JP6328996B2 - Conductive paste, connection structure, and manufacturing method of connection structure - Google Patents

Description

  The present invention relates to a conductive paste containing conductive particles, and can be used to electrically connect electrodes of various connection target members such as a flexible printed circuit board, a glass substrate, a glass epoxy substrate, and a semiconductor chip. The present invention relates to a conductive paste. The present invention also relates to a connection structure using the conductive paste and a method for manufacturing the connection structure.

  Pasty or film-like anisotropic conductive materials are widely known. In the anisotropic conductive material, a plurality of conductive particles are dispersed in a binder resin.

  In order to obtain various connection structures, the anisotropic conductive material is, for example, a connection between a flexible printed circuit board and a glass substrate (FOG (Film on Glass)) or a connection between a semiconductor chip and a flexible printed circuit board (COF ( Chip on Film)), connection between a semiconductor chip and a glass substrate (COG (Chip on Glass)), connection between a flexible printed circuit board and a glass epoxy substrate (FOB (Film on Board)), and the like.

  As an example of the anisotropic conductive material, Patent Document 1 below discloses an adhesive composition used for bonding circuit members to each other and electrically connecting circuit electrodes included in each circuit member. It is disclosed. This adhesive composition includes an epoxy resin, an epoxy resin curing agent, and an acrylic copolymer having a crosslinked structure and having a weight average molecular weight of 30,000 to 80,000. The adhesive composition may contain conductive particles and can be used as an anisotropic conductive material.

  Patent Document 2 below discloses a conductive adhesive (anisotropic conductive paste) containing an epoxy adhesive having a flux action and SnBi solder powder.

Patent Document 3 below, the shear modulus measured in the previous 70 ° C. curing, strain of 1% of the storage modulus _{G 1} of the strain amount ratio of 10% of the storage modulus _{G 10 G} 1 _{/ G 10} The melt viscosity is 100 Pa · s to 250,000 Pa · s measured under conditions of a shear rate of 0.1 (s ⁻¹ ) at 70 ° C. before curing and a strain amount of 0.4%. An adhesive sheet is disclosed.

WO2009 / 44732A1 JP 2006-199937 A JP 2008-81734 A

  In the conventional anisotropic conductive paste as described in Patent Document 1, bubbles may be contained in the anisotropic conductive paste at the time of curing. In particular, since volatile components such as water contained in the bonding object are transferred into the anisotropic conductive paste, bubbles are easily included in the anisotropic conductive paste. When the anisotropic conductive paste containing bubbles is cured, voids are generated in the cured product.

  As described in Patent Document 2, when a film (sheet) is used instead of a paste, the embedding property with respect to the uneven surface of the film tends to deteriorate. In addition, when a film is used, bubbles are not included in the anisotropic conductive paste at the time of curing, but when the paste is used, bubbles are included in the anisotropic conductive paste at the time of curing. There is a problem that it is easy.

  An object of the present invention is to provide a conductive paste capable of suppressing the generation of voids in a cured product by suppressing the inclusion of bubbles during curing in the conductive paste, and the connection using the conductive paste It is to provide a manufacturing method of a structure and a connection structure.

  According to a wide aspect of the present invention, the binder resin includes conductive particles, the binder resin contains a thermal radical polymerizable compound and a thermal radical polymerization initiator, and the binder resin at 90 ° C. There is provided a conductive paste having a storage elastic modulus of 8 Pa or more and less than 500 MPa, or a storage elastic modulus of the conductive paste at 90 ° C. of 8 Pa or more and less than 500 MPa.

  In certain aspects of the conductive paste according to the present invention, only heating is performed to cure.

  In a specific aspect of the conductive paste according to the present invention, no light irradiation is performed to cure the conductive paste.

  On the specific situation with the electrically conductive paste which concerns on this invention, the said binder resin contains an epoxy compound and the thermosetting agent different from a thermal radical polymerization initiator.

  On the specific situation with the electrically conductive paste which concerns on this invention, the said binder resin contains a thiol compound.

  On the specific situation with the electrically conductive paste which concerns on this invention, the said thiol compound has two or more thiol groups.

  On the specific situation with the electrically conductive paste which concerns on this invention, the said electroconductive particle is an electroconductive particle whose electroconductive outer surface is a solder at least.

  In a specific aspect of the conductive paste according to the present invention, the storage elastic modulus at 90 ° C. of the binder resin is 8 Pa or more and less than 500 MPa, and in another specific aspect, the storage elasticity of the conductive paste at 90 ° C. The rate is 8 Pa or more and less than 500 MPa.

  On the specific situation with the electrically conductive paste which concerns on this invention, this electrically conductive paste is a circuit connection material used for the electrical connection between electrodes.

  According to a wide aspect of the present invention, a first connection target member having a first electrode on the surface, a second connection target member having a second electrode on the surface, the first connection target member, and the A connecting portion connecting to a second connection target member, wherein the connecting portion is formed of the conductive paste described above, and the first electrode and the second electrode are the conductive particles. To provide a connection structure that is electrically connected.

  According to the wide aspect of the present invention, using the first connection target member having the first electrode on the surface, the second connection target member having the second electrode on the surface, and the above-described conductive paste, Placing the conductive paste between the first connection target member and the second connection target member; heating and curing the conductive paste; and the first connection target member and the second connection paste. Forming a connection portion connecting the connection target member, and obtaining a connection structure in which the first electrode and the second electrode are electrically connected by the conductive particles A method for manufacturing a connection structure is provided.

  On the specific situation with the manufacturing method of the connection structure which concerns on this invention, in order to harden the said electrically conductive paste, light is not irradiated.

  The conductive paste according to the present invention includes a binder resin and conductive particles, the binder resin contains a thermal radical polymerizable compound and a thermal radical polymerization initiator, and the binder resin is stored at 90 ° C. Since the elastic modulus is 8 Pa or more and less than 500 MPa, or the storage elastic modulus at 90 ° C. of the conductive paste is 8 Pa or more and less than 500 MPa, it is possible to suppress the inclusion of bubbles at the time of curing, and voids in the cured product Can be prevented from occurring.

FIG. 1 is a cross-sectional view schematically showing conductive particles contained in a conductive paste according to an embodiment of the present invention. FIG. 2 is a cross-sectional view showing a modification of the conductive particles. FIG. 3 is a cross-sectional view showing another modification of the conductive particles. FIG. 4 is a front sectional view schematically showing a connection structure using a conductive paste according to an embodiment of the present invention. FIG. 5 is a front cross-sectional view schematically showing an enlarged connection portion between conductive particles and electrodes in the connection structure shown in FIG. 4.

  Details of the present invention will be described below.

  The conductive paste according to the present invention is not a film but a paste. The conductive paste according to the present invention includes a binder resin and conductive particles. In the conductive paste according to the present invention, the storage elastic modulus at 90 ° C. of the binder resin is 8 Pa or more and less than 500 MPa, or the storage elastic modulus at 90 ° C. of the conductive paste according to the present invention is 8 Pa or more and 500 MPa. Is less than.

  By adopting the above-described configuration in the present invention, bubbles are less likely to be included in the conductive paste during curing. In particular, volatile components such as water contained in the bonding object are less likely to move into the conductive paste, and bubbles are less likely to be included in the conductive paste. As a result, generation of voids can be suppressed in the cured product obtained by curing the conductive paste according to the present invention.

  The present inventors have found that the occurrence of voids in the cured product may not be sufficiently suppressed by merely controlling the melt viscosity of the binder resin or conductive paste. Furthermore, the present inventors have studied to sufficiently suppress the occurrence of voids in the cured product, and as a result, the storage elastic modulus at 90 ° C. of the binder resin contained in the conductive paste is set to the above lower limit or more, The inventors have found that the storage elastic modulus at 90 ° C. of the conductive paste may be set to the above lower limit or more. Since the storage elastic modulus is equal to or higher than the lower limit, a three-dimensional structure sufficient to suppress voids is formed, so that the generation of voids can be effectively suppressed.

  The reason why the temperature defining the storage elastic modulus is 90 ° C. is that, as a result of the study, 90 ° C. becomes the resin temperature at the time of void generation. In addition, storage elastic modulus and melt viscosity do not necessarily correlate.

  Each storage elastic modulus at 90 ° C. of the binder resin and the conductive paste is preferably less than 50 Pa, more preferably less than 10 Pa.

  The storage elastic modulus is measured using a rheometer device, with the shear rate and strain as constant conditions. Examples of commercially available rheometer devices include “VAR-100” manufactured by Jusco.

  In the conductive paste according to the present invention, the storage elastic modulus at 90 ° C. of the binder resin may be 8 Pa or more and less than 500 MPa, and the storage elastic modulus at 90 ° C. of the conductive paste according to the present invention is 8 Pa or more and 500 MPa. It may be less. If the storage elastic modulus at 90 ° C. of the binder resin is 8 Pa or more and less than 500 MPa, or the storage elastic modulus at 90 ° C. of the conductive paste is 8 Pa or more and less than 500 MPa, the binder resin at 90 ° C. The generation of voids can be suppressed as compared with the case where the storage elastic modulus is not 8 Pa or more and less than 500 MPa and the conductive elastic paste at 90 ° C. is not 8 Pa or more and less than 500 MPa.

  The storage elastic modulus at 90 ° C. of the binder resin is preferably 8 Pa or more and less than 500 MPa, the storage elastic modulus at 90 ° C. of the binder resin is 8 Pa or more and less than 500 MPa, and the conductive paste has a 90 ° C. It is more preferable that the storage elastic modulus at is 8 Pa or more and less than 500 MPa.

  The binder resin is a liquid component that is not solid. The binder resin is a mixture of components excluding the conductive particles in the conductive paste and the solid content different from the conductive particles. The binder resin does not include conductive particles. The binder resin includes a thermosetting component. The binder resin contains a thermoradical polymerizable compound which is a thermosetting compound as the thermosetting component, preferably contains an epoxy compound which is a curable compound, preferably contains a thermosetting agent, and a thermal radical. It preferably contains a polymerization initiator and a thermosetting agent different from the thermal radical polymerization initiator.

  In the conductive paste according to the present invention, the binder resin contains a thermal radiopolymerizable compound and a thermal radical polymerization initiator as essential components. In the present invention, even when a thermal radical reaction system is employed, bubbles are less likely to be included in the conductive paste during curing. In particular, volatile components such as water contained in the bonding object are less likely to move into the conductive paste, and bubbles are less likely to be included in the conductive paste. As a result, generation of voids can be suppressed in the cured product obtained by curing the conductive paste according to the present invention.

  In the present invention, a configuration in which the storage elastic modulus at 90 ° C. of the binder resin or the conductive paste is controlled within a specific range, and the binder resin includes, as essential components, a thermal radical polymerizable compound and a thermal radical polymerization initiator. And a configuration including

  Hereinafter, each component contained in the conductive paste according to the present invention and each component preferably contained will be described in detail.

(Curable compound)
The binder resin contains a thermal radical polymerizable compound as a thermosetting compound. As for the said heat radical polymerizable compound, only 1 type may be used and 2 or more types may be used together.

  The binder resin may contain another curable compound (may be described as “curable compound”). The curable compound is not particularly limited as long as it can be cured by the action of the curing agent. As for the said sclerosing | hardenable compound, only 1 type may be used and 2 or more types may be used together.

  Specific examples of the thermal radical polymerizable compound include divinylbenzene, trimethylpropane trimethacrylate, and allyl methacrylate.

  The curable compound is not particularly limited, and examples thereof include a curable compound having an unsaturated double bond and a curable compound having an epoxy group (epoxy compound). The binder resin preferably contains an epoxy compound as the curable compound. By using an epoxy compound, the generation of voids can be further suppressed and the adhesive strength can be further increased.

  Examples of the curable compound having an unsaturated double bond include a curable compound having a vinyl group or a (meth) acryloyl group. From the viewpoint of easily controlling the curing of the conductive paste or further enhancing the conduction reliability in the connection structure, the curable compound having an unsaturated double bond is a curing having a (meth) acryloyl group. It is preferable that it is an ionic compound. By using the curable compound having the (meth) acryloyl group, it becomes easy to control the curing rate in a suitable range in the entire B-staged conductive paste, and the conduction reliability in the obtained connection structure is further increased. Get higher.

  From the viewpoint of further improving the conduction reliability between the electrodes, the curable compound having the (meth) acryloyl group preferably has one or two (meth) acryloyl groups.

  As the curable compound having the (meth) acryloyl group, an ester compound obtained by reacting a (meth) acrylic acid and a compound having a hydroxyl group, an epoxy obtained by reacting (meth) acrylic acid and an epoxy compound ( A (meth) acrylate, a urethane (meth) acrylate obtained by reacting a (meth) acrylic acid derivative having a hydroxyl group with an isocyanate, or the like is preferably used. The “(meth) acryloyl group” refers to an acryloyl group and a methacryloyl group. The “(meth) acryl” refers to acryl and methacryl. The “(meth) acrylate” refers to acrylate and methacrylate.

  The ester compound obtained by making the said (meth) acrylic acid and the compound which has a hydroxyl group react is not specifically limited. As the ester compound, any of a monofunctional ester compound, a bifunctional ester compound, and a trifunctional or higher functional ester compound can be used.

  The curable compound having an unsaturated double bond may be a crosslinkable compound or a non-crosslinkable compound.

  Specific examples of the crosslinkable compound include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, (poly ) Ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, glycerol methacrylate acrylate, pentaerythritol tri (meth) acrylate, tri Examples include methylolpropane trimethacrylate, allyl (meth) acrylate, vinyl (meth) acrylate, divinylbenzene, polyester (meth) acrylate, and urethane (meth) acrylate.

  Specific examples of the non-crosslinkable compound include ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) ) Acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, decyl (Meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, and the like.

  The curable compound having an epoxy group preferably has an aromatic ring. Examples of the aromatic ring include a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, tetracene ring, chrysene ring, triphenylene ring, tetraphen ring, pyrene ring, pentacene ring, picene ring, and perylene ring. Especially, it is preferable that the said aromatic ring is a benzene ring, a naphthalene ring, or an anthracene ring, and it is more preferable that it is a benzene ring or a naphthalene ring. A naphthalene ring is preferred because it has a planar structure and can be cured more rapidly.

  Examples of the curable compound having an epoxy group include resorcinol type epoxy compounds, naphthalene type epoxy compounds, anthracene type epoxy compounds, bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, cresol novolac type epoxy compounds, phenol novolac type epoxy compounds, Glycidyl ester type epoxy compound obtained by reacting polybasic acid compound having aromatic skeleton and epichlorohydrin, glycidyl ether type epoxy compound having aromatic skeleton, 2- (3,4-epoxy) cyclohexyl-5 , 5-spiro- (3,4-epoxy) cyclohexane-m-dioxane, 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate, dicyclopentadienedio Sid, vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane, 1,2: 8,9-diepoxylimonene, ε-caprolactone modified tetra (3,4-epoxycyclohexylmethyl) butanetetracarboxylate, 2 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2-bis (hydroxymethyl) -1-butanol and the like.

  In 100% by weight of the conductive paste, the content of the thermal radical polymerizable compound is preferably 1% by weight or more, more preferably 2% by weight or more, preferably 5% by weight or less, more preferably 3% by weight or less.

  In 100% by weight of the conductive paste, the content of the epoxy compound is preferably 40% by weight or more, more preferably 45% by weight or more, preferably 55% by weight or less, more preferably 50% by weight or less.

  In 100% by weight of the conductive paste, the total content of the curable compound is preferably 41% by weight or more, more preferably 47% by weight or more, preferably 60% by weight or less, more preferably 53% by weight or less.

(Curing agent)
The binder resin contains a thermal radical polymerization initiator as the curing agent. As for the said thermal radical polymerization initiator, only 1 type may be used and 2 or more types may be used together.

  Moreover, it is preferable that the said binder resin contains the thermosetting agent (it may describe as a "curing agent") different from a thermal radical polymerization initiator as the said hardening | curing agent. The said hardening | curing agent is not specifically limited. As for the said hardening | curing agent, only 1 type may be used and 2 or more types may be used together.

  Examples of the curing agent include an imidazole curing agent, an amine curing agent, a phenol curing agent, a polythiol curing agent, a cation generator, and an acid anhydride.

  The binder resin contains a thermal radical polymerization initiator as the curing agent. Moreover, it is preferable that the said binder resin contains the thermosetting agent different from a thermal radical polymerization initiator as the said hardening | curing agent.

  From the viewpoint of making the conductive paste more curable at a low temperature, an imidazole curing agent, a polythiol curing agent, or an amine curing agent is preferable. In addition, a latent curing agent is preferable from the viewpoint of further improving the storage stability when a curable compound curable by heating and the thermosetting agent are mixed. The latent curing agent is preferably a latent imidazole curing agent, a latent polythiol curing agent or a latent amine curing agent. Only 1 type may be used for these hardening | curing agents, and 2 or more types may be used together. In addition, the said hardening | curing agent may be coat | covered with polymeric substances, such as a polyurethane resin or a polyester resin.

  Examples of the thermal radical polymerization initiator include azobisisobutylnitrile, azobismethylbutylnitrile, azobisdimethylbarrel nitrile, and the like.

  The imidazole curing agent is not particularly limited, and 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2, 4-Diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine and 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s- Examples include triazine isocyanuric acid adducts.

  The polythiol curing agent is not particularly limited, and examples thereof include trimethylolpropane tris-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, and dipentaerythritol hexa-3-mercaptopropionate. .

  The amine curing agent is not particularly limited, and hexamethylene diamine, octamethylene diamine, decamethylene diamine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraspiro [5.5]. Examples include undecane, bis (4-aminocyclohexyl) methane, metaphenylenediamine, and diaminodiphenylsulfone.

  Examples of the cation generator include iodonium cation curing agents, oxonium cation curing agents, and sulfonium cation curing agents. Examples of the iodonium-based cationic curing agent include bis (4-tert-butylphenyl) iodonium hexafluorophosphate. Examples of the oxonium-based cationic curing agent include trimethyloxonium tetrafluoroborate. Examples of the sulfonium-based cationic curing agent include tri-p-tolylsulfonium hexafluorophosphate.

  From the viewpoint of further enhancing the flux effect, the curing agent preferably contains a cation generator. The conductive paste preferably contains a cation generator.

  The content of the curing agent is not particularly limited. The content of the thermosetting agent is preferably 0.01 parts by weight or more, more preferably 1 part by weight or more, preferably 200 parts by weight or less, more preferably 100 parts by weight with respect to 100 parts by weight of the curable compound. Hereinafter, it is more preferably 75 parts by weight or less. When the content of the curing agent is not less than the lower limit, it is easy to sufficiently cure the conductive paste. When the content of the curing agent is not more than the above upper limit, it is difficult for an excess curing agent that did not participate in curing after curing to remain, and the heat resistance of the cured product is further increased.

  The content of the thermal radical polymerization initiator is preferably 1 part by weight or more, more preferably 2 parts by weight or more, preferably 7 parts by weight or less, and more preferably 5 parts by weight with respect to 100 parts by weight of the thermal radical polymerizable compound. Or less.

  The content of the thermosetting agent different from the thermal radical polymerization initiator is preferably 10 parts by weight or more, more preferably 15 parts by weight or more, preferably 35 parts by weight or less, more preferably 100 parts by weight of the epoxy compound. 25 parts by weight or less.

  When the curing agent contains a cation generator, the content of the cation generator is preferably 0.01 parts by weight or more, more preferably 0.05 parts by weight with respect to 100 parts by weight of the curable compound. The amount is preferably 10 parts by weight or less, more preferably 5 parts by weight or less. When the content of the cation generator is not less than the above lower limit and not more than the above upper limit, the conductive paste is sufficiently cured.

(Thiol compound)
The binder resin preferably contains a thiol compound. The thiol compound has a thiol group. By using the thiol compound, the low-temperature curing performance is further improved. As a result, it is possible to further suppress the inclusion of bubbles at the time of curing and further suppress the generation of voids in the cured product. Further, the use of the thiol compound can further enhance the adhesive force. The thiol compound is preferably different from the thermosetting agent. As for the said thiol compound, only 1 type may be used and 2 or more types may be used together.

  The thiol compound preferably has a plurality of thiol groups. In this case, the low temperature curing performance is further improved. As a result, it is possible to further suppress the inclusion of bubbles at the time of curing, to further suppress the generation of voids in the cured product, and to further increase the adhesive force.

  In 100% by weight of the conductive paste, the total content of the thiol compound is preferably 2% by weight or more, more preferably 4% by weight or more, preferably 20% by weight or less, more preferably 10% by weight or less.

(flux)
The binder resin preferably contains a flux. The use of the flux makes it difficult to form an oxide film on the solder surface, and the oxide film formed on the solder surface or electrode surface can be effectively removed. As a result, the conduction reliability in the connection structure is further increased. In addition, the said electrically conductive paste does not necessarily contain the flux.

  The flux is not particularly limited. As the flux, it is possible to use a flux generally used for soldering or the like. Examples of the flux include zinc chloride, a mixture of zinc chloride and an inorganic halide, a mixture of zinc chloride and an inorganic acid, a molten salt, phosphoric acid, a derivative of phosphoric acid, an organic halide, hydrazine, an organic acid, and pine resin. Etc. As for the said flux, only 1 type may be used and 2 or more types may be used together.

  Examples of the molten salt include ammonium chloride. Examples of the organic acid include lactic acid, citric acid, stearic acid, and glutamic acid. Examples of the pine resin include activated pine resin and non-activated pine resin. The flux is preferably rosin. By using rosin, the connection resistance between the electrodes is further reduced.

  The rosin is a rosin composed mainly of abietic acid. The flux is preferably a rosin, and more preferably abietic acid. By using this preferable flux, the connection resistance between the electrodes is further reduced. The flux is preferably an organic acid having a carboxyl group. Examples of the compound having a carboxyl group include a compound having a carboxyl group bonded to an alkyl chain and a compound having a carboxyl group bonded to an aromatic ring. In these compounds having a carboxyl group, a hydroxyl group may be further bonded to an alkyl chain or an aromatic ring. The number of carboxyl groups bonded to the alkyl chain or aromatic ring is preferably 1 to 3, more preferably 1 or 2. The number of carbon atoms in the alkyl chain in the compound in which a carboxyl group is bonded to the alkyl chain is preferably 3 or more, preferably 8 or less, more preferably 6 or less. Specific examples of the compound having a carboxyl group bonded to an alkyl chain include hexanoic acid (5 carbon atoms, 1 carboxyl group), glutaric acid (4 carbon atoms, 2 carboxyl groups), and the like. Specific examples of the compound having a carboxyl group and a hydroxyl group include malic acid and citric acid. Specific examples of the compound having a carboxyl group bonded to an aromatic ring include benzoic acid, phthalic acid, benzoic anhydride, and phthalic anhydride.

  The flux may be dispersed in the binder resin, or may be attached on the surface of the conductive particles.

  In 100% by weight of the conductive paste, the content of the flux is preferably 0.5% by weight or more, preferably 30% by weight or less, more preferably 25% by weight or less. When the content of the flux is not less than the lower limit and not more than the upper limit, an oxide film is hardly formed on the solder surface, and the oxide film formed on the solder surface or the electrode surface can be more effectively removed. . Further, when the content of the flux is equal to or more than the lower limit, the effect of adding the flux is more effectively expressed. When the content of the flux is not more than the above upper limit, the hygroscopic property of the cured product is further lowered, and the reliability of the connection structure is further enhanced.

(Conductive particles)
Examples of the conductive particles include organic particles, inorganic particles other than metal particles, organic-inorganic hybrid particles, or metal particles whose surfaces are covered with a conductive portion (such as a conductive layer), or substantially metal only. Metal particles composed of

  The conductive part is not particularly limited. Gold, silver, copper, nickel, palladium, tin, etc. are mentioned as a metal which comprises the said electroconductive part. Examples of the conductive layer include a gold layer, a silver layer, a copper layer, a nickel layer, a palladium layer, or a conductive layer containing tin.

  From the viewpoint of increasing the contact area between the electrode and the conductive particle and further improving the conduction reliability between the electrodes, the conductive particle is composed of the base material and the conductive material disposed on the surface of the base material particle. Part (first conductive part). From the viewpoint of further improving the conduction reliability between the electrodes, the conductive particles are preferably conductive particles having at least a conductive outer surface made of solder.

  The conductive particles are preferably conductive particles having base particles and a conductive layer disposed on the surface of the base particles, and at least an outer surface of the conductive layer being a solder layer. Examples of the substrate particles include resin particles, inorganic particles excluding metal particles, organic-inorganic hybrid particles, and metal particles. The base particles may be core-shell particles. The substrate particles are preferably substrate particles that are not metal particles, and more preferably resin particles, inorganic particles excluding metal particles, or organic-inorganic hybrid particles. The substrate particles are preferably resin particles formed of a resin. When connecting the electrodes, the conductive particles are generally compressed after the conductive particles are arranged between the electrodes. When the substrate particles are resin particles, the conductive particles are easily deformed by compression, and the contact area between the conductive particles and the electrode is increased. For this reason, the conduction | electrical_connection reliability between electrodes can be improved. From the viewpoint of further improving the thermal shock resistance in the connection structure, the conductive particles include resin particles and a conductive layer disposed on the surface of the resin particles, and at least the outer surface of the conductive layer is soldered. The layer is preferably a conductive particle.

  In FIG. 1, the electroconductive particle contained in the electrically conductive paste which concerns on one Embodiment of this invention is shown with sectional drawing.

  A conductive particle 1 shown in FIG. 1 has resin particles 2 (base material particles) and a conductive layer 3 disposed on the surface 2 a of the resin particles 2. The conductive layer 3 covers the surface 2 a of the resin particle 2. The conductive particle 1 is a coated particle in which the surface 2 a of the resin particle 2 is coated with the conductive layer 3. Accordingly, the conductive particles 1 have the conductive layer 3 on the surface 1a. Instead of the resin particles 2, base material particles different from the resin particles may be used.

  The conductive layer 3 includes a first conductive layer 4 disposed on the surface 2a of the resin particle 2, and a solder layer 5 (second conductive layer) disposed on the surface 4a of the first conductive layer 4. Have The outer surface layer of the conductive layer 3 is a solder layer 5. Accordingly, the conductive particle 1 has the solder layer 5 as a part of the conductive layer 3 (conductive part), and further, as a part of the conductive layer 3 (conductive part) between the resin particle 2 and the solder layer 5. A first conductive layer 4 is provided separately from the solder layer 5. Thus, the conductive layer 3 may have a multilayer structure, or may have a laminated structure of two or more layers. Instead of the solder layer 5, a conductive layer different from the solder layer may be formed.

  As described above, the conductive layer 3 has a two-layer structure. As in the modification shown in FIG. 2, the conductive particles 11 may have a solder layer 12 as a single conductive layer. It is preferable that at least the outer surface of the conductive portion in the conductive particle is a solder. For example, at least the outer surface layer of the conductive layer in the conductive particle is preferably a solder layer. However, the conductive particles 1 are preferable among the conductive particles 1 and the conductive particles 11 because the conductive particles can be easily produced. Further, as in the modification shown in FIG. 3, solder particles 16 that are not core-shell particles and do not have base particles in the core may be used. The solder particles 16 are formed of solder at both the central portion and the outer surface. However, among the conductive particles 1, the conductive particles 11, and the solder particles 16, the conductive particles 1 and the conductive particles 11 are preferable. Instead of the solder layer 12, a conductive layer different from the solder layer may be formed.

  Various organic materials are suitably used as the resin for forming the resin particles. Examples of the resin for forming the resin particles include polyolefin resins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyisobutylene, and polybutadiene; acrylic resins such as polymethyl methacrylate and polymethyl acrylate; Alkylene terephthalate, polycarbonate, polyamide, phenol formaldehyde resin, melamine formaldehyde resin, benzoguanamine formaldehyde resin, urea formaldehyde resin, phenol resin, melamine resin, benzoguanamine resin, urea resin, epoxy resin, unsaturated polyester resin, saturated polyester resin, polysulfone, polyphenylene Oxide, polyacetal, polyimide, polyamideimide, polyether ether Tons, polyethersulfone, and polymers such as obtained by a variety of polymerizable monomer having an ethylenically unsaturated group is polymerized with one or more thereof. Resin for forming the resin particles can be designed and synthesized, and the hardness of the base particles can be easily controlled within a suitable range, which is suitable for the conductive paste and having physical properties at the time of compression. Is preferably a polymer obtained by polymerizing one or more polymerizable monomers having a plurality of ethylenically unsaturated groups.

  When the resin particles are obtained by polymerizing a monomer having an ethylenically unsaturated group, the monomer having an ethylenically unsaturated group includes a non-crosslinkable monomer and a crosslinkable monomer. And so on.

  Examples of the non-crosslinkable monomer include styrene monomers such as styrene and α-methylstyrene; carboxyl group-containing monomers such as (meth) acrylic acid, maleic acid, and maleic anhydride; (Meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl ( Alkyl (meth) acrylates such as meth) acrylate and isobornyl (meth) acrylate; oxygen such as 2-hydroxyethyl (meth) acrylate, glycerol (meth) acrylate, polyoxyethylene (meth) acrylate and glycidyl (meth) acrylate (Meth) acrylates; nitrile-containing monomers such as (meth) acrylonitrile; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether; vinyl acids such as vinyl acetate, vinyl butyrate, vinyl laurate, vinyl stearate Esters; Unsaturated hydrocarbons such as ethylene, propylene, isoprene and butadiene; Halogen-containing monomers such as trifluoromethyl (meth) acrylate, pentafluoroethyl (meth) acrylate, vinyl chloride, vinyl fluoride and chlorostyrene Is mentioned.

  Examples of the crosslinkable monomer include tetramethylolmethane tetra (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and dipenta Erythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, glycerol tri (meth) acrylate, glycerol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) Polyfunctional (meth) acrylates such as acrylate, (poly) tetramethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate; triallyl (iso) cyanure And silane-containing monomers such as triallyl trimellitate, divinylbenzene, diallyl phthalate, diallylacrylamide, diallyl ether, γ- (meth) acryloxypropyltrimethoxysilane, trimethoxysilylstyrene, vinyltrimethoxysilane It is done.

  The resin particles can be obtained by polymerizing the polymerizable monomer having an ethylenically unsaturated group by a known method. Examples of this method include a method of suspension polymerization in the presence of a radical polymerization initiator, and a method of polymerizing by swelling a monomer together with a radical polymerization initiator using non-crosslinked seed particles.

  In the case where the substrate particles are inorganic particles or organic-inorganic hybrid particles excluding metal particles, examples of the inorganic material for forming the substrate particles include silica and carbon black. This inorganic substance is preferably not a metal. The particles formed by the silica are not particularly limited. For example, after forming a crosslinked polymer particle by hydrolyzing a silicon compound having two or more hydrolyzable alkoxysilyl groups, firing may be performed as necessary. The particle | grains obtained by performing are mentioned. Examples of the organic / inorganic hybrid particles include organic / inorganic hybrid particles formed of a crosslinked alkoxysilyl polymer and an acrylic resin.

  When the substrate particles are metal particles, examples of the metal for forming the metal particles include silver, copper, nickel, silicon, gold, and titanium. However, the substrate particles are preferably not metal particles.

  The average particle diameter of the substrate particles is preferably 1 μm or more, more preferably 2 μm or more, preferably 100 μm or less, more preferably 50 μm or less, still more preferably 30 μm or less, and particularly preferably 5 μm or less. When the average particle diameter of the substrate particles is equal to or more than the above lower limit, the conduction reliability between the electrodes is further enhanced. The space | interval between electrodes can be narrowed as the average particle diameter of a base particle is below the said upper limit.

  The method for forming a conductive layer on the surface of the base particle and the method for forming a solder layer on the surface of the base particle or the surface of the first conductive layer are not particularly limited. As a method of forming the conductive layer and the solder layer, for example, a method by electroless plating, a method by electroplating, a method by physical collision, a method by mechanochemical reaction, a method by physical vapor deposition or physical adsorption, And a method of coating the surface of the substrate particles with a paste containing metal powder or metal powder and a binder. Among these, a method using electroless plating, electroplating, or physical collision is preferable. Examples of the method by physical vapor deposition include methods such as vacuum vapor deposition, ion plating, and ion sputtering. Further, in the method based on the physical collision, for example, a sheeter composer (manufactured by Tokuju Kogakusha Co., Ltd.) or the like is used.

  The method of forming the solder layer on the surface of the base particle or the first conductive layer is preferably a method by physical collision. It is preferable that the solder layer is disposed on the surface of the base particle or the first conductive layer by physical impact.

  The material constituting the solder (solder layer) is preferably a filler material having a liquidus of 450 ° C. or less based on JIS Z3001: Welding terms. Examples of the solder composition include metal compositions containing zinc, gold, lead, copper, tin, bismuth, indium and the like. Among them, a tin-indium system (117 ° C. eutectic) or a tin-bismuth system (139 ° C. eutectic) which is low-melting and lead-free is preferable. That is, the solder preferably does not contain lead, and is preferably a solder containing tin and indium or a solder containing tin and bismuth.

  The melting point of the solder (solder layer) is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, preferably 200 ° C. or lower, more preferably 160 ° C. or lower, still more preferably 150 ° C. or lower, still more preferably 140 ° C. or lower. It is. The melting point of the solder (solder layer) is more preferably 100 ° C. or higher and 140 ° C. or lower.

  In order to further increase the bonding strength between the solder (solder layer) and the electrode, the solder is nickel, copper, antimony, aluminum, zinc, iron, gold, titanium, phosphorus, germanium, tellurium, cobalt, bismuth, manganese. Further, it may contain a metal such as chromium, tungsten, molybdenum and palladium. From the viewpoint of further increasing the bonding strength between the solder and the electrode, the solder preferably contains nickel, copper, antimony, aluminum, or zinc. From the viewpoint of further increasing the bonding strength between the solder and the electrode, the content of these metals for increasing the bonding strength is preferably 0.0001% by weight or more in 100% by weight of the solder (solder layer). Is 1% by weight or less.

  The conductive particles include base particles and a conductive layer disposed on the surface of the base particles, and the outer surface of the conductive layer is a solder layer, and the resin particles and the solder layer In the meantime, it is preferable to have the first conductive layer separately from the solder layer. In this case, the solder layer is a part of the whole conductive layer, and the first conductive layer is a part of the whole conductive layer.

  The first conductive layer different from the solder layer preferably contains a metal. The metal constituting the first conductive layer is not particularly limited. Examples of the metal include gold, silver, copper, platinum, palladium, zinc, lead, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, germanium, tungsten, molybdenum and cadmium, and alloys thereof. Is mentioned. Further, tin-doped indium oxide (ITO) may be used as the metal. As for the said metal, only 1 type may be used and 2 or more types may be used together.

  The first conductive layer is preferably a nickel layer, a palladium layer, a copper layer, or a gold layer, more preferably a nickel layer or a gold layer, and even more preferably a copper layer. The conductive particles preferably have a nickel layer, a palladium layer, a copper layer, or a gold layer, more preferably have a nickel layer or a gold layer, and still more preferably have a copper layer. By using the conductive particles having these preferable conductive layers for the connection between the electrodes, the connection resistance between the electrodes is further reduced. In addition, a solder layer can be more easily formed on the surface of these preferable conductive layers. The first conductive layer may be a solder layer. The conductive particles may have a plurality of solder layers.

  Conventionally, the particle diameter of conductive particles having a solder layer on the outer surface layer of the conductive layer has been about several hundred μm. This is because the solder layer could not be formed uniformly even if conductive particles having a particle size of several tens of μm and the surface layer being a solder layer were obtained. On the other hand, when the solder layer is formed by optimizing the dispersion conditions during electroless plating, the conductive particles have a particle size of several tens of μm, in particular, conductive particles having a particle size of 0.1 μm or more and 50 μm or less. Even when obtaining conductive particles, the solder layer can be uniformly formed on the surface of the first conductive layer. Further, even when a theta composer is used, even when conductive particles having a particle diameter of 50 μm or less are obtained, the solder layer can be uniformly formed on the surface of the first conductive layer.

  In 100% by weight of the solder and the solder layer, the content of tin is preferably less than 90% by weight, more preferably 85% by weight or less. Further, the content of tin in 100% by weight of the solder and the solder layer is appropriately determined in consideration of the melting point of the solder and the solder layer. The content of tin in 100% by weight of the solder and solder layer is preferably 5% by weight or more, more preferably 10% by weight or more, and still more preferably 20% by weight or more.

  The thicknesses of the first conductive layer and the solder layer are each preferably 10 nm or more, more preferably 50 nm or more, still more preferably 100 nm or more, preferably 2000 nm or less, more preferably 1000 nm or less. When the thickness of the first conductive layer and the solder layer is not less than the above lower limit, the conductivity is sufficiently high. When the thickness of the first conductive layer and the solder layer is not more than the above upper limit, the difference in coefficient of thermal expansion between the base particles and the first conductive layer and the solder layer is reduced, and the first conductive layer and the solder layer Peeling is less likely to occur.

  The first conductive layer may have a stacked structure of two or more layers. When the first conductive layer has a laminated structure of two or more layers, the thickness of the outermost layer in the first conductive layer is preferably 5 nm or more, more preferably 10 nm or more, still more preferably 25 nm or more, and particularly preferably Is 50 nm or more, preferably 1000 nm or less, more preferably 500 nm or less. When the thickness of the outermost layer in the first conductive layer is not less than the above lower limit, the conductivity is sufficiently high. When the thickness of the outermost layer in the first conductive layer is not more than the above upper limit, the difference in thermal expansion coefficient between the base particles and the outermost layer of the first conductive layer is reduced, and the outermost layer of the first conductive layer Peeling is less likely to occur.

  The average particle diameter of the conductive particles is preferably 0.1 μm or more, more preferably 1 μm or more, preferably 100 μm or less, more preferably 80 μm or less, still more preferably 50 μm or less, and particularly preferably 40 μm or less. When the average particle diameter of the conductive particles is not less than the above lower limit and not more than the above upper limit, the contact area between the conductive particles and the electrode is sufficiently large, and aggregated conductive particles are formed when the conductive layer is formed. It becomes difficult. Moreover, it becomes a size suitable for the conductive particles in the conductive paste, the interval between the electrodes connected via the conductive particles does not become too large, and the conductive layer is difficult to peel from the surface of the base particle.

  The average particle diameter of the conductive particles is particularly preferably 10 μm or more, and most preferably 10 μm or more and 40 μm or less. A configuration in which the storage elastic modulus at 90 ° C. of the binder resin or the conductive paste is controlled within a specific range, and the binder resin includes a thermal radical polymerizable compound and a thermal radical polymerization initiator as essential components. Furthermore, by adopting a configuration in which the average particle diameter of the conductive particles is 10 μm or more, it is possible to further suppress the inclusion of bubbles at the time of curing, and to further generate voids in the cured product. Can be suppressed.

  The resin particles can be properly used depending on the electrode size or land diameter of the substrate to be mounted.

  From the viewpoint of more reliably connecting the upper and lower electrodes and further suppressing the short circuit between the electrodes adjacent in the lateral direction, the ratio of the average particle diameter C of the conductive particles to the average particle diameter A of the resin particles ( C / A) is more than 1.0, preferably 3.0 or less. When the first conductive layer is between the resin particles and the solder layer, the ratio of the average particle diameter B of the conductive particle portion excluding the solder layer to the average particle diameter A of the resin particles (B / A) is greater than 1.0, preferably 2.0 or less. Further, when there is the first conductive layer between the resin particles and the solder layer, the average particle diameter B of the conductive particle portion excluding the solder layer having the average particle diameter C of the conductive particles including the solder layer. The ratio (C / B) to is more than 1.0, preferably 2.0 or less. When the ratio (B / A) is within the above range or the ratio (C / B) is within the above range, electrodes that are more reliably connected between the upper and lower electrodes and that are adjacent in the lateral direction The short circuit between them can be further suppressed.

Conductive paste for FOB and FOF applications:
The conductive paste according to the present invention is suitably used for connection between a flexible printed circuit board and a glass epoxy board (FOB (Film on Board)) or connection between a flexible printed circuit board and a flexible printed circuit board (FOF (Film on Film)). It is done.

  In FOB and FOF applications, L & S, which is the size of a portion (line) with an electrode and a portion (space) without an electrode, is generally 100 to 500 μm. The average particle diameter of the resin particles used for FOB and FOF applications is preferably 10 to 100 μm. When the average particle diameter of the resin particles is 10 μm or more, the thickness of the conductive paste disposed between the electrodes and the connection portion is sufficiently increased, and the adhesive force is further increased. When the average particle diameter of the resin particles is 100 μm or less, a short circuit is more unlikely to occur between adjacent electrodes.

Conductive paste for flip chip applications:
The conductive paste according to the present invention is suitably used for flip chip applications.

  For flip chip applications, the land diameter is generally 15-80 μm. The average particle size of the resin particles used for flip chip applications is preferably 1 to 15 μm. When the average particle diameter of the resin particles is 1 μm or more, the thickness of the solder layer disposed on the surface of the resin particles can be sufficiently increased, and the electrodes can be more reliably electrically connected. it can. When the average particle diameter of the resin particles is 15 μm or less, a short circuit is more unlikely to occur between adjacent electrodes.

Conductive paste for COF:
The electrically conductive paste which concerns on this invention is used suitably for the connection (COF (Chip on Film)) of a semiconductor chip and a flexible printed circuit board.

  In a COF application, L & S, which is a dimension between a portion (line) with an electrode and a portion (space) without an electrode (space), is generally 10 to 50 μm. The average particle diameter of the resin particles used for COF applications is preferably 1 to 10 μm. When the average particle diameter of the resin particles is 1 μm or more, the thickness of the solder layer disposed on the surface of the resin particles can be sufficiently increased, and the electrodes can be more reliably electrically connected. it can. When the average particle diameter of the resin particles is 10 μm or less, a short circuit is more unlikely to occur between adjacent electrodes.

  The “average particle diameter” of the base material particles (the resin particles and the like) and the conductive particles indicates a number average particle diameter. The average particle diameter of the substrate particles (resin particles and the like) and the conductive particles is obtained by observing 50 arbitrary conductive particles with an electron microscope or an optical microscope and calculating an average value.

  In 100% by weight of the conductive paste, the content of the conductive particles is preferably 3% by weight or more, and preferably 40% by weight or less. When the content of the conductive particles is 3% by weight or more and 40% by weight or less, both conductivity and insulation can be achieved at a higher level when performing anisotropic conductive connection. . In 100% by weight of the conductive paste, the content of the conductive particles is more preferably 5% by weight or more, still more preferably 10% by weight or more, still more preferably 15% by weight or more, more preferably 35% by weight or less, more More preferably, it is 30% by weight or less. When the content of the conductive particles in 100% by weight of the conductive paste is not less than the above lower limit and not more than the above upper limit, the conductive particles can be easily disposed between the upper and lower electrodes to be connected. Furthermore, it becomes difficult to electrically connect adjacent electrodes that should not be connected via a plurality of conductive particles. That is, a short circuit between adjacent electrodes can be further prevented.

(Other ingredients)
The conductive paste preferably contains a filler. By using the filler, the thermal expansion coefficient of the cured product of the conductive paste can be suppressed. Specific examples of the filler include silica, aluminum nitride, alumina, glass, boron nitride, silicon nitride, silicone, carbon, graphite, graphene, and talc. As for a filler, only 1 type may be used and 2 or more types may be used together. When a filler having a high thermal conductivity is used, the main curing time is shortened.

  The conductive paste may contain a solvent. By using the solvent, the viscosity of the conductive paste can be easily adjusted. Examples of the solvent include ethyl acetate, methyl cellosolve, toluene, acetone, methyl ethyl ketone, cyclohexane, n-hexane, tetrahydrofuran, and diethyl ether.

  From the viewpoint of further improving the connection reliability of the connection target member, the conductive paste preferably contains an adhesion promoter. Examples of the adhesion-imparting agent include a coupling agent and a flexible material. As for the said adhesion imparting agent, only 1 type may be used and 2 or more types may be used together.

  In 100% by weight of the conductive paste, the content of the adhesion-imparting agent is preferably 0.1% by weight or more, more preferably 1% by weight or more, preferably 10% by weight or less, more preferably 5% by weight or less. When the content of the adhesion imparting agent is not less than the above lower limit and not more than the above upper limit, the connection reliability of the connection target member is further increased.

(Details and uses of conductive paste)
In the conductive paste according to the present invention, it is preferable that only heating is performed for curing, and it is preferable that no light irradiation is performed for curing. Note that light irradiation is not performed does not include exposure to natural light, and the conductive paste is not actively irradiated with light using a light irradiation device or the like in order to cure the conductive paste. Means.

  The conductive paste according to the present invention is preferably an anisotropic conductive paste. The conductive paste according to the present invention is preferably used for connection between electrodes, preferably a circuit connection material, and more preferably a circuit connection material used for electrical connection between electrodes.

  The conductive paste according to the present invention is a conductive paste, and is preferably a conductive paste that is applied on a connection target member in a paste state.

  The viscosity of the conductive paste at 25 ° C. is preferably 3 Pa · s or more, more preferably 5 Pa · s or more, preferably 500 Pa · s or less, more preferably 300 Pa · s or less. When the viscosity is equal to or higher than the lower limit, sedimentation of conductive particles in the conductive paste can be suppressed. When the viscosity is equal to or lower than the upper limit, the dispersibility of the conductive particles is further increased. If the viscosity of the conductive paste before coating is within the above range, after applying the conductive paste on the first connection target member, the flow of the conductive paste before curing can be further suppressed, and the voids are further reduced. It becomes difficult to occur. The paste form includes liquid.

  It is preferable that the electrically conductive paste which concerns on this invention is an electrically conductive paste used in order to connect the connection object member which has a copper electrode. When a connection target member having a copper electrode is connected using a conductive paste, there is a problem that migration is likely to occur due to the copper electrode in the connection structure. On the other hand, by using the conductive paste according to the present invention, even if a connection target member having a copper electrode is connected, migration in the connection structure can be effectively suppressed, and insulation reliability can be effectively increased. it can.

  The electrically conductive paste which concerns on this invention can be used in order to adhere | attach various connection object members. The conductive paste is suitably used for obtaining a connection structure in which the first and second connection target members are electrically connected.

  The connection structure according to the present invention includes a first connection target member having a first electrode on the surface, a second connection target member having a second electrode on the surface, and the first and second connection targets. A connecting portion for connecting members, wherein the connecting portion is formed of the above-described conductive paste, and the first electrode and the second electrode are electrically connected by the conductive particles. ing.

  The manufacturing method of the connection structure according to the present invention includes a first connection target member having a first electrode on the surface, a second connection target member having a second electrode on the surface, and the above-described conductive paste. Using the step of disposing the conductive paste between the first connection target member and the second connection target member, heating and curing the conductive paste, and the first connection target member Forming a connection portion connecting the second connection target member. In the manufacturing method of the connection structure according to the present invention, a connection structure in which the first electrode and the second electrode are electrically connected by the conductive particles is obtained.

  In the connection structure according to the present invention and the method for manufacturing the connection structure according to the present invention, it is preferable to perform only heating in order to cure the conductive paste, and no light is irradiated to cure the conductive paste. It is preferable.

  The connection structure 21 shown in FIG. 4 includes a first connection target member 22, a second connection target member 23, and a connection portion that electrically connects the first and second connection target members 22 and 23. 24. The first connection target member 22 and the second connection target member 23 are electronic components. The connection part 24 is formed of a conductive paste containing the conductive particles 1. In FIG. 4, the conductive particles 1 are schematically shown for convenience of illustration.

  The first connection target member 22 has a plurality of first electrodes 22b on the surface 22a (upper surface). The second connection target member 23 has a plurality of second electrodes 23b on the surface 23a (lower surface). The first electrode 22 b and the second electrode 23 b are electrically connected by one or a plurality of conductive particles 1. Accordingly, the first and second connection target members 22 and 23 are electrically connected by the conductive particles 1.

The manufacturing method of the connection structure is not particularly limited. As an example of the manufacturing method of this connection structure, after arrange | positioning the said electrically conductive paste between the said 1st connection object member and the said 2nd connection object member, obtaining a laminated body, heating this laminated body And a method of applying pressure. The solder layer of the conductive particles 1 is melted by heating and pressurization, and the electrodes are electrically connected by the conductive particles 1. Further, when the binder resin contains a thermosetting compound, the binder resin is cured, and the first and second connection target members 22 and 23 are connected by the cured binder resin. The pressure of the said pressurization is about 9.8 * 10 < ⁴ > -4.9 * 10 < ⁶ > Pa. The temperature of the said heating is about 120-220 degreeC.

  FIG. 5 is an enlarged front sectional view of a connection portion between the conductive particle 1 and the first and second electrodes 22b and 23b in the connection structure 21 shown in FIG. As shown in FIG. 5, in the connection structure 21, after the solder layer 5 in the conductive particles 1 is melted by heating and pressurizing the laminate, the melted solder layer portions 5a are first and second. It is in sufficient contact with the electrodes 22b and 23b. That is, by using the conductive particles 1 whose surface layer is the solder layer 5, the conductive particles are compared with the case where the surface layer of the conductive layer is a metal such as nickel, gold or copper. 1 and the contact area between the electrodes 22b and 23b increase. For this reason, the conduction | electrical_connection reliability of the connection structure 21 becomes high. In general, the flux is gradually deactivated by heating.

  If the said 1st, 2nd connection object member is an electronic component, it will not specifically limit. Specifically, the first and second connection target members include electronic components such as semiconductor chips, capacitors, and diodes, and circuit boards such as printed boards, flexible printed boards, glass epoxy boards, and glass boards. Examples include parts. The conductive paste is preferably a conductive paste used for connecting electronic components. The conductive paste according to the present invention is preferably used for electrical connection of electrodes of electronic components.

  In the connection structure, 1/5 or more of the total area of the connection portion between the connection portion and the first connection target member, and the connection portion between the connection portion and the second connection target member, It is preferable that they are connected by components other than the conductive particles contained in the conductive paste. In other words, in the connection structure, 1/5 of the total area of the connection portion between the connection portion and the first connection target member and the connection portion between the connection portion and the second connection target member. It is preferable that less than is connected by the conductive particles contained in the conductive paste. In this case, the thermal shock resistance of the connection structure is further enhanced.

  Examples of the electrode provided on the connection target member include metal electrodes such as a gold electrode, a nickel electrode, a tin electrode, an aluminum electrode, a copper electrode, a silver electrode, a molybdenum electrode, and a tungsten electrode. When the connection object member is a flexible printed board, the electrode is preferably a gold electrode, a nickel electrode, a tin electrode, or a copper electrode. When the connection target member is a glass substrate, the electrode is preferably an aluminum electrode, a copper electrode, a molybdenum electrode, or a tungsten electrode. In addition, when the said electrode is an aluminum electrode, the electrode formed only with aluminum may be sufficient and the electrode by which the aluminum layer was laminated | stacked on the surface of the metal oxide layer may be sufficient. Examples of the material for the metal oxide layer include indium oxide doped with a trivalent metal element and zinc oxide doped with a trivalent metal element. Examples of the trivalent metal element include Sn, Al, and Ga.

  It is preferable that at least one of the first electrode and the second electrode is a copper electrode. Both the first electrode and the second electrode are preferably copper electrodes. In this case, the flux effect by the electrically conductive paste which concerns on this invention is acquired further, and the conduction | electrical_connection reliability in a connection structure becomes still higher.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. The present invention is not limited only to the following examples.

  In the examples and comparative examples, the following materials were used.

[Binder resin]
(Curable compound)
Thermal radical polymerizable compound 1 (“Divinylbenzene” manufactured by Wako Pure Chemical Industries, Ltd.)
Thermally radical polymerizable compound 2 (“Trimethylpropane trimethacrylate” manufactured by Wako Pure Chemical Industries, Ltd.)
Epoxy compound 1 (DIC Corporation "HP-4032D")
Epoxy compound 2 (“EXA-830CRP” manufactured by DIC)

(Curing agent)
Thermal radical polymerization initiator 1 (“V-60” manufactured by Wako Pure Chemical Industries, Ltd.)
Thermal radical polymerization initiator 2 (“V-601” manufactured by Wako Pure Chemical Industries, Ltd.)
Thermosetting agent 1 ("HX-3722" manufactured by Asahi Kasei Corporation)
Thermosetting agent 2 ("HX-3922" manufactured by Asahi Kasei Corporation)

(Thiol compound)
Thiol compound 1 (having three thiol groups, “TMMP” manufactured by Sakai Chemical Industry Co., Ltd.)
Thiol compound 2 (having 6 thiol groups, “DPMP” manufactured by Sakai Chemical Industry Co., Ltd.)

(flux)
Glutaric acid citric acid

(Conductive particles)
Conductive particles 1: Au plated particles of divinylbenzene resin particles (“Au-210” manufactured by Sekisui Chemical Co., Ltd., average particle diameter: 10 μm)
Conductive particle A: Conductive particle A (average particle diameter of 15 μm) having a metal layer in which a nickel plating layer is formed on the surface of divinylbenzene resin particles and a gold plating layer is formed on the surface of the nickel plating layer )
Conductive particle B: conductive particle B in which a copper layer is formed on the surface of divinylbenzene resin particles, and a solder layer is formed on the surface of the copper layer
[Method for Producing Conductive Particle B]
Divinylbenzene resin particles having an average particle diameter of 10 μm (“Micropearl SP-210” manufactured by Sekisui Chemical Co., Ltd.) were subjected to electroless nickel plating to form a base nickel plating layer having a thickness of 0.1 μm on the surface of the resin particles. Next, the resin particles on which the base nickel plating layer was formed were subjected to electrolytic copper plating to form a 1 μm thick copper layer. Furthermore, electrolytic plating was performed using an electrolytic plating solution containing tin and bismuth to form a solder layer having a thickness of 1 μm. Thus, a 1 μm thick copper layer is formed on the surface of the resin particles, and a 1 μm thick solder layer (tin: bismuth = 43 wt%: 57 wt%) is formed on the surface of the copper layer. Conductive particles B were prepared.
Conductive particles C: SnBi solder particles (“DS-10” manufactured by Mitsui Kinzoku Co., Ltd., average particle diameter (median diameter) 12 μm)
Conductive particle D: SnBi solder particle (average particle diameter (median diameter) 8 μm)
Conductive particle E: SnBi solder particle (average particle diameter (median diameter) 35 μm)
Conductive particle F: SnBi solder particle (average particle diameter (median diameter) 50 μm)

(Other ingredients)
Adhesive agent (Shin-Etsu Chemical Co., Ltd. “KBE-403”)

(Examples 1 to 26 and Comparative Examples 1 and 2)
The components shown in Tables 1 and 2 below were blended in the blending amounts shown in Tables 1 and 2 to obtain anisotropic conductive pastes.

(Preparation of connection structure A)
A glass epoxy substrate (FR-4 substrate) having a copper electrode pattern (copper electrode thickness 10 μm) with L / S of 100 μm / 100 μm on the upper surface was prepared. Moreover, the flexible printed circuit board which has a copper electrode pattern (copper electrode thickness 10 micrometers) with L / S of 100 micrometers / 100 micrometers on the lower surface was prepared.

  The obtained anisotropic conductive paste was applied on the upper surface of the glass epoxy substrate so as to have a thickness of 30 μm to form an anisotropic conductive paste layer. Next, in order to advance hardening of an anisotropic electrically conductive paste layer, it heated at 70 degreeC. Next, the said flexible printed circuit board was laminated | stacked so that electrodes might oppose on the upper surface of the anisotropic conductive paste layer which hardening advanced. Then, while adjusting the temperature of the head so that the temperature of the anisotropic conductive paste layer is 185 ° C., a pressure heating head is placed on the upper surface of the flexible printed circuit board, and a pressure of 2.0 MPa is applied. The conductive paste layer was fully cured at 185 ° C. to obtain a connection structure A. Here, when obtaining the connection structure, in order to cure the anisotropic conductive paste, only heating was performed and no light was irradiated.

(Preparation of connection structure B)
A glass epoxy substrate (FR-4 substrate) having a copper electrode pattern (copper electrode thickness 10 μm) with L / S of 75 μm / 75 μm on the upper surface was prepared. Moreover, the flexible printed circuit board which has a copper electrode pattern (copper electrode thickness 10 micrometers) whose L / S is 75 micrometers / 75 micrometers on the lower surface was prepared.

  A connection structure B was obtained in the same manner as the connection structure A except that a glass epoxy substrate and a flexible printed circuit board having different L / S were used.

(Evaluation)
(1) Storage elastic modulus About the obtained anisotropic conductive paste, it measured using a rheometer apparatus ("VAR-100" by Jusco) as conditions of a shear rate and constant strain, and stored at 90 degreeC. The elastic modulus was determined.

  Further, a binder resin was obtained in the same manner except that the conductive particles were not blended when producing the anisotropic conductive paste. About the obtained binder resin, it measured using the rheometer apparatus ("VAR-100" by Jusco) as conditions of a shear rate and a fixed strain, and calculated | required the storage elastic modulus in 90 degreeC. As a result, the storage elastic modulus at 90 ° C. of the binder resin showed the same value as the storage elastic modulus at 90 ° C. of the conductive paste. The storage modulus of the binder resin may be measured using the obtained binder resin after removing conductive particles from the obtained conductive paste to obtain a binder resin.

(2) Presence / absence of voids At the time of producing the connection structure, the connection structure was observed with a microscope, and the voids were evaluated. The presence or absence of voids was determined according to the following criteria.

[Judgment criteria for occurrence of voids]
○: No void at all △: Several voids exist ×: Many voids exist

(3) Conductivity test between upper and lower electrodes The connection resistance between the upper and lower electrodes of the obtained connection structure was measured by a four-terminal method, respectively. The average value of the two connection resistances was calculated. Note that the connection resistance can be obtained by measuring the voltage when a constant current is passed from the relationship of voltage = current × resistance. The continuity test between the upper and lower electrodes was judged according to the following criteria.

[Criteria for continuity test]
○○: Average value of connection resistance is 8.0Ω or less ○: Average value of connection resistance exceeds 8.0Ω and 10.0Ω or less △: Average value of connection resistance exceeds 10.0Ω and 15.0Ω or less × Average connection resistance exceeds 15.0Ω

(4) Insulation test between electrodes adjacent in the lateral direction In the obtained connection structure, the presence or absence of leakage between adjacent electrodes was evaluated by measuring resistance with a tester. The insulation test was judged according to the following criteria.

[Criteria for insulation test]
○: Resistance exceeds 1000 MΩ Δ: Resistance exceeds 500 MΩ and less than 1000 MΩ ×: Resistance is 500 MΩ or less

(5) Adhesive strength In the obtained connection structure, 90 degree | times peeling was performed and the adhesive strength was measured. The adhesive strength was determined according to the following criteria.

[Adhesion criteria]
○: Adhesive strength of 15 N or more Δ: Adhesive strength of 5 N or more and less than 15 N

  The compositions and results are shown in Tables 1 and 2 below.

DESCRIPTION OF SYMBOLS 1 ... Conductive particle 1a ... Surface 2 ... Resin particle 2a ... Surface 3 ... Conductive layer 4 ... 1st conductive layer 4a ... Surface 5 ... Solder layer 5a ... Molten solder layer part 11 ... Conductive particle 12 ... Solder layer 16 ... Solder particles 21 ... Connection structure 22 ... First connection object member 22a ... Surface 22b ... First electrode 23 ... Second connection object member 23a ... Surface 23b ... Second electrode 24 ... Connection part

Claims (13)

Including a binder resin and conductive particles,
The binder resin contains a thermal radical polymerizable compound and a thermal radical polymerization initiator,
The electrically conductive paste whose storage elastic modulus in 90 degreeC of the said binder resin is 8 Pa or more and less than 50 Pa , or whose storage elastic modulus in 90 degreeC of an electrically conductive paste is 8 Pa or more and less than 50 Pa .   The conductive paste according to claim 1, wherein only heating is performed for curing.   The conductive paste according to claim 1 or 2, wherein irradiation with light is not performed for curing.   The electrically conductive paste of any one of Claims 1-3 in which the said binder resin contains an epoxy compound and the thermosetting agent different from a thermal radical polymerization initiator.   The electrically conductive paste of any one of Claims 1-4 in which the said binder resin contains a thiol compound.   The conductive paste according to claim 5, wherein the thiol compound has a plurality of thiol groups.   The conductive paste according to claim 1, wherein the conductive particles are conductive particles having at least a conductive outer surface made of solder. The electrically conductive paste of any one of Claims 1-7 whose storage elastic modulus in 90 degreeC of the said binder resin is 8 Pa or more and less than 50 Pa . The electrically conductive paste of any one of Claims 1-8 whose storage elastic modulus in 90 degreeC of an electrically conductive paste is 8 Pa or more and less than 50 Pa .   The electrically conductive paste of any one of Claims 1-9 which is a circuit connection material used for the electrical connection between electrodes. A first connection object member having a first electrode on its surface;
A second connection target member having a second electrode on its surface;
A connection portion that connects the first connection target member and the second connection target member, and the connection portion is formed of the conductive paste according to any one of claims 1 to 10. And
A connection structure in which the first electrode and the second electrode are electrically connected by the conductive particles. A first connection target member having a first electrode on the surface, a second connection target member having a second electrode on the surface, and the conductive paste according to any one of claims 1 to 10. And
Disposing the conductive paste between the first connection target member and the second connection target member;
Heating and curing the conductive paste, and forming a connection portion connecting the first connection target member and the second connection target member,
A method for manufacturing a connection structure, wherein a connection structure in which the first electrode and the second electrode are electrically connected by the conductive particles is obtained.   The manufacturing method of the connection structure of Claim 12 which does not irradiate light in order to harden the said electrically conductive paste.

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