JP5750342B2 - Insulating fine particles, insulating fine particle-coated conductive fine particles, anisotropic conductive adhesive composition, and anisotropic conductive molded body - Google Patents

Description

  The present invention relates to insulating fine particles. More specifically, the present invention relates to insulating fine particles suitable for use for coating conductive fine particles.

  The present invention also relates to conductive fine particles coated with insulating fine particles. More specifically, the present invention relates to insulating fine particle-coated conductive fine particles in which insulating fine particles are present on the surface of conductive fine particles.

  The present invention also relates to an anisotropic conductive adhesive composition containing insulating fine particle-coated conductive fine particles.

  The present invention also relates to an anisotropic conductive molded body obtained from the anisotropic conductive adhesive composition.

  2. Description of the Related Art In recent years, with the trend toward high-density mounting of electronic components, there is a trend that the electrodes of electronic circuits are miniaturized and the bump (projection electrode) size of the IC chip to be mounted is further narrowed.

  On the other hand, an anisotropic conductive adhesive composition in which conductive fine particles are dispersed in a resin has been used in order to make electrical connection between a number of opposing electrodes. For example, anisotropic conductive paste, anisotropic conductive ink, anisotropic conductive film, anisotropic conductive sheet and the like are widely known.

  In order to use these anisotropic conductive adhesive compositions to ensure stable conductivity between electrodes that are miniaturized and narrowed, it is necessary to increase the number of conductive fine particles captured by the electrodes. However, in that case, there is a problem that when adjacent conductive fine particles come into contact with each other, a short circuit occurs between the electrodes, and it is a problem to ensure further insulation reliability together with conductivity.

  Insulating coated conductive fine particles in which the surface of the conductive fine particles is coated with an insulating layer are arranged between electrodes as an anisotropic conductive material for electrical connection. By applying pressure or heat and pressure between the electrodes, the electrodes Conductivity is generated in the connecting direction. Furthermore, in such insulating coated conductive fine particles, since an insulating layer always exists between the fine particles, it is possible to effectively suppress a lateral short circuit caused by the occurrence of undesired lateral conduction. it can.

  For example, anisotropic conductive particles for electrical connection in which fine particles made of a conductive material are covered with a film of an electrically insulating substance have been proposed (see Patent Document 1, particularly FIG. 2). In addition, as an application of the invention described in Patent Document 1, insulating coated conductive fine particles (Patent Document 2) in which an insulating resin coating layer that is torn by pressure is formed on the surface of the conductive fine particles, the surface of the conductive fine particles is heated. Insulating coated conductive fine particles (Patent Document 3) in which an insulating resin coating layer having increased fluidity is formed, and insulating coated conductive fine particles (in which at least two insulating resin coating layers are formed on the surface of the conductive fine particles ( Patent Document 4), insulating coated conductive fine particles (Patent Document 5) in which an insulating resin coating layer controlled to a predetermined covering state is formed on the surface of the conductive fine particles, and the surface of the conductive particles is subjected to a specific surface treatment. Insulating coated conductive particles (Patent Documents 6 and 7) on which an insulating resin coating layer is formed have been proposed.

  On the other hand, a form in which an insulating material is provided in the form of fine particles on the surface of the conductive fine particles to form insulating coated conductive fine particles is known. As the insulating fine particles used in such a form, for example, insulating fine particles made of an epoxy resin, a polyolefin resin, an acrylic resin, a styrene resin or the like (Patent Document 8, in particular, a crosslinked acrylic resin is used in Examples) Inorganic oxide fine particles having hydroxyl groups on the surface (Patent Document 9, especially using silica fine particles in Examples), inorganic oxide (Patent Document 10, particularly silica fine particles in Examples), amino resin fine particles (Patent Document 11) Has been reported.

  However, in the conventional insulating fine particle-coated conductive fine particles, the adhesion of the insulating fine particles to the conductive fine particles is insufficient. Therefore, when the anisotropic conductive adhesive composition is produced, the insulating fine particles are electrically conductive. There is a problem that it easily falls off from the surface of the conductive fine particles. Therefore, when finally used as an anisotropic conductive molded article, although there is no problem in conductivity, there is a problem that the insulation reliability is inferior.

  For this reason, in order to avoid contact of the conductive fine particles due to the removal of the insulating fine particles from the surface of the conductive fine particles during compression deformation, the adhesion between the conductive fine particles and the insulating fine particles is higher than before. It has been demanded. Further, even when conductive fine particles are adjacent to each other, it is required that the insulating fine particles have sufficient elasticity and do not undergo plastic deformation.

Japanese Patent No. 2779409 JP 2000-67647 A Japanese Patent Laid-Open No. 2000-100239 JP 2000-129157 A JP 2004-146261 A JP 2005-63904 A JP 2006-236759 A JP 2006-59721 A JP 2009-170414 A JP 2009-102731 A JP 2011-86598 A

  An object of the present invention is an insulating fine particle suitable for use for coating conductive fine particles, which has strong adhesion to the surface of the conductive fine particles, and is difficult to fall off / detach from the surface of the conductive fine particles. When the insulating fine particle-coated conductive fine particles coated with the insulating fine particles are contained in the anisotropic conductive adhesive composition, the density of the insulating fine particle-coated conductive fine particles is increased to increase the density of the insulating fine particles. To provide insulating fine particles that can exhibit excellent electrical conductivity and insulation properties because even if the coated conductive fine particles are adjacent to each other, the insulating fine particles have sufficient elasticity and do not undergo plastic deformation. . Another object of the present invention is to provide insulating fine particle-coated conductive fine particles in which such insulating fine particles are present on the surface of the conductive fine particles. Another object of the present invention is to provide an anisotropic conductive adhesive composition containing such insulating fine particle-coated conductive fine particles. Furthermore, it is providing the anisotropic conductive molded object obtained from such an anisotropic conductive adhesive composition.

The insulating fine particles for coating the conductive fine particles of the present invention are:
Insulating fine particles for coating conductive fine particles, having a core-shell structure with a shell layer on the outer periphery of the core layer,
The core layer comprises a vinyl polymer, the shell layer comprises an amino resin,
When the diameter of the core part is Dnm and the thickness of the shell part is dnm, 0.10 <d / D <2.0.

  The insulating fine particle-coated conductive fine particles of the present invention have the insulating fine particles of the present invention on the surface of the conductive fine particles.

  In a preferred embodiment, the insulating fine particle-coated conductive fine particles of the present invention have at least one selected from gold, palladium, silver, copper, tin, and alloys thereof on the outermost surface of the conductive fine particles.

  In a preferred embodiment, the insulating fine particle-coated conductive fine particles of the present invention have an average particle size of 1.0 μm to 5.0 μm of the conductive fine particles.

  The anisotropic conductive adhesive composition of the present invention is obtained by dispersing the insulating fine particle-coated conductive fine particles of the present invention in a binder resin.

  The anisotropic conductive molded body of the present invention is obtained from the anisotropic conductive adhesive composition of the present invention.

  According to the present invention, the insulating fine particles are suitable for use in coating the conductive fine particles, have strong adhesion to the surface of the conductive fine particles, are not easily detached from the surface of the conductive fine particles, When the insulating fine particle-coated conductive fine particles coated with the insulating fine particles are contained in the anisotropic conductive adhesive composition, the density of the insulating fine particle-coated conductive fine particles is increased to increase the density of the insulating fine particles. Even if the coated conductive fine particles are adjacent to each other, since the insulating fine particles have sufficient elasticity and do not undergo plastic deformation, it is possible to provide insulating fine particles that can exhibit excellent conductivity and insulation. . Further, it is possible to provide insulating fine particle-coated conductive fine particles in which such insulating fine particles are present on the surface of the conductive fine particles. Moreover, an anisotropic conductive adhesive composition containing such insulating fine particle-coated conductive fine particles can be provided. Furthermore, the anisotropic conductive molded object obtained from such an anisotropic conductive adhesive composition can be provided.

≪A. Insulating fine particles >>
The insulating fine particles of the present invention are insulating fine particles for coating conductive fine particles. In other words, the insulating fine particles of the present invention are insulating fine particles that can be formed into insulating fine particle-coated conductive fine particles by being disposed on the surface of the conductive fine particles.

  The insulating fine particles of the present invention have a core-shell structure having a shell layer on the outer periphery of the core layer.

  In the insulating fine particles of the present invention, 0.10 <d / D <2.0, where Dnm is the diameter of the core and dnm is the thickness of the shell. d / D is preferably 0.12 <d / D <1.50.

  The diameter of the core can be measured by any suitable method. The diameter of the core part can be obtained, for example, by measuring the volume average particle diameter with a dynamic light scattering particle size distribution device.

  The thickness of the shell portion can be measured by any appropriate method. The thickness of the shell part can be calculated by the following formula based on, for example, the insulating fine particles measured by a dynamic light scattering particle size distribution device and the volume average particle diameter of the core part.

  Shell part thickness = (volume average particle diameter of insulating fine particles−volume average particle diameter of core part) / 2

  Such d / D is one of the indexes representing the size of the shell portion with respect to the size of the core portion in the core-shell structure. In the insulating fine particles of the present invention, such d / D is 0. .10 <d / D <2.0, it has a strong adhesiveness to the surface of the conductive fine particles, and does not easily fall off or detach from the surface of the conductive fine particles. Insulating fine particle-coated conductive fine particles coated with insulating fine particles include an insulating fine particle-coated conductive fine particle by increasing the density of the conductive fine particle-coated conductive fine particles. Even if the fine particles are adjacent to each other, since the insulating fine particles have sufficient elasticity and do not undergo plastic deformation, it is possible to provide insulating fine particles that can exhibit excellent electrical conductivity and insulation.

  When such d / D is 0.10 or less or 2.0 or more, it becomes difficult to exhibit the effects of the present invention as described above.

  In the insulating fine particles of the present invention, when the ratio of the thickness of the shell part to the diameter of the core part (d / D) is not less than a certain value, good adhesion to the conductive fine particles can be ensured. However, on the other hand, in the process of completing the present invention, it has been found that when the thickness of the shell portion with respect to the diameter of the core portion increases, the adhesion with the conductive fine particles is excellent, but the insulating property is deteriorated. This is because the elastic recovery force against compression of the shell portion in the insulating fine particles of the present invention is low, and when the insulating fine particles are deformed due to contact between adjacent conductive fine particles, the plastic deformation of the insulating fine particles is large. This is presumably because the distance between the conductive fine particles is narrowed and contact between the surfaces of the conductive fine particles is likely to occur.

  Any appropriate volume average particle diameter can be adopted as the volume average particle diameter of the insulating fine particles of the present invention. The volume average particle diameter of the insulating fine particles of the present invention can be very precisely controlled by the specific core-shell structure of the insulating fine particles.

  The volume average particle diameter of the insulating fine particles of the present invention is preferably 0.005 μm to 1.0 μm, and more preferably 0.01 μm to 0.8 μm.

  If the volume average particle diameter of the insulating fine particles of the present invention can be controlled very precisely as described above, it has strong adhesion to the surface of the conductive fine particles, and it is difficult for the conductive fine particles to fall off or detach from the surface. When the insulating fine particle-coated conductive fine particles coated with the insulating fine particles are contained in the anisotropic conductive adhesive composition, the density of the insulating fine particle-coated conductive fine particles is increased to increase the density of the insulating fine particles. Even if the coated conductive fine particles are adjacent to each other, since the insulating fine particles have sufficient elasticity and do not undergo plastic deformation, it is possible to provide insulating fine particles that can exhibit excellent conductivity and insulation. .

  A method for evaluating the volume average particle diameter will be described later.

  The sharpness of the particle size distribution of the insulating fine particles of the present invention can be indicated by the coefficient of variation (CV value) of the particle diameter. The particle size distribution of the insulating fine particles of the present invention can be very sharp depending on the specific core-shell structure of the insulating fine particles.

  The coefficient of variation (CV value) of the particle size of the insulating fine particles of the present invention is preferably 40% or less, more preferably 30% or less, and even more preferably 20% or less.

  The insulating fine particles of the present invention can have sufficiently low hygroscopicity due to the specific core-shell structure of the insulating fine particles. Such hygroscopicity can be represented by, for example, saturated moisture absorption.

  The saturated moisture absorption amount of the insulating fine particles of the present invention is preferably 10% by weight or less, more preferably 7% by weight or less, still more preferably 5% by weight or less, and particularly preferably 4% by weight or less. Most preferably, it is 3% by weight or less.

  The amount of residual formalin in the insulating fine particles of the present invention is preferably 1000 ppm or less, more preferably 500 ppm or less, still more preferably 100 ppm or less, and particularly preferably 50 ppm or less.

  When the amount of residual formalin in the insulating fine particles of the present invention falls within the above range, even in an environment where low formalin is strongly desired, it has strong adhesion to the surface of the conductive fine particles, and from the surface of the conductive fine particles. The density of the conductive fine particles covered with the insulating fine particles when the conductive fine particles coated with the insulating fine particles are difficult to fall off or detached and the conductive fine particles covered with the insulating fine particles are contained in the anisotropic conductive adhesive composition. Even if the conductive fine particles coated with the insulating fine particles are adjacent to each other, the insulating fine particles have sufficient elasticity and are not plastically deformed. Fine particles can be provided.

  The core layer in the insulating fine particles of the present invention contains a vinyl polymer. The content ratio of the vinyl polymer in the core layer in the insulating fine particles of the present invention is preferably 80% by weight to 100% by weight, more preferably 90% by weight to 100% by weight, and still more preferably 95% by weight. -100% by weight, particularly preferably 98% -100% by weight, most preferably substantially 100% by weight.

  When the core layer in the insulating fine particles of the present invention contains a component other than the vinyl polymer, it can contain any appropriate component as long as the effects of the present invention are not impaired.

  Examples of the vinyl polymer include a polymer of a compound containing at least one ethylenically unsaturated group in the molecule. Examples of vinyl polymers include monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate; methoxypolyethylene glycol (meth) Monomers having a polyethylene glycol component such as acrylate; butyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, isoamyl acrylate, lauryl (meth) acrylate, tetrahydroful methacrylate Alkyl (meth) acrylates such as furyl; fluorine atoms such as trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, pentanefluoropropyl (meth) acrylate, and octafluoroamyl (meth) acrylate (Meth) acrylates; glycidyl (meth) acrylate; (meth) acrylic acid; (meth) acrylamide; polymers such as (meth) acrylonitrile; aromatic polymers such as vinyl polymers having aromatic rings and crosslinked vinyl polymers having aromatic rings Ring structure-containing resin; and the like.

  Only one type of vinyl polymer may be used, or two or more types of vinyl polymers may be used.

  Among the above, the vinyl polymer is preferably a polymer of alkyl (meth) acrylates and an aromatic ring structure-containing resin.

  As alkyl (meth) acrylates, Preferably, methacrylic acid ester is mentioned, More preferably, methyl methacrylate is mentioned.

  The aromatic ring structure-containing resin preferably includes a vinyl polymer having an aromatic ring and a crosslinked vinyl polymer having an aromatic ring. This is because a vinyl polymer having an aromatic ring and a crosslinked vinyl polymer having an aromatic ring are industrially easy to produce or easily obtain those having an average particle size of 1 μm or less.

  Examples of the vinyl polymer having an aromatic ring include a polymer of a vinyl monomer that essentially contains an aromatic ring-containing vinyl compound.

  Examples of the polymer of the vinyl monomer that essentially contains an aromatic ring-containing vinyl compound include a copolymer of one or more aromatic ring-containing vinyl compounds and one or more other vinyl compounds.

  As the aromatic ring-containing vinyl compound, an aromatic vinyl compound is preferable, and among them, for example, a styrene monomer is preferable. Examples of the styrenic monomer include divinylbenzene, styrene, methylstyrene, ethylstyrene (ethylvinylbenzene), and the like. Examples of the aromatic ring-containing vinyl compound include (meth) acrylates having an aromatic ring such as benzyl methacrylate in addition to the styrene monomer.

  Examples of other vinyl compounds that can be copolymerized with the aromatic ring-containing vinyl compound include compounds containing at least one ethylenically unsaturated group in the molecule. Examples of such other vinyl compounds include monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate; methoxypolyethylene Monomers having a polyethylene glycol component such as glycol (meth) acrylate; butyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, isoamyl acrylate, lauryl (meth) acrylate, Alkyl (meth) acrylates such as tetrahydrofurfuryl methacrylate; trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, pentanefluoropropyl (meth) acrylate, octafluoroamyl (meth) acrylate, etc. Tsu atom-containing (meth) acrylates; glycidyl (meth) acrylate; (meth) acrylic acid; (meth) acrylamide; (meth) acrylonitrile; and the like.

  Among these, as the other vinyl compound that can be copolymerized with the aromatic ring-containing vinyl compound, (meth) acrylic acid ester is preferable, methacrylic acid ester is more preferable, and methyl methacrylate is further preferable.

  Therefore, as the vinyl polymer having an aromatic ring, a copolymer of one or more aromatic ring-containing vinyl compounds and one or more other vinyl compounds is preferable, and a styrene monomer and a (meth) acrylic ester are used. A copolymer is more preferred.

  Since the crosslinked vinyl polymer having an aromatic ring has an appropriate crosslinked structure, when insulating fine particles having a core layer made of such a polymer are used as insulating fine particles for coating conductive fine particles, insulating fine particle coating Appropriate elasticity can be imparted to the conductive fine particles.

  Examples of the crosslinked vinyl polymer having an aromatic ring include, for example, a polymer of a vinyl monomer essentially containing a polyfunctional aromatic ring-containing vinyl compound, a monofunctional aromatic ring-containing vinyl compound, and a vinyl monomer essentially containing a polyfunctional vinyl compound. Coalescence is mentioned. As the former, a polymer of a vinyl monomer essentially containing a polyfunctional aromatic ring-containing vinyl compound and a monofunctional vinyl compound, a polymer of a vinyl monomer essentially containing a polyfunctional aromatic ring-containing vinyl compound and a polyfunctional vinyl compound, a polyfunctional aroma Examples thereof include polymers of vinyl monomers that essentially contain a ring-containing vinyl compound and a monofunctional aromatic ring-containing vinyl compound.

  As a polymer of a vinyl monomer essentially including a polyfunctional aromatic vinyl compound and a monofunctional vinyl compound, for example, a copolymer of one or more polyfunctional aromatic ring-containing vinyl compounds and one or more other monofunctional vinyl compounds is used. A polymer is mentioned.

  As a polymer of a vinyl monomer which essentially contains a polyfunctional aromatic ring-containing vinyl compound and a polyfunctional vinyl compound, for example, one or more polyfunctional aromatic ring-containing vinyl compounds and one or more polyfunctional vinyl compounds may be used as necessary. And copolymers of one or more other monofunctional vinyl compounds.

  Examples of the polymer of the vinyl monomer essentially including the polyfunctional aromatic ring-containing vinyl compound and the monofunctional aromatic ring-containing vinyl compound include one or more polyfunctional aromatic ring-containing vinyl compounds and one or more monofunctional aromatic rings. Examples thereof include a copolymer of a vinyl compound and, if necessary, one or more other monofunctional vinyl compounds or polyfunctional vinyl compounds.

  As a polymer of a vinyl monomer that essentially contains a monofunctional aromatic ring-containing vinyl compound and a polyfunctional vinyl compound, for example, one or more monofunctional aromatic ring-containing vinyl compounds and one or more polyfunctional vinyl compounds, and as necessary And copolymers of one or more other monofunctional vinyl compounds.

  Among the polyfunctional aromatic ring-containing vinyl compounds, polyfunctional aromatic vinyl compounds are preferable, and examples of the polyfunctional aromatic vinyl compound include divinylbenzene.

  The other monofunctional vinyl compound may be a compound containing at least one ethylenically unsaturated group in the molecule, for example. Specifically, for example, monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate; methoxypolyethylene glycol (meth) acrylate Monomers having a polyethylene glycol component such as, butyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, isoamyl acrylate, lauryl (meth) acrylate, benzyl methacrylate, methacryl Alkyl (meth) acrylates such as tetrahydrofurfuryl acid; trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, pentanefluoropropyl (meth) acrylate, octafluoroamyl (meth) acrylate, etc. Atom-containing (meth) acrylates; glycidyl (meth) acrylate; (meth) acrylic acid; (meth) acrylamide; (meth) acrylonitrile; and the like.

  Among the monofunctional aromatic ring-containing vinyl compounds, monofunctional aromatic vinyl compounds are preferable, and among them, monofunctional styrene monomers are preferable. Examples of the monofunctional styrene monomer include styrene, methyl styrene, ethyl styrene (ethyl vinyl benzene), and the like.

  Examples of the polyfunctional vinyl compound include (poly) ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, Examples include tetramethylol methane tri (meth) acrylate, tetramethylolpropane tetra (meth) acrylate, dipentaerythritol hexaacrylate, diallyl phthalate and its isomer, triallyl isocyanurate and its derivative, and the like.

  Among these, (poly) ethylene glycol di (meth) acrylate is preferable as the polyfunctional vinyl compound, and ethylene glycol dimethacrylate is more preferable.

  The content of the crosslinkable monomer (polyfunctional aromatic ring-containing vinyl compound, polyfunctional vinyl compound) in the monomer capable of forming a crosslinkable vinyl polymer having an aromatic ring is preferably 1% by weight to 90% by weight. More preferably, the content is 10% to 70% by weight, still more preferably 20% to 60% by weight, and particularly preferably 30% to 50% by weight.

  The shell layer in the insulating fine particles of the present invention contains an amino resin. The amino resin is preferably composed of a condensate of an amino compound and formaldehyde.

  The content ratio of the amino resin in the shell layer in the insulating fine particles of the present invention is preferably 80% by weight to 100% by weight, more preferably 90% by weight to 100% by weight, and still more preferably 95% by weight to 100 wt%, particularly preferably 98 wt% to 100 wt%, most preferably substantially 100 wt%.

  When the shell layer in the insulating fine particles of the present invention contains a component other than the amino resin, it can contain any appropriate component as long as the effects of the present invention are not impaired.

  The amino compound is preferably a polyfunctional amino compound, and more preferably a polyfunctional amino compound having a triazine ring structure.

  Only 1 type may be used for an amino compound and it may use 2 or more types together.

  Examples of the polyfunctional amino compound having a triazine ring structure include melamine; an amino compound represented by the general formula (1); a diaminotriazine compound represented by the general formula (2) or the general formula (3); And guanamine compounds such as cyclohexanecarboguanamine, cyclohexenecarboguanamine, acetoguanamine, norbornenecarboguanamine, and spiroguanamine. Among these, melamine and benzoguanamine are preferable.

Formula (1), R ^1, identical or different, represent an alkyl group which may if there is a hydrogen atom or a substituent, at least one of R ¹ is an alkyl group which may have a substituent.

In general formula (1), R ¹ is preferably a hydrogen atom or a hydroxyalkyl group.

In General Formula (2), R ² is the same or different, and is a hydrocarbon group having 1 to 2 carbon atoms (—CH ₂ —, —CH ₂ CH ₂ —, —, which is a linear structure or a structure having a side chain. CH _(CH 3) -) is.

In general formula (3), R ³ is any one of a linear structure, a structure having a side chain, a structure having an aromatic ring which may have a substituent, and a structure having an alicyclic ring which may have a substituent. It is a C1-C8 hydrocarbon group which is.

  The structure having an aromatic ring or the structure having an alicyclic ring may be a structure having a side chain.

  The amino compound preferably comprises a guanamine compound.

  Examples of the guanamine compound include benzoguanamine, cyclohexanecarboguanamine, cyclohexenecarboguanamine, acetoguanamine, norbornenecarboguanamine, and spiroguanamine, and benzoguanamine is preferable. Such guanamine compounds may be used alone or in combination of two or more.

  The content ratio of the guanamine compound in the amino compound is preferably 10% by weight to 100% by weight, more preferably 20% by weight to 100% by weight, still more preferably 40% by weight to 100% by weight, Preferably they are 50 weight%-100 weight%, More preferably, they are 60 weight%-100 weight%, More preferably, they are 70 weight%-100 weight%, More preferably, they are 80 weight%-100 weight%. More preferably, it is 90 to 100% by weight, particularly preferably 95 to 100% by weight, and most preferably 100% by weight.

  When the content ratio of the guanamine compound in the amino compound falls within the above range, the obtained insulating fine particles have a sharp particle size distribution, the particle diameter is precisely controlled, and suitable for the insulating fine particle-coated conductive fine particles. Can be used.

  The amino compound other than the guanamine compound in the amino compound that is a raw material of the condensate constituting the shell layer in the insulating fine particles of the present invention is, for example, melamine; an amino compound represented by the above general formula (1); Diaminotriazine compounds represented by the formula (2) and the above general formula (3); and the like, and the like, preferably melamine and amino compounds represented by the above general formula (1), more preferably melamine. is there.

  In the shell layer in the insulating fine particles of the present invention, phenols may be used as components other than amino compounds. A phenol means a compound having a phenolic hydroxyl group. A compound having a phenolic hydroxyl group is added to the shell layer as a condensate of formaldehyde, a co-condensate of the phenols with the amino compound and formaldehyde by cocondensing with the amino compound and formaldehyde, such as by adding together with the amino compound. Can be combined. About the addition conditions etc. of phenol, the desired hygroscopic suppression effect can be show | played in the range which does not impair the effect of this invention.

  The amount of the phenols to be used is preferably 0.1 to 3 mol, more preferably 0.2 to 1.5 mol, with respect to 1 mol of the amino compound.

  Examples of the phenols include phenol, o-ethylphenol, p-ethylphenol, mixed cresol, pn-propylphenol, o-isopropylphenol, p-isopropylphenol, mixed isopropylphenol, o-sec-butylphenol, m-tert-butylphenol, p-tert-butylphenol, pentylphenol, p-octylphenol, p-nonylphenol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,6-dimethylphenol, 3,4- Dimethylphenol, 2,4-di-s-butylphenol, 3,5-dimethylphenol, 2,6-di-s-butylphenol, 2,6-di-t-butylphenol, 3-methyl-4-isopropylphenol, 3 −Me Phenols such as ru-5-isopropylphenol, 3-methyl-6-isopropylphenol, 2-t-butyl-4-methylphenol, 3-methyl-6-t-butylphenol, 2-t-butyl-4-ethylphenol A compound having a hydroxyl group; a compound having two or more phenolic hydroxyl groups in the molecule, such as catechol, resorcin, biphenol, bisphenol A, bisphenol S, bisphenol F, and the like.

  The insulating fine particles of the present invention can be produced by any suitable method for constructing a core-shell structure. For example, a shell layer made of an amino resin is formed by reacting an amino compound and formaldehyde (addition condensation reaction) in a state in which particles serving as a core layer are dispersed in an aqueous medium. Usually, this reaction is performed under heating (50 to 100 ° C.), and is performed in the presence of an acid catalyst such as dodecylbenzenesulfonic acid or sulfuric acid in order to increase the degree of crosslinking.

  As a method for producing the core layer, for example, any suitable resin particle production method such as emulsion polymerization, miniemulsion polymerization, soap-free emulsion polymerization, microemulsion polymerization, suspension polymerization or the like can be adopted. Preferably, a production method by emulsion polymerization using a redox initiator can be employed. When a production method by emulsion polymerization using a redox initiator is employed, a core layer having a sharp particle size distribution and a precisely controlled particle size can be produced.

  Examples of the method for producing the shell layer include, for example, JP 2000-256432 A, JP 2002-293854 A, JP 2002-293855 A, JP 2002-293856 A, JP 2002-293857 A, JP 2003-55422 A, JP 2003-82049 A, JP 2003-138023 A, JP 2003-147039 A, JP 2003-171432 A, JP 2003-176330 A, JP It is preferable to apply the amino resin crosslinked particles described in JP 2005-97575 A, JP 2007-186716 A, JP 2008-101040 A, JP 2010-248475 A, and the like, and the production method thereof. Specifically, for example, the polyfunctional amino compound and formaldehyde are reacted (addition condensation reaction) in an aqueous medium (preferably a basic aqueous medium) in which particles serving as a core layer are dispersed and contained, thereby resulting in a condensate oligomer. And a shell layer containing a condensate (amino resin) of an amino compound and formaldehyde can be formed. Preferably, an aqueous medium in which the condensate oligomer is dissolved or dispersed, such as dodecylbenzenesulfonic acid or sulfuric acid. A shell layer containing a crosslinked amino resin can be formed by mixing and curing the acid catalyst. It is preferable that both the step of generating the condensate oligomer and the step of preparing the amino resin having a crosslinked structure are performed in a state of being heated at a temperature of 50 to 100 ° C. In order to obtain a shell layer having a uniform thickness, the shell layer formation reaction is preferably performed in the presence of a surfactant.

  Further, as a post-treatment method (solid-liquid separation, drying, pulverization, classification, etc.) of the obtained insulating fine particles, a method described in JP 2010-248475 A can be applied as appropriate.

≪B. Conductive fine particles coated with insulating fine particles >>
The insulating fine particle-coated conductive fine particles of the present invention have the insulating fine particles of the present invention on the surface of the conductive fine particles.

  Since the insulating fine particles coated conductive fine particles of the present invention have the insulating fine particles of the present invention as insulating fine particles, the insulating fine particles have strong adhesion to the surface of the conductive fine particles. Is difficult to fall off from the surface of the conductive fine particles, and when the insulating fine particle-coated conductive fine particles coated with the insulating fine particles are contained in the anisotropic conductive adhesive composition, the insulating property Even if the insulating fine particle-coated conductive fine particles are adjacent to each other by increasing the density of the fine particle-coated conductive fine particles, the insulating fine particles have sufficient elasticity and do not undergo plastic deformation. Can demonstrate.

  Any appropriate coating method can be adopted as a method for causing the insulating fine particles of the present invention to be present on the surface of the conductive fine particles. For example, a method in which the conductive fine particles after the electroless plating treatment and the insulating fine particles of the present invention are dispersed in a liquid such as an organic solvent or an aqueous medium and then spray-dried, conductive in a liquid such as an organic solvent or an aqueous medium. A method of chemically bonding the conductive fine particles and the insulating fine particles of the present invention after the insulating fine particles of the present invention are attached to the surface of the conductive fine particles, the coexistence of the conductive fine particle powder and the insulating fine particle powder of the present invention Examples of the method include stirring with a high-speed stirrer and a hybridization treatment.

  In the conductive fine particles coated with the insulating fine particles of the present invention, the coverage of the conductive fine particles with the insulating fine particles of the present invention is preferably 1% to 98%, more preferably 5% to 95%. When the coverage of the conductive fine particles by the insulating fine particles of the present invention is less than 1%, there is a possibility that insulation between the adjacent insulating fine particle-coated conductive fine particles cannot be ensured. If the coverage of the conductive fine particles by the insulating fine particles of the present invention exceeds 98%, sufficient conductivity may not be obtained.

  The insulating fine particle-coated conductive fine particles of the present invention are suitable as a constituent material of an anisotropic conductive material. The anisotropic conductive material is used to electrically connect opposing substrates and electrode terminals in various forms.

  Any appropriate method can be adopted as a method of electrically connecting the electrodes using the anisotropic conductive material. For example, a method of producing an anisotropic conductive adhesive composition by dispersing the insulating fine particle-coated conductive fine particles of the present invention in an insulating binder resin and then connecting with the anisotropic conductive adhesive composition A method in which the insulating binder resin and the insulating fine particle-coated conductive fine particles of the present invention are separately used for connection; and the like.

  The average particle diameter of the conductive fine particles is preferably 1.0 μm to 5.0 μm, more preferably 1.5 μm to 3.5 μm, and still more preferably 2.0 μm to 3.0 μm. Insulating fine particle-coated conductive fine particles are often used in anisotropic conductive adhesive compositions. In this case, in particular, the insulating fine particle-coated conductive fine particles are increased by increasing the density of the insulating fine particle-coated conductive fine particles. In recent years, it has been required that the average particle size of the conductive fine particles be small in order to be able to exhibit excellent electrical conductivity and insulation even when adjacent to each other.

  The conductive fine particles have substrate particles and a conductive metal layer that covers the surface of the substrate particles.

  Any appropriate base material particle can be adopted as the base material particle as long as it can be used as the base material particle of the conductive fine particles. Examples of the material for the base particles include inorganic materials such as silica; silicone resins (polymethylsilsesquioxane, phenylsilsesquioxane), polyolefin resins (polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride). , Polytetrafluoroethylene, polybutadiene, etc.), vinyl polymer resin ((meth) acrylic resin, styrene resin, (meth) acrylic-styrene resin etc.), polysulfone, polycarbonate, phenolic resin, amino resin (melamine resin, melamine-benzoguanamine) Resin, benzoguanamine resin, etc.), organic materials such as urea resin; organic-inorganic composite materials; and the like. Among these, vinyl polymer resin ((meth) acrylic resin, styrene resin, (meth) acrylic-styrene resin, etc.), amino resin (melamine resin, melamine-benzoguanamine resin) in terms of having an appropriate elastic modulus and recovery characteristics. Benzoguanamine resin, etc.) and organic-inorganic composite materials are preferred. Any appropriate organic-inorganic composite material can be adopted as the organic-inorganic composite material. Preferably, those having the same form as the forms a) to e) of the organic-inorganic composite fine particles in the form 3 of the amino resin fine particles used as insulating fine particles, which will be described later, can be employed. As the organic-inorganic composite material, those described in JP-A No. 2003-183337 and JP-A No. 8-81561 can be preferably employed.

  The average particle diameter of the substrate particles is preferably 1.0 μm to 5.0 μm, more preferably 1.5 μm to 3.5 μm, and still more preferably 2.0 μm to 3.0 μm. When the average particle diameter of the substrate particles is less than 1.0 μm, when the conductive metal layer is coated by electroless plating or the like, the particles are likely to aggregate and there is a possibility that a uniform conductive metal layer cannot be formed. . When the average particle diameter of the base particles exceeds 5.0 μm, there is a possibility that the base particles cannot be used for stable electrical connection between electrodes that are made finer and narrower.

  A method for evaluating the average particle diameter will be described later.

  Any appropriate metal can be adopted as the metal constituting the conductive metal layer. Examples of such metals include gold, silver, copper, platinum, iron, lead, aluminum, chromium, palladium, nickel, rhodium, ruthenium, antimony, bismuth, germanium, tin, cobalt, indium, nickel-phosphorus, nickel. -Metals and metal compounds such as boron, and alloys thereof. Among these, gold, palladium, silver, copper, tin, and these are formed on the outermost surface of the conductive fine particles in that they are excellent in conductivity, industrially inexpensive, and can sufficiently exhibit the effects of the present invention. It is preferable to have at least one selected from alloys, and it is more preferable to have at least one selected from gold, palladium, and alloys thereof. As the metal having a low resistance value such as these is applied, the insulating fine particles have stronger adhesion to the surface of the conductive fine particles, and the insulating fine particles are less likely to fall off from the surface of the conductive fine particles. When the insulating fine particle-coated conductive fine particles coated with the insulating fine particles are contained in the anisotropic conductive adhesive composition, the density of the insulating fine particle-coated conductive fine particles is increased to cover the insulating fine particles. Even if the conductive fine particles are adjacent to each other, the insulating fine particles have sufficient elasticity and are not plastically deformed, so that excellent conductivity and insulation can be exhibited.

  The thickness of the conductive metal layer is preferably 10 to 500 nm, more preferably 20 to 400 nm, and still more preferably 50 to 300 nm. When the conductive metal layer has a thickness of less than 10 nm, it may be difficult to maintain a stable electrical connection when used as an anisotropic conductive adhesive composition as conductive fine particles. When the thickness of the conductive metal layer exceeds 500 nm, the surface hardness when the conductive fine particles are formed becomes too high, and there is a possibility that the mechanical properties such as the recovery rate cannot be sufficiently exhibited.

  The conductive metal layer preferably has no substantial cracks or a surface on which no conductive metal layer is formed on the surface. Here, “substantially cracked or a surface on which the conductive metal layer is not formed” means that when the surface of any 10,000 conductive fine particles is observed using an electron microscope (magnification 1000 times), It means that the crack of the conductive metal layer and the exposure of the surface of the base material particles are not substantially visually observed.

  Arbitrary appropriate methods can be employ | adopted for the method of coat | covering the electroconductive metal layer on the surface of the said base particle. For example, plating method by electroless plating method, displacement plating method, etc .; method of coating a base particle with a paste obtained by mixing metal fine powder alone or in a binder; physical such as vacuum deposition, ion plating, ion sputtering Vapor deposition method; and the like. Among these, the electroless plating method is preferable because a conductive metal layer can be easily formed without requiring a large-scale apparatus.

  In general, the electroless plating method includes three steps: (1) a hydrophilization step (etching), (2) a catalyst step, and (3) an electroless plating step. The hydrophilization step (etching) can be omitted depending on the type of the base particle.

  The hydrophilization step (etching) is performed in order to improve the adhesion of the conductive metal layer by forming minute irregularities on the surface of the substrate particles. The hydrophilization step (etching) includes, for example, an oxidizing agent such as chromic acid, sulfuric acid-chromic acid mixed solution, permanganic acid solution; strong acid such as hydrochloric acid and sulfuric acid; strong alkaline solution such as sodium hydroxide and potassium hydroxide; Is used to form minute irregularities on the surface of the substrate particles.

  The catalyzing step is performed in order to form a catalyst layer that can serve as a starting point for the electroless plating step on the surface of the substrate particles. Any appropriate method can be adopted as a method of forming the catalyst layer. For example, it can be carried out using a catalytic reagent etc. commercially available for electroless plating. Examples of such commercially available catalyzing reagents include pink summers (manufactured by Nippon Kanisen Co., Ltd.) and red summers (manufactured by Nippon Kanisen Co., Ltd.). As a method for forming the catalyst layer, specifically, for example, after immersing the substrate particles in a solution composed of palladium chloride and tin chloride, a strong acid such as sulfuric acid or hydrochloric acid or a strong alkali solution such as sodium hydroxide is used. Method of activating and precipitating palladium on the surface of the base particle; Method of activating palladium with a solution containing a reducing agent such as dimethylamine borane after immersing the base particle in a palladium sulfate solution and precipitating palladium on the surface of the base particle And so on.

  In the electroless plating step, preferably, the base particles are sufficiently dispersed in an aqueous medium to prepare an aqueous slurry. Here, the base particles are preferably sufficiently dispersed in an aqueous medium. If the conductive metal layer is formed in a state where the base particles are aggregated, the untreated surface may be exposed. Arbitrary appropriate dispersion methods can be employ | adopted for dispersion | distribution of a base particle. For example, normal stirring, high speed stirring, dispersion using a shearing dispersion device such as a colloid mill or a homogenizer, and the like can be mentioned. When dispersing, ultrasonic irradiation may be used in combination. Moreover, you may use dispersing agents, such as surfactant, in the case of dispersion | distribution.

  Next, the dispersion-treated substrate particle slurry is added to an electroless plating bath containing a metal salt, a reducing agent, a complexing agent, etc., and electroless plating is performed.

  As said metal salt, the salt of the metal mentioned above as a metal which comprises a conductive metal layer is mentioned, for example. For example, when nickel salt is used, nickel chloride, nickel sulfate, nickel acetate and the like can be mentioned. What is necessary is just to set the density | concentration of the said metal salt in an electroless-plating bath suitably according to the size (surface area) of a base particle so that the electroconductive metal layer of desired thickness may be formed.

  Examples of the reducing agent include sodium hypophosphite, dimethylamine borane, sodium borohydride, potassium borohydride, hydrazine and the like.

  Examples of the complexing agent include citric acid, hydroxyacetic acid, tartaric acid, malic acid, lactic acid, gluconic acid, carboxylates such as alkali metal salts and ammonium salts thereof, amino acids such as glycine, ethylenediamine, alkylamine, and the like. Aminic acid, ammonium compound, EDTA, pyrophosphoric acid (salt) and the like. Only 1 type may be used for the said complexing agent and it may use 2 or more types together.

  The pH of the electroless plating bath in the electroless plating method is preferably 4-14.

  In the electroless plating method, when a slurry of base material particles is added, the reaction starts quickly and is accompanied by generation of hydrogen gas. The end of the electroless plating process in the electroless plating method ends when the generation of hydrogen gas is no longer recognized. After completion of the reaction, the conductive fine particles are taken out from the reaction system, and washed and dried as necessary.

  The electroless plating process may be repeated a plurality of times. By doing in this way, a base metal particle can be coat | covered with a multilayer conductive metal layer. For example, after obtaining nickel-coated particles by performing nickel plating on the substrate particles, the nickel-coated particles are put into an electroless gold plating bath and gold-plated, so that the outermost layer has a gold coating layer. Fine particles are obtained.

≪C. Anisotropic conductive adhesive composition >>
The anisotropic conductive adhesive composition of the present invention is obtained by dispersing the insulating fine particle-coated conductive fine particles of the present invention in a binder resin.

  Any appropriate binder resin can be adopted as the binder resin. For example, thermoplastic resins such as acrylate resins, ethylene-vinyl acetate resins, styrene-butadiene block copolymers; curable resin compositions obtained by reaction with curing agents such as monomers and oligomers having glycidyl groups and isocyanate Examples thereof include curable resin compositions by light and heat.

  As said anisotropic conductive adhesive composition, it can apply to arbitrary appropriate uses. Examples thereof include anisotropic conductive paste, anisotropic conductive ink, anisotropic conductive adhesive, and conductive spacers contained in a liquid crystal display element (LCD) sealant.

  The anisotropic conductive paste is obtained, for example, by making an anisotropic conductive adhesive composition into a paste. The obtained anisotropic conductive paste is put in, for example, a suitable dispenser, applied to a desired thickness on the electrode to be connected, and the counter electrode is superimposed on the coated anisotropic conductive paste. It is used for connection between electrodes by heating and pressurizing to cure the resin.

  The anisotropic conductive ink is obtained, for example, by adding a solvent to the anisotropic conductive adhesive composition to obtain a viscosity suitable for printing. The obtained anisotropic conductive ink is, for example, screen-printed on the electrode to be bonded, the solvent is evaporated, the counter electrode is superimposed on the printed anisotropic conductive ink, and the resultant is heated and compressed. Therefore, it is used for the connection between the electrodes.

≪D. Anisotropic conductive compact >>
The anisotropic conductive molded body of the present invention is obtained from the anisotropic conductive adhesive composition of the present invention. Specific examples of the anisotropic conductive molded body of the present invention include an anisotropic conductive film, an anisotropic conductive film, and an anisotropic conductive sheet.

  The anisotropic conductive molded body of the present invention is prepared by, for example, adding a solvent to the anisotropic conductive adhesive composition of the present invention to form a solution, pouring the solution onto a release film, and then evaporating the solvent. It is obtained by forming an anisotropic conductive adhesive composition into a film.

  The anisotropic conductive molded body of the present invention is disposed, for example, on electrodes to be bonded, and is used for connection between electrodes by superposing a counter electrode on the disposed anisotropic conductive molded body and compressing by heating. Is done.

  The film thickness, coating film thickness and printed film thickness in the anisotropic conductive molded body are calculated from the average particle diameter of the conductive fine particles covered with the insulating fine particles and the specifications of the electrodes to be connected, and the electrodes to be connected It is preferable to set so that the gap between the bonding substrates on which the insulating fine particle-coated conductive fine particles are sandwiched and the electrodes to be connected are formed is sufficiently filled with the binder resin layer.

  The anisotropic conductive molded body using the conductive fine particles coated with the insulating fine particles of the present invention can ensure electrical connection between opposing electrode substrates and at the same time prevent short-circuiting between adjacent electrodes. Can do. In addition, since the stability over time is excellent, the electrical connection between the electrode substrates can be maintained and the reliability can be improved without deteriorating the conductivity even during long-term use.

  Hereinafter, the present invention will be described more specifically by way of examples. However, the present invention is not limited to these examples. In the following, “parts by weight” may be simply referred to as “parts” for convenience. In addition, “wt%” may be described as “wt%”. In this specification, “weight” may be read as “mass”.

<Insulating fine particles, volume average particle diameter of core, coefficient of variation (CV)>
The volume average particle diameter and coefficient of variation (CV) of the insulating fine particles and the core part (core particle) were measured with a dynamic light scattering particle size distribution measuring device (“NICOMP 380” manufactured by PS Japan Ltd.).

<Thickness of shell part>
Based on the value of the volume average particle diameter of the insulating fine particles and the core part (core particle) measured by a dynamic light scattering particle size distribution measuring device (“NICOMP 380” manufactured by PS Japan Co., Ltd.), The thickness (d) was calculated.
Shell part thickness = (average particle diameter of insulating fine particles−average particle diameter of core part (core particle)) / 2

<Base material particles>
A particle size distribution measuring device (Beckman Coulter, “Coulter Multisizer III type”) measures the particle size of 30000 particles, obtains the number average particle size, the standard deviation of the particle size, and calculates the particle size according to the following formula: CV value (coefficient of variation) was calculated.
Coefficient of variation of base material particle (%) = 100 × (standard deviation of particle diameter / number average particle diameter)

<Conductive fine particles>
Using a flow type particle image analyzer (manufactured by Sysmex Corporation, “FPIA (registered trademark) -3000”), the particle diameter (μm) of 3000 conductive fine particles was measured, and the number average particle diameter was determined.

<Evaluation of coating state of insulating fine particles>
Using SEM, the coating state of the insulating fine particles was evaluated according to the following criteria.
(A): Covering ratio of insulating fine particles in conductive fine particles coated with insulating fine particles before production of anisotropic conductive adhesive composition (%)
(B): After the anisotropic conductive adhesive composition is diluted with toluene, the dispersion rate of the insulating fine particles in the conductive fine particle-coated conductive fine particles taken out by performing ultrasonic dispersion treatment for 30 minutes, followed by filtration ( %)
Degree of coverage reduction (%) = 100 × ((A) − (B)) / (A)
Coverage reduction degree is less than 10%: ○
Coverage reduction is 10% or more: ×

<Evaluation of conductivity>
The resistance value between the electrodes of the anisotropic conductive molded body was measured by a four-terminal method.
Resistance value is less than 10Ω: ○
Resistance value is 10Ω or more: ×

<Evaluation of insulation>
Insulating fine particle-coated conductive fine particles were dispersed in struct bond XN-5A (manufactured by Mitsui Chemicals) as a binder resin so as to be 50000 pieces / mm ³ , and applied between 30 μm pitch opposed comb pattern films and pressure-bonded. Then, the resistance between patterns was measured and evaluated according to the following criteria.
Resistance value is 100 MΩ or more: ○
Resistance value is less than 100 MΩ: ×

[Example 1]: Insulating fine particles (1)
(Production of core particles)
To a stainless steel reaction kettle equipped with a stirrer, a thermometer, and a cooler, 800 parts of deionized water and 2.3 parts of sodium dodecylbenzenesulfonate (active ingredient 60% by weight; hereinafter referred to as “DBSNa”) are added, The internal temperature was raised to 75 ° C. and kept at the same temperature.
On the other hand, 140 parts of methyl methacrylate (hereinafter referred to as “MMA”) and 60 parts of divinylbenzene (81% by weight of active ingredient; hereinafter referred to as “DVB”) are mixed in a container different from the above reaction vessel. 200 parts of the monomer composition was prepared.
After replacing the inside of the reaction kettle with nitrogen gas, 20 parts of the monomer composition (10% by weight of the total amount of the monomer composition), 50 parts of 0.4% by weight of hydrogen peroxide water, and 0.4% by weight An initial polymerization reaction was carried out by adding 50 parts of a% L-ascorbic acid aqueous solution to the reaction kettle.
Subsequently, the remainder of the monomer composition (90% by weight of the total amount of the monomer composition) 180 parts, 450 parts by weight of 0.4% by weight hydrogen peroxide water, and 450 parts by weight of 0.4% by weight L-ascorbic acid aqueous solution Were dripped uniformly into the reaction kettle over 6 hours from different inlets. Thereafter, the internal temperature was raised to 90 ° C., and the mixture was aged for 6 hours at the same temperature to obtain a vinyl polymer core particle dispersion (1) in which the vinyl polymer core particles (1) were dispersed. A part of this dispersion was extracted, and the total weight of the dispersion was 200 parts.
In addition, when the average particle diameter and coefficient of variation of the vinyl polymer core particles (1) being dispersed were measured, the volume average particle size was 72 nm and the coefficient of variation was 11%.
(Manufacture of insulating fine particles by forming a shell layer)
100 parts of benzoguanamine (hereinafter referred to as “BG”), 130 parts of 37% by weight formalin, 12 parts of 65% by weight DBSNa, 10 parts of dodecylbenzenesulfonic acid (hereinafter referred to as “DBS”) and 1300 parts of ion-exchanged water are uniformly dispersed and mixed. A BG dispersion was obtained.
The BG dispersion was dropped into 200 parts of the vinyl polymer core particle dispersion (1) maintained at 90 ° C. over 8 hours. After the dropping, the mixture is further held at 90 ° C. for 4 hours, and then cooled to 30 ° C. to contain insulating fine particles (1) whose surfaces of the vinyl polymer core particles (1) are coated with a condensate of BG and formaldehyde. A dispersion was obtained. When the average particle size and variation coefficient of the insulating fine particles (1) in this dispersion were measured, the volume average particle size was 146 nm, and the variation coefficient was 8%.
The dispersion containing the insulating fine particles (1) was subjected to solid-liquid separation using a centrifuge, the supernatant was discarded, and the obtained filter cake was diluted with methanol for redispersion. The re-dispersed methanol slurry was subjected to solid-liquid separation by centrifugation, and the filtrate obtained by discarding the supernatant was vacuum-dried at 190 ° C. for 5 hours, and then a jet mill grinder (pulverization pressure: 0.7 MPa). ) And air classification to obtain insulating fine particles (1).
Since the volume average particle diameter of the vinyl polymer core particle (1) is 72 nm and the volume average particle diameter of the insulating fine particles (1) is 146 nm, d / D = 0.51 in the insulating fine particles (1). Met.
The results are shown in Table 1.

[Example 2]: Insulating fine particles (2)
(Production of core particles)
Except having changed the quantity of DBSNa into 1.5 parts, it carried out similarly to Example 1 and obtained the vinyl polymer core particle dispersion liquid (2) in which the vinyl polymer core particle (2) was disperse | distributed. When the average particle diameter and coefficient of variation of the vinyl polymer core particles (2) in this dispersion were measured, the volume average particle diameter was 110 nm and the coefficient of variation was 12%.
(Manufacture of insulating fine particles by forming a shell layer)
Changed the amount of BG to 18 parts, 37% by weight formalin to 18.2 parts, 65% by weight DBSNa to 1.7 parts, DBS to 1.4 parts, and ion-exchanged water to 180 parts. A dispersion containing insulating fine particles (2) was obtained in the same manner as in Example 1 except that. When the average particle size and variation coefficient of the insulating fine particles (2) in this dispersion were measured, the volume average particle size was 136 nm, and the variation coefficient was 5%. Next, solid-liquid separation, drying, pulverization, and classification were performed in the same manner as in Example 1 to obtain insulating fine particles (2).
Since the volume average particle diameter of the vinyl polymer core particle (2) is 110 nm and the volume average particle diameter of the insulating fine particles (2) is 136 nm, d / D = 0.12 in the insulating fine particles (2). Met.
The results are shown in Table 1.

[Example 3]: Insulating fine particles (3)
(Production of core particles)
Except having changed the quantity of DBSNa into 3 parts, it carried out similarly to Example 1 and obtained the vinyl polymer core particle dispersion liquid (3) in which the vinyl polymer core particle (3) was disperse | distributed. When the average particle diameter and coefficient of variation of the vinyl polymer core particles (3) in this dispersion were measured, the volume average particle diameter was 50 nm and the coefficient of variation was 13%.
(Manufacture of insulating fine particles by forming a shell layer)
Except for changing the amount of BG to 1500 parts, the amount of 37% by weight formalin to 1950 parts, the amount of 65% by weight DBSNa to 185 parts, the amount of DBS to 220 parts, and the amount of ion-exchanged water to 19500 parts. 1 was performed to obtain a dispersion containing insulating fine particles (3). When the average particle size and coefficient of variation of the insulating fine particles (3) in this dispersion were measured, the volume average particle size was 240 nm and the coefficient of variation was 6%. Next, solid-liquid separation, drying, pulverization, and classification were performed in the same manner as in Example 1 to obtain insulating fine particles (3).
Since the volume average particle diameter of the vinyl polymer core particle (3) is 50 nm and the volume average particle diameter of the insulating fine particles (3) is 240 nm, d / D = 1.90 in the insulating fine particles (3). Met.
The results are shown in Table 1.

[Comparative Example 1]: Insulating fine particles (C1)
(Production of core particles)
In the same manner as in Example 1, a vinyl polymer core particle dispersion (C1) in which the vinyl polymer core particles (C1) were dispersed was obtained. When the average particle size and coefficient of variation of the vinyl polymer core particles (C1) in this dispersion were measured, the volume average particle size was 112 nm and the coefficient of variation was 12%.
(Manufacture of insulating fine particles by forming a shell layer)
Other than changing the amount of BG to 8 parts, the amount of 37% by weight formalin to 10.4 parts, the amount of 65% by weight DBSNa to 1 part, the amount of DBS to 1.2 parts, and the amount of ion-exchanged water to 105 parts Was carried out in the same manner as in Example 1 to obtain a dispersion containing insulating fine particles (C1). When the average particle size and coefficient of variation of the insulating fine particles (C1) in this dispersion were measured, the volume average particle size was 132 nm and the coefficient of variation was 5%. Next, solid-liquid separation, drying, pulverization, and classification were performed in the same manner as in Example 1 to obtain insulating fine particles (C1).
Since the volume average particle diameter of the vinyl polymer core particle (C1) is 112 nm and the volume average particle diameter of the insulating fine particles (C1) is 132 nm, d / D = 0.09 in the insulating fine particles (C1). Met.
The results are shown in Table 1.

[Comparative Example 2]: Insulating fine particles (C2)
(Production of core particles)
In the same manner as in Example 3, a vinyl polymer core particle dispersion (C2) in which the vinyl polymer core particles (C2) were dispersed was obtained. When the average particle size and coefficient of variation of the vinyl polymer core particles (C2) in this dispersion were measured, the volume average particle size was 50 nm and the coefficient of variation was 16%.
(Manufacture of insulating fine particles by forming a shell layer)
Except for changing the amount of BG to 1900 parts, the amount of 37% by weight formalin to 2470 parts, the amount of 65% by weight DBSNa to 345 parts, the amount of DBS to 280 parts, and the amount of ion-exchanged water to 25,000 parts. 1 was performed to obtain a dispersion containing insulating fine particles (C2). When the average particle size and variation coefficient of the insulating fine particles (C2) in this dispersion were measured, the volume average particle size was 260 nm and the variation coefficient was 7%. Next, solid-liquid separation, drying, pulverization, and classification were performed in the same manner as in Example 1 to obtain insulating fine particles (C2).
Since the volume average particle diameter of the vinyl polymer core particle (C2) is 50 nm and the volume average particle diameter of the insulating fine particles (C2) is 260 nm, d / D = 2.10 in the insulating fine particles (C2). Met.
The results are shown in Table 1.

[Example 4]: Insulating fine particle-coated conductive fine particles (1), anisotropic conductive adhesive composition (1), anisotropic conductive molded body (1)
(Synthesis of conductive fine particles (1))
Polyoxyethylene styrenated phenyl ether sulfate ammonium salt (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Hightenol (registered trademark) NF-08) as a surfactant in a four-necked flask equipped with a condenser, thermometer, and dropping port 150 parts of an aqueous solution prepared by dissolving 2 parts with ion-exchanged water was charged. There were prepared 50 parts of styrene, 50 parts of 1,6-hexanediol diacrylate, and 2,2′-azobis (2,4-dimethylvaleronitrile) (Wako Pure Chemical Industries, Ltd.) as a polymerization initiator. Product, V-65) 2 parts were charged and emulsified and dispersed at 7000 rpm for 5 minutes using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to prepare a suspension. To this suspension, 250 parts of ion-exchanged water was added, the temperature was raised to 65 ° C. under a nitrogen atmosphere, and the mixture was held at 65 ° C. for 2 hours to perform radical polymerization. After radical polymerization, the produced emulsion was subjected to solid-liquid separation, and the resulting cake was washed with ion-exchanged water and then with methanol. Thereafter, classification was performed, and vacuum drying was performed at 40 ° C. for 2 hours under a nitrogen atmosphere to obtain polymer fine particles (1). When the particle diameter of the polymer fine particles (1) was measured by Coulter Multisizer III type (manufactured by Beckman Coulter, Inc.), the average particle diameter was 2.7 μm and the coefficient of variation (CV) was 3.7%.
In a beaker, 50 parts of “Pink Summer” (manufactured by Nippon Kanisen Co., Ltd.) and 400 parts of ion-exchanged water were mixed to obtain a mixture. Separately, 10 parts of the polymer fine particles (1) were added to 50 parts of ion-exchanged water, and prepared by ultrasonic dispersion. The mixture was added to the above mixture and stirred at 30 ° C. for 10 minutes to form a suspension. This suspension was subjected to solid-liquid separation, and the resulting cake was washed with ion-exchanged water and methanol in this order, and then vacuum-dried at 100 ° C. for 2 hours in a nitrogen atmosphere.
Next, 100 parts of “Red Schumer” (manufactured by Nippon Kanisen Co., Ltd.) and 350 parts of ion-exchanged water were added and mixed to obtain a mixed solution. Separately, 10 parts of the dry particles obtained above were added to 50 parts of ion-exchanged water to prepare an ultrasonic dispersion, and the mixture was put into the mixed solution and stirred at 30 ° C. for 10 minutes. Then, this suspension was subjected to solid-liquid separation, and the resulting cake was washed with ion-exchanged water and methanol in this order, and then vacuum-dried at 100 ° C. for 2 hours in a nitrogen atmosphere.
By the above operation, palladium active polymer fine particles (1) having palladium adsorbed on the surface of the polymer fine particles (1) were obtained.
Palladium activated polymer fine particles (1) were added to 500 parts of ion exchange water, and ultrasonic dispersion treatment was performed for 30 minutes to sufficiently disperse the particles, thereby obtaining a fine particle suspension. While stirring this fine particle suspension at 50 ° C., nickel sulfate hexahydrate 50 g / L, sodium hypophosphite monohydrate 20 g / L, dimethylamine borane 2.5 g / L, citric acid 50 g / L An electroless plating solution (pH = 7.5) consisting of the following is gradually added to the fine particle suspension, electroless nickel plating is performed, displacement gold plating is performed, and the resulting fine particles are filtered and ion exchanged After washing with water, it was further washed with methanol and vacuum dried at 60 ° C. for 12 hours to obtain conductive fine particles (1). The average particle diameter of the conductive fine particles (1) was 2.8 μm.
(Production of insulating fine particle-coated conductive fine particles (1))
Ultrasonic dispersion was performed in methanol so that the concentration of the insulating fine particles (1) obtained in Example 1 was 5.0% by weight. After adding 50 parts of the conductive fine particles (1) to 100 parts of the methanol dispersion liquid of the obtained insulating fine particles (1) and uniformly dispersing using ultrasonic waves, the methanol is distilled off by an evaporator, The surface of the conductive fine particles (1) was coated with the insulating fine particles (1) to obtain insulating fine particle-coated conductive fine particles (1).
The results are shown in Table 2.
(Manufacture of anisotropic conductive adhesive composition (1))
2 parts of the insulating fine particle-coated conductive fine particles (1) are added to 100 parts of struct bond XN-5A (manufactured by Mitsui Chemicals) as a binder resin, and the insulating fine particle-coated conductive material is added to the binder resin using a planetary stirrer. The anisotropic fine particles (1) were uniformly dispersed to obtain an anisotropic conductive adhesive composition (1).
The obtained anisotropic conductive adhesive composition (1) is diluted with toluene, and then subjected to ultrasonic dispersion treatment for 30 minutes, followed by filtration, taking out the conductive fine particles coated with the conductive fine particles, and insulating with an SEM. The covering state of the conductive fine particles was evaluated.
The results are shown in Table 2.
(Manufacture of anisotropic conductive molded body (1))
The obtained anisotropic conductive adhesive composition (1) was sandwiched between two ITO glass substrates so that the patterns were orthogonal and opposed, and heated and pressurized at 160 ° C. for 20 minutes and with a load of 6 kg / cm ^2. An anisotropic conductive molding (1) was obtained.
(Evaluation of conductivity and insulation)
Using the obtained insulating fine particle-coated conductive fine particles (1) and anisotropic conductive molded body (1), conductivity and insulation were evaluated.
The results are shown in Table 2.

[Example 5]: Insulating fine particle-coated conductive fine particles (2), anisotropic conductive adhesive composition (2), anisotropic conductive molded body (2)
(Synthesis of conductive fine particles (2))
Conductive fine particles (2) were obtained in the same manner as in Example 1 except that instead of displacement gold plating in Example 1, substitution palladium plating was performed.
The average particle size of the conductive fine particles (2) was 2.8 μm.
(Production of insulating fine particle-coated conductive fine particles (2))
Ultrasonic dispersion was performed in methanol so that the concentration of the insulating fine particles (1) obtained in Example 1 was 5.0% by weight. After adding 50 parts of the conductive fine particles (2) to 100 parts of the methanol dispersion of the obtained insulating fine particles (1) and uniformly dispersing using ultrasonic waves, the methanol is distilled off by an evaporator, The surface of the conductive fine particles (2) was coated with the insulating fine particles (1) to obtain insulating fine particle-coated conductive fine particles (2).
The results are shown in Table 2.
(Manufacture of anisotropic conductive adhesive composition (2))
2 parts of the above-mentioned insulating fine particle-coated conductive fine particles (2) are added to 100 parts of struct bond XN-5A (manufactured by Mitsui Chemicals) as a binder resin, and the insulating fine particle-coated conductive material is added to the binder resin using a planetary stirrer. The anisotropic fine particles (2) were uniformly dispersed to obtain an anisotropic conductive adhesive composition (2).
The obtained anisotropic conductive adhesive composition (2) is diluted with toluene, and then subjected to ultrasonic dispersion treatment for 30 minutes, followed by filtration, taking out the conductive fine particles coated with the conductive fine particles, and insulating with an SEM. The covering state of the conductive fine particles was evaluated.
The results are shown in Table 2.
(Manufacture of anisotropic conductive molded body (2))
The obtained anisotropic conductive adhesive composition (2) was sandwiched between two ITO glass substrates so that the patterns were orthogonal and opposed, and heated and pressurized at 160 ° C. for 20 minutes and with a load of 6 kg / cm ^2. An anisotropic conductive molded body (2) was obtained.
(Evaluation of conductivity and insulation)
Using the obtained insulating fine particle-coated conductive fine particles (2) and anisotropic conductive molded body (2), conductivity and insulation were evaluated.
The results are shown in Table 2.

[Example 6]: Insulating fine particle-coated conductive fine particles (3), anisotropic conductive adhesive composition (3), anisotropic conductive molded body (3)
(Production of insulating fine particle-coated conductive fine particles (3))
Ultrasonic dispersion was performed in methanol so that the concentration of the insulating fine particles (2) obtained in Example 2 was 5.0% by weight. After adding 50 parts of the above-mentioned conductive fine particles (1) to 100 parts of the methanol dispersion liquid of the obtained insulating fine particles (2) and uniformly dispersing using ultrasonic waves, the methanol is distilled off by an evaporator, The surface of the conductive fine particles (1) was coated with the insulating fine particles (2) to obtain the conductive fine particles (3) coated with the insulating fine particles.
The results are shown in Table 2.
(Production of anisotropic conductive adhesive composition (3))
2 parts of the insulating fine particle-coated conductive fine particles (3) are added to 100 parts of struct bond XN-5A (manufactured by Mitsui Chemicals) as a binder resin, and the insulating fine particle-coated conductive material is added to the binder resin using a planetary stirrer. Conductive fine particles (3) were uniformly dispersed to obtain an anisotropic conductive adhesive composition (3).
The obtained anisotropic conductive adhesive composition (3) is diluted with toluene, and then subjected to ultrasonic dispersion treatment for 30 minutes, followed by filtration, taking out the conductive fine particles coated with the insulating fine particles, and insulating with an SEM. The covering state of the conductive fine particles was evaluated.
The results are shown in Table 2.
(Manufacture of anisotropic conductive molded body (3))
The obtained anisotropic conductive adhesive composition (3) was sandwiched between two ITO glass substrates so that the patterns were orthogonal and opposed, and heated and pressurized at 160 ° C. for 20 minutes and with a load of 6 kg / cm ^2. An anisotropic conductive compact (3) was obtained.
(Evaluation of conductivity and insulation)
Using the obtained insulating fine particle-coated conductive fine particles (3) and anisotropic conductive molded body (3), conductivity and insulation were evaluated.
The results are shown in Table 2.

[Example 7]: Insulating fine particle-coated conductive fine particles (4), anisotropic conductive adhesive composition (4), anisotropic conductive molded body (4)
(Production of insulating fine particle-coated conductive fine particles (4))
Ultrasonic dispersion was performed in methanol so that the concentration of the insulating fine particles (3) obtained in Example 3 was 5.0% by weight. After adding 50 parts of the above-mentioned conductive fine particles (1) to 100 parts of the methanol dispersion liquid of the obtained insulating fine particles (3) and uniformly dispersing using ultrasonic waves, the methanol is distilled off with an evaporator, The surface of the conductive fine particles (1) was coated with the insulating fine particles (3) to obtain conductive fine particles (4) coated with the insulating fine particles.
The results are shown in Table 2.
(Manufacture of anisotropic conductive adhesive composition (4))
2 parts of the above-mentioned insulating fine particle-coated conductive fine particles (4) are added to 100 parts of struct bond XN-5A (manufactured by Mitsui Chemicals) as a binder resin, and the insulating fine particle-coated conductive material in the binder resin using a planetary stirrer. Conductive fine particles (4) were uniformly dispersed to obtain an anisotropic conductive adhesive composition (4).
The obtained anisotropic conductive adhesive composition (4) is diluted with toluene, then subjected to ultrasonic dispersion treatment for 30 minutes, and then filtered to take out the conductive fine particles coated with insulating fine particles, and insulate with SEM. The covering state of the conductive fine particles was evaluated.
The results are shown in Table 2.
(Manufacture of anisotropic conductive molded body (4))
The obtained anisotropic conductive adhesive composition (4) was sandwiched between two ITO glass substrates so that the patterns were orthogonal and opposed to each other, and heated and pressurized at 160 ° C. for 20 minutes with a load of 6 kg / cm ^2. An anisotropic conductive compact (4) was obtained.
(Evaluation of conductivity and insulation)
Using the obtained insulating fine particle-coated conductive fine particles (4) and anisotropic conductive molded body (4), conductivity and insulation were evaluated.
The results are shown in Table 2.

[Comparative Example 3]: Insulating fine particle-coated conductive fine particles (C1), anisotropic conductive adhesive composition (C1), anisotropic conductive molded body (C1)
(Production of insulating fine particle-coated conductive fine particles (C1))
Ultrasonic dispersion was performed in methanol so that the concentration of the insulating fine particles (C1) obtained in Comparative Example 1 was 5.0% by weight. After adding 50 parts of the conductive fine particles (1) to 100 parts of the methanol dispersion of the obtained insulating fine particles (C1) and uniformly dispersing using ultrasonic waves, the methanol is distilled off with an evaporator, The surface of the conductive fine particles (1) was coated with the insulating fine particles (C1) to obtain insulating fine particle-coated conductive fine particles (C1).
The results are shown in Table 2.
(Manufacture of anisotropic conductive adhesive composition (C1))
2 parts of the insulating fine particle-coated conductive fine particles (C1) are added to 100 parts of struct bond XN-5A (Mitsui Chemical Co., Ltd.) as a binder resin, and the insulating fine particle coated conductive material is added to the binder resin using a planetary stirrer. Conductive fine particles (C1) were uniformly dispersed to obtain an anisotropic conductive adhesive composition (C1).
The obtained anisotropic conductive adhesive composition (C1) is diluted with toluene, and then subjected to ultrasonic dispersion treatment for 30 minutes, followed by filtration, taking out the insulating fine particle-coated conductive fine particles, and insulating with an SEM. The covering state of the conductive fine particles was evaluated.
The results are shown in Table 2.
(Manufacture of anisotropic conductive molded body (C1))
The obtained anisotropic conductive adhesive composition (C1) was sandwiched between two ITO glass substrates so that the patterns were orthogonal and opposed, and heated and pressurized at 160 ° C. for 20 minutes and with a load of 6 kg / cm ^2. An anisotropic conductive molded body (C1) was obtained.
(Evaluation of conductivity and insulation)
Using the obtained insulating fine particle-coated conductive fine particles (C1) and anisotropic conductive molded body (C1), conductivity and insulation were evaluated.
The results are shown in Table 2.

[Comparative Example 4]: Insulating fine particle-coated conductive fine particles (C2), anisotropic conductive adhesive composition (C2), anisotropic conductive molded body (C2)
(Production of insulating fine particle-coated conductive fine particles (C2))
Ultrasonic dispersion was performed in methanol so that the concentration of the insulating fine particles (C2) obtained in Comparative Example 2 was 5.0% by weight. To 100 parts of the resulting dispersion of insulating fine particles (C2) in methanol, 50 parts of the conductive fine particles (1) are added and dispersed uniformly using ultrasonic waves, and then the methanol is distilled off with an evaporator. The surface of the conductive fine particles (1) was coated with insulating fine particles (C2) to obtain conductive fine particles coated with insulating fine particles (C2).
The results are shown in Table 2.
(Manufacture of anisotropic conductive adhesive composition (C2))
2 parts of the insulating fine particle-coated conductive fine particles (C2) are added to 100 parts of struct bond XN-5A (manufactured by Mitsui Chemicals) as a binder resin, and the insulating fine particle-coated conductive material is added to the binder resin using a planetary stirrer. Conductive fine particles (C2) were uniformly dispersed to obtain an anisotropic conductive adhesive composition (C2).
The obtained anisotropic conductive adhesive composition (C2) is diluted with toluene, then subjected to ultrasonic dispersion treatment for 30 minutes, and then filtered to take out the conductive fine particles coated with insulating fine particles, and insulate with SEM. The covering state of the conductive fine particles was evaluated.
The results are shown in Table 2.
(Manufacture of anisotropic conductive molded body (C2))
The obtained anisotropic conductive adhesive composition (C2) was sandwiched between two ITO glass substrates so that the patterns were orthogonal and opposed, and heated and pressurized at 160 ° C. for 20 minutes and with a load of 6 kg / cm ^2. An anisotropic conductive molded body (C2) was obtained.
(Evaluation of conductivity and insulation)
Using the obtained insulating fine particle-coated conductive fine particles (C2) and anisotropic conductive molded body (C2), conductivity and insulation were evaluated.
The results are shown in Table 2.

As shown in Tables 1 and 2, in Example 4-7 using the insulating fine particles of the present invention (Example 1-3) satisfying 0.10 <d / D <2.0, the insulating fine particles The evaluation of the coating state based on the degree of coverage reduction is ○ (the degree of coverage reduction is less than 10%), the insulating fine particles have strong adhesion to the surface of the conductive fine particles, and the insulating fine particles are conductive. It can be seen that it is difficult for the fine particles to fall off from the surface. Moreover, in Example 4-7, the evaluation of both conductivity and insulation is ○, and the insulating fine particle-coated conductive fine particles coated with the insulating fine particles are contained in the anisotropic conductive adhesive composition. In the anisotropic conductive material having the high density insulating fine particle coated conductive fine particles of 50000 / mm ³ employed in this example, the insulating fine particle coated conductive fine particles are adjacent to each other. However, since the insulating fine particles have sufficient elasticity and do not undergo plastic deformation, it can be seen that excellent conductivity and insulation can be exhibited.

  On the other hand, in Comparative Example 3 using insulating fine particles having a d / D of 0.10 or less (Comparative Example 1: d / D = 0.09), the coating state based on the degree of decrease in the coverage of the insulating fine particles The evaluation is x (the degree of coverage reduction is 10% or more), the insulating fine particles do not have sufficient adhesion to the surface of the conductive fine particles, and the insulating fine particles are dropped from the surface of the conductive fine particles. It turns out that it is easy to release. Moreover, in the comparative example 3, evaluation of insulation is x and it turns out that the outstanding insulation cannot be exhibited.

  Further, in Comparative Example 4 using insulating fine particles having a d / D of 2.0 or more (Comparative Example 2: d / D = 2.10), the evaluation of insulating property was x, which was excellent. It turns out that insulation cannot be demonstrated.

  The insulating fine particles of the present invention can be suitably used as an anisotropic conductive material for electrical connection by using the insulating fine particles coated conductive fine particles.

Claims (6)

Insulating fine particles for coating conductive fine particles, having a core-shell structure with a shell layer on the outer periphery of the core layer,
The core layer comprises a vinyl polymer, the shell layer comprises an amino resin,
When the diameter of the core part is Dnm and the thickness of the shell part is dnm, 0.10 <d / D <2.0.
Insulating fine particles for coating conductive fine particles.   2. Conductive fine particles coated with insulating fine particles, wherein the insulating fine particles according to claim 1 are present on the surface of the conductive fine particles.   The insulating fine particle-coated conductive fine particles according to claim 2, comprising at least one selected from gold, palladium, silver, copper, tin, and alloys thereof on the outermost surface of the conductive fine particles.   The insulating fine particle-coated conductive fine particles according to claim 2 or 3, wherein the conductive fine particles have an average particle diameter of 1.0 µm to 5.0 µm.   An anisotropic conductive adhesive composition comprising the insulating fine particle-coated conductive fine particles according to any one of claims 2 to 4 dispersed in a binder resin. An anisotropic conductive molded body obtained from the anisotropic conductive adhesive composition according to claim 5.