TW201120920A - Conductive particle - Google Patents

Abstract

Disclosed is a conductive particle (8b) comprising: a core particle (11); a palladium layer (12) which covers the core particle (11) and which has a phosphorus concentration of between 1 wt% and 10 wt% and a thickness of between 20 nm and 130 nm; and insulating particles (1) which are disposed at the surface of the palladium layer (12) and which have a particle size of between 20 nm and 500 nm.

Description

201120920 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to conductive particles. [Prior Art] Two types of liquid crystal driving Ic are assembled on a liquid crystal display without a glass panel, and can be roughly classified into two types of COG (Chip-on-Glass) assembly and COF on-Flex assembly. In the COG assembly, the liquid crystal was directly bonded to the glass panel by 1C using an anisotropic conductive agent containing conductive particles. On the other hand, in the assembly, the liquid crystal driving 1C is bonded to the wiring having the metal wiring, and the glass panels are bonded to each other using an anisotropic conductive adhesive containing conductive particles. The anisotropy as used herein means conduction in the pressurizing direction and insulation in the pressurizing direction. However, with the recent refinement of the liquid crystal display, the bumps of the circuit electrodes for driving 1C are narrowly pitched, and the conductive particles of the narrow-area anisotropic conductive adhesive flow out to the adjacent circuit to be short-circuited. The problem. Further, when the conductive particles flow out between the adjacent circuit electrodes, the derivative in the anisotropic conductive adhesive which is complemented by the glass panel is reduced, and the connection resistance between the opposing circuit electrodes is increased, which causes problems such as failure. . As a method for solving such problems, as shown in the following Patent Document 1, there is a method in which at least one surface of the anisotropic conductive adhesive is formed, (Chip-ability is followed by COF tape bonding to glass, and non-liquid crystallizing Therefore, a method of preventing the deterioration of the bonding quality in COG assembly or COF assembly in the case of the insulator -3-201120920 as an adhesive in the bump electric particle connection, or as in the following Patent Document 2 A method of coating the entire surface of the conductive particles with an insulating film is exemplified. In the following Patent Documents 3 and 4, a method of coating the polymer core particles coated with the gold layer with insulating sub-particles is shown. In Patent Document 4 below, it is shown that the surface of the gold layer covering the core particles is treated with a compound having any of a mercapto group or a thiol 'dithiol group, and a functional group is formed on the surface of the gold layer. In this way, a strong functional group can be formed on the gold layer. In Patent Document 5 below, as an attempt to improve the conductivity of the conductive particles, it is shown that copper/gold plating is performed on the resin fine particles. In the following Patent Document 6, a conductive layer containing a non-metallic fine particle, a metal layer containing 50% by weight or more of copper, a nickel layer covering a metal layer, and a gold layer coated with a nickel layer is provided. By the conductive particles, the conductivity is improved as compared with the conductive particles of the general nickel and gold. In the following Patent Document 7, a substrate-containing fine particle and a metal coating provided on the substrate fine particles are described. The conductive particles of the layer are characterized in that the content of the gold in the metal coating layer is 90% by weight or more and 99% by weight in the metal coating layer. The prior art is disclosed in the patent document 1: JP-A-2008-279371. Patent Document 2: Japanese Patent No. 2794〇09 Patent Document 3: Japanese Patent No. 2 748 705 Patent Document 4: International Publication No. 03/02955 Manual Patent Document 5: JP-A-2006-02843 No. 8 [Problem to be Solved by the Invention] However, as shown in the above Patent Document 1, the above-mentioned Patent Document 1 In the method of forming an insulating adhesive on one side of the circuit connecting member, when the bump area is narrowed to less than 3000 μm 2 , in order to obtain a stable connection resistance, it is necessary to increase the conductive particles in the circuit connecting member. When the conductive particles are added, there is room for improvement in the insulating layer between the adjacent electrodes. Further, as shown in the above Patent Document 2, the conductive particles are coated with an insulating film in order to improve the insulation between the adjacent electrodes. In the method of the entire surface, the insulation between the circuit electrodes is increased, but the conductivity of the conductive particles is likely to be low. Further, as shown in the above Patent Documents 3 and 4, the insulating particles are used. In the method of coating the surface of the conductive particles, it is necessary to use a resin particle such as acrylic resin due to the problem of adhesion between the daughter particles and the conductive particles. At this time, the resin seed particles are melted by thermal compression bonding of the circuits, and the conductive particles are brought into contact with the two circuits to obtain conduction between the circuits. In this case, when the resin of the molten daughter particles is coated on the surface of the conductive particles, it is known that the conductivity of the conductive particles is likely to be low similarly to the method of coating the entire surface of the conductive particles with an insulating film. For this reason, it is suitable as an insulating subparticle such as a relatively high hardness such as an inorganic oxide and a high melting temperature. For example, in the above-mentioned Patent Document 4, a method of treating a vermiculite surface with 3-isocyanatepropyltriethoxysilane to react a vermiculite having an isocyanate group on the surface with a conductive particle having an amine group on the surface is exemplified. However, it is generally difficult to modify the surface of a particle having a particle diameter of 500 nm or less with a functional group, and when it is subjected to centrifugation or filtration after modification with a functional group, aggregation of inorganic oxide such as vermiculite is likely to occur. Further, in the method exemplified in the above Patent Document 4, it is difficult to control the coverage of the insulating sub-particles. Further, when the metal surface is treated with a compound having any of a mercapto group, a thiol group, and a disulfide group, a metal such as a niobium metal such as nickel or a copper such as copper is easily oxidized on the metal, and the reaction between the metal and the compound occurs. It is also difficult to carry out the investigation by the inventors of the present invention. When the conductive particles are coated with an inorganic substance such as vermiculite, the vermiculite crushes the metal surface on the conductive particles to exhibit electrical conductivity. Therefore, since the vermiculite destroys the conductive metal, if the foreign metal enters the conductive metal, the migration property tends to deteriorate. Further, as shown in the above-mentioned Patent Document 6, a conductive particle type of a type in which gold plating is performed on a nickel layer has been in the mainstream, but among such conductive particles, there is a problem that nickel is eluted and migration occurs. Further, when the thickness of the gold plating is set to 4 Å or less, the tendency becomes remarkable. In addition, as shown in the above-mentioned Patent Document 7, the conductive particles coated with the metal coating layer having a content of gold or more are excellent in cost, but the cost is high. Therefore, it is difficult to say that the conductive particles having a layer having a high gold content are practical, and in recent years, there has been a tendency to lower the gold content of the layer. On the other hand, the copper plating is excellent in conductivity and cost. However, in the case of copper plating, migration is likely to occur, and this is due to the hygroscopicity resistance, and there are attempts to compensate for the shortcomings of both (gold and copper). For example, in the method described in the above Patent Document 5, there is no shortcoming of the two (gold and copper). The present invention has been made in view of the above problems, and has an object of promoting migration, low cost, high conductivity, and reliable connection of conductive particles between electrodes. Means for Solving the Problem In order to achieve the above object, the conductive particle core particles (resin fine particles) and the coated core particles of the first aspect of the invention have a phosphorus concentration of not more than 1% by weight and a thickness of 20 nm or more and 130 nm or less. The particles are characterized by comprising a conductive layer in which a resin is finely formed on the surface of the resin fine particles, and the conductive layer contains a phosphorus concentration in the phosphorus-palladium layer of from 8% by weight to 10% by weight or less, and palladium is from 20 nm to 130 nm. The present invention is characterized in that the surface is formed directly on the surface of the resin fine particles. In other words, the amount of metal (e.g., nickel) other than palladium on the surface of the resin fine particles is 90 weights. Reliability Metal coating Metal coating Electroconductive particles Conductive particles. However, it is not possible to fully provide a palladium layer having a nuclear weight of 1% by weight. The palladium layer of the particles and the shape, the thickness of the layer, the palladium layer is in the middle, and the good does not exist in 201120920. Such a feature of the present invention is not deficient in achieving the effects of the present invention described below. In the first aspect of the invention, since the palladium layer has ductility, when the pair of electrodes are connected by using the anisotropic conductive adhesive having the conductive particles, the palladium layer is less likely to be broken even after the conductive particles are compressed. Therefore, the conductivity of the conductive particles after compression and the connection reliability between the electrodes can be improved, and the migration of palladium due to the cracking of the palladium layer can be prevented. Further, palladium is cheaper and more practical than precious metals such as gold and platinum. Therefore, the above-described first conductive particles of the present invention having a palladium layer are low in cost compared with conductive particles using only gold or platinum. In the first invention described above, since the thickness of the palladium layer is 20 nm or more, sufficient conductivity can be obtained. In the first aspect of the invention, since the phosphorus is contained in the palladium layer in an amount of 1% by weight or more and 10% by weight or less, the hardness is high and the surface of the electrode is deeper, and a conductive film having sufficient strength is obtained. The conductive particle of the second aspect of the invention includes: a core particle; a core particle, a palladium layer having a phosphorus concentration of 1% by weight or more and 10% by weight or less, a thickness of 20 nm or more and 130 nm or less; and a surface of the palladium layer having a particle diameter of Insulating particles of 20 to 500 nm. An anisotropic conductive adhesive (isotropic conductive film) obtained by dispersing a plurality of the above-mentioned conductive particles in an adhesive is disposed between a pair of electrodes, and is connected (hot pressed) to a pair of electrodes in a longitudinal direction (a pair) In the direction in which the electrodes face each other, the entire conductive particles are compressed by a pair of electrodes. As a result, the insulating particles are pressed from the surface of the palladium layer to the core particle side, and the exposed palladium layer -8-201120920 may be in contact with a pair of electrodes. That is, a pair of electrodes are electrically connected via a palladium layer of conductive particles. On the other hand, in the lateral direction (the direction perpendicular to the direction in which the pair of electrodes face), the insulating particles provided in the respective conductive particles are interposed between the adjacent conductive particles, and the insulating particles are in contact with each other. Therefore, in the lateral direction, the pair of electrodes maintain insulation between the electrodes adjacent thereto. In the second aspect of the invention, since the palladium layer has ductility, the conductivity of the conductive particles after compression and the connection reliability between the electrodes can be improved, and the migration of palladium can be prevented, as in the first invention. Further, palladium is cheaper and more practical than precious metals such as gold and uranium. Therefore, the second conductive particle of the present invention having a palladium layer is low in cost compared with the conductive particles using only gold or platinum. In the second aspect of the invention, as the conductive layer, a palladium layer having a thickness of 20 nm or more is provided, whereby sufficient conductivity can be obtained. In the first and second inventions described above, the palladium layer is preferably a palladium layer obtained by reduction plating. Thereby, the coverage of the core particles by the palladium layer is increased, and the conductivity of the conductive particles is easily improved. Further, since the palladium layer is a palladium layer of a reduction plating type, a dense and homogeneous palladium layer can be formed on the resin fine particles, and conductive particles having little exposed surface of the resin fine particles can be provided. Further, the thickness of the palladium layer can be arbitrarily set in accordance with the amount of the plating solution. That is, the thickness of the palladium layer can be controlled as needed. In the above invention, the components (the elemental composition of the conductive layer and the phosphorus concentration) in the conductive layer are preferably qualitatively and quantitatively determined by Energy Dispersive X-ray Spectroscopy (EDX). 201120920 In the first and second inventions described above, the insulating particles are preferably vermiculite. The insulating particles made of vermiculite are excellent in insulation property, and it is easy to control the particle size and is inexpensive. Further, when the vermiculite is dispersed in water to form a water-dispersed colloidal vermiculite, since it has a hydroxyl group on its surface, it is excellent in the bondability with the palladium layer. Further, the hydroxyl group on the surface of the vermiculite is also excellent in the bonding property with the functional group formed on the surface of the palladium layer. Therefore, the insulating particles formed of vermiculite may be strongly adsorbed on the surface of the palladium layer or the gold layer. Advantageous Effects of Invention According to the present invention, it is possible to provide conductive particles which do not cause migration, are inexpensive, have high conductivity, and are excellent in connection reliability between electrodes. [Embodiment] Mode for Carrying Out the Invention The best mode for carrying out the invention will be described in detail below. However, the present invention is not limited by the following embodiments. [First Embodiment] (Electrically Conductive Particles) As shown in Fig. 1, the conductive particles 8a of the first embodiment of the present invention have a core particle 1 1 and a coated core particle 1 having a thickness of 2 〇 nm or more and 130 nm. Hereinafter, the palladium layer 12 having a phosphorus concentration of 1% by weight or more and 1% by weight or less is used. Hereinafter, the conductive particles 8 a of the first embodiment will be referred to as "master particles 2 a" as appropriate. -10·201120920 <core particle 1 1 > The particle diameter of the core particle 11 used in the present invention is preferably smaller than the minimum interval between the first electrode 5 and the second electrode 7 of Fig. 3 to be described later. Further, when the height of the electrode (the interval between the electrodes) fluctuates, the particle diameter of the core particle 11 is preferably larger than the fluctuation of the height (the maximum interval of the electrode). For these reasons, the particle diameter of the core particle 1 1 is preferably 1 to ΙΟμηι, more preferably 1 to 5 μη, and particularly preferably 2.0 to 3·5 μη. The core particles of the conventional conductive particles are either particles made of a metal or particles made of an organic or inorganic substance. However, the core particles in the present embodiment are resin fine particles made of a resin. The core particle 11 as an organic substance is not particularly limited, and is preferably an acrylic resin such as polymethyl methacrylate or polymethyl acrylate, polyethylene, polypropylene, polyisobutylene, polybutadiene or the like. A resin particle formed of an olefin resin, a polystyrene, a divinylbenzene polymer, a divinylbenzene-styrene copolymer, a benzoguanamine formaldehyde resin, or the like. <Palladium layer 1 2 > Since the palladium layer 12 has ductility, after the conductive particles 8a are compressed, metal cracking is less likely to occur, and migration accompanying metal cracking is less likely to occur. Further, the palladium layer 12 is superior in acid resistance and alkali resistance to base metal or copper. Further, since the palladium layer 12 is an alloy containing phosphorus, it is more excellent in acid resistance and alkali resistance. Therefore, it is stably bonded to a functional group such as a thiol group, a thiol group or a disulfide group described later. Further, in the binding property to these functional groups, palladium has the same tendency as gold and platinum, but when compared with the same volume of such precious metals, the palladium system is most inexpensive and practical. Further, the palladium layer 12 is excellent in electrical conductivity. Based on these reasons, the palladium layer 12 is suitable as a metal layer covering the core particles 11. The phosphorus concentration in the palladium layer 12 is from 1% by weight to 10% by weight or less, preferably from 1% by weight to 8% by weight, and more preferably from 1% by weight to 6% by weight, based on the connection resistance. Further, the palladium layer containing phosphorus is high in hardness compared with the pure palladium layer containing no phosphorus (see Non-Patent Document 1 "Surface Technology P651, Vol55, NolO, 2004"). If the hardness of the surface of the palladium layer in contact with the electrode is high, the conductive particles easily penetrate the surface of the electrode to puncture the oxidized electrode, and it is easy to ensure the conduction performance. On the other hand, when the content of phosphorus exceeds 10% by weight, the on-resistance of the palladium layer is excessively large. Further, when the content of phosphorus is more than 10% by weight, for example, when the palladium layer 12 is formed by plating, the palladium plating system is difficult to carry out, and the time required for the plating step becomes long. The palladium layer 12 is preferably a reduced-plating palladium layer. Thereby, the coverage of the core particles 11 by the palladium layer 12 is increased, and the conductivity of the conductive particles 8a is further improved. The reducing agent for co-depositing phosphorus and alloying palladium is preferably a phosphorus-containing reducing agent containing at least hypophosphorous acid or a salt thereof, phosphorous acid or a salt. The reducing agent may contain other reducing agents as long as it contains the above-mentioned phosphorus-containing reducing agent, and is not particularly limited. It is known that when other reducing agents are contained, the phosphorus is co-deposited from the phosphorus-containing reducing agent in the palladium film. The plating thickness of the palladium layer 12 is easily controlled by using reduction plating. For example, since the plating thickness after precipitation can be calculated in advance from the palladium ion concentration contained in the plating solution to be used, palladium or a reagent can be used without waste, and the cost can be reduced. The thickness of the palladium layer 12 is 20 nm or more and 130 nm or less, preferably 20 nm or more, -12 to 201120920 and 100 nm or less, more preferably 20 nm or more and 80 nm or less. If the thickness of the palladium layer is less than 20 nm, sufficient conductivity cannot be obtained. On the other hand, when the thickness of the palladium layer I2 exceeds 130 nm, the elasticity of the entire core particle 11 is lowered. When the elasticity of the entire mother particle 2a is lowered, when the conductive particle 8a is sandwiched by a pair of electrodes and crushed in the longitudinal direction, it is difficult to obtain the palladium layer 12 to sufficiently press the electrode surface by the elasticity of the mother particle 2a. effect. Therefore, the contact area between the palladium layer 12 and the two electrodes is small, and the effect of the present invention for improving the connection reliability between the electrodes tends to be small. Further, the thicker the palladium layer 12 is, the higher the cost is, and it is not only economically unsatisfactory, but also the palladium which is a conductive layer of the conductive particles 8a which are crushed in the longitudinal direction by the pair of electrodes at the time of assembly and pressure bonding. In the layer 12, cracking occurs, and the connection resistance between the electrodes tends to increase. (Analysis of plating layer) In the component analysis of the palladium layer 12 covering the surface of the core particle 11, an atomic absorption photometer can be used. For example, a liquid in which a palladium layer 12 is dissolved in an acid or the like is analyzed by an atomic absorption spectrophotometer, and the metal ion concentration is measured and calculated. Further, the palladium layer 12 can also be analyzed using an ICP luminescence analyzer. When an ICP luminescence analyzer is used, quantification of phosphorus can be performed simultaneously with qualitative analysis. Further, the phosphorus concentration in the palladium layer 12 can also be quantified using EDX. Further, since the information from the plurality of particles is obtained by the EDX measurement at a low magnification, it is preferably measured by EDX at a high magnification. [Second embodiment] Next, a method for producing conductive particles and conductive particles of the first embodiment of the present invention - 13-201120920 will be described. In the following, only the differences between the first embodiment and the second embodiment will be described, and the description of the common items will be omitted. (Electrically conductive particles) As shown in FIG. 2, the conductive particles 8b of the second embodiment are provided with not only the core particles 11 and the palladium layer 12 but also a plurality of insulating particles 1 disposed on the surface of the palladium layer 12, and The conductive particles 8a of one embodiment are different. <Insulating Particles 1 > The insulating particles 1 are preferably inorganic oxides. When the insulating particles 1 are organic compounds, the insulating particles 1 are deformed in the production step of the anisotropic conductive adhesive, and the properties of the obtained anisotropic conductive adhesive tend to change easily. The inorganic oxide constituting the insulating particles 1 preferably contains an oxide of at least one element selected from the group consisting of ruthenium, aluminum, cone, titanium, lanthanum, zinc, tin, antimony and magnesium. These oxides may be used alone or in combination of two or more. Further, as the inorganic oxide, among the oxides containing the above elements, water-dispersed colloidal vermiculite (SiO 2 ) having excellent insulating properties and controlled particle size is preferred. Commercial products of the insulating particles (hereinafter referred to as inorganic oxide fine particles) formed by such an inorganic oxide include, for example, Snowtex, Snowtex UP (manufactured by Seiko Chemical Co., Ltd.), and Quartron PL series (for example). Fusang Chemical Industry Co., Ltd.). -14- 201120920 The particle diameter of the inorganic oxide fine particles is preferably smaller than that of the resin fine particles. Specifically, the inorganic oxide fine particles have an average particle diameter of 20 to 500 nm, preferably 30 to 400 nm, more preferably 40 to 350 nm. Further, the particle diameter of the inorganic oxide fine particles is measured by a specific surface area conversion algorithm of the B ET method or an X-ray small angle scattering method. When the particle diameter is less than 20 nm, the inorganic oxide fine particles adsorbed on the mother particles 2a do not function as an insulating film, and a short circuit tends to occur in a part between the electrodes. On the other hand, when the particle diameter exceeds 500 nm, when the electrode is assembled and pressed, the electrode and the conductive layer (palladium layer 12) of the conductive particles 8b are hard to be contacted, and the connection resistance between the electrodes becomes high, and the connection resistance is high. The tendency to good electrical conductivity. (Manufacturing Method of Conductive Particles) The method for producing the conductive particles 8a according to the first embodiment of the present invention includes the step (S1) of forming the palladium layer 12 on the surface of the core particles 11. The method for producing the conductive particles 8b according to the second embodiment of the present invention is provided after the step S1, and the surface of the palladium layer 12 is treated with a compound having a thiol group, a thiol group or a disulfide group. a step (S2) of forming a functional group on the surface of the palladium layer 12, a step (S3) of treating the surface of the palladium layer having the functional group with a polymer electrolyte, and a high degree of formation by a functional group The step of immobilizing the surface of the palladium layer 12 of the molecular electrolyte treatment by chemically adsorbing the insulating particles 1 (S4). Further, the case where the insulating particles 1 are formed of inorganic oxide fine particles having a hydroxyl group on the surface will be described below. <S 1 > -15- 201120920 First, the palladium layer 12 is formed on the surface of the core particle 11 to obtain the mother particle 2a (the conductive particle 8a of the first embodiment). As a specific method, for example, plating of palladium can be mentioned. In the plating step, the surface of the core particle 11 is degreased with an alkali or the like, and then the surface of the core particle 1 is adjusted by acid neutralization. Then, a palladium catalyst is applied, and reduced electroless palladium plating can be carried out by the above phosphorus-containing reducing agent. As the composition of the reduced electroless palladium ore dressing liquid, it is preferred to add (1) a water-soluble palladium salt such as palladium sulfate, (2) a reducing agent, (3) a distoring agent, and (4) a pH adjuster. As a method of adjusting the phosphorus concentration in the palladium layer 12 to 1% by weight or more and 1% by weight or less, for example, a method of adjusting the components (1) to (4) constituting the palladium plating solution described above is used. In particular, a method of controlling the phosphorus concentration in the palladium plating solution, such as a method of selecting a reducing agent containing phosphorus, a method of adjusting the amount of the reducing agent, a method of controlling the pH of the plating reaction, a method of adjusting the plating temperature, and the like Wait. Further, in the method of adjusting the type or concentration of the dismuting agent, the adjustment of the phosphorus concentration may be possible. Among them, a method of controlling the pH of the plating reaction is suitably used from the viewpoint of excellent reaction control. The above-described methods can be used singly, but if the respective combinations are combined, the adjustment of the phosphorus concentration is easy, and the control of the stability of the plating solution is also easy. S2 > When the conductive particles 8b of the second embodiment are formed, A compound having any one of a mercapto group, a thiol group or a disulfide group which forms a coordinate bond to palladium is used to treat the surface of the palladium layer 12. Thereby, a functional group is formed on the surface of the palladium layer 12. -16-201120920 Specific examples of the compound used for the surface treatment of the palladium layer 12 include mercaptoacetic acid, 2-mercaptoethanol, methyl thioglycolate, mercapto succinic acid, thioglycerol 'cysteine, and the like. . The functional group formed on the surface of the palladium layer ruthenium 2 treated with these compounds may, for example, be a hydroxyl group, a carboxyl group, an alkoxy group or an alkoxycarbonyl group. The palladium system is easily reacted with a thiol group (fluorenyl group), whereas a base metal such as nickel is difficult to react with a thiol group. Therefore, compared with the conventional type of nickel/gold particles (core particles coated with a nickel layer and a gold layer), the palladium particles (core particles 1 1 coated with the palladium layer 12) of the present embodiment are easily thiol-based. reaction. Further, when the thickness of gold in the nickel/gold particles is 30 nm or less, the proportion of nickel on the surface of the particles tends to be high. Specific examples of the method for treating the surface of the palladium layer 12 with the above-mentioned compound include a compound obtained by dispersing a compound such as thioglycolic acid of 1 〇1 to 100 mmol/1 in an organic solvent such as methanol or ethanol. A method of dispersing palladium particles. <S3, S4 > Next, after the surface of the palladium layer 12 on which the functional group is formed is treated with a polymer electrolyte, the insulating particles 1 are chemically adsorbed on the surface of the palladium layer 12. The surface potential ((potential) of the palladium layer 12 having a functional group such as a hydroxyl group, a carboxyl group, an alkoxy group or an alkoxycarbonyl group is usually negative at a pH in the neutral region. On the other hand, it is adsorbed to the palladium layer 1 in a later step. Since the surface of the insulating particles 1 on the surface of the insulating particles 1 is made of an inorganic oxide having a hydroxyl group, the surface potential of the insulating particles 1 is also generally negative. Thus, the palladium having a surface potential of -17-201120920 is negative. The insulating particles 1 having a negative surface potential tend to be adsorbed around the layer 12. Therefore, the surface of the palladium layer 12 is treated with a polymer electrolyte, and the surface of the palladium layer 12 is easily coated with the insulating particles 1. As a method of adsorbing the insulating particles 1 on the surface of the palladium layer 12 after the polymer electrolyte treatment, a method of alternately laminating a polymer electrolyte and an inorganic oxide on the surface of the palladium layer 12 is preferable. More specifically, By performing the following steps (1) and (2) in sequence, it is possible to manufacture a part of the mother particles 2a which is coated on the surface of the insulating coating film laminated with the polymer electrolyte and the inorganic oxide fine particles, that is, conductive Step 8 (1): a step of dispersing the mother particles 2a having a functional group on the surface of the palladium layer 12 in a polymer electrolyte solution, adsorbing the polymer electrolyte on the surface of the IG layer 12, and rinsing the mother particles 2a Step (2): a step of dispersing the washed mother particles 2a in a dispersion solution of the inorganic oxide fine particles, adsorbing the inorganic oxide fine particles on the surface of the mother particles 2a (palladium layer 12), and then washing the mother particles 2a. That is, in the step (1), a polymer electrolyte film is formed on the surface of the mother particle 2a, and in the step (2), the inorganic oxide fine particles are chemically adsorbed to the surface of the mother particle 2a via the polymer electrolyte film ' By using this polymer electrolyte film, the surface of the mother particle 2a can be uniformly coated with inorganic oxide fine particles without defects. The circuit electrode is connected using an anisotropic conductive adhesive, and the anisotropic conductive adhesive is used. After the conductive particles obtained in the steps (1) and (2), the insulation can be ensured even when the circuit electrodes are spaced apart from each other, and the electrical resistance is connected between the electrodes. Low and good. -18- 201120920 The method with steps (1) and (2) above is called Layer-by-Layer assembly. The interaction layer law was published by G. Decher et al. in 1992. A method of forming an organic thin film (refer to Thin Solid Films, 210/211, p8 3 1 (1 992)). In this interactive lamination method, by having a positively charged polymer electrolyte (polycation) and having a negative In the aqueous solution of the charged polymer electrolyte (polyanion), the substrate is alternately impregnated, and the group of polycations and polyanions adsorbed by electrostatic attraction is laminated on the substrate to obtain a composite film (interactive laminate film). In the interactive layering method, by the electrostatic attraction, the charge of the material formed on the substrate and the material having the opposite charge in the solution are pulled together to grow the film, so if the adsorption proceeds, the neutralization of the charge does not occur. An adsorption occurs beyond it. Therefore, the film thickness beyond which it does not increase before reaching a certain saturation point.

Lvov et al. report the application of interactive layering to microparticles, using a fine dispersion of vermiculite or titanium dioxide or cerium oxide, and laminating a polymer electrolyte having an opposite charge to the surface charge of the microparticles by cross-layering (see Langmuir, Vol. 13, (1997) p6195-6203). If this method is used, by alternately laminating microparticles having a negative surface charge of vermiculite, polydiallyldimethylammonium chloride (PDDA) or polyethyleneimine having a polycation having an opposite charge ( PEI) or the like can form a fine particle laminated film in which the vermiculite particles and the polymer electrolyte are alternately laminated. In the method for producing the conductive particles 8b of the second embodiment, the mother -19-201120920 particles 2a are immersed in a dispersion of a polymer electrolyte solution or inorganic oxide fine particles, and then immersed in a dispersion of fine particles having opposite charges or Before the polymer electrolyte solution, it is preferred to wash away the excess polymer electrolyte solution or the dispersion of the inorganic oxide fine particles from the mother particles 2a by washing only with a solvent. The polymer electrolyte and the inorganic oxide fine particles adsorbed on the mother particles 2a are electrostatically adsorbed on the surface of the mother particles 2a, so that they are not peeled off from the surface of the mother particles 2a in this rinsing step. However, if the excess polymer electrolyte or the inorganic oxide fine particles which are not adsorbed by the mother particles 2a are brought into a solution having opposite charges, the cations and anions are mixed in the solution, and the polymer electrolyte and the inorganic oxide are generated. Coagulation or precipitation of microparticles. This deficiencies can be prevented by flushing. The solvent used for the rinsing is water, alcohol, acetone, etc., and generally, an ion having a specific resistance 1 of 18 Ω·cm or more is used from the viewpoint of easily removing the excess polymer electrolyte solution or the dispersion of the inorganic oxide fine particles. Exchange water (so-called ultrapure water). The polymer electrolyte solution is one in which a polymer electrolyte is dissolved in water or a mixed solvent of water and a water-soluble organic solvent. Examples of the water-soluble organic solvent that can be used include methanol, ethanol, propanol, acetone, dimethylformamide, and acetonitrile. As the polymer electrolyte, a polymer which ionizes in an aqueous solution and holds a functional group having a charge in a main chain or a side chain can be used. At this time, polycation ions should be used. As the polycation, generally, those having a functional group capable of charging with positive-20-201120920 such as polyethyleneimine (PEI), polyallylamine hydrochloride (PAH), and poly are used. Allyldimethylammonium chloride (PDDA), polyvinylpyridine (PVP), polylysine, polypropylene decylamine, and copolymers containing at least one or more of them. Among the polymer electrolytes, polyethyleneimine has a high charge density and a strong binding force. Among these polymer electrolytes, in order to avoid electron migration or corrosion, it is more preferable that the alkali metal (Li, Na, K, Rb, Cs) ions and the alkaline earth metal (Ca, Sr, Ba, Ra) ions are not contained. Halide ions (fluoride, chloride, bromide, iodide). These polymer electrolytes are all water-soluble or soluble in a mixture of water and an organic solvent. The molecular weight of the polymer electrolyte depends on the type of polymer electrolyte used, and cannot be determined at all, and is generally preferably 500~ About 200,000. Further, the concentration of the polymer electrolyte in the solution is generally preferably about 1 to 10% by weight. Further, the pH of the polymer electrolyte solution is not particularly limited. The coverage of the inorganic oxide fine particles can be controlled by adjusting the type, molecular weight or concentration of the polymer electrolyte membrane of the coated mother particles 2a. Specifically, when a polymer electrolyte film having a high charge density such as polyethyleneimine is used, the coverage of the inorganic oxide fine particles tends to be high, and the charge density such as polydiallyldimethylammonium chloride is low. In the case of a molecular electrolyte film, the coverage of the inorganic oxide fine particles tends to be low. Further, when the molecular weight of the polymer electrolyte is large, the coverage of the inorganic oxide fine particles tends to be high, and the inorganic oxide fine particles can be strongly adsorbed to the palladium layer 12 at the same time. From the viewpoint of bonding strength, the molecular weight of the polymer electrolysis -21 - 201120920 is preferably 10,000 or more. On the other hand, when the high molecular weight is small, the coverage of the inorganic oxide fine particles is oriented. In addition, when the polymer electrolyte is used at a high concentration, the coverage of the inorganic particles tends to be high, and when a high concentration is used at a low concentration, the coverage of the inorganic oxide fine particles tends to be low. When the coverage of the fine particles is high, the insulating property is high and the conductivity is high. When the coverage of the inorganic oxide fine particles is low, the conductivity tends to be poor. The inorganic oxide fine particle system can be coated in only one layer. If the control of the complex lamination amount becomes difficult. Further, the coverage of the surface of the inorganic oxide fine particles palladium layer 12 is preferably in the range of 20 to 100%, and more preferably 60%. The concentration of the alkali metal ion-containing metal ion in the dispersion solution of the inorganic oxide fine particles is preferably 10,000 ppm or less. Thereby, the insulation reliability between the electrodes is easy. Further, the so-called sol-gel method inorganic oxide fine particles in which the inorganic oxide is slightly hydrolyzed by the metal alkoxide are suitable. Particularly, as the inorganic oxide fine particles, ettringite (SiO 2 ) is preferable. The water-dispersed colloidal vermiculite has excellent adhesion to the mother particles 2a on the surface, and the particle diameter is easily uniform, and the inorganic oxide fine particles are suitable. It is generally known that a hydroxyl group forms a strong bond with a hydroxyl group, a carboxyl group, or an alkoxy group. As a result of the electrolysis of a hydroxyl group and a bond of this functional group, the deuterated oxide micro-electrode has a high tendency to be inferior in inorganic oxide and the insulating layer is laminated, so that it is preferable that the oxidized layer and the alkaline earth increase the adjacent particles. The dispersed colloidal hydroxyl group is produced, so it is preferable to use the covalent bond or hydrogen bond of the dehydration condensation in the specific form of the oxonyl group of the middle courtyard *22-201120920. Therefore, the palladium layer 12 (the surface of the mother 2 a) which forms a functional group such as a group, a carboxyl group, an alkoxy group or an alkoxycarbonyl group can strongly adsorb the inorganic oxide fine particles having a hydroxyl group on the surface. Further, the hydroxyl group on the surface of the inorganic oxide fine particles can be modified into an amine group, a carboxyl group or an epoxy group by a coupling agent or the like, but it is difficult when the particle diameter of the inorganic oxygen is 500 nm or less. Therefore, it is preferred that the mother particles 2a coated with the inorganic oxide fine particles are not subjected to functional modification. The bonding of the insulating particles 1 to the mother particles 2a can be further performed by heating and drying the conductive particles 8b as described above. Examples of the increase in the bonding strength include a chemical bond between a functional group such as a carboxyl group on the surface of the palladium layer 12 and a hydroxyl group on the surface of the insulating layer 1, or an amine group on the surface of the carboxyl group-containing particle 1 on the surface of the palladium layer 12. Dehydration condensation is promoted. Further, when the vacancy is carried out, it is preferable from the viewpoint of rust prevention of the metal. Further, in the case where the outermost surface of the mother particles is a gold layer, the temperature of the insulating particles and the mother particles can be further strengthened by heat drying in the same manner as in the case of the palladium layer 12, and the heating and drying temperature is preferably 60 to 2 0. 0 ° C, heating time is 10 to 180 minutes. When the temperature is less than 60 ° C or the heating time is less than 1 minute, the insulating particles 1 are easily peeled off from the mother particles 2a, and when the temperature exceeds 200 ° C, when the heat time exceeds 180 minutes, the mother particles 2a are easily deformed. (observation of particles) In the observation of the coating of the resin fine particles (palladium layer) or the deposition of the upper particles of the film, a scanning electron microscope (a particle with a hydroxy particle solid sulfonate group) and an absolute particle are used. , in the sample, 〇佳 for the time, or add the absolute SEM, -23- 201120920

Scanning Electron Microscope). The position or number of the coated surface or the insulating fine particles can be confirmed by the image. (Anisotropic Conductive Adhesive) As shown in Fig. 3 (a), the conductive particles 8b produced as described above are dispersed in the adhesive 3 to obtain an anisotropic conductive adhesive 40. A method of manufacturing the connection structure 42 using the anisotropic conductive adhesive 40 is shown in Figs. 3 (b) and (c). Further, in FIGS. 3(a) to 3(b) and 3(c), the conductive particles 8b are referred to as conductive particles 8. Moreover, for the simplification of the drawing, the palladium layer 12 provided in the conductive particles 8 is omitted. As shown in Fig. 3(b), the first substrate 4 and the second substrate 6 are prepared, and the anisotropic conductive adhesive 4? is disposed therebetween. At this time, the first electrode 5 included in the first substrate 4 and the second electrode 7 included in the second substrate 6 are opposed to each other. Then, the first substrate 4 and the second substrate 6 are laminated while being heated and heated in the direction in which the first electrode 5 and the second electrode 7 face each other, whereby the connection structure 42 shown in Fig. 3(c) is obtained. When the connection structure 42 is produced in this manner, the vertical insulating particles 1 penetrate the mother particles 2, and the first electrode 5 and the second electrode 7 are electrically connected to each other via the surface (palladium layer) of the mother particles 2. Maintain insulation between the mother particles. The anisotropic conductive adhesive for COG is required to have a narrow pitch insulation reliability at a level of 1 μm in recent years. However, when the anisotropic conductive adhesive 40 of the present embodiment is used, a narrow pitch of 1 Ο μη level can be improved. Insulation reliability. As the adhesive 3 used for the anisotropic conductive adhesive 40, a mixture of a thermal anti-24-201120920 resin and a hardener is used, and specifically, a mixture of an epoxy resin and a latent hardener is preferable. As the epoxy resin, a bisphenol type epoxy resin derived from epichlorohydrin and bisphenol A or F, AD or the like, an epichlorohydrin and a phenol novolak or a cresol novolac may be used singly or in combination of two or more kinds. Epoxy novolac resin derived from varnish or naphthalene epoxy resin having a naphthalene ring-containing skeleton, glycidylamine, glycidyl ether, biphenyl, alicyclic or the like, having two or more glycidol in one molecule Based on various epoxy compounds and the like. It is preferable to use such a high-purity product which has reduced impurity ions (Na+, Cl+, etc.) or hydrolyzable chlorine to 300 ppm or less. This makes it easy to prevent electron migration. Examples of the latent curing agent include an imidazole-based, an anthraquinone-based, a boron trifluoride-amine complex, a phosphonium salt, an amine imide, a polyamine salt, and dicyandiamide. Further, in the adhesive, a mixture of a radical reactive resin and an organic peroxide or an energy ray curable resin such as ultraviolet rays is used. In the adhesive 3, a butadiene rubber, an acrylic rubber, a styrene-butadiene rubber, a polyoxymethylene rubber or the like may be mixed in order to reduce the stress after the adhesion or to improve the adhesion. Further, as the adhesive 3, a paste or a film is used. In order to form the adhesive into a film form, it is effective to blend a thermoplastic resin such as a phenoxy resin, a polyester resin or a polyamide resin. These film-forming polymers are also effective in stress relaxation during curing of the reactive resin. In particular, when the film-forming polymer has a functional group such as a hydroxyl group, it is more preferable to improve the adhesion. 0 - 25 - 201120920 The film is formed by forming an epoxy resin, an acrylic rubber, a latent curing agent, and a film. The subsequent composition of the polymer is dissolved or dispersed in an organic solvent, liquidized, applied to a release substrate, and the solvent is removed at a temperature lower than the activation temperature of the curing agent to perform the "organic solvent used at this time". Among the points for improving the solubility of the material, an aromatic hydrocarbon-based and oxygen-containing mixed solvent is preferred. The thickness of the anisotropic conductive adhesive 40 is relatively determined in consideration of the particle diameter of the conductive particles 8 and the characteristics of the anisotropic conductive adhesive 40, and is preferably 1 to ΙΟΟμηη. When it is less than πμπι, sufficient adhesion is not obtained, and if it exceeds 100 μm, a large amount of conductive particles are required to obtain conductivity, which is not practical. For this reason, the thickness is more preferably 3 to 50 μm. Examples of the first substrate 4 and the second substrate 6 include a glass substrate, a tape substrate such as polyimide, a bare wafer for driving 1C, and a rigid package substrate. The preferred embodiments of the method for producing the conductive particles and the conductive particles of the present invention are described in detail above, but the present invention is not limited to the above embodiments. For example, the conductive particles 8a of the first embodiment may include resin fine particles 1 1 , a palladium layer 12 covering the surface of the resin fine particles 、, and another conductive layer (for example, a gold layer) covering the surface of the palladium layer 12 . Further, the conductive particles 8b of the second embodiment may include the resin fine particles 11, the palladium layer 12 on the surface of the coated resin fine particles, the other conductive layer (for example, a gold layer) covering the surface of the palladium layer 12, and the surface of the conductive layer. A plurality of insulating particles 1 . EXAMPLES -26- 201120920 Hereinafter, the present invention will be described by way of examples. (Mother particles 1) After 3 g of crosslinked polystyrene particles (resin fine particles) having an average particle diameter of 3.5 μηη were subjected to alkali degreasing, they were neutralized with an acid. The resin fine particles were added to 100 ml of the cationic polymer liquid adjusted to ρΗ6·0, and the mixture was stirred at 60° C. for 1 hour, and then filtered through a membrane filter (manufactured by 1×丨丨4〇1) having a diameter of 3 μm. , washed. To the palladium catalyst solution of Atotechneoguand 834 (trade name, manufactured by ATOTECH Co., Ltd.) containing 8 wt% of palladium catalyst at 1 〇0 m L, water-washed resin fine particles were added and stirred at 35 ° C. After 30 minutes, it was filtered with a membrane filter (manufactured by Millipore) having a diameter of 3 μm, and washed with water. Resin fine particles are repeatedly added to the palladium catalyst liquid to impart a sufficient amount of palladium catalyst to the surface of the resin fine particles. Further, the so-called "catalyst" is a catalyst for forming a palladium layer on the surface of the resin fine particles, and is not the palladium layer itself in the present invention. Next, the washed resin fine particles were added to a 3 g/L sodium hypophosphite solution adjusted to pH 6.0 to obtain surface-activated resin fine particles (resin core particles). Then, the surface-activated resin fine particles were immersed in distilled water to perform ultrasonic dispersion. The above solution was filtered through a membrane filter (manufactured by Millipore) having a diameter of 3 μm, and impregnated with a surface of the electroless palladium plating solution (manufactured by Ishihara Pharmaceutical Co., Ltd., trade name) at 50 ° C. The activated resin fine particles were subjected to electroless Pd plating of 20 nm on the surface of the resin fine particles. It is known that the APP of the electroless palladium plating solution contains hypophosphorous acid or a salt thereof as a reducing agent, and a phosphorus-containing substance such as -27-201120920 phosphoric acid or a salt thereof as a main component. Then, it was washed with a membrane filter (manufactured by Millipore) having a diameter of 3 μm for 3 times. After drying under vacuum at 40 ° C for 7 hours, the aggregation was decomposed by pulverization to prepare a mother particle 1 having a palladium layer of 20 nm thick on the resin fine particles. (Mother particles 2) In addition to the electroless Pd plating by the above-mentioned electroless palladium plating solution APP, in the electroless palladium plating solution, Melplate Pal6700 (product name manufactured by MELTEX Co., Ltd.) at 50 ° C In the same manner as in the mother particle 1, a mother particle having a palladium layer having a thickness of 40 nm on the resin core particle was prepared by impregnating the surface of the activated resin fine particles with p Η 8 . 2. Melplate Pal6700, which is known as an electroless palladium plating solution, is a main component of a phosphorous substance such as hypophosphorous acid or a salt thereof containing a reducing agent, phosphoric acid or a salt thereof. (Mother particles 3) The resin core particles are produced in the same manner as the mother particles 2 except that sodium hypophosphite is added to the above-mentioned electroless palladium plating solution Melplate Pal6700 (product name manufactured by MELTEX Co., Ltd.). Mother particle 3 of a 80 nm thick palladium layer. (Mother Particles 4) The palladium catalyst was supplied in the same manner as the mother particles 1, and the resin fine particles activated by the polymerization of 28:201120920 were dispersed in a bath of 70 ° C in which 50 g/L of sodium citrate was dissolved. Then, using a metering pump, the plating liquid a and the plating liquid b were added simultaneously and in parallel at 1, and the resin fine particles were subjected to electroless palladium plating. As the plating solution a, 20 g/L of palladium, 50 g/L of sodium citrate, and 20 g/L of ethylenediamine were mixed, and a liquid adjusted to pH = 6.0 was used. Further, in the plating solution a, palladium is dissolved in the state of ion or a complex, and the amount of palladium "2 〇 g/L" is converted into 値 by weight represented by metal palladium. As the mineral liquid b, 1.2 mol/L of sodium hypophosphite was mixed, and a solution adjusted to ΡΗ = 6.00 with sodium hydroxide was used. The thickness of the electroless palladium layer formed on the surface of the resin fine particles was adjusted by analysis of the atomic absorption spectrophotometer of the sampled particles. When the thickness of the electroless palladium layer became 1 3 Onm, the addition of the electroless plating solution was stopped. After the addition is completed, wait for the bubble to stop, and perform filtration and washing. When the reaction was stopped, the pH was 6.0. The mother particles 4 having an electroless palladium layer having a thickness of 130 nm on the resin core particles were produced by the above method. The obtained mother particles 4 are gray. (Mother Particles 5) The palladium catalyst was supplied in the same manner as the mother particles 1, and the activated resin fine particles were dispersed in a bath of 70 ° C in which 5 μg/L of sodium citrate was dissolved. Then, the resin fine particles were subjected to electroless palladium plating by adding the plating solution c and the plating solution d simultaneously and in parallel using a metering pump. As the plating solution c, 20 g/L of palladium, 80 g/L of sodium citrate, and 20 g/L of ethylenediamine were mixed, and a liquid adjusted to pH = 5.0 was used. As the plating solution d, 2.4 mol/L of sodium hypophosphite was mixed, and a solution adjusted to pH = 5.0 with sodium hydroxide was used. The thickness of the electroless palladium layer formed on the surface of the resin fine particles -29-201120920 was adjusted by analysis of the atomic absorption spectrophotometer of the sampled particles. The electroless plating solution was stopped at a time point when the thickness of the electroless palladium layer became 8 Onm. After the addition is completed, wait for the stop of the bubble generation, and perform filtration and washing. When the reaction was stopped, the pH was 4.8. The mother particles 5 having an electroless palladium layer having a thickness of 80 nm on the resin core particles were produced by the above method. The obtained mother particles 5 are gray. (Mother Particles 6) The fine catalyst is supplied in the same manner as the mother particles 1, and the activated resin fine particles are dispersed in a solution of sodium tartrate 20 g/L dissolved in 7 (TC). Simultaneously and in parallel, the plating solution e and the plating solution f were added at 15 ml/miη, and the resin fine particles were subjected to electroless nickel plating. As the plating solution e', a liquid mixed with 224 g/L of nickel and 20 g/L of sodium tartrate was used. As the plating solution f, a solution containing 226 g/L of sodium hypophosphite and 85 g/L of sodium hydroxide was used. The thickness of the nickel was adjusted by analysis of the atomic absorption spectrophotometer of the sampled particles. When the thickness is 4 Onm, the addition of the electroless plating solution is stopped. After the addition is completed, the bubble is stopped, and the filtration and washing are performed. When the reaction is stopped, the pH is 6.2, and the particles are gray. Next, at 50°. Under the condition of C, the resin fine particles after electroless nickel plating were immersed in APP (manufactured by Ishihara Pharmaceutical Co., Ltd., trade name) of an electroless palladium plating solution to perform electroless palladium plating. Membrane filter (manufactured by Millipore) filters the above liquid, After three times of water washing, vacuum drying was carried out for 7 hours at 40 ° C, and the agglomeration was released by pulverization, whereby mother particles 6 having resin fine particles and 40 nm thick electroless surface of the surface of the coated resin fine particles were obtained. Nickel layer, -30- 201120920 The 40 nm electroless ruthenium layer on the surface of the electroless nickel layer is coated. (Mother particles 7) Instead of electroless palladium plating, HGS·5 无 (Hitachi Chemical Co., Ltd.) Industrial Co., Ltd. product name) is immersed in a bath liquid under the conditions of 80 ° C, and the nickel-plated resin fine particles formed by the same method as in the case of the mother particles 6 are immersed, and subjected to displacement gold plating, followed by filtration and washing. Then, HGS-2000 (product name manufactured by Hitachi Chemical Co., Ltd.), which is an electroless gold plating solution, was immersed in a bath at 60 ° C, and the particles were immersed, and filtered and washed with water. The mother particles 7 having resin fine particles, a nickel layer of 40 nm thick covering the resin fine particles, and a 4 nm thick Au layer covering the surface of the nickel layer were produced by the same method as the mother particles 6 (insulation coating treatment). Secondly, make The conductive particles 1 to 7 are produced by using the mother particles 1 to 7 obtained above. The insulating coating process for adsorbing the fine particles of the insulating particles on the surface of the mother particles is carried out by the method disclosed in JP-A-2008-20 20990. In addition, in the embodiment, the mother particles having insulating particles on the surface are described as "conductive particles", and are different from the mother particles having no insulating particles on the surface, but the mother particles are the same. 1 to 5 and the conductive particles 1 to 5 to be described later correspond to the conductive particles of the present invention. (Electrically conductive particles 1) -31 - 201120920 8 mmol of thioglycolic acid was dissolved in 200 ml of methanol to prepare a reaction liquid. Next, the mother particle 1 was added to 1 g of the above reaction liquid, and stirred at room temperature (25 ° C) for three hours with a three-one motor and a stirring blade of 45 mm in diameter. After washing with methanol, the mother particle 1 was filtered with a membrane filter (manufactured by Millipore) having a diameter of 3 μm to obtain a mother particle 1 having a carboxyl group on the surface. Then, a 30% polyethyleneimine aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) having a molecular weight of 70,000 was diluted with ultrapure water to obtain a 0.3% by weight aqueous solution of polyethyleneimine. 1 g of the above-mentioned mother particle 1 having a carboxyl group was added to a 3% by weight aqueous solution of polyethyleneimine, and stirred at room temperature for 15 minutes. Then, the mother particle 1 was filtered through a membrane filter (manufactured by Millipore) having a diameter of 3 μm, placed in 200 g of ultrapure water, and stirred at room temperature for 5 minutes. Further, the mother particle 1 was filtered with a membrane filter (manufactured by Millipore) having a diameter of 3 μm, and washed twice with 200 g of ultrapure water on the membrane filter to remove polyethyleneimine which was not adsorbed on the mother particle 1. Next, a dispersion of colloidal vermiculite (in a mass concentration of 20%, manufactured by Fuso Chemical Industry Co., Ltd., product name: Quartron PL-3, average particle diameter: 35 nm), which is diluted with ultrapure water, gives 0.1 weight. % sand stone dispersion solution. The mother particle 1 treated with the above polyethyleneimine was placed in a 0.1 wt% vermiculite dispersion solution, and stirred at room temperature for 15 minutes. Next, the mother particle 1 was filtered through a membrane filter (manufactured by Millipore) having a diameter of 3 μm, placed in 200 g of ultrapure water, and stirred at room temperature for 5 minutes. The mother particle 1 was filtered with a membrane filter (manufactured by Millipore) having a diameter of 3 μm, and washed twice with 200 g of ultrapure water on the above-mentioned -32-201120920 film furnace to remove the ruthenium which was not adsorbed to the mother particle 1. stone. Then, drying was carried out under the conditions of 80 ° C for 30 minutes, and heat-dried at 120 ° C for 1 hour to prepare conductive particles 1 on which the vermiculite (subparticles) were adsorbed on the surface of the mother particle 1. (Electrically conductive particle 2) In place of the mother particle 2, PL-7 (mass concentration 20%, manufactured by Fuso Chemical Industry Co., Ltd., product name: Quartron PL-7, average particle size 75 ηιη) was used instead of PL- 3 The conductive particles 2 were produced in the same manner as the conductive particles 1 except that the colloidal vermiculite dispersion was used. (Electrically conductive particle 3) In place of the mother particle 3, instead of the parent particle 1, PL-1 3 (mass concentration 20%, manufactured by Fuso Chemical Industry Co., Ltd., product name: Quartron PL-13, average particle diameter 130 ηπι) was used instead of PL. -3 The conductive particles 3 were produced in the same manner as the conductive particles 1 except that the colloidal vermiculite dispersion was used. (Electrically conductive particles 4) In place of the mother particles 4 instead of the mother particles 1, PL-20 (mass concentration 20%, manufactured by Fuso Chemical Industry Co., Ltd., product name: Quartron PL-20, average particle diameter 2 0 0 nm) was used instead. PL - 3 The conductive particles 4 were produced in the same manner as the conductive particles 1 except that the colloidal vermiculite dispersion was used. (Electrically conductive particles 5) -33- 201120920 In addition to using mother particles 5 instead of mother particles 1 'Use PL-50 (mass concentration 20%, manufactured by Fuso Chemical Industry Co., Ltd., product name: Quartron PL-50, average particle size 500 nm) The conductive particles 5 were produced in the same manner as the conductive particles 1 except that PL-3 was used as the colloidal vermiculite dispersion. (Electrically conductive particles 6) The conductive particles 6 were produced by the same method as the conductive particles 3 except that the mother particles 6 were used instead of the mother particles 3. (Electrically conductive particles 7) The conductive particles 7 were produced by the same method as the conductive particles 3 except that the mother particles 7 were used instead of the mother particles 3. (Example 1) <Preparation of adhesive solution> 1 g of phenoxy resin (manufactured by Union Carbide Co., Ltd., trade name: PKHC) and 7.5 g of acryl rubber (40 parts of butyl acrylate, 30 parts of acrylic acid B) Ester, 30 parts of acrylonitrile, 3 parts of copolymer of glycidyl methacrylate, molecular weight: 850,000) dissolved in 30g of ethyl acetate to obtain 30% by weight solution. Secondly, 30g contains microcapsule type potential A liquid epoxy resin (epoxy equivalent 185, manufactured by Asahi Kasei Epoxy Co., Ltd., trade name: Novacure HX-394 1 ) is added to the solution and stirred to prepare an adhesive solution. • 34- 201120920 4 g of the conductive particles 1 prepared above were dispersed in 10 g of ethyl acetate. The above-mentioned particle dispersion liquid was dispersed in an adhesive solution in such a manner that the conductive particles 1 became 37% by weight with respect to the adhesive, and the solution was applied to the separator by a roll coater (polyoxygenated polycondensation) A film of ethylene terephthalate (thickness 40 μm) was dried at 90 ° C for 10 minutes to prepare an anisotropic conductive adhesive film having a thickness of 25 μm. Next, using the produced anisotropic conductive adhesive film, a wafer (1.7 x 17 mm, thickness: 0.5 mm) with gold bumps (area: 30 χ 90 μm, spacer ΙΟμηι, height: 15 μηι, bump number 362) was produced by the following method. A sample of a structure connected to a glass substrate (thickness: 0.7 mm) with an ITO circuit. First, an anisotropic conductive adhesive film (2x19 mm) was adhered to a glass substrate with an ITO circuit at 0.98 MPa (10 kgf/cm2) at 80 ° C, and then the separator was peeled off to carry out bumps of the wafer and an ITO circuit. The positioning of the glass substrate. Subsequently, heating and pressurization were carried out from above the wafer at 190 ° C for 5 seconds to carry out main connection to obtain a sample. (Example 2) The number of conductive particles dispersed per unit area of the anisotropic conductive film produced in Example 2 was changed in the same manner as in Example 1 except that the conductive particles 2 were used instead of the conductive particles 1. A sample was produced in the same manner as in Example 1 except that the ratio of the conductive particles 2 in the subsequent agent was changed. (Example 3) -35-201120920 A sample was produced in the same manner as in Example 2 except that the conductive particles 3 were used instead of the conductive particles 2. (Example 4) A sample was produced in the same manner as in Example 2 except that the conductive particles 4 were used instead of the conductive particles 2. (Example 5) A sample was produced in the same manner as in Example 2 except that the conductive particles 5 were used instead of the conductive particles 2. (Comparative Example 1) A sample was produced in the same manner as in Example 2 except that the conductive particles 6 were used instead of the conductive particles 2. (Comparative Example 2) A sample was produced in the same manner as in Example 2 except that the conductive particles 7 were used instead of the conductive particles 2. (Measurement of film thickness of metal) In the measurement of each film thickness of Pd, Ni, and Au, each particle was dissolved in 50% by volume of aqua regia, and then separated by filtration using a membrane filter (manufactured by MilliP〇re) having a diameter of 3 μm. In the resin fine particles and the solid matter, the amount of -36 to 201120920 of each metal was measured by an atomic absorption spectrophotometer S 4700 (product name manufactured by Hitachi, Ltd.), and then converted into a thickness. (Ingredient analysis in the coating) In the component analysis in the mineral film, 'the particles were dissolved in 5 vol% of aqua regia, and then separated by a membrane filter (manufactured by Millipore) having a diameter of 3 μm to remove the resin, and ICP was used. Coupling plasma) luminescence analyzer P 4 0 1 0 (product name manufactured by Hitachi, Ltd.). (Covering ratio of the sub-particles) The coverage of the sub-particles (insulating particles) was calculated by analyzing an image of an electron microscope of each of the conductive particles. In an electron microscope, S4700 (product name manufactured by Hitachi, Ltd.) was used, and it was observed at 5,000 times or more. (Picking test of particles) Any one of lg conductive particles 1 to 7 was collected and dispersed in 50 g of pure water. Next, the sample was placed in a 60 ml pressure vessel and allowed to stand at 100 ° C for 1 hour. Then, the dispersion solvent of the conductive particles was filtered with a 0.2 μm filter, and each metal ion in the filtrate was measured by an atomic absorption spectrophotometer. The amount of boiled (ion measurement 値) was obtained by the following formula. [Number 1] Determination of cesium (ppm) for each ion = metal concentration in boiling solution (PPm) x weight of pure water (g) weight of conductive particles (g) -37- 201120920 (ingredient analysis) before application of insulation coating Each of the mother particles was spread on a conductive tape (Cat No7311 manufactured by Nisshin EM Co., Ltd.) fixed on the sample stage, and the sample stage was inverted to vibrate to drop excess conductive particles. Next, an EDX analysis device attached to a scanning electron microscope S47〇0 (product name manufactured by Hitachi, Ltd.): EMAX EX-3 00 (product name manufactured by Horiba, Ltd.) was used to analyze the mother particles amplified by 30,000 times. The conductive layer on the surface is characterized. Further, the phosphorus concentration in the palladium was measured for 10 mother particles, and the average enthalpy was calculated. Also, a sheet of a conductive layer portion of the conductive particles is cut out by a concentrated ion beam. The sheet was observed at a magnification of 100,000 times or more using a transmission electron microscope HF-22 00 (product name manufactured by Hitachi, Ltd.), and component analysis of each region of the conductive layer was carried out by EDX manufactured by NOR AN Co., Ltd. attached to the above apparatus. From the obtained enthalpy, the concentrations of nickel, palladium and phosphorus in each region were calculated. (Insulation resistance test and on-resistance test) The insulation resistance test (insulation reliability test) and the on-resistance test of the samples prepared in Examples 1 to 5 and Comparative Examples 1 and 2 were carried out. It is important that the isotropic conductive film is high in insulation resistance between the wafer electrodes and the on-resistance (connection resistance) between the wafer electrode and the glass electrode is low. The insulation resistance between the wafer electrodes is determined by measuring 20 samples and measuring the minimum enthalpy. Regarding the insulation resistance, the minimum value of the results before and after the bias test (endurance test of humidity 60%, 90 ° C, 20 V DC voltage) is shown. Further, the values of 100 hours, 300 hours, 50,000 hours, and 1,000 hours shown in Table 1 mean the time of the bias test. -38- 201120920 Resistance, measurement and moisture absorption test.) , Further, the average 値 of 14 samples between the wafer electrode and the glass electrode. The on-resistance was measured in the initial test (1000 ° C at a temperature of 85 ° C and a humidity of 85% (result), and the measurement results of 2 show the above Examples 1 to 5 and Comparative Examples 1 - 39 to 201120920. Comparative Example 2 I 〇〇瞧C0 1〇5 CO ο <2 0 1 1_>20 I 〇〇X 〇to ο — X ο V \η Ο X ο «Η V *〇Ο X ο V ο ι*· Η X ο VX Comparative Example 1 1 〇1 5 CV3 rA — ΙΛ m Ο ο CN3 <2 0 I_>2〇_1 〇〇X 〇«-Η ΙΟ Ο X ο VU) ο X ο V \η Ο « Η X ο — V ΙΑ Ο • «Η X ο — VX Example 5 1 1 1 S 1 10.0 1 Ο g Ο ο <2 0 1_<20__I 1 1. οχ 1 〇10 1 ο Ο — X ο ο ο — X ο ο Ο Η Η X ο - ο Ο X ο 〇 1 1 Another CO ο eg \Λ in ο ο CS9 <20 I__<20__I 1 i.oxi 〇10I Ο Ο X ο ο Ο X ο ο Ο — X ο *·η ο Ο r-< X Ο 〇 Example 3 1 1 S ο CO ο ο Ν <20 1__<20__I ο Ο X ο Ο Ο — X Ο «Η ο Ο X ο ο Ο X Ο Ο Ο — X ο 〇 Example 2 1 1 5 CO CO S ο ο 00 <2 0 1__<20__I 1 ι. οχ ι ο 101 1 ι. ο χ ι ο 101 ο Ο X ο ο Ο X Ο ο Ο X ο 〇 Example 1 1 1 o 兵 s ο ο ΙΛ <2 0 1_<20__I 1 ι. οχ ι ο 10 1 ο Ο — X ο ο Ο X ο 1 i.oxi ο 101 1 1.0X1 0 101 〇1 Town (nrn) 1 Gold (nm) V 1 £ 〇M ifrnil Paste m 1 ϊ w μ? 矽石被层(%) 1 Town (ppm 1 gold (ppm) palladium (ppm) 1 initial 1 after test 1 1 0 0 1 1 10 0 hour 1 3 0 0 hour 1 5 00 hour ι 7 ο ο Comprehensive determination of on-resistance (Ω) insulation reliability Test (Ω) Conductive Layer 1 Disc Insulation Coating in Palladium Layer Cooking Test Results Anisotropic Conductive Film -40-201120920 As shown in Table 1, in the conductive particles of Examples 1 to 5 in which nickel was not used at all, such as boiling As shown in the test results, almost no metal was eluted. On the other hand, in Comparative Examples 1 and 2 in which nickel was used for the substrate, nickel was eluted in comparison with Examples 1 to 5. Therefore, it is safe to use nickel in a narrow-pitch C Ο G substrate. Further, the palladium system of the noble metal is hardly eluted. The results of the apparent insulation reliability test were almost dependent on the amount of nickel eluted, and the examples in which nickel was eluted less showed good results, and the comparative examples in which nickel was eluted were low in insulation reliability. Palladium is relatively inexpensive and practical in precious metals, but it is also expensive compared to nickel which is used as a conductive particle for an electrically conductive film, so that the amount of palladium used is to be minimized. On the other hand, when it is in contact with the electrode, the palladium layer on the surface of the conductive particles must penetrate into the electrode without being damaged. Further, sufficient strength is required for the palladium layer, which is such a degree that cracking or peeling does not occur due to an external force in the conductive particle forming step. Although palladium is ductile than nickel, it is poor in hardness. In the present invention, a phosphate-based electroless palladium plating solution such as hypophosphorous acid or phosphorous acid is used as a reducing agent to eprecipitate phosphorus in a palladium layer, thereby providing conductive particles having high hardness and excellent corrosion resistance. The components of each of the mineral films of Examples 1 to 5 were qualitatively analyzed by an ICP (inductively coupled plasma) luminescence analyzer P4〇l〇 (product name manufactured by Hitachi, Ltd.), and as a result, palladium and phosphorus were mainly composed, and other elements were obtained. It is not detected within the detection error range. (Example 6) -41 - 201120920 In addition to the use of the mother particle 2 in place of the conductive particle 1, the mother was adjusted to become half of the number of conductive particles dispersed per unit area of the anisotropic conductive film produced in Example 1. A sample was produced in the same manner as in Example 1 except for the amount of the particles 2. (Comparative Example 3) The mother particles 7 were used instead of the conductive particles 1 to adjust the amount of the mother particles 7 so as to be half the number of the conductive particles dispersed per unit area of the anisotropic conductive film produced in Example 1. A sample was produced in the same manner as in Example 1. The pellet boiling test and the on-resistance test of the particles of Example 6 and Comparative Example 3 were carried out in the same manner as in Examples 1 to 5. The test results of Example 6 and Comparative Example 3 are shown in Table 2. [Table 2]

Example 6 Comparative Example 3 Conductive layer Nickel (nm) - 40 Gold (nm) - 40 Palladium (nm) 40 - Phosphorus concentration in the palladium layer (% by weight) 3.3 One boiling test result Nickel (ppm) 0 68 Gold ( Ppm) 0 5 iGbpm) 2 0 On-conducting film on-resistance (Ω) Initial <10 <10 After test <10 >10 Comprehensive judgment 〇X -42- 201120920 (Evaluation of particles without insulation coating treatment As shown in Table 2, the connection resistance of Example 6 was good, but the connection resistance of Comparative Example 3 became higher as time passed. This is because the gold layer of Comparative Example 3 is soft, so that it is difficult to penetrate the electrode and it is impossible to follow the shift of the electrode position which occurs with the passage of time. The sample was observed by an optical microscope from the glass surface side, and as a result, it was observed that the particles of Comparative Example 3 were agglomerated. The mother particles 7 of Comparative Example 3 were analyzed by EDX, and the phosphorus concentration in the nickel was as low as 2% by weight. Therefore, in Comparative Example 3, aggregation of the mother particles 7 due to magnetic properties was considered. As shown in Table 2, in Example 6 in which only the palladium layer was used as the metal layer, only a small amount of palladium was eluted in the boiling test, but in Comparative Example 3, the nickel was eluted in a large amount. The eluted nickel causes a short-circuit defect due to migration, or an oxide film is formed on the surface of the palladium to lower the on-resistance. Metals (such as nickel, etc.) that have the potential for dissolution should be avoided. As a method of electroless palladium plating in which a palladium layer is formed on the resin fine particles, in the present embodiment, a method of immersing the resin fine particles activated by the catalyst in the electroless palladium squeegee liquid in which the bath has been built is used, and The resin fine particles activated by the catalyst are immersed in the heated distilled water, and the electroless palladium plating solution is sequentially added while being dispersed by stirring, but the method of palladium plating is not affected by such methods. Limited. Further, in the method of sequentially adding the electroless palladium plating solution, the electroless plating solution which has been bathed may be dropped, or the components of the electroless palladium plating solution may be divided into at least two or more, and simultaneously and in parallel Add this. As a method of dividing the components of the electroless palladium plating solution, for example, a method in which a palladium ion, a palladium complex component, and a reducing agent component are added as a separate liquid from -43 to 201120920 is added. INDUSTRIAL APPLICABILITY As described above, according to the present invention, it is possible to provide conductive particles which do not cause migration, are inexpensive, have high conductivity, and are excellent in connection reliability between electrodes. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing conductive particles according to a first embodiment of the present invention. Fig. 2 is a schematic cross-sectional view showing conductive particles according to a second embodiment of the present invention. Fig. 3 (a) is a schematic cross-sectional view of an anisotropic conductive adhesive having conductive particles according to a second embodiment of the present invention, and Figs. 3(b) and 3(e) illustrate the use of anisotropic conductivity. A schematic cross-sectional view for a method of producing a connecting structure of a subsequent agent. [Description of main component symbols] 1 : Insulating particles 2, 2 a : Mother particles 3 : Adhesive 4 : First substrate 5 : First electrode 6 : Second substrate - 44 - 201120920 7 : Second electrode 8, 8 a , 8 b : conductive particles 1 1 : core particles 1 2 : palladium layer 40 : anisotropic conductive adhesive 42 : connection structure - 45

Claims (1)

201120920 VII. Patent application scope: 1. A conductive particle characterized by comprising resin microparticles and a conductive layer formed on the surface of the resin microparticles, wherein the conductive layer comprises a layer of a disk, and the phosphorus concentration in the palladium layer is 1 weight. % or more and 10% by weight or less 'The thickness of the palladium layer is 20 nm or more and 130 nm or less. 2. The conductive particles according to claim 1, wherein the conductive particles are disposed on the surface of the palladium layer and have a particle diameter of 20 to 50,000 nm. 3. The conductive particle according to claim 1 or 2, wherein the palladium layer is a palladium layer of a reduction plating type. 4. The conductive particles according to any one of claims 1 to 3, wherein the components in the conductive layer are legally quantified and quantified by energy dispersive X-ray spectrometry. -46-