JP2013140756A - Insulative material, multilayer film, laminate, connection structure, manufacturing method of laminate, and manufacturing method of connection structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an insulative material which offers good laminatability or easiness of pickup because of having less surface stickiness, and which allows the alignment between electrodes because of its high transparency.SOLUTION: An insulative material according to the invention is used on a first connection target member 2 having a plurality of first protruding electrodes 2b on a surface 2a thereof in such a way that it is placed over the first electrodes 2b and gaps X therebetween to cover the first electrodes 2b. The insulative material is shaped in a film form. The insulative material has a haze value of 70% or smaller. As to the insulative material, the surface probe tack measured by use of a 5-mmφ probe at 25°C is 500 mN/5 mmφ or smaller.

Description

  In the first connection object member having a plurality of protruding first electrodes on the surface, the present invention provides a plurality of the plurality of the first electrodes and a plurality of the first electrodes on the gaps between the plurality of the first electrodes. The present invention relates to an insulating material used by being laminated so as to cover a first electrode. The present invention also relates to a multilayer film, a laminate, a connection structure, a method for manufacturing the laminate, and a method for manufacturing the connection structure using the insulating material.

  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 manufacturing method of the connection structure, in Patent Document 1 below, a protruding electrode formed to protrude on a main surface of an electronic component is connected to a connection electrode formed on a mounting substrate, and the main structure is described above. A method of manufacturing a connection structure is disclosed in which the electronic component is mounted on the mounting substrate with the surface facing the mounting substrate. The manufacturing method of the connection structure described in Patent Document 1 is an electronic component preparation step of preparing the electronic component in which an insulating adhesive layer is formed on the main surface so as to embed the protruding electrode on the main surface. A mounting substrate preparing step for forming an anisotropic conductive adhesive layer including an insulating adhesive base material and conductive particles dispersed in the adhesive base material on the mounting substrate; and the electronic component preparation. An electronic component crimping step of pressurizing and crimping the electronic component prepared in the step and the mounting substrate prepared in the mounting substrate preparing step.

  In the electronic component preparation step, the thickness of the insulating adhesive layer of the electronic component is formed to be substantially the same as the height of the protruding electrode. In the mounting substrate preparing step, the anisotropic conductive adhesive layer is formed so that the thickness of the anisotropic conductive adhesive layer is substantially the same as the particle size of the conductive particles.

  Patent Document 1 describes a reactive resin, a latent curing agent, an organic solvent, an inorganic filler, rubber particles, and the like as components used in the insulating adhesive layer.

  In Patent Document 2 below, an insulating adhesive layer is projected on at least one projecting electrode surface on a first substrate having a projecting electrode and a second substrate having a projecting electrode facing the projecting electrode. Anisotropic conductivity in which conductive particles are dispersed in an adhesive having an insulating property between the first substrate and the second substrate, and disposed at the same height as the electrode or thicker than the protruding electrode. Disclosed is a method for manufacturing a connection structure in which an adhesive is placed and pressed or heated under pressure. In the manufacturing method of the connection structure described in Patent Document 2, the protruding electrodes facing each other between the first substrate and the second substrate are electrically connected by contacting conductive particles, and adjacent to each other. The projecting electrodes to be insulated are insulated and fixed.

  Patent Document 2 describes that the adhesive constituting the insulating adhesive layer is preferably a reactive resin such as an epoxy resin or an acrylic resin that reacts with heat or light.

JP 2009-147231 A Japanese Patent No. 3596572

  The surface of the insulating adhesive layer described in Patent Documents 1 and 2 may be sticky. For this reason, when an adhesive bond layer is a film, there exists a problem that the laminating property of this film is low. Further, for example, when the electronic component or substrate with an adhesive layer is picked up after temporarily storing the electronic component or substrate with an adhesive layer in a container, a pickup failure may occur.

  Furthermore, the transparency of conventional insulating adhesive layers may be low. For this reason, it may be difficult to confirm the position of the electrode in an electronic component or a board | substrate through an adhesive bond layer. Therefore, it may be difficult to reliably connect the electrodes by facing the electrodes of the electronic component or the substrate on the substrate.

  Further, when a conventional insulating adhesive layer is used, there is a problem that in the obtained connection structure, electrode migration occurs and insulation failure is likely to occur.

  Furthermore, in the manufacturing method of the conventional connection structure as described in Patent Document 1, the thickness of the insulating adhesive layer is substantially the same as the height of the protruding electrode so as to embed the protruding electrode on the main surface, And the thickness of an anisotropic conductive adhesive layer is substantially the same as the particle size of electroconductive particle. For this reason, the flow of the insulating adhesive layer and the anisotropic conductive adhesive layer hardly occurs in the crimping process. Therefore, it is difficult to eliminate voids generated between the insulating adhesive layer and the anisotropic conductive adhesive layer, or between the protruding electrode and the anisotropic conductive adhesive layer, and further improve the insulation reliability. It is difficult to improve.

  An object of the present invention is that the surface is less sticky, so that the laminating property or pick-up property can be improved, and furthermore, since the transparency is high, an insulating material that can easily perform alignment between electrodes, and It is providing the multilayer film, laminated body, connection structure, manufacturing method of a laminated body, and manufacturing method of a connection structure using this insulating material.

  A limited object of the present invention is to provide an insulating material capable of obtaining a connection structure with high insulation reliability, and a multilayer film, a laminate, a connection structure, a method for manufacturing the laminate, and a connection structure using the insulating material It is to provide a body manufacturing method.

  According to a wide aspect of the present invention, in the first connection target member having a plurality of protruding first electrodes on the surface, on the plurality of first electrodes and on the gaps between the plurality of first electrodes. , An insulating material used by being laminated so as to cover the plurality of first electrodes, in a film form, having a haze value of 70% or less, and measured at 25 ° C. using a 5 mmφ probe An insulating material having a surface probe tack of 500 mN / 5 mmφ or less is provided.

  In a specific aspect of the insulating material according to the present invention, an epoxy compound and a polymer having a weight average molecular weight of 10,000 or more and 250,000 or less are included.

  In another specific aspect of the insulating material according to the present invention, an ion scavenger is included.

  In another specific aspect of the insulating material according to the present invention, the first connection target member is a semiconductor wafer or a semiconductor chip.

  In still another specific aspect of the insulating material according to the present invention, the first electrode is a copper electrode.

  The multilayer film according to the present invention includes an insulating film and a B-staged anisotropic conductive film laminated on one surface of the insulating film, and the insulating film is formed of the insulating material described above. The B-staged anisotropic conductive film uses an anisotropic conductive material containing a curable component and conductive particles, and removes the solvent of the anisotropic conductive material or advances the curing. Is formed.

  The laminate according to the present invention includes a first connection target member having a plurality of protruding first electrodes on the surface, a plurality of the first electrodes, and a gap between the plurality of first electrodes. And an insulating layer laminated so as to cover the plurality of first electrodes, and the insulating layer is formed of the above-described insulating material.

  In a specific aspect of the laminate according to the present invention, a B-staged anisotropic conductive layer is further provided on the surface of the insulating layer opposite to the first connection target member side, and the B The staged anisotropic conductive layer is formed by using an anisotropic conductive material containing a curable component and conductive particles, by removing the solvent of the anisotropic conductive material or by proceeding with curing. Yes.

  The connection structure according to the present invention includes a first connection target member having a plurality of protruding first electrodes on the surface, an insulating layer stacked on a gap between the plurality of first electrodes, and the insulation A cured product layer laminated on a surface opposite to the first connection target member side of the layer, a cured product layer laminated on a surface opposite to the insulating layer side of the cured product layer, and a plurality of layers A second connection target member having a second electrode on the surface, the insulating layer is formed of the above-described insulating material, and the cured product layer is a different material containing a curable component and conductive particles. The anisotropic conductive material is formed by main curing using an anisotropic conductive material, and the plurality of first electrodes and the plurality of second electrodes are electrically connected by the conductive particles. It is connected.

  On the specific situation with the connection structure which concerns on this invention, the said insulating layer is laminated | stacked on the at least one part area | region on the said some 1st electrode, and the clearance gap between the said 1st electrode.

  The manufacturing method of the laminated body which concerns on this invention uses the 1st connection object member which has the several 1st electrode which protruded on the surface, and on between several said 1st electrodes and between several said 1st electrodes A step of laminating an insulating layer on the gap so as to cover the plurality of first electrodes, and the insulating layer is formed of the above-described insulating material.

  The manufacturing method of the connection structure according to the present invention includes a first connection target member having a plurality of protruding first electrodes on the surface, a plurality of the first electrodes, and a plurality of the first electrodes. A laminate comprising an insulating layer laminated to cover the plurality of first electrodes in the gap, a second connection target member having a plurality of second electrodes on the surface, and the second connection target member And a second laminate including a B-staged anisotropic conductive layer laminated on the surface of the first connection target member, the insulating layer, and the B-staged anisotropic conductive layer, The second connection target member is laminated in this order, or the first connection target member having a plurality of protruding first electrodes on the surface, the plurality of first electrodes, and the plurality of the above An insulating layer laminated so as to cover a plurality of the first electrodes in a gap between the first electrodes; A laminated body comprising a B-staged anisotropic conductive layer laminated on a surface opposite to the first connection target member side of the second connection target member having a plurality of second electrodes on the surface And laminating the first connection target member, the insulating layer, the B-staged anisotropic conductive layer, and the second connection target member in this order, and the B-staged anisotropic And a main curing step of electrically connecting the first and second connection target members by the cured material layer to form a cured material layer, and the insulating layer is as described above. Whether the B-staged anisotropic conductive layer formed of an insulating material uses an anisotropic conductive material containing a curable component and conductive particles to remove the solvent of the anisotropic conductive material. Alternatively, the first electrode and the B stage are formed by advancing curing. Excluding the insulating layer portion between the conductive particles contained in the anisotropic conductive layer, bringing the conductive particles into contact with the first and second electrodes, and a plurality of the first particles A connection structure in which the insulating layer is laminated on the gap between the electrodes is obtained.

  The insulating material according to the present invention is in the form of a film, has a haze value of 70% or less, and has a surface probe tack at 25 ° C. measured using a 5 mmφ probe of 500 mN / 5 mmφ or less. Less sticky and highly transparent.

  Since the surface of the insulating material according to the present invention has little stickiness, the laminating property or picking up property can be improved. Furthermore, since the insulating material according to the present invention is highly transparent, alignment between the electrodes can be easily performed.

FIG. 1 is a cross-sectional view schematically showing a laminate according to the first embodiment of the present invention. FIGS. 2A to 2C are schematic cross-sectional views for explaining each step of the method for manufacturing a laminate according to the first embodiment of the present invention. FIG. 3 is a cross-sectional view schematically showing the connection structure according to the first embodiment of the present invention. 4A to 4C are schematic cross-sectional views for explaining each step of the method for manufacturing the connection structure according to the first embodiment of the present invention. FIGS. 5A to 5C are views of a method for manufacturing a second laminate having a second connection target member and a B-staged anisotropic conductive layer used for manufacturing the connection structure shown in FIG. It is typical sectional drawing for demonstrating each process. FIG. 6 is a cross-sectional view schematically showing a laminate according to the second embodiment of the present invention. FIGS. 7A to 7C are schematic cross-sectional views for explaining each step of the method for manufacturing a laminate according to the second embodiment of the present invention. FIG. 8 is a cross-sectional view schematically showing a connection structure according to the second embodiment of the present invention. FIGS. 9A to 9C are schematic cross-sectional views for explaining each step of the method for manufacturing the connection structure according to the second embodiment of the present invention. FIG. 10 is a cross-sectional view showing a laminated film in which a film-like insulating material used for obtaining a laminated body according to the first and second embodiments of the present invention is laminated on a release film. FIG. 11 is a cross-sectional view showing a multilayer film that can be used to obtain a laminate according to the second embodiment of the present invention.

  Details of the present invention will be described below.

(Insulation material)
In the first connection object member having a plurality of protruding first electrodes on the surface, the insulating material according to the present invention is formed on the plurality of first electrodes and on the gaps between the plurality of first electrodes. The insulating material is used by being laminated so as to cover the plurality of first electrodes. The insulating material according to the present invention has insulating properties.

  The insulating material according to the present invention is in the form of a film. The insulating material according to the present invention is an insulating film. The haze value of the insulating material according to the present invention is 70% or less. In the insulating material according to the present invention, the probe tack on the surface at 25 ° C. measured using a 5 mmφ probe is 500 mN / 5 mmφ or less.

  Since the insulating material according to the present invention has the above-described configuration, the surface of the insulating material is less sticky and the insulating material is highly transparent.

  Since the surface of the insulating material according to the present invention has little stickiness, the laminating property or picking up property can be improved. For example, a film-like insulating material can be satisfactorily laminated on the first connection target member or the B-staged anisotropic conductive film. Further, the film-like insulating material, the first connection target member laminated with the film-like insulating material, or the B-staged anisotropic conductive film laminated with the film-like insulating material was temporarily stored in the container. Later, when these are picked up, the occurrence of chipping can be suppressed and the pickup can be made well and easily.

  Furthermore, since the insulating material according to the present invention is highly transparent, alignment between the electrodes can be easily performed. For example, the position of the electrode can be easily confirmed via a film-like insulating material. For this reason, the conduction | electrical_connection reliability of the connection structure using a film-form insulating material can be improved.

  Furthermore, since the insulating material according to the present invention has the above-described configuration, in the first connection target member having a plurality of protruding first electrodes on the surface using the insulating material according to the present invention, a plurality of the above A laminated body is obtained by laminating an insulating layer (film-like insulating material) on the first electrode and on the gaps between the plurality of first electrodes so as to cover the plurality of first electrodes, Furthermore, when a connection structure is obtained using the laminate, the insulation reliability of the obtained connection structure is improved.

  When the haze value of the insulating material is 70% or less, the position of the electrode can be confirmed through the insulating material in the first connection target member on which the insulating material is laminated. The haze value of the insulating material is preferably 60% or less, more preferably 20% or less. The haze value can be obtained from Th = Td / Tt (Td is scattered light transmittance, Tt is total light transmittance) obtained by measuring the transmittance in accordance with JIS K7136.

  The probe tack (25 ° C.) of the surface at 25 ° C. measured using a 5 mmφ probe of the film-like insulating material is 500 mN / 5 mmφ or less, preferably 300 mN / 5 mmφ or less. When the probe tack (25 ° C.) in the film-like insulating material is not more than the above upper limit, stickiness of the surfaces of the insulating material and the insulating layer is reduced, and the handleability of the insulating material and the laminate is improved. In particular, when an insulating material is laminated or a laminated body is temporarily placed on another member, the handleability of the insulating material and the laminated body is improved. In addition, the preferable minimum of the said probe tack in an insulating material is zero.

  The maximum value of the surface probe tack (60 ° C. to 100 ° C.) at 60 ° C. to 100 ° C. measured using a 5 mmφ probe of the film-like insulating material is preferably 1000 mN / 5 mmφ or less, more preferably 800 mN. The minimum value is preferably 300 mN / 5 mmφ, and more preferably 500 mN / 5 mmφ. Further, the maximum value of the surface probe tack (60 ° C. to 100 ° C.) at 60 ° C. to 100 ° C. measured using a 5 mmφ probe of the insulating layer formed using the insulating material according to the present invention is the above value. Similar to the film-like insulating material, it is preferably 1000 mN / 5 mmφ or less, more preferably 800 mN / 5 mmφ or less, and the minimum value is preferably 300 mN / 5 mmφ, more preferably 500 mN / 5 mmφ. When the maximum value of the probe tack (60 ° C. to 100 ° C.) in the film-like insulating material is not more than the above upper limit, the handleability of the insulating material and the laminate is improved. In particular, when laminating an insulating material, applying an anisotropic conductive paste to an insulating layer in a laminate, or laminating a B-staged anisotropic conductive film on an insulating layer in a laminate, the insulating material and the laminate The body is easy to handle. In addition, the temperature range which prescribes | regulates the maximum value and minimum value of probe tack (60 degreeC-100 degreeC) was made into 60 degreeC-100 degreeC, the heating temperature at the time of formation of the lamination temperature of a film-like insulating material, or an insulating layer Is generally about 60 to 100 ° C.

  A probe tack device is used for the measurement of the probe tack. As the probe tack device, a “tacking tester TAC-II” manufactured by RHESCA is used. The probe tack device conforms to JIS Z0237 “Adhesive tape / adhesive sheet test method”. The probe tack is a measured value of tack force by the probe tack device. The measurement conditions are a probe descending speed of 2 mm / s, a probe pressing time of 1 second, and a probe ascending speed of 10 mm / s.

  In the first connection object member having a plurality of protruding first electrodes on the surface, the insulating material according to the present invention is formed on the plurality of first electrodes and on the gaps between the plurality of first electrodes. It is preferable that the insulating material be used for forming an insulating layer stacked so as to cover the plurality of first electrodes. The insulating material according to the present invention is preferably used together with an anisotropic conductive material containing a thermosetting agent for curing the thermosetting compound contained in the insulating material. The insulating material according to the present invention is preferably used together with a B-staged anisotropic conductive layer (B-staged anisotropic conductive film) using the anisotropic conductive material. The insulating material according to the present invention is preferably used by being laminated on a B-staged anisotropic conductive layer (B-staged anisotropic conductive film) using the anisotropic conductive material.

  Specifically as said 1st, 2nd connection object member, electronic components, such as a semiconductor wafer, a semiconductor chip (semiconductor wafer after division | segmentation), a capacitor | condenser, a diode, a printed circuit board, a flexible printed circuit board, a glass substrate, and glass An electronic component that is a circuit board such as an epoxy board is exemplified.

  The first connection target member is preferably a semiconductor wafer or a semiconductor chip.

  Each of the first and second electrodes is formed of, for example, ITO or metal. The first electrode is preferably a copper electrode. The connection resistance is lowered by using a copper electrode. Copper electrodes are susceptible to corrosion and oxidation, and migration is likely to be a problem. On the other hand, by disposing the insulating layer so as to cover the copper electrode using the insulating material according to the present invention, corrosion and oxidation of the copper electrode can be suppressed, and migration resistance can be effectively improved. . Moreover, even if it is other than a copper electrode, by arranging the insulating layer so as to cover the first electrode, it is possible to prevent the first electrode from deteriorating due to contact with corrosive gas in the atmosphere. Further, migration resistance can be improved. When the insulating material according to the present invention contains an ion scavenger, the migration resistance is considerably increased.

  Hereinafter, details of each material included in the insulating material will be described.

[Thermosetting compound]
The insulating material according to the present invention preferably contains a thermosetting compound. The insulating material according to the present invention preferably includes a thermosetting compound having a molecular weight of less than 10,000 and having a thermosetting functional group. When the molecular weight of the thermosetting compound is less than 10,000, the melt viscosity of the insulating material exhibits an appropriate value, voids are less likely to occur in the connection structure, and the electrical conductivity is further enhanced. The thermosetting compound is preferably liquid at 25 ° C. The said thermosetting compound contributes to improving the adhesive force of the hardened | cured material which hardened the insulating material. As for the said thermosetting compound, only 1 type may be used and 2 or more types may be used together.

  The thermosetting functional group is preferably an epoxy group or a radical polymerizable functional group. Examples of the radical polymerizable functional group include (meth) acryloyl group, vinyl group and maleimide group. Among these, a (meth) acryloyl group is preferable because of excellent reactivity.

  The thermosetting compound preferably has an epoxy group or a radical polymerizable functional group. The curable compound having a radical polymerizable functional group is a radical polymerizable compound. In view of excellent reactivity, the thermosetting compound preferably has a (meth) acryloyl group. The thermosetting compound is preferably a curable compound having an epoxy group (epoxy compound) or a curable compound having a (meth) acryloyl group ((meth) acrylic compound), and a curing having a (meth) acryloyl group. It is more preferable that it is an ionic compound.

  “Molecular weight” in the thermosetting compound means a molecular weight that can be calculated from the structural formula when the thermosetting compound is not a polymer and when the structural formula of the thermosetting compound can be specified. Moreover, when this thermosetting compound is a polymer, a weight average molecular weight is meant. The weight average molecular weight indicates a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography.

  The insulating material may contain a first thermosetting compound having a molecular weight of 1000 or more and less than 10,000. The insulating material may contain a second thermosetting compound having a molecular weight of less than 1000. The insulating material may include both a first thermosetting compound having a molecular weight of 1000 or more and less than 10,000 and a second thermosetting compound having a molecular weight of less than 1000. The combined use of the first and second thermosetting compounds effectively increases the adhesive strength of the cured product obtained by curing the insulating material.

  Examples of the curable compound having a vinyl group corresponding to the thermosetting compound include vinyl acetate and divinylbenzene.

  The curable compound having a (meth) acryloyl group corresponding to the thermosetting compound may be a crosslinkable compound or a non-crosslinkable compound. Further, the thermosetting compound may be a polymer (for example, an oligomer) in which a component containing the following crosslinkable compound is polymerized.

  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, glycerine methacrylate acrylate, pentaerythritol tri (meth) acrylate, tri Examples include methylolpropane trimethacrylate, allyl (meth) acrylate, polyester (meth) acrylate, epoxy (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.

  From the viewpoint of improving the reactivity of the insulating material, the thermosetting compound preferably has two or more (meth) acryloyl groups.

  From the viewpoint of improving the reactivity of the insulating material, the thermosetting compound preferably contains an epoxy (meth) acrylate.

  The said epoxy (meth) acrylate is obtained by making (meth) acrylic acid react with a part or all of the epoxy group of the compound which has an epoxy group. The said epoxy (meth) acrylate is a compound which converted a part or all of the epoxy group of the compound which has an epoxy group into the (meth) acryloyl group. The epoxy (meth) acrylate has at least one (meth) acryloyl group. From the viewpoint of improving the reactivity of the insulating material, the epoxy (meth) acrylate preferably has two or more (meth) acryloyl groups. The epoxy (meth) acrylate may have an epoxy group or may not have an epoxy group. That is, the epoxy (meth) acrylate includes a compound in which a part of the epoxy group remains without being converted to a (meth) acryloyl group.

  The above “(meth) acryloyl” refers to acryloyl and methacryloyl. The “(meth) acrylate” refers to acrylate and methacrylate. The “(meth) acryl” refers to acryl and methacryl.

  Examples of the compound having an epoxy group include a novolac type epoxy compound, a bisphenol type epoxy compound, a biphenyl type epoxy compound, a resorcinol type epoxy compound, a naphthalene type epoxy compound, an anthracene type epoxy compound, and a tris (hydroxyphenyl) alkyl type epoxy compound. And tetrakis (hydroxyphenyl) alkyl type epoxy compounds.

  The epoxy (meth) acrylate 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.

  The thermosetting compound preferably includes an epoxy (meth) acrylate having a structural unit represented by the following formula (Y). The thermosetting compound is preferably an epoxy (meth) acrylate having a structural unit represented by the following formula (Y).

  In said formula (Y), R represents a C2-C10 alkylene group, n represents the integer of 1-25.

  In 100% by weight of the insulating material, the content of the thermosetting compound is preferably 10% by weight or more, more preferably 20% by weight or more, 100% by weight or less, preferably 80% by weight or less, more preferably 60% by weight or less. More preferably, it is 40% by weight or less, particularly preferably 30% by weight or less. All the components of the insulating material may be the thermosetting compound, and all the components of the insulating material may be the thermosetting compound. When the content of the thermosetting compound is not less than the above lower limit, voids are less likely to occur in the connection structure, and the conduction reliability is further enhanced.

  In the case where the insulating material includes both a first thermosetting compound having a molecular weight of 1000 or more and less than 10,000 and a second thermosetting compound having a molecular weight of less than 1000, the insulating material includes the first The thermosetting compound and the second thermosetting compound are preferably contained in a weight ratio of 1: 3 to 3: 1, and preferably 1: 1.5 to 1.5: 1. When the weight ratio of the first and second thermosetting compounds satisfies the above range, the continuity and migration resistance of the connection structure are further increased, and the adhesive strength of the cured product obtained by curing the insulating material is further increased. It gets even higher.

(polymer)
The insulating material according to the present invention preferably further includes a polymer having a weight average molecular weight of 10,000 or more and 250,000 or less. The polymer is preferably solid at 25 ° C. The polymer may have a thermosetting functional group. The thermosetting functional group is preferably an epoxy group or a radical polymerizable functional group. Examples of the radical polymerizable functional group in the polymer include a (meth) acryloyl group, a vinyl group, and a maleimide group. As for the said polymer, only 1 type may be used and 2 or more types may be used together.

  Examples of the polymer include phenoxy resins, polyether ester amide resins, polyimide resins, polyamide resins, poly (meth) acrylate resins, and polyester resins. From the viewpoint of further increasing the strength of the film-like insulating material and the strength of the insulating layer, the polymer preferably contains a phenoxy resin or a polyetheresteramide resin. The polymer may contain a phenoxy resin or a polyetheresteramide resin. In addition, the use of the polyether ester amide resin improves the resistance to microphones of the connection structure using the insulating material.

  The phenoxy resin is generally a resin obtained by reacting, for example, epihalohydrin and a divalent phenol compound, or a resin obtained by reacting a divalent epoxy compound and a divalent phenol compound. The phenoxy resin generally has an epoxy group.

  The polyether ester amide resin has an amide bond. The polyether ester amide resin preferably has at least one radical polymerizable functional group.

  From the viewpoint of further improving the adhesive strength of the cured product, the polyether ester amide resin preferably has an amide bond in the main chain. From the viewpoint of further improving the adhesive strength of the cured product, the polyether ester amide resin preferably has a structural unit represented by the following formula (X).

  R in the above formula (X) represents a hydrocarbon group having 3 to 6 carbon atoms, and n represents an integer of 2 to 50. The hydrocarbon group is preferably an alkylene group.

  From the viewpoint of improving the reactivity of the insulating material, the polyether ester amide resin preferably has the radical polymerizable group at the terminal. From the viewpoint of improving both the reactivity and the storage stability of the insulating material, the polyether ester amide resin preferably has one radical polymerizable group.

  The weight average molecular weight of the polymer is preferably 10,000 or more, more preferably 40000 or more, preferably 250,000 or less, more preferably 70000 or less. By using a polymer having a weight average molecular weight that is preferably not less than the above lower limit and not more than the above upper limit, the strength of the film-like insulating material and the strength of the insulating layer are further improved, and further, the film-like insulation for the first connection target member Good laminating properties of the material. The said weight average molecular weight shows the weight average molecular weight in polystyrene conversion measured by gel permeation chromatography.

  The content of the polymer in 100% by weight of the insulating material is preferably 40% by weight or more, more preferably 50% by weight or more, 100% by weight or less, preferably 90% by weight or less, more preferably 70% by weight or less. When the content of the polymer is not less than the above lower limit and not more than the above upper limit, generation of voids in the connection structure is further less likely to occur, and the conduction reliability is further enhanced.

[Thermosetting agent]
In order to cure the insulating material by heating, the insulating material may contain a thermosetting agent. The insulating material preferably does not contain the thermosetting agent. It is preferable that the insulating material does not contain an amount of a thermosetting agent effective for reacting all the thermosetting functional groups of the thermosetting compound. However, when the insulating material contains a thermosetting agent, the content of the thermosetting agent is preferably as small as possible in order to further improve the property stability of the insulating material. Examples of the thermosetting agent include a thermal radical generator, an imidazole curing agent, an amine curing agent, a phenol curing agent, a polythiol curing agent, an acid anhydride, and a thermal cation initiator. As for the said thermosetting agent, only 1 type may be used and 2 or more types may be used together.

  The content of the thermosetting agent is not particularly limited. The content of the thermosetting agent in the insulating material with respect to 100 parts by weight of the thermosetting compound in the insulating material is preferably 40 parts by weight or less, more preferably 30 parts by weight or less, and still more preferably 20 parts. Less than parts by weight. The content of the thermosetting agent in the insulating material may be 0% by weight or may be 0.01 part by weight or more with respect to 100 parts by weight of the thermosetting compound in the insulating material. 0.05 parts by weight or more, 5 parts by weight or more, or 10 parts by weight or more. When the content of the thermosetting agent is not less than the above lower limit, the insulating material is sufficiently easily thermoset. Curing of an insulating material is suppressed as content of the said thermosetting agent is below the said upper limit.

  The thermosetting agent preferably contains a thermal radical generator. By using the thermal radical generator, the melt viscosity of the insulating material exhibits a more appropriate value, and the conductivity of the connection structure is further increased. Furthermore, the conductivity between the electrodes and the connection reliability of the connection structure under high temperature and high humidity are also improved.

  The thermal radical generator is not particularly limited. As the thermal radical generator, a conventionally known thermal radical generator can be used. As for the said thermal radical generator, only 1 type may be used and 2 or more types may be used together. The “thermal radical generator” means a compound that generates radical species by heating.

  The thermal radical generator is not particularly limited, and examples thereof include azo compounds and peroxides. Examples of the peroxide include diacyl peroxide compounds, peroxyester compounds, hydroperoxide compounds, peroxydicarbonate compounds, peroxyketal compounds, dialkyl peroxide compounds, and ketone peroxide compounds.

  Examples of the azo compound include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), and 2,2′-azobis (2,4-dimethylvaleronitrile). 1,1′-azobis-1-cyclohexanecarbonitrile, dimethyl-2,2′-azobisisobutyrate, dimethyl-2,2′-azobis (2-methylpropionate), dimethyl-1,1 ′ -Azobis (1-cyclohexanecarboxylate), 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobis (2-amidinopropane) dihydrochloride, 2-tert-butylazo-2-cyanopropane 2,2′-azobis (2-methylpropionamide) dihydrate, 2,2′-azobis (2,4,4-trimethylpentane), and the like.

  Examples of the diacyl peroxide compound include benzoyl peroxide, diisobutyryl peroxide, di (3,5,5-trimethylhexanoyl) peroxide, dilauroyl peroxide, and disuccinic acid peroxide. Examples of the peroxyester compound include cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, tert-hexylperoxyneodecanoate, and tert-butylperoxyneo. Decanoate, tert-butylperoxyneoheptanoate, tert-hexylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2 , 5-di (2-ethylhexanoylperoxy) hexane, tert-hexylperoxy-2-ethylhexanoate, tert-butylperoxypivalate, tert-butylperoxy-2-ethylhexanoate, tert -Butyl peroxyisobutyrate, tert-butyl per Kishiraureto, tert- butylperoxy isophthalate, tert- butylperoxy acetate, tert- butylperoxy octoate and tert- butyl peroxybenzoate, and the like. Examples of the hydroperoxide compound include cumene hydroperoxide and p-menthane hydroperoxide. Examples of the peroxydicarbonate compound include di-sec-butyl peroxydicarbonate, di (4-t-butylcyclohexyl) peroxydicarbonate, di-n-propyl peroxydicarbonate, diisopropyl peroxycarbonate, and di- (2-ethylhexyl) peroxycarbonate and the like. Other examples of the peroxide include methyl ethyl ketone peroxide, potassium persulfate, and 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane.

  The decomposition temperature for obtaining the 10-hour half-life of the thermal radical generator is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, preferably 90 ° C. or lower, more preferably 80 ° C. or lower. If the decomposition temperature for obtaining the 10-hour half-life of the thermal radical generator is less than 30 ° C., the storage stability of the insulating material tends to be reduced, and if it exceeds 90 ° C., the insulating material is sufficiently heated. It tends to be difficult to cure.

  When the thermosetting agent includes a thermal radical generator, 100 parts by weight of the thermosetting compound in the insulating material (100 parts by weight of the epoxy compound when the thermosetting compound is an epoxy compound) The content of the thermal radical generator in the insulating material is preferably 10 parts by weight or less, more preferably 5 parts by weight or less. Further, the content of the thermal radical generator in the insulating material is preferably 10 parts by weight or less, more preferably 5 parts by weight or less with respect to 100 parts by weight of the radical polymerizable curable compound in the insulating material. It is. Even if the content of the thermal radical generator in the insulating material is 0 part by weight with respect to 100 parts by weight of the thermosetting compound or 100 parts by weight of the radical polymerizable curable compound in the insulating material. It may be 0.01 parts by weight or more, or 0.05 parts by weight or more. When the content of the thermal radical generator is equal to or higher than the lower limit, the insulating material is sufficiently thermally cured. Curing of an insulating material is suppressed as content of the said thermal radical generator is below the said upper limit.

  When the said thermosetting compound has an epoxy group etc., the said insulating material may further contain the other thermosetting agent different from the said thermal radical generator.

  From the viewpoint of curing the curable composition more rapidly at a low temperature, the thermosetting agent contains an imidazole curing agent, an amine curing agent, a phenol curing agent, a polythiol curing agent, an acid anhydride, or a thermal cation initiator. Are preferred, and more preferably contain an imidazole curing agent, a polythiol curing agent, an amine curing agent or a thermal cation initiator.

  Moreover, since the storage stability of a curable composition can be improved, a latent hardening | curing agent is preferable. The latent curing agent is preferably a latent imidazole curing agent, a latent polythiol curing agent or a latent amine curing agent. The thermosetting agent may be coated with a polymer material such as polyurethane resin or polyester resin.

  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.

  The thermosetting agent preferably contains a thermal cation initiator. As the thermal cation initiator, iodonium salts and sulfonium salts are preferably used. For example, commercially available products of the above thermal cation initiator include San-Aid SI-45L, SI-60L, SI-80L, SI-100L, SI-110L, SI-150L manufactured by Sanshin Chemical Co., Ltd., and ADEKA manufactured by ADEKA Optomer SP-150, SP-170 etc. are mentioned.

Preferred anionic portions of the thermal cationic initiator include SbF ₆ , PF ₆ , BF ₄ , and B (C ₆ F ₅ ) ₄ .

  When the thermosetting agent contains a thermal cation initiator, 100 parts by weight of the thermosetting compound in the insulating material (100 parts by weight of the epoxy compound when the thermosetting compound is an epoxy compound) The content of the thermal cation initiator in the insulating material is preferably 10 parts by weight or less, more preferably 5 parts by weight or less. The content of the thermal cation initiator may be 0.01 parts by weight or more, or 0.05 parts by weight or more with respect to 100 parts by weight of the thermosetting compound. When the content of the thermal cation initiator is equal to or higher than the lower limit, the insulating material is sufficiently thermally cured. When the content of the thermal cation initiator is not more than the above upper limit, curing of the insulating material is suppressed.

[Ion scavenger]
The insulating material preferably contains an ion scavenger. The ion scavenger is not particularly limited. As the ion scavenger, a conventionally known ion scavenger can be used. By using the ion scavenger, the migration resistance in the connection structure is further enhanced, and the insulation reliability is further enhanced. As for the said ion trapping agent, only 1 type may be used and 2 or more types may be used together.

  Examples of the ion scavenger include cation exchangers and anion exchangers. As for the said cation exchanger, only 1 type may be used and 2 or more types may be used together. As for the said anion exchanger, only 1 type may be used and 2 or more types may be used together.

  Examples of the cation exchanger include Zr-based cation exchangers and Sb-based cation exchangers. From the viewpoint of further suppressing migration in the connection structure and further improving the insulation reliability, the cation exchanger is preferably a Zr-based cation exchanger, and preferably contains a zirconium atom.

  Examples of commercially available products of the cation exchanger include IXE-100 and IXE-300 (all of which are manufactured by Toagosei Co., Ltd.).

  Examples of the anion exchanger include Bi-based anion exchangers, Mg-Al-based anion exchangers, and Zr-based anion exchangers. From the viewpoint of further suppressing the migration in the connection structure and further improving the insulation reliability, the cation exchanger is preferably an Mg-Al anion exchanger, and includes a magnesium atom and an aluminum atom. It is preferable to include.

  Examples of the commercial product of the anion exchanger include IXE-500, IXE-530, IXE-550, IXE-700F, and IXE-800 (all of which are manufactured by Toagosei Co., Ltd.).

  The neutral exchange capacity of the cation exchanger is preferably 1 meq / g or more, more preferably 2 meq / g or more, preferably 10 meq / g or less, more preferably 4 meq / g or less. When the neutral exchange capacity of the cation exchanger is not less than the above lower limit and not more than the above upper limit, migration in the connection structure can be further suppressed, and insulation reliability can be further enhanced.

  The neutral exchange capacity of the anion exchanger is preferably 0.1 meq / g or more, more preferably 1 meq / g or more, preferably 10 meq / g or less, more preferably 5 meq / g or less. When the neutral exchange capacity of the anion exchanger is not less than the above lower limit and not more than the above upper limit, migration in the connection structure can be further suppressed, and insulation reliability can be further enhanced.

  The median diameter of the cation exchanger is preferably 0.1 μm or more, more preferably 0.5 μm or more, preferably 10 μm or less, more preferably 3 μm or less. When the median diameter of the cation exchanger is not less than the above lower limit and not more than the above upper limit, migration in the connection structure can be further suppressed, and insulation reliability can be further enhanced.

  The median diameter of the anion exchanger is preferably 0.1 μm or more, more preferably 0.5 μm or more, preferably 10 μm or less, more preferably 3 μm or less. When the median diameter of the anion exchanger is not less than the above lower limit and not more than the above upper limit, migration in the connection structure can be further suppressed, and insulation reliability can be further enhanced.

  In 100% by weight of the insulating material, the content of the ion scavenger is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, preferably 10% by weight or less, more preferably 5% by weight or less, More preferably, it is 4% by weight or less. When the content of the ion scavenger is not less than the above lower limit and not more than the above upper limit, the migration resistance in the connection structure is further enhanced, and the insulation reliability is further enhanced.

[Other ingredients]
A solvent may be used to form the film-like insulating material. An insulating material containing a solvent is applied onto the surface of the first connection target member or the surface of the B-staged anisotropic conductive film, and the solvent is removed by drying to form a film-like insulating material. May be.

  Examples of the solvent include an aliphatic solvent, a ketone solvent, an aromatic solvent, an ester solvent, an ether solvent, an alcohol solvent, a paraffin solvent, and a petroleum solvent.

  The temperature at which the solvent is removed by drying is appropriately set according to the type of solvent used. The temperature at which the solvent is removed by drying is, for example, about 60 to 130 ° C. The lower the temperature at which the solvent is removed by drying, the lower the thermal degradation of the first connection target member.

  From the viewpoint of further improving the connection reliability of the connection structure when receiving a thermal history, the insulating material preferably contains a thixotropic agent. Examples of the thixotropic agent include elastomer particles and silica. Examples of the elastomer particles include rubber particles. Examples of the rubber particles include natural rubber particles, isoprene rubber particles, butadiene rubber particles, styrene butadiene rubber particles, chloroprene rubber particles, and acrylonitrile butadiene rubber particles. The silica is preferably nano silica. The average particle diameter of the nano silica is less than 1000 nm.

  In 100% by weight of the insulating material, the content of the thixotropic agent is preferably 0.1% by weight or more, more preferably 1% by weight or more, preferably 30% by weight or less, more preferably 15% by weight or less. When the content of the thixotropic agent is not less than the above lower limit and not more than the above upper limit, the connection reliability of the connection structure when receiving a thermal history is further enhanced.

  From the viewpoint of further improving the connection reliability of the first and second connection target members, it is preferable that the insulating material contains an adhesion-imparting agent. Examples of the adhesion-imparting agent include a coupling agent and a flexible material.

  In 100% by weight of the insulating material, the content of the adhesion-imparting agent is preferably 1% by weight or more, more preferably 5% by weight or more, preferably 50% by weight or less, more preferably 25% 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 first and second connection target members is further increased.

(Laminated body and laminated body manufacturing method)
The laminate according to the present invention includes a first connection target member having a plurality of protruding first electrodes on the surface, a plurality of the first electrodes, and a gap between the plurality of first electrodes. And an insulating layer stacked to cover the plurality of first electrodes. In the laminate according to the present invention, the insulating layer is formed of the insulating material described above.

  The laminate according to the present invention may further include a B-staged anisotropic conductive layer laminated on the surface of the insulating layer opposite to the first connection target member side. The B-staged anisotropic conductive layer is formed using an anisotropic conductive material containing a curable component and conductive particles, by removing the solvent of the anisotropic conductive material or by proceeding with curing. It is preferable that

  The manufacturing method of the laminated body which concerns on this invention uses the 1st connection object member which has the several 1st electrode which protruded on the surface, and on between several said 1st electrodes and between several said 1st electrodes. A step of laminating an insulating layer on the gap so as to cover the plurality of first electrodes. In the method for manufacturing a laminate according to the present invention, the insulating layer is formed of the insulating material described above. In the step of laminating the insulating layer, a film-like insulating material may be laminated on the first connection target member. By using the insulating material according to the present invention, the lamination can be carried out satisfactorily.

  The manufacturing method of the laminated body which concerns on this invention arrange | positions the anisotropic conductive material containing a sclerosing | hardenable component and electroconductive particle on the surface on the opposite side to the said 1st connection object member side of the said insulating layer. A step of laminating an anisotropic conductive material layer, and a B-staging step of forming a B-staged anisotropic conductive layer by removing the solvent of the anisotropic conductive material layer or by proceeding with curing. Furthermore, you may provide.

  In FIG. 1, the laminated body which concerns on the 1st Embodiment of this invention is typically shown with sectional drawing.

  A laminate 1 shown in FIG. 1 includes a first connection target member 2 and an insulating layer 6A.

  The first connection target member 2 has a plurality of protruding first electrodes 2b on the surface 2a. The insulating layer 6A is stacked on the plurality of first electrodes 2b and on the gaps X between the plurality of first electrodes 2b. The gap X between the plurality of first electrodes 2b is a concave portion where there is no first electrode 2b.

  The insulating layer 6A is made of the insulating material described above. The insulating layer 6A does not contain conductive particles. The insulating layer 6A insulates a plurality of adjacent first electrodes 2b in contact with the insulating layer 6A.

  The protruding height of the protruding first electrode 2b is preferably 3 μm or more, more preferably 10 μm or more, preferably 50 μm or less, more preferably 20 μm or less. The distance of the gap X between the adjacent first electrodes 2b is preferably 4 μm or more, more preferably 8 μm or more, preferably 50 μm or less, more preferably 20 μm or less. The distance of the gap between the adjacent first electrodes 2b is the width of the recess, and is the dimension of the portion where the first electrode 2b is not provided. When the protruding height of the first electrode and the distance between the adjacent first electrodes are not less than the above lower limit and not more than the above upper limit, the conventional connection structure manufacturing method is provided with an insulating layer in particular. When the connection structure is manufactured using the first connection target member that is not present, the connection reliability between the electrodes tends to be particularly low. On the other hand, the protrusion height of the first electrode and the adjacent first electrode are produced by producing a connection structure using the laminate (first connection target member with an insulating layer) according to the present invention. Even if the distance between the gaps is not less than the above lower limit and not more than the above upper limit, the connection reliability is sufficiently high. In particular, even when the distance between the first electrodes is equal to or less than the upper limit, it is possible to effectively suppress electrical connection between the first electrodes adjacent in the lateral direction by the conductive particles.

  The thickness of the insulating layer 6A on the protruding first electrode 2b in the first connection target member 2 is preferably 0.1 μm or more, more preferably 1 μm or more, further preferably 3 μm or more, preferably 20 μm or less, more preferably. Is 10 μm or less, more preferably 5 μm or less.

  The laminated body 1 can be obtained as follows through the respective steps shown in FIGS. Here, the manufacturing method of the laminated body 1 in case the 1st connection object member 2 is a semiconductor chip (semiconductor wafer after division | segmentation) is demonstrated.

  As shown in FIG. 2A, a first connection target member 2A (semiconductor wafer) which is an aggregate of a plurality of first connection target members 2 (individual semiconductor chips, divided semiconductor wafers) is prepared. The first connection target member 2A has a plurality of protruding first electrodes 2b on the surface 2a. The first connection target member 2A is arranged so that the first electrode 2b is on the upper side.

  Next, as shown in FIG. 2B, using the first connection target member 2A, the plurality of first electrodes 2b and the gaps X between the plurality of first electrodes 2b are arranged on the plurality of first electrodes 2b. An insulating layer 6AA (insulating layer before division) is laminated so as to cover one electrode 2b. The insulating layer 6AA is formed of the above-described insulating material. At this time, as shown in FIG. 10, by using a laminated film in which a film-like insulating material 6X (insulating film) is laminated on a release film 41, the film-like insulating material 6X is laminated to obtain an insulating layer. 6AA may be formed.

  Next, at the broken line portion shown in FIG. 2B, the first connection target member 2A (semiconductor wafer) is cut to form the first connection target member 2 (individual semiconductor chips, divided semiconductor wafers). The laminate 1 is obtained. By cutting the insulating layer 6AA together with the first connection target member 2A, an insulating layer 6A that is an insulating layer after division is obtained.

  The obtained laminate 1 is picked up and placed on the insulating layer 6A side in the container 51 before the connection structure is manufactured, as shown in FIG. 2 (c). As described above, when many connection structures are manufactured, the laminate 1 is generally temporarily stored in the container 51.

  In a state where the laminate 1 is placed in the container 51, the surface 6 a of the insulating layer 6 </ b> A is in contact with the container 51. For this reason, it is preferable that the surface 6a of the insulating layer 6A has less stickiness. When there is little stickiness, the laminated body 1 can be easily taken out from the container 51 when the laminated body 1 is picked up again to obtain a connection structure. By using the insulating material according to the present invention, the stickiness of the surface of the insulating layer 6A can be suppressed, so that the laminate 1 can be easily taken out from the container 51.

  The manufacturing method of the laminated body which concerns on this invention uses a semiconductor wafer as said 1st connection object member, forms the said insulating layer, cuts a semiconductor wafer, and divides each semiconductor chip which is a semiconductor wafer after a division | segmentation The process to perform may be further provided.

  In FIG. 6, the laminated body which concerns on the 2nd Embodiment of this invention is typically shown with sectional drawing.

  The laminated body 21 shown in FIG. 6 includes a first connection target member 2, an insulating layer 6A, and a B-staged anisotropic conductive layer 22B. In the gap X between the plurality of first electrodes 2b, the B-staged anisotropic conductive layer 22B is not disposed. It is preferable that a B-staged anisotropic conductive layer is not disposed in the gap between the plurality of first electrodes.

  The B-staged anisotropic conductive layer 22B is laminated on the surface 6a opposite to the first connection target member 2 side of the insulating layer 6A. The B-staged anisotropic conductive layer 22B uses an anisotropic conductive material containing a curable component and conductive particles 5 to remove the solvent of the anisotropic conductive material (anisotropic conductive material layer). Or it is formed by advancing hardening. An insulating layer 6A is disposed between the conductive particles 5 and the first electrode 2b. The B-staged anisotropic conductive layer 22B may be formed by removing the solvent of the anisotropic conductive material layer after forming the anisotropic conductive material layer, and curing the anisotropic conductive material layer. You may form by making it advance. The B-staged anisotropic conductive layer 22B is preferably formed by advancing curing of the anisotropic conductive material layer. When the B-staged anisotropic conductive layer 22B is formed by removing the solvent of the anisotropic conductive material layer, the anisotropic conductive material contains a solvent.

  The anisotropic conductive material may be an anisotropic conductive film or an anisotropic conductive paste. The anisotropic conductive material is preferably a paste-like anisotropic conductive paste. When the anisotropic conductive material is an anisotropic conductive film, a film containing no conductive particles may be laminated on the anisotropic conductive film containing conductive particles.

  The thickness of the B-staged anisotropic conductive layer 22B in the laminate 21 is preferably 1.2 times or more, more preferably 2 times or more, and more than 3 times the average particle diameter of the conductive particles 5. More preferably, it is preferably 20 times or less, and more preferably 10 times or less.

  The laminated body 21 can be obtained using the laminated body 1 through the steps shown in FIGS. 7A to 7C as follows. Here, as the anisotropic conductive material, an anisotropic conductive material including a photocurable component curable by light irradiation, a thermosetting component curable by heating, and the conductive particles 5 is used. The manufacturing method of the laminated body 21 is demonstrated concretely. Instead of the photocurable component and the thermosetting component, light and thermosetting components that can be cured by both light irradiation and heating may be used.

  First, as shown to Fig.7 (a), the laminated body 1 is arrange | positioned so that the 1st connection object member 2 may become a lower side, and 6 A of insulating layers may become an upper side.

  Next, as shown in FIG. 7B, the anisotropic conductive material is disposed on the surface 6a opposite to the first connection target member 2 side of the insulating layer 6A, and the anisotropic conductive material is disposed. Layer 22A is laminated. At this time, it is preferable that one or a plurality of conductive particles 5 be disposed on the insulating layer 6A located on the first electrode 2b.

  Next, the anisotropic conductive material layer 22A is cured by irradiating the anisotropic conductive material layer 22A with light. Here, the anisotropic conductive material layer 22A is irradiated with light to advance the curing of the anisotropic conductive material layer 22A, so that the anisotropic conductive material layer 22A is B-staged (B-stage forming step). . That is, as illustrated in FIG. 7C, a B-staged anisotropic conductive layer 22 </ b> B is formed on the surface 6 a opposite to the first connection target member 2 side of the insulating layer 6 </ b> A, and the laminate 21. Get. By the B-staging, the insulating layer 6A and the B-staged anisotropic conductive layer 22B are temporarily bonded. The B-staged anisotropic conductive layer 22B is a semi-cured product in a semi-cured state. The B-staged anisotropic conductive layer 22B is not completely cured, and thermal curing can further proceed. The anisotropic conductive material layer 22A may be cured by heating instead of the light irradiation. When the anisotropic conductive material layer 22A contains a solvent, the B-staged anisotropic conductive layer 22B may be formed by removing the solvent of the anisotropic conductive material layer 22A.

  It is preferable to irradiate the anisotropic conductive material layer 22A with light while applying the anisotropic conductive material. Furthermore, it is also preferable to irradiate light to the anisotropic conductive material layer 22A simultaneously with the application of the anisotropic conductive material or immediately after the application. When the application and the light irradiation are performed as described above, the flow of the anisotropic conductive material layer 22A can be further suppressed. For this reason, the conduction | electrical_connection reliability in a connection structure becomes still higher. The time from the placement of the anisotropic conductive material, that is, the time from stacking the anisotropic conductive material layer 22A to the irradiation of light is 0 second or more, preferably 180 seconds or less, more preferably 60 seconds or less. is there.

The light irradiation intensity for appropriately proceeding the curing of the anisotropic conductive material layer 22A is, for example, preferably about 0.1 to 300 mW / cm ² . Moreover, the irradiation energy of light for appropriately proceeding the curing of the anisotropic conductive material layer 22A is, for example, preferably about 100 to 10,000 mJ / cm ² . The light source used when irradiating light is not specifically limited. Examples of the light source include a light source having a sufficient light emission distribution at a wavelength of 420 nm or less. Specific examples of the light source include, for example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a chemical lamp, a black light lamp, a microwave excitation mercury lamp, a metal halide lamp, and an LED lamp.

  In order to obtain the laminate 21, as shown in FIG. 11A, an insulating film 6XA (film-like insulating material) and a B-staged anisotropic conductive film laminated on one surface of the insulating film 6XA A multilayer film 46 provided with 22X (film-like B-staged anisotropic conductive layer) may be used. A release film may be laminated on the outer surface of the insulating film 6XA. A release film may be laminated on the outer surface of the B-staged anisotropic conductive film 22X. The insulating film 6XA is formed of the insulating material described above. The B-staged anisotropic conductive film 22X is formed by using an anisotropic conductive material containing a curable component and conductive particles, by removing the solvent of the anisotropic conductive material or by proceeding with curing. Has been.

(Connection structure and method of manufacturing connection structure)
The connection structure according to the present invention includes a first connection target member having a plurality of protruding first electrodes on the surface, an insulating layer stacked on a gap between the plurality of first electrodes, and the insulation. A cured product layer laminated on a surface opposite to the first connection target member side of the layer, a cured product layer laminated on a surface opposite to the insulating layer side of the cured product layer, and a plurality of layers And a second connection target member having a second electrode on the surface. In the connection structure according to the present invention, the insulating layer is formed of the insulating material described above. In the connection structure according to the present invention, the cured product layer is formed by main-curing the anisotropic conductive material using an anisotropic conductive material including a curable component and conductive particles. . In the connection structure according to the present invention, the plurality of first electrodes and the plurality of second electrodes are electrically connected by the conductive particles.

  In the connection structure according to the present invention, the insulating layer may be stacked on at least a part of the regions on the plurality of first electrodes and the gaps between the first electrodes.

  The manufacturing method of the connection structure according to the present invention includes (1) a first connection target member having a plurality of protruding first electrodes on the surface, a plurality of the first electrodes, and a plurality of the first electrodes. A laminated body comprising a plurality of insulating layers laminated so as to cover the plurality of first electrodes above the gaps between the electrodes, a second connection target member having a plurality of second electrodes on the surface, and the second Using the second laminate including the B-staged anisotropic conductive layer laminated on the surface of the connection target member, the first connection target member, the insulating layer, and the B-staged anisotropy Laminate the conductive layer and the second connection target member in this order, or (2) a first connection target member having a plurality of protruding first electrodes on the surface, and a plurality of the first connection target members. An insulating layer laminated on the electrodes and on the gaps between the plurality of first electrodes so as to cover the plurality of first electrodes A second laminate having a B-staged anisotropic conductive layer laminated on a surface opposite to the first connection target member side of the insulating layer, and a second electrode having a plurality of second electrodes on the surface. A step of laminating the first connection object member, the insulating layer, the B-staged anisotropic conductive layer, and the second connection object member in this order using the connection object member of A main curing step in which the stiffened anisotropic conductive layer is fully cured to form a cured product layer, and the first and second connection target members are electrically connected by the cured product layer. In the method for manufacturing a connection structure according to the present invention, the insulating layer is formed of the insulating material described above. In the method for manufacturing a connection structure according to the present invention, the B-staged anisotropic conductive layer uses an anisotropic conductive material containing a curable component and conductive particles, and a solvent for the anisotropic conductive material. Or by proceeding with curing. In the manufacturing method of the connection structure according to the present invention, the insulating layer portion between the first electrode and the conductive particles contained in the B-staged anisotropic conductive layer is excluded, The conductive particles are brought into contact with the first and second electrodes to obtain a connection structure in which the insulating layer is stacked in the gaps between the plurality of first electrodes. In the above-described lamination step, lamination may be performed by the method (1) described above, or lamination may be performed by the method (2) described above. It is preferable to perform lamination by the method (1) described above.

  In the method for manufacturing a connection structure according to the present invention, a connection structure in which the insulating layer is stacked on at least a part of the plurality of the first electrodes and a gap between the first electrodes is obtained. Also good.

  FIG. 3 is a cross-sectional view schematically showing the connection structure according to the first embodiment of the present invention.

  A connection structure 11 shown in FIG. 3 includes a first connection target member 2, a second connection target member 4, an insulating layer 6, and a cured product layer 3. The connection structure 11 shown in FIG. 3 is formed using the laminated body 1 shown in FIG.

  The insulating layer 6 is laminated on a partial region on the plurality of first electrodes 2b and on the gaps X (concave portions) between the plurality of first electrodes 2b. In the portion where the conductive particles 5 are in contact with the first electrode 2b, the insulating layer 6 is not laminated on the plurality of first electrodes 2b. The insulating layer 6 is not disposed between the plurality of first electrodes 2b and the conductive particles 5 that are in contact with the first electrodes 2b.

  The cured product layer 3 is a connection part that electrically connects the first and second connection target members 2 and 4. The cured product layer 3 is laminated on the surface 6 a opposite to the first connection target member 2 side of the insulating layer 6. The cured product layer 3 is formed by main-curing the anisotropic conductive material using an anisotropic conductive material including a curable component and the conductive particles 5. The cured product layer 3 is subjected to main curing after removing the solvent of the anisotropic conductive material using the anisotropic conductive material containing the curable component and the conductive particles 5 or allowing the curing to proceed. It is preferable that it is formed by. The cured product layer 3 is not disposed in the gap X between the plurality of first electrodes 2b.

  The 2nd connection object member 4 is laminated | stacked on the surface on the opposite side to the insulating layer 6 side of the hardened | cured material layer 3. As shown in FIG. The second connection target member 4 has a plurality of protruding second electrodes 4b on the surface 4a. The 1st, 2nd connection object members 2 and 4 are arrange | positioned so that the 1st electrode 2b and the 2nd electrode 4b may oppose. One or a plurality of conductive particles 5 are arranged between the first electrode 2b and the second electrode 4b. The first electrode 2b and the second electrode 4b are electrically connected by one or a plurality of conductive particles 5. No component other than the conductive particles 5 in the insulating layer 6 and the cured product layer 3 is disposed between the first electrode 2b and the conductive particles 5 in contact with the first electrode 2b. Components other than the conductive particles 5 in the cured product layer 3 are not disposed between the second electrode 4b and the conductive particles 5 in contact with the second electrode 4b.

  The connection structure 11 can be obtained as follows through the steps shown in FIGS. 4A to 4C using the laminate 1. Here, as the anisotropic conductive material, an anisotropic conductive material including a photocurable component curable by light irradiation, a thermosetting component curable by heating, and the conductive particles 5 is used. A method for manufacturing the connection structure 11 will be specifically described. Instead of the photocurable component and the thermosetting component, light and thermosetting components that can be cured by both light irradiation and heating may be used.

  First, as shown to Fig.4 (a), the laminated body 1 is arrange | positioned so that the 1st connection object member 2 may become an upper side and the insulating layer 6A may become a lower side. In addition, a second connection target member 4 having a plurality of second electrodes 4b on the surface and a B-staged anisotropic conductive layer 3B stacked on the surface 4a of the second connection target member 4 are provided. The laminate 16 is prepared. The second stacked body 16 is arranged so that the B-staged anisotropic conductive layer 3B is on the upper side and the second connection target member 4 is on the lower side. Further, the first electrode 2b and the second electrode 4b are opposed to each other.

  Next, as shown in FIG. 4B, the first connection target member 2, the insulating layer 6A, the B-staged anisotropic conductive layer 3B, and the second connection target member 4 are laminated in this order. The second connection target member 4 is laminated on the surface 3a opposite to the insulating layer 6A side of the B-staged anisotropic conductive layer 3B. The second connection target so that the plurality of first electrodes 2b on the surface 2a of the first connection target member 2 and the plurality of second electrodes 4b on the surface 4a of the second connection target member 4 face each other. The member 4 is laminated. In this state, the insulating layer 6A portion between the first electrode 2b and the B-staged anisotropic conductive layer 3B is not excluded. The first electrode 2b and the conductive particles 5 are not in contact.

  Thus, by connecting the first connection object member 2, the insulating layer 6A, the B-staged anisotropic conductive layer 3B, and the second connection object member 4 in this order, a connection with high insulation reliability. The structure 11 can be obtained. In particular, in the gap X between the plurality of first electrodes 2b, the insulating layer 6A is disposed instead of the B-staged anisotropic conductive layer 3B including the conductive particles 5, and therefore the plurality of first electrodes 2b. It becomes difficult for the conductive particles 5 to be disposed in the gaps X between them, and as a result, the insulation reliability of the connection structure 11 is increased.

  On the other hand, when an anisotropic conductive material is directly applied on the surface of a connection target member having a protruding electrode on the surface as in the conventional method for manufacturing a connection structure, a conductive material is formed in the gap between the electrodes. The conductive particles are disposed, and the conductive particles disposed on the electrodes flow and easily move to the gaps between the electrodes. For this reason, it is difficult to obtain a connection structure having high insulation reliability.

  Next, as shown in FIG. 4C, the B-staged anisotropic conductive layer 3 </ b> B is heated by heating the B-staged anisotropic conductive layer 3 </ b> B when the second connection target member 4 is laminated. Is cured to form a cured product layer 3 (main curing step). At this time, the insulating layer 6A (insulating material) is also preferably fully cured. Moreover, it is preferable to cure the thermosetting compound contained in the insulating layer 6A with a thermosetting agent contained in the B-staged anisotropic conductive layer 3B. In the main curing step, the conductive particles 5 are brought into contact with the first and second electrodes 2b and 4b, excluding the insulating layer 6A portion between the first electrode 2b and the B-staged anisotropic conductive layer 3B. Let As a result of eliminating the insulating layer 6A portion between the first electrode 2b and the B-staged anisotropic conductive layer 3B, the insulating layer 6 is formed. However, the B-staged anisotropic conductive layer 3B may be heated before the second connection target member 4 is laminated. Further, the B-staged anisotropic conductive layer 3 </ b> B may be heated after the second connection target member 4 is laminated. The B-staged anisotropic conductive layer 3B may be fully cured by irradiation with light instead of heating. Further, in the stacking process of the second connection object member 4, the insulating layer 6A portion between the first electrode 2b and the B-staged anisotropic conductive layer 3B is excluded, and the first and second electrodes 2b , 4b may be brought into contact with the conductive particles 5. However, in the main curing step, it is preferable to exclude the insulating layer 6A portion between the first electrode 2b and the B-staged anisotropic conductive layer 3B.

  The heating temperature for curing the B-staged anisotropic conductive layer 3B by heating is preferably 140 ° C. or higher, more preferably 160 ° C. or higher, preferably 250 ° C. or lower, more preferably 200 ° C. or lower.

  It is preferable to apply pressure when the B-staged anisotropic conductive layer 3B is fully cured. By compressing the conductive particles 5 with the first electrode 2b and the second electrode 4b by pressurization, the contact area between the first and second electrodes 2b, 4b and the conductive particles 5 can be increased. it can. Moreover, it is preferable to form the insulating layer 6 by excluding the insulating layer 6A portion between the first electrode 2b and the B-staged anisotropic conductive layer 3B by pressurization. It is preferable that the fluidity of the insulating layer 6A is increased by heating during the main curing. The insulating layer 6A is preferably cured during the main curing of the B-staged anisotropic conductive layer 3B.

  In this way, the first connection target member 2 and the second connection target member 4 are connected via the cured product layer 3 or the insulating layer 6. Further, the first electrode 2 b and the second electrode 4 b are electrically connected through the conductive particles 5. As a result, the connection structure 11 shown in FIG. 3 is obtained.

  In addition, the 2nd laminated body 16 shown by Fig.4 (a) can be obtained as follows through each process shown to Fig.5 (a)-(c).

  First, as shown to Fig.5 (a), the 2nd connection object member 4 which has the 2nd electrode 4b in the surface 4a is prepared. The second connection target member 4 is arranged so that the second electrode 4b is on the upper side.

  Next, as shown in FIG. 5B, the anisotropic conductive material is disposed on the surface 4a of the second connection target member 4, and the anisotropic conductive material layer 3A is laminated. At this time, it is preferable that one or a plurality of conductive particles 5 be disposed on the second electrode 4b.

  Next, the anisotropic conductive material layer 3A is cured by irradiating the anisotropic conductive material layer 3A with light. Here, the anisotropic conductive material layer 3A is irradiated with light to advance the curing of the anisotropic conductive material layer 3A, and the anisotropic conductive material layer 3A is B-staged (B-stage forming step). . That is, as shown in FIG. 5C, the B-staged anisotropic conductive layer 3 </ b> B is formed on the surface 4 a of the second connection target member 4 to obtain the second stacked body 16. The second connection target member 4 and the B-staged anisotropic conductive layer 3B are temporarily bonded by the B-staging. The B-staged anisotropic conductive layer 3B is a semi-cured product in a semi-cured state. The B-staged anisotropic conductive layer 3B is not completely cured, and thermal curing can further proceed. Curing of the anisotropic conductive material layer 3A may be advanced by heating instead of light irradiation. When the anisotropic conductive material layer 3A contains a solvent, the B-staged anisotropic conductive layer 3B may be formed by removing the solvent of the anisotropic conductive material layer 3A.

  The application conditions for forming the anisotropic conductive material layer 3A and the light irradiation conditions for proceeding with the curing of the anisotropic conductive material layer 3A are the same as in the anisotropic conductive material layer 22A.

  In FIG. 8, the connection structure which concerns on the 2nd Embodiment of this invention is typically shown with sectional drawing.

  A connection structure 31 shown in FIG. 8 includes a first connection target member 2, a second connection target member 4, an insulating layer 6, and a cured product layer 22. The connection structure 31 shown in FIG. 8 is formed using the laminated body 21 shown in FIG. The connection structure 31 and the connection structure 11 differ only in the cured product layers 22 and 3.

  The connection structure 31 can be obtained as follows using the stacked body 21 and using FIGS. 9A to 9C.

  First, as shown to Fig.9 (a), the laminated body 21 is arrange | positioned so that the 1st connection object member 2 may become an upper side, and B-staged anisotropic conductive layer 22B may become a lower side. Moreover, the 2nd connection object member 4 which has the some 2nd electrode 4b on the surface is prepared. The 2nd connection object member 4 is arrange | positioned so that the 2nd electrode 4b may become an upper side. Further, the first electrode 2b and the second electrode 4b are opposed to each other.

  Next, as shown in FIG. 9B, the first connection target member 2, the insulating layer 6A, the B-staged anisotropic conductive layer 22B, and the second connection target member 4 are laminated in this order. On the surface 4a of the second connection target member 4, the laminate 21 is laminated from the B-staged anisotropic conductive layer 22B side. The second connection target so that the plurality of first electrodes 2b on the surface 2a of the first connection target member 2 and the plurality of second electrodes 4b on the surface 4a of the second connection target member 4 face each other. A laminated body 21 is laminated on the surface 4 a of the member 4. In this state, the insulating layer 6A portion between the first electrode 2b and the B-staged anisotropic conductive layer 22B is not excluded. The conductive particles 5 and the first electrode 2b are not in contact with each other.

  Furthermore, as shown in FIG. 9C, the B-staged anisotropic conductive layer 22 </ b> B is fully cured by heating the B-staged anisotropic conductive layer 22 </ b> B when the stacked body 21 is stacked, The cured product layer 22 is formed (main curing process). At this time, the insulating layer 6A (insulating material) is also preferably fully cured. Moreover, it is preferable to cure the thermosetting compound contained in the insulating layer 6A with a thermosetting agent contained in the B-staged anisotropic conductive layer 22B. In the main curing step, the conductive particles 5 are brought into contact with the first and second electrodes 2b and 4b, excluding the insulating layer 6A portion between the first electrode 2b and the B-staged anisotropic conductive layer 22B. Let As a result of eliminating the insulating layer 6A portion between the first electrode 2b and the B-staged anisotropic conductive layer 22B, the insulating layer 6 is formed.

  The heating temperature for curing the B-staged anisotropic conductive layer 22B by heating is the same as that for the B-staged anisotropic conductive layer 3B.

  In this way, the first connection target member 2 and the second connection target member 4 are connected via the cured product layer 22 or the insulating layer 6. Further, the first electrode 2 b and the second electrode 4 b are electrically connected through the conductive particles 5. As a result, the connection structure 31 shown in FIG. 8 is obtained.

  In addition, by using the multilayer film 46 mentioned above without using the laminated body 21, the multilayer film 46 is arrange | positioned between the 1st connection object member 2 and the 2nd connection object member 4, FIG. It is also possible to obtain the laminated structure shown in b). In this case, in the state shown in FIG. 9B, an insulating material is laminated on the surface 2a of the first connection target member 2, and an insulating layer is formed by the insulating film 6XA.

  Furthermore, without using the laminated body 21, the insulating film and the B-staged anisotropic conductive film are used separately, and between the first connection target member 2 and the second connection target member 4. By arranging the insulating film and the B-staged anisotropic conductive film, it is also possible to obtain a laminated structure shown in FIG. Also in this case, in the state shown in FIG. 9B, the insulating material is laminated on the surface 2a of the first connection target member 2, and the insulating layer is formed by the insulating film.

  In the connection structure manufacturing method described above, since photocuring and thermosetting are used in combination, the anisotropic conductive material can be cured in a short time. Anisotropic conductive material layer or B-stage anisotropic by heating and main-curing after anisotropically conductive material layer is made B-stage by applying heat or irradiating light at the time of producing connection structure The conductive particles contained in the conductive layer become difficult to flow excessively in the curing stage. Accordingly, the conductive particles are easily arranged in a predetermined region. Specifically, conductive particles can be arranged between upper and lower electrodes to be connected, and adjacent electrodes that should not be connected are electrically connected via a plurality of conductive particles. It can be further suppressed. For this reason, the insulation reliability and conduction | electrical_connection reliability between electrodes in a connection structure can be improved further.

  In addition, when the connection structure is manufactured, the anisotropic conductive material layer is B-staged by light irradiation, and then heated to be fully cured, so that the cured state of the B-staged anisotropic conductive layer can be easily achieved. And it can be controlled accurately. For this reason, it can further suppress that the electroconductive particle contained in the B-staged anisotropic conductive layer flows excessively in the main curing stage. Accordingly, the conductive particles are easily arranged in a predetermined region. For this reason, the insulation reliability and conduction | electrical_connection reliability between electrodes in a connection structure can be improved further.

  The connection structure according to the present invention and the method for manufacturing the connection structure according to the present invention include, for example, connection between a flexible printed circuit board and a glass substrate (FOG (Film on Glass)), 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)), or the like.

  The connection structure according to the present invention and the method for manufacturing the connection structure according to the present invention are suitable for COG applications. In the manufacturing method of the connection structure according to the present invention, it is preferable to use a semiconductor wafer or semiconductor chip (divided semiconductor wafer) and a glass substrate as the first connection target member and the second connection target member.

  In COG applications, in particular, it is often difficult to reliably connect the electrodes of the semiconductor chip and the glass substrate with conductive particles of an anisotropic conductive material. For example, in the case of COG use, the distance between adjacent electrodes of a semiconductor chip and the distance between adjacent electrodes of a glass substrate may be about 8 to 20 μm, and fine wiring is often formed. Even if fine wiring is formed, the method for manufacturing a connection structure according to the present invention enables the conductive particles to be accurately placed between the electrodes, so that there is high accuracy between the electrodes of the semiconductor chip and the glass substrate. It is possible to improve the conduction reliability.

  For COG applications, both the semiconductor chip and the glass substrate are particularly hard. For this reason, the insulation reliability in the connection structure tends to be low. On the other hand, in the present invention, even when a hard semiconductor chip and a glass substrate are connected, the insulation reliability can be sufficiently increased.

  In the COG application, the surface of the first electrode protruding from the first connection target member is flattened before the insulating layer is laminated, so that the first connection target member and the second connection target member Connection reliability increases. When the protruding first electrode of the first connection target member is a copper electrode, the electrode has a high Young's modulus, and therefore the deformation of the protruding electrode at the time of connection is small. For this reason, since the deformation amount of the conductive particles may vary between the plurality of electrodes of the connection structure, it is preferable to planarize the surface of the first electrode in advance.

  In addition, the connection structure according to the present invention and the method for manufacturing the connection structure according to the present invention are suitably used for connection between a semiconductor wafer and another connection target member. Furthermore, in order to obtain a connection structure in which the semiconductor chip and other connection target members are connected, it is preferably used to obtain a connection structure in which the semiconductor wafer and other connection target members are connected. In this case, a semiconductor wafer is used as the first connection target member or the second connection target member. In particular, it is preferable to use a semiconductor wafer as the first connection target member. In the connection structure, the first connection target member is preferably a semiconductor wafer or an individual semiconductor chip that is a semiconductor wafer after division. When a semiconductor wafer is used as the first connection target member or the second connection target member, the method for manufacturing a connection structure according to the present invention cuts the semiconductor wafer, and after dividing the semiconductor wafer The step of forming individual semiconductor chips may be further provided. In the method for manufacturing a connection structure according to the present invention, after the cured product layer is formed, a laminate of the first connection target member, the insulating layer, the cured product layer, and the second connection target member is formed. A step of cutting and dividing the semiconductor wafer into individual semiconductor chips may be further provided.

  When the first connection target member or the second connection target member is a semiconductor wafer, the concentration unevenness of the conductive particles occurs when the first connection target member and the second connection target member are stacked. However, there is a problem that it is difficult to ensure insulation between adjacent electrodes. On the other hand, by the connection structure according to the present invention and the method for manufacturing the connection structure according to the present invention, the first connection target member or the second connection target member is adjacent to the semiconductor wafer. The insulating property between the electrodes can be improved.

  The minimum melt viscosity in the measurement temperature range of 60 to 150 ° C. of the insulating layer and the anisotropic conductive material is preferably 1 Pa · s or more, more preferably 10 Pa · s or more, and preferably 20000 Pa · s or less. The minimum melt viscosity in the measurement temperature range of 60 to 100 ° C. of the insulating layer is 20000 Pa · s or less. If the minimum melt viscosity is less than 1 Pa · s, voids tend to occur due to the outflow of the resin. When the minimum melt viscosity is not more than the above upper limit, the insulation reliability and the conduction reliability are further enhanced.

  The minimum melt viscosity is determined by measuring the minimum complex viscosity η * using a rheometer. The measurement conditions are strain control 1 rad, frequency 1 Hz, temperature rising rate 20 ° C./min, and measurement temperature range 60 to 150 ° C.

  Examples of the rheometer include STRESTTECH (manufactured by EOLOGICA).

  The minimum melt viscosity of the anisotropic conductive material is preferably higher than the minimum melt viscosity of the insulating layer. The minimum melt viscosity of the insulating layer is preferably 1 Pa · s or more, more preferably 100 Pa · s or more, preferably 10000 Pa · s or less, more preferably 7000 Pa · s or less, and further preferably 4500 Pa · s or less. The minimum melt viscosity of the anisotropic conductive material is preferably 100 Pa · s or more, more preferably 1000 Pa · s or more, preferably 50000 Pa · s or less, more preferably 30000 Pa · s or less, and further preferably 8000 Pa · s or less. is there. The absolute value of the difference between the minimum melt viscosity of the insulating layer and the minimum melt viscosity of the anisotropic conductive material is preferably 1000 Pa · s or more, more preferably 3000 Pa · s or more. When the minimum melt viscosity of the insulating layer and the minimum melt viscosity of the anisotropic conductive material exhibit the above preferable values, void discharge and conductive particle capture rate are improved. When the minimum melt viscosity of the insulating layer is higher than the minimum melt viscosity of the anisotropic conductive material, if the minimum melt temperature of the anisotropic conductive material is not less than the lower limit and not more than the upper limit, The discharge property and the capture rate of conductive particles are improved.

  It is preferable that the minimum melting temperature of the insulating layer is lower than the minimum melting temperature of the anisotropic conductive material. The minimum melting temperature of the insulating layer is preferably 60 ° C. or higher, more preferably 70 ° C. or higher, preferably 110 ° C. or lower, more preferably 100 ° C. or lower. The minimum melting temperature of the anisotropic conductive material is preferably 60 ° C. or higher, more preferably 70 ° C. or higher, preferably 150 ° C. or lower, more preferably 120 ° C. or lower. The absolute value of the difference between the minimum melting temperature of the insulating layer and the minimum melting temperature of the anisotropic conductive material is preferably 5 ° C. or higher, more preferably 10 ° C. or higher. When the minimum melting temperature of the insulating layer and the minimum melting temperature of the anisotropic conductive material are equal to or higher than the lower limit and equal to or lower than the upper limit, the void discharge property and the capturing rate of conductive particles are improved. The minimum melting temperature is a temperature indicating the minimum melt viscosity.

  Viscosity ratio (η3 / η4) of viscosity η3 (Pa · s) at 1 Hz at a temperature showing the minimum melt viscosity of the anisotropic conductive material to viscosity η4 (Pa · s) at 10 Hz at a temperature showing the minimum melt viscosity ) Is preferably 2 or more, more preferably 3 or more, and still more preferably 4 or more. If the viscosity ratio (η3 / η4) is greater than or equal to the lower limit, voids are less likely to occur in the cured product layer. When the viscosity ratio (η3 / η4) is 3 or more, voids are hardly generated in the cured product layer.

  Furthermore, when the viscosity ratio (η3 / η4) is equal to or higher than the lower limit, the anisotropic conductive material can be prevented from unintentionally spreading before or during curing, and contamination in the connection structure is less likely to occur. . Therefore, when the viscosity ratio (η3 / η4) is equal to or higher than the lower limit, it is possible to suppress voids in the cured product layer and to suppress contamination due to the flow of the anisotropic conductive material layer or the B-staged anisotropic conductive layer. Both effects can be obtained. The upper limit of the viscosity ratio (η3 / η4) is not particularly limited, but the viscosity ratio (η3 / η4) is preferably 8 or less.

  Regarding the exothermic peak temperature by DSC (differential scanning calorimetry) between the insulating layer and the anisotropic conductive material, the exothermic peak temperature of the insulating layer is higher than the exothermic peak temperature of the anisotropic conductive material. It is preferable. The absolute value of the difference between the exothermic peak temperature of the anisotropic conductive material and the exothermic peak temperature of the insulating layer is preferably 5 ° C. or higher, more preferably 10 ° C. or higher. Thereby, the void discharge property and the capture rate of the conductive particles are improved.

  Regarding the heat generation by DSC (differential scanning calorimetry) between the insulating layer and the anisotropic conductive material, the heat generation of the insulating layer is preferably smaller than the heat generation of the anisotropic conductive material. Thereby, the void discharge property and the capture rate of the conductive particles are improved.

  The elastic modulus of the cured insulating layer and the cured product layer obtained by curing the anisotropic conductive material is preferably 100 MPa or more, preferably 4 GPa or less at 25 ° C., and further preferably 10 MPa or more, preferably 3 GPa or less at 85 ° C. . When the elastic modulus is not less than the above lower limit and not more than the above upper limit, connection reliability when receiving a thermal history is increased.

  The glass transition temperature Tg of the cured insulating layer and the cured product layer obtained by curing the anisotropic conductive paste is preferably 50 ° C. or higher, and preferably 180 ° C. or lower. When the glass transition temperature is not less than the above lower limit and not more than the above upper limit, the connection reliability of the connection structure when receiving a thermal history is increased.

  The elastic modulus and the Tg are measured using a viscoelasticity measuring device DVA-200 (manufactured by IT Measurement & Control Co., Ltd.) under conditions of a heating rate of 5 ° C./min, a deformation rate of 0.1% and 10 Hz. The temperature at the peak of tan δ is defined as Tg (glass transition point).

  The anisotropic conductive material is cured by irradiating the anisotropic conductive material with light to form a B-stage and then further irradiating with light to fully cure the anisotropic conductive material. A method of further curing by heating after B-stage, a method of further curing by heating to a B-stage by irradiating light to the anisotropic conductive material, and heating the anisotropic conductive material Then, after making the B stage, there is a method of further irradiating light to perform the main curing. In addition, when the photocuring speed and the thermosetting speed are different, light irradiation and heating may be performed simultaneously. In the B-stage forming step, the anisotropic conductive material is cured by light irradiation to form a B-stage anisotropic conductive layer. In the main curing step, the B-stage is formed by heating. It is preferable to fully cure the anisotropic conductive layer. By the combined use of photocuring and heat curing, the anisotropic conductive material can be efficiently cured in a short time.

  Further, as a method of curing the anisotropic conductive material, after removing the solvent of the anisotropic conductive material to make a B-stage, the method of further irradiating with light to perform the main curing, and the anisotropic conductive material There is also a method in which after the solvent is removed to form a B stage, the film is further heated to be fully cured.

  The anisotropic conductive material is an anisotropic conductive material curable by heating, and a curable compound (thermosetting compound or light and thermosetting compound) curable by heating is used as the curable compound. May be included. The curable compound curable by heating may be a curable compound (thermosetting compound) that is not cured by light irradiation, and is curable by both light irradiation and heating (light and light). Thermosetting compound).

  The anisotropic conductive material is an anisotropic conductive material that can be cured by light irradiation. As the curable compound, a curable compound that can be cured by light irradiation (a photocurable compound or light and heat curing). A functional compound). The curable compound that can be cured by irradiation with light may be a curable compound that is not cured by heating (photocurable compound), or a curable compound that can be cured by both irradiation of light and heating (light and light). Thermosetting compound).

  The anisotropic conductive material is preferably an anisotropic conductive material that can be cured by both light irradiation and heating. The curable compound preferably contains a curable compound that can be cured by light irradiation and a curable compound that can be cured by heating. In this case, the anisotropic conductive material is semi-cured (B-stage) by light irradiation, and after the fluidity of the anisotropic conductive material is lowered, the anisotropic conductive material is easily cured by heating. Can be made. The curable component contained in the anisotropic conductive material includes a photocurable component capable of being irradiated by light and a thermosetting component capable of being cured by heating, or by both irradiation of light and heating. It is preferred to include a curable light and thermosetting component.

(Anisotropic conductive material)
Hereinafter, the detail of each component used suitably for the said anisotropic conductive material is demonstrated.

[Curable compound]
The curable compound contained in the anisotropic conductive material is not particularly limited. A conventionally known curable compound can be used as the curable compound. As for the said sclerosing | hardenable compound, only 1 type may be used and 2 or more types may be used together.

  Examples of the curable compound include oxetane compounds, epoxy compounds, episulfide compounds, (meth) acrylic compounds, phenolic compounds, amino compounds, unsaturated polyester compounds, polyurethane compounds, silicone compounds, and polyimide compounds. As for the said sclerosing | hardenable compound, only 1 type may be used and 2 or more types may be used together.

  The curable compound preferably contains a curable compound having an epoxy group or a thiirane group. The curable compound having an epoxy group is an epoxy compound. The curable compound having a thiirane group is an episulfide compound. As for the said curable compound which has an epoxy group or thiirane group, only 1 type may be used and 2 or more types may be used together.

  More preferably, the curable compound contains a curable compound having a thiirane group. Since the episulfide compound has a thiirane group instead of an epoxy group, it can be quickly cured at a low temperature. That is, the episulfide compound having a thiirane group can be cured at a lower temperature derived from the thiirane group as compared with the epoxy compound having an epoxy group.

  The curable compound having an epoxy group or thiirane group preferably has an aromatic ring. Examples of the aromatic ring include the aromatic rings described above. 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.

  From the viewpoint of enhancing the curability of the anisotropic conductive material, the content of the curable compound having the epoxy group or thiirane group is preferably 10% by weight or more in the total 100% by weight of the curable compound. Preferably they are 20 weight% or more and 100 weight% or less. The total amount of the curable compound may be a curable compound having the epoxy group or thiirane group. When the curable compound having the epoxy group or thiirane group and another curable compound different from the curable compound having the epoxy group or thiirane group are used in combination, in the total 100% by weight of the curable compound, The content of the curable compound having an epoxy group or thiirane group is preferably 99% by weight or less, more preferably 95% by weight or less, still more preferably 90% by weight or less, and particularly preferably 80% by weight or less.

  The curable compound may further contain another curable compound different from the curable compound having an epoxy group or a thiirane group. Examples of the other curable compounds include curable compounds having an unsaturated double bond, phenol curable compounds, amino curable compounds, unsaturated polyester curable compounds, polyurethane curable compounds, silicone curable compounds, and polyimide curable compounds. Compounds and the like. As for said other curable compound, only 1 type may be used and 2 or more types may be used together.

  From the viewpoint of easily controlling the curing of the anisotropic conductive material or further improving the conduction reliability in the connection structure, the curable compound contains a curable compound having an unsaturated double bond. It is preferable to do. From the viewpoint of easily controlling the curing of the anisotropic conductive material and further improving the conduction reliability in the connection structure, the curable compound having an unsaturated double bond is a (meth) acryloyl group. It is preferable that it is a curable compound which has. By using the curable compound having the (meth) acryloyl group, the curing rate can be improved in the entire B-staged anisotropic conductive material (including the portion directly irradiated with light and the portion not directly irradiated with light). It becomes easy to control within a suitable range, and the conduction reliability in the resulting connection structure is further increased.

  From the viewpoint of easily controlling the curing rate of the B-staged anisotropic conductive material layer and further improving the conduction reliability of the resulting connection structure, the curable compound having the (meth) acryloyl group is: It is preferable to have one or two (meth) acryloyl groups.

  The curable compound having the (meth) acryloyl group has no epoxy group and thiirane group, and has a (meth) acryloyl group, and has an epoxy group or thiirane group, and (meth) A curable compound having an acryloyl group may be mentioned.

  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 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 epoxy group or thiirane group and having a (meth) acryloyl group is a part of the epoxy group or part of thiirane group of the compound having two or more epoxy groups or two or more thiirane groups. It is preferable that it is a curable compound obtained by converting into a (meth) acryloyl group. This curable compound is a partially (meth) acrylated epoxy compound or a partially (meth) acrylated episulfide compound.

  The curable compound preferably contains a reaction product of a compound having two or more epoxy groups or two or more thiirane groups and (meth) acrylic acid. This reaction product is obtained by reacting a compound having two or more epoxy groups or two or more thiirane groups with (meth) acrylic acid in the presence of a catalyst such as a basic catalyst according to a conventional method. It is preferable that 20% or more of the epoxy group or thiirane group is converted (converted) to a (meth) acryloyl group. The conversion is more preferably 30% or more, preferably 80% or less, more preferably 70% or less. Most preferably, 40% or more and 60% or less of the epoxy group or thiirane group is converted to a (meth) acryloyl group.

  Examples of the partially (meth) acrylated epoxy compound include bisphenol type epoxy (meth) acrylate, cresol novolac type epoxy (meth) acrylate, carboxylic acid anhydride-modified epoxy (meth) acrylate, and phenol novolac type epoxy (meth) acrylate. Is mentioned.

  As the curable compound, a modified phenoxy resin obtained by converting a part of epoxy groups of a phenoxy resin having two or more epoxy groups or two or more thiirane groups or a part of thiirane groups into a (meth) acryloyl group may be used. Good. That is, a modified phenoxy resin having an epoxy group or thiirane group and a (meth) acryloyl group may be used.

  The curable compound may be a crosslinkable compound or a non-crosslinkable compound. Examples of the crosslinkable compound and the non-crosslinkable compound include the above-described crosslinkable compounds and non-crosslinkable compounds that can be used in the insulating material.

  When a thermosetting compound and a photocurable compound are used in combination, the blending ratio of the photocurable compound and the thermosetting compound is appropriately adjusted according to the type of the photocurable compound and the thermosetting compound. The The anisotropic conductive material preferably contains a photocurable compound and a thermosetting compound in a weight ratio of 1:99 to 90:10, more preferably 5:95 to 60:40, More preferably, it is included at 10:90 to 40:60.

[Thermosetting agent]
The anisotropic conductive material preferably contains a thermosetting agent that is a thermosetting component. The anisotropic conductive material preferably contains a thermosetting agent for curing the thermosetting compound contained in the insulating material. The thermosetting agent is not particularly limited. A conventionally known thermosetting agent can be used as the thermosetting agent. Examples of the thermosetting agent include imidazole curing agents, amine curing agents, phenol curing agents, polythiol curing agents, acid anhydrides, thermal cation curing agents, and thermal radical generators. As for the said thermosetting agent, only 1 type may be used and 2 or more types may be used together.

  From the viewpoint of curing the anisotropic conductive material more rapidly at a low temperature, the anisotropic conductive material preferably contains an imidazole curing agent, a polythiol curing agent, an amine curing agent, or a thermal cation curing agent. Examples of the curing agent include the above-described curing agents that can be used for the insulating material.

  From the viewpoint of further improving the connection reliability between the electrodes and the connection reliability of the connection structure under high temperature and high humidity, the anisotropic conductive material preferably contains a thermal radical generator. The thermal radical generator is not particularly limited. As the thermal radical generator, a conventionally known thermal radical generator can be used. As for the said thermal radical generator, only 1 type may be used and 2 or more types may be used together. Examples of the thermal radical generator include the thermal radical generators described above that can be used for the insulating material.

  The content of the thermosetting agent is not particularly limited. The content of the thermosetting agent in the anisotropic conductive material is preferably 0.01 parts by weight or more with respect to 100 parts by weight of the curable compound curable by heating in the anisotropic conductive material. More preferably 0.05 parts by weight or more, still more preferably 5 parts by weight or more, particularly preferably 10 parts by weight or more, preferably 40 parts by weight or less, more preferably 30 parts by weight or less, still more preferably 20 parts by weight or less. .

  Further, the content of the thermosetting agent is preferably 100 parts by weight with respect to a total of 100 parts by weight of the thermosetting compound in the insulating material and the curable compound curable by heating in the anisotropic conductive material. Is 0.01 parts by weight or more, more preferably 0.05 parts by weight or more, still more preferably 5 parts by weight or more, particularly preferably 10 parts by weight or more, preferably 40 parts by weight or less, more preferably 30 parts by weight or less, The amount is preferably 20 parts by weight or less. When the content of the thermosetting agent is not less than the above lower limit and not more than the above upper limit, the insulating material and the anisotropic conductive material are sufficiently thermoset.

  When the thermosetting agent contains a thermal radical generator, it is contained in the anisotropic conductive material with respect to 100 parts by weight of the curable compound that is curable by heating and contained in the anisotropic conductive material. The content of the thermal radical generator is preferably 0.01 parts by weight or more, more preferably 0.05 parts by weight or more, preferably 10 parts by weight or less, more preferably 5 parts by weight or less. When the content of the thermal radical generator is not less than the above lower limit and not more than the above upper limit, the anisotropic conductive material is sufficiently thermally cured.

  Further, with respect to a total of 100 parts by weight of the thermosetting compound in the insulating material and the curable compound curable by heating in the anisotropic conductive material, the content of the thermal radical generator is Preferably it is 0.01 weight part or more, More preferably, it is 0.05 weight part or more, Preferably it is 10 weight part or less, More preferably, it is 5 weight part or less. When the content of the thermal radical generator is not less than the above lower limit and not more than the above upper limit, the insulating material and the anisotropic conductive material are sufficiently thermally cured.

[Photocuring initiator]
The anisotropic conductive material preferably contains a photocuring initiator that is a photocuring component. The photocuring initiator is not particularly limited. A conventionally known photocuring initiator can be used as the photocuring initiator. From the viewpoint of further improving the connection reliability between the electrodes and the connection reliability of the connection structure, the anisotropic conductive material preferably contains a photoradical generator. As for the said photocuring initiator, only 1 type may be used and 2 or more types may be used together.

  The photocuring initiator is not particularly limited, and is not limited to acetophenone photocuring initiator (acetophenone photoradical generator), benzophenone photocuring initiator (benzophenone photoradical generator), thioxanthone, ketal photocuring initiator (ketal photoradical). Generator), halogenated ketones, acyl phosphinoxides, acyl phosphonates, and the like. Examples of the photocuring initiator include a photocationic initiator.

  Specific examples of the acetophenone photocuring initiator include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, methoxy Examples include acetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, and 2-hydroxy-2-cyclohexylacetophenone. Specific examples of the ketal photocuring initiator include benzyldimethyl ketal.

  The anisotropic conductive material preferably contains a photocationic initiator. By using a photocation initiator, curing of the anisotropic conductive material after light irradiation can be rapidly advanced. Furthermore, the anisotropic conductive material layer portion that is blocked by the conductive particles and not directly irradiated with light can be sufficiently cured by the cation reaction due to the action of the photocation initiator.

  Examples of the photocationic curing agent include iodonium-based photocationic curing agents, oxonium-based photocationic curing agents, and sulfonium-based photocationic curing agents. Examples of the iodonium-based photocationic curing agent include bis (4-tert-butylphenyl) iodonium hexafluorophosphate. Examples of the oxonium-based photocationic curing agent include trimethyloxonium tetrafluoroborate. Examples of the sulfonium-based photocationic curing agent include tri-p-tolylsulfonium hexafluorophosphate and triphenylsulfonium bromide. Of these, a sulfonium-based photocationic curing agent is preferable from the viewpoint of further improving the curability of the anisotropic conductive material and further enhancing the conduction reliability between the electrodes.

  The content of the photocuring initiator is not particularly limited. For 100 parts by weight of the curable compound curable by light irradiation, the content of the photocuring initiator (the content of the photocationic initiator when the photocuring initiator is a photocationic initiator) is , Preferably 0.1 parts by weight or more, more preferably 0.2 parts by weight or more, preferably 2 parts by weight or less, more preferably 1 part by weight or less. When the content of the photocuring initiator is not less than the above lower limit and not more than the above upper limit, the anisotropic conductive material can be appropriately photocured. By irradiating the anisotropic conductive material with light to form a B stage, the flow of the anisotropic conductive material can be suppressed.

[Conductive particles]
The conductive particles contained in the anisotropic conductive material electrically connect the electrodes of the first and second connection target members. The conductive particles are not particularly limited as long as they are conductive particles. The surface of the conductive layer of the conductive particles may be covered with an insulating layer. The surface of the conductive layer of the conductive particles may be covered with insulating particles. In these cases, the insulating layer or insulating particles between the conductive layer and the electrode are excluded when the connection target member is connected. Examples of the conductive particles include conductive particles whose surfaces are covered with a conductive layer, such as organic particles, inorganic particles, organic-inorganic hybrid particles, or metal particles, and metal particles that are substantially composed only of metal. It is done. The conductive layer is not particularly limited. Examples of the conductive layer include a gold layer, a silver layer, a copper layer, a nickel layer, a palladium layer, and 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 includes a resin particle and a conductive layer disposed on the surface of the resin particle. It is preferable to have. From the viewpoint of further improving the conduction reliability between the electrodes, the conductive particles are preferably conductive particles having at least an outer surface of a low melting point metal layer. More preferably, 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 a low melting point metal layer. Further, the metal particles may be a low melting point metal.

  The low melting point metal layer is a layer containing a low melting point metal. The low melting point metal is a metal having a melting point of 450 ° C. or lower. The melting point of the low melting point metal is preferably 300 ° C. or lower. The low-melting-point metal has a role of melting by heating and joining to the electrodes and conducting between the electrodes.

  The low melting point metal constituting the low melting point metal is not particularly limited, but is preferably tin or an alloy containing tin. Examples of the alloy include a tin-silver alloy, a tin-copper alloy, a tin-silver-copper alloy, a tin-bismuth alloy, and a tin-zinc alloy. The low melting point metal layer preferably contains tin. In 100% by weight of the metal contained in the low melting point metal layer, the content of tin is preferably 30% by weight or more, more preferably 50% by weight or more, still more preferably 70% by weight or more, and particularly preferably 90% by weight or more. . Especially, since wettability is excellent with respect to each electrode material, it is preferable that a low melting metal is a tin, a tin-silver alloy, or a tin-silver-copper alloy. The tin content is determined using a high frequency inductively coupled plasma optical emission spectrometer (“ICP-AES” manufactured by Horiba, Ltd.) or a fluorescent X-ray analyzer (“EDX-800HS” manufactured by Shimadzu). It can be measured.

  The low melting point metal layer is preferably a solder layer. Although the material which comprises the said solder layer is not specifically limited, Based on JISZ3001: solvent term, it is preferable that it is a meltable material whose liquidus is 450 degrees C or less. Examples of the composition of the solder layer include metal compositions containing zinc, gold, silver, 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 layer preferably does not contain lead, and is preferably a solder layer containing tin and indium or a solder layer containing tin and bismuth.

  Furthermore, in order to improve the bonding strength between the low melting point metal and the electrode, the low melting point metal includes nickel, copper, antimony, aluminum, zinc, iron, gold, titanium, phosphorus, germanium, tellurium, cobalt, bismuth, Metals such as manganese, chromium, molybdenum, and palladium may be included. Especially, since it is excellent in the effect which improves the joining strength of the said low melting metal and an electrode, it is suitable to make the said low melting metal contain nickel, copper, antimony, aluminum, and zinc. From the viewpoint of further increasing the bonding strength between the low melting point metal layer and the electrode, the content of these metals for increasing the bonding strength is 100 wt% of the low melting point metal layer, preferably 0.0001 wt% or more, Preferably it is 1 weight% or less.

  The conductive particles include resin particles and a conductive layer disposed on the surface of the resin particles, and the outer surface of the conductive layer is a low-melting metal layer, and the resin particles and the low-melting metal In addition to the low melting point metal layer, it is preferable to have a second conductive layer between the layers (such as solder layers). In this case, the low melting point metal layer is a part of the entire conductive layer, and the second conductive layer is a part of the entire conductive layer.

  The second conductive layer different from the low melting point metal layer preferably contains a metal. The metal constituting the second 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 and cadmium, and alloys thereof. 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 second 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 low melting point metal layer can be more easily formed on the surface of these preferable conductive layers. The second conductive layer may be a low melting point metal layer such as a solder layer. The conductive particles may have a plurality of low melting point metal layers.

  The thickness of the low melting point metal layer is preferably 5 nm or more, more preferably 10 nm or more, further preferably 20 nm or more, preferably 40000 nm or less, more preferably 30000 nm or less, still more preferably 20000 nm or less, particularly preferably 10,000 nm or less. . When the thickness of the low melting point metal layer is not less than the above lower limit, the conductivity is sufficiently high. When the thickness of the low melting point metal layer is not more than the above upper limit, the difference in thermal expansion coefficient between the resin particles and the low melting point metal layer becomes small, and the low melting point metal layer is hardly peeled off.

  When the conductive layer is a conductive layer other than the low melting point metal layer, or when the conductive layer has a multilayer structure, the total thickness of the conductive layer is preferably 10 nm or more, preferably 40000 nm or less, more preferably 30000 nm or less, More preferably, it is 20000 nm or less, Most preferably, it is 10,000 nm or less.

  The average particle diameter of the conductive particles is preferably 0.5 μm or more, more preferably 1 μm or more, preferably 100 μm or less, more preferably 20 μm or less, still more preferably 15 μm or less, and particularly preferably 10 μm or less. From the viewpoint of further improving the connection reliability of the connection structure when subjected to a thermal history, the average particle diameter of the conductive particles is particularly preferably 1 μm or more and 10 μm or less, and is 1 μm or more and 4 μm or less. Most preferred.

  The “average particle size” of the conductive particles indicates a number average particle size. The average particle diameter of the conductive particles can be obtained by observing 50 arbitrary conductive particles with an electron microscope or an optical microscope and calculating an average value.

  The compressive elastic modulus (10% K value) at 23 ° C. of the conductive particles is preferably 1 GPa or more, more preferably 2 GPa or more, preferably 7 GPa or less, more preferably 5 GPa or less. The compression recovery rate of the conductive particles is preferably 20% or more, more preferably 30% or more, preferably 60% or less, more preferably 50% or less.

  The content of the conductive particles is not particularly limited. The content of the conductive particles in 100% by weight of the anisotropic conductive material is preferably 0.1% by weight or more, more preferably 0.5% by weight or more, still more preferably 1% by weight or more, preferably 40% by weight. % Or less, more preferably 30% by weight or less, still more preferably 19% by weight or less. A conductive particle can be easily arrange | positioned between the upper and lower electrodes which should be connected as content of the said electroconductive particle is more than the said minimum and below the said upper limit. 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 anisotropic conductive material preferably contains a filler. By using the filler, the thermal expansion coefficient of the cured product of the anisotropic conductive material 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 anisotropic conductive material preferably further contains a curing accelerator. By using a curing accelerator, the curing rate can be further increased. As for a hardening accelerator, only 1 type may be used and 2 or more types may be used together.

  Specific examples of the curing accelerator include imidazole curing accelerators and amine curing accelerators. Of these, imidazole curing accelerators are preferred. In addition, an imidazole hardening accelerator or an amine hardening accelerator can be used also as an imidazole hardening agent or an amine hardening agent.

  The anisotropic conductive material may contain a solvent. By using the solvent, the viscosity of the anisotropic conductive material can be easily adjusted. As said solvent, the solvent mentioned above etc. which can be used for the said insulating material are mentioned.

  The anisotropic conductive material preferably contains a thixotropic agent. Examples of the thixotropic agent include the above-mentioned thixotropic agents that can be used for the insulating material.

  In 100% by weight of the anisotropic conductive material, the content of the thixotropic agent is preferably 0.1% by weight or more, more preferably 1% by weight or more, preferably 30% by weight or less, more preferably 15% by weight or less. It is. When the content of the thixotropic agent is not less than the above lower limit and not more than the above upper limit, the connection reliability of the connection structure when receiving a thermal history is further enhanced.

  From the viewpoint of further improving the connection reliability of the first and second connection target members, it is preferable that the anisotropic conductive material contains an adhesion-imparting agent. Examples of the adhesion imparting agent include the above-described adhesion imparting agents that can be used for the insulating material.

  In 100% by weight of the anisotropic conductive material, the content of the adhesion-imparting agent is preferably 1% by weight or more, more preferably 5% by weight or more, preferably 50% by weight or less, more preferably 25% 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 first and second connection target members is further increased.

  The anisotropic conductive material may contain the above-described ion trapping agent or the like for the purpose of reducing impurity ions.

  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 components were used for the insulating material.

[polymer]
(1) Phenoxy resin (“4275” manufactured by Mitsubishi Chemical Corporation, weight average molecular weight 60000)
(2) Polyetheresteramide resin (weight average molecular weight 28000, synthesized in Synthesis Example 1 below)

(Synthesis Example 1)
In a 3 L separable flask, 219 parts by weight of Pripol 1009 (formula: HOOC— (CH ₂ ) ₃₄ —COOH, molecular weight 567, manufactured by Croda Japan Co., Ltd.), 5 parts by weight of ethylenediamine (molecular weight 60), and piperazine (molecular weight 86) 27 parts by weight and 0.8 parts by weight of 5% by weight aqueous phosphorous acid solution were added. A water separation tube was attached, the temperature was raised to 190 ° C. with stirring under a nitrogen flow, and a polycondensation reaction was performed until the number average molecular weight reached 1400. Thereafter, 83 parts by weight of dodecanedioic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and stirred at 190 ° C. until the contents became transparent. Thereafter, 358 parts by weight of polytetramethylene ether glycol ("PTMG1000" manufactured by Mitsubishi Chemical Corporation, weight average molecular weight 1000) and 1 part by weight of Irganox 1098 (manufactured by BASF Japan) were added and stirred until uniform. Thereafter, 0.1 part by weight of antimony trioxide and 0.1 part by weight of monobutylhydroxytin oxide were added, the temperature was raised to 250 ° C., and the mixture was stirred for 30 minutes. The pressure was reduced to 1 mmHg, and the reaction was performed at 250 ° C. for 4 hours.

  In this way, a polyetheresteramide resin (polyamide / polyester block polymer) having a weight average molecular weight of 32000 and a melting point of 120 ° C. was obtained.

  60 parts by weight of the polyetheresteramide resin, 1.5 parts by weight of 4-hydroxybutyl acrylate glycidyl ether (manufactured by Nippon Kasei Co., Ltd.), 0.1 part by weight of Irganox 1010 (manufactured by BASF Japan), and p-methoxy Phenol (manufactured by Wako Pure Chemical Industries, Ltd.) 0.1 part by weight was added and stirred until uniform. Thereafter, 0.5 part by weight of a chromium naphthenate solution was added and the temperature was raised to 85 ° C., followed by reaction at 85 ° C. for 12 hours to obtain a polyetheresteramide resin. The obtained polyetheresteramide resin has one acryloyl group at the terminal.

[Thermosetting compound]
(1) Epoxy compound A (solid at 25 ° C., “EXA-4816” manufactured by DIC)
(2) Epoxy compound B (solid at 25 ° C., “YD-014” manufactured by Nippon Steel Chemical Co., Ltd.)

[Ion scavenger]
(1) IXE-700 (Mg, Al-based anion exchanger, neutral exchange capacity 1.5 meq / g, manufactured by Toagosei Co., Ltd.)
(2) IXE-100 (Zr-based cation exchanger, neutral exchange capacity 3.3 meq / g, manufactured by Toagosei Co., Ltd.)

[solvent]
Methyl ethyl ketone

  In the examples and comparative examples, the following components were used for the anisotropic conductive material.

[Thermosetting compound]
Episulfide compound Y1 having a structure represented by the following formula (Y1)

  Episulfide compound Y2 represented by the following formula (Y2)

  EP-3300P (manufactured by ADEKA, flexible episulfide resin)

[Photocurable compound]
EBECRYL 3702 (manufactured by Daicel-Cytec, fatty acid-modified epoxy acrylate)
EBECRYL 3708 (manufactured by Daicel-Cytec, caprolactone-modified epoxy acrylate)
4HBAGE (Nippon Kasei Co., Ltd., 4-hydroxybutyl acrylate glycidyl ether)

[Thermosetting agent]
TEP-2E4MZ (Nippon Soda Co., Ltd., Inclusion Imidazole)
[Photocuring initiator]
Irgacure 819 (BASF)
[Adhesive agent]
KBE-402 (manufactured by Shin-Etsu Chemical Co., Ltd., silane coupling agent)
[Filler]
Surface methylated silica (average particle size 0.7mm, manufactured by Tokuyama)
[Thixotropic agent]
Nanosilica PM20L (manufactured by Tokuyama)
[Flexible particles]
KW-8800 (manufactured by Mitsubishi Rayon Co., Ltd., core-shell particles)

[Conductive particles]
The conductive particles A are conductive particles 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. The average particle diameter and 10% K value of the conductive particles A are as follows.

  Conductive particles A (average particle size 3 μm, 10% K value: 4.5 GPa)

Example 1
(1) Preparation of insulating material The components shown in Table 1 below were blended in the blending amounts shown in Table 1 below, and the mixture was stirred for 10 minutes at 2000 rpm using a planetary stirrer to obtain a blend. The obtained compound was filtered using nylon filter paper (pore diameter: 10 μm) to obtain an insulating material. The obtained insulating material was applied onto a release PET (polyethylene terephthalate) film, and then the solvent was removed by drying in an oven at 80 ° C. for 20 minutes to form a film to obtain a film-like insulating material. .

(2) Preparation of anisotropic conductive material The components shown in Table 1 below were blended in the blending amounts shown in Table 1 below, followed by stirring at 2000 rpm for 5 minutes using a planetary stirrer to obtain a blend. It was. The obtained compound was filtered using nylon filter paper (pore diameter 10 μm) to obtain an anisotropic conductive material (anisotropic conductive paste).

(3) Production of First Laminate A semiconductor wafer (thickness 400 μm) having copper bumps (protruding electrodes, height 12 μm) with a bump size of 20 μm × 100 μm and a pitch of 30 μm on the upper surface was prepared. The obtained film-like insulating material is vacuum-laminated at 80 ° C. over the entire upper surface of the semiconductor wafer to cover the protruding electrodes on the protruding electrodes and the gaps between the electrodes. Thus, a semiconductor wafer having an insulating layer formed thereon was obtained. The thickness of the insulating layer on the protruding electrode was 4 μm, and the thickness of the insulating layer on the gap between the protruding electrodes was 15 μm.

  Then, the semiconductor wafer with an insulating layer was diced using a dicer (“DFD6361” manufactured by DISCO) and separated into pieces of 15 mm × 1.6 mm × 0.415 mm. In this way, the semiconductor chip (the divided semiconductor wafer, the first connection target member) having a plurality of protruding electrodes on the upper surface, and the insulating layer on the plurality of electrodes and on the gaps between the plurality of electrodes. The 1st laminated body which has was obtained.

(4) Production of Connection Structure (COG) A glass substrate (second connection target member) having an ITO electrode with an L / S of 20 μm / 10 μm on the upper surface was prepared. On the glass substrate, the obtained anisotropic conductive material was applied by screen printing so as to have a thickness of 20 μm to form an anisotropic conductive material layer, thereby obtaining a second laminate.

  Next, on the surface opposite to the glass substrate side of the B-staged anisotropic conductive layer of the obtained second laminate, the electrode / bump faces the first laminate from the insulating layer side. Laminated so that. Thereafter, a pressure heating head is placed on the surface opposite to the insulating layer side of the semiconductor chip while adjusting the head temperature so that the temperature of the B-staged anisotropic conductive layer becomes 190 ° C. The B-staged anisotropic conductive layer was cured at 190 ° C. for 20 seconds to obtain a connection structure. In the obtained connection structure, an insulating layer was also disposed in a partial region on the first electrode.

(Examples 2 to 4)
An insulating material was obtained in the same manner as in Example 1 except that the types and amounts of the blending components were changed as shown in Table 1 below when the insulating material was prepared. A connection structure was obtained in the same manner as in Example 1 except that the obtained insulating material was used.

(Example 5)
A connection structure was obtained in the same manner as in Example 1 except that the material of the bumps in the semiconductor wafer was changed from copper to gold.

(Comparative Example 1)
The film-like insulating material obtained in Example 1 was vacuum-laminated at 80 ° C. on the semiconductor wafer used in Example 1 to form a gap between the plurality of electrodes without forming an insulating layer on the plurality of electrodes. A semiconductor wafer having an insulating layer formed only on the top was obtained. The thickness of the insulating layer above the gaps between the plurality of electrodes was 12 μm. Thereafter, the semiconductor wafer with the insulating layer and the B-staged anisotropic conductive layer was diced in the same manner as in Example 1 to obtain a first laminate.

  A connection structure was produced in the same manner as in Example 1 except that the obtained first laminate was used.

(Comparative Example 2)
During the preparation of the insulating material, the types and amounts of the blending components were changed as shown in Table 1 below to obtain a film-like insulating material. A connection structure was obtained in the same manner as in Example 1 except that the obtained film-like insulating material was used.

(Evaluation)
(1) Storage stability of insulating material The film-like insulating material (insulating layer) immediately after production was left at 25 ° C. for 1 month. The storage stability of the insulating material was evaluated from the change in melt viscosity at 80 ° C. of the insulating material before and after standing. Using a rheometer (“STRESSTECH” manufactured by EOLOGICA), the melt viscosity was measured under the measurement conditions: strain control 1 rad, frequency 1 Hz, temperature rising rate 20 ° C./min, measurement temperature range 60 to 150 ° C. The storage stability of the insulating material was determined according to the following criteria.

[Criteria for storage stability of insulating materials]
◯: Melt viscosity is 1 or more and less than 1.5 times ○: Melt viscosity is 1.5 or more times and less than 2.0 times ×: Melt viscosity is 2.0 or more times

(2) Probe tack of film-like insulating material After coating the insulating material used in Examples and Comparative Examples on a release PET (polyethylene terephthalate) film, the solvent is removed by drying in an oven at 80 ° C. for 20 minutes. Thus, a film-like insulating material (insulating layer) having a thickness of 15 μm was obtained.

  The obtained film-like insulating material was stored at 25 ° C. A cylindrical probe having a diameter of 5 mm was pressed against the surface of the film-like insulating material at 25 ° C. for 1 second at a pressure of 1 N / 5 mmφ, and then the probe was peeled off from the film-like insulating material at a speed of 10 mm / min. The value of the peeling force at the time of peeling was defined as the tack value. In addition, "Tacking test machine TAC-II" manufactured by RHESCA was used as a measuring apparatus. Further, after storing the temperature of the film-like insulating material at 60 ° C. to 100 ° C., the maximum value of the probe tack on the surface at 60 ° C. to 100 ° C. was obtained in the same manner as at 25 ° C.

(3) Laminating property A semiconductor wafer (thickness 400 μm) having copper bumps (protruding electrodes, height 12 μm) with a bump size of 20 μm × 100 μm and a pitch of 30 μm on the upper surface was prepared.

  The insulating material used in the examples and comparative examples was released from PET (polyethylene terephthalate film), then the solvent was removed by drying in an oven at 80 ° C. for 20 minutes, and a film-like insulating material having a thickness of 15 μm (insulating Layer).

  The obtained film-like insulating material is vacuum-laminated on the semiconductor wafer at 80 ° C. and insulated so as to cover the plurality of protruding electrodes on the protruding electrodes and the gaps between the plurality of electrodes. A semiconductor wafer having a layer formed thereon was obtained. The thickness of the insulating layer on the protruding electrode was 3 μm, and the thickness of the insulating layer on the gap between the protruding electrodes was 15 μm.

  The obtained semiconductor wafer on which the insulating layer was formed was observed, and the laminate property was determined according to the following criteria.

[Judgment criteria for laminating properties]
◯: As a result of observing between 25 bumps, there are 0 voids that are 1/3 or more of the distance between the bumps. ○: As a result of observing between 25 bumps, 1/3 or more of the distance between the bumps, 1/2. 1 or more voids less than 0, and 0 voids greater than or equal to 1/2 of the distance between bumps. X: As a result of observing between 25 bumps, 1 or more voids greater than or equal to 1/2 the distance between bumps.

(4) Stickiness of surface of insulating layer 100 laminated bodies of the first connection object member and the insulating layer were placed on a polystyrene chip tray from the insulating layer side and left at 23 ° C. for 48 hours. Then, when picking up a laminated body, it was evaluated whether the pick-up defect accompanying the stickiness of the surface of an insulating layer would arise. The stickiness of the surface of the insulating layer was determined according to the following criteria. The pickup failure means that the laminate cannot be picked up or the insulating layer is chipped or cracked after peeling.

[Criteria for stickiness of insulating layer surface]
○○: No pickup failure in all 100 laminates ○: No more than 1 pickup failure in 100 laminates ×: 2 or more pickup failures in 100 laminates

(5) Indentation of Insulating Layer and Maximum Depth of Indentation In the first connection object member, it was evaluated whether or not the upper surface of the insulating layer was recessed on the gaps (concave portions) between the plurality of protruding first electrodes. In the case of depression, the maximum depth of the depression was measured. For the measurement, a laser microscope (“VK-8700” manufactured by Keyence Corporation) was used.

(6) Measurement of haze value After coating the insulating material used in Examples and Comparative Examples on a release PET (polyethylene terephthalate) film, the solvent was removed by drying in an oven at 80 ° C. for 20 minutes, and the thickness was 20 μm. A film-like insulating material (insulating layer) was obtained. Both sides of the obtained adhesive film having a thickness of 20 μm were sandwiched between two 25 μm-thick PET films to obtain test pieces. The obtained test piece was installed in a haze meter (“HM-150” manufactured by Murakami Color Research Laboratory Co., Ltd.), and the haze value (%) was measured.

(7) Migration resistance The resulting connection structure (COG) was exposed for 500 hours in an atmosphere of 85 ° C. and 85% RH with a voltage of 20 V applied between the measurement terminals insulated from each other (insulation) Reliability test). During this time, the change in resistance value between the measurement terminals was measured. The case where the resistance value was 10 ⁵ Ω or less was judged as an insulation failure. Migration resistance was determined according to the following criteria.

[Judgment criteria for migration resistance]
◯: Among 10 connection structures, there is no connection structure in which an insulation failure occurs, and the average resistance value after the insulation reliability test is 10 ⁷ Ω or more. ○: Among 10 connection structures, There is no connection structure in which insulation failure has occurred, and the average resistance value after the insulation reliability test is 10 ⁶ Ω or more and less than 10 ⁷ Ω Δ: Of 10 connection structures, connection in which insulation failure has occurred There is no structure, and the average resistance value after the insulation reliability test is 10 ⁵ Ω or more and less than 10 ⁶ Ω x: Among 10 connection structures, there is one or more connection structures in which insulation failure occurs

(8) Connection reliability (Evaluation of adhesive strength of insulating layer)
In the obtained connection structure, the shear strength of the obtained connection structure was measured using a universal bond tester series 4000 manufactured by Days. Connection reliability was determined according to the following criteria from the value of the obtained shear strength.

[Connection reliability criteria]
○○: shear strength is, 800N / cm ² or more ○: shear strength is, 675N / cm ² or more and less than 800N / cm ² △: shear strength is, 550N / cm ² or more, 675N / cm ² less than ×: shear strength Is less than 550 N / cm ²

(9) Presence / absence of voids in the cured product layer in the connection structure In the obtained connection structure, whether or not voids occurred in the cured product layer obtained by curing the anisotropic conductive material layer was observed with an optical microscope. The presence or absence of voids was determined according to the following criteria. If there are no voids, the connection reliability increases, and the fewer the voids, the higher the connection reliability.

[Criteria for the presence or absence of voids]
○: No void △: There is a slight void, but there is no void larger than the electrode L / S, pitch ×: There is a void larger than the size between adjacent electrodes

(10) Capture rate of conductive particles between electrodes (conducting accuracy of conductive particles)
The number of conductive particles present between the upper and lower electrodes facing each other in the obtained connection structure was counted with an optical microscope. The capture rate of conductive particles was determined according to the following criteria.

[Criteria for trapping rate of conductive particles]
○: 10 or more particles between each electrode ×: 9 or less particles between each electrode

(11) Conductivity 20 resistance values of the obtained connection structure were evaluated by a four-terminal method. The conductivity was determined according to the following criteria.

[Conductivity criteria]
○: The resistance value is 3Ω or less in all locations. Δ: There are one or more locations where the resistance value exceeds 3Ω. ×: There are one or more locations that are not conducting at all.

(12) Insulating property It was measured with a tester whether or not leakage occurred in 20 adjacent electrodes of the obtained connection structure. Insulation was judged according to the following criteria.

[Insulation criteria]
○: No leak point ×: Leak point

(13) Connection reliability when subjected to thermal history 100 obtained connection structures are held at −30 ° C. for 5 minutes, then heated to 120 ° C. in 25 minutes, and held at 120 ° C. for 5 minutes. After that, a cold cycle test was performed in which the process of lowering the temperature to −30 ° C. in 25 minutes was one cycle. After 1000 cycles, the connection structure was removed.

  About 100 connection structures after the thermal cycle test, it was evaluated whether or not conduction failure between the upper and lower electrodes occurred. Of the 100 connection structures, the case where the number of defective conductions is 1 or less is “◯”, the case of 2 or more, 3 or less is “Δ”, the case of 4 or more It was determined as “x”.

  The blending components of the insulating material and the anisotropic conductive material are shown in Table 1 below. The evaluation results are shown in Table 2 below.

DESCRIPTION OF SYMBOLS 1 ... Laminated body 2 ... 1st connection object member 2A ... 1st connection object member 2a ... Surface 2b ... 1st electrode 3 ... Cured material layer 3a ... Surface 3A ... Anisotropic conductive material layer 3B ... B-staging Anisotropic conductive layer 4 ... second connection target member 4a ... surface 4b ... second electrode 5 ... conductive particles 6 ... insulating layer 6A ... insulating layer 6AA ... insulating layer 6X ... film-like insulating material 6XA ... insulating film 6a ... surface 11 ... connection structure 16 ... second laminate 21 ... laminate 22 ... cured product layer 22A ... anisotropic conductive material layer 22B ... B-stage anisotropic conductive layer 22X ... B-stage anisotropic Conductive film 31 ... connection structure 41 ... release film 46 ... multilayer film 51 ... container X ... gap between first electrodes

Claims (12)

In the first connection target member having a plurality of protruding first electrodes on the surface, the plurality of first electrodes are disposed on the plurality of first electrodes and on the gaps between the plurality of first electrodes. It is an insulating material used by being laminated so as to cover,
A film,
Haze value is 70% or less,
An insulating material having a probe tack on the surface at 25 ° C. measured with a probe of 5 mmφ of 500 mN / 5 mmφ or less. An epoxy compound,
The insulating material according to claim 1, comprising a polymer having a weight average molecular weight of 10,000 or more and 250,000 or less.   The insulating material according to claim 1, comprising an ion scavenger.   The insulating material according to claim 1, wherein the first connection target member is a semiconductor wafer or a semiconductor chip.   The insulating material according to claim 1, wherein the first electrode is a copper electrode. An insulating film;
B-staged anisotropic conductive film laminated on one surface of the insulating film,
The insulating film is formed of the insulating material according to any one of claims 1 to 5,
The B-staged anisotropic conductive film is formed by using an anisotropic conductive material containing a curable component and conductive particles to remove the solvent of the anisotropic conductive material or to proceed with curing. Is a multilayer film. A first connection target member having a plurality of protruding first electrodes on the surface;
An insulating layer stacked on the plurality of first electrodes and on the gaps between the plurality of first electrodes so as to cover the plurality of first electrodes;
The laminated body in which the said insulating layer is formed with the insulating material of any one of Claims 1-5. A B-staged anisotropic conductive layer laminated on the surface of the insulating layer opposite to the first connection target member side;
The B-staged anisotropic conductive layer is formed by using an anisotropic conductive material containing a curable component and conductive particles, by removing the solvent of the anisotropic conductive material or by proceeding with curing. The laminate according to claim 7, wherein A first connection target member having a plurality of protruding first electrodes on the surface;
An insulating layer stacked on a gap between the plurality of first electrodes;
A cured product layer laminated on a surface opposite to the first connection target member side of the insulating layer;
A second connection target member that is laminated on a surface opposite to the insulating layer side of the cured product layer and has a plurality of second electrodes on the surface;
The insulating layer is formed of the insulating material according to any one of claims 1 to 5,
The cured product layer is formed by fully curing the anisotropic conductive material using an anisotropic conductive material containing a curable component and conductive particles,
A connection structure in which a plurality of the first electrodes and a plurality of the second electrodes are electrically connected by the conductive particles.   The connection structure according to claim 9, wherein the insulating layer is stacked on at least a part of the plurality of first electrodes and a gap between the first electrodes. Using the first connection target member having a plurality of protruding first electrodes on the surface, a plurality of the first electrodes on the plurality of first electrodes and on a gap between the plurality of first electrodes. Comprising a step of laminating an insulating layer so as to cover the electrode;
The manufacturing method of a laminated body which forms the said insulating layer with the insulating material of any one of Claims 1-5. A first connection target member having a plurality of protruding first electrodes on the surface, and the plurality of first electrodes are covered on the plurality of first electrodes and on the gaps between the plurality of first electrodes. A laminated body comprising insulating layers laminated in this manner, a second connection target member having a plurality of second electrodes on its surface, and a B-stage anisotropic layered on the surface of the second connection target member The first connection target member, the insulating layer, the B-staged anisotropic conductive layer, and the second connection target member in this order using a second laminate including a conductive conductive layer. Laminating or
A first connection target member having a plurality of protruding first electrodes on the surface, and the plurality of first electrodes are covered on the plurality of first electrodes and on the gaps between the plurality of first electrodes. A laminated body comprising an insulating layer laminated in this manner, and a B-staged anisotropic conductive layer laminated on the surface of the insulating layer opposite to the first connection target member side, and a plurality of second layers The first connection target member, the insulating layer, the B-staged anisotropic conductive layer, and the second connection target member are arranged in this order using the second connection target member having the electrode on the surface. Laminating with,
A main curing step in which the B-staged anisotropic conductive layer is fully cured to form a cured product layer, and the first and second connection target members are electrically connected by the cured product layer;
The insulating layer is formed of the insulating material according to any one of claims 1 to 5,
The B-staged anisotropic conductive layer is formed by using an anisotropic conductive material containing a curable component and conductive particles, by removing the solvent of the anisotropic conductive material or by proceeding with curing. Has been
Excluding the insulating layer portion between the first electrode and the conductive particles contained in the B-staged anisotropic conductive layer, the conductive particles are formed on the first and second electrodes. To obtain a connection structure in which the insulating layer is laminated on the gaps between the plurality of first electrodes.

Images