polymerizable double bond and a hydroxyl group in the molecule and tetrahydroxyphthalic anhydride, a reaction product of a compound containing an addition-polymerizable double bond and a hydroxyl group in the molecule and trimellitic anhydride, a reaction product of a compound containing an addition-polymerizable double bond and a hydroxyl group in the molecule and pyromellitic dianhydride, acrylic acid, acrylic acid dimer, acrylic acid oligomer, maleic acid, itaconic acid, fumaric acid, 4-vinylbenzoic acid, vinylphenol, 4-hydroxyphenylmethacrylamide, and the like.

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

[0136] · ethylenically unsaturated group Resin A may contain an ethylenically unsaturated group. The ethylenically unsaturated group is not particularly limited, and examples thereof include (meth)acryloyl group, vinyl group, and styryl group, and the (meth)acryloyl group is preferred. Among them, 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 (meth)acrylate (hereinafter, also referred to as "side chain ethylenically unsaturated group-containing (meth)acrylic repeating unit"). (Meth)acrylic repeating units containing ethylenically unsaturated groups in the side chain can be obtained, for example, by subjecting the carboxylic acid groups in resin A containing (meth)acrylic repeating units containing carboxylic acid groups to an addition reaction with an ethylenically unsaturated compound containing a glycidyl group or an alicyclic epoxy group. By reacting the thus-introduced ethylenically unsaturated group (glycidyl group or alicyclic epoxy group), (meth)acrylic repeating units containing ethylenically unsaturated groups in the side chain can be obtained.

[0137] When resin A contains repeating units containing ethylenically unsaturated groups, the content thereof is preferably 30 to 70% by mass, more preferably 40 to 60% by mass, in terms of mass, based on the total mass of resin A.

[0138] · Other repeating units Furthermore, for the purpose of improving various properties such as film-forming ability, resin A may further have other repeating units having various functions, which are different from repeating units containing graft chains, hydrophobic repeating units, and repeating units containing functional groups capable of forming interactions with magnetic particles, 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, for example, acrylonitriles and methacrylonitriles. Resin A can use one or more of these other repeating units, and the content thereof is preferably 0 to 80% by mass, more preferably 10 to 60% by mass, in terms of mass, based on the total mass of resin A.

[0139] · Physical properties of resin A The acid value of resin A is not particularly limited, but for example, 0 to 400 mgKOH / g is preferable, 10 to 350 mgKOH / g is more preferable, 30 to 300 mgKOH / g is still more preferable, and a range of 50 to 200 mgKOH / g is particularly preferable. If the acid value of resin A is 50 mgKOH / g or more, the sedimentation stability of magnetic particles can be further improved.

[0140] In this specification, the acid value can be calculated, for example, from the average content of acid groups in a compound. Further, by changing the content of repeating units containing acid groups in the resin, a resin having a desired acid value can be obtained.

[0141] The weight average molecular weight of Resin A is not particularly limited. For example, it is preferably 3,000 or more, more preferably 4,000 or more, still more preferably 5,000 or more, and particularly preferably 6,000 or more. Further, as the upper limit value, for example, it is preferably 300,000 or less, more preferably 200,000 or less, still more preferably 100,000 or less, and particularly preferably 50,000 or less. Resin A can be synthesized based on known methods.

[0142] Note that as examples of specific examples of Resin A, reference can be made to the polymer compounds described in paragraphs 0127 to 0129 of JP-A-2013-249417, and the contents thereof are incorporated herein.

[0143] Further, as Resin A, the graft copolymers described in paragraphs 0037 to 0115 of JP-A-2010-106268 (paragraphs 0075 to 0133 of the corresponding US2011 / 0124824) can also be used, and the contents thereof can be incorporated herein by reference.

[0144] (Agglomeration control agent) Examples of the dispersion resin include an agglomeration control agent. The agglomeration control agent binds to relatively high-density aggregates such as magnetic particles, and further has a function of dispersing other components (for example, alkali-soluble resin, etc.) optionally contained in the composition to form bulky aggregates. When the dispersion resin contains an agglomeration control agent, hard caking of magnetic particles in the composition is suppressed, and further bulky aggregates are formed, so that the redispersibility can be improved.

[0145] Examples of the agglomeration control agent include cellulose derivatives. Examples of the cellulose derivative include carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxypropyl ethyl cellulose, and salts thereof.

[0146] When the composition contains an aggregation control agent, the content of the aggregation control agent is preferably 0.1 to 20% by mass, particularly preferably 0.5 to 10% by mass, based on the total mass of the composition.

[0147] (Aggregation dispersant) Examples of the dispersion resin include an aggregation dispersant. The aggregation dispersant adsorbs on the surface of the magnetic particles, and while separating the magnetic particles from each other, it can keep the distance between the magnetic particles at a certain level or more by the interaction between the dispersants, preventing the magnetic particles from directly aggregating. As a result, the aggregation of the magnetic particles is suppressed, and even when aggregates are formed, relatively low-density aggregates are formed. Furthermore, since other components (for example, an alkali-soluble resin, etc.) optionally contained in the composition can be dispersed in the composition to form bulky aggregates, the redispersibility can be improved.

[0148] As the aggregation dispersant, an alkylolammonium salt of a polybasic acid is preferable. The polybasic acid only needs to have two or more acid groups. For example, acidic polymers containing repeating units having acid groups (for example, polyacrylic acid, polymethacrylic acid, polyvinyl sulfonic acid, and polyphosphoric acid, etc.) can be mentioned. In addition, examples of polybasic acids other than the above include polymers obtained by polymerizing unsaturated fatty acids such as crotonic acid. The alkylolammonium salt of a polybasic acid is obtained by reacting these polybasic acids with alkylolammonium. The salt obtained by such a reaction usually contains the following partial structure. -C(=O)-N(-R 1 )(-R 2 -OH) Here, R 1 is an alkyl group, and R 2 is an alkylene group. As the alkylol ammonium salt of the polybasic acid, it is preferably a polymer containing a plurality of the above partial structures. When the alkylol ammonium salt of the polybasic acid is a polymer, the weight average molecular weight is preferably from 1,000 to 100,000, more preferably from 5,000 to 20,000. The polymer of the alkylol ammonium salt of the polybasic acid binds to the surface of the magnetic particles and forms hydrogen bonds with other aggregation dispersant molecules, so that the main chain structure of the polymer can enter between the magnetic particles and separate the magnetic particles from each other.

[0149] One preferred embodiment of the aggregation dispersant is an amide wax which is a condensate obtained by dehydration condensation of at least any one of (a) saturated aliphatic monocarboxylic acids and hydroxy group-containing aliphatic monocarboxylic acids, (b) polybasic acids, and (c) diamines and tetraamines. It is preferable to use the above (a) to (c) in a molar ratio of (a):(b):(c) = 1 to 3:0 to 5:1 to 6.

[0150] The saturated aliphatic monocarboxylic acids preferably have 12 to 22 carbon atoms. Specifically, lauric acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid and the like can be mentioned. The hydroxy group-containing aliphatic monocarboxylic acids preferably have 12 to 22 carbon atoms. Specifically, 12-hydroxystearic acid and dihydroxystearic acid can be mentioned. These saturated aliphatic monocarboxylic acids and hydroxy group-containing aliphatic monocarboxylic acids may be used alone or in combination of a plurality.

[0151] The polybasic acids are preferably carboxylic acids having 2 to 12 carbon atoms and having two or more carboxyl groups, 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 of two or more.

[0152] The diamines preferably have 2 to 14 carbon atoms. 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 2 to 14 carbon atoms. 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 of two or more.

[0153] The amounts of the diamines and tetraamines are adjusted so that the total number of carboxy groups and the total number of amino groups are equivalent according to the number of moles of the saturated aliphatic monocarboxylic acid or the hydroxy group-containing aliphatic monocarboxylic acid and the number of moles of the polybasic acids. For example, when there are 2 moles of an aliphatic monocarboxylic acid and n moles (n = 0 to 5) of an aliphatic dicarboxylic acid as the polybasic acid, if the amount of the diamines is (n + 1) moles, the acid and the amine are equivalent.

[0154] This amide wax is obtained as a mixture of a plurality of compounds having different molecular weights. The amide wax is preferably represented by the following chemical formula (I). Note that the amide wax may be a single compound or a mixture. A-C-(B-C) m -A···(I) In formula (I), A is a dehydration acid group residue of a saturated aliphatic monocarboxylic acid and / or a hydroxy group-containing saturated aliphatic monocarboxylic acid, B is a dehydration acid group residue of a polybasic acid, C is a dehydrogenation residue of a diamine and / or a tetraamine, and m satisfies 0 ≦ m ≦ 5.

[0155] One preferred embodiment of the flocculating dispersant is a compound represented by the following formula (II).

[0156]

Chemical formula

[0157] 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 represent 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, and R 4 represents a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, and R 5 and R 6 each independently represent a monovalent aliphatic hydrocarbon group having 1 to 3 carbon atoms or a hydroxyalkyl ether group. In formula (II), L 1 ~L 3 each independently represent an amide bond. When L 1 and L 3 is -CONH-, L 2 is -NHCO-, and when L 1 and L 3 is -NHCO-, L 2 is -CONH-.

[0158] R 1is a monovalent linear aliphatic hydrocarbon group having 10 to 25 carbon atoms, for example, linear alkyl groups such as decyl group, lauryl group, myristyl group, pentadecyl group, stearyl group, palmityl group, nonadecyl group, eicosyl group, behenyl group; linear alkenyl groups such as decenyl group, pentadecenyl group, oleyl group, eicosenyl group; and linear alkynyl groups such as pentadecinyl group, octadecinyl group, nonadecinyl group. Among them, R 1 is preferably a monovalent linear aliphatic hydrocarbon group having 14 to 25 carbon atoms, and particularly preferably a monovalent linear aliphatic hydrocarbon group having 18 to 21 carbon atoms, in that it has an excellent thickening effect and can extremely lowly suppress the residual ash even when fired at a low temperature. The linear aliphatic hydrocarbon group is preferably an alkyl group.

[0159] R 2 and R 3 Examples of the divalent aliphatic hydrocarbon group having 2, 4, 6 or 8 carbon atoms in R and R 2 include, for example, ethylene group, n-butylene group, n-hexylene group, n-octylene group. 3 Examples of the divalent alicyclic hydrocarbon group having 6 carbon atoms in R and R 2 include, for example, 1,4-cyclohexylene group, 1,3-cyclohexylene group, 1,2-cyclohexylene group. 3 Examples of the divalent aromatic hydrocarbon group in R

[0160] Among them, R 2 and R 3 are preferably divalent aliphatic hydrocarbon groups having 2, 4, 6 or 8 carbon atoms, more preferably divalent aliphatic hydrocarbon groups having 2, 4 or 6 carbon atoms, still more preferably divalent aliphatic hydrocarbon groups having 2 or 4 carbon atoms, and particularly preferably divalent aliphatic hydrocarbon groups having 2 carbon atoms, in that they have an excellent thickening effect. The divalent aliphatic hydrocarbon group is preferably a linear alkylene group.

[0161] R 4 represents a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms. Among them, a linear or branched alkylene group is preferable, and a linear alkylene group is particularly preferable in terms of excellent thickening effect. Also, R 4 The number of carbon atoms of the divalent aliphatic hydrocarbon group in is 1 to 8, and 1 to 7 is preferable, 3 to 7 is more preferable, 3 to 6 is still more preferable, and 3 to 5 is particularly preferable in terms of excellent thickening effect. 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.

[0162] R 5 and R 6 Examples of the monovalent aliphatic hydrocarbon group having 1 to 3 carbon atoms in include linear or branched alkyl groups having 1 to 3 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group; linear or branched alkenyl groups having 2 to 3 carbon atoms such as vinyl group, 1-methylvinyl group, 2-propenyl group; linear or branched alkynyl groups having 2 to 3 carbon atoms such as ethynyl group, propynyl group, etc.

[0163] R 5 and R 6 Examples of the hydroxyalkyl ether group in include mono- or di(hydroxy)C 1-3 alkyl ether groups such as 2-hydroxyethoxy group, 2-hydroxypropoxy group, 2,3-dihydroxypropoxy group.

[0164] 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.

[0165] As the compound represented by the formula (II), compounds represented by the following formulas (II-1) to (II-9) are preferable.

[0166]

Chemical formula

[0167] Examples of the aggregation dispersant include ANTI-TERRA-203, 204, 206, 250 (all are trade names, manufactured by BYK): ANTI-TERRA-U (trade name, manufactured by BYK): DISPER BYK-102, 180, 191 (all are trade names, manufactured by BYK): BYK-P105 (trade name, manufactured by BYK): TEGO Disper630, 700 (all are trade names, manufactured by Evonik Degussa Japan): Turen VA-705B (trade name, manufactured by Kyoeisha Chemical Co., Ltd.): FLOWNON RCM-300TL (trade name, manufactured by Kyoeisha Chemical Co., Ltd., amide wax), and the like.

[0168] When the composition contains an aggregation dispersant, the content of the aggregation dispersant is preferably 0.1 to 20% by mass, and particularly preferably 0.5 to 10% by mass, based on the total mass of the composition.

[0169] <Alkali-soluble resin> The resin in the present invention may contain an alkali-soluble resin. In this specification, the alkali-soluble resin means a resin containing a group that promotes alkali solubility (an alkali-soluble group, for example, an acid group such as a carboxylic acid group), and means a resin different from the resin A already described.

[0170] Examples of the alkali-soluble resin include resins containing at least one alkali-soluble group in the molecule, such as polyhydroxystyrene resin, polysiloxane resin, (meth)acrylic resin, (meth)acrylamide resin, (meth)acrylic / (meth)acrylamide copolymer, epoxy resin, and polyimide resin.

[0171] Specific examples of the alkali-soluble resin include copolymers of unsaturated carboxylic acids and ethylenically unsaturated compounds. The unsaturated carboxylic acid is not particularly limited, and 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 polyvalent carboxylic acid monoesters such as phthalic acid mono(2-(meth)acryloyloxyethyl); and the like.

[0172] Examples of the copolymerizable ethylenically unsaturated compound include methyl (meth)acrylate and the like. In addition, the compounds described in paragraph 0027 of JP-A-2010-97210 and paragraphs 0036 to 0037 of JP-A-2015-68893 can also be used, and the above contents are incorporated herein.

[0173] In addition, a copolymerizable ethylenically unsaturated compound containing an ethylenically unsaturated group in the side chain may be used in combination. That is, the alkali-soluble resin may contain a repeating unit containing an ethylenically unsaturated group in the side chain. The ethylenically unsaturated group contained in the side chain is preferably a (meth)acrylic acid group. The repeating unit containing an ethylenically unsaturated group in the side chain can be obtained, for example, by subjecting the carboxylic acid group of a (meth)acrylic-based 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.

[0174] As the alkali-soluble resin, an alkali-soluble resin containing a curable group is also preferable. Examples of the curable group include ethylenically unsaturated groups (for example, (meth)acryloyl group, vinyl group, styryl group, etc.) and cyclic ether groups (for example, epoxy group, oxetanyl group, etc.), but are not limited thereto. Among them, from the viewpoint of being able to control polymerization by a radical reaction, the curable group is preferably an ethylenically unsaturated group, and more preferably a (meth)acryloyl group. As the alkali-soluble resin containing a curable group, an alkali-soluble resin having a curable group in the side chain or the like is preferable. Examples of the alkali-soluble resin containing a curable group include Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing polyurethane acrylic oligomer, manufactured by Diamond Shamrock Co., Ltd.), Biscoat R-264, KS Resist 106 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series (for example, ACA230AA), Placcel CF200 series (all manufactured by Daicel Corporation), Ebecryl 3800 (manufactured by Daicel Ornex Co., Ltd.), and Acry Cure RD-F8 (manufactured by Nippon Shokubai Co., Ltd.).

[0175] Examples of the alkali-soluble resin include radical polymers containing a carboxylic acid group in the side chain described in JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-54-92723, JP-A-59-53836, and JP-A-59-71048; acetal-modified polyvinyl alcohol-based binder resins containing an alkali-soluble group described in EP 993966, EP 1204000, and JP-A-2001-318463; polyvinylpyrrolidone; polyethylene oxide; alcohol-soluble nylon, and polyethers which are reaction products of 2,2-bis-(4-hydroxyphenyl)-propane and epichlorohydrin; and polyimide resins described in WO 2008 / 123097 pamphlet; etc. can be used.

[0176] As the alkali-soluble resin, for example, the compounds described in paragraphs 0225 to 0245 of JP-A-2016-75845 can also be used, and the above content is incorporated herein.

[0177] As the alkali-soluble resin, a polyimide precursor can also be used. The polyimide precursor means a resin obtained by addition polymerization reaction of a compound containing an acid anhydride group and a diamine compound at 40 to 100°C. Specific examples of the polyimide precursor include, for example, the compounds described in paragraphs 0011 to 0031 of JP-A-2008-106250, the compounds described in paragraphs 0022 to 0039 of JP-A-2016-122101, the compounds described in paragraphs 0061 to 0092 of JP-A-2016-68401, the resin described in paragraph 0050 of JP-A-2014-137523, the resin described in paragraph 0058 of JP-A-2015-187676, and the resin described in paragraphs 0012 to 0013 of JP-A-2014-106326, etc. The above content is incorporated herein.

[0178] As the alkali-soluble resin, [benzyl (meth) acrylate / (meth) acrylic acid / other addition-polymerizable vinyl monomers as required] copolymer and [allyl (meth) acrylate / (meth) acrylic acid / other addition-polymerizable vinyl monomers as required] copolymer are excellent in the balance of film strength, sensitivity, and developability, and are suitable. The above other addition-polymerizable vinyl monomers may be used alone or in combination of two or more. From the viewpoint that the cured film has more excellent moisture resistance, the copolymer preferably has a curable group, and more preferably contains an ethylenically unsaturated group such as a (meth) acryloyl group. For example, a monomer having a curable group may be used as the above other addition-polymerizable vinyl monomer to introduce a curable group into the copolymer. Further, 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 in the copolymer and / or the units derived from the above other addition-polymerizable vinyl monomers. Examples of the above other addition-polymerizable vinyl monomers include methyl (meth) acrylate, styrene monomers (such as hydroxystyrene), and ether dimers. Examples of the above ether dimer include compounds represented by the following general formula (ED1) and compounds represented by the following general formula (ED2).

[0179]

Chemical formula

[0180] 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.

[0181]

Chemical formula

[0182] In general formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. As a specific example of general formula (ED2), the description in JP-A-2010-168539 can be referred to.

[0183] As a specific example of the ether dimer, for example, paragraph 0317 of JP-A-2013-29760 can be referred to, and this content is incorporated herein. The ether dimer may be only one kind or two or more kinds.

[0184] The acid value of the alkali-soluble resin is not particularly limited, but generally, 30 to 500 mgKOH / g is preferable, and 50 to 200 mgKOH / g or more is more preferable.

[0185] When the composition contains an alkali-soluble resin, the content of the alkali-soluble resin is preferably 0.1 to 40% by mass, more preferably 0.5 to 30% by mass, and particularly preferably 1 to 20% by mass with respect to the total mass of the composition.

[0186] 〔Solvent〕 The composition contains a solvent. Examples of the solvent include water and organic solvents, and organic solvents are preferable. From the viewpoint of coatability, the boiling point of the solvent is preferably 100 to 400°C, preferably 150 to 300°C, and particularly preferably 170 to 250°C. In this specification, the boiling point means the standard boiling point unless otherwise specified.

[0187] Examples of the organic solvent include, but are not limited to, acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetylacetone, cyclohexanone, cyclopentanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 1,4-butanediol diacetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N,N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, butyl acetate, methyl lactate, N-methyl-2-pyrrolidone, and ethyl lactate.

[0188] From the viewpoint of more excellent effects of the present invention, the content of the solvent is preferably 1 to 60% by mass, more preferably 2 to 50% by mass, and particularly preferably 3 to 40% by mass based on the total mass of the composition.

[0189] 〔Polymerization initiator〕 The composition may contain a polymerization initiator. The polymerization initiator is not particularly limited, and a known polymerization initiator can be used. Examples of the polymerization initiator include, for example, a photopolymerization initiator and a thermal polymerization initiator, and a photopolymerization initiator is preferred. In addition, as the polymerization initiator, a so-called radical polymerization initiator is preferred. The content of the polymerization initiator in the composition is not particularly limited, but is preferably 0.5 to 15% by mass, more preferably 1.0 to 10% by mass, and still more preferably 1.5 to 8.0% by mass based on the total solid content of the composition.

[0190] <Thermal polymerization initiator> Examples of the thermal polymerization initiator include azo compounds such as 2,2'-azobisisobutyronitrile (AIBN), 3-carboxypropionitrile, azobismalononitrile, 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, for example, the polymerization initiators described on pages 65 to 148 of "UV Curing System" written by Kiyoshi Kato (published by General Technology Center Co., Ltd.: 1989).

[0191] <Photoinitiator> The photoinitiator is not particularly limited as long as it can initiate the polymerization of the polymerizable compound, and a known photoinitiator can be used. As the photoinitiator, for example, a photoinitiator having photosensitivity from the ultraviolet region to the visible light region is preferable. Further, it may be an activator that causes some action with the photoexcited sensitizer to generate active radicals, or an initiator that initiates cationic polymerization according to the type of the polymerizable compound. Further, the photoinitiator preferably contains at least one compound having a molar extinction coefficient of at least 50 in the range of 300 to 800 nm (more preferably 330 to 500 nm).

[0192] Examples of the photoinitiator include halogenated hydrocarbon derivatives (for example, compounds containing a triazine skeleton, compounds containing an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, oxime compounds such as hexaarylbiimidazole and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, aminoacetophenone compounds, and hydroxyacetophenone. Specific examples of the photoinitiator can refer to paragraphs 0265 to 0268 of JP-A No. 2013-29760, and this content is incorporated herein.

[0193] As the photoinitiator, more specifically, for example, the aminoacetophenone-based initiator described in JP-A-10-291969 and the acylphosphine-based initiator described in Japanese Patent No. 4225898 can also be used. As the hydroxyacetophenone compound, for example, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names, all manufactured by BASF) can be used. As the aminoacetophenone compound, for example, commercially available products such as IRGACURE-907, IRGACURE-369, and IRGACURE-379EG (trade names, all manufactured by BASF) can be used. As the aminoacetophenone compound, the compounds described in JP-A-2009-191179 whose absorption wavelengths are matched to long-wavelength light sources such as a wavelength of 365 nm or a wavelength of 405 nm can also be used. As the acylphosphine compound, commercially available products such as IRGACURE-819 and IRGACURE-TPO (trade names, all manufactured by BASF) can be used.

[0194] As the photoinitiator, an oxime ester-based polymerization initiator (oxime compound) is more preferable. In particular, the oxime compound is preferable because it has high sensitivity and high polymerization efficiency, and it is easy to design a high content of the colorant in the composition. As specific examples of the oxime compound, the compounds described in JP-A-2001-233842, the compounds described in JP-A-2000-80068, or the compounds described in JP-A-2006-342166 can be used. 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. In addition, 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, Japanese Patent Application Laid-Open No. 2000-66385, and compounds described in Japanese Patent Application Laid-Open No. 2004-534797, etc. may also be mentioned. As commercial products, IRGACURE - OX01 (manufactured by BASF), IRGACURE - OX02 (manufactured by BASF), IRGACURE - OX03 (manufactured by BASF), or IRGACURE - OX04 (manufactured by BASF) are also preferable. In addition, TR - PBG - 304 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), Adeka Arcles NCI - 831, Adeka Arcles NCI - 930 (manufactured by ADEKA), or N - 1919 (a photoinitiator containing a carbazole - oxime ester skeleton, manufactured by ADEKA) can also be used.

[0195] In addition, as oxime compounds other than those described above, compounds described in Japanese Patent Application Laid-Open No. 2009-519904 in which an oxime is linked to the N - position of carbazole; compounds described in U.S. Patent No. 7626957 in which a hetero - substituent is introduced into the benzophenone moiety; compounds described in Japanese Patent Application Laid-Open No. 2010-15025 and U.S. Patent Publication No. 2009-292039 in which a nitro group is introduced into the dye moiety; keto - oxime compounds described in International Publication Pamphlet No. 2009-131189; and compounds described in U.S. Patent No. 7556910 in which a triazine skeleton and an oxime skeleton are contained in the same molecule; compounds described in Japanese Patent Application Laid-Open No. 2009-221114 having a maximum absorption at 405 nm and good sensitivity to a g - line light source; etc. may be used. For example, paragraphs 0274 to 0275 of Japanese Patent Application Laid-Open No. 2013-29760 can be referred to, and this content is incorporated herein. Specifically, as the oxime compound, a compound represented by the following formula (OX - 1) is preferable. Note that the N - O bond of the oxime compound may be an (E) - form oxime compound, a (Z) - form oxime compound, or a mixture of the (E) - form and the (Z) - form.

[0196] [Chem.]

[0197] 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), as the monovalent substituent represented by R, a monovalent non-metallic atomic group is preferred. Examples of the monovalent non-metallic 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, etc. Also, these groups may have one or more substituents. Further, the aforementioned substituents may be further substituted with other substituents. Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group, etc. In formula (OX-1), as the monovalent substituent represented by B, an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group is preferred, and an aryl group or a heterocyclic group is more preferred. These groups may have one or more substituents. Examples of the substituent include the aforementioned substituents. In formula (OX-1), as the divalent organic group represented by A, an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, or an alkynylene group is preferred. These groups may have one or more substituents. Examples of the substituent include the aforementioned substituents.

[0198] 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-2010-262,028; compounds 24, 36 to 40 described in JP-T-2014-500,852; and compound (C-3) described in JP-A-2013-164,471; etc. This content is incorporated herein.

[0199] As a photoinitiator, compounds represented by the following general formulas (1) to (4) can also be used.

[0200]

Chemical formula

[0201]

Chemical formula

[0202] In formula (1), R 1 and R 2 each independently represent 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. When R 1 and R 2 are phenyl groups, the phenyl groups may be bonded to each other to form a fluorene group. R 3 and R 4 each independently represent 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. X represents a direct bond or a carbonyl group.

[0203] In formula (2), R 1 , R 2 , R 3 , and R 4 are synonymous with R 1 , R 2 , R 3 , and R 4 in formula (1). R 5 is -R 6 , -OR 6 , -SR 6 , -COR 6 , -CONR 6 R 6 , -NR 6 COR 6 , -OCOR 6 , -COOR 6 , -SCOR 6 , -OCSR 6, -COSR 6 , -CSOR 6 , -CN, a halogen atom, or a hydroxyl group, and 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.

[0204] 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 represent 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.

[0205] In formula (4), R 1 , R 3 , and R 4 are synonymous with R 1 , R 3 , and R 4 in formula (3), and R 5 is -R 6 , -OR 6 , -SR 6 , -COR 6 , -CONR 6 R 6 , -NR 6 COR 6 , -OCOR 6 , -COOR 6 , -SCOR 6 , -OCSR 6 , -COSR 6 , -CSOR 6 , -CN, a halogen atom, or a hydroxyl group, and 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.

[0206] In the above formulas (1) and (2), R 1 and R 2 are preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclohexyl group, or a phenyl group. R 3 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group, or a xylyl group. R 4 is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group. R 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. Also, in the above formulas (3) and (4), R 1 are preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclohexyl group, or a phenyl group. R 3 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group, or a xylyl group. R 4 is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group. R 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, for example, the compounds described in paragraphs 0076 to 0079 of JP-A-2014-137466. This content is incorporated herein.

[0207] Specific examples of the oxime compound 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 preferable. Also, as the oxime compound, the compounds described in Table 1 of WO 2015 / 036910 pamphlet can also be used, and the above content is incorporated herein.

[0208]

Chemical formula

[0209]

Chemical formula

[0210] The oxime compound preferably has a maximum absorption wavelength in the wavelength range of 350 to 500 nm, more preferably has a maximum absorption wavelength in the wavelength range of 360 to 480 nm, and even more preferably has high absorbance at the wavelengths of 365 nm and 405 nm. From the viewpoint of sensitivity, the molar extinction coefficient of the oxime compound at 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and even more preferably 5,000 to 200,000. The molar extinction coefficient of the compound can be measured by a known method. For example, it is preferably measured at a concentration of 0.01 g / L using ethyl acetate with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian). Two or more kinds of photoinitiators may be used in combination as necessary.

[0211] In addition, as the photoinitiator, the compounds described in paragraph 0052 of JP-A No. 2008-260927, paragraphs 0033 to 0037 of JP-A No. 2010-97210, and paragraph 0044 of JP-A No. 2015-68893 can also be used, and the above contents are incorporated herein.

[0212] 〔Polymerizable compound〕 The composition of the present invention may contain a polymerizable compound. In the present specification, the polymerizable compound means a compound that polymerizes under the action of the above-described photoinitiator, and means a component different from the resin in the composition of the present invention described above.

[0213] The content of the polymerizable compound in the composition is not particularly limited, but is preferably 1 to 25% by mass, more preferably 1 to 20% by mass, and even more preferably 3 to 15% by mass based on the total solid content of the composition. The molecular weight (or weight average molecular weight) of the polymerizable compound is not particularly limited, but is preferably 2000 or less.

[0214] The polymerizable compound is preferably a compound containing a group having an ethylenically unsaturated bond (hereinafter, also simply referred to as an “ethylenically unsaturated group”). That is, the composition of the present invention preferably contains a low molecular weight compound containing an ethylenically unsaturated group as a polymerizable compound. The polymerizable compound is preferably a compound containing one or more ethylenically unsaturated bonds, more preferably a compound containing two or more ethylenically unsaturated bonds, still more preferably a compound containing three or more ethylenically unsaturated bonds, and particularly preferably a compound containing five or more ethylenically unsaturated bonds. 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.

[0215] As the polymerizable compound, for example, the compounds described in paragraph 0050 of JP-A-2008-260927 and paragraph 0040 of JP-A-2015-68893 can be used, and the above contents are incorporated herein.

[0216] The polymerizable compound may be in any chemical form such as, for example, a monomer, a prepolymer, an oligomer, a mixture thereof, and a multimer thereof. The polymerizable compound is preferably a (meth)acrylate compound having 3 to 15 functional groups, and more preferably a (meth)acrylate compound having 3 to 6 functional groups.

[0217] The polymerizable compound is also preferably a compound containing one or more ethylenically unsaturated groups and having a boiling point of 100° C. or higher under normal pressure. For example, the compounds described in paragraph 0227 of JP-A-2013-29760 and paragraphs 0254 to 0257 of JP-A-2008-292970 can be referred to, and this content is incorporated herein.

[0218] The polymerizable compounds include dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.), and structures in which these (meth)acryloyl groups are via ethylene glycol residues or propylene glycol residues (for example, SR454 and SR499 commercially available from Sartomer) are preferred. These oligomer types can also be used. Also, 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 are trade names, manufactured by Nippon Kayaku Co., Ltd.) etc. may be used. The following shows preferred embodiments of the polymerizable compound.

[0219] The polymerizable compound may have acid groups such as carboxylic acid groups, sulfonic acid groups, and phosphoric acid groups. As the polymerizable compound containing an acid group, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferred, and a polymerizable compound having an acid group by reacting an unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride is more preferred. In this ester, a compound in which the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol is even more preferred. Commercially available products include, for example, Aronix TO-2349, M-305, M-510, and M-520 etc. manufactured by Toagosei Co., Ltd.

[0220] 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 characteristics are 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 curability is excellent.

[0221] The polymerizable compound is also a preferred embodiment of a compound containing a caprolactone structure. The compound containing a caprolactone structure is not particularly limited as long as it contains a caprolactone structure in the molecule. For example, polyhydric alcohols such as trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, or trimethylolmelamine, and (meth)acrylic acid and ε-caprolactone are esterified to obtain ε-caprolactone-modified polyfunctional (meth)acrylates. Among them, the compound containing a caprolactone structure represented by the following formula (Z-1) is preferred.

[0222]

Chemical formula

[0223] In formula (Z-1), all six Rs are groups represented by the following formula (Z-2), or 1 to 5 of the six Rs are groups represented by the following formula (Z-2), and the remainder is a group represented by the following formula (Z-3).

[0224]

Chemical formula

[0225] In formula (Z-2), R 1 represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and "*" represents a bond.

[0226]

Chemical formula

[0227] In formula (Z-3), R 1 represents a hydrogen atom or a methyl group, and "*" represents a bond.

[0228] The polymerizable compound containing a caprolactone structure is commercially available, for example, from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series. DPCA-20 (in the above formulas (Z-1) to (Z-3), m = 1, the number of groups represented by formula (Z-2) = 2, R 1 being a compound in which all are hydrogen atoms), DPCA-30 (same formula, m = 1, the number of groups represented by formula (Z-2) = 3, R 1 being a compound in which all are hydrogen atoms), DPCA-60 (same formula, m = 1, the number of groups represented by formula (Z-2) = 6, R 1 being a compound in which all are hydrogen atoms), and DPCA-120 (in the same formula, m = 2, the number of groups represented by formula (Z-2) = 6, R 1 being a compound in which all are hydrogen atoms), etc. can be mentioned. Further, as commercially available products of the polymerizable compound containing a caprolactone structure, M-350 (trade name) (trimethylolpropane triacrylate) manufactured by Toagosei Co., Ltd. can also be mentioned.

[0229] As the polymerizable compound, a compound represented by the following formula (Z-4) or (Z-5) can also be used.

[0230]

Chemical formula

[0231] In formulas (Z-4) and (Z-5), E represents -((CH2) y CH2O)- or ((CH2) y CH(CH3)O)-, y represents an integer from 0 to 10, and X represents a (meth)acryloyl group, a hydrogen atom, or a carboxylic acid group. In formula (Z-4), the total number of (meth)acryloyl groups is 3 or 4, m represents an integer from 0 to 10, and the total of each m is an integer from 0 to 40. In formula (Z-5), the total number of (meth)acryloyl groups is 5 or 6, n represents an integer from 0 to 10, and the sum of each n is an integer from 0 to 60.

[0232] In formula (Z-4), m is preferably an integer from 0 to 6, more preferably an integer from 0 to 4. Also, the sum of each m is preferably an integer from 2 to 40, more preferably an integer from 2 to 16, and even more preferably an integer from 4 to 8. In formula (Z-5), n is preferably an integer from 0 to 6, more preferably an integer from 0 to 4. Also, the sum of each n is preferably an integer from 3 to 60, more preferably an integer from 3 to 24, and even more preferably an integer from 6 to 12. Also, in formula (Z-4) or formula (Z-5), -((CH2) y CH2O)- or ((CH2) y CH(CH3)O)- preferably has a form in which the terminal on the oxygen atom side is bonded to X.

[0233] 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), an embodiment in which all six Xs are acryloyl groups, or a mixture of a compound in which all six Xs in formula (Z-5) are acryloyl groups and a compound in which at least one of the six Xs is a hydrogen atom is preferred. With such a configuration, the developability can be further improved.

[0234] Also, the total content of the compound represented by formula (Z-4) or formula (Z-5) in the polymerizable compound is preferably 20% by mass or more, 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.

[0235] Also, the polymerizable compound may contain a cald skeleton. As the polymerizable compound containing a cald skeleton, a polymerizable compound containing a 9,9-bisarylfluorene skeleton is preferred. Examples of the polymerizable compound containing a cardo skeleton include, but are not limited to, Oncoat EX series (manufactured by Nagase Sangyo Co., Ltd.) and Ogsoal (manufactured by Osaka Gas Chemical Co., Ltd.). The polymerizable compound is preferably a compound containing an isocyanuric acid skeleton as a central nucleus. Examples of such a polymerizable compound include, for example, NK Ester A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.). The content of the ethylenically unsaturated group in the polymerizable compound (which means 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 generally it is 20.0 mmol / g or less.

[0236] It is also preferable to use an oxacyclo compound as the polymerizable compound. As the oxacyclo compound, a compound having an epoxy group or an oxetanyl group is preferable, and a compound having an epoxy group (epoxy compound) is particularly preferable. Specific examples of such a polymerizable compound include monofunctional or polyfunctional glycidyl ether compounds. Moreover, as commercially available products, polyfunctional aliphatic glycidyl ether compounds such as Denacol EX-212L, EX-214L, EX-216L, EX-321L, EX-850L (manufactured by Nagase ChemteX Corporation) can be mentioned. These are low-chlorine products, but EX-212, EX-214, EX-216, EX-321, EX-614, EX-850, etc., which are not low-chlorine products, can also be used in the same manner. Moreover, as a commercially available product, Celloxide 2021P (manufactured by Daicel Corporation, polyfunctional epoxy monomer) can also be used.

[0237] 〔Polymerization inhibitor〕 The composition may contain a polymerization inhibitor. The polymerization inhibitor is not particularly limited, and known polymerization inhibitors can be used. Examples of the polymerization inhibitor include phenolic polymerization inhibitors (e.g., p-methoxyphenol, 2,5-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-methylphenol, 4,4'-thiobis(3-methyl-6-t-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), 4-methoxynaphthol, etc.); hydroquinone-based polymerization inhibitors (e.g., hydroquinone, 2,6-di-tert-butylhydroquinone, 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 them, phenolic polymerization inhibitors or free radical-based polymerization inhibitors are preferred.

[0238] 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 0.0001 to 0.5% by mass, more preferably 0.0001 to 0.2% by mass, and still more preferably 0.0001 to 0.05% by mass based on the total solid content of the composition. Also, the ratio of the content of the polymerization inhibitor to the content of the polymerizable compound in the composition (content of polymerization inhibitor / content of polymerizable compound (mass ratio)) is preferably more than 0.0005, more preferably 0.0006 to 0.02, and still more preferably 0.0006 to 0.005.

[0239] 〔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 0.001 to 2.0% by mass, more preferably 0.005 to 0.5% by mass, and still more preferably 0.01 to 0.1% by mass based on the total solid content of the composition.

[0240] Examples of the surfactant include fluorosurfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants.

[0241] For example, if the composition contains a fluorosurfactant, the liquid properties (especially fluidity) of the composition are further improved. That is, when forming a film using a composition containing a fluorosurfactant, the interfacial tension between the surface to be coated and the coating liquid is reduced, the wettability to the surface to be coated is improved, and the coatability to the surface to be coated is enhanced. Therefore, even when a thin film of about several μm is formed with a small amount of liquid, it is effective in that a uniform-thickness film with little thickness unevenness can be more suitably formed.

[0242] The fluorine content in the fluorosurfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and still more preferably 7 to 25% by mass. The fluorosurfactant having a fluorine content within this range is effective in terms of the uniformity of the thickness of the coating film and / or liquid-saving property, and also has good solubility in the composition.

[0243] Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, and F780 (manufactured by DIC Corporation); Fluorad FC430, FC431, and FC171 (manufactured by Sumitomo 3M Limited); Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, and KH-40 (manufactured by AGC Inc.); and PF636, PF656, PF6320, PF6520, and PF7002 (manufactured by OMNOVA Solutions Inc.), etc. Block polymers can also be used as fluorosurfactants. Specific examples include, for example, the compounds described in JP-A No. 2011-89090.

[0244] [Other Optional Components] The composition may further contain other optional components in addition to the components described above. For example, sensitizers, co-sensitizers, crosslinking agents (hardening agents), hardening accelerators, heat hardening accelerators, plasticizers, diluents, fat-sensitizing agents, rubber components, etc. can be mentioned. Further, adhesion promoters to the substrate surface and other auxiliaries (for example, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension regulators, and chain transfer agents, etc.) and other known additives may be added as necessary.

[0245] [Physical Properties of the Composition] When the shear rate is 0.1 (1 / s), the viscosity of the composition at 23°C is preferably 1 to 10000 Pa·s, more preferably 10 to 5000 Pa·s, and particularly preferably 50 to 1000 Pa·s from the viewpoint of better 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 particularly preferably 10 Pa·s or less from the viewpoint of better sedimentation stability of the magnetic particles. The lower limit when the shear rate is 1000 (1 / s) is preferably 0.001 Pa·s or more. Here, the viscosity of the composition at 23°C is obtained by measuring at 23°C while increasing the speed from 0.1 / s to 1000 / s using an MCR-102 (manufactured by Anton Paar).

[0246] [Method for Producing the Composition] The composition can be prepared by mixing the above components by a known mixing method (for example, a mixing method using a stirrer, a homogenizer, a high-pressure emulsifying device, a wet grinder, or a wet disperser, etc.). When preparing the composition of the present invention, the components may be blended all at once, or each component may be dissolved or dispersed in a solvent and then sequentially blended. Further, the charging order and working conditions during blending are not particularly limited.

[0247] [Magnetic particle-containing film] The magnetic particle-containing film of the present invention is formed using the magnetic particle-containing composition of the present invention described above. The film thickness of the magnetic particle-containing film is preferably 1 to 10,000 μm, more preferably 10 to 1,000 μm, and particularly preferably 15 to 800 μm from the viewpoint of excellent magnetic permeability. The magnetic particle-containing film is suitably used as electronic components such as antennas and inductors equipped in electronic communication devices and the like.

[0248] 〔Method for producing magnetic particle-containing film〕 The magnetic particle-containing film of the present invention is obtained, for example, by curing the above composition. The method for producing the magnetic particle-containing film is not particularly limited, but preferably includes the following steps. ·Composition layer formation step ·Curing step

[0249] <Composition layer formation step> In the composition layer formation step, a magnetic particle-containing composition is applied onto a substrate (support) or the like to form a layer of the magnetic particle-containing composition (composition layer). As the substrate, for example, a wiring substrate having an antenna portion or an inductor portion can be used.

[0250] As the method for applying the magnetic particle-containing composition onto the substrate, various coating methods such as a slit coating method, an inkjet method, a spin coating method, a casting coating method, a roll coating method, and a screen printing method can be applied. The film thickness of the composition layer is preferably 1 to 10,000 μm, more preferably 10 to 1,000 μm, and particularly preferably 15 to 800 μm. Drying (pre-baking) of the composition layer applied onto the substrate can be performed, for example, on a hot plate, in an oven, etc. at a temperature of 50 to 140 °C for 10 to 1800 seconds.

[0251] <Curing step> The curing step is not particularly limited as long as the composition layer can be cured, and examples include a heat treatment for heating the composition layer and an exposure treatment for irradiating the composition layer with actinic rays or radiation.

[0252] When performing heat treatment, the heat treatment can be carried out continuously or batchwise using heating means such as a hot plate, a convection oven (hot air circulation dryer), or a high-frequency heater. The heating temperature in the heat treatment is preferably 120 to 260 °C, and particularly preferably 150 to 240 °C. Note that the pre-baking in the composition layer forming step may also serve as the heat treatment in the curing step.

[0253] When performing exposure treatment, the irradiation method of actinic rays or radiation is not particularly limited, but it is preferably performed through a photomask having a pattern-shaped opening. Exposure is preferably performed by irradiation with radiation. As the radiation that can be used for exposure, ultraviolet rays such as g-rays, h-rays, and i-rays are preferable, and a high-pressure mercury lamp is preferred as the light source. The irradiation intensity is preferably 5 to 1500 mJ / cm 2 is preferable, and 10 to 1000 mJ / cm 2 is more preferable. Note that when the magnetic particle-containing composition contains a thermal polymerization initiator, the composition layer may be heated in the above exposure treatment. The heating temperature is not particularly limited, but 80 to 250 °C is preferable. Also, the heating time is not particularly limited, but 30 to 300 seconds is preferable. Note that when heating the composition layer in the exposure treatment, it may also serve as the post-heating step described later. In other words, when heating the composition layer in the exposure treatment, the method for producing the magnetic particle-containing film may not include the post-heating step.

[0254] <Development step> When performing exposure treatment in the curing step, the development step may further be included. The development step is a step of developing the composition layer after exposure to form a magnetic particle-containing film. By this step, the composition layer in the unirradiated portion of the light in the exposure treatment is eluted, and only the photocured portion remains, and a patterned magnetic particle-containing film is obtained. The type of developer used in the development process is not particularly limited, but an alkaline developer that does not damage the circuit or the like is desirable. The development temperature is, for example, 20 to 30°C. The development time is, for example, 20 to 90 seconds. In recent years, in order to better remove residues, it may be carried out for 120 to 180 seconds. Furthermore, in order to further improve the residue removability, the developer may be shaken off every 60 seconds, and the process of supplying a new developer may be repeated several times.

[0255] As the alkaline developer, an alkaline aqueous solution prepared by dissolving an alkaline compound in water so that the concentration is 0.001 to 10% by mass (preferably 0.01 to 5% by mass) is preferable. Examples of the alkaline compound include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo[5.4.0]-7-undecene, etc. (Among these, organic alkalis are preferable.). When used as an alkaline developer, generally, a washing treatment with water is performed after development.

[0256] <Post-bake> When performing an exposure treatment in the curing process, it is preferable to perform a heat treatment (post-bake) after the curing process. Post-bake is a post-development heat treatment for complete curing. The heating temperature is preferably 240°C or lower, more preferably 220°C or lower. There is no particular lower limit, but considering efficient and effective treatment, 50°C or higher is preferable, and 100°C or higher is more preferable. Post-bake can be performed continuously or batchwise using heating means such as a hot plate, a convection oven (hot air circulation dryer), or a high-frequency heater.

[0257] The above post-baking is preferably carried out in an atmosphere of low oxygen concentration. The oxygen concentration is preferably 19% by volume or less, more preferably 15% by volume or less, still more preferably 10% by volume or less, particularly preferably 7% by volume or less, and most preferably 3% by volume or less. There is no particular lower limit, but 10 ppm by volume or more is practical.

[0258] Alternatively, instead of the above post-baking by heating, curing may be completed by UV (ultraviolet) irradiation. In this case, the magnetic particle-containing composition preferably further contains a UV curable agent. The UV curable agent is preferably a UV curable agent that can be cured at a wavelength shorter than 365 nm, which is the exposure wavelength of the polymerization initiator added for the normal i-line lithography process. Examples of the UV curable agent include Omnirad 2959 (trade name) (manufactured by IGM Resins B.V.). When performing UV irradiation, it is preferable that the composition layer is a material that cures at a wavelength of 340 nm or less. There is no particular lower limit for the wavelength, but 220 nm or more is common. Also, the exposure amount of UV irradiation is preferably 100 to 5000 mJ, more preferably 300 to 4000 mJ, and still more preferably 800 to 3500 mJ. This UV curing process is preferably carried out after the exposure process in order to perform low-temperature curing more effectively. It is preferable to use an ozone-free mercury lamp as the exposure light source.

[0259] [Electronic component] The electronic component of the present invention includes the above-described magnetic particle-containing film of the present invention. That is, the electronic component of the present invention may include the magnetic particle-containing film as a part of the component. Examples of the electronic component include an inductor and an antenna. As the electronic component, those having a known structure can be used.

Example

[0260] The present invention will be described in more detail based on the following examples. The materials, amounts used, ratios, processing details, processing procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention should not be construed in a limited manner by the examples shown below.

[0261] [Various Components Used in the Preparation of the Magnetic Particle-Containing Composition] In preparing the magnetic particle-containing composition, each component described in Table 1 was prepared. The outlines of each component described in Table 1 are shown below.

[0262] [Magnetic Particles] M-1: Fe-based amorphous particles (product name "AW2-08 PF-5F", manufactured by Epson Atmix Corporation, average primary particle diameter 3 μm) M-2: Fe-based amorphous particles (product name "AW2-08 PF-8F", manufactured by Epson Atmix Corporation, average primary particle diameter 5 μm) M-3: Fe-Si-Cr alloy particles (product name "MA-XCQ-4", manufactured by DOWA Electronics Co., Ltd., average primary particle diameter 3 μm) M-4: Fe-Si-Cr alloy particles (product name "MA-XCQ-5", manufactured by DOWA Electronics Co., Ltd., average primary particle diameter 5 μm) M-5: Fe-based amorphous particles (product name "KUAMET6B2-V1-38μm", manufactured by Epson Atmix Corporation, average primary particle diameter 15 μm) M-6: Fe-based amorphous particles (product name "KUAMET6B2-53μm", manufactured by Epson Atmix Corporation, average primary particle diameter 24 μm) M-7: Fe-based amorphous particles (product name "KUAMET6B2-150μm", manufactured by Epson Atmix Corporation, average primary particle diameter 50 μm) M-8: Co-based amorphous particles (product name "KUAMET-CT5-25μm", manufactured by Epson Atmix Corporation, average primary particle diameter 25 μm) M-9: Co-based amorphous particles (product name "KUAMET-CT5-5μm", manufactured by Epson Atmix Corporation, average primary particle diameter 5 μm) M-10: Supermalloy particles (product name "80% NI-4MO WA13", manufactured by Epson Atmix Corporation, average primary particle diameter 15 μm) M-11: Supermalloy particles (product name "80% NI-4MO PF-15F", manufactured by Epson Atmix Corporation, average primary particle diameter 8 μm) M-12: Supermalloy particles (product name "80% NI-4MO PF-5F", manufactured by Epson Atmix Corporation, average primary particle diameter 4 μm) M-13: Ni-Zn ferrite particles (product name "BSN-125", manufactured by Toda Kogyo Corporation, average primary particle diameter 5 μm) M-14: Mn-Zn ferrite particles (product name "BSF-547", manufactured by Toda Kogyo Corporation, average primary particle diameter 11 μm) M-15: Ni-Zn ferrite particles (product name "NB4", manufactured by Nippon Heavy Chemical Industry Co., Ltd., average primary particle diameter 3 μm) M-16: Magnetoplumbite-type hexagonal ferrite particles (SrFe (9.58) Al (2.42) O 19 manufactured in the same manner as the method described in Example 1 of International Publication No. 2019 / 131675, single-layer crystal phase, average primary particle diameter 0.1 μm) M-17: Magnetoplumbite-type hexagonal ferrite particles (SrFe (9.58) Al (2.42) O 19 manufactured in the same manner as the method described in Example 1 of International Publication No. 2019 / 131675, single-layer crystal phase, average primary particle diameter 5 μm) M-18: Magnetoplumbite-type hexagonal ferrite particles (SrFe (9.58) Al (2.42) O 19 manufactured in the same manner as the method described in Example 1 of International Publication No. 2019 / 131675, single-layer crystal phase, average primary particle diameter 15 μm)

[0263] Note that the average primary particle diameters of the magnetic particles are all measured values measured by the above-described method.

[0264] [Resin (Dispersant)] D-1: The following compound (weight average molecular weight 10,000, amine value 50 mg KOH / g, acid value 50 mg KOH / g, solubility in solvent S-1 300 g / L, solubility in solvent S-2 300 g / L) D-2: The following compound (weight average molecular weight 10,000, solubility in solvent S-1 300 g / L, solubility in solvent S-2 300 g / L, acid value 70 mg KOH / g) D-3: The following compound (weight average molecular weight 10,000, acid value 40 mg KOH / g, solubility in solvent S-1 400 g / L, solubility in solvent S-2 400 g / L) D-4: Product name "BYK-P105" (manufactured by BYK), polymer of low molecular weight unsaturated carboxylic acid, acid value 365 mg KOH / g, solubility in solvent S-1 500 g / L, solubility in solvent S-2 500 g / L D-5: Product name "ANTI-TERRA-204" (manufactured by BYK), solution of polycarboxylate of polyaminoamide, amine value 37 mg KOH / g, acid value 41 mg KOH / g, solubility in solvent S-1 300 g / L, solubility in solvent S-2 300 g / L D-6: Product name "TALEN VA-705B" (manufactured by Kyoeisha Chemical Co., Ltd.), higher fatty acid amide, solubility in solvent S-1 100 g / L, solubility in solvent S-2 100 g / L D-7: Product name "FLOWNON RCM-300TL" (manufactured by Kyoeisha Chemical Co., Ltd.), higher fatty acid amide, solubility in solvent S-1 100 g / L, solubility in solvent S-2 100 g / L D-8: The following compound

[0265]

Chemical formula

[0266]

Chemical formula

[0267]

Chemical formula

[0268]

Chem.

[0269] 〔Solvent〕 S-1: Propylene glycol monomethyl ether acetate (PGMEA), boiling point 146 °C S-2: 1,4-Butanediol diacetate (1,4-BDDA), boiling point 232 °C

[0270] 〔Other components〕 A-1: Curing accelerator (Triphenylphosphine, manufactured by Tokyo Chemical Industry Co., Ltd.) A-2: Photoinitiator (Product name "IRGACURE-OXE03", manufactured by BASF) A-3: Polymerizable compound (Product name "KAYARAD RP-1040", manufactured by Nippon Kayaku Co., Ltd., multifunctional acrylic monomer) A-4: Polymerizable compound (Product name "Celloxide 2021P", manufactured by Daicel Corporation, multifunctional epoxy monomer) A-5: Polymerizable compound (Product name "Denacol EX-614", manufactured by Nagase ChemteX Corporation, multifunctional epoxy monomer) A-6: Photoinitiator (Product name "ADEKA ARKULES NCI-831", manufactured by ADEKA) A-7: Polymerizable compound (Product name "A-TMMT", manufactured by Toagosei Co., Ltd., multifunctional acrylic monomer)

[0271] 〔Preparation of magnetic particle-containing compositions of Examples and Comparative Examples〕 For the components other than the solvents shown in Table 1, the components described in Table 1 were mixed so as to have the composition ratios (by mass) shown in Table 1, and then charged into a sealed container made of PTFE (polytetrafluoroethylene). Subsequently, after adding the solvent so as to have the composition ratios (by mass) shown in Table 1, the container was sealed, and using a RAM (low-frequency resonance acoustic mixer) manufactured by Resodyn, dispersion was carried out at 50 G for 2 hours to prepare the magnetic particle-containing compositions of each Example and Comparative Example.

[0272] <Physical properties of magnetic particle-containing compositions> Regarding the magnetic particle-containing composition, according to the above-described method, a particle size distribution curve representing a volume-based frequency distribution was measured, and Dmax (μm), Dmin (μm), and Dmax / Dmin of the magnetic particles contained in the magnetic particle-containing composition were determined respectively. The results are shown in Table 1.

[0273] The viscosity of the magnetic particle-containing composition at 23°C was measured according to the method described above. The viscosity was classified according to the following criteria based on the measured values. The results are shown in Table 1. (Rate of increase in speed condition: 0.1 (1 / s)) A: 50 Pa·s or more B: 1 Pa·s or more and less than 50 Pa·s C: Less than 1 Pa·s (Rate of increase in speed condition: 1000 (1 / s)) A: Less than 10 Pa·s B: 10 Pa·s or more and less than 50 Pa·s C: 50 Pa·s or more

[0274] [Manufacture of magnetic particle-containing film for magnetic permeability evaluation] Using the magnetic particle-containing composition obtained as described above, a magnetic particle-containing film for magnetic permeability evaluation described later was manufactured. Specifically, after dropping each magnetic particle-containing composition on a silicon wafer (film thickness: 100 μm) (hereinafter also referred to as "substrate A"), using a baker applicator, coating was performed so that the film thickness would be 100 μm after baking described later. Then, after performing drying baking for 10 minutes using a hot plate at 100°C, curing baking was performed for 15 minutes using a hot plate at 230°C to obtain a magnetic particle-containing film for magnetic permeability evaluation. However, when the magnetic particle-containing composition contains a photoinitiator, instead of curing baking, the coating film was entirely exposed with an exposure amount of 20 J / cm 2 using a UV (ultraviolet) Cure device (manufactured by USHIO INC.) to obtain a magnetic particle-containing film for magnetic permeability evaluation.

[0275] [Manufacture of magnetic particle-containing film for pattern shape evaluation] Among the magnetic particle-containing compositions obtained as described above, for the magnetic particle-containing composition containing a photopolymerization initiator, a magnetic particle-containing film for pattern shape evaluation described below was produced. Specifically, each magnetic particle-containing composition was dropped onto a silicon wafer (film thickness: 700 μm) with an undercoat layer (CT-4000L, thickness: 0.1 μm, manufactured by Fujifilm Electronic Materials Co., Ltd.) (hereinafter also referred to as "substrate B"). After that, using a baker applicator, coating was performed so that the film thickness would be 30 μm after baking described below. Then, drying bake was carried out for 10 minutes using a hot plate at 100 °C to obtain a dried film. Subsequently, through a mask of a line and space pattern (line width: 300 μm, space width: 300 μm), exposure treatment of the dried film was carried out with a proximity exposure machine under the condition of 100 mJ / cm 2 . After exposure, shower development treatment was carried out at 23 °C for 60 seconds using a simple developing device (manufactured by Mikasa Co., Ltd.). Note that, as the developer, an aqueous solution in which the content of tetramethylammonium hydroxide (TMAH) is 0.3 mass% was used. After development, rinsing treatment was carried out by spin shower using pure water. Then, after spin drying, heat treatment (post bake) was carried out for 5 minutes using a hot plate at 200 °C. In this way, a magnetic particle-containing film for pattern shape evaluation was obtained.

[0276] [Evaluation Test] [Sedimentation Stability (Stability over Time)] 3 mL of the magnetic particle-containing composition obtained as described above was put into a glass sample bottle (cylindrical shape with a diameter of 23 mm and a height of 35 mm), sealed, and then left standing at 25 °C for 30 days. After that, the magnetic particle-containing composition in the sample bottle was visually observed, and the distance d1 from the gas-liquid interface to the interface between the transparent region and the opaque region, and the distance d2 from the gas-liquid interface to the bottom surface of the sample bottle were measured. Using the distance d1 and the distance d2, sedimentation stability was evaluated according to the following criteria. If the following criteria were "2" or more, it was judged that the sedimentation stability was excellent. The results are shown in Table 1. 3: d1 / d2 = 0 2: 0.4 ≥ d1 / d2 > 0 1: d1 / d2 > 0.4

[0277] 〔Magnetic permeability〕 The magnetic particle-containing film for magnetic permeability evaluation obtained as described above was cut into a size of 10 mm × 28 mm. For the cut samples, the relative magnetic permeability μ' at 100 MHz was measured using a high-frequency magnetic permeability measuring device (manufactured by Keycom Co., Ltd., Model No. PER01), and evaluated based on the following evaluation criteria. If the following evaluation criteria were "3" or more, it was judged that the magnetic permeability was excellent. The results are shown in Table 1. 5: The relative magnetic permeability μ' is 20 or more 4: The relative magnetic permeability μ' is 15 or more and less than 20 3: The relative magnetic permeability μ' is 10 or more and less than 15 2: The relative magnetic permeability μ' is 5 or more and less than 10 1: The relative magnetic permeability μ' is 1 or more and less than 5

[0278] 〔Pattern shape〕 The magnetic particle-containing film for pattern shape evaluation obtained as described above was observed using an optical microscope (product name "BX53M", manufactured by Olympus Corporation), and the pattern shape was evaluated based on the following evaluation criteria. The results are shown in Table 1. 3: The line pattern is in close contact with the substrate, a space is also formed, and there is no residue with a size of 50 μm or more. 2: The line pattern is in close contact with the substrate, a space is also formed, but there is a residue with a size of 50 μm or more in the space part. 1: The line pattern is not in close contact with the substrate, or the space is filled (there is no space).

[0279]

Table 1

[0280]

Table 2

[0281]

Table 3

[0282]

Table 4

[0283]

Table 5

[0284]

Table 6

[0285]

Table 7

[0286] As shown in Table 1, the magnetic particle-containing composition containing magnetic particles having a plurality of peak tops in the particle size distribution curve representing the volume-based frequency distribution, a resin, and a solvent is excellent in sedimentation stability, and the magnetic particle-containing film formed using this composition has excellent magnetic permeability (Example).

[0287] From the comparison of Examples 1 to 12, it was shown that if Dmax / Dmin is more than 2 (Examples 1 to 9, 11, 12), the magnetic particle-containing film formed using this composition has more excellent magnetic permeability. From the comparison with Example 3 and Examples 21 to 24, it was shown that if a resin having an acid group, a basic group, or an amide group is used (Examples 21 to 24), the sedimentation stability of the magnetic particle-containing composition is more excellent. From the comparison of Examples 50 to 55, it was shown that if the content of the magnetic particles is 60% by mass or more based on the total mass of the magnetic particle-containing composition (Examples 50, 51, and 53), both the sedimentation stability of the magnetic particle-containing composition and the magnetic permeability of the magnetic particle-containing film can be achieved at a higher level.

[0288] On the other hand, when there is one peak top in the particle size distribution curve representing the volume-based frequency distribution of the magnetic particles contained in the magnetic particle-containing composition, it has been shown that at least one of the sedimentation stability of the magnetic particle-containing composition and the magnetic permeability of the magnetic particle-containing film formed using the same is inferior (Comparative Example).

Claims

1. A magnetic particle-containing composition comprising magnetic particles having a plurality of peak tops in a particle size distribution curve representing a frequency distribution based on volume, a resin, and a solvent, wherein the magnetic particles contain ferrite.

2. Among the plurality of peak tops in the particle size distribution curve representing the frequency distribution based on volume, when the particle size at the smallest peak top Pmin in terms of particle diameter is defined as Dmin and the particle size at the largest peak top Pmax in terms of particle diameter is defined as Dmax, the magnetic particle-containing composition according to Claim 1, wherein the ratio of Dmax to Dmin is more than 2.

3. Among the plurality of peak tops in the particle size distribution curve representing the frequency distribution based on volume, when the particle size at the smallest peak top Pmin in terms of particle diameter is defined as Dmin, wherein Dmin is the particle diameter D when the frequency in the particle size distribution curve representing the volume-based cumulative distribution is 20%. ２０ The magnetic particle-containing composition according to claim 1 or 2, which is as follows.

4. the magnetic particle-containing composition according to Claim 2 or 3, wherein Dmin is 1 to 10 μm.

5. the magnetic particle-containing composition according to any one of Claims 1 to 4, wherein the number of the plurality of peak tops in the particle size distribution curve representing the frequency distribution based on volume is two.

6. the magnetic particle-containing composition according to any one of Claims 1 to 5, wherein the content of the magnetic particles is 60% by mass or more based on the total mass of the magnetic particle-containing composition.

7. the magnetic particle-containing composition according to any one of Claims 1 to 6, wherein the resin has an acid group, a basic group, or an amide group.

8. the magnetic particle-containing composition according to any one of Claims 1 to 7, wherein the solubility of the resin in the solvent is 10 g / L or more.

9. the magnetic particle-containing composition according to any one of Claims 1 to 8, wherein the magnetic particles contain spinel ferrite.

10. the magnetic particle-containing composition according to any one of Claims 1 to 9, wherein the magnetic particles contain Ni.

11. the magnetic particle-containing composition according to any one of Claims 1 to 10, wherein the magnetic particles contain Ni-Zn-based ferrite.

12. the magnetic particle-containing composition according to any one of Claims 1 to 11, wherein the resin has an amide group.

13. the magnetic particle-containing composition according to any one of Claims 1 to 12, wherein the resin contains amide wax.

14. the magnetic particle-containing composition according to any one of Claims 1 to 13, wherein the resin contains a higher fatty acid amide.

15. the resin contains a resin A having a repeating unit containing a graft chain, The magnetic particle-containing composition according to any one of claims 1 to 14, wherein the graft chain contains at least one of a polyester structure and a polyether structure.

16. The resin contains a resin A having a repeating unit containing a graft chain, The magnetic particle-containing composition according to any one of claims 1 to 15, wherein the graft chain contains a polyester structure.

17. The magnetic particle-containing composition according to any one of claims 1 to 16, wherein the content of the solvent is 1 to 30% by mass based on the total mass of the magnetic particle-containing composition.

18. The magnetic particle-containing composition according to any one of claims 1 to 17, wherein the content of the solvent is 1 to 20% by mass based on the total mass of the magnetic particle-containing composition.

19. The magnetic particle-containing composition according to any one of claims 1 to 18, wherein the solvent contains a solvent having a boiling point of 150 to 300 °C.

20. When the shear rate at 23 °C of the magnetic particle-containing composition is 0.1 (1 / s), the viscosity is 1 to 10,000 Pa·s, The magnetic particle-containing composition according to any one of claims 1 to 19, wherein when the shear rate at 23 °C of the magnetic particle-containing composition is 1000 (1 / s), the viscosity is 0.001 Pa·s or more and 10 Pa·s or less.

21. [[ID=]14]A magnetic particle-containing film formed using the magnetic particle-containing composition according to any one of claims 1 to 20.

22. An electronic component including the magnetic particle-containing film according to claim 21.

23. The electronic component according to claim 22, which is used as an inductor.

24. The electronic component according to claim 22, which is used as an antenna.

Images