Boron nitride material, resin composition containing the boron nitride material, and insulating material

Abstract

The purpose of the present invention is to provide a boron nitride material that is suitable as an insulation material that can be applied to a high-frequency circuit board.　The present invention relates to a boron nitride material having: (A) an average thickness of 10 to 700 nm; (B) an aspect ratio of 10 to 400; and (C) an orientation index of 30 or less as determined by X-ray diffraction.

Description

[Technical Field]

[0001] The present invention relates to a boron nitride material suitable for insulating materials, a resin composition containing the boron nitride material, and an insulating material. [Background technology]

[0002] Next-generation communication devices such as smartphones, tablet devices, satellite communications, and television broadcasting require the transmission and reception of larger amounts of data at higher speeds, and consequently, the use of higher frequency electrical signals is being considered. For example, in the field of mobile information communications, the development of fifth-generation mobile communication systems (5G) is progressing globally. The communication speed of this fifth-generation mobile communication system will be tens of times faster than the previous generation, and to achieve this, electrical signals in the high-frequency band of 10 GHz or higher are being used. In the automotive sector, the use of electrical signals in the high-frequency band of 60 GHz or higher, known as millimeter waves, is being considered for in-vehicle radar systems.

[0003] Circuit boards for high-capacity, high-speed communication utilizing high-frequency bands require materials with low dielectric properties such as relative permittivity and dielectric loss tangent, as well as excellent heat resistance and mechanical properties.

[0004] Here, relative permittivity is a parameter that indicates the degree of polarization within a dielectric material. The higher the relative permittivity, the greater the propagation delay of electrical signals. Therefore, to increase the propagation speed of electrical signals and enable high-speed calculations, a lower relative permittivity is preferable.

[0005] Furthermore, the dielectric loss tangent (also called tanδ) is a parameter that indicates the amount of electrical signals propagating within a dielectric material that are converted into heat and lost. The lower the dielectric loss tangent, the less electrical signal loss there is, and the higher the electrical signal transmission rate. In the high-frequency band, the dielectric loss tangent increases with increasing frequency, so in order to minimize electrical signal loss, it is necessary to use materials with a low value. Therefore, for circuit boards used in the high-frequency band above 10 GHz, materials with low relative permittivity and dielectric loss tangent are highly desirable.

[0006] Boron nitride is known as a material with excellent thermal conductivity and insulation properties, and its use in circuit boards is progressing as a material that provides high heat dissipation while ensuring insulation.

[0007] For example, Patent Document 1 proposes a laminate comprising an insulating resin layer containing boron nitride as a thermally conductive filler.

[0008] Patent Document 2 proposes a gold foil-coated sheet using boron nitride of a specific shape and a laminate for circuit boards using the same.

[0009] Patent Document 3 describes an aspect ratio of approximately 50 to approximately 300, and at least approximately 20m 2 / g surface A powder containing hexagonal boron nitride particles with a product, a diameter greater than approximately 1 μm, and a thickness of approximately 50 nm or less has been proposed. [Prior art documents] [Patent Documents]

[0010] [Patent Document 1] Japanese Patent Publication No. 2020-102554 [Patent Document 2] Japanese Patent Publication No. 2010-76955 [Patent Document 3] Japanese Patent Publication No. 2008-280243 [Overview of the project] [Problems that the invention aims to solve]

[0011] However, conventional boron nitride does not have satisfactory dielectric properties and further improvement has been demanded. In addition, when an insulating material containing thick boron nitride is formed into a sheet or film, there is a problem that its surface becomes rough. Patent Document 3 only describes using a powder containing hexagonal boron nitride particles as a processing aid in cosmetics or polymer extrusion, and does not describe using it as an insulating material. Naturally, no consideration has been given to dielectric properties either.

[0012] Therefore, an object of the present invention is to provide a boron nitride material suitable as an insulating material for a circuit board for a high-frequency band.

Means for Solving the Problems

[0013] As a result of intensive studies, the present inventors have found that a boron nitride material satisfying specific parameters can solve the above problems, and have completed the present invention. That is, the present invention is shown in the following [1] to [5].

[0014] [1] A boron nitride material having (A) an average thickness of 10 nm to 700 nm, (B) an aspect ratio of 10 to 400, and (C) an orientation index determined by X-ray diffraction of 30 or less.

[0015] [2] The boron nitride material according to [1], having (D) an average particle size of 1 μm to 14 μm and (E) a bulk density of 0.05 g / cm 3 ~ 0.25 g / cm 3 .

[0016] [3] A resin composition containing the boron nitride material according to [1] or [2].

[0017] [4] The resin composition according to [3], containing an epoxy resin as a resin component.

[0018] [5] An insulating material using the resin composition according to [3] or [4].

Effects of the Invention

[0019] According to the present invention, a boron nitride material suitable as an insulating material for circuit boards used in high-frequency bands can be provided. [Modes for carrying out the invention]

[0020] The present invention will be described in detail below based on preferred embodiments. <Boron nitride materials> In the present invention, boron nitride material is a general term for compounds containing nitrogen (N) and boron (B) as constituent elements. Specific examples of this boron nitride material include boron nitride (BN) and boron-carbon nitride (BCN).

[0021] The boron nitride material of the present invention can be manufactured by applying an external impact to boron nitride as a raw material and peeling off the layered structure of the boron nitride. The boron nitride used as a raw material is a hexagonal boron nitride having a layered structure, and may be a commercially available product, or it may be a mixture of two or more types of boron nitride with different particle size distributions, or two or more classified types of boron nitride combined in an appropriate ratio.

[0022] The layered structure of boron nitride refers to a structure in which one to several thousand unit layers are stacked. As the number of layers decreases, the boron nitride tends to aggregate more easily, and the effect of improving the physical properties of boron nitride is impaired. However, boron nitride materials with average thickness, aspect ratio, and orientation index within a specific range exhibit excellent physical property improvement effects, and the decrease in the dielectric constant of boron nitride is significant.

[0023] In this invention, the average thickness of the boron nitride material is the value obtained by arithmetic mean by measuring the thickness of 30 or more boron nitride materials using SEM images taken with an electron microscope. The average thickness of the boron nitride material in this invention is 10 nm to 700 nm, and is preferably 50 nm to 400 nm from the viewpoint of significantly reducing the dielectric constant of the boron nitride material.

[0024] In the present invention, the aspect ratio of the boron nitride material is the value obtained by measuring the major axis and thickness of the boron nitride material by image observation using an electron microscope, calculating the ratio of the major axis to the thickness (major axis / thickness) measured using 30 or more boron nitride materials, and then arithmetically averaging these ratios. The aspect ratio of the boron nitride material in the present invention is 10 to 400, and is preferably 10 to 300 from the viewpoint of improving the thermal conductivity of the cured product of the resin composition containing the boron nitride material.

[0025] In the present invention, the orientation index of the boron nitride material is the ratio (I002 / I100) of the diffraction line intensity I002 of the (002) plane and the diffraction line intensity I100 of the (100) plane, obtained by measuring the diffraction pattern of the boron nitride material with an X-ray diffractometer and determining the diffraction line intensity I002 of the (002) plane and the diffraction line intensity I100 of the (100) plane. The orientation index of the boron nitride material in the present invention is 30 or less, and is preferably 25 or less from the viewpoint of significantly reducing the dielectric constant of the boron nitride material.

[0026] In this invention, the average particle size of the boron nitride material represents the 50% particle diameter of the volume-based diameter measured by laser diffraction / light scattering. From the viewpoint of significantly reducing the dielectric constant of the boron nitride material, the average particle size of the boron nitride material of this invention is preferably 1 μm to 14 μm, and more preferably 3 μm to 10 μm.

[0027] In this invention, the bulk density of the boron nitride material is the value obtained by dividing the mass of the boron nitride material lightly packed into a graduated cylinder by its volume. The boron nitride material of this invention has a bulk density of 0.05 g / cm³, from the viewpoint of significantly reducing the dielectric constant of the boron nitride material. 3 ~0.25 g / cm 3 Preferably, it is 0.08 g / cm³. 3 ~0.20 g / cm³ 3 That is More preferable.

[0028] In this invention, the dielectric constant of the boron nitride material is expressed as a value measured using a dielectric constant measuring device (E4991E, Agilent Technologies) at a frequency of 1 GHz and an applied voltage of 0.1 V, after pelletizing the boron nitride material using a press machine (Labo Press LP-200; manufactured by Labonext) under the conditions of applied pressure: 40 MPa and pressure application time: 10 minutes. The boron nitride material of this invention is characterized in that its dielectric constant in the range of 800 MHz to 100 GHz is 3.15 or less. If the dielectric constant of the boron nitride material exceeds 3.15, the insulating properties of the cured resin composition containing the boron nitride material are insufficient, and dielectric breakdown may occur when used in a high-frequency band.

[0029] In the present invention, the surface of the boron nitride material may be coated with metal powder, alloy powder, fatty acid partial esters of anhydrous sorbitol, titanates, zirconates, benzoic acid derivatives, asyloxysilanes, alkoxysilanes, methoxysilanes, sorbitan monostearate, sorbitan monolaurate, sorbitan monooleate, sorbitan monopalmitate, polyoxyethylene monolaurate, polyoxyethylene monostearate, polyoxyethylene monooleate, polyoxyethylene monopalmitate, sorbitan polyoxyethylene monopalmitate, silazanes, silanols, silane compounds, siloxane compounds, polymers containing alkoxy groups, hydroxyl groups, or Si-H groups, or polymers containing titanates, zirconates, benzoic acid derivatives, or mixtures selected from these groups.

[0030] The boron nitride material of the present invention is characterized by having a dielectric constant of 3.15 or less. From the viewpoint of ease of manufacture, the lower limit of the dielectric constant is preferably 2.0 or higher, and more preferably 2.5 or higher.

[0031] Next, the method for producing the boron nitride material of the present invention will be described. The boron nitride material of the present invention can be manufactured by applying an external impact to boron nitride as a raw material to exfoliate the layered structure of the boron nitride. Methods for applying an external impact to boron nitride include using known devices such as high-speed rotary shear stirrers, media stirring mills, container-driven mills, colloidal mills, high-pressure emulsifiers, and ultrasonic emulsifiers, and processing under appropriate conditions. Specifically, by applying an external impact of a moderate force to the boron nitride as a raw material, the layered structure of the boron nitride can be exfoliated, reducing the average thickness and increasing the aspect ratio. However, if an excessive external impact is applied to the boron nitride as a raw material, not only will the layered structure be exfoliated, but the boron nitride itself will be crushed. Therefore, while the average thickness can be reduced, the aspect ratio will not change significantly.

[0032] Before applying external shock to the boron nitride, it is preferable to mix the boron nitride with a solvent to form a boron nitride slurry before applying external shock. Examples of solvents that can be mixed with boron nitride include alcohol-based solvents such as methanol, ethanol, isopropanol, butanol, hexanol, octanol, hexafluoroisopropanol, ethylene glycol, propylene glycol, tetramethylene glycol, tetraethylene glycol, hexamethylene glycol, diethylene glycol, and methoxyethanol; ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester-based solvents such as ethyl acetate and butyl acetate; heterocyclic solvents such as pyridine, piperidine, morpholine, tetrahydrofuran, and dioxane; aliphatic solvents such as pentane, hexane, neopentane, cyclohexane, heptane, octane, isooctane, nonane, and decane; oils such as silicone oil and liquid paraffin; dimethylformamide, N-methylpyrrolidone, and water. From the viewpoint of efficiently removing the layered structure of boron nitride, the boron nitride content in the slurry is preferably 1% to 45% by mass, and more preferably 1% to 10% by mass, relative to the slurry.

[0033] In a slurry containing boron nitride, coupling agents such as silanes, siloxanes, myristic acid, stearic acid, behenic acid, and other long-chain carboxylates may be added to enhance the function of boron nitride; dispersants may be added to disperse the exfoliated boron nitride material; and substances may be added to coat the surface of the exfoliated boron nitride material.

[0034] As the dispersant described above, in addition to known surfactants, dispersants described in, for example, Japanese Patent Publication No. 8-127793, Japanese Patent Publication No. 2015-65242, Japanese Patent Publication No. 2015-199064 may be used. From the viewpoint of easily obtaining the boron nitride material of the present invention, it is preferable to add an anionic surfactant to the slurry containing boron nitride in the method for producing the boron nitride material of the present invention.

[0035] Examples of materials used to coat the surface of the exfoliated boron nitride material include polyvinyl compounds such as polyacrylate, polymethacrylate, polystyrene, polyacrylonitrile, polyacrylamide, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, ethylene vinyl acetate copolymer, polyvinyl ether, polyvinylpyrrolidone, and polyvinylacetamide; polymer compounds such as olefin maleic acid copolymer, olefin fumaric acid copolymer, methylcellulose, ethylcellulose, acetylcellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and polysiloxane; diglycidyl ethers of bisphenols such as bisphenol A diglycidyl ether and bisphenol F diglycidyl ether; epoxy compounds such as phenol novolac type epoxy resin, cresol novolac type epoxy resin, and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate; and 3-ethyl-3-[(phenoxy)methyl] Oxetane compounds such as xetane and 3,7-bis(3-oxetanyl)-5-oxa-nonane; isocyanate compounds such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, and 1,6-hexamethylene diisocyanate; methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, and ethylene glycol diacrylate. Acrylate compounds such as propylene glycol diacrylate; methacrylate compounds such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and dodecyl methacrylate; vinyl ether compounds such as butyl vinyl ether, cyclohexyl vinyl ether, and hydroxyethyl vinyl ether; vinyl ester compounds of vinyl hexanoate, vinyl neodecanoate, and vinyl benzoate; alkoxysilane compounds such as methyltrimethoxysilane, butyltrimethoxysilane, and phenyltrimethoxysilane;Antioxidants such as dibutylhydroxytoluene, butylhydroxyanisole, stearyl(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, tridecyl phosphite, dilaurylthiodipropionate, ditridecylthiodipropionate, phenylnaphthylamine, and 4,4'-bis(dialkyl)diphenylamine; UV absorbers such as benzotriazole-based UV absorbers, triazine-based UV absorbers, and cyanoacrylate-based UV absorbers; hindered amine-based light stabilizers such as 2,2,6,6-tetramethyl-4-piperidinol fatty acid ester; flame retardants such as tetrabromobisphenol A, tetrachlorophthalic anhydride, and tricresyl phosphate; and diheptyl phthalate. Examples include plasticizers such as dioctyl phthalate, dioctyl adipate, diisodecyl adipate, dioctyl sebacate, trioctyl trimellitate, and tetraoctyl pyromelitate; lubricants such as fatty acid amides, ethylenebis-fatty acid amides, metal soaps, polyethylene wax, montan wax, and hydrogenated castor oil; surfactants such as anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants; hydrocarbons such as paraffinic mineral oil, naphthenic mineral oil, aromatic mineral oil, polybutene, and poly-α-olefin; and ionic liquids such as 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide and 1-butyl-3-methylimidazolium dicyanimide.

[0036] Next, we will describe a device for applying external shock to boron nitride. A high-speed rotary shear agitator is a dispersion device that has a rotor and a stator with openings on its sides. The rotor rotates at high speed to draw up the boron nitride slurry from below and push it out to the outer circumference through the openings on the sides of the stator. A large shear force is obtained when the slurry passes through the gap between the rotor and the stator and when it is discharged from the openings on the sides of the stator. From the viewpoint of efficiently producing the boron nitride material of the present invention, the gap between the rotor and the stator is preferably 0.1 mm to 0.3 mm, more preferably 0.15 mm to 0.2 mm, and the rotor rotation speed is preferably 2,000 rpm to 15,000 rpm, more preferably 3,000 rpm to 10,000 rpm. A high-speed rotary shear agitator is sometimes called a high-speed homomixer or high-shear mixer.

[0037] A container-driven mill is a disperser in which a boron nitride slurry and a grinding medium are placed in a container and dispersed by rotating or vibrating the container. Shear force is generated when the container and the grinding medium, or the grinding mediums themselves, collide. Examples of container-driven mills include container mills in which the container rotates, vibrating mills in which the container vibrates, and planetary mills in which a rotating container is subjected to orbital rotation. The grinding medium is usually a ball-shaped grinding medium with a diameter of 0.2 mm or more. Container mills are sometimes called ball mills because they use ball-shaped grinding media.

[0038] A media stirring mill stirs a boron nitride slurry and a grinding medium, generating shear force through collisions between the grinding medium particles. Typically, beads with a diameter of 0.03 mm to 10 mm are used as the grinding medium. Examples of media stirring mills include sand mills, attritors, and bead mills.

[0039] A colloidal mill is a disperser that disperses a boron nitride slurry by flowing it between two very close, high-speed rotating discs and a stationary disc, generating shear force between the discs. Furthermore, using discs with grooves formed in a millstone-like pattern from the center outward is preferable because it generates cavitation and improves dispersibility.

[0040] A high-pressure emulsifier is a disperser that applies a pressure of at least 130 MPa to a boron nitride slurry, causing a rapid pressure drop and turbulence, generating shear force and cavitation, and thus breaking down the material by methods such as passing the slurry through pores, causing it to collide with flat surfaces such as valves or spherical surfaces such as balls, or causing the slurries that have passed through the pores to collide with each other. From the viewpoint of easily obtaining the boron nitride material of the present invention, the pore diameter is preferably 0.05 mm to 0.5 mm, and more preferably 0.1 mm to 0.4 mm.

[0041] An ultrasonic emulsifier is a disperser that applies ultrasound to a boron nitride slurry, breaking it down through ultrasonic shear force and cavitation caused by bubble generation. From the viewpoint of easily obtaining the boron nitride material of the present invention, the frequency of the ultrasound is preferably 15kHz to 40kHz, and more preferably 15kHz to 25Hz.

[0042] Furthermore, the boron nitride material of the present invention can be manufactured by dissolving boron nitride in a solvent having a strong affinity for boron nitride and then using any microwave oven. When using a general 2.4 GHz microwave oven, the microwave output is preferably 300 W to 3,000 W. There are no particular restrictions on the microwave application time, but from the viewpoint of easily obtaining the boron nitride material of the present invention, it is preferably 10 seconds or more, and more preferably 10 seconds to 10 minutes. Also, when using a microwave oven that applies low-energy microwaves of 1 W to 100 W, the application time is preferably 20 minutes to 48 hours.

[0043] <Resin composition> Next, the resin composition of the present invention will be described. The resin composition of the present invention contains a resin component and the boron nitride material described above. From the viewpoint of exhibiting excellent thermal conductivity and high insulating properties, the resin composition of the present invention preferably contains 1 to 1,000 parts by mass of the boron nitride material, and more preferably 5 to 900 parts by mass, per 100 parts by mass of the resin component.

[0044] The resin composition of the present invention contains one or more resin components selected from the group consisting of olefin resins, polyvinyl chloride, polyvinylidene chloride, polylactone, polystyrene, ABS resin, AS resin, polyacrylate, polymethacrylate, polyimide, polyamideimide, polyvinyl alcohol, polyacetal, polycarbonate, silicone resin, polydimethylsiloxane, polyethylene terephthalate, polybutylene terephthalate, polyether, polyether ketone, polyether ether ketone, polyphenylene sulfide, and epoxy resin. Among these, epoxy resin is preferred as the resin component from the viewpoint of excellent heat resistance and mechanical properties.

[0045] Examples of olefin resins that can be used in the resin composition of the present invention include low-density polyethylene (LDPE), linear low-density polyethylene (L-LDPE), high-density polyethylene (HDPE), isotactic polypropylene, syndiotactic polypropylene, hemiisotactic polypropylene, cycloolefin polymers, stereoblock polypropylene, α-olefin polymers such as poly-3-methyl-1-butene, poly-3-methyl-1-pentene, and poly-4-methyl-1-pentene, ethylene / propylene block or random copolymers, impact copolymer polypropylene, ethylene-methyl methacrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-vinyl acetate copolymer, and α-olefin copolymers such as ethylene-vinyl alcohol resin (EVOH), and may also be elastomers. In the resin composition of the present invention, two or more of these polymers may be mixed and used, block copolymers may be formed and used as block polymer type resins, and alloyed resins may be used. Furthermore, chlorinated products of these polyolefin resins may also be used. These may be used individually, or two or more may be used in combination.

[0046] The above-mentioned elastomers include elastomers obtained by blending polyolefins such as polypropylene and polyethylene as hard segments and rubber such as ethylene-propylene rubber as soft segments, or elastomers obtained by dynamic crosslinking. Examples of hard segments include at least one selected from polypropylene homopolymer, polypropylene block copolymer, polypropylene random copolymer, etc. Examples of soft segments include ethylene-propylene copolymer (EPM), ethylene-propylene-diene copolymer (EPDM), ethylene-vinyl acetate copolymer (EVA), vinyl acetate homopolymer, maleic acid-modified ethylene-butene resin, etc. Two or more of these elastomers may be used in mixture form.

[0047] The resin composition of the present invention may also use a rubber component as a resin component. Examples of rubber components include natural rubber, isoprene rubber, chloroprene rubber, silicone rubber, hydrogenated styrene-based thermoplastic elastomer, polyamide elastomer, polyetheramide elastomer, urethane rubber, fluororubber, and the like. These may be used individually or in combination of two or more.

[0048] Examples of epoxy resins that can be used in the resin composition of the present invention include compounds having two or more epoxy rings, compounds having a glycidyl group, compounds having an alicyclic epoxy group, epoxy resins using amines as precursors, and epoxy resins using carboxylic acids as precursors. More specifically, examples include bisphenol-type epoxy resins such as bisphenol A-type epoxy resins and bisphenol F-type epoxy resins; biphenyl-type epoxy resins such as biphenyl-type epoxy resins and tetramethylbiphenyl-type epoxy resins; dicyclopentadiene-type epoxy resins; naphthalene-type epoxy resins; alicyclic epoxy resins obtained from cyclohexanedimethanol or hydrogenated bisphenol A, etc.; novolac-type epoxy resins such as phenol novolac-type epoxy resins, cresol novolac-type epoxy resins, bisphenol A novolac-type epoxy resins, epoxides which are condensates of phenols and aromatic aldehydes having a phenolic hydroxyl group, and biphenyl novolac-type epoxy resins; triphenylmethane-type epoxy resins; tetraphenylethane-type epoxy resins; dicyclopentadiene-phenol addition reaction type epoxy resins; and phenol aralkyl-type epoxy resins. These may be used individually or in combination of two or more. The epoxy resin may be a substituted product with alkyl groups or halogen atoms. Furthermore, these may be modified into epoxy resins using urethane compounds or isocyanate compounds. In this invention, the term epoxy resin refers to the monomer used as the main component and does not refer to the cured product obtained by adding a curing agent.

[0049] When epoxy resin is used as the resin component, the resin composition of the present invention may contain a curing agent, a curing accelerator, and a polymerization initiator. Examples of curing agents, curing accelerators, and polymerization initiators include primary and secondary amine curing agents, amide curing agents, acid anhydride curing agents, phenol curing agents, thiol curing agents, latent thermosetting agents, imidazole curing agents, organophosphine curing agents, phosphonium salt curing agents, Lewis acid curing accelerators, tertiary amine curing accelerators, and cationic polymerization initiators. These may be used individually or in combination of two or more.

[0050] Examples of the primary and secondary amine-based curing agents mentioned above include aliphatic amines, polyetheramines, alicyclic amines, and aromatic amines. These may be used individually or in combination of two or more.

[0051] Examples of the above-mentioned aliphatic amines include ethylenediamine, 1,3-diaminopropane, 1,4-diaminopropane, hexamethylenediamine, 2,5-dimethylhexamethylenediamine, trimethylhexamethylenediamine, diethylenetriamine, iminobispropylamine, bis(hexamethylene)triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-hydroxyethylethylenediamine, and tetra(hydroxyethyl)ethylenediamine. These may be used individually or in combination of two or more.

[0052] Examples of the polyetheramines mentioned above include triethylene glycol diamine, tetraethylene glycol diamine, diethylene glycol bis(propylamine), polyoxypropylenediamine, and polyoxypropylene triamines. These may be used individually or in combination of two or more.

[0053] Examples of the above-mentioned alicyclic amines include isophoronediamine, metacenediamine, N-aminoethylpiperazine, bis(4-amino-3-methyldicyclohexyl)methane, bis(aminomethyl)cyclohexane, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro(5,5)undecane, norbornenediamine, etc. These may be used individually or in combination of two or more.

[0054] Examples of the above aromatic amines include tetrachloro-p-xylenediamine, m-xylenediamine, p-xylenediamine, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 2,4-diaminoanisole, 2,4-toluenediamine, 2,4-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diamino-1,2-diphenylethane, 2,4-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, m-aminophenol, m-aminobenzylamine, benzyldimethylamine, 2-dimethylaminomethyl)phenol, triethanolamine, methylbenzylamine, α-(m-aminophenyl)ethylamine, α-(p-aminophenyl)ethylamine, diaminodiethyldimethyldiphenylmethane, and α,α'-bis(4-aminophenyl)-p-diisopropylbenzene. These may be used individually or in combination of two or more.

[0055] Examples of the above-mentioned amide-based curing agents include dicyandiamide and polyamide resins.

[0056] Examples of the above acid anhydride-based curing agents include tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, methylcyclohexenetetracarboxylic dianhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, ethylene glycol bis-anhydrotrimellitate, glycerin bis(anhydrotrimellitate) monoacetate, dodecenyl succinic anhydride, polyadipic anhydride, polyazelaic anhydride, polysebacic anhydride, poly(ethyloctadecanediic acid) anhydride, poly(phenylhexadecanedioic acid) anhydride, aliphatic dibasic acid polyanhydride, and methyl hydroxyanhydride. Examples include citric acid, methylcyclohexenedicarboxylic acid anhydride, methylcyclohexenetetracarboxylic acid anhydride, benzophenonetetracarboxylic acid anhydride, ethylene glycol bistrimellitate dianhydride, hetic anhydride, nadic anhydride, methylnadic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexane-1,2-dicarboxylic acid anhydride, chloride anhydride, methylbutenyltetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, methylhymic anhydride, alkenyl-substituted succinic anhydride, glutaric acid anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid dianhydride, 1-methyl-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid dianhydride, etc. These may be used individually or in combination of two or more.

[0057] Examples of the above phenolic curing agents include bisphenol A, bisphenol F, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl ether, 1,4-bis(4-hydroxyphenoxy)benzene, 1,3-bis(4-hydroxyphenoxy)benzene, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, phenol novolac, bisphenol A novolac, o-cresol novolac, m-cresol novolac, p-cresol novolac, xylenol novolac, poly-p-hydroxystyrene, hydroquinone, resorcinol, catechol, tert-butylcatechol, tert-butylhydroquinone, fluoroglycinol, pyrogallol, tert-butylpyrogallol, allylated pyrogallol, polyallylated pyrogallol, 1,2,4-benzenetriol, 2,3,4-trihydroxybenzophenone, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene Examples include rhene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,4-dihydroxynaphthalene, 2,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,8-dihydroxynaphthalene, allyl or polyallylated derivatives of the above dihydroxynaphthalenes, allylated bisphenol A, allylated bisphenol F, allylated phenol novolac, allylated pyrogallol, etc. These may be used individually or in combination of two or more.

[0058] Examples of the thiol-based curing agent include tris(mercapto propionate) of N,N’N”-cyanuric triethanol, tris(mercapto propionate) of pentaerythritol, bis(2-mercapto butanoate) of 1,4-butanol, tris(2-mercapto butanoate) of pentaerythritol, tris(2-mercapto butanoate) of N,N’N”-cyanuric triethanol, and the like. These may be used alone or in combination of two or more.

[0059] Examples of the latent heat curing agent include, for example, a modified amine latent curing agent having at least one amino group having active hydrogen in the molecule obtained by reacting a polyamine compound and an epoxy resin, a latent curing agent containing a phenolic resin, dicyandiamide, modified polyamine, hydrazides, 4,4’-diaminodiphenyl sulfone, boron trifluoride amine complex salt, ureas, and melamine. In addition, those described in International Publication No. 2012 / 020572 and JP-A-2014-177525 may be mentioned. These may be used alone or in combination of two or more.

[0060] The cationic polymerization initiator may be any compound that can release a substance that initiates cationic polymerization by light irradiation or heating, but preferably an onium salt is used.

[0061] Examples of the onium salt include a salt of a cation and an anion represented by [M] r+ [G] r- . Here, the cation [M] r+ is preferably an onium, and its structure can be represented by, for example, the formula, [(R 13 ) f Q] r+ .

[0062] The above R 13 is an organic group having 1 to 60 carbon atoms and may contain a plurality of any atoms other than carbon atoms. f is an integer of 1 to 5. f R 13Each is independent and may be the same or different. Also, R 13 At least one of them is preferably an organic group having an aromatic ring. Q is an atom or group of atoms selected from the group consisting of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F, and N=N. Also, a cation [M] r+ When the valence of Q in the atom is q, the relationship r=fq must hold (where N=N is treated as having a valence of 0).

[0063] Also, anions [G] r-Specific examples include, as monovalent, halide ions such as chloride ions, bromide ions, iodide ions, and fluoride ions; inorganic anions such as perchlorate ions, chlorate ions, thiocyanate ions, hexafluorophosphate ions, hexafluoroantimonate ions, and tetrafluoroborate ions; borate anions such as tetrakis(pentafluorophenyl)borate, tetra(3,5-difluoro-4-methoxyphenyl)borate, tetrafluoroborate, tetraarylborate, and tetrakis(pentafluorophenyl)borate; methanesulfonate ions, dodecylsulfonate ions, benzenesulfonate ions, toluenesulfonate ions, trifluoromethanesulfonate ions, naphthalenesulfonate ions, diphenylamine-4-sulfonate ions, and 2-amino-4-methyl-5-chlorobenzenesulfonate ions. Sulfonate ion, 2-amino-5-nitrobenzenesulfonate ion, phthalocyanine sulfonate ion, fluorosulfonate ion, trinitrobenzenesulfonate anion, camphor sulfonate ion, nonafluorobutane sulfonate ion, hexadecafluorooctanesulfonate ion, sulfonate ion having polymerizable substituents, Japanese Patent Publication No. 10-235999, Japanese Patent Publication No. 10-337959, Japanese Patent Publication No. 11- Organic sulfonic acid anions such as sulfonate ions described in Japanese Patent Publication No. 102088, Japanese Patent Publication No. 2000-108510, Japanese Patent Publication No. 2001-209969, Japanese Patent Publication No. 2001-322354, Japanese Patent Publication No. 2006-248180, Japanese Patent Publication No. 2006-297907, Japanese Patent Publication No. Hei 8-253705, Japanese Patent Publication No. 2004-503379, Japanese Patent Publication No. 2005-336150, International Publication No. 2006 / 28006, etc.;Examples include organophosphate anions such as octyl phosphate ion, dodecyl phosphate ion, octadecyl phosphate ion, phenyl phosphate ion, nonylphenyl phosphate ion, and 2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphonate ion; bistrifluoromethylsulfonylimide ion, bisperfluorobutanesulfonylimide ion, perfluoro-4-ethylcyclohexanesulfonate ion, tetrakis(pentafluorophenyl)borate ion, and tris(fluoroalkylsulfonyl)carbanion. Divalent examples include benzenedisulfonate ion and naphthalenedisulfonate ion. These may be used individually or in combination of two or more.

[0064] Among such onium salts, aromatic onium salts such as aryldiazonium salts, diaryliodonium salts, and triarylsulfonium salts can be preferably used in the resin composition of the present invention.

[0065] Aromatic sulfonium salts can be commercially available and include, for example, WPAG-336, WPAG-367, WPAG-370, WPAG-469, WPAG-638 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), CPI-100P, CPI-101A, CPI-200K, CPI-210S (all manufactured by Sunapro Co., Ltd.), Adeka Arcluz SP-056, Adeka Arcluz SP-066, Adeka Arcluz SP-130, Adeka Arcluz SP-140, Adeka Arcluz SP-082, Adeka Arcluz SP-103, Adeka Arcluz SP-601, Adeka Arcluz SP-606, Adeka Arcluz SP-701, Adeka Arcluz SP-150, Adeka Arcluz SP-170 (all manufactured by ADEKA Corporation).

[0066] Examples of the above imidazole-based curing agents include 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyano-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, and 2,4-diamino-6-[2'-methylimidazole Examples include lyl-(1')-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanurate adduct, 2-phenylimidazole isocyanurate adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and adducts of epoxy resins with the above imidazoles.

[0067] Examples of organic phosphine-based curing agents include tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, and phenylphosphine, while examples of phosphonium salt-based curing agents include tetraphenylphosphonium-tetraphenylborate, tetraphenylphosphonium-ethyltriphenylborate, and tetrabutylphosphonium-tetrabutylborate.

[0068] Lewis acid-based curing accelerators that can be used as curing accelerators include boron trifluoride, aluminum chloride, tin chloride, iron chloride, zinc chloride, titanium chloride, and acetylacetonate complexes of transition metals.

[0069] Examples of tertiary amine-based curing accelerators that can be used as curing accelerators include 1,8-diazabicyclo(5,4,0)undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol, and adducts of epoxy resins with the above tertiary amines.

[0070] The curing agents and curing accelerators listed above may be used individually or mixed in any ratio of two or more. It is preferable to use a substance generally known as an epoxy resin curing agent in such a ratio of 0.3 to 1.8 between the epoxy groups of the epoxy resin and the reaction sites that react with the epoxy groups in the curing agent to form a cross-linked structure; more preferably, it is in the range of 0.8 to 1.5; and even more preferably, it is in the range of 0.9 to 1.2. If the ratio is outside this range, unreacted epoxy groups or reaction sites of the curing agent may remain, resulting in undesirable physical properties. On the other hand, when using a substance generally known as an epoxy resin curing accelerator, it is preferable to use it in an amount of 0.1 to 20 parts by mass, and more preferably, 0.2 to 10 parts by mass, per 100 parts by mass of epoxy resin. If the amount of curing accelerator is too small, sufficient curing may not be achieved; if the amount of curing accelerator is too large, the effect of the curing accelerator on the cured resin increases, potentially degrading the properties of the cured resin.

[0071] The resin composition of the present invention may contain a solvent to appropriately adjust the viscosity during processing. Examples of solvents used in the resin composition of the present invention include alcohol-based solvents, ketone-based solvents, amide-based solvents, ether-based solvents, ester-based solvents, aliphatic hydrocarbon-based solvents, aromatic solvents, halogen-containing solvents, and the like.

[0072] Examples of alcohol-based solvents include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, 2-methylbutanol, sec-pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, heptanol-3, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethylheptanol-4, n-decanol, sec-undecyl alcohol, and trimethylnonyl alcohol. Monoalcohol solvents such as chol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, furfuryl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, and diacetone alcohol; polyhydric alcohol solvents such as ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, pentanediol-2,4, 2-methylpentanediol-2,4, hexanediol-2,5, heptanediol-2,4, 2-ethylhexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol, and tripropylene glycol;Examples of polyhydric alcohol partial ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and dipropylene glycol monopropyl ether. These may be used individually or in combination of two or more.

[0073] Examples of ketone solvents include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-isobutyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-isobutyl ketone, trimethylnonanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone, and phenthone. These may be used individually or in combination of two or more.

[0074] Examples of amide solvents include N,N-dimethylimidazolidinone, N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, and N-methylpyrrolidone. These may be used individually or in combination of two or more.

[0075] Examples of ether solvent systems include ethyl ether, isopropyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, dioxane, dimethyldioxane, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, and diethylene glycol dimethyl ether. Examples include diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol di-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, diphenyl ether, anisole, etc. These may be used individually or in combination of two or more.

[0076] Examples of ester solvents include diethyl carbonate, propylene carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, and diethylene glycol monomethyl ether acetate. Examples include noethyl ether, diethylene glycol acetate mono-n-butyl ether, propylene glycol acetate monomethyl ether, propylene glycol acetate monoethyl ether, propylene glycol acetate monopropyl ether, propylene glycol acetate monobutyl ether, dipropylene glycol acetate monomethyl ether, dipropylene glycol acetate monoethyl ether, glycol diacetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, isoamyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, and diethyl phthalate. These may be used individually or in combination of two or more.

[0077] Examples of aliphatic hydrocarbon solvents include n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, 2,2,4-trimethylpentane, n-octane, isooctane, cyclohexane, and methylcyclohexane. These may be used individually or in combination of two or more.

[0078] Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, isopropylbenzene, diethylbenzene, isobutylbenzene, triethylbenzene, di-isopropylbenzene, n-amylnaphthalene, trimethylbenzene, tetralin, and anisole. These may be used individually or in combination of two or more.

[0079] Examples of halogen-containing solvents include dichloromethane, chloroform, chlorofluorocarbons (CFCs), chlorobenzene, and dichlorobenzene. These may be used individually or in combination of two or more.

[0080] Any one of the above solvents may be used alone, or two or more may be used in combination. The types and amounts of these solvents should be selected as appropriate depending on the intended use.

[0081] The resin composition of the present invention may contain known resin additives in known amounts. Examples of known resin additives include coupling agents such as silane coupling agents and titanate coupling agents, ultraviolet absorbers, light stabilizers, flame retardants, adhesion aids, polymerization inhibitors, sensitizers, antioxidants, smoothing agents, orientation control agents, infrared absorbers, thixotropic agents, antistatic agents, defoaming agents, colorants, emulsifiers, surfactants, photopolymerization initiators, thermal polymerization initiators, curing agents, conductivity imparters, hydrolysis inhibitors, neutralizing agents, and fillers.

[0082] Examples of the silane coupling agents mentioned above include epoxysilanes such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; aminosilanes such as γ-aminopropyltriethoxysilane, N-β(aminoethyl)γ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, and γ-ureidopropyltriethoxysilane; mercaptosilanes such as 3-mercaptopropyltrimethoxysilane; p-styryltrimethoxysilane, vinyltrichlorosilane, vinyltris(8-methoxyethoxy)silane, vinyltrimethoxysilane, vinyltriethoxysilane, and γ-methacryloxypropyltrimethoxysilane; and polymeric silanes of epoxy, amino, and vinyl types. These may be used individually or in combination of two or more.

[0083] Examples of the titanate coupling agents mentioned above include isopropyl triisostearoyl titanate, isopropyl tri(N-aminoethyl / aminoethyl) titanate, diisopropyl bis(dioctyl phosphate) titanate, tetraisopropyl bis(dioctyl phosphite) titanate, tetraoctyl bis(ditridecyl phosphite) titanate, tetra(2,2-diallyloxymethyl-1-butyl)bis(ditridecyl) phosphite titanate, bis(dioctyl pyrophosphate) oxyacetate titanate, and bis(dioctyl pyrophosphate) ethylene titanate. These may be used individually or in combination of two or more.

[0084] As fillers, for example, talc, mica, calcium carbonate, calcium silicate, calcium oxide, calcium hydroxide, magnesium carbonate, magnesium hydroxide, magnesium oxide, magnesium sulfate, aluminum hydroxide, barium sulfate, glass powder, glass fibers, carbon fibers, clay, dolomite, mica, silica, alumina, potassium titanate whiskers, wollastonite, fibrous magnesium oxysulfate, cellulose nanofibers, etc. are preferred. These may be used individually or in combination of two or more. Among these fillers, those with an average particle size (for flat plates) or average fiber diameter (for needle-shaped to fibrous shapes) of 5 μm or less are preferred. The amount of filler to be blended may be set appropriately depending on the application.

[0085] The resin composition of the present invention can be used to obtain molded articles using known molding methods. The molding method is arbitrary and can be appropriately selected depending on the application. The molded article may be a cured product of the resin composition. There are no restrictions on the shape of the molded article; it may be in the form of a plate, sheet, or film, it may be coated on a substrate, or it may be molded in a form that exists between two substrates.

[0086] When manufacturing plate-shaped or sheet-shaped molded products, examples of molding methods include extrusion molding, flat pressing, irregular extrusion molding, blow molding, compression molding, vacuum molding, and injection molding. When manufacturing film-shaped molded bodies, examples of molding methods include melt extrusion, solution casting, inflation film molding, cast molding, extrusion lamination molding, calendering, sheet molding, fiber molding, blow molding, injection molding, rotational molding, and coating molding. In the case of a resin composition that hardens with heat or active energy rays, the resin composition of the present invention may be molded using various hardening methods that utilize heat or active energy rays.

[0087] If the resin composition is liquid, it may be molded by coating. Examples of coating methods include spray coating, spin coating, dip coating, roll coating, blade coating, doctor roll coating, doctor blade coating, curtain coating, slit coating, screen printing, inkjet coating, dispensing, die coating, comma coating, gravure coating, flexo coating, knife coating, reverse roll coating, brush coating, dip coating, and wire bar coating.

[0088] The resin composition of the present invention has sufficient processability for application in processes such as film molding and coating, and exhibits excellent heat resistance and thermal conductivity when cured. Therefore, the resin composition of the present invention can be applied to various fields such as adhesives, paints, civil engineering and construction materials, and insulating materials for electrical and electronic components, and is particularly useful as insulating casting, laminating materials, and encapsulating materials in the electrical and electronic field. Applications of resin compositions containing epoxy resin as a resin component include multilayer printed circuit boards, film adhesives, liquid adhesives, semiconductor encapsulating materials, underfill materials, chip fills for LSIs, prepresses, and heat dissipation materials. Among these, the resin composition of the present invention is preferably used as an insulating material.

[0089] <Insulating materials> The insulating material of the present invention utilizes the excellent insulating and heat dissipating properties of the resin composition of the present invention. Specifically, the insulating material of the present invention is suitable for electronic material applications such as circuit boards and semiconductors, and can be used in shapes corresponding to the application, such as grease, adhesive, gel, pad, tape, packaging material, and housing. [Examples]

[0090] The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

[0091] Boron nitride, used as a raw material, was evaluated using the following commercially available products. Boron Nitride A1; "BN-N" manufactured by Yingkou Liaobin Fine Chemical Industry Co. Ltd. Boron Nitride B1: "HSL-MDX" manufactured by Dandong Chemical Engineering Institute Co. Ltd. Boron nitride C1: ZIBO "PW30" manufactured by JONYE CERAMIC TECHNOLOGIES Co. Ltd.

[0092] The following evaluations (1) to (5) were performed on boron nitride A1, boron nitride B1, and boron nitride C1.

[0093] (1) Average thickness (nm), aspect ratio Using a scanning electron microscope (Hitachi High-Technologies Corporation product name "SU5000"), the major axis and thickness of boron nitride were measured. The average thickness (nm) was calculated from the average of the thicknesses of 30 or more boron nitride samples, and the aspect ratio was calculated from the average of the major axis / thickness ratios of 30 or more boron nitride samples. The results are shown in Table 1.

[0094] (2) Orientation Index The diffraction pattern of boron nitride was measured using an X-ray diffractometer (Ultima IV, a horizontal sample-type multi-purpose X-ray diffractometer). The intensity I002 of the diffraction line around 2θ = 27~28° ((002) plane) and the intensity I100 of the diffraction line around 2θ = 41~42° ((100) plane) were determined. The ratio (I002 / I100) of the diffraction line intensity I002 from the (002) plane to the diffraction line intensity I100 from the (100) plane was defined as the orientation index. The results are shown in Table 1.

[0095] (3) Average particle size (μm) 0.1 g of boron nitride was weighed into a 100 ml beaker, 9.9 g of water was added, and the boron nitride was dispersed by ultrasonic treatment (oscillation frequency: 36 kHz, 10 minutes). The volume-average particle size of the boron nitride was measured using a wet method with a particle size distribution analyzer (Horiba, Ltd. product name "LA-950V2"). The results are shown in Table 1.

[0096] (4) Bulk density (g / cm³) 3 ) A boron nitride material is lightly packed into a graduated cylinder, and the mass and volume of the charged boron nitride material are measured. The bulk density (g / cm³) is calculated by dividing the mass by the volume. 3 The result was calculated. The results are shown in Table 1.

[0097] (5) Dielectric constant Using a press machine (LaboNext Co., Ltd. product name "LaboPress LP-200"), 1.0 g of boron nitride material was pelletized under the conditions of applied pressure: 11 tons and pressure application time: 10 minutes. The dielectric constant of the pelletized boron nitride material was measured using a dielectric constant measuring device (Agilent Technologies product name "Agilent E4991E") under the conditions of frequency: 1 GHz and applied voltage: 0.1 V. The results are shown in Table 1.

[0098] [Table 1]

[0099] [Example 1-1] Five parts by mass of boron nitride A1 and 95 parts by mass of water as a solvent were mixed to form a boron nitride slurry. Using a high-pressure emulsifier, the slurry was subjected to a pressure of 130 MPa to allow it to pass through the pores. After treatment, the slurry was filtered and the solid content was dried, resulting in an average thickness of 150 nm, an aspect ratio of 20, an orientation index of 19.7, an average particle size of 7.5 μm, and a bulk density of 0.12 g / cm³. 3 ,dielectric Boron nitride A2 with a ratio of 2.80 was obtained. The physical properties of the obtained boron nitride A2 are shown in Table 2.

[0100] [Examples 1-2] Except for changing boron nitride A1 to boron nitride B1, the procedure was carried out in the same manner as in Example 1-1, resulting in an average thickness of 220 nm, an aspect ratio of 21, an orientation index of 28.7, an average particle size of 9.2 μm, and a bulk density of 0.14 g / cm³. 3 Boron nitride B2 with a dielectric constant of 3.10 was obtained. The physical properties of B2 are shown in Table 2.

[0101] [Examples 1-3] Except for changing boron nitride A1 to boron nitride C1, the procedure was carried out in the same manner as in Example 1-1, resulting in an average thickness of 124 nm, an aspect ratio of 21, an orientation index of 24.3, an average particle size of 4.8 μm, and a bulk density of 0.21 g / cm³. 3 Boron nitride C2 with a dielectric constant of 3.14 was obtained. The physical properties of C2 are shown in Table 2.

[0102] [Examples 1-4] Except for changing the pressure from 130 MPa to 200 MPa, the procedure was carried out in the same manner as in Example 1-1, resulting in an average thickness of 127 nm, an aspect ratio of 17, an orientation index of 18.0, an average particle size of 7.2 μm, and a bulk density of 0.18 g / cm³. 3 Boron nitride A3 with a dielectric constant of 2.95 was obtained. The physical properties of element A3 are shown in Table 2.

[0103] [Examples 1-5] Except for changing boron nitride A1 to boron nitride B1 and changing the pressure from 130 MPa to 200 MPa, the procedure was carried out in the same manner as in Example 1-1, resulting in an average thickness of 190 nm, an aspect ratio of 22, an orientation index of 22.5, an average particle size of 8.8 μm, and a bulk density of 0.13 g / cm³. 3 , dielectric constant 2.98 Boron nitride B3 was obtained. The physical properties of the obtained boron nitride B3 are shown in Table 2.

[0104] [Comparative Example 1-1] Except for changing boron nitride A1 to boron nitride C1 and changing the pressure from 130 MPa to 200 MPa, the procedure was carried out in the same manner as in Example 1-1, resulting in an average thickness of 99 nm, an aspect ratio of 9, an orientation index of 22.2, an average particle size of 4.0 μm, and a bulk density of 0.25 g / cm³. 3 , nitrogen with dielectric constant 3.25 Boron nitride (C3) was obtained. The physical properties of the obtained boron nitride (C3) are shown in Table 2.

[0105] [Examples 1-6] 74 parts by mass of 1-butyl-3-methylimidazolium hexafluorophosphate and 26 parts by mass of polyethylene glycol (Fujifilm Wako Pure Chemical Industries, Ltd. product name "Polyethylene Glycol 20000") were mixed at 25°C to dissolve the polyethylene glycol, and then 10 parts by mass of boron nitride A1 was added and mixed to obtain a dispersion medium in which boron nitride A1 was dispersed. 0.6 g of this dispersion medium was spread to 0.5 cm 3 Weigh the contents into a vial, seal it tightly, and microwave it. Using a synthesis apparatus, the vial was irradiated with microwaves for 30 minutes at 170°C and 2450MHz. After irradiation, the dispersion medium was washed with acetone, filtered, and the solid content was dried to obtain an average thickness of 690 nm, an aspect ratio of 15, an orientation index of 22.0, an average particle size of 17.1 μm, and a bulk density of 0.33 g / cm³. 3 Boron nitride A4 with a dielectric constant of 3.13 was obtained. The physical properties of element A4 are shown in Table 2.

[0106] [Examples 1-7] Except for changing boron nitride A1 to boron nitride B1, the procedure was carried out in the same manner as in Examples 1-6, resulting in an average thickness of 321 nm, an aspect ratio of 13, an orientation index of 29.0, an average particle size of 11.1 μm, and a bulk density of 0.19 g / cm³. 3 Boron nitride B4 with a dielectric constant of 3.14 was obtained. The physical properties of element B4 are shown in Table 2.

[0107] [Examples 1-8] Except for changing boron nitride A1 to boron nitride C1, the procedure was carried out in the same manner as in Examples 1-6, resulting in an average thickness of 110 nm, an aspect ratio of 19, an orientation index of 29.0, an average particle size of 8.6 μm, and a bulk density of 0.20 g / cm³. 3 Boron nitride C4 with a dielectric constant of 3.13 was obtained. The physical properties of C4 are shown in Table 2.

[0108] [Comparative Example 1-2] Except for changing the microwave irradiation time from 30 minutes to 15 minutes, the procedure was carried out in the same manner as in Examples 1-6, resulting in an average thickness of 923 nm, an aspect ratio of 13, an orientation index of 29.0, an average particle size of 20.3 μm, and a bulk density of 0.41 g / cm³. 3 Boron nitride A5 with a dielectric constant of 3.20 was obtained. The physical properties of boron A5 are shown in Table 2.

[0109] [Comparative Examples 1-3] Except for changing boron nitride A1 to boron nitride B1 and changing the microwave irradiation time from 30 minutes to 15 minutes, the procedure was carried out in the same manner as in Examples 1-6, resulting in an average thickness of 470 nm, an aspect ratio of 11, an orientation index of 45.0, an average particle size of 12.2 μm, and a bulk density of 0.35 g / cm³. 3 , dielectric constant 3 Boron nitride B5 with a coefficient of 0.22 was obtained. The physical properties of the obtained boron nitride B5 are shown in Table 2.

[0110] [Comparative Examples 1-4] Except for changing boron nitride A1 to boron nitride C1 and changing the microwave irradiation time from 30 minutes to 15 minutes, the procedure was carried out in the same manner as in Examples 1-6, resulting in an average thickness of 128 nm, an aspect ratio of 18, an orientation index of 35.0, an average particle size of 9.9 μm, and a bulk density of 0.19 g / cm³. 3 , dielectric constant 3. Eighteen boron nitride (C5) molecules were obtained. The properties of the obtained boron nitride (C5) molecules are shown in Table 2.

[0111] [Examples 1-9] Five parts by mass of boron nitride (C1) and 95 parts by mass of water were mixed to form a boron nitride slurry. Using a planetary ball mill, the slurry and 250 parts by mass of ceramic balls with a diameter of 20 mm were placed in a container, sealed, and processed for 3 hours at a rotation speed of 200 rpm / 200 rpm (orbital side / rotational side) to grind the boron nitride (C1). After grinding, the solid was filtered and dried to obtain an average thickness of 130 nm, an aspect ratio of 20, an orientation index of 27.0, an average particle size of 5.3 μm, and a bulk density of 0.19 g / cm³. 3 Boron nitride C6 with a dielectric constant of 3.10 was obtained. The physical properties of the obtained boron nitride (C6) are shown in Table 2.

[0112] [Comparative Examples 1-5] Except for changing boron nitride C1 to boron nitride A1, the procedure was carried out in the same manner as in Examples 1-9, resulting in an average thickness of 297 nm, an aspect ratio of 18, an orientation index of 33.0, an average particle size of 8.4 μm, and a bulk density of 0.18 g / cm³. 3 Boron nitride A6 with a dielectric constant of 3.34 was obtained. The physical properties of boron A6 are shown in Table 2.

[0113] [Comparative Examples 1-6] Except for changing boron nitride C1 to boron nitride B1, the procedure was the same as in Examples 1-9, resulting in an average thickness of 251 nm, an aspect ratio of 19, an orientation index of 31.0, an average particle size of 8.5 μm, and a bulk density of 0.17 g / cm³. 3 Boron nitride B6 with a dielectric constant of 3.20 was obtained. The physical properties of boron B6 are shown in Table 2.

[0114] [Table 2]

[0115] From the results of Comparative Examples 1-1 to 1-6, the dielectric constant of boron nitride exceeded 3.15 when even one of the parameters—average thickness of 10 nm to 700 nm, aspect ratio of 10 to 400, and orientation index of 30 or less—was not met. In contrast, from the results of Examples 1-1 to 1-9, it was confirmed that the dielectric constant of boron nitride was 3.15 or less when all of the above parameters were met.

[0116] <Evaluation using epoxy resin> To 100 parts by mass of epoxy resin (ADEKA Corporation product name "EP-4100"), 20 parts by mass of boron nitride as described in Table 1 or Table 2 was added, and 5 parts by mass of 1-benzyl-2-methylimidazole was added as a curing agent. The mixture was then stirred using a planetary mixer. After mixing, a 3 mm thick sheet was formed using a heater press at 150°C, a molding load of 10 kN, and a pressing time of 1 hour. The obtained sheet was evaluated under the following conditions.

[0117] (1) Dielectric constant The dielectric constant of the obtained sheet was measured using a dielectric constant measuring device (Agilent Technologies product name "Agilent E4991E") under the conditions of frequency: 1 GHz and applied voltage: 0.1 V. The results are shown in Table 3.

[0118] (2) Thermal conductivity The thermal conductivity of the prepared sheets was measured using a hot disk method thermophysical property measurement device (Kyoto Electronics Manufacturing Co., Ltd. product name "TPS-2500") in accordance with ISO 22007-2. Thermal conductivity was evaluated as the average value of the thermal conductivity in the thickness direction and the sheet surface direction. The results are shown in Table 3.

[0119] (3) Appearance The surface of the obtained sheets was observed using SEM images obtained with an electron microscope. A smooth surface was evaluated as good, while rough surfaces or surfaces with foreign matter were evaluated as NG. The results are shown in Table 3.

[0120] [Table 3]

[0121] From the results of Comparative Examples 2-1 to 2-9, the dielectric constant of sheets made using resin compositions containing boron nitride that did not satisfy the parameters of an average thickness of 10 nm to 700 nm, an aspect ratio of 10 to 400, and an orientation index of 30 or less was unsatisfactory. From the results of Examples 2-1 to 2-8, it was confirmed that sheets made using resin compositions containing boron nitride that satisfied the parameters of an average thickness of 10 nm to 700 nm, an aspect ratio of 10 to 400, and an orientation index of 30 or less exhibited a low dielectric constant, high thermal conductivity, and good sheet appearance.

Claims

1. A boron nitride material having (A) an average thickness of 110 nm to 700 nm, (B) an aspect ratio of 13 to 400, and (C) an orientation index of 30 or less determined by X-ray diffraction.

2. (D) The average particle size is 1 μm to 14 μm, and (E) the bulk density is 0.05 g / cm³. ３ ~0.25 g / cm ３ The boron nitride material according to claim 1.

3. A resin composition containing the boron nitride material according to claim 1 or 2.

4. The resin composition according to claim 3, which contains an epoxy resin as a resin component.

5. An insulating material comprising the resin composition described in claim 3 or 4.

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