Composition, magnetic particle-containing film, and electronic component

Abstract

To provide a composition which enables the formation of a magnetic particles-containing membrane with excellent isotropy of magnetism, while also exhibiting excellent temporal stability, a magnetic particles-containing membrane regarding the composition, and an electronic component including a magnetic particles-containing membrane.SOLUTION: A composition contains magnetic particles and a rheology control agent, where the magnetic particles contains metal atoms, the metal atoms include one or more specific atoms selected from the group consisting of Ni atoms and Co atoms, the content of the specific atoms is 50 mass% or more relative to the total mass of the metal atoms, the content of the magnetic particles having an aspect ratio of less than 8 is 25 mass% or more relative to the total mass of the magnetic particles.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to compositions, magnetic particle-containing films, and electronic components. [Background technology]

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

[0003] For example, Patent Document 1 discloses "a soft magnetic resin composition characterized by containing flattened soft magnetic particles, a resin component, and a rheology control agent." [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2015-082554 [Overview of the project] [Problems that the invention aims to solve]

[0005] Incidentally, the composition is required to have good stability over time. Furthermore, in some cases, magnetic films require that their magnetism be isotropic. The present inventors investigated the composition (soft magnetic resin composition) described in Patent Document 1 and confirmed that using a large amount of flattened soft magnetic particles improved the composition's stability over time to a certain extent. However, they also confirmed that using a large amount of flattened soft magnetic particles made it difficult for the film formed from the composition to become isotropic.

[0006] Therefore, the object of the present invention is to provide a composition that can form a magnetic particle-containing film with excellent magnetic isotropy and has excellent temporal stability. Furthermore, the object of the present invention is to provide a magnetic particle-containing film related to the above composition, and an electronic component containing the magnetic particle-containing film. [Means for solving the problem]

[0007] As a result of diligent research to solve the above problems, the inventors of this invention have found that the above problems can be solved by the following configuration.

[0008] [1] A composition containing magnetic particles and a rheology control agent, The content of the above magnetic particles having an aspect ratio of less than 8 is 25% by mass or more relative to the total mass of the above magnetic particles. The above magnetic particles contain metal atoms, The above metal atom contains one or more specific atoms selected from the group consisting of Ni atoms and Co atoms. A composition in which the content of the above-mentioned specific atom is 50% by mass or more relative to the total mass of the above-mentioned metal atoms. [2] The composition according to [1], wherein the specified atom is the Ni atom. [3] The composition according to [1] or [2], wherein the content of the above-mentioned specific atoms is 70% by mass or more relative to the total mass of the above-mentioned metal atoms. [4] The composition according to any one of [1] to [3], wherein the particle size of the magnetic particles is 5 μm or larger. [5] The composition according to any one of [1] to [4], wherein the rheology control agent is an organic rheology control agent. [6] The composition according to any one of [1] to [5], wherein the rheology control agent is one or more selected from the group consisting of polycarboxylic acids, polyanhydrides, and amide waxes. [7] Furthermore, the composition according to any one of [1] to [6] further comprises an epoxy-curable compound as a polymerizable compound. [8] A magnetic particle-containing film formed using any of the compositions described in [1] to [7]. [9] An electronic component comprising the magnetic particle-containing film described in [8].

[10] An electronic component used as an inductor, as described in [9].

[11] An electronic component used as an antenna, as described in [9]. [Effects of the Invention]

[0009] According to the present invention, it is possible to form a magnetic particle-containing film with excellent magnetic isotropy and to provide a composition with excellent temporal stability. Furthermore, the present invention can also provide a magnetic particle-containing film related to the above composition, and an electronic component containing the magnetic particle-containing film. [Modes for carrying out the invention]

[0010] The present invention will be described in detail below. The following description of the constituent elements may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In this specification, regarding the notation of groups (atomic groups), unless contrary to the spirit of the present invention, notations that do not specify substituted or unsubstituted include both substituted and unsubstituted groups. For example, "alkyl group" includes not only unsubstituted alkyl groups but also substituted alkyl groups. Furthermore, in this specification, "organic group" means a group containing at least one carbon atom.

[0011] In this specification, "active light" or "radiation" means, for example, the emission line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV light), X-rays, and electron beams (EB). In this specification, "light" means active light or radiation. In this specification, "exposure" includes not only exposure using emission line spectra from mercury lamps, far ultraviolet light such as those from excimer lasers, extreme ultraviolet light, X-rays, and EUV light, but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified.

[0012] In this specification, "~" is used to mean that the numbers before and after it are included as the lower and upper limits, respectively.

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

[0014] In this specification, "solid content" of a composition means the components that form a magnetic particle-containing film, and if the composition contains a solvent (organic solvent, water, etc.), it means all components excluding the solvent. Furthermore, liquid components that form a magnetic particle-containing film are also considered to be solid content.

[0015] Furthermore, in this specification, the weight-average molecular weight (Mw) is the polystyrene equivalent value obtained by GPC (Gel Permeation Chromatography). In this specification, the GPC method is based on a method using HLC-8020GPC (manufactured by Tosoh Corporation), TSKgel SuperHZM-H, TSKgel SuperHZ4000, or TSKgel SuperHZ2000 (manufactured by Tosoh Corporation, 4.6 mm ID × 15 cm) as the column, and THF (tetrahydrofuran) as the eluent.

[0016] Furthermore, in this specification, unless otherwise specified, each component may be represented by a single substance or by a combination of two or more substances. Here, when two or more substances are used in combination for each component, the content of that component refers to the total content of the combined substances, unless otherwise specified.

[0017] [Composition] The composition of the present invention is a composition containing magnetic particles and a rheology control agent, The content of the above magnetic particles having an aspect ratio of less than 8 is 25% by mass or more relative to the total mass of the above magnetic particles. The above magnetic particles contain metal atoms, The above metal atom contains one or more specific atoms selected from the group consisting of Ni atoms and Co atoms. The content of the above-mentioned specific atoms is 50% by mass or more relative to the total mass of the above-mentioned metal atoms. The detailed reasons why this composition solves the problems of the present invention are not clear, but we generally presume the following.

[0018] When a predetermined amount or more of magnetic particles with an aspect ratio of less than 8 are included, the magnetic particles are arranged isotropically within the magnetic particle-containing film, improving the isotropy of the magnetism within the film. On the other hand, magnetic particles with an aspect ratio of less than 8 tend to settle more easily in the composition than magnetic particles with an aspect ratio of 8 or more, and a high content of magnetic particles with an aspect ratio of less than 8 tends to adversely affect the stability over time. To improve this problem, rheology control agents are sometimes applied to the composition, but the degree of improvement in stability over time is insufficient with the application of rheology control agents alone. Therefore, in addition to containing magnetic particles and a rheology control agent, the composition of the present invention also specifies that the magnetic particles contain a predetermined amount or more of one or more specific atoms selected from the group consisting of Ni atoms and Co atoms. Since specific atoms are less likely to ionize than atoms such as iron, the magnetic particles having the above-mentioned characteristics can achieve appropriate interaction with the rheology control agent without excessive interaction. Therefore, the rheology control agent interacting with the magnetic particles can fully perform its function as a rheology control agent, with a portion of it interacting with the magnetic particles while other portions being easily incorporated into networks of rheology control agents or forming appropriate steric hindrance structures. As a result, the settling suppression effect of the rheology control agent on the magnetic particles is considered to be better than usual, and the stability over time is significantly improved. Furthermore, since the magnetic particle-containing film is mounted during the composition coating process, it is subjected to more processes during the electronic circuit manufacturing process compared to magnetic materials mounted in individual piece form in the later stages of the process. Therefore, it is preferable that the magnetic particle-containing film has various durability properties. In particular, considering that the magnetic particle-containing film contains metal atoms, it is preferable that it has good chemical resistance to chemicals such as acids. It has been found that the chemical resistance of the formed magnetic particle-containing film can be obtained by using the composition of the present invention. This is thought to be because the standard oxidation-reduction potential of specific atoms in the magnetic particles contained in the composition is within an appropriate range. Hereinafter, if at least one of the following is superior: the temporal stability of the composition, the isotropy of the magnetism of the formed magnetic particle-containing film, and the chemical resistance of the formed magnetic particle-containing film, then the effect of the present invention will also be referred to as superior.

[0019] [Magnetic particles] The composition contains magnetic particles. The above magnetic particles contain metal atoms. In this specification, the above-mentioned metal atoms also include metalloid atoms such as boron, silicon, germanium, arsenic, antimony, and tellurium. The above-mentioned metal atoms may be included in magnetic particles as an alloy containing a metal element (preferably a magnetic alloy), a metal oxide (preferably a magnetic oxide), a metal nitride (preferably a magnetic oxide), or a metal carbide (preferably a magnetic carbide). The content of metal atoms relative to the total mass of the above magnetic particles is preferably 50 to 100% by mass, more preferably 75 to 100% by mass, and even more preferably 95 to 100% by mass.

[0020] The above magnetic particles contain one or more specific atoms selected from the group consisting of Ni atoms and Co atoms as metal atoms. The specific atom may be a Ni atom, a Co atom, or both a Ni atom and a Co atom. From the viewpoint of superior effects of the present invention, the specific atom is preferably a Ni atom. The content of specific atoms is 50% by mass or more, preferably 60% by mass or more, and more preferably 70% by mass or more, relative to the total mass of metal atoms in the magnetic particles. There is no upper limit to the above content, but it is 100% by mass or less, preferably 98% by mass or less, and more preferably 95% by mass or less. If the above magnetic particles contain Ni atoms, the Ni content is preferably 50 to 100% by mass, more preferably 60 to 95% by mass, and even more preferably 70 to 90% by mass, relative to the total mass of the metal atoms. If the magnetic particles contain Co atoms, their content is preferably 40 to 100% by mass, more preferably 50 to 95% by mass, even more preferably 60 to 90% by mass, and particularly preferably 70 to 90% by mass, relative to the total mass of the metal atoms.

[0021] The magnetic particles described above may contain both of the specific atoms, or substantially only one of them. When substantially only one of the specific atoms is contained, the content of one of the Ni atoms and Co atoms relative to the total mass of the specific atoms is, for example, 98 to 100% by mass, preferably 99 to 100% by mass, and more preferably 99.5 to 100% by mass. When the above magnetic particles contain both specific atoms, the content of Ni atoms may be higher, the content of Co atoms may be higher, or the content of both may be equal. If the magnetic particles described above contain both specific atoms, the content of one of the specific atoms (Ni atoms or Co atoms) is, for example, 50% by mass or more and less than 98% by mass, relative to the total mass of the specific atoms (the combined content of Ni atoms and Co atoms).

[0022] Examples of materials other than the specific atoms that constitute the magnetic particles mentioned above include Fe, Mo, 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. It is preferable to include metal atoms in addition to the specific atoms constituting the magnetic particles described above, and it is more preferable to include one or more selected from the group consisting of Fe, Si, Cr, B, and Mo. In the above magnetic particles, the content of metal atoms other than the specified atoms is preferably 0 to 50% by mass, more preferably 5 to 40% by mass, and even more preferably 10 to 30% by mass, relative to the total mass of the metal atoms. In the above magnetic particles, the Fe (Fe atom) content is preferably 0 to 50% by mass, more preferably 0 to 35% by mass, and even more preferably 0 to 25% by mass, relative to the total mass of metal atoms. In the above magnetic particles, the Si (Si atoms) content is preferably 0 to 20% by mass, more preferably 0 to 15% by mass, and even more preferably 0 to 8% by mass, relative to the total mass of metal atoms. In the above magnetic particles, the Cr (Cr atoms) content is preferably 0 to 20% by mass, more preferably 0 to 15% by mass, and even more preferably 0 to 8% by mass, relative to the total mass of metal atoms. In the above magnetic particles, the B (B atoms) content is preferably 0 to 15% by mass, more preferably 0 to 8% by mass, and even more preferably 0 to 5% by mass, relative to the total mass of metal atoms. In the above magnetic particles, the Mo (Mo atoms) content is preferably 0 to 50% by mass, more preferably 0 to 35% by mass, and even more preferably 0 to 25% by mass, relative to the total mass of metal atoms.

[0023] Specific examples of the magnetic particles mentioned above include Fe-Co alloys (preferably Permendur), Fe-Ni alloys (e.g., Permalloy), Ni-Mo alloys (preferably Supermalloy), Fe-Ni-Cu-Cr alloys (preferably Mu-metal), Fe-Ni-Co alloys, Fe-Co-Si-B alloys, Co-based amorphous alloys, and Ni-Zn ferrites. The above alloys may also be amorphous. In particular, permalloy is preferred as the magnetic particle because it exhibits superior effects compared to the present invention. Examples of permalloy include supermalloy and mu-metal, with supermalloy being preferred. Here, permalloy refers to, for example, a ferromagnetic alloy mainly composed of Fe and Ni. The above permalloy may also be an alloy containing one or more of Cr, Cu, and Mo in addition to Fe and Ni. Supermalloy refers to, for example, a ferromagnetic alloy mainly composed of Fe, Ni, and Mo, and is a type of permalloy. Mu-metal refers to, for example, a ferromagnetic alloy mainly composed of Fe, Ni, Cu, and Cr, and is a type of permalloy.

[0024] The composition of the magnetic particles described above is confirmed by inductively coupled plasma (ICP) emission spectroscopy. Specifically, a pressure-resistant container containing 12 mg of sample particles and 10 mL of a 4 mol / L (liter; the same applies hereafter) hydrochloric acid aqueous solution is held in an oven at a set temperature of 120°C for 12 hours to obtain a solution. Next, 30 mL of pure water is added to the obtained solution, and then it is filtered using a 0.1 μm membrane filter. Elemental analysis of the filtrate obtained in this way is performed using an inductively coupled plasma (ICP) emission spectrometer. Based on the results of the elemental analysis, the content of each metal atom is determined. Based on the obtained content, the composition is confirmed. As a measuring device, for example, Shimadzu Corporation's high-frequency inductively coupled plasma (ICP) emission spectrometer (model number: ICPS-8100) can be suitably used. However, the measuring device is not limited to this.

[0025] A surface layer may be provided on the surface of the magnetic particles. By having a surface layer on the magnetic particles, functions corresponding to the material of the surface layer can be imparted to the magnetic particles. Examples of surface layers include inorganic layers and organic layers.

[0026] As compounds for forming inorganic layers, metal oxides, metal nitrides, metal carbides, metal phosphate compounds, metal borate compounds, or silicate compounds (for example, silicate esters such as tetraethyl orthosilicate, and silicates such as sodium silicate) are preferred because they can form a surface layer that is excellent in at least one of the following: insulating properties, gas barrier properties, and chemical stability. Specific examples of elements contained in these compounds include Fe, Al, Ca, Mn, Zn, Mg, V, Cr, Y, Ba, Sr, Ge, Zr, Ti, Si, and rare earth elements. Materials that constitute the inorganic layer obtained using the inorganic layer-forming compound include silicon dioxide, germanium oxide, titanium dioxide, aluminum oxide, zirconium oxide, and magnesium oxide, and the inorganic layer may contain two or more of these materials.

[0027] Examples of compounds for forming organic layers include acrylic monomers. Specific examples of acrylic monomers include the compounds described in paragraphs 0022 to 0023 of Japanese Patent Publication No. 2019-67960. Acrylic resin is an example of a material that constitutes an organic layer obtained using an organic layer-forming compound.

[0028] The thickness of the surface layer is not particularly limited, but 3 to 1000 nm is preferred because it allows the surface layer to perform its function more effectively.

[0029] The particle size of the magnetic particles is preferably 0.1 μm or larger, more preferably 1 μm or larger, and even more preferably 5 μm or larger. In particular, when the particle size is 5 μm or larger, the chemical resistance of the magnetic particle-containing film obtained from the composition tends to be superior (especially when the magnetic particles contain Ni atoms as a specific atom, when the magnetic particles contain Ni atoms as the most abundant specific atom, or when the magnetic particles contain substantially only Ni atoms as a specific atom). Furthermore, when the particle size is 20 μm or larger, the chemical resistance of the magnetic particle-containing film obtained from the composition tends to be better (especially when the magnetic particles contain Co atoms as a specific atom, when the magnetic particles contain Co atoms as the most abundant specific atom, or when the magnetic particles contain substantially only Co atoms as a specific atom). The particle size of the magnetic particles is preferably 100 μm or less, more preferably 50 μm or less, and even more preferably 30 μm or more. In this specification, the particle size of magnetic particles refers to the average primary particle diameter of the particles. The particle diameter of primary magnetic particles is measured by photographing the magnetic particles with a transmission electron microscope at a magnification of 100,000x, printing the resulting image onto photographic paper at a total magnification of 500,000x, tracing the contour of the particles (primary particles) with a digitizer, and calculating the diameter of a circle with the same area as the traced region (circular area phase diameter). Here, primary particles refer to independent particles that are not aggregated. The imaging using the transmission electron microscope shall be performed using the direct method with an accelerating voltage of 300kV. Transmission electron microscope observation and measurement can be performed, for example, using a Hitachi H-9000 transmission electron microscope and Carl Zeiss KS-400 image analysis software.

[0030] The aspect ratio of the above magnetic particles is preferably 1 to 8, more preferably 1 or more and less than 8, even more preferably 1 to 5, and particularly preferably 1 to 3. Furthermore, if there is only one type of magnetic particle in the composition, the aspect ratio of the magnetic particle is 1 or more and less than 8. If the composition contains two or more types of magnetic particles, at least one of them is a magnetic particle having an aspect ratio of less than 8 (preferably 1 to 5, more preferably 1 to 3). The content of the magnetic particles having an aspect ratio of less than 8 (preferably 1 to 5, more preferably 1 to 3) is at least 25% by mass, preferably 50% by mass or more, more preferably 75% by mass or more, and even more preferably 90% by mass or more, based on the total mass of the magnetic particles. There is no upper limit to the above content, for example, 100% by mass or less. In this specification, the aspect ratio of a particle is determined as follows: The particle whose aspect ratio is to be determined is observed using a transmission electron microscope (TEM), and for 200 particles randomly selected from the observation, the ratio (A / B) is calculated by dividing the longest width A by the shortest width B. The average of these 200 "A / B" values ​​is taken as the aspect ratio of that particle.

[0031] The composition may contain only one type of magnetic particle, or it may contain two or more types. One or more of the above-mentioned magnetic particles may be plate-shaped, elliptical, spherical, or amorphous, as long as the magnetic particles as a whole in the composition satisfy the above-mentioned aspect ratio requirements.

[0032] The content of the above magnetic particles is preferably 30 to 99% by mass, more preferably 35 to 97% by mass, and even more preferably 40 to 95% by mass, based on the total mass of the composition. The content of the magnetic particles is preferably 50 to 99% by mass, more preferably 60 to 97% by mass, and even more preferably 70 to 95% by mass, based on the total solid content of the composition.

[0033] <> The composition of the present invention is a composition formed using a magnetic particle raw material containing at least magnetic particles X having an aspect ratio of less than 8 and a rheology control agent, wherein the content of magnetic particles X is preferably 25% by mass or more relative to the total mass of magnetic particles in the composition (in other words, the total mass of magnetic particle raw materials in the composition).

[0034] Furthermore, the magnetic particle X contains metal atoms, The above metal atom contains one or more specific atoms selected from the group consisting of Ni atoms and Co atoms, and further, It is preferable that the content of the above-mentioned specific atoms is 50% by mass or more relative to the total mass of the above-mentioned metal atoms.

[0035] Here, the metal atoms contained in the magnetic particles X are synonymous with the metal atoms described in the section on [magnetic particles] above, and their preferred configuration is also the same. The content of metal atoms relative to the total mass of magnetic particles X is preferably 50 to 100% by mass, more preferably 75 to 100% by mass, and even more preferably 95 to 100% by mass.

[0036] Furthermore, the specific atoms contained in the magnetic particles X are the same as the specific atoms described in the section on [magnetic particles] above, and their preferred configuration is also the same. The content of specific atoms is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more, relative to the total mass of metal atoms in the magnetic particle X. There is no upper limit to the above content, but it is 100% by mass or less, preferably 98% by mass or less, and more preferably 95% by mass or less. If the magnetic particle X contains Ni atoms, the Ni content is preferably 50 to 100% by mass, more preferably 60 to 95% by mass, and even more preferably 70 to 90% by mass, relative to the total mass of metal atoms in the magnetic particle X. If the magnetic particle X contains Co atoms, the Co content is preferably 40 to 100% by mass, more preferably 50 to 95% by mass, even more preferably 60 to 90% by mass, and particularly preferably 70 to 90% by mass, relative to the total mass of metal atoms in the magnetic particle X. The magnetic particle X may contain both of the specific atoms, or substantially only one of them. When substantially only one of the specific atoms is contained, the content of one of the Ni atoms and Co atoms relative to the total mass of the specific atom is, for example, 98 to 100% by mass, preferably 99 to 100% by mass, and more preferably 99.5 to 100% by mass. If magnetic particle X contains both specific atoms, the content of Ni atoms may be higher, the content of Co atoms may be higher, or the content of both may be equal. If magnetic particle X contains both specific atoms, the content of one of the specific atoms (Ni atom or Co atom) is, for example, 50% by mass or more and less than 98% by mass, relative to the total mass of the specific atoms (total content of Ni and Co atoms).

[0037] Furthermore, the materials other than the specific atoms constituting the magnetic particle X are the same as the materials described in the section on [magnetic particles] above, and their preferred embodiments are also the same. The magnetic particles X preferably contain metal atoms in addition to specific atoms, and more preferably contain one or more selected from the group consisting of Fe, Si, Cr, B, and Mo. In magnetic particles X, the content of metal atoms other than specific atoms is preferably 0 to 50% by mass, more preferably 5 to 40% by mass, and even more preferably 10 to 30% by mass, relative to the total mass of metal atoms in magnetic particles X. The Fe (Fe atom) content in magnetic particle X is preferably 0 to 50% by mass, more preferably 0 to 35% by mass, and even more preferably 0 to 25% by mass, relative to the total mass of metal atoms in magnetic particle X. The Si (Si atoms) content in magnetic particle X is preferably 0 to 20% by mass, more preferably 0 to 15% by mass, and even more preferably 0 to 8% by mass, relative to the total mass of metal atoms in magnetic particle X. In magnetic particles X, the Cr (Cr atoms) content is preferably 0 to 20% by mass, more preferably 0 to 15% by mass, and even more preferably 0 to 8% by mass, relative to the total mass of metal atoms in magnetic particles X. In magnetic particle X, the B (B atom) content is preferably 0 to 15% by mass, more preferably 0 to 8% by mass, and even more preferably 0 to 5% by mass, relative to the total mass of metal atoms in magnetic particle X. In magnetic particle X, the Mo (Mo atom) content is preferably 0 to 50% by mass, more preferably 0 to 35% by mass, and even more preferably 0 to 25% by mass, relative to the total mass of metal atoms in magnetic particle X.

[0038] Specific examples of magnetic particles X are the same as the specific examples of magnetic particles described in the section above under [Magnetic Particles]. Among these, permalloy is preferred for magnetic particles X because it exhibits superior effects compared to the present invention. Examples of permalloy include supermalloy and mu-metal, with supermalloy being preferred.

[0039] Furthermore, the method for confirming the composition of magnetic particles X and the particle size of magnetic particles are the same as those described in the section on magnetic particles above, and the preferred embodiment is also the same. Furthermore, a surface layer may be provided on the surface of the magnetic particle X. The surface layer of the magnetic particle X is the same as the surface layer of the magnetic particle described in the upper section [Magnetic Particles], and the preferred embodiment is also the same.

[0040] The aspect ratio of the magnetic particle X is preferably 1 to 8, more preferably 1 or more and less than 8, even more preferably 1 to 5, and particularly preferably 1 to 3. The content of magnetic particles X having an aspect ratio of less than 8 (preferably 1 to 5, more preferably 1 to 3) is at least 25% by mass, preferably 50% by mass or more, more preferably 75% by mass or more, and even more preferably 90% by mass or more, based on the total mass of magnetic particles in the composition (in other words, the total mass of magnetic particle raw materials in the composition). There is no upper limit to the above content, for example, 100% by mass or less. The definition of aspect ratio is as previously described.

[0041] As the magnetic particle raw material mentioned above, at least magnetic particles X having an aspect ratio of less than 8 may be used, and magnetic particles Y having an aspect ratio of 8 or more may also be used. Only one type of magnetic particle X may be used, or two or more types may be used.

[0042] The magnetic particle X may be plate-shaped, elliptical, spherical, or amorphous. When preparing the composition, the total content of magnetic particles (in other words, the total content of magnetic particle raw materials in the composition) is preferably 30 to 99% by mass, more preferably 35 to 97% by mass, and even more preferably 40 to 95% by mass, based on the total mass of the composition. Furthermore, the total content of magnetic particles (in other words, the total content of magnetic particle raw materials in the composition) is preferably 50 to 99% by mass, more preferably 60 to 97% by mass, and even more preferably 70 to 95% by mass, based on the total solid content of the composition.

[0043] [Rheology control agent] The composition contains a rheology control agent. Rheology control agents are components that impart thixotropic properties to a composition, exhibiting high viscosity at low shear forces (shear rates) and low viscosity at high shear forces (shear rates). The content of the rheology control agent is preferably 0.1 to 35% by mass, more preferably 0.5 to 30% by mass, and even more preferably 1 to 27% by mass, based on the total mass of the composition. The content of the rheology control agent is preferably 0.1 to 35% by mass, more preferably 0.5 to 30% by mass, and even more preferably 1 to 27% by mass, based on the total solid content of the composition.

[0044] Examples of rheology control agents include organic rheology control agents and inorganic rheology control agents, with organic rheology control agents being preferred.

[0045] <Organic rheology control agent> The content of the organic rheology control agent is preferably 0.1 to 35% by mass, more preferably 0.5 to 30% by mass, and even more preferably 1 to 25% by mass, based on the total mass of the composition. The content of the organic rheology control agent is preferably 0.1 to 35% by mass, more preferably 0.5 to 30% by mass, and even more preferably 1 to 25% by mass, relative to the total solid content of the composition. Organic rheology control agents may be used individually or in combination of two or more types.

[0046] Examples of organic rheology control agents include compounds having one or more (preferably two or more) adsorption groups, and further having steric repulsion structural groups. The adsorption groups interact with the surface of the magnetic particles, causing the organic rheology control agent to be adsorbed onto the surface of the magnetic particles. Examples of the adsorption groups mentioned above include acidic groups, basic groups, and amide groups. Examples of acidic groups include carboxyl groups, phosphoric acid groups, sulfol groups, phenolic hydroxyl groups, and their acid anhydride groups (such as the acid anhydride group of a carboxyl group). Carboxyl groups are preferred because they exhibit superior effects compared to the present invention. Examples of basic groups include amino groups (ammonia, primary amines, or secondary amines with one hydrogen atom removed) and imino groups. Among these, the adsorbent group is preferably a carboxyl group or an amide group, with the carboxyl group being more preferable. The steric repulsion structural group has a sterically bulky structure, which introduces steric hindrance to the magnetic particles to which the organic rheology control agent is adsorbed, thereby maintaining an appropriate space between the magnetic particles. As for the steric repulsion structural group, chain-like groups are preferred, long-chain fatty acid groups are more preferred, and long-chain alkyl groups are even more preferred. The organic rheology control agent may also preferably have hydrogen bonding units. The hydrogen-bonding unit is a substructure that functions to construct a hydrogen-bonding network between organic rheology control agents and between organic rheology control agents and other components. The organic rheology control agents that contribute to the formation of the above network may or may not be adsorbed on the surface of the magnetic particles. The hydrogen bonding unit may be the same as or different from the adsorption group described above. When the hydrogen bonding unit is the same as the adsorption group described above, a portion of the adsorption group is bonded to the surface of the magnetic particle, and the other portion functions as the hydrogen bonding unit. As the hydrogen bonding unit, a carboxyl group or an amide group is preferred. The carboxyl group as the hydrogen bonding unit is preferred because it is easy to incorporate into the curing reaction when producing a magnetic particle-containing film, while the amide group is preferred because it provides better long-term stability of the composition.

[0047] When the organic rheology control agent is a resin, the resin organic rheology control agent may have repeating units including the graft chains described below, or it may not have substantially any. When the resin organic rheology control agent does not substantially have repeating units including the graft chains described below, the content of repeating units including the graft chains described below relative to the total mass of the resin organic rheology control agent is preferably less than 2% by mass, more preferably 1% by mass or less, and even more preferably less than 0.1% by mass. The lower limit is 0% by mass or more.

[0048] The organic rheology control agent is preferably one or more selected from the group consisting of polycarboxylic acids (compounds having two or more carboxyl groups), polyanhydrides (compounds having two or more acid anhydride groups consisting of carboxyl groups), and amide waxes. These may be made of resin or other materials. Furthermore, these may also fall under the categories of flocculation control agents and / or flocculation dispersants, as described later.

[0049] Examples of organic rheology control agents include modified ureas, urea-modified polyamides, fatty acid amides, polyurethanes, polyamide amides, high molecular weight urea derivatives, and their salts (carboxylate salts, etc.). Modified ureas are reaction products of isocyanate monomers or their adducts with organic amines. Modified ureas are modified with polyoxyalkylene polyols (polyoxyethylene polyols, polyoxypropylene polyols, etc.) and / or alkyd chains. Urea-modified polyamides are, for example, compounds containing urea bonds and compounds to which a medium-polarity or low-polarity group has been introduced at the end. Examples of medium-polarity or low-polarity groups include polyoxyalkylene polyols (polyoxyethylene polyols, polyoxypropylene polyols, etc.) and alkyd chains. Fatty acid amides are compounds having a long-chain fatty acid group and an amide group in their molecule. These may be made of resin or other materials. Furthermore, these may also fall under the categories of flocculation control agents and / or flocculation dispersants, as described later.

[0050] The molecular weight (or weight-average molecular weight if it has a molecular weight distribution) of the organic rheology control agent is preferably in the range of 200 to 50,000. If the organic rheology control agent has an acid value, the acid value is preferably 5 to 400 mg KOH / g. If the organic rheology control agent has an amine acid value, the amine value is preferably 5 to 300 mg KOH / g.

[0051] (Agglutination control agent) Organic rheology control agents also include flocculation control agents. Flocculation control agents may be resins or other materials. The flocculation control agent has the function of binding to relatively dense aggregates such as magnetic particles, and further dispersing other optionally included components (e.g., polymerizable compounds) in the composition to create bulky aggregates. When the composition contains an aggregation control agent, the hard cake formation of magnetic particles in the composition is suppressed, and bulkier aggregates are formed, which can improve redispersibility.

[0052] Examples of flocculation control agents include cellulose derivatives. Examples of cellulose derivatives include carboxymethylcellulose, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, hydroxypropylethylcellulose, and salts thereof.

[0053] If the composition contains a flocculation control agent, the content of the flocculation control agent is preferably 0.1 to 20% by mass, preferably 0.3 to 15% by mass, and more preferably 0.5 to 10% by mass, based on the total mass of the composition. The content of the flocculation control agent is preferably 0.1 to 20% by mass, more preferably 0.3 to 15% by mass, and more preferably 0.5 to 10% by mass, relative to the total solid content of the composition.

[0054] (Agglomerating agent) Organic rheological control agents also include flocculants and dispersants. The flocculant / dispersant may be a resin or something other than a resin. The flocculating dispersant adsorbs onto the surface of magnetic particles, separating them from one another. Through interactions between the dispersants, it maintains a certain distance between magnetic particles, preventing direct aggregation. As a result, aggregation of magnetic particles is suppressed, and even when aggregates form, they are relatively low-density aggregates. Furthermore, other components optionally included in the composition (e.g., polymerizable compounds) can be dispersed within the composition to create bulky aggregates, potentially improving redispersibility.

[0055] As a flocculant / dispersant, an alkylol ammonium salt of a polybasic acid is preferred. Polybasic acids only need to have two or more acidic groups. Examples include acidic polymers containing repeating units with acidic groups (e.g., polyacrylic acid, polymethacrylic acid, polyvinyl sulfonic acid, and polyphosphate). Other examples of polybasic acids include polymers obtained by polymerizing unsaturated fatty acids such as crotonic acid. Alkyloll ammonium salts of polybasic acids are obtained by reacting these polybasic acids with alkylloll ammonium. Salts obtained by such reactions usually contain the following substructures. -C(=O)-N(-R 1 )(-R 2 -OH) Here, R 1 R is an alkyl group. 2 This is an alkylene group. The alkylol ammonium salt of the polybasic acid is preferably a polymer containing multiple of the above-mentioned substructures. When the alkylol ammonium salt of the polybasic acid is a polymer, the weight-average molecular weight is preferably 1,000 to 100,000, and more preferably 5,000 to 20,000. The polymer of the alkylol ammonium salt of the polybasic acid can bond to the surface of magnetic particles and form hydrogen bonds with other flocculant dispersant molecules, allowing the polymer's main chain structure to penetrate between magnetic particles and separate them.

[0056] One preferred embodiment of the flocculant and dispersant is an amide wax, which is a condensate obtained by dehydration condensation of (a) saturated aliphatic monocarboxylic acids and hydroxyl group-containing aliphatic monocarboxylic acids, and (b) at least one of the polybasic acids and (c) at least one of the diamines and tetraamines. It is preferable to use (a) to (c) above in a molar ratio of (a):(b):(c) = 1 to 3: 0 to 5: 1 to 6.

[0057] The saturated aliphatic monocarboxylic acids preferably have 12 to 22 carbon atoms. Specifically, examples include lauric acid, myristic acid, pentadecyl acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid, arachidic acid, and behenic acid. The hydroxyl group-containing aliphatic monocarboxylic acids preferably have 12 to 22 carbon atoms. Specifically, examples include 12-hydroxystearic acid and dihydroxystearic acid. These saturated aliphatic monocarboxylic acids and hydroxyl group-containing aliphatic monocarboxylic acids may be used individually or in combination.

[0058] Polybasic acids are preferably dibasic acids or carboxylic acids having 2 to 12 carbon atoms, and dicarboxylic acids are more preferred. Examples of such dicarboxylic acids include aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,10-decanedicarboxylic acid, and 1,12-dodecanedicarboxylic acid; aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid; and alicyclic dicarboxylic acids such as 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and cyclohexylsuccinic acid. These polybasic acids may be used individually or in combination.

[0059] Diamines are preferably those having 2 to 14 carbon atoms. Specifically, examples include ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, hexamethylenediamine, metaxylenediamine, tolylenediamine, paraxylenediamine, phenylenediamine, isophoronediamine, 1,10-decanediamine, 1,12-dodecanediamine, 4,4-diaminodicyclohexylmethane, and 4,4-diaminodiphenylmethane. Tetraamines are preferably those having 2 to 14 carbon atoms. Specifically, examples include butane-1,1,4,4-tetraamine and pyrimidine-2,4,5,6-tetraamine. These diamines and tetraamines may be used individually or in combination.

[0060] The amounts of diamines and tetraamines are adjusted according to the number of moles of saturated aliphatic monocarboxylic acid or hydroxyl group-containing aliphatic monocarboxylic acid and the number of moles of polybasic acids, so that the total number of carboxyl groups and the total number of amino groups are equivalent. For example, if there are 2 moles of aliphatic monocarboxylic acid and n moles (n=0~5) of aliphatic dicarboxylic acid, which is a polybasic acid, then if the amount of diamines is (n+1) moles, the acid and amine will be equivalent.

[0061] This amide wax may also be obtained as a mixture of multiple compounds having different molecular weights. The amide wax is preferably a compound represented by the following chemical formula (I). Note that the amide wax may be a single compound or a mixture. AC-(BC) m -A···(I) In formula (I), A is a dehydrated residue of a saturated aliphatic monocarboxylic acid and / or a hydroxyl group-containing saturated aliphatic monocarboxylic acid, B is a dehydrated residue of a polybasic acid, C is a dehydrogenated residue of a diamine and / or a tetraamine, and m is 0 ≤ m ≤ 5.

[0062] One preferred embodiment of the flocculant / dispersant is a compound represented by the following formula (II).

[0063] [Chemical formula]

[0064] In formula (II), R 1 represents a monovalent linear aliphatic hydrocarbon group having 10 to 25 carbon atoms, and 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 to L 3 each independently represent an amide bond. When L 1 and L 3 is -CONH-, L 2 is -NHCO-. When L 1 and L 3 is -NHCO-, L 2 is -CONH-.

[0065] R 1 is 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, and behenyl group; linear alkenyl groups such as decenyl group, pentadecenyl group, oleyl group, and eicosenyl group; and linear alkynyl groups such as pentadecinyl group, octadecinyl group, and nonadecinyl group. Among them, R 1 is preferably a monovalent linear aliphatic hydrocarbon group having 14 to 25 carbon atoms, and more preferably a monovalent linear aliphatic hydrocarbon group having 18 to 21 carbon atoms. The linear aliphatic hydrocarbon group is preferably an alkyl group.

[0066] R 2 and R 3Examples of divalent aliphatic hydrocarbon groups having 2, 4, 6, or 8 carbon atoms include ethylene, n-butylene, n-hexylene, and n-octylene groups. R 2 and R 3 Examples of divalent alicyclic hydrocarbon groups having 6 carbon atoms in this context include the 1,4-cyclohexylene group, the 1,3-cyclohexylene group, and the 1,2-cyclohexylene group. R 2 and R 3 Examples of divalent aromatic hydrocarbon groups in this context include arylene groups having 6 to 10 carbon atoms, such as 1,4-phenylene, 1,3-phenylene, and 1,2-phenylene.

[0067] Among them, R 2 and R 3 In terms of excellent thickening effect, divalent aliphatic hydrocarbon groups having 2, 4, 6, or 8 carbon atoms are preferred, more preferably divalent aliphatic hydrocarbon groups having 2, 4, or 6 carbon atoms, even more preferably divalent aliphatic hydrocarbon groups having 2 or 4 carbon atoms, and most preferably divalent aliphatic hydrocarbon groups having 2 carbon atoms. Linear alkylene groups are preferred for the divalent aliphatic hydrocarbon groups.

[0068] R 4 This represents a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, and among these, linear or branched alkylene groups are preferred, with linear alkylene groups being more preferred, due to their excellent thickening effect. Also, R 4 The number of carbon atoms in the divalent aliphatic hydrocarbon group is 1 to 8, and in terms of excellent thickening effect, 1 to 7 is preferred, 3 to 7 is more preferred, 3 to 6 is even more preferred, and 3 to 5 is particularly preferred. Therefore, R 4 The linear or branched alkylene group having 1 to 8 carbon atoms is preferred, a linear alkylene group having 1 to 7 carbon atoms is more preferred, a linear alkylene group having 3 to 7 carbon atoms is even more preferred, a linear alkylene group having 3 to 6 carbon atoms is particularly preferred, and a linear alkylene group having 3 to 5 carbon atoms is most preferred.

[0069] R5 and R 6 Examples of monovalent aliphatic hydrocarbon groups having 1 to 3 carbon atoms include linear or branched alkyl groups having 1 to 3 carbon atoms such as methyl, ethyl, propyl, and isopropyl groups; linear or branched alkenyl groups having 2 to 3 carbon atoms such as vinyl, 1-methylvinyl, and 2-propenyl groups; and linear or branched alkynyl groups having 2 to 3 carbon atoms such as ethynyl and propynyl groups.

[0070] R 5 and R 6 Examples of hydroxyalkyl ether groups in this context include mono- or di(hydroxy)C groups such as 2-hydroxyethoxy, 2-hydroxypropoxy, and 2,3-dihydroxypropoxy. 1-3 Alkyl ether groups are one example.

[0071] Among them, R 5 and R 6 Each of these groups is preferably a monovalent aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably a linear or branched alkyl group having 1 to 3 carbon atoms, even more preferably a linear alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group.

[0072] The compounds represented by formula (II) are preferably those represented by the following formulas (II-1) to (II-9).

[0073] [ka]

[0074] Examples of flocculants and dispersants include ANTI-TERRA-203, 204, 206, and 250 (all trade names, manufactured by BYK); ANTI-TERRA-U (trade name, manufactured by BYK); DISPER BYK-102, 180, and 191 (all trade names, manufactured by BYK); BYK-P105 (trade name, manufactured by BYK); TEGO Disper630 and 700 (both trade names, manufactured by Evonik Degussa Japan); TALENE VA-705B (trade name, manufactured by Kyoeisha Chemical Co., Ltd.); FLOWNON RCM-300TL and RCM-230AF (trade names, manufactured by Kyoeisha Chemical Co., Ltd., amide wax).

[0075] If the composition contains a flocculant, the content of the flocculant is preferably 0.1 to 35% by mass, more preferably 0.3 to 30% by mass, and more preferably 0.5 to 27% by mass, based on the total mass of the composition. The content of the flocculant and dispersant is preferably 0.1 to 35% by mass, more preferably 0.3 to 30% by mass, and more preferably 0.5 to 27% by mass, relative to the total solid content of the composition.

[0076] <Inorganic rheology control agent> Examples of inorganic rheological control agents include bentonite, silica, calcium carbonate, and smectite.

[0077] [Other resins] The composition may also preferably contain other resins. The term "other resins" above refers to resins that do not fall under the category of rheology control agents, which are resins. For other resins, it is preferable that the weight-average molecular weight is greater than 2000.

[0078] Other resins include (meth)acrylic resins, epoxy resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyarylene etherphosphine oxide resins, polyimide resins, polyamide-imide resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, and phenoxy resins. One of these resins may be used alone, or two or more may be used in mixture form. Among cyclic olefin resins, norbornene resin is preferred from the viewpoint of improving heat resistance. Examples of commercially available norbornene resins include the ARTON series (e.g., ARTON F4520) manufactured by JSR Corporation. Examples of epoxy resins include epoxy resins that are glycidyl ethers of phenol compounds, epoxy resins that are glycidyl ethers of various novolac resins, alicyclic epoxy resins, aliphatic epoxy resins, heterocyclic epoxy resins, glycidyl ester epoxy resins, glycidylamine epoxy resins, epoxy resins obtained by glycidylating halogenated phenols, condensates of silicon compounds having epoxy groups and other silicon compounds, and copolymers of polymerizable unsaturated compounds having epoxy groups and other polymerizable unsaturated compounds. In addition, epoxy resins such as Marproof G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, and G-01758 (manufactured by NOF Corporation, epoxy group-containing polymers) can also be used. Furthermore, other resins may be those described in the examples of International Publication No. 2016 / 088645. In addition, if the other resin has an ethylenically unsaturated group, particularly a (meth)acryloyl group, in its side chain, it is also preferable that the main chain and the ethylenically unsaturated group are linked via a divalent linking group having an alicyclic structure.

[0079] Another preferred embodiment of the resin is a resin having polymerizable groups such as unsaturated double bonds (e.g., ethylenically unsaturated double bonds), epoxy groups, or oxetanyl groups. When the polymerizable groups react during the formation of the magnetic particle-containing film, a magnetic particle-containing film with excellent mechanical strength can be obtained. Other resins of this kind include, for example, polymers having epoxy groups in their side chains, and polymerizable monomers or oligomers having two or more epoxy groups in their molecules. Specific examples include bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, and aliphatic epoxy resins. These other resins may be commercially available or obtained by introducing epoxy groups into the side chains of polymers. For commercially available products, for example, the description in paragraph 0191 of Japanese Patent Publication No. 2012-155288 can be considered, and the contents of these are incorporated into the present specification. Other examples include the ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (all manufactured by ADEKA), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (all manufactured by ADEKA), and JER1031S. Furthermore, commercially available phenol novolac type epoxy resins include JER-157S65, JER-152, JER-154, and JER-157S70 (all manufactured by Mitsubishi Chemical Corporation). Specific examples of polymers having oxetanyl groups in their side chains, and polymerizable monomers or oligomers having two or more oxetanyl groups in the molecule mentioned above, include Aronoxetane OXT-121, OXT-221, OX-SQ, and PNOX (all manufactured by Toagosei Co., Ltd.). When synthesizing other resins having epoxy groups by introducing epoxy groups into polymer side chains, the introduction reaction can be carried out by reacting in an organic solvent at a reaction temperature of 50 to 150°C for a predetermined time, using, for example, tertiary amines such as triethylamine and benzylmethylamine, quaternary ammonium salts such as dodecyltrimethylammonium chloride, tetramethylammonium chloride, and tetraethylammonium chloride, pyridine, and triphenylphosphine as catalysts. The amount of alicyclic epoxy unsaturated compound introduced can be controlled so that the acid value of the resulting polymer is within the range of 5 to 200 KOH·mg / g. The weight-average molecular weight can be in the range of 500 to 5,000,000, preferably 1,000 to 500,000. Instead of alicyclic epoxy unsaturated compounds, those having a glycidyl group as the epoxy group, such as glycidyl (meth)acrylates and allyl glycidyl ethers, can also be used. For example, one can refer to the description in paragraph 0045 of Japanese Patent Application Publication No. 2009-265518, and these contents are incorporated into the present specification.

[0080] Other preferred embodiments of the resin include other resins having acidic groups, basic groups, or amide groups. Other resins having acidic groups, basic groups, or amide groups are preferred because they readily function as dispersants for dispersing magnetic particles, and thus exhibit superior effects in the present invention. Examples of acidic groups include carboxyl groups, phosphate groups, sulfo groups, and phenolic hydroxyl groups, and carboxyl groups are preferred because they exhibit superior effects compared to the present invention. Basic groups include amino groups (ammonia, primary amines, or secondary amines with one hydrogen atom removed) and imino groups. In particular, from the viewpoint of achieving superior effects in the present invention, it is preferable that the other resins have carboxyl groups or amide groups.

[0081] If the other resin has acidic groups, the acid value of the other resin is preferably 10 to 500 mg KOH / g, and particularly preferably 30 to 400 mg KOH / g or more, from the viewpoint of achieving superior effects of the present invention.

[0082] As for other resins, it is preferable to use other resins with a solubility of 10 g / L or more in the solvent, and more preferable to use other resins with a solubility of 20 g / L or more in the solvent, since this improves the dispersibility of the other resins in the composition and further enhances the effects of the present invention. The upper limit of the solubility of other resins in the solvent is preferably 2000 g / L or less, and particularly preferably 1000 g / L or less. The solubility of a resin in a solvent refers to the amount of resin (in grams) that dissolves in 1 liter of solvent at 25°C.

[0083] The content of other resins is preferably 0.1 to 30% by mass, more preferably 1 to 20% by mass, even more preferably 2 to 15% by mass, and particularly preferably 2.5 to 10% by mass, based on the total mass of the composition, in order to achieve superior effects of the present invention. The content of other resins is preferably 0.1 to 30% by mass, more preferably 1 to 20% by mass, even more preferably 2 to 15% by mass, and particularly preferably 2.5 to 10% by mass, relative to the total solid content of the composition.

[0084] <Resin containing repeating units including graft chains (Resin A)> Other resins include, for example, resins having repeating units including graft chains (hereinafter also referred to as "Resin A"). Resin A can assist the effect of rheology control agents and improve the effect of improving the long-term stability of the composition.

[0085] If the composition contains resin A, the content of resin A is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, and even more preferably 1 to 10% by mass, based on the total mass of the composition, from the viewpoint of achieving superior effects of the present invention. The content of resin A is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, and even more preferably 1 to 10% by mass, relative to the total solid content of the composition. When using resin A, the mass ratio of the rheology control agent content to the resin A content (rheology control agent / resin A) is preferably 10 / 90 to 90 / 10, more preferably 30 / 70 to 80 / 20, and even more preferably 50 / 50 to 70 / 30.

[0086] (Repeating units including graft chains) In repeating units containing graft chains, the steric repulsion effect increases as the graft chain length increases, improving the dispersibility of magnetic particles. On the other hand, if the graft chain is too long, the adsorption force to the magnetic particles decreases, and the dispersibility of magnetic particles tends to decrease. For this reason, the number of atoms excluding hydrogen atoms in the graft chain is preferably 40 to 10,000, more preferably 50 to 2,000, and even more preferably 60 to 500. Here, a graft chain refers to the chain from the base of the main chain (the atom bonded to the main chain in a group branching off from the main chain) to the end of the group branching off from the main chain.

[0087] Furthermore, the graft chains preferably contain a polymer structure, and examples of such polymer structures include poly(meth)acrylate structures (e.g., poly(meth)acrylic structures), polyester structures, polyurethane structures, polyurea structures, polyamide structures, and polyether structures. To improve the interaction between the graft chain and the solvent, thereby enhancing the dispersibility of the magnetic particles, the graft chain is preferably a graft chain comprising at least one selected from the group consisting of polyester structure, polyether structure, and poly(meth)acrylate structure, and more preferably a graft chain comprising at least one of polyester structure and polyether structure.

[0088] Resin A may be a resin obtained using macromonomers containing graft chains (monomers that have a polymer structure and are bonded to the main chain to constitute graft chains). The macromonomers containing graft chains (monomers having a polymer structure that are bonded to the main chain to constitute graft chains) are not particularly limited, but macromonomers containing reactive double bond groups can be preferably used.

[0089] Commercially available macromonomers suitable for the synthesis of resin A, corresponding to the repeating units including the graft chains described above, include AA-6, AA-10, AB-6, AS-6, AN-6, AW-6, AA-714, AY-707, AY-714, AK-5, AK-30, and AK-32 (all trade names, manufactured by Toagosei Co., Ltd.), as well as Brembo PP-100, Brembo PP-500, Brembo PP-800, Brembo PP-1000, Brembo 55-PET-800, Brembo PME-4000, Brembo PSE-400, Brembo PSE-1300, and Brembo 43PAPE-600B (all trade names, manufactured by NOF Corporation). Among these, AA-6, AA-10, AB-6, AS-6, AN-6, or Brembo PME-4000 are preferred.

[0090] Resin A preferably contains at least one structure selected from the group consisting of methyl polyacrylate, polymethyl methacrylate, and cyclic or chain-like polyesters, more preferably contains at least one structure selected from the group consisting of methyl polyacrylate, polymethyl methacrylate, and chain-like polyesters, and even more preferably contains at least one structure selected from the group consisting of methyl polyacrylate structures, polymethyl methacrylate structures, polycaprolactone structures, and polyvalerolactone structures. Resin A may contain one of the above structures alone, or it may contain a plurality of these structures. Here, a polycaprolactone structure refers to a structure that contains a ring-opened ε-caprolactone as a repeating unit. A polyvalerolactone structure refers to a structure that contains a ring-opened δ-valerolactone as a repeating unit.

[0091] Furthermore, if resin A contains repeating units in formula (1) and formula (2) described later, where j and k are 5, the polycaprolactone structure described above can be introduced into resin A. Furthermore, if resin A contains repeating units in formula (1) and formula (2) described later, where j and k are 4, the polyvalerolactone structure described above can be introduced into the resin. Furthermore, resin A is X in equation (4) described later. 5 is a hydrogen atom, and R 4 If the resin A contains repeating units that are methyl groups, the above-described methyl polyacrylate structure can be introduced into resin A. Furthermore, resin A is X in equation (4) described later. 5 is a methyl group, R 4 If the resin A contains repeating units that are methyl groups, the polymethyl methacrylate structure described above can be introduced into resin A.

[0092] Resin A preferably contains repeating units represented by any of the following formulas (1) to (4) as repeating units including graft chains, and more preferably contains repeating units represented by any of the following formulas (1A), (2A), (3A), (3B), and (4).

[0093] [ka]

[0094] In equations (1) to (4), W 1 , W 2 , W 3 , and, W 4 Each of these independently represents either an oxygen atom or NH. 1 , W 2 , W 3 , and, W 4 It is preferable that it is an oxygen atom. In equations (1) to (4), X 1 , X 2 , X 3 , X 4 , and, X 5Each of these independently represents a hydrogen atom or a monovalent organic group. 1 , X 2 , X 3 , X 4 , and, X 5 From the standpoint of synthetic constraints, each is independently preferred to be a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, each is independently preferred to be a hydrogen atom or a methyl group, and a methyl group is even more preferred.

[0095] In equations (1) to (4), Y 1 , Y 2 , Y 3 , and Y 4 Each of these independently represents a divalent linking group, and the linking group is not particularly structurally restricted. 1 , Y 2 , Y 3 , and Y 4 Examples of divalent linking groups represented by the formulas (Y-1) to (Y-21) below include the following linking groups. In the structures shown below, A and B represent the bonding sites to the left terminal group and the right terminal group in formulas (1) to (4), respectively. Of the structures shown below, (Y-2) or (Y-13) are more preferred due to the ease of synthesis.

[0096] [ka]

[0097] In equations (1) to (4), Z 1 , Z 2 , Z 3 , and Z 4 Each of these independently represents a hydrogen atom or a monovalent substituent. The structure of the above substituents is not particularly limited, but specifically, examples include alkyl groups, hydroxyl groups, alkoxy groups, aryloxy groups, heteroaryloxy groups, alkylthioether groups, arylthioether groups, heteroarylthioether groups, and amino groups. Among these, Z 1 , Z 2 , Z 3 , and Z 4The groups represented by are preferably those that include a steric repulsion effect, particularly in terms of improving dispersibility, and more preferably each is an alkyl group or alkoxy group having 5 to 24 carbon atoms, and among these, particularly preferably each is a branched alkyl group, a cyclic alkyl group, or an alkoxy group having 5 to 24 carbon atoms. The alkyl group contained in the alkoxy group may be linear, branched, or cyclic. Also, Z 1 , Z 2 , Z 3 , and Z 4 The substituent represented by is preferably a group containing a curable group such as a (meth)acryloyl group, an epoxy group, and / or an oxetanyl group. Examples of groups containing the above curable group include "-O-alkylene group-(-O-alkylene group-) AL An example is the "(meth)acryloyloxy group". AL represents an integer from 0 to 5, with 1 being preferred. Each of the above alkylene groups independently preferably has 1 to 10 carbon atoms. If the above alkylene group has a substituent, the substituent is preferably a hydroxyl group. The substituents described above may also be groups containing an onium structure. A group containing an onium structure is a group having an anionic part and a cationic part. An example of the anionic part is the oxygen anion (-O - Examples of substructures containing ) include oxygen anions (-O - ) is preferably directly bonded to the end of the repeating structure that is attached to n, m, p, or q in the repeating unit represented by formulas (1) to (4), and in the repeating unit represented by formula (1), the end of the repeating structure that is attached to n (i.e., -(-OC j H 2j -CO-) n It is more preferable that it is directly connected to the rightmost (of -). Examples of cations in the cation portion of a group containing an onium structure include ammonium cations. When the cation portion is an ammonium cation, the cation portion is a cationic nitrogen atom (>N). + This is a substructure containing a cationic nitrogen atom (>N).+ <) is preferably bonded to four substituents (preferably organic groups), and among them, 1 to 4 are preferably alkyl groups having 1 to 15 carbon atoms. Further, it is also preferable that one or more (preferably one) of the four substituents is a group containing a curable group such as a (meth)acryloyl group, an epoxy group, and / or an oxetanyl group. Examples of the group containing the curable group that the above substituent can be include, for example, the above-mentioned "-O-alkylene group-(-O-alkylene group-) AL -(meth)acryloyloxy group".

[0098] In formulas (1) to (4), n, m, p, and q are each independently an integer of 1 to 500. Further, in formulas (1) and (2), j and k each independently represent an integer of 2 to 8. In formulas (1) and (2), j and k are preferably integers of 4 to 6, and more preferably 5. Further, in formulas (1) and (2), n and m are, for example, integers of 2 or more, preferably integers of 6 or more, more preferably integers of 10 or more, and still 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 the polyvalerolactone is preferably an integer of 10 or more, and more preferably an integer of 20 or more.

[0099] In formula (3), R 3 represents a branched or linear alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms. When p is 2 to 500, a plurality of Rs 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 substituent 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. R 4When it is an alkyl group, as the alkyl group, 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 is preferable, a linear alkyl group having 1 to 20 carbon atoms is more preferable, and a linear alkyl group having 1 to 6 carbon atoms is even more preferable. In formula (4), when q is 2 to 500, a plurality of X present in the graft chain 5 and R 4 may be the same as or different from each other.

[0100] Further, the resin A may contain repeating units containing graft chains having two or more different structures. That is, the molecule of the 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 different structures from each other, and in formulas (3) and (4), a plurality of R present in the molecule 3 、R 4 、and X 5 may be the same as or different from each other.

[0101] As the repeating unit represented by formula (1), a repeating unit represented by the following formula (1A) is more preferable. Further, as the repeating unit represented by formula (2), a repeating unit represented by the following formula (2A) is more preferable.

[0102]

Chemical formula

[0103] In formula (1A), X 1 、Y 1 、Z 1 、and n are synonymous with 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 is X in equation (2). 2 , Y 2 , Z 2 , and are synonymous with m, and the preferred range is also the same.

[0104] Furthermore, the repeating unit represented by formula (3) is more preferably the repeating unit represented by formula (3A) or formula (3B) below.

[0105] [ka]

[0106] In equation (3A) or (3B), X 3 , Y 3 , Z 3 , and p is X in equation (3). 3 , Y 3 , Z 3 , and are synonymous with p, and the preferred range is also similar.

[0107] Resin A more preferably contains repeating units represented by formula (1A) as repeating units including graft chains.

[0108] Furthermore, it is preferable that resin A includes repeating units comprising a polyalkyleneimine structure and a polyester structure. In the repeating units comprising a polyalkyleneimine structure and a polyester structure, it is preferable that the main chain contains a polyalkyleneimine structure and the graft chain contains a polyester structure.

[0109] The above polyalkyleneimine structure is a polymerized structure containing two or more identical or different alkyleneimine chains. Specifically, examples of alkyleneimine chains include those represented by the following formulas (4A) and (4B).

[0110] [ka]

[0111] In formula (4A), R X1 and R X2 Each of these independently represents either a hydrogen atom or an alkyl group. 1 * represents an integer greater than or equal to 2. 1 The symbol represents the bond position with the polyester chain, the adjacent alkyleneimine chain, or a hydrogen atom or substituent.

[0112] [ka]

[0113] In formula (4B), R X3 and R X4 Each of these independently represents a hydrogen atom or an alkyl group. 2 represents an integer greater than or equal to 2. The alkyleneimine chain represented by formula (4B) consists of a polyester chain having an anionic group and the N specified in formula (4B). + The anionic groups contained in the polyester chain bond together by forming salt crosslinking groups.

[0114] * in equations (4A) and (4B), and * in equation (4B) 2 Each of these independently represents a position where the atom bonds to an adjacent alkylene imine chain, or to a hydrogen atom or substituent. In formulas (4A) and (4B), * preferably represents a position where the molecule binds to an adjacent alkylene imine chain.

[0115] R in equation (4A) X1 and R X2 , and R in equation (4B) X3 and R X4 Each of these independently represents either a hydrogen atom or an alkyl group. The alkyl group preferably has 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms. In formula (4A), R X1 and R X2 Preferably, all of these are hydrogen atoms. In formula (4B), R X3 and R X4Preferably, all of them are hydrogen atoms.

[0116] a in formula (4A) 1 and a in formula (4B) 2 There is no particular limitation as long as it is an integer of 2 or more. As the upper limit value, 10 or less is preferable, 6 or less is more preferable, 4 or less is still more preferable, 2 or 3 is still more preferable, and 2 is particularly preferable.

[0117] In formula (4A) and formula (4B), * represents the position of bonding to an adjacent alkyleneimine chain, a hydrogen atom, or a substituent. Examples of the above-mentioned substituent include substituents such as an alkyl group (for example, an alkyl group having 1 to 6 carbon atoms). Further, a polyester chain may be bonded as the substituent.

[0118] 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 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 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. Examples of the above-mentioned polyester chain include a polyester chain represented by the following formula (5A).

[0119]

Chemical formula

[0120] 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).

[0121]

Chemical formula

[0122] L in equation (5A) X1 , and L in equation (5B) X2 Each of these independently represents a divalent linking group. Preferably, the divalent linking group is an alkylene group having 3 to 30 carbon atoms.

[0123] b in equation (5A) 11 , and b in equation (5B) 21 Each of these independently represents an integer of 2 or more, preferably an integer of 6 or more, with an upper limit of, for example, 200 or less.

[0124] b in equation (5A) 12 , and b in equation (5B) 22 Each of these independently represents either 0 or 1.

[0125] X in equation (5A) A , and X in equation (5B) B Each of these independently represents a hydrogen atom or a substituent. Examples of substituents include alkyl groups, alkoxy groups, polyalkylene oxyalkyl groups, and aryl groups.

[0126] The alkyl group (which may be linear, branched, or cyclic) and the alkyl group contained in the alkoxy group (which may be linear, branched, or cyclic) may have 1 to 30 carbon atoms, with 1 to 10 being preferred. The alkyl group may also have further substituents, and examples of substituents include hydroxyl groups and halogen atoms (such as fluorine, chlorine, bromine, and iodine atoms).

[0127] Polyalkylene oxyalkyl groups are R X6 (OR X7 ) p (O) q - is a substituent represented by R X6 represents an alkyl group, R X7 represents an alkylene group, p represents an integer greater than or equal to 2, and q represents 0 or 1. RX6 The alkyl group represented by X A It is synonymous with the alkyl group represented by . Also, R X7 The alkylene group represented by X A An example is a group obtained by removing one hydrogen atom from an alkyl group represented by . p is an integer greater than or equal to 2, and its upper limit is, for example, 10 or less, preferably 5 or less.

[0128] Examples of aryl groups include aryl groups having 6 to 24 carbon atoms (which may be monocyclic or polycyclic). The above aryl group may have further substituents, such as alkyl groups, halogen atoms, and cyano groups.

[0129] The polyester chains described above are preferably structures in which lactones such as ε-caprolactone, δ-caprolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone, γ-valerolactone, enantractone, β-butyrolactone, γ-hexanolactone, γ-octanolactone, δ-hexalanolactone, δ-octanolactone, δ-dodecanolactone, α-methyl-γ-butyrolactone, and lactide (which may be the L or D form) are opened, and structures in which ε-caprolactone or δ-valerolactone are opened are more preferred.

[0130] The repeating units containing the polyalkylene imine structure and polyester structure described above can be synthesized according to the synthesis method described in Japanese Patent No. 5923557.

[0131] In resin A, the content of repeating units including graft chains is, for example, 2 to 100% by mass, preferably 2 to 95% by mass, more preferably 2 to 90% by mass, and even more preferably 5 to 30% by mass, based on the total mass of resin A. The effects of the present invention are better when the repeating units including graft chains are included within this range.

[0132] (Hydrophobic repeating unit) Furthermore, resin A may contain hydrophobic repeating units that are different from (i.e., do not correspond to) repeating units containing graft chains. However, in this specification, hydrophobic repeating units are repeating units that do not have acidic groups (e.g., carboxylic acid groups, sulfonic acid groups, phosphate groups, phenolic hydroxyl groups, etc.).

[0133] The hydrophobic repeating units are preferably repeating units derived from (corresponding to) compounds (monomers) with a ClogP value of 1.2 or higher, and more preferably repeating units derived from compounds with a ClogP value of 1.2 to 8. This allows the effects of the present invention to be more reliably expressed.

[0134] The ClogP value is calculated using the "CLOGP" program available from Daylight Chemical Information System, Inc. This program provides a "calculated logP" value derived from the fragment approach by Hansch, Leo (see reference below). The fragment approach is based on the chemical structure of a compound, dividing the chemical structure into substructures (fragments) and estimating the compound's logP value by summing the logP contributions assigned to each fragment. Details are described in the following reference. In this specification, we use ClogP values ​​calculated using the CLOGP v4.82 program. 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.

[0135] logP represents the common logarithm of the partition coefficient P, which is a physical property value that quantitatively represents how an organic compound is distributed at the equilibrium of a two-phase system of oil (generally 1-octanol) and water, and is expressed by the following formula. logP = log(Coil / Cwater) In the formula, Coil represents the molar concentration of the compound in the oil phase, and Cwater represents the molar concentration of the compound in the water phase. When the value of logP is between 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.

[0136] Resin A preferably contains, as hydrophobic repeating units, one or more repeating units selected from the repeating units derived from the monomers represented by the following formulas (i) to (iii).

[0137]

Chemical formula

[0138] In the above formulas (i) to (iii), R 1 , R 2 , and, R3 Each of these independently represents a hydrogen atom, a halogen atom (e.g., fluorine atom, chlorine atom, and bromine atom), or an alkyl group having 1 to 6 carbon atoms (e.g., methyl group, ethyl group, and propyl group). R 1 , R 2 , and R 3 R is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group. 2 and R 3 It is even more preferable that it be a hydrogen atom. X represents either an oxygen atom (-O-) or an imino group (-NH-), with the oxygen atom being preferred.

[0139] L is a single bond or a divalent linking group. Examples of divalent linking groups include divalent aliphatic groups (e.g., alkylene groups, substituted alkylene groups, alkenylene groups, substituted alkenylene groups, alkynylene groups, substituted alkynylene groups), divalent aromatic groups (e.g., arylene groups, substituted arylene groups), divalent heterocyclic groups, oxygen atoms (-O-), sulfur atoms (-S-), imino groups (-NH-), and substituted imino groups (-NR-). 31 -, here R 31 Examples include aliphatic groups, aromatic groups, or heterocyclic groups, carbonyl groups (-CO-), and combinations thereof.

[0140] The divalent aliphatic group may have a cyclic or branched structure. The number of carbon atoms in the aliphatic group is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 10. The aliphatic group may be unsaturated or saturated, but saturated aliphatic groups are preferred. The aliphatic group may also have substituents. Examples of substituents include halogen atoms, aromatic groups, and heterocyclic groups.

[0141] The number of carbon atoms in the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and even more preferably 6 to 10. The aromatic group may also have substituents. Examples of substituents include halogen atoms, aliphatic groups, aromatic groups, and heterocyclic groups.

[0142] The divalent heterocyclic group preferably contains a five-membered or six-membered ring as the heterocycle. Another heterocycle, aliphatic ring, or aromatic ring may be fused to the heterocycle. The heterocyclic group may also have substituents. Examples of substituents include halogen atoms, hydroxyl groups, oxo groups (=O), thioxo groups (=S), imino groups (=NH), and substituted imino groups (=NR). 32 Here, R 32 Examples include aliphatic groups, aromatic groups, or heterocyclic groups.

[0143] L is preferably a divalent linking group containing a single bond, an alkylene group, or an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. L may also contain a polyoxyalkylene structure containing two or more repeating oxyalkylene structures. The polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure. The polyoxyethylene structure is represented as -(OCH2CH2)n-, where n is preferably an integer of 2 or more, and more preferably an integer from 2 to 10.

[0144] Examples of Z include aliphatic groups (e.g., alkyl groups, substituted alkyl groups, unsaturated alkyl groups, substituted unsaturated alkyl groups), aromatic groups (e.g., aryl groups, substituted aryl groups, arylene groups, substituted arylene groups), heterocyclic groups, and combinations thereof. These groups include oxygen atoms (-O-), sulfur atoms (-S-), imino groups (-NH-), substituted imino groups (-NR-). 31 -, here R 31 The group may contain an aliphatic group, an aromatic group, or a heterocyclic group, or a carbonyl group (-CO-).

[0145] Aliphatic groups may have a cyclic or branched structure. The number of carbon atoms in the aliphatic group is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 10. Aliphatic groups further include ring-assembled hydrocarbon groups and crosslinked cyclic hydrocarbon groups. Examples of ring-assembled hydrocarbon groups include bicyclohexyl groups, perhydronaphthalenyl groups, biphenyl groups, and 4-cyclohexylphenyl groups. Examples of crosslinked cyclic hydrocarbon rings include bicyclic hydrocarbon rings such as pinane, bornane, norpinane, norbornane, bicyclooctane rings (bicyclo[2.2.2]octane rings and bicyclo[3.2.1]octane rings, etc.), homobredan, adamantane, and tricyclo[5.2.1.0 2,6 ] Decane and tricyclo[4.3.1.1 2,5 ]Tricyclic hydrocarbon rings such as undecane rings, and tetracyclo[4.4.0.1 2,5 .1 7,10 Examples include dodecane and tetracyclic hydrocarbon rings such as the perhydro-1,4-methano-5,8-methanonaphthalene ring. Bridged cyclic hydrocarbon rings also include condensed cyclic hydrocarbon rings, such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and perhydrophenalene rings, which are condensed rings formed by the fusion of multiple 5-8 membered cycloalkane rings. A saturated aliphatic group is preferred over an unsaturated aliphatic group. The aliphatic group may also have substituents. Examples of substituents include halogen atoms, aromatic groups, and heterocyclic groups. However, the aliphatic group does not have an acidic group as a substituent.

[0146] The aromatic group has 6 to 20 carbon atoms, more preferably 6 to 15, and even more preferably 6 to 10. The aromatic group may also have substituents. Examples of substituents include halogen atoms, aliphatic groups, aromatic groups, and heterocyclic groups. However, the aromatic group does not have an acid group as a substituent.

[0147] The heterocyclic group preferably includes a 5-membered or 6-membered ring as the heterocycle. Other heterocycles, aliphatic rings, or aromatic rings may be fused to the heterocycle. The heterocyclic group may also have substituents. Examples of substituents include halogen atoms, hydroxyl groups, oxo groups (=O), thioxo groups (=S), imino groups (=NH), and substituted imino groups (=NR). 32 Here, R 32 Examples include aliphatic groups, aromatic groups, or heterocyclic groups. However, heterocyclic groups do not have acidic groups as substituents.

[0148] In the above formula (iii), R 4 , R 5 , and R 6 Each of these independently represents a hydrogen atom, a halogen atom (e.g., fluorine, chlorine, and bromine), an alkyl group with 1 to 6 carbon atoms (e.g., methyl, ethyl, and propyl groups), Z, or LZ. Here, L and Z are synonymous with the groups described above. 4 , R 5 , and R 6 Preferably, the element is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.

[0149] As the monomer represented by the above formula (i), R 1 , R 2 , and R 3 A compound is preferred in which is a hydrogen atom or a methyl group, L is a divalent linking group containing a single bond or an alkylene group or oxyalkylene structure, X is an oxygen atom or an imino group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group. Furthermore, as a monomer represented by the above formula (ii), R 1 A compound in which is a hydrogen atom or a methyl group, L is an alkylene group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group is preferred. Also, as the monomer represented by the above formula (iii), R 4 , R 5 , and R 6 A compound in which is a hydrogen atom or a methyl group and Z is an aliphatic group, a heterocyclic group, or an aromatic group is preferred.

[0150] Representative compounds represented by formulas (i) to (iii) include radical polymerizable compounds selected from acrylic acid esters, methacrylic acid esters, and styrenes. For examples of representative compounds represented by formulas (i) to (iii), refer to the compounds described in paragraphs 0089 to 0093 of Japanese Patent Publication No. 2013-249417, and the contents of these are incorporated herein by reference.

[0151] In resin A, the content of hydrophobic repeating units is preferably 10 to 90% by mass, and more preferably 20 to 80% by mass, relative to the total mass of resin A.

[0152] (Functional groups that can form interactions with magnetic particles) Resin A may have functional groups that can form interactions with magnetic particles. Resin A preferably further comprises repeating units containing functional groups that can form interactions with magnetic particles. Examples of functional groups that can form interactions with magnetic particles include acidic groups, basic groups, coordinating groups, and reactive functional groups. If resin A contains acidic groups, basic groups, coordinating groups, or reactive functional groups, it is preferable that it contains repeating units containing acidic groups, repeating units containing basic groups, repeating units containing coordinating groups, or repeating units having reactive functional groups, respectively.

[0153] The repeating unit containing the acid group may be the same as the repeating unit containing the graft chain described above, or it may be a different repeating unit, but the repeating unit containing the acid group is a different repeating unit from the hydrophobic repeating unit described above (i.e., it does not correspond to the hydrophobic repeating unit described above).

[0154] Examples of acidic groups that can form interactions with magnetic particles include carboxylic acid groups, sulfonic acid groups, phosphoric acid groups, and phenolic hydroxyl groups. At least one of the carboxylic acid group, sulfonic acid group, and phosphoric acid group is preferred, with the carboxylic acid group being more preferred. Carboxylic acid groups have good adsorption to magnetic particles and high dispersibility. In other words, it is preferable that resin A further contains repeating units comprising at least one of a carboxylic acid group, a sulfonic acid group, and a phosphate group.

[0155] Resin A may have one or more repeating units containing acid groups. If resin A contains repeating units containing acid groups, the content is preferably 5 to 80% by mass, and more preferably 10 to 60% by mass, relative to the total mass of resin A.

[0156] Examples of basic groups that can form interactions with magnetic particles include primary amino groups, secondary amino groups, tertiary amino groups, heterocycles containing N atoms, and amide groups. The preferred basic group is the tertiary amino group because it has good adsorption to magnetic particles and high dispersibility. Resin A may contain one or more of these basic groups. If resin A contains repeating units containing basic groups, the content thereof is preferably 0.01 to 50% by mass, and more preferably 0.01 to 30% by mass, relative to the total mass of resin A.

[0157] Examples of coordinating groups and reactive functional groups that can interact with magnetic particles include acetylacetoxy groups, trialkoxysilyl groups, isocyanate groups, acid anhydrides, and acid chlorides. The preferred functional group is the acetylacetoxy group, which has good adsorption to magnetic particles and high dispersibility of magnetic particles. Resin A may have one or more of these groups. If resin A contains repeating units containing coordinating groups or repeating units containing reactive functional groups, the content of these is preferably 10 to 80% by mass, and more preferably 20 to 60% by mass, relative to the total mass of resin A.

[0158] If the above resin A contains functional groups that can interact with magnetic particles in addition to graft chains, it is sufficient that it contains functional groups that can interact with the various magnetic particles mentioned above, and there are no particular restrictions on how these functional groups are introduced. For example, it is preferable that the resin contained in the composition contains one or more repeating units selected from repeating units derived from monomers represented by the following formulas (iv) to (vi).

[0159] [ka]

[0160] In formulas (iv) to (vi), R 11 , R 12 , and R 13 Each of these independently represents a hydrogen atom, a halogen atom (e.g., fluorine atom, chlorine atom, and bromine atom), or an alkyl group having 1 to 6 carbon atoms (e.g., methyl group, ethyl group, and propyl group). In formulas (iv) to (vi), R 11 , R 12 , and R 13 As such, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferred, and a hydrogen atom or a methyl group is more preferred. In general formula (iv), R 12 and R 13 Hydrogen atoms are even more preferable.

[0161] In formula (iv), X1 represents an oxygen atom (-O-) or an imino group (-NH-), with the oxygen atom being preferred. Furthermore, Y in formula (v) represents either a methine group or a nitrogen atom.

[0162] Furthermore, L1 in formulas (iv) to (v) represents a single bond or a divalent linking group. The definition of a divalent linking group is the same as the definition of a divalent linking group represented by L in formula (i) above.

[0163] L1 is preferably a divalent linking group containing a single bond, an alkylene group, or an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. L1 may also contain a polyoxyalkylene structure containing two or more repeating oxyalkylene structures. The polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure. The polyoxyethylene structure is represented as -(OCH2CH2)n-, where n is preferably an integer of 2 or more, and more preferably an integer between 2 and 10.

[0164] In formulas (iv) to (vi), Z1 represents a functional group that can interact with magnetic particles in addition to the graft chain, and is preferably a carboxylic acid group or a tertiary amino group, with a carboxylic acid group being more preferred.

[0165] In formula (vi), R 14 , R 15 , and R 16 Each of these independently represents a hydrogen atom, a halogen atom (e.g., a fluorine atom, a chlorine atom, and a bromine atom), an alkyl group having 1 to 6 carbon atoms (e.g., a methyl group, an ethyl group, and a propyl group), -Z1, or L1-Z1. Here, L1 and Z1 are synonymous with L1 and Z1 above, and the preferred examples are similar. 14 , R 15 , and R 16 Preferably, the element is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.

[0166] As a monomer represented by equation (iv), R 11 , R 12 , and R 13A compound is preferred in which each of the following is independently a hydrogen atom or a methyl group, L1 is a divalent linking group containing an alkylene group or an oxyalkylene structure, X1 is an oxygen atom or an imino group, and Z1 is a carboxylic acid group. Furthermore, as a monomer represented by equation (v), R 11 A compound in which is a hydrogen atom or a methyl group, L1 is an alkylene group, Z1 is a carboxylic acid group, and Y is a methine group is preferred. Furthermore, as a monomer represented by equation (vi), R 14 , R 15 , and R 16 A compound in which each of the elements is independently a hydrogen atom or a methyl group, and Z1 is a carboxylic acid group, is preferred.

[0167] The following are representative examples of monomers (compounds) represented by formulas (iv) to (vi). Examples of monomers include methacrylic acid, crotonic acid, isocrotonic acid, reaction products of compounds containing an addition-polymerizable double bond and a hydroxyl group in the molecule (e.g., 2-hydroxyethyl methacrylate) with succinic anhydride, reaction products of compounds containing an addition-polymerizable double bond and a hydroxyl group in the molecule with phthalic anhydride, reaction products of compounds containing an addition-polymerizable double bond and a hydroxyl group in the molecule with tetrahydroxyphthalic anhydride, reaction products of compounds containing an addition-polymerizable double bond and a hydroxyl group in the molecule with trimellitic anhydride, reaction products of compounds containing an addition-polymerizable double bond and a hydroxyl group in the molecule with pyromellitic anhydride, acrylic acid, acrylate dimer, acrylate oligomer, maleic acid, itaconic acid, fumaric acid, 4-vinylbenzoic acid, vinylphenol, and 4-hydroxyphenylmethacrylamide.

[0168] The content of repeating units containing functional groups that can form interactions with magnetic particles is preferably 0.05 to 90% by mass, more preferably 1.0 to 80% by mass, and even more preferably 10 to 70% by mass, relative to the total mass of resin A, from the viewpoint of interaction with magnetic particles, stability over time, and permeability to the developing solution.

[0169] (ethylenically unsaturated group) Resin A may contain ethylenically unsaturated groups. The ethylenically unsaturated group is not particularly limited, but examples include (meth)acryloyl, vinyl, and styryl groups, with (meth)acryloyl being preferred. Among resins A, it is preferable that the resin A contains repeating units with ethylenically unsaturated groups in the side chains, and more preferably that the resin A contains repeating units with ethylenically unsaturated groups in the side chains and that are derived from (meth)acrylate (hereinafter also referred to as "(meth)acrylic repeating units with ethylenically unsaturated groups in the side chains"). (Meth)acrylic repeating units containing ethylenically unsaturated groups in their side chains can be obtained, for example, by adding an ethylenically unsaturated compound containing a glycidyl group or an alicyclic epoxy group to the carboxylic acid group in resin A, which contains a (meth)acrylic repeating unit containing a carboxylic acid group. By reacting the ethylenically unsaturated group (glycidyl group or alicyclic epoxy group) introduced in this way, (meth)acrylic repeating units containing ethylenically unsaturated groups in their side chains can be obtained.

[0170] If resin A contains repeating units containing ethylenically unsaturated groups, the content of these units is preferably 30 to 70% by mass, and more preferably 40 to 60% by mass, relative to the total mass of resin A.

[0171] (Other curing groups) Resin A may contain other curable groups in addition to ethylenically unsaturated groups. Other curable groups include, for example, epoxy groups and oxetanyl groups. Among resin A, it is preferable that it contains repeating units with other curable groups in the side chains, and more preferably that it contains repeating units with other curable groups in the side chains and derived from (meth)acrylate (hereinafter also referred to as "(meth)acrylic repeating units with other curable groups in the side chains"). Examples of (meth)acrylic repeating units containing other curable groups in the side chain include glycidyl (meth)acrylate.

[0172] If resin A contains repeating units that include other curable groups, the content of these units is preferably 5 to 50% by mass, and more preferably 10 to 30% by mass, relative to the total mass of resin A.

[0173] (Other repeating units) Furthermore, resin A may have other repeating units having various functions different from the repeating units described above, in order to improve various properties such as film-forming ability, provided that the effects of the present invention are not impaired. Other examples of such repeating units include repeating units derived from radical polymerizable compounds selected from acrylonitriles and methacrylonitriles. Resin A may use one or more of these other repeating units, and the content thereof is preferably 0 to 80% by mass, and more preferably 10 to 60% by mass, relative to the total mass of resin A.

[0174] (Physical properties of resin A) The acid value of resin A is not particularly limited, but for example, 0 to 400 mg KOH / g is preferred, 10 to 350 mg KOH / g is more preferred, 30 to 300 mg KOH / g is even more preferred, and the range of 50 to 200 mg KOH / g is particularly preferred. If the acid value of resin A is 50 mgKOH / g or higher, the sedimentation stability of magnetic particles can be further improved.

[0175] In this specification, the acid value can be calculated, for example, from the average content of acid groups in the compound. Furthermore, a resin having a desired acid value can be obtained by changing the content of repeating units containing acid groups in the resin.

[0176] The weight-average molecular weight of resin A is not particularly limited, but for example, it is preferably 3,000 or more, more preferably 4,000 or more, even more preferably 5,000 or more, and particularly preferably 6,000 or more. As for the upper limit, for example, it is preferably 300,000 or less, more preferably 200,000 or less, even more preferably 100,000 or less, and particularly preferably 50,000 or less. Resin A can be synthesized based on known methods.

[0177] For specific examples of resin A, refer to the polymer compounds described in paragraphs 0127 to 0129 of Japanese Patent Publication No. 2013-249417, and the contents of these are incorporated herein.

[0178] Furthermore, as resin A, graft copolymers described in paragraphs 0037 to 0115 of Japanese Patent Application Publication No. 2010-106268 (corresponding to columns 0075 to 0133 of US2011 / 0124824) can also be used, and the contents of these can be incorporated herein by reference.

[0179] <Alkali-soluble resin> Other resins may include alkali-soluble resins. In this specification, "alkali-soluble resin" means a resin containing a group that promotes alkali solubility (alkali-soluble group, such as an acidic group like a carboxylic acid group), and means a resin different from resin A described above.

[0180] Examples of alkali-soluble resins include resins containing at least one alkali-soluble group in their molecule, such as polyhydroxystyrene resins, polysiloxane resins, (meth)acrylic resins, (meth)acrylamide resins, (meth)acrylic / (meth)acrylamide copolymers, epoxy resins, and polyimide resins.

[0181] Specific examples of alkali-soluble resins include copolymers of unsaturated carboxylic acids and ethylenically unsaturated compounds. The unsaturated carboxylic acids are not particularly limited, but examples include monocarboxylic acids such as (meth)acrylic acid, crotonic acid, and vinylacetic acid; dicarboxylic acids such as itaconic acid, maleic acid, and fumaric acid, or their acid anhydrides; and polycarboxylic acid monoesters such as phthalic acid mono(2-(meth)acryloyloxyethyl); and the like.

[0182] Examples of copolymerizable ethylenically unsaturated compounds include methyl (meth)acrylate. Compounds described in paragraph 0027 of Japanese Patent Publication No. 2010-97210 and paragraphs 0036-0037 of Japanese Patent Publication No. 2015-68893 can also be used, and the above information is incorporated herein.

[0183] Furthermore, copolymerizable ethylenically unsaturated compounds containing ethylenically unsaturated groups in their side chains may be used in combination. In other words, alkali-soluble resins may contain repeating units with ethylenically unsaturated groups in their side chains. The preferred ethylenically unsaturated group in the side chain is the (meth)acrylic acid group. Repeating units containing ethylenically unsaturated groups in their side chains can be obtained, for example, by adding an ethylenically unsaturated compound containing a glycidyl group or an alicyclic epoxy group to a carboxylic acid group in a (meth)acrylic repeating unit containing a carboxylic acid group.

[0184] As for alkali-soluble resins, alkali-soluble resins containing curable groups are also preferred. Examples of the curable groups mentioned above include, but are not limited to, ethylenically unsaturated groups (e.g., (meth)acryloyl groups, vinyl groups, and styryl groups) and cyclic ether groups (e.g., epoxy groups, oxetanyl groups). In particular, ethylenically unsaturated groups are preferred as curable groups, and (meth)acryloyl groups are more preferred, as they allow polymerization control via radical reactions. As alkali-soluble resins containing curable groups, alkali-soluble resins having curable groups in their side chains are preferred. Examples of alkali-soluble resins containing curable groups include the Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing polyurethane acrylic oligomer, manufactured by Diamond Shamrock Co., Ltd.), Viscoat R-264, KS Resist 106 (both manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series (e.g., ACA230AA), Praxel CF200 series (both manufactured by Daicel Corporation), Ebecryl 3800 (manufactured by Daicel Ornex Co., Ltd.), and Acrycure RD-F8 (manufactured by Nippon Shokubai Co., Ltd.).

[0185] Examples of alkali-soluble resins include radical polymers containing carboxylic acid groups in the side chains described in Japanese Patent Publication No. 59-44615, Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577, Japanese Patent Publication No. 54-25957, Japanese Patent Publication No. 54-92723, Japanese Patent Publication No. 59-53836, and Japanese Patent Publication No. 59-71048; European Patent No. 993966, European Patent No. 1204000, and Japanese Patent Publication No. 200 Acetal-modified polyvinyl alcohol-based binder resin containing alkali-soluble groups as described in Publication No. 1-318463; polyvinylpyrrolidone; polyethylene oxide; alcohol-soluble nylon; and polyethers, etc., which are reaction products of 2,2-bis-(4-hydroxyphenyl)-propane and epichlorohydrin; as well as polyimide resins as described in International Publication No. 2008 / 123097; etc. can be used.

[0186] As alkali-soluble resins, for example, compounds described in paragraphs 0225 to 0245 of Japanese Patent Publication No. 2016-75845 can also be used, and the above content is incorporated herein.

[0187] Polyimide precursors can also be used as alkali-soluble resins. A polyimide precursor refers to a resin obtained by an addition polymerization reaction between a compound containing an acid anhydride group and a diamine compound at 40-100°C. Specific examples of the above polyimide precursors include, for example, the compounds described in paragraphs 0011 to 0031 of Japanese Patent Publication No. 2008-106250, the compounds described in paragraphs 0022 to 0039 of Japanese Patent Publication No. 2016-122101, the compounds described in paragraphs 0061 to 0092 of Japanese Patent Publication No. 2016-68401, the resin described in paragraph 0050 of Japanese Patent Publication No. 2014-137523, the resin described in paragraph 0058 of Japanese Patent Publication No. 2015-187676, and the resin described in paragraphs 0012 to 0013 of Japanese Patent Publication No. 2014-106326, and the above contents are incorporated herein by reference.

[0188] As alkali-soluble resins, copolymers of [benzyl (meth)acrylate / (meth)acrylic acid / other addition polymerizable vinyl monomers as needed] and [allyl (meth)acrylate / (meth)acrylic acid / other addition polymerizable vinyl monomers as needed] are preferred because they offer an excellent balance of film strength, sensitivity, and developability. The above-mentioned other addition polymerizable vinyl monomers may be one type or two or more types. The above copolymer preferably has a curable group, and more preferably contains an ethylenically unsaturated group such as a (meth)acryloyl group, as this provides superior moisture resistance to the cured film. For example, a monomer having a curable group may be used as the other addition polymerizable vinyl monomer mentioned above to introduce a curable group into the copolymer. Alternatively, a curable group (preferably an ethylenically unsaturated group such as a (meth)acryloyl group) may be introduced into some or all of one or more units derived from (meth)acrylic acid and / or the other addition polymerizable vinyl monomer in the copolymer. Examples of other addition polymerizable vinyl monomers include methyl (meth)acrylate, styrene monomers (such as hydroxystyrene), and ether dimers. Examples of the ether dimers mentioned above include compounds represented by the following general formula (ED1) and compounds represented by the following general formula (ED2).

[0189] [ka]

[0190] In general formula (ED1), R 1 and R 2 Each of these independently represents either a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms.

[0191] [ka]

[0192] In general formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. For specific examples of general formula (ED2), refer to the description in Japanese Patent Publication No. 2010-168539.

[0193] For specific examples of ether dimers, see, for example, paragraph 0317 of Japanese Patent Publication No. 2013-29760, which is incorporated herein by reference. The ether dimer may be one type or two or more types.

[0194] The acid value of the alkali-soluble resin is not particularly limited, but generally, 30 to 500 mg KOH / g is preferred, and 50 to 200 mg KOH / g or more is more preferred.

[0195] If 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 even more preferably 1 to 20% by mass, based on the total mass of the composition. If the composition contains an alkali-soluble resin, the content of the alkali-soluble resin is preferably 0.1 to 40% by mass, more preferably 0.5 to 30% by mass, and even more preferably 1 to 20% by mass, based on the total solid content of the composition.

[0196] [Polymerizable compound] The composition of the present invention may also contain polymerizable compounds as components different from those described above.

[0197] The polymerizable compound content is preferably 1 to 35% by mass, more preferably 1 to 30% by mass, and even more preferably 3 to 27% by mass, based on the total mass of the composition. The polymerizable compound content is preferably 1 to 35% by mass, more preferably 1 to 30% by mass, and even more preferably 3 to 27% 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.

[0198] <Compounds containing groups with ethylenically unsaturated bonds> Polymerizable compounds include, for example, compounds containing a group that includes an ethylenically unsaturated bond (hereinafter also simply referred to as an "ethylenically unsaturated group"). In other words, the composition of the present invention preferably contains a low molecular weight compound containing an ethylenically unsaturated group as a polymerizable compound. The polymerizable compounds described above are preferably compounds containing one or more ethylenically unsaturated bonds, more preferably compounds containing two or more, even more preferably compounds containing three or more, and particularly preferably compounds containing five or more. The upper limit is, for example, 15 or less. Examples of ethylenically unsaturated groups include vinyl groups, (meth)allyl groups, and (meth)acryloyl groups.

[0199] As the polymerizable compounds mentioned above, for example, the compounds described in paragraph 0050 of Japanese Patent Publication No. 2008-260927 and paragraph 0040 of Japanese Patent Publication No. 2015-68893 can be used, and the above contents are incorporated herein.

[0200] The polymerizable compound may be in any chemical form, such as monomers, prepolymers, oligomers, mixtures thereof, or polymers thereof. The polymerizable compound is preferably a (meth)acrylate compound with 3 to 15 functions, and more preferably a (meth)acrylate compound with 3 to 6 functions.

[0201] The polymerizable compounds described above are also preferably compounds 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 Japanese Patent Publication No. 2013-29760 and paragraphs 0254-0257 of Japanese Patent Publication No. 2008-292970 can be referenced, and this information is incorporated herein.

[0202] The polymerizable compounds described above are preferably dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH-12E; manufactured by Shin Nakamura Chemical Co., Ltd.), and structures in which the (meth)acryloyl group of these compounds is mediated by an ethylene glycol residue or a propylene glycol residue (for example, SR454 and SR499, commercially available from Sartomer). These oligomer types can also be used. In addition, NK ester A-TMMT (pentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD RP-1040, KAYARAD DPEA-12LT, KAYARAD DPHA LT, KAYARAD RP-3060, and KAYARAD DPEA-12 (all trade names, manufactured by Nippon Kayaku Co., Ltd.) may also be used.

[0203] The polymerizable compounds described above may have acidic groups such as carboxylic acid groups, sulfonic acid groups, and phosphoric acid groups. Preferably, the polymerizable compounds containing acidic groups are esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids. More preferably, the polymerizable compounds are obtained by reacting the unreacted hydroxyl groups of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to give it an acidic group. In this ester, compounds in which the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol are even more preferred. Examples of commercially available products include Aronics TO-2349, M-305, M-510, and M-520 from Toagosei Co., Ltd.

[0204] The acid value of the polymerizable compound containing the acid group is preferably 0.1 to 40 mg KOH / g, and more preferably 5 to 30 mg KOH / g. If the acid value of the polymerizable compound is 0.1 mg KOH / g or higher, the development and dissolution characteristics are good, and if it is 40 mg KOH / g or lower, it is advantageous in terms of manufacturing and / or handling. Furthermore, it exhibits good photopolymerization performance and excellent curability.

[0205] The polymerizable compound described above may also contain a caprolactone structure, which is a preferred embodiment. Compounds containing a caprolactone structure are not particularly limited as long as they contain a caprolactone structure within the molecule, but examples include ε-caprolactone-modified polyfunctional (meth)acrylates obtained by esterifying polyhydric alcohols such as trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, or trimethylolmelamine with (meth)acrylic acid and ε-caprolactone. Among these, compounds containing a caprolactone structure represented by the following formula (Z-1) are preferred.

[0206] [ka]

[0207] In equation (Z-1), all six Rs are groups represented by equation (Z-2) below, or 1 to 5 of the six Rs are groups represented by equation (Z-2) below, and the remainder are groups represented by equation (Z-3) below.

[0208] [ka]

[0209] In formula (Z-2), R 1 The symbol (*) indicates a hydrogen atom or a methyl group, m indicates a number (1 or 2), and "*" indicates a bond.

[0210] [ka]

[0211] In formula (Z-3), R 1 * indicates a hydrogen atom or a methyl group, and * indicates a bonding bond.

[0212] The polymerizable compounds containing the caprolactone structure are commercially available, for example, from Nippon Kayaku as the KAYARAD DPCA series, such as DPCA-20 (where m=1 in formulas (Z-1) to (Z-3) above, the number of groups represented by formula (Z-2) = 2, R 1 (A compound in which all atoms are hydrogen atoms), DPCA-30 (same formula, m=1, number of groups represented by formula (Z-2) = 3, R 1 (A compound in which all atoms are hydrogen atoms), DPCA-60 (same formula, m=1, number of groups represented by formula (Z-2) = 6, R 1 Compounds in which all atoms are hydrogen atoms), and DPCA-120 (in the same formula, m=2, the number of groups represented by formula (Z-2) = 6, R 1 Examples include compounds in which all atoms are hydrogen atoms. Furthermore, a commercially available polymerizable compound containing a caprolactone structure is M-350 (trade name) (trimethylolpropane triacrylate) manufactured by Toagosei Co., Ltd.

[0213] The polymerizable compounds mentioned above may also be compounds represented by the following formulas (Z-4) or (Z-5).

[0214] [ka]

[0215] In equations (Z-4) and (Z-5), E is -((CH2) y CH2O)-, or ((CH2) y The symbol CH(CH3)O)- represents a group, y represents an integer from 0 to 10, and X represents a (meth)acryloyl group, a hydrogen atom, or a carboxylic acid group. In formula (Z-4), the total number of (meth)acryloyl groups is 3 or 4, m represents an integer from 0 to 10, and the sum of each m is an integer from 0 to 40. In formula (Z-5), the total number of (meth)acryloyl groups is 5 or 6, n represents an integer from 0 to 10, and the sum of each n is an integer from 0 to 60.

[0216] In equation (Z-4), m is preferably an integer between 0 and 6, and more preferably an integer between 0 and 4. Furthermore, the sum of each m is preferably an integer between 2 and 40, more preferably an integer between 2 and 16, and even more preferably an integer between 4 and 8. In equation (Z-5), n is preferably an integer between 0 and 6, and more preferably an integer between 0 and 4. Furthermore, the sum of each n is preferably an integer between 3 and 60, more preferably an integer between 3 and 24, and even more preferably an integer between 6 and 12. Also, -((CH2) in equation (Z-4) or equation (Z-5) y CH2O)- or ((CH2) y The CH(CH3)O)- group is preferably formed with the oxygen atom end bonded to X.

[0217] The compounds represented by formula (Z-4) or formula (Z-5) may be used individually or in combination of two or more. Particularly preferred are the form in which all six X in formula (Z-5) are acryloyl groups, and the form in which a mixture of a compound in which all six X in formula (Z-5) are acryloyl groups and a compound in which at least one of the six X is a hydrogen atom. Such a configuration can further improve developability.

[0218] Furthermore, the total content of the compound represented by formula (Z-4) or formula (Z-5) in the polymerizable compound is preferably 20% by mass or more, and more preferably 50% by mass or more. Among the compounds represented by formula (Z-4) or formula (Z-5), pentaerythritol derivatives and / or dipentaerythritol derivatives are more preferred.

[0219] Furthermore, the polymerizable compound may also contain a cardo skeleton. As the polymerizable compound containing the cardo skeleton, the polymerizable compound containing the 9,9-bisarylfluorene skeleton is preferred. The polymerizable compounds containing the cardo skeleton are not limited, but examples include the Oncoat EX series (manufactured by Nagase & Co., Ltd.) and Ogusol (manufactured by Osaka Gas Chemical Co., Ltd.). The polymerizable compounds described above are also preferably compounds that contain an isocyanuric acid skeleton as a central core. An example of such a polymerizable compound is NK ester A-9300 (manufactured by Shin Nakamura Chemical Co., Ltd.). The content of ethylenically unsaturated groups in the polymerizable compound (meaning the value obtained by dividing the number of ethylenically unsaturated groups in the polymerizable compound by the molecular weight (g / mol) of the polymerizable compound) is preferably 5.0 mmol / g or more. There is no particular upper limit, but it is generally 20.0 mmol / g or less.

[0220] <Compounds having epoxy groups and / or oxetanyl groups> Polymerizable compounds that have epoxy groups and / or oxetanyl groups are also preferred. The polymerizable compound described above preferably has one or more epoxy groups and / or oxetanyl groups, and more preferably two to ten. Among the polymerizable compounds, epoxy-curable compounds (epoxy compounds) having an epoxy group are more preferred. In the polymerizable compound described above, the epoxy group and / or oxetanyl group (preferably the epoxy group) may be fused with a cyclic group (such as an alicyclic group). The cyclic group fused with the epoxy group and / or oxetanyl group preferably has 5 to 15 carbon atoms. In addition, the portion of the cyclic group other than the fused epoxy group and / or oxetanyl group may be monocyclic or polycyclic. A single cyclic group may have only one epoxy group or oxetanyl group fused with it, or it may have two or more epoxy groups and / or oxetanyl groups fused with it.

[0221] Examples of the polymerizable compounds mentioned above include monofunctional or polyfunctional glycidyl ether compounds. The polymerizable compound mentioned above may be, for example, (poly)alkylene glycol diglycidyl ether.

[0222] The polymerizable compound described above may also be a compound containing a caprolactone structure represented by formula (Z-1) above, in which the group represented by formula (Z-2) is changed to the group represented by formula (Z-2E) below, and the group represented by formula (Z-3) is changed to the group represented by formula (Z-3E).

[0223] [ka]

[0224] In formula (Z-2E), m represents a number of 1 or 2, X and Y independently represent a hydrogen atom or a substituent (preferably an alkyl group, preferably having 1 to 3 carbon atoms), and "*" represents a bond. In formula (Z-3E), X and Y each independently represent a hydrogen atom or a substituent (preferably an alkyl group, preferably having 1 to 3 carbon atoms), and "*" indicates a bond.

[0225] The polymerizable compound described above may also be a compound represented by formula (Z-4) above, in which X is changed to represent a group represented by formula (Z-3E) or a hydrogen atom. In the modified equation (Z-4), the total number of bases represented by equation (Z-3E) is between 2 and 4.

[0226] The polymerizable compound described above may also be a compound represented by the above formula (Z-5), in which X is changed to represent a group represented by formula (Z-3E) or a hydrogen atom. In the modified formula (Z-5) in this way, the total number of groups represented by formula (Z-3E) is 2 to 6 (preferably 5 or 6).

[0227] The polymerizable compounds described above may also be compounds in which N cyclic groups fused with epoxy groups and / or oxetanyl groups are linked via linking groups. N is an integer of 2 or more, preferably an integer between 2 and 6, and more preferably 2. The linking group preferably has a total number of atoms other than hydrogen atoms of 1 to 20, and more preferably 2 to 6. When N is 2, an example of the linking group is an alkyleneoxycarbonyl group.

[0228] Examples of commercially available polymerizable compounds include polyfunctional aliphatic glycidyl ether compounds such as Denacol EX-212L, EX-214L, EX-216L, EX-321L, and EX-850L (all manufactured by Nagase ChemteX Corporation). These are low-chlorine products, but non-low-chlorine products such as EX-212, EX-214, EX-216, EX-321, EX-614, and EX-850 can also be used in the same way. Additionally, commercially available products such as Celoxide 2021P (manufactured by Daicel Corporation, a polyfunctional epoxy monomer) can also be used.

[0229] The composition may contain both a polymerizable compound containing a group with an ethylenically unsaturated bond and a compound having an epoxy group and / or an oxetanyl group. In this case, the mass ratio of their contents (content of "compound containing a group with an ethylenically unsaturated bond" / content of "compound having an epoxy group and / or an oxetanyl group") is preferably 10 / 90 to 90 / 10, more preferably 20 / 80 to 80 / 20, and even more preferably 30 / 70 to 70 / 30.

[0230] [Curing accelerator] The composition may contain a curing accelerator. In particular, it is preferable to include a curing accelerator when the composition contains a compound having an epoxy group and / or an oxetanyl group as a polymerizable compound. Examples of curing accelerators include triphenylphosphine, methyltributylphosphonium dimethyl phosphate, tris-orthototrilphosphine, and boron trifluoride amine complexes. Other examples include 2-methylimidazole (trade name; 2MZ), 2-undecylimidazole (trade name; C11-Z), 2-heptadecylimidazole (trade name; C17Z), 1,2-dimethylimidazole (trade name; 1,2DMZ), 2-ethyl-4-methylimidazole (trade name; 2E4MZ), 2-phenylimidazole (trade name; 2PZ), 2-phenyl-4-methylimidazole (trade name; 2P4MZ), 1-benzyl-2-methylimidazole (trade name; 1B2MZ), and 1-benzyl 2-phenylimidazole (trade name: 1B2PZ), 1-cyanoethyl-2-methylimidazole (trade name: 2MZ-CN), 1-cyanoethyl-2-undecylimidazole (trade name: C11Z-CN), 1-cyanoethyl-2-phenylimidazolium trimellitate (trade name: 2PZCNS-PW), 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine (trade name: 2MZ-A), 2,4-diamino-6-[2'-undecylimidazol -(1')]-ethyl-s-triazine (trade name: C11Z-A), 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine (trade name: 2E4MZ-A), 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanurate adduct (trade name: 2MA-OK), 2-phenyl-4,5-dihydroxymethylimidazole (trade name: 2PHZ-PW), 2-phenyl-4-methyl-5-hydroxymethyl Examples of imidazole-based curing accelerators include tilimidazole (trade name: 2P4MHZ-PW), 1-cyanoethyl-2-phenylimidazole (trade name: 2PZ-CN), 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine (trade name: 2MZA-PW), and 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct (trade name: 2MAOK-PW) (all manufactured by Shikoku Chemicals, Inc.).Furthermore, as a triarylphosphine-based curing accelerator, the compound described in paragraph 0052 of Japanese Patent Publication No. 2004-43405 is also an example. As a phosphorus-based curing accelerator in which triphenylborane is added to triarylphosphine, the compound described in paragraph 0024 of Japanese Patent Publication No. 2014-5382 is also an example. The curing accelerator content is preferably 0.0002 to 3% by mass, more preferably 0.002 to 2% by mass, and even more preferably 0.02 to 1% by mass, based on the total mass of the composition. The content of the curing accelerator is preferably 0.0002 to 3% by mass, more preferably 0.002 to 2% by mass, and even more preferably 0.02 to 1% by mass, based on the total solid content of the composition.

[0231] [Polymerization initiator] The composition may contain a polymerization initiator. The polymerization initiator is not particularly limited, and known polymerization initiators can be used. Examples of polymerization initiators include photopolymerization initiators and thermal polymerization initiators, with photopolymerization initiators being preferred. In particular, so-called radical polymerization initiators are preferred as polymerization initiators. If the composition contains a polymerization initiator, its content is preferably 0.5 to 15% by mass, more preferably 1.0 to 10% by mass, and even more preferably 1.5 to 8.0% by mass, based on the total mass of the composition. If the composition contains a polymerization initiator, its content is preferably 0.5 to 15% by mass, more preferably 1.0 to 10% by mass, and even more preferably 1.5 to 8.0% by mass, based on the total solid content of the composition.

[0232] <Thermal polymerization initiator> Examples of thermal polymerization initiators include azo compounds such as 2,2'-azobisisobutyronitrile (AIBN), 3-carboxypropionitrile, azobismalenonitrile, and dimethyl-(2,2')-azobis(2-methylpropionate)[V-601], as well as organic peroxides such as benzoyl peroxide, lauroyl peroxide, and potassium persulfate. Specific examples of polymerization initiators include those described on pages 65-148 of "Ultraviolet Curing Systems" by Kiyoshi Kato (published by Sogo Gijutsu Center Co., Ltd., 1989).

[0233] <Photopolymerization initiator> The photopolymerization initiator is not particularly limited as long as it can initiate polymerization of the polymerizable compound, and known photopolymerization initiators can be used. Preferred photopolymerization initiators include, for example, those that are photosensitive to light in the ultraviolet to visible light range. Alternatively, an activator that interacts with a photoexcited sensitizer to generate active radicals may be used, or an initiator that initiates cationic polymerization depending on the type of polymerizable compound. Furthermore, the photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least 50 in the range of 300 to 800 nm (more preferably 330 to 500 nm).

[0234] Examples of photopolymerization initiators include halogenated hydrocarbon derivatives (e.g., compounds containing a triazine skeleton, compounds containing an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxides, oxime compounds such as hexaarylbiimidazole and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, aminoacetophenone compounds, and hydroxyacetophenone. For specific examples of photopolymerization initiators, see, for example, paragraphs 0265 to 0268 of Japanese Patent Publication No. 2013-29760, which are incorporated herein by reference.

[0235] More specifically, as photopolymerization initiators, for example, the aminoacetophenone-based initiator described in Japanese Patent Publication No. 10-291969 and the acylphosphine-based initiator described in Japanese Patent Publication No. 4225898 can also be used. Examples of hydroxyacetophenone compounds that can be used include Omnirad-184, Omnirad-1173, Omnirad-500, Omnirad-2959, and Omnirad-127 (trade names, all manufactured by IGM Resins BV). As aminoacetophenone compounds, for example, commercially available products such as Omnirad-907, Omnirad-369, and Omnirad-379EG (trade names, all manufactured by IGM Resins BV) can be used. As aminoacetophenone compounds, compounds described in Japanese Patent Application Publication No. 2009-191179, whose absorption wavelengths are matched to long-wave light sources such as 365 nm or 405 nm, can also be used. As acylphosphine compounds, commercially available products such as Omnirad-819 and Omnirad-TPO (trade names, both manufactured by IGM Resins BV) can be used.

[0236] As a photopolymerization initiator, oxime ester-based polymerization initiators (oxime compounds) are more preferred. Oxime compounds are particularly preferred because they are highly sensitive, have high polymerization efficiency, and allow for easy design of high colorant content in the composition. Specific examples of oxime compounds include the compounds described in Japanese Patent Publication No. 2001-233842, the compounds described in Japanese Patent Publication No. 2000-80068, or the compounds described in Japanese Patent Publication No. 2006-342166. Examples of oxime compounds include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one. Other examples include compounds described in JCSPerkin II (1979) pp.1653-1660, JCSPerkin II (1979) pp.156-162, Journal of Photopolymer Science and Technology (1995) pp.202-232, Japanese Patent Publication No. 2000-66385, Japanese Patent Publication No. 2000-80068, Japanese Patent Publication No. 2004-534797, and Japanese Patent Publication No. 2006-342166. Commercially available options include IRGACURE-OXE01 (BASF), IRGACURE-OXE02 (BASF), IRGACURE-OXE03 (BASF), or IRGACURE-OXE04 (BASF). Additionally, TR-PBG-304 (Changzhou Strong Electronic New Materials Co., Ltd.), ADEKA Arclus NCI-831, ADEKA Arclus NCI-930 (ADEKA), or N-1919 (carbazole oxime ester skeleton-containing photoinitiator (ADEKA)) can also be used.

[0237] In addition, other oxime compounds not listed above may be used, such as the compound described in Japanese Patent Publication No. 2009-519904, in which an oxime is linked to the N position of carbazole; the compound described in U.S. Patent No. 7626957, in which a heterosubstituted group is introduced to the benzophenone moiety; the compound described in Japanese Patent Application Publication No. 2010-15025 and U.S. Patent Publication No. 2009-292039, in which a nitro group is introduced to the dye moiety; the ketoxime compound described in International Publication No. 2009-131189; and the compound described in U.S. Patent No. 7556910, which contains a triazine skeleton and an oxime skeleton in the same molecule; and the compound described in Japanese Patent Application Publication No. 2009-221114, which has an absorption maximum at 405 nm and good sensitivity to g-line light sources. For example, paragraphs 0274 to 0275 of Japanese Patent Publication No. 2013-29760 can be referenced, and their contents are incorporated herein. Specifically, the oxime compound is preferably a compound represented by the following formula (OX-1). The NO bond of the oxime compound may be the (E) oxime compound, the (Z) oxime compound, or a mixture of the (E) and (Z) oxime compounds.

[0238] [ka]

[0239] In formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group. In formula (OX-1), a monovalent nonmetallic group is preferred as the monovalent substituent represented by R. Examples of monovalent nonmetallic atomic groups include alkyl groups, aryl groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, heterocyclic groups, alkylthiocarbonyl groups, and arylthiocarbonyl groups. These groups may also have one or more substituents. Furthermore, the aforementioned substituents may be further substituted with other substituents. Examples of substituents include halogen atoms, aryloxy groups, alkoxycarbonyl groups or aryloxycarbonyl groups, acyloxy groups, acyl groups, alkyl groups, and aryl groups. In formula (OX-1), the monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group, with the aryl group or heterocyclic group being preferred. These groups may have one or more substituents. Examples of substituents include those mentioned above. In formula (OX-1), the divalent organic group represented by A is preferably an alkylene group, a cycloalkylene group, or an alkylylene group having 1 to 12 carbon atoms. These groups may have one or more substituents. Examples of substituents include those mentioned above.

[0240] Oxime compounds containing a fluorine atom can also be used as photopolymerization initiators. Specific examples of oxime compounds containing a fluorine atom include the compound described in Japanese Patent Publication No. 2010-262028; compounds 24, 36-40 described in Japanese Patent Publication No. 2014-500852; and compound (C-3) described in Japanese Patent Publication No. 2013-164471; etc. This information is incorporated herein by reference.

[0241] Compounds represented by the following general formulas (1) to (4) can also be used as photopolymerization initiators.

[0242] [ka]

[0243] [ka]

[0244] In equation (1), R 1 and R 2 Each of these independently represents an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms. 1 and R 2 If R is a phenyl group, the phenyl groups may bond together to form a fluorene group, 3 and R 4 Each of these independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms, and X represents a direct bond or a carbonyl group.

[0245] In equation (2), R 1 , R 2 , R 3 , and R 4 R in equation (1) 1 , R 2 , R 3 , and R 4 It is synonymous with R 5 is, -R 6, -OR 6 , -SR 6 , -COR 6 ,-CONR 6 R 6 , -NR 6 COR 6 , -OCOR 6 ,-COOR 6 , -SCOR 6 ,-OCSR 6 ,-COSR 6 -CSOR 6 -CN represents a halogen atom or a hydroxyl group, R 6 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms; X represents a direct bond or a carbonyl group; and a represents an integer from 0 to 4.

[0246] In equation (3), R 1 R represents an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms. 3 and R 4 Each of these independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms, and X represents a direct bond or a carbonyl group.

[0247] In equation (4), R 1 , R 3 , and R 4 R in equation (3) is 1 , R 3 , and R 4 It is synonymous with R 5 is, -R 6 , -OR 6 , -SR 6 , -COR 6 ,-CONR 6 R 6 , -NR 6 COR 6 , -OCOR 6 ,-COOR 6 , -SCOR 6 ,-OCSR6 ,-COSR 6 -CSOR 6 -CN represents a halogen atom or a hydroxyl group, R 6 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms; X represents a direct bond or a carbonyl group; and a represents an integer from 0 to 4.

[0248] In the above equations (1) and (2), R 1 and R 2 The group is preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclohexyl group, or a phenyl group. 3 The group is preferably a methyl group, ethyl group, phenyl group, tolyl group, or xylyl group. 4 A C1-C6 alkyl group or phenyl group is preferred. 5 The group is preferably a methyl group, ethyl group, phenyl group, tolyl group, or naphthyl group. X is preferably directly bonded. Furthermore, in the above equations (3) and (4), R 1 The group is preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclohexyl group, or a phenyl group. 3 The group is preferably a methyl group, ethyl group, phenyl group, tolyl group, or xylyl group. 4 A C1-C6 alkyl group or a phenyl group is preferred. 5 The group is preferably a methyl group, ethyl group, phenyl group, tolyl group, or naphthyl group. X is preferably directly bonded. Specific examples of compounds represented by formulas (1) and (2) include, for example, the compounds described in paragraphs 0076 to 0079 of Japanese Patent Publication No. 2014-137466. This information is incorporated herein by reference.

[0249] Specific examples of oxime compounds preferably used in the above composition are shown below. Among the oxime compounds shown below, the oxime compound represented by the general formula (C-13) is more preferred. Furthermore, as oxime compounds, those listed in Table 1 of International Publication No. 2015-036910 may also be used, and the above information is incorporated herein.

[0250] [ka]

[0251] [ka]

[0252] The oxime compound preferably has a maximum absorption wavelength in the 350-500 nm wavelength range, more preferably in the 360-480 nm wavelength range, and even more preferably has high absorbance at wavelengths of 365 nm and 405 nm. From the viewpoint of sensitivity, the molar extinction coefficient of the oxime compound at 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and even more preferably 5,000 to 200,000. The molar extinction coefficient of a compound can be determined using known methods, but it is preferable to measure it using an ultraviolet-visible spectrophotometer (Varian Cary-5 spctrophotometer) at a concentration of 0.01 g / L with ethyl acetate. Two or more photopolymerization initiators may be used in combination as needed.

[0253] Furthermore, as photopolymerization initiators, compounds described in paragraph 0052 of Japanese Patent Publication No. 2008-260927, paragraphs 0033-0037 of Japanese Patent Publication No. 2010-97210, and paragraph 0044 of Japanese Patent Publication No. 2015-68893 can also be used, and the above contents are incorporated herein.

[0254] [Polymerization inhibitors] The composition may contain a polymerization inhibitor. The polymerization inhibitor is not particularly limited, and known polymerization inhibitors can be used. Examples of polymerization inhibitors include phenolic polymerization inhibitors (e.g., p-methoxyphenol, 2,5-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-methylphenol, 4,4'-thiobis(3-methyl-6-t-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), 4-methoxynaphthol, etc.); hydroquinone polymerization inhibitors (e.g., hydroquinone, 2,6-di-tert-butylhydro) Examples include: loquinone, quinone-based polymerization inhibitors (e.g., benzoquinone, etc.); free radical polymerization inhibitors (e.g., 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, etc.); nitrobenzene-based polymerization inhibitors (e.g., nitrobenzene, 4-nitrotoluene, etc.); and phenothiazine-based polymerization inhibitors (e.g., phenothiazine, 2-methoxyphenothiazine, etc.). Among these, phenolic polymerization inhibitors or free radical polymerization inhibitors are preferred.

[0255] Polymerization inhibitors are particularly effective when used in conjunction with resins containing curable groups. The content of polymerization inhibitor in the composition is not particularly limited, but is preferably 0.0001 to 0.5% by mass, more preferably 0.0001 to 0.2% by mass, and even more preferably 0.0001 to 0.05% by mass, relative to the total mass of the composition. The polymerization inhibitor content is preferably 0.0001 to 0.5% by mass, more preferably 0.0001 to 0.2% by mass, and even more preferably 0.0001 to 0.05% by mass, relative to the total solid content of the composition. Furthermore, the ratio of the content of polymerization inhibitors to the content of polymerizable compounds (particularly compounds containing ethylenically unsaturated bonds) in the composition (content of polymerization inhibitors / content of polymerizable compounds (mass ratio)) is preferably greater than 0.0005, more preferably 0.0006 to 0.02, and even more preferably 0.0006 to 0.005.

[0256] [Surfactants] The composition may contain a surfactant. The surfactant contributes to improving the applicability of the composition. If the composition contains a surfactant, the surfactant content is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 0.5% by mass, and even more preferably 0.01 to 0.1% by mass, based on the total mass of the composition. The surfactant content is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 0.5% by mass, and even more preferably 0.01 to 0.1% by mass, relative to the total solid content of the composition.

[0257] Examples of surfactants include fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone-based surfactants.

[0258] For example, if the composition contains a fluorine-based surfactant, the liquid properties of the composition (especially its fluidity) are further improved. That is, when forming a film using a composition containing a fluorine-based surfactant, the interfacial tension between the surface to be coated and the coating liquid is reduced, improving the wettability to the surface and thus improving the coatability to the surface. Therefore, even when forming a thin film of several micrometers with a small amount of liquid, it is effective in more favorably forming a film of uniform thickness with less thickness variation.

[0259] The fluorine content in the fluorinated surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and even more preferably 7 to 25% by mass. Fluorinated surfactants with a fluorine content within this range are effective in terms of uniformity of coating film thickness and / or liquid saving, and also have good solubility in the composition.

[0260] Examples of fluorine-based surfactants include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, and F780 (all manufactured by DIC); Florard FC430, FC431, and FC171 (and others). Examples include: Sumitomo 3M's Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, and KH-40 (all manufactured by AGC); and PF636, PF656, PF6320, PF6520, and PF7002 (manufactured by OMNOVA). Block polymers can also be used as fluorine-based surfactants, and a specific example is the compound described in Japanese Patent Publication No. 2011-89090. An example of a silicone-based surfactant is KF6007 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0261] 〔solvent〕 The composition may contain a solvent. Examples of solvents include water and organic solvents, with organic solvents being preferred. From the standpoint of coatability, the boiling point of the solvent is preferably 100 to 400°C, preferably 150 to 300°C, and more preferably 170 to 250°C. In this specification, unless otherwise specified, boiling point refers to the standard boiling point.

[0262] Examples of organic solvents include 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, and ethylene glycol monobutyl ether. Examples include, but are not limited to, 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, ethyl acetate, butyl acetate, methyl lactate, N-methyl-2-pyrrolidone, and ethyl lactate.

[0263] If the composition contains a solvent, the amount of solvent is preferably 1 to 60% by mass, more preferably 1 to 40% by mass, and even more preferably 1 to 25% by mass, based on the total mass of the composition, from the viewpoint of achieving superior effects of the present invention. The composition is preferably substantially solvent-free. A composition is considered substantially solvent-free if the solvent content is less than 1% by mass of the total mass of the composition. For example, 0% by mass or more and less than 1% by mass is preferred, 0 to 0.5% by mass is more preferred, and 0 to 0.1% by mass is even more preferred. The solid content concentration of the composition is preferably 20 to 100% by mass, preferably 40 to 100% by mass, and more preferably 75 to 100% by mass.

[0264] [Other optional ingredients] The composition may further contain other optional components in addition to those described above. Examples include magnetic particles other than those described above, sensitizers, co-sensitizers, crosslinking agents (curing agents), curing accelerators, thermosetting accelerators, plasticizers, diluents, oil-sensitive agents, and rubber components. Furthermore, known additives such as adhesion promoters to the substrate surface and other auxiliary agents (e.g., defoamers, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension modifiers, and chain transfer agents) may be added as needed.

[0265] [Physical properties of the composition] The viscosity of the composition at 23°C is preferably 1 to 1,000,000 Pa·s, more preferably 10 to 50,000 Pa·s, and even more preferably 50 to 10,000 Pa·s, from the viewpoint of superior settling stability of magnetic particles when the shear rate is 0.1 (1 / s). The viscosity of the composition at 23°C is preferably 100 Pa·s or less, more preferably 50 Pa·s or less, and even more preferably 10 Pa·s or less, when the shear rate is 1000 (1 / s), from the viewpoint of superior settling stability of the magnetic particles. The lower limit when the shear rate is 1000 (1 / s) is preferably 0.001 Pa·s or more. Here, the viscosity of the composition at 23°C is obtained by measuring it at 23°C using an MCR-102 (manufactured by Anton Paar) while increasing the speed from 0.1 / s to 1000 / s.

[0266] [Method for manufacturing the composition] The composition can be prepared by mixing the above components using a known mixing method (for example, a mixing method using a stirrer, homogenizer, high-pressure emulsifier, wet grinder, or wet disperser). When preparing the composition of the present invention, each component may be blended together, or each component may be dissolved or dispersed in a solvent and then blended sequentially. Furthermore, there are no particular restrictions on the order of addition or working conditions during blending. For example, when using multiple types of other resins, they may be blended together, or each type may be blended in multiple separate steps.

[0267] [Magnetic particle-containing film] The magnetic particle-containing film of the present invention is formed using the composition of the present invention described above. The thickness of the magnetic particle-containing film is preferably 1 to 10,000 μm, more preferably 10 to 1,000 μm, and even more preferably 15 to 800 μm, from the standpoint of superior magnetic permeability. Magnetic particle-containing films are suitably used as electronic components such as antennas and inductors installed in electronic communication equipment and the like.

[0268] [Method for manufacturing magnetic particle-containing film] The magnetic particle-containing film of the present invention can be obtained, for example, by curing the above composition. The method for manufacturing a magnetic particle-containing film is not particularly limited, but it is preferable to include the following steps. ·Composition layer formation process ·Curing process

[0269] <Composition layer formation process> In the composition layer formation process, a composition is applied to a substrate (support) to form a layer of the composition (composition layer). As the substrate, for example, a wiring board having an antenna portion or an inductor portion can be used.

[0270] Various coating methods can be applied to the substrate, including slit coating, inkjet coating, rotary coating, casting coating, roll coating, and screen printing. The film thickness of the composition layer is preferably 1 to 10,000 μm, more preferably 10 to 1,000 μm, and even more preferably 15 to 800 μm. The composition layer coated on the substrate may be heated (pre-baked), which can be done, for example, by heating it at a temperature of 50 to 140°C for 10 to 1,800 seconds using a hot plate, oven, etc. Pre-baking is especially preferable when the composition contains a solvent.

[0271] <Curing process> The curing process is not particularly limited as long as it can cure the composition layer, but examples include a heat treatment to heat the composition layer and an exposure treatment to irradiate the composition layer with active light or radiation.

[0272] When heat treatment is performed, the heat treatment can be carried out continuously or in batches using heating means such as a hot plate, convection oven (hot air circulation dryer), or high-frequency heater. The heating temperature during the heat treatment is preferably 120 to 260°C, and more preferably 150 to 240°C. While there are no particular restrictions on the heating time, 10 to 1800 seconds is preferred. Furthermore, the pre-baking process in the composition layer formation step may also serve as the heat treatment in the curing step.

[0273] When performing exposure processing, there are no particular limitations on the method of irradiation with active light or radiation, but it is preferable to irradiate through a photomask having a patterned opening. Exposure is preferably carried out by irradiation with radiation. Preferred radiation for exposure is ultraviolet light such as g-rays, h-rays, or i-rays, and a high-pressure mercury lamp is preferred as the light source. The irradiation intensity is 5 to 1500 mJ / cm². 2 Preferably, 10 to 1000 mJ / cm² 2 This is preferable. If the composition contains a thermal polymerization initiator, the composition layer may be heated during the exposure treatment described above. The heating temperature is not particularly limited, but 80 to 250°C is preferred. The heating time is also not particularly limited, but 30 to 300 seconds is preferred. Furthermore, when the composition layer is heated during the exposure process, this process may also serve as a post-heating step, as described later. In other words, when the composition layer is heated during the exposure process, the method for manufacturing the magnetic particle-containing film does not need to include a post-heating step.

[0274] <Developing process> If exposure is performed during the curing process, a developing process may be included in the process. The development process involves developing the above-mentioned composition layer after exposure to form a magnetic particle-containing film. In this process, the un-irradiated portions of the composition layer during the exposure process are dissolved, leaving only the photo-cured portions, resulting in a patterned magnetic particle-containing film. While there are no particular restrictions on the type of developer used in the development process, an alkaline developer is preferable as it will not damage the circuitry. The development temperature is, for example, 20-30°C. The development time is typically 20 to 90 seconds. In recent years, development has sometimes been extended to 120 to 180 seconds to better remove residue. Furthermore, to further improve residue removal, the developer solution may be shook out every 60 seconds, and the process of supplying fresh developer solution may be repeated several times.

[0275] As the alkaline developer, an alkaline aqueous solution prepared by dissolving an alkaline compound in water to a concentration of 0.001 to 10% by mass (preferably 0.01 to 5% by mass) is preferred. Examples of alkaline compounds include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo[5.4.0]-7-undecene (of which organic alkalis are preferred). When used as an alkaline developer, the film is generally washed with water after development.

[0276] <Post-bake> When exposure treatment is performed in the curing process, it is preferable to perform a heat treatment (post-bake) after the curing process. Post-bake is a heat treatment to complete the curing. When a development process is performed, it is preferable to perform post-bake after the development process. The heating temperature is preferably 240°C or lower, and more preferably 220°C or lower. There is no particular lower limit, but considering efficient and effective processing, 50°C or higher is preferable, and 100°C or higher is preferable. There is no particular limit to the heating time, but 10 to 1800 seconds is preferable. Post-baking can be carried out continuously or in batches using heating means such as a hot plate, convection oven (hot air circulation dryer), or high-frequency heater.

[0277] The above post-bake is preferably carried out in a low-oxygen atmosphere. The oxygen concentration is preferably 19% by volume or less, more preferably 15% by volume or less, even more preferably 10% by volume or less, particularly preferably 7% by volume or less, and most preferably 3% by volume or less. There is no lower limit, but 10 ppm by volume or more is practical.

[0278] Alternatively, instead of post-baking by heating as described above, curing may be completed by UV (ultraviolet) irradiation. In this case, the composition preferably further contains a UV curing agent. The UV curing agent is preferably one that can cure at a wavelength shorter than 365 nm, which is the exposure wavelength of the polymerization initiator added for the lithography process using normal i-line exposure. An example of a UV curing agent is Ciba IrgaCure 2959 (trade name). When UV irradiation is performed, it is preferable that the composition layer is made of a material that cures at a wavelength of 340 nm or less. There is no particular lower limit for the wavelength, but 220 nm or more is common. The exposure amount for UV irradiation is preferably 100 to 5000 mJ, more preferably 300 to 4000 mJ, and even more preferably 800 to 3500 mJ. It is preferable to perform this UV curing process after the exposure treatment in order to perform low-temperature curing more effectively. It is preferable to use an ozone-free mercury lamp as the exposure light source.

[0279] [Electronic components] The electronic component of the present invention includes the magnetic particle-containing film described above. That is, the electronic component of the present invention may include the magnetic particle-containing film as part of the component. Examples of electronic components include inductors and antennas. Known electronic components can be used. [Examples]

[0280] The present invention will be described in more detail based on the following examples. The materials, amounts used, ratios, treatment details, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention should not be construed in a limited manner by the examples shown below. In the following, unless otherwise specified, “%” means “mass %” and “parts” means “parts by mass”.

[0281] [Various components used in the preparation of the composition] In preparing the composition, each component described in Table 1 was prepared. An overview of each component described in Table 1 is shown below.

[0282] [Magnetic particles] · P-1; 80% Ni - 4Mo PF-5F (manufactured by Epson Atmix Corporation), particle size (average primary particle size): 4 μm, Ni content: 80%, aspect ratio: 1 - 2 · P-2; 80% Ni - 4Mo PF-15F (manufactured by Epson Atmix Corporation), particle size: 8 μm, Ni content: 80%, aspect ratio: 1 - 2 · P-3; 80% Ni - 4Mo WA13 (manufactured by Epson Atmix Corporation), particle size: 12.5 μm, Ni content: 80%, aspect ratio: 1 - 2 · P-4; Particles produced by subjecting 80% Ni - 4Mo WA13 to mechanochemical treatment, particle size: 12.5 μm, Ni content: 80%, aspect ratio: 3 - 4 · P-5; Particles produced by subjecting 80% Ni - 4Mo WA13 to mechanochemical treatment, particle size: 12.5 μm, Ni content: 80%, aspect ratio: 5 - 6 · P-6; Particles produced by subjecting 80% Ni - 4Mo WA13 to mechanochemical treatment, particle size: 12.5 μm, Ni content: 80%, aspect ratio: 7 or more and less than 8 · P-7; KUAMET-CT5-25um (manufactured by Epson Atmix Corporation), particle size: 15 μm, Co content: 81%, aspect ratio: 1 - 2 · P-8; KUAMET-CT5-38um (manufactured by Epson Atmix Corporation), particle size: 20 μm, Co content: 81%, aspect ratio: 1 - 2 • P-9; KUAMET-CT5-53um (manufactured by Epson Atomics), particle size: 25 μm, Co content: 81%, aspect ratio: 1-2 P-10; Particles manufactured by water atomization containing elements Co: 70%, Fe: 15%, Si: 9%, Cr: 4%, B: 2%. Particle size: 15 μm, Co content: 70%, aspect ratio: 1-2 P-11; Particles manufactured by water atomization containing elements Co: 60%, Fe: 25%, Si: 9%, Cr: 4%, B: 2%, particle size: 15 μm, Co content: 60%, aspect ratio: 1-2 Particles produced by water atomization containing the elements P-12; Co: 50%, Fe: 35%, Si: 9%, Cr: 4%, B: 2%; particle size: 15 μm; Co content: 50%; aspect ratio: 1-2 P-13; Particles manufactured by water atomization containing elements Co: 90%, Si: 4%, Cr: 4%, B: 2%, particle size: 15 μm, Co content: 90%, aspect ratio: 1-2 P-14; Particles manufactured by water atomization containing elements Ni: 80%, Fe: 19%, Mo: 1%, particle size: 12.5 μm, Ni content: 80%, aspect ratio: 1-2 P-15; Particles manufactured by water atomization containing elements Ni: 80%, Fe: 10%, Mo: 10%, particle size: 12.5 μm, Ni content: 80%, aspect ratio: 1-2 P-16; Particles manufactured by water atomization containing elements Ni: 80%, Mo: 15%, Fe: 5%, particle size: 12.5 μm, Ni content: 80%, aspect ratio: 1-2 P-17; Particles manufactured by water atomization containing elements Co: 40%, Fe: 45%, Si: 9%, Cr: 4%, B: 2%, particle size: 15 μm, Co content: 40%, aspect ratio: 1-2 Particles manufactured by mechanochemical treatment of P-18; 80%Ni-4Mo WA13, particle size: 12.5 μm, Ni content: 80%, aspect ratio: 8-9 P-19; Particles manufactured by water atomization containing elements Ni: 40%, Fe: 55%, Mo: 5%, particle size: 12.5 μm, Ni content: 40%, aspect ratio: 1-2 P-20;AW2-08 PF-3F (manufactured by Epson Atomics), particle size: 3μm, Ni and Co content: 0%, aspect ratio: 1-2 Furthermore, all of these magnetic particles consisted almost entirely of metal atoms. Furthermore, the particle size (average primary particle diameter) of the magnetic particles was measured by the method described in the specification. Furthermore, among the magnetic particles mentioned above, P-1 to P-16 also correspond to the "magnetic particle X with an aspect ratio of less than 8" as previously described in the upper section.

[0283] [Rheology control agents or other resins] • D-1; Product name "BYK-P105" (manufactured by BYK), low molecular weight unsaturated carboxylic acid polymer, acid value 365 mg KOH / g, solids content 100% • D-2; Product name "ANTI-TERRA-204" (manufactured by BYK), solution of polyaminoamide polycarboxylate, amine value 37 mg KOH / g, acid value 41 mg KOH / g, solids concentration 52% • D-3; Product name "Tallen VA-705B" (manufactured by Kyoeisha Chemical Co., Ltd.), higher fatty acid amide, solid content concentration 100% • D-4; Product name "FLOWNON RCM-230AF" (manufactured by Kyoeisha Chemical Co., Ltd.), higher fatty acid amide, solid content concentration 10% • D-5; The following compound (weight-average molecular weight 10000, amine value 50 mgKOH / g, acid value 50 mgKOH / g, solid content concentration 30%) • D-6; The following compound (weight-average molecular weight 25000, acid value 100 mg KOH / g), solid content concentration 30% • D-7; The following compound (weight-average molecular weight 10000, acid value 40 mg KOH / g), solid content concentration 30% Note that D-1 and D-3 are rheology control agents themselves, while D-2 and D-4 are solutions containing rheology control agents (solid content). Solutions D-5 to D-7 are solutions containing other resins (solids) that do not fall under the category of rheology control agents. In the compounds shown below for D-5 to D-7, the numerical values ​​attached to each repeating unit indicate the mass ratio.

[0284] [ka]

[0285] [ka]

[0286] [ka]

[0287] [Polymerizable compound] M-1; Celoxide 2021P (manufactured by Daicel Chemical Industries, Ltd.), 3',4'-Epoxycyclohexylmethyl 3,4-Epoxycyclohexanecarboxylate • M-2; Denacol EX-411 (manufactured by Nagase ChemteX), Pentaerythritol Polyglycidyl Ether • M-3; KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), the following compound M-4; A-TMMT (manufactured by Toagosei), pentaerythritol tetraacrylate

[0288] [ka]

[0289] [Additives (curing accelerators or polymerization initiators)] A-1; Triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.), curing accelerator A-2; Hishikorin PX-4MP (manufactured by Nippon Chemical Industrial Co., Ltd.), methyltributylphosphonium dimethyl phosphate, curing accelerator • A-3; IRGACURE-OXE03 (manufactured by BASF), photopolymerization initiator • A-4; Omnirad-369 (manufactured by IGM Resins BV), photopolymerization initiator

[0290] [Surfactants] • Sur-1; MEGAFAC F-781F (manufactured by DIC Corporation), fluorine-based surfactant • Sur-2; KF6001 (manufactured by Shin-Etsu Chemical Co., Ltd.), silicone-based surfactant

[0291] 〔solvent〕 • S-1; Propylene glycol monomethyl ether acetate (PGMEA) S-2: 1,4-butanediol diacetate (1,4-BDDA)

[0292] [Preparation of compositions for the examples and comparative examples] For components other than the solvent shown in Table 1, the components listed in Table 1 were mixed to achieve the composition ratio (by mass) shown in Table 1 and placed in a sealed container made of PTFE (polytetrafluoroethylene). Subsequently, the solvent was added to achieve the composition ratio (by mass) shown in Table 1, the container was sealed, and the mixture was dispersed at 50 G for 2 hours using a Resodyn RAM (low-frequency resonant acoustic mixer) to prepare the compositions for each example and comparative example.

[0293] [Evaluation Test] [Settlement Stability] Three mL of the composition obtained as described above was placed in a glass sample bottle (cylindrical, 23 mm in diameter and 35 mm in height), sealed, and left to stand at 25°C for 30 days. Subsequently, the composition in the sample bottle was visually observed, and the distance d1 from the gas-liquid interface to the interface between the transparent and opaque regions, and the distance d2 from the gas-liquid interface to the bottom surface of the sample bottle were measured. Subsequently, the same sample bottle was stirred at 3300 r / min for 30 seconds using a shaker Se-08 manufactured by Taitec Corporation, and then allowed to stand at 25°C for 12 hours. Thereafter, the composition was visually observed, and the distance d´1 from the gas-liquid interface to the interface between the transparent region and the opaque region, and the distance d´2 from the gas-liquid interface to the bottom surface of the sample bottle were measured. The sedimentation stability was evaluated using the distances d1 and d2, and the distances d´1 and d´2 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: 0 ≦ d1 / d2 ≦ 0.1, and 0 ≦ d´1 / d´2 ≦ 0.1 2: 0.1 < d1 / d2 ≦ 0.3, and 0 ≦ d´1 / d´2 ≦ 0.1 1: 0.3 < d1 / d2, or 0.1 ≦ d´1 / d´2

[0294] [Isotropy of Magnetism of Magnetic Particle-Containing Film] Each composition was applied onto a Si wafer (film thickness: 100 μm) using an applicator to form a composition layer such that the film thickness of the magnetic particle-containing film after film formation became 100 μm. Thereafter, when the applied composition was a composition not containing a photopolymerization initiator, the composition layer was heated at 100°C for 10 minutes and then further heated at 230°C for 10 minutes to obtain a magnetic particle-containing film. Also, when the applied composition was a composition containing a photopolymerization initiator, exposure treatment was performed using a proximity exposure machine under the condition of 1000 mJ / cm 2 and then further heated at 230°C for 10 minutes to obtain a magnetic particle-containing film. Hereinafter, the Si wafer with a magnetic particle-containing film is also simply referred to as a substrate. One obtained substrate was cut into 1 cm × 2.8 cm, and substrates A cut so that the long axis came in the coating direction of the applicator and substrates B cut so that the short axis direction came were obtained. Thereafter, using PER-01 (a high-frequency magnetic permeability measuring device manufactured by Keycom Corporation), the magnetic permeability at 100 MHz was measured, and the specific magnetic permeability μ´A and μ´B of the magnetic particle-containing film on each substrate were obtained, and the value of "μ´A / μ´B" was determined. Note that μ'A is the permeability measured using substrate A, and μ'B is the permeability measured using substrate B. The same procedure was repeated nine more times, and substrates were prepared and their magnetic permeability measured ten times for each composition. The number of substrates n (where n is an integer from 0 to 10) for which 0.9 < μ'A / μ'B < 1.1 was evaluated according to the following criteria. If the following criteria were "2", the magnetic particle-containing film was judged to have excellent magnetic isotropy. The results are shown in Table 1. 2:n≦3 1:3 <n

[0295] [Chemical resistance of magnetic particle-containing films] Each composition was applied to a Si wafer (film thickness: 100 μm) using an applicator to form a composition layer such that the thickness of the magnetic particle-containing film after deposition was 100 μm. If the applied composition did not contain a photopolymerization initiator, the composition layer was heated at 100°C for 10 minutes, and then further heated at 230°C for 10 minutes to obtain a magnetic particle-containing film. If the applied composition contained a photopolymerization initiator, it was heated at 1000 mJ / cm² using a proximity exposure machine. 2 The film containing magnetic particles was obtained by exposure treatment under the specified conditions and then heating at 230°C for 10 minutes. Hereafter, a Si wafer with a magnetic particle-containing film will also simply be referred to as a substrate. The obtained magnetic particle-containing film was cut into 1 cm × 2.8 cm sections along with the substrate, and the magnetic permeability at 100 MHz was measured using PER-01 to obtain the relative magnetic permeability μ'X of the magnetic particle-containing film on the substrate. Subsequently, the same substrate was immersed in a 10% hydrochloric acid aqueous solution at 25°C for 30 minutes, and then the relative permeability μ'Y of the magnetic particle-containing film was obtained in the same manner. The rate of change Δμ' before and after immersion in a 10% hydrochloric acid aqueous solution was calculated using the following formula and evaluated according to the following criteria. If the result was "2" or higher in the following criteria, the magnetic particle-containing film was judged to have excellent chemical resistance. The results are shown in Table 1. Formula: Δμ´(%)=|μ´Y-μ´X| / μ´X×100 3:Δμ'<5% 2: 5% ≤ Δμ' < 10% 1:10%≦Δμ´

[0296] [result] The table below shows the formulation of each composition and the results of the evaluation tests conducted for each composition. The values ​​listed in the "Quantity" column of the table indicate the mass ratio (mass%) of that component relative to the total mass of the composition.

[0297] [Table 1]

[0298] [Table 2]

[0299] As shown in Table 1, the composition of the present invention exhibits good stability over time, and it has been confirmed that a magnetic particle-containing film with excellent magnetic isotropy can be formed using the composition of the present invention. Furthermore, it has been confirmed that it also exhibits good chemical resistance.

[0300] It was confirmed that the effects of the present invention are superior when the magnetic particles contain Ni atoms as specific atoms and when the particle size of the magnetic particles is 5 μm or larger (see comparison of results in Examples 1-3, etc.).

[0301] When the magnetic particles contain Co atoms as a specific atom, and when the particle size of the magnetic particles is 20 μm or larger, it has been confirmed that the effects of the present invention are superior (see comparison of results in Examples 7-9, etc.).

[0302] From the perspective of superior effects of the present invention, it was confirmed that the content of specific atoms is preferably 70% by mass or more, and more preferably 85% by mass or more, of the total mass of metal atoms (see Comparison of Results in Examples 7, 10-13, etc.).

[0303] It was confirmed that the effects of the present invention are superior when the magnetic particles contain Ni atoms as specific atoms (see comparison of results in Examples 3 and 7, etc.). As a general trend in the examples, the larger the particle size of the magnetic particles, the superior the effects of the present invention. On the other hand, Example 3, which used magnetic particles P-3 with smaller particle size and containing Ni atoms, achieved superior effects of the present invention compared to Example 7, which used magnetic particles P-7 with larger particle size and containing Co atoms).

[0304] It was confirmed that the effects of the present invention are superior when the solid content concentration of the composition is 75% by mass or higher (see the comparison of results in Examples 25, 53-60, etc.).

[0305] It has been confirmed that the effects of the present invention are superior when the composition contains an epoxy compound (an epoxy-curable compound) as a polymerizable compound (see comparison of the results in Examples 37-43, etc.).

Claims

1. A composition containing magnetic particles and a rheology control agent, The content of the magnetic particles having an aspect ratio of less than 8 is 25% by mass or more relative to the total mass of the magnetic particles. The aforementioned magnetic particles contain metal atoms, The aforementioned metal atom contains one or more specific atoms selected from the group consisting of Ni atoms and Co atoms. The aforementioned metal atoms contain metalloid atoms, The aforementioned metalloid atom is at least one selected from the group consisting of silicon and boron. The content of the aforementioned specific atom is 50% by mass or more relative to the total mass of the metal atoms. A composition in which the particle size of the magnetic particles is 15 μm or larger.

2. The composition according to claim 1, wherein the content of the specified atom is 70% by mass or more relative to the total mass of the metal atoms.

3. The composition according to claim 1 or 2, wherein the rheology control agent is an organic rheology control agent.

4. The composition according to any one of claims 1 to 3, wherein the rheology control agent is one or more selected from the group consisting of polycarboxylic acids, polyanhydrides, and amide waxes.

5. Furthermore, the composition according to any one of claims 1 to 4, comprising an epoxy-curable compound as the polymerizable compound.

6. A magnetic particle-containing film formed using the composition described in any one of claims 1 to 5.

7. An electronic component comprising a magnetic particle-containing film as described in claim 6.

8. The electronic component according to claim 7, used as an inductor.

9. An electronic component according to claim 7, used as an antenna.

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