WO2014129006A1 - 硬化剤、該硬化剤を含む熱硬化性樹脂組成物、それを用いた接合方法、および熱硬化性樹脂の硬化温度の制御方法 - Google Patents
硬化剤、該硬化剤を含む熱硬化性樹脂組成物、それを用いた接合方法、および熱硬化性樹脂の硬化温度の制御方法 Download PDFInfo
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- WO2014129006A1 WO2014129006A1 PCT/JP2013/077089 JP2013077089W WO2014129006A1 WO 2014129006 A1 WO2014129006 A1 WO 2014129006A1 JP 2013077089 W JP2013077089 W JP 2013077089W WO 2014129006 A1 WO2014129006 A1 WO 2014129006A1
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- thermosetting resin
- curing agent
- curing
- metal
- temperature
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
- B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
- B23K35/0244—Powders, particles or spheres; Preforms made therefrom
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
- B23K35/262—Sn as the principal constituent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
- B23K35/3612—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest with organic compounds as principal constituents
- B23K35/3613—Polymers, e.g. resins
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
- H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
- H05K3/321—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
- H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
- H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
- H05K3/3457—Solder materials or compositions; Methods of application thereof
- H05K3/3463—Solder compositions in relation to features of the printed circuit board or the mounting process
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/10—Details of components or other objects attached to or integrated in a printed circuit board
- H05K2201/10613—Details of electrical connections of non-printed components, e.g. special leads
- H05K2201/10954—Other details of electrical connections
- H05K2201/10977—Encapsulated connections
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
- H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
- H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
- H05K3/341—Surface mounted components
- H05K3/3431—Leadless components
- H05K3/3442—Leadless components having edge contacts, e.g. leadless chip capacitors, chip carriers
Definitions
- the present invention relates to a curing agent used for curing a thermosetting resin, a thermosetting resin composition containing the curing agent, a bonding method using the thermosetting resin composition, and curing of the thermosetting resin.
- the present invention relates to a temperature control method.
- soldering method As a method for mounting electronic components on a mounting target such as a printed circuit board, a soldering method is widely used.
- Patent Document 1 discloses solder particles made of tin-bismuth solder and thermosetting that cures at a temperature higher than the melting point of the solder in the reflow process.
- a solder paste comprising a functional resin and an activator that is activated by heat during soldering to remove an oxide film on the surface of the solder, wherein the activator is activated at a temperature equal to or higher than the melting point of the solder. Solder paste has been proposed.
- solder paste (joining material) of Patent Document 1 contains solder, a thermosetting resin, and an activator. When the strength of the solder material itself used is low and it is difficult to ensure sufficient joining strength, It has the characteristic that a junction part can be reinforced with resin. Such a solder paste (bonding material) is also proposed in Patent Document 2.
- thermosetting resin in order to obtain a normal joining state, the melting point of the solder and the curing temperature of the thermosetting resin
- the relationship is important, and usually the curing temperature of the thermosetting resin needs to be higher than the melting point of the solder. That is, when the curing temperature of the thermosetting resin is lower than the melting point of the solder, the temperature is increased during the soldering process, and when the solder is melted, the thermosetting resin has been cured. There is a problem that the flow of the solder is hindered by the cured resin, the bonding between the molten solders is hindered, and the solder cannot spread on the object to be joined (for example, the surface of the electrode formed on the substrate).
- Patent Document 1 the melting point of the solder, the reaction temperature of the thermosetting resin, and the fact that the activator also functions as a curing agent for the thermosetting resin are activated. Focusing on the temperature relationship including temperature, these relationships are limited. Incidentally, the start of the curing reaction of the resin and the progress speed are determined by the activity of the curing agent.
- the curing reaction of the thermosetting resin is not only influenced by the curing agent blended at the same time, but also greatly influenced by the rate of temperature rise. That is, when the temperature is gradually increased, the curing reaction occurs at a lower temperature than when the temperature is rapidly increased.
- thermosetting resin in order to accurately control the curing temperature of the thermosetting resin, it is necessary to grasp the temperature rising rate and the thermal conductivity of the substance to be heated, and perform overall management.
- thermosetting resin since the thermosetting resin has a property that the temperature further rises due to self-heating when the curing reaction starts, it is actually difficult to perform detailed temperature control.
- Patent Document 1 a melting point of 139 ° C., a solder having a relatively low melting point is used among general solder materials, and the curing temperature of the thermosetting resin may be 139 ° C. or more. Therefore, temperature rising profile management for controlling the curing temperature is relatively easy.
- thermosetting resin for example, a bonding material containing a solder powder having a relatively high melting point, such as Sn-3.0Ag-0.5Cu (melting point 218 ° C.), a thermosetting resin, 2
- a bonding material that can withstand re-reflow and high-temperature environments by blending more than one type of alloy or metal powder and reacting with each other during heat treatment to form a high melting point intermetallic compound.
- the temperature at which the resin starts to be cured is 218 ° C. for the reasons described above. It is necessary to select a curing agent exceeding 1, and there is a problem that the options are narrow.
- imidazole compounds are well known as latent curing agents that are melted and activated by heat, but the melting point of imidazole compounds is a measure of the temperature at which the curing reaction starts, but the reaction temperature itself is accurately determined. It is not shown. Since the curing reaction of the thermosetting resin follows the reaction kinetics, it is greatly influenced by the heating conditions.
- the favorable junction structure here refers to a structure in which electrodes are securely soldered to each other, solder balls are not left, and the periphery thereof is sealed with a thermosetting resin. If this structure is not obtained, it cannot be said to be a highly reliable joint structure.
- thermosetting resin having a melting point equivalent to the curing temperature of the thermosetting resin
- thermoplastic resin since thermoplastic resin has low thermal conductivity, it does not develop fluidity at the same time as it reaches its temperature, but fluidity is generated in response to heat transfer. On the other hand, distribution occurs in the fluidity. In addition, since the characteristics have a distribution due to the variation in molecular weight, the heating conditions having a margin must be set accordingly, and there is a problem that the process becomes complicated and the productivity is lowered.
- Patent Document 6 discloses a technique for controlling the curing reaction temperature.
- the outer shell portion of the capsule is made of an organic substance such as a resin, the sensitivity to develop fluidity with respect to temperature is not high. Therefore, there is a problem that heating conditions must be managed with high accuracy, the process becomes complicated, and productivity is restricted.
- JP 2006-150413 A JP 2002-176248 A JP 2011-56527 A JP 2004-363052 A JP 2002-256303 A JP 2011-208098 A
- the present invention solves the above-mentioned problem, a curing agent capable of initiating a curing reaction of a thermosetting resin at a target temperature, a thermosetting resin composition containing the curing agent, and the thermosetting It is an object of the present invention to provide a bonding method using a curable resin composition and a method for controlling the curing temperature of a thermosetting resin.
- the curing agent of the present invention is characterized in that the surface of the curing agent for curing the thermosetting resin is coated with a metal having a melting point of 400 ° C. or lower.
- the metal that coats the surface of the curing agent may be a single metal (pure metal) or an alloy composed of a plurality of metals, and has a melting point of 400 ° C. or less. That's fine. Moreover, you may consist of several metal which is not alloyed.
- thermosetting resin composition of the present invention is characterized by containing the above-described curing agent of the present invention and a thermosetting resin that reacts with the curing agent to start curing.
- thermosetting resin composition of the present invention can further contain a metal powder.
- a metal powder for soldering or a metal powder for imparting conductivity can be contained.
- the metal powder may be configured to contain a metal powder for soldering.
- thermosetting resin By including a metal powder for soldering, it is possible to reliably perform both electrical and mechanical connection between objects to be joined by solder and strong joining by thermosetting resin. This is particularly significant because a high bonding can be realized.
- the metal that covers the surface of the curing agent includes a metal that forms the metal powder for solder bonding and a metal that forms an intermetallic compound having a higher melting point.
- the metal that coats the surface of the curing agent contains a metal that forms a metal powder for solder joints and a metal that forms an intermetallic compound with a higher melting point, the solder joint has a higher melting point, so it is more reliable. Both high-solder bonding and strong bonding with resin can be more reliably performed, and the present invention can be made more effective.
- the method for controlling the curing temperature of the thermosetting resin of the present invention uses the thermosetting resin composition of the present invention, and the surface of the curing agent constituting the curing agent contained in the thermosetting resin composition.
- the metal to be coated is selected according to the temperature at which the thermosetting resin is to be cured.
- the surface of the curing agent is coated with a metal having a melting point of 400 ° C. or lower, so that the curing reaction of the thermosetting resin can be started at a target temperature. That is, according to the present invention, until the metal coating the surface of the curing agent reaches the melting point, the curing agent cannot contact the thermosetting resin (base resin), and the curing reaction does not start. The starting temperature of the reaction can be controlled. On the other hand, when the temperature of the metal covering the surface of the curing agent reaches the melting point, it quickly melts and flows. As a result, the curing agent is exposed and comes into contact with the thermosetting resin to initiate the curing reaction.
- curing agent which can start the hardening reaction of a thermosetting resin rapidly with target temperature
- medical agent is a material which forms an oxide film on the surface
- a metal having a melting point of 400 ° C. or lower is used widely in consideration of the heat resistance of the thermosetting resin, without causing decomposition or alteration of the thermosetting resin. This is to provide a curing agent that can be used.
- thermosetting resin composition of the present invention contains the curing agent of the present invention, a thermosetting resin composition capable of promptly starting a curing reaction at a target temperature is provided. Can do.
- the method for controlling the curing temperature of the thermosetting resin of the present invention uses a metal that coats the surface of the curing agent that constitutes the curing agent contained in the thermosetting resin composition, using the thermosetting resin composition of the present invention. Since the temperature is selected according to the temperature at which the thermosetting resin is desired to be cured, the curing temperature (temperature at which curing is started) of the thermosetting resin can be easily and reliably controlled.
- thermosetting resin composition of the present invention is interposed between one and the other objects to be bonded, heated to a temperature equal to or higher than the melting point of the metal covering the curing agent, and thermoset. Since the adhesive resin is cured, one joining object and the other joining object can be reliably joined.
- thermosetting resin composition was provided on the electrode of a board
- substrate is a ceramic electronic component. It is a figure which shows the state mounted so that the said electrode might be opposed through a resin composition. It is a figure which shows the state which performed the reflow soldering by letting the board
- the curing agent of the present invention reacts with the thermosetting resin ⁇ http://www.weblio.jp/content/%E5%8F%8D%E5%BF%9C> to initiate the curing reaction.
- the surface of the drug is covered with a metal having a melting point of 400 ° C. or lower.
- the curing agent of the present invention controls the starting temperature of the curing reaction of the thermosetting resin because the curing agent does not come into contact with the base resin and the curing reaction does not start until the surface-coated metal reaches the melting point. can do.
- the temperature of the metal covering the surface of the curing agent reaches the melting point, it quickly melts and flows to expose the curing agent, and the thermosetting resin and the exposed curing agent come into contact with each other to cure. The reaction starts. Therefore, by using the curing agent of the present invention, it becomes possible to quickly start the curing reaction of the thermosetting resin at the target temperature.
- the curing agent constituting the curing agent of the present invention may be liquid or solid at the melting point of the metal that coats the surface, and may be of any type as long as the surface can be coated with metal. There are no restrictions.
- a method of coating the surface of the curing agent with metal a method such as electroless plating or immersion in molten metal can be applied.
- a method of coating the surface of the curing agent with metal there are no particular restrictions on the method of coating the surface of the curing agent with metal, and various other methods can be used.
- an alloy composed of a plurality of metals or a single metal can be used.
- medical agent the metal material which has melting
- the alloy etc. which are used for a solder material can be used, for example.
- the method for controlling the curing temperature of the thermosetting resin of the present invention uses the above-described thermosetting resin composition of the present invention, starts the curing of the thermosetting resin, and selects the type of metal that covers the surface of the curing agent.
- the curing temperature is controlled by selecting according to the desired temperature.
- the curing agent when the surface of the curing agent is coated with a metal, the curing agent is blocked by the metal that coats the surface until the temperature reaches the melting point of the coated metal, and cannot be contacted with the thermosetting resin. The reaction does not start. Thereafter, when the temperature reaches the melting point of the metal and the metal covering the surface of the curing agent starts to melt and flow, the curing agent is exposed and comes into contact with the thermosetting resin, and a curing reaction starts. Therefore, by selecting a metal having a desired melting point as the metal that coats the surface of the curing agent, the starting temperature for curing the thermosetting resin can be controlled.
- the joining of objects to be joined by the method of the present invention uses the above-mentioned thermosetting resin composition of the present invention, and interposes it between one and the other objects to be coated, and coats the surface of the curing agent. It is performed by heating to a temperature equal to or higher than its melting point to cure the thermosetting resin. By doing in this way, one joining target object and the other joining target object can be joined reliably.
- the thermosetting resin composition can contain, for example, a solder material such as Bi-Sn solder.
- a solder material such as Bi-Sn solder.
- the melting point of the solder material needs to be lower than the curing reaction start temperature of the thermosetting resin.
- the starting temperature of the curing reaction of the thermosetting resin can be set to 272 ° C. or higher. Therefore, a soldering material having a melting point lower than the melting point of Bi (for example, a Bi—Sn soldering material having a melting point of 139 ° C.) is contained in the thermosetting resin composition.
- the solder material is first melted and soldered, then the thermosetting resin is cured, and the joining with the thermosetting resin can be performed.
- the melting point of the solder material needs to be lower than the curing reaction start temperature of the thermosetting resin because the thermosetting resin is cured before the solder material melts. Once started, the melted solder cannot flow sufficiently in the thermosetting resin. As a result, the solder particles are not joined to each other, and the solder and electrodes and other objects to be joined are not joined. This is because the electrical connectivity between the objects to be joined may be impaired.
- an intermetallic compound is generated at the solder joint to increase the melting point. Is possible. As a result, more reliable bonding can be realized.
- thermosetting resin composition of the present invention can be configured not to contain a solder material.
- a thermosetting resin composition that does not contain a solder material for example, a thermosetting resin composition comprising a thermosetting resin and a curing agent
- an electronic component such as an IC chip is flipped to the substrate. After chip mounting, it can be suitably used as an underfill material for sealing the gap between the electronic component and the substrate surface.
- thermosetting resin composition since the curing reaction between the thermosetting resin and the curing agent needs to be performed after solder bonding (flip chip mounting), the heat of the present invention.
- the curable resin composition is also significant when used in such applications.
- Thermosetting resin containing a curing agent in which the surface of a curing agent exhibiting high reactivity at a relatively low temperature is coated with a metal having a melting point considerably higher than the temperature at which the curing agent becomes highly reactive since the reaction takes place rapidly at the temperature at which the coated metal melts, the reaction time can be shortened.
- the curing reaction of the thermosetting resin is completed in a reflow continuous furnace or the like. be able to.
- hardening reaction of a thermosetting resin can be completed.
- thermosetting resin composition of the present invention a metal powder other than the solder material (for example, a metal powder for imparting conductivity) can be contained to give a new function.
- curing agent examples include aliphatic amines, aromatic amines, and imidazoles. It is also possible to use a compound obtained by reacting (adducting) another substance with these substances in advance.
- Curing agents that can be used in the present invention are not limited to these, and various substances that are used as curing agents for thermosetting resins can be used. Although it may be liquid or solid, it is preferable to use a solid at room temperature from the viewpoint of covering the surface with metal. When a solid curing agent is used, it is usually desirable to use a particulate curing agent having a diameter of 0.1 to 50 ⁇ m.
- Metal that covers the surface of the curing agent As the metal that covers the surface of the curing agent, either an alloy having a melting point of 400 ° C. or less or a pure metal (single metal) may be used. Examples of alloys and single metals (pure metals) having a melting point of 400 ° C. or lower that can be used in the present invention are shown below.
- Alloys having a melting point of 400 ° C. or less used for coating the surface of the curing agent include Sn—Bi, Sn—In, Sn—Zn, Sn—Ag—Bi, and Sn—Cu.
- the melting point is 400 ° C. or lower
- an alloy other than the above can be used.
- the alloy that coats the curing agent is made of Sn, Cu, Ag, Bi, Sb, In, and Zn.
- An alloy containing at least one selected from the group is preferably used.
- the thickness of the metal (alloy or pure metal) that coats the curing agent is preferably 0.1 to 10 ⁇ m. This is because if the thickness of the metal covering the curing agent is less than 0.1 ⁇ m, the coating reliability of the curing agent by the metal becomes insufficient, and if it exceeds 10 ⁇ m, the proportion of the metal becomes unnecessarily large, which is not preferable. .
- thermosetting resin used in the thermosetting resin composition of the present invention examples include an epoxy resin, a phenol resin, an unsaturated polyester resin, an amino resin, a urea resin, a melamine resin, and a urea resin. Alkyd resin, silicone resin, urethane resin, acrylic resin, polyimide and the like. However, it is not restricted to these, It is also possible to use another thermosetting resin.
- the ratio of the curing agent to the thermosetting resin may be appropriately selected as a blending amount capable of curing the thermosetting resin.
- thermosetting resin composition of the present invention it is possible to further contain metal powder.
- the metal powder to be included include at least one selected from the group consisting of Sn, Cu, Ag, Au, Bi, Sb, In, Ni, and Zn, which are solder materials for enabling solder bonding.
- An alloy powder may be mentioned.
- thermosetting resin composition containing such a metal (or alloy) powder
- the objects to be joined are soldered together in such a manner that they are electrically connected, and the thermosetting resin is strong. Joining (mechanical joining) can be performed.
- the ratio of the metal powder that is a solder material to the thermosetting resin is usually preferably about 10.0 to 1800.0 parts by mass with respect to 100 parts by mass of the thermosetting resin.
- thermosetting resin composition of the present invention not only the metal powder for soldering but also metal powder can be blended for the purpose of imparting functions such as conductivity.
- thermosetting resin composition of the present invention can contain an activator and a reducing agent as necessary in addition to the above-described components.
- the activator include amines, amine salts, organic acids, amino acids, amide compounds, and the like.
- thermosetting resin composition contains, for example, a metal powder for soldering or used for joining solder formed on an electrode in advance, it contains an activator, a reducing agent, etc. By doing so, it becomes possible to improve solder fluidity, oxide removability, etc., and to improve solder joint property.
- thermosetting resin composition of the present invention ⁇ Joint method using the thermosetting resin composition of the present invention> Next, in the case where a surface mount type ceramic electronic component is mounted on an electrode of a substrate using the thermosetting resin composition according to the embodiment of the present invention, that is, an electrode on the substrate which is one object to be joined. Next, a joining method in the case of joining the external electrodes of the ceramic electronic component which is the other joining object will be described.
- a ceramic electronic component when a ceramic electronic component is mounted on a Ni / Au plated electrode of a printed wiring board, the surface of a curing agent (here, 4,4′-diaminodiphenylsulfone) is coated with a metal (here, Sn).
- a thermosetting resin composition containing a curing agent, a thermosetting resin (here, bisphenol A liquid epoxy resin), a solder material (metal powder) of Sn-3.0Ag-0.5Cu, and adipic acid 1 is applied onto the electrodes 11a and 11b of the substrate 10 as shown in FIG. Then, the pair of external electrodes 21a and 21b of the ceramic electronic component 20 are opposed to the electrodes 11a and 11b through the thermosetting resin composition 1 applied on the electrodes 11a and 11b of the substrate 10. Place.
- reflow soldering is performed by allowing the substrate 10 on which the ceramic electronic component 20 is placed to pass through a reflow continuous furnace under predetermined conditions (FIG. 2).
- the surface of the curing agent constituting the curing agent is covered with Sn having a melting point of 232 ° C., and Sn-3.0Ag-0.5Cu solder having a melting point of 218 ° C. is used as the solder material.
- Sn-3.0Ag-0.5Cu solder which is a solder material, is first melted, and the external electrodes 21a and 21b of the ceramic electronic component 20 and the electrodes 11a and 11b of the substrate 10 are connected (bonded) by the solder 31.
- the coating metal (Sn) flows, the curing agent comes into contact with the thermosetting resin, and the curing reaction proceeds.
- the external electrodes 21a and 21b of the ceramic electronic component 20 and the electrodes 11a and 11b of the substrate 10 are firmly joined by a cured resin (thermosetting resin) 32.
- the external electrodes 21a and 21b of the ceramic electronic component 20 and the electrodes 11a and 11b of the substrate 10 are electrically connected by the solder 31 and mechanically strong by the thermosetting resin. Can be efficiently mounted with high reliability.
- thermosetting resin is cured at a temperature lower than the melting point of Sn-3.0Ag-0.5Cu solder.
- the solder was not sufficiently joined between the electrodes, and a soldering state in which many solder particles remained in the thermosetting resin was obtained.
- a metal for example, Cu
- the melting point of the solder joint is increased.
- fusing point can also be comprised so that it may be supplied from the metal which coat
- thermosetting resin composition of the present invention by appropriately selecting the type of metal that coats the surface of the curing agent according to the temperature at which the thermosetting resin is to be cured (temperature at which curing is to be initiated), The temperature at which the thermosetting resin begins to cure can be easily and reliably controlled. Therefore, in consideration of the melting point of the solder material, by starting the curing of the thermosetting resin at a temperature higher than the appropriate temperature range ( ⁇ T), it is possible to easily and reliably perform the above-described reliable bonding. Can be realized.
- thermosetting resin composition of the present invention that does not contain a solder material or the like is used as an underfill material for sealing a gap between the electronic component and the substrate surface after flip-chip mounting an electronic component such as an IC chip, for example. be able to. Also in the case of a so-called pre-applied type material, since the curing reaction between the thermosetting resin and the curing agent needs to be performed after the solder joint, the thermosetting resin composition of the present invention has such a configuration. It can also be used meaningfully in applications.
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Abstract
Description
しかしながら、熱硬化性樹脂は、硬化反応が始まると自己発熱によって、さらに温度が上昇する性質を有しているため、詳細な温度管理は難しいのが実情である。
このように、金属粉末を含有させることにより、新たな機能を備えた熱硬化性樹脂組成物を提供することが可能になる。
すなわち、本発明によれば、硬化薬剤の表面を被覆した金属が融点に達するまで、硬化薬剤は、熱硬化性樹脂(ベース樹脂)と接触することができず、硬化反応は開始しないため、硬化反応の開始温度を制御することができる。
一方、硬化薬剤の表面を被覆している金属の温度が融点に達すると、速やかに溶融して流動する。その結果、硬化薬剤が露出し、熱硬化性樹脂と接触して硬化反応が開始される。
なお、硬化薬剤の表面を被覆している金属材料が、表面に酸化膜を形成する材料の場合は、この酸化膜を除去する材料を、熱硬化性樹脂組成物中に配合してもよい。
また、本発明において、融点が400℃以下の金属を用いるようにしているのは、熱硬化性樹脂の耐熱性を考慮し、熱硬化性樹脂の分解や変質などを招くことがなく、広く適用することが可能な硬化剤を提供できるようにするためである。
本発明の硬化剤は、熱硬化性樹脂と反応 <http://www.weblio.jp/content/%E5%8F%8D%E5%BF%9C>して硬化反応を開始させるもので、硬化薬剤の表面を融点が400℃以下の金属により被覆したことを特徴としている。
一方、硬化薬剤の表面を被覆している金属の温度が融点に達すると、速やかに溶融して流動して硬化薬剤が露出し、熱硬化性樹脂と、露出した硬化薬剤とが接触し、硬化反応が開始する。
したがって、本発明の硬化剤を用いることにより、目標とする温度で速やかに熱硬化性樹脂の硬化反応を開始させることが可能になる。
また、硬化薬剤の表面を被覆する金属材料としては、熱硬化性樹脂材料の使用温度限界に近い400℃以下に融点を持つ金属材料が用いられる。そして、これらの金属材料として、例えば、はんだ材料に用いられる合金などを用いることができる。
(1)硬化薬剤
本発明において用いることが可能な硬化薬剤として、具体的には、脂肪族アミン、芳香族アミン、イミダゾール類などが例示される。また、これらに別の物質をあらかじめ反応(アダクト)させた化合物を用いることも可能である。
また、固形の硬化薬剤を用いる場合、通常、直径が0.1~50μmの粒子状の硬化薬剤を用いることが望ましい。
硬化薬剤の表面を被覆する金属としては、融点が400℃以下の合金、純金属(単一金属)のいずれを用いてもよい。以下に、本発明において用いることが可能な、融点が400℃以下の合金および単一金属(純金属)の例を示す。
硬化薬剤の表面を被覆するのに用いられる融点が400℃以下の合金としては、Sn―Bi系、Sn―In系、Sn―Zn系、Sn―Ag―Bi系、Sn―Cu―Bi系、Sn―Ag―In系、Sn―Cu―In系、Sn―Zn―Bi系、Sn―Bi―In系、Sn―Zn―In系、 Sn―Ag―Cu―Bi系、Sn―Ag―Cu―In系、Sn―Ag―In―Bi系、Sn―Ag―Zn―In系、Sn―Zn―In―Bi系、Sn―Ag―Cu―Sb―Bi系、Sn―Ag系、Sn―Sb系、Sn―Cu系、Sn―Ni系、Sn―Ag―Cu系、Sn―Ag―Ni系、Sn―Ag―Sb系、Sn―Cu―Sb系合金などが挙げられる。
ただし、はんだ接合剤として用いる場合に適正な融点を得る観点、および、はんだ接合強度を確保する観点から、硬化薬剤を被覆する合金としては、Sn、Cu、Ag、Bi、Sb、InおよびZnからなる群より選ばれる少なくとも一種を含む合金が好ましく用いられる。
硬化薬剤の表面を被覆するのに用いられる融点が400℃以下の金属としては、Li(融点:181℃)、Se(融点:221℃)、Sn(融点:232℃)、Bi(融点:272℃)、Tl(融点:304℃)などが例示される。
場合によっては、これらの単一金属を混合した金属粉末を用いることも可能である。
本発明の熱硬化性樹脂組成物において用いられる熱硬化性樹脂としては、例えば、エポキシ樹脂、フェノール樹脂、不飽和ポリエステル樹脂、アミノ樹脂、ユリア樹脂、メラミン樹脂、尿素樹脂、アルキド樹脂、シリコーン樹脂、ウレタン樹脂、アクリル樹脂、ポリイミドなどが挙げられる。ただし、これらに限られるものではなく、他の熱硬化性樹脂を用いることも可能である。
本発明の熱硬化性樹脂組成物では、さらに金属粉末を含有させることが可能である。
含有させる金属粉末としては、例えば、はんだ接合を可能にするためのはんだ材料である、Sn、Cu、Ag、Au、Bi、Sb、In、NiおよびZnからなる群より選ばれる少なくとも1種を含む合金の粉末が挙げられる。
なお、熱硬化性樹脂に対するはんだ材料である金属粉末の割合は、通常、熱硬化性樹脂100質量部に対し、金属粉末が10.0~1800.0質量部程度の割合とすることが望ましい。
本発明の熱硬化性樹脂組成物は、上述の成分以外にも、必要に応じて活性剤や還元剤を含有させることができる。
活性剤としては、例えば、アミン類、アミン塩類、有機酸類、アミノ酸類、アミド系化合物などが例示される。
熱硬化性樹脂組成物が、例えば、はんだ付け用の金属粉末を含有するものである場合やあらかじめ電極上に形成されたはんだを接合する用途で用いられる場合において、活性剤や還元剤などを含有させることにより、はんだの流動性や酸化物の除去性などを向上させてはんだ接合性を高めることが可能になる。
次に、本発明の実施形態にかかる熱硬化性樹脂組成物を用いて表面実装型のセラミック電子部品を、基板の電極上に実装する場合、すなわち、一方の接合対象物である基板上の電極に、他方の接合対象物であるセラミック電子部品の外部電極を接合する場合の接合方法について説明する。
それから、セラミック電子部品20を、その一対の外部電極21a,21bが、基板10の電極11a,11b上に付与された熱硬化性樹脂組成物1を介して、電極11a,11bと対向するように載置する。
なお、はんだ接合部に金属間化合物を生じさせて高融点化させる金属は、硬化薬剤を被覆する金属から供給されるように構成することもできるが、熱硬化性樹脂組成物に含有させておくことも可能であり、また、一方の接合対象物および他方の接合対象物の少なくとも一方から供給されるようにすることも可能である。
10 基板(プリント配線基板)
11a,11b 基板上の電極
20 セラミック電子部品
21a,21b セラミック電子部品の外部電極
31 はんだ
32 硬化した樹脂(熱硬化性樹脂)
Claims (7)
- 熱硬化性樹脂を硬化させる硬化薬剤の表面が、融点が400℃以下の金属により被覆されていることを特徴とする硬化剤。
- 請求項1記載の硬化剤と、
前記硬化剤と反応して硬化を開始する熱硬化性樹脂と
を含有することを特徴とする熱硬化性樹脂組成物。 - さらに金属粉末を含有していることを特徴とする請求項2記載の熱硬化性樹脂組成物。
- 前記金属粉末が、はんだ接合用の金属粉末であることを特徴とする請求項3記載の熱硬化性樹脂組成物。
- 前記硬化薬剤の表面を被覆する前記金属が、前記はんだ接合用の金属粉末を構成する金属と、さらに融点の高い金属間化合物を形成する金属を含むものであることを特徴とする請求項4記載の熱硬化性樹脂組成物。
- 請求項2~5のいずれかに記載の熱硬化性樹脂組成物を用い、
前記熱硬化性樹脂組成物に含まれる前記硬化剤を構成する前記硬化薬剤の表面を被覆する前記金属を、前記熱硬化性樹脂を硬化させたい温度に応じて選択することを特徴とする熱硬化性樹脂の硬化温度の制御方法。 - 請求項2~5のいずれかに記載の熱硬化性樹脂組成物を、一方の接合対象物と他方の接合対象物との間に介在させた状態で、前記硬化薬剤を被覆する前記金属の融点以上の温度に加熱して、前記熱硬化性樹脂を硬化させることにより、前記一方の接合対象物と前記他方の接合対象物とを接合することを特徴とする接合方法。
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