CN113785027A - Adhesive composition - Google Patents

Adhesive composition Download PDF

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Publication number
CN113785027A
CN113785027A CN202080026360.2A CN202080026360A CN113785027A CN 113785027 A CN113785027 A CN 113785027A CN 202080026360 A CN202080026360 A CN 202080026360A CN 113785027 A CN113785027 A CN 113785027A
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China
Prior art keywords
particles
adhesive composition
silicone
electronic component
average particle
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Granted
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CN202080026360.2A
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CN113785027B (en
Inventor
佐藤大祐
樋口明史
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Dexerials Corp
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Dexerials Corp
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/06Non-macromolecular additives organic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08Macromolecular additives
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/30Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/35Heat-activated
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02Electrically-conducting adhesives
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00Additional features of adhesives in the form of films or foils
    • C09J2301/30Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention provides an adhesive composition with high reliability. The adhesive composition contains: silicone particles, a silane coupling agent, a polymerizable compound and a curing agent, wherein the total of the surface areas of true spherical particles calculated from the average particle diameter of the silicone particles per 100g of the composition is 10X 103m2The above. Thereby, the moisture permeability is improved, and a high permeability can be obtainedReliability.

Description

Adhesive composition
Technical Field
The present technology relates to an adhesive composition for connecting, for example, an Integrated Circuit (IC) chip and a flexible wiring (wiring) board. The present application claims priority on the basis of japanese patent application No. 2019-068612, filed in japan on 3/29 of 2019, which is incorporated herein by reference.
Background
Conventionally, in a device (device) in which a Liquid Crystal Display (LCD) driver IC is connected to a flexible wiring board, for example, when the device is heated, moisture entering the device may rapidly expand and damage the device.
In order to solve this problem, patent document 1 proposes: the wiring exposed from the inside of the display panel has a moisture permeability of 5-6 g/m2Sealing materials with a length of 24h or less.
Patent document 2 describes: a mode of arranging a moisture-proof material on a base film of an electrode connection portion of a flexible wiring board and forming a lead electrode thereon; a method of covering lead electrodes formed in an electrode connection portion of a flexible wiring board with a moisture-proof material, etc., and it has been proposed to use a material having a moisture permeability of 10g/m2Materials below 24 hours as moisture barrier materials.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2000-090840;
patent document 2: japanese patent laid-open publication No. 2004-327873.
Disclosure of Invention
Problems to be solved by the invention
In the methods described in patent documents 1 and 2, a sealing resin having low moisture permeability is used for the wiring (outer lead) to improve moisture resistance. However, if a sealing resin having low moisture permeability is used, an increase in the number of materials or a margin for material selection occurs, and thus it is difficult to obtain high reliability in HAST (high Accelerated Temperature and Humidity Stress Test), which is one of the Test methods for evaluating moisture resistance.
The present technology solves the above problems and provides an adhesive composition that can provide high reliability.
Means for solving the problems
The present inventors have studied an adhesive composition blended to obtain a high moisture permeability in order to immediately discharge moisture penetrating into the inside of the device. As a result, the present technology has been completed based on the knowledge that the moisture permeability is improved by blending predetermined amounts of silicone particles and a silane coupling agent.
That is, the adhesive composition according to the present technology contains: silicone particles, a silane coupling agent, a polymerizable compound and a curing agent, wherein the total of the surface areas of true spherical particles calculated from the average particle diameter of the silicone particles per 100g of the composition is 10X 103m2The above.
Further, a method for manufacturing a connected body according to the present technology includes the steps of: a disposing step of disposing a1 st electronic component and a 2 nd electronic component via an adhesive composition containing: silicone particles, a silane coupling agent, a polymerizable compound and a curing agent, wherein the total of the surface areas of true spherical particles calculated from the average particle diameter of the silicone particles per 100g of the composition is 10X 103m2The above; and a curing step of curing the adhesive composition while pressing the 2 nd electronic component onto the 1 st electronic component with a pressing tool.
Further, a connector according to the present technology includes: a1 st electronic component, a 2 nd electronic component, and an adhesive film having the 1 st electronic component and the 2 nd electronic component adhered thereto, wherein the adhesive film is formed by curing an adhesive composition and has a moisture permeability of 80g/m224 hours or longer, the adhesive composition comprising: silicone particles, a silane coupling agent, a polymerizable compound and a curing agent, wherein the total of the surface areas of true spherical particles calculated from the average particle diameter of the silicone particles per 100g of the composition is 10X 103m2The above。
Effects of the invention
According to this technique, by blending predetermined amounts of the silicone particles and the silane coupling agent, the moisture permeability is improved, and high reliability can be obtained.
Drawings
Fig. 1 is a sectional view schematically showing the arrangement steps of the method for producing a connected body according to the present embodiment.
Detailed Description
Hereinafter, embodiments of the present technology will be described in detail in the following order with reference to the drawings.
1. An adhesive composition;
2. a method for producing a connector;
3. examples are given.
< 1. adhesive composition >
The adhesive composition according to the present embodiment contains: silicone particles, a silane coupling agent, a polymerizable compound and a curing agent, wherein the total of the surface areas of true spherical particles calculated from the average particle diameter of the silicone particles per 100g of the composition is 10X 103m2The above. Thus, moisture permeability is improved, and high reliability can be obtained in HAST (high Accelerated Temperature and Humidity Stress Test), which is one of Test methods for evaluating moisture resistance.
The adhesive composition may be either film-like or paste-like. The film is preferable from the viewpoint of ease of handling, and the paste is preferable from the viewpoint of cost. Further, examples of the curing type of the adhesive composition include: a thermosetting type, a photo-curing type, a photo-thermal curing type, a curing type using a combination of photo and heat, and the like, and they can be appropriately selected according to the application.
The thermosetting adhesive composition will be described below by way of example. The thermosetting type may be, for example, a cationic curing type, an anionic curing type, a radical curing type, or a combination thereof. Examples of the polymerizable compound include: epoxy compounds having an ionic polymerizable group (cationic polymerization or anionic polymerization), oxetane compounds, and (meth) acrylic acid (ester) compounds having a radical polymerizable group, and these may be used singly or in combination of 2 or more. Further, examples of the silane coupling agent include: the silane coupling agent having a functional group such as an epoxy group, a (meth) acryloyl group, or a vinyl group can be appropriately selected according to the kind of the polymerizable compound.
As a specific example of the thermosetting type, an anionic curing type epoxy resin composition is shown. The adhesive composition shown as a specific example contains: organosilicon particles, an epoxy silane coupling agent, an epoxy compound and an epoxy curing agent. Thus, an epoxy adhesive having high moisture permeability can be obtained.
Examples of the silicone particles include: silicone rubber powder having a structure obtained by crosslinking an organopolysiloxane, silicone-crosslinked silicone rubber powder having a siloxane bond (RSiO)3/2)nThe silicone resin powder having a three-dimensional network structure shown in the figure, the silicone composite powder which is a spherical powder obtained by coating the surface of a spherical silicone rubber powder with a silicone resin, and the like, 1 of these can be used alone, or 2 or more of these can be used in combination. Among these, the silicone-based particles preferably contain a silicone composite powder from the viewpoint of dispersibility. As specific examples of the silicone composite powder available on the market, there can be mentioned: trade names "KMP-600", "KMP-605", "X-52-7030" of shin-Etsu chemical industries, Ltd.
The average particle diameter of the silicone particles is preferably 5μm is less than or equal to, more preferably 3μm is preferably 1 or lessμm is less than or equal to m. This can increase the total value of the surface area of the spherical particles calculated from the average particle diameter of the silicone particles in the adhesive composition.
The total of the surface areas of the true spherical particles calculated from the average particle diameter of the silicone particles per 100g of the composition was 10X 103m2The content of the above is more preferably 25X 10 per 100g of the composition3m2Above and 150 × 103m2The following is more preferably 50X 10 per 100g of the composition3m2Above and 150 × 103m2The following. Calculation from the average particle diameter of the Silicone-based particlesThe larger the total surface area of the true spherical particles (2) is, the higher the moisture permeability is, but the adhesive strength tends to decrease.
The total of the surface areas of the spherical particles calculated from the average particle diameter of the silicone particles in the adhesive composition can be calculated from, for example, the specific surface area of the silicone particles and the amount of the silicone particles added. The specific surface area of the silicone particles can be determined, for example, from the surface area per 1 particle calculated from the average particle diameter and the mass per 1 particle calculated from the average particle diameter and the true specific gravity.
The amount of the silicone particles blended is, for example, preferably 1 to 30 parts by mass, more preferably 5 to 30 parts by mass, and still more preferably 10 to 30 parts by mass, per 100 parts by mass of the adhesive composition excluding the silicone particles. When the conductive particles are incorporated into the adhesive composition, the range refers to the range of the mass part relative to 100 mass parts of the adhesive composition excluding the conductive particles.
The epoxy silane coupling agent is an organosilicon compound having both an epoxy group and a hydrolyzable group, and chemically bonds silicone particles and an epoxy resin as a matrix resin to improve dispersibility.
Examples of the epoxy silane coupling agent include: silane compounds having an epoxy structure such as 3-glycidoxypropyltrimethoxysilane and 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane. Specific examples of commercially available epoxy silane coupling agents include: "A-187" by Momentive Performance Materials Japan, and the like.
The amount of the epoxy silane coupling agent blended is, for example, preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and still more preferably 0.5 to 1 part by mass, per 100 parts by mass of the adhesive composition excluding the silicone particles.
The epoxy compound is not particularly limited, and includes: naphthalene type epoxy compounds, glycidyl ether type epoxy compounds, glycidyl ester type epoxy compounds, alicyclic epoxy compounds, bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, dicyclopentadiene type epoxy compounds, novolac type epoxy compounds, biphenyl type epoxy compounds, etc., and from these, can be used alone 1, or a combination of 2 or more. Specific examples of the naphthalene type bifunctional epoxy resin available on the market include "HP 4032D" of DIC (Co., Ltd.).
The amount of the epoxy compound to be incorporated is, for example, preferably 1 to 30 parts by mass, more preferably 1 to 20 parts by mass, and still more preferably 1 to 10 parts by mass, per 100 parts by mass of the adhesive composition excluding the silicone particles.
Examples of the epoxy curing agent include: imidazoles, polyphenols, acid anhydrides, amines, hydrazides, polythiols, lewis acid-amine complexes, and the like, and 1 kind of them may be used alone or 2 or more kinds may be used in combination. Among these, the epoxy curing agent more preferably contains an imidazole group from the viewpoint of storage stability and heat resistance of the cured product. From the viewpoint of storage stability and pot life, a microcapsule-type latent curing agent microencapsulated with an epoxy curing agent coated with a polyurethane-based or polyester-based polymer material is preferably used. Examples of the imidazole-based latent curing agent available on the market include: "HP 3941" of Asahi chemical Chemicals (L.) and the like.
The amount of the epoxy curing agent to be blended is, for example, preferably 5 to 70 parts by mass, more preferably 10 to 60 parts by mass, and still more preferably 20 to 50 parts by mass, per 100 parts by mass of the adhesive composition excluding the silicone particles.
The adhesive composition shown as a specific example preferably contains a polymer and a rubber component.
Examples of the polymer include: bisphenol a phenoxy resin, bisphenol F phenoxy resin, bisphenol S phenoxy resin, phenoxy resin having a fluorene skeleton, polystyrene, polyacrylonitrile, polyphenylene sulfide, polytetrafluoroethylene, polycarbonate, and the like, and these may be used alone or in combination of 2 or more. Among these, bisphenol a type phenoxy resins are suitably used from the viewpoints of film formation state, connection reliability, and the like. The phenoxy resin is polyhydroxy polyether synthesized from bisphenols and epichlorohydrin. As specific examples of phenoxy resins available on the market, there can be mentioned: trade name "YP-50" of Xinri Cijin chemical (trade name) and the like.
The amount of the polymer to be blended is, for example, preferably 10 to 60 parts by mass, and more preferably 20 to 50 parts by mass, per 100 parts by mass of the adhesive composition excluding the silicone particles.
Examples of the rubber component include: acrylic rubber (ACR), Butadiene Rubber (BR), nitrile rubber (NBR), and the like, and these may be used alone or in combination of 2 or more. Among these, acrylic rubbers are preferably used from the viewpoints of film formation state, connection reliability, and the like. Specific examples of commercially available acrylic rubbers include: tradename of tradename "SG 80H" of chantex (kojie), and the like.
In addition, the rubber component preferably contains elastic particles. The elastic particles can absorb internal stress without causing solidification hindrance, and thus can give high connection reliability. As the elastic particles, there can be mentioned: crosslinked acrylonitrile butadiene rubber particles, crosslinked styrene butadiene rubber particles, acrylic rubber particles, silicone particles, and the like. As specific examples of the cross-linked acrylonitrile butadiene rubber particles available on the market, there can be mentioned: XER-91 (average particle diameter 0.5)μm, manufactured by JSR corporation), and the like.
The amount of the rubber component blended is, for example, preferably 1 to 30 parts by mass, more preferably 5 to 25 parts by mass, and still more preferably 10 to 20 parts by mass, per 100 parts by mass of the adhesive composition excluding the silicone particles.
The minimum melt viscosity of the adhesive composition is preferably 1 to 100000 pas, more preferably 10 to 10000 pas. If the minimum melt viscosity is too high, the adhesive between the electrodes cannot be sufficiently removed at the time of thermal compression, and therefore the connection resistance tends to increase. On the other hand, if the minimum melt viscosity is too low, the deformation of the adhesive composition due to the load at the time of thermal compression increases, and therefore the restoring force of the adhesive composition at the time of releasing the pressurization is applied to the interface of the connection portion or the like as a force in the peeling direction. Therefore, immediately after the thermocompression bonding, the connection resistance tends to increase, or air bubbles tend to be generated in the connection portion.
The adhesive composition having such a constitution preferably has a moisture permeability of 80g/m measured under conditions of a temperature of 40 ℃ and a relative humidity of 90% after curing224 hours or longer, more preferably 85g/m224 hours or longer, more preferably 90g/m224 hours or longer. Thus, moisture penetrating into the interior of the device bonded with the adhesive composition can be immediately discharged, and high reliability can be obtained in HAST. The moisture permeability can be measured under the conditions of 40 ℃ and 90% relative humidity in accordance with the moisture permeability test method (cup method) for moisture-proof packaging materials according to JIS Z0208.
According to this adhesive composition, moisture penetrating into the inside of the device can be immediately discharged, and therefore, excellent connection reliability can be obtained. In the case of having water resistance, the immersed water remains. In other words, the present invention may allow a certain amount of moisture to enter, but does not allow moisture that excessively deteriorates adhesion to remain. In terms of adjusting the required water-resistant conditions, there is an effect of widening the selectivity of the design conditions of the equipment and the instruments in which it is installed. For example, the following advantages can be enumerated: in addition to portable terminals and wearable terminals that require weather resistance, the present invention is also applicable to electric devices for bicycles (bikes, motorcycles), automobiles, flying devices (unmanned planes, airplanes, etc.), moving bodies such as ships, etc., and vehicles that are expected to require higher weather resistance.
The adhesive composition can be a conductive adhesive further containing conductive particles having an average particle diameter larger than that of the silicone particles. In the case of containing the conductive particles, the average particle diameter of the conductive particles is preferably larger than the average particle diameter of the solid blend other than the conductive particles so as not to hinder the sandwiching. From the viewpoint of conductivity, the ratio of the average particle diameter of the conductive particles to the average particle diameter of the silicone particles is preferably 1.5 or more, more preferably 2.0 or more, and even more preferably 3.5 or more. This is because: the larger the value, the better the conductive particles are, so that the silicone particles do not inhibit the compression or flattening of the conductive particles. On the other hand, when the conductive particles are held between the electrodes, it is sometimes preferable to hold the silicone-based particles together with the compressed or flattened conductive particles in order to assist in breaking through oxides and the like on the electrodes, and therefore the numerical value is sometimes as small as possible. Preferably 1.1 or less, more preferably 1.07 or less, and still more preferably 1.05 or less. These may be appropriately adjusted according to the purpose.
The conductive adhesive may be any of a film-like conductive film or a paste-like conductive paste. The conductive film is preferable from the viewpoint of ease of handling, and the conductive paste is preferable from the viewpoint of cost. In addition, the conductive adhesive and the conductive film can also be used as an anisotropic conductive adhesive and an anisotropic conductive film. In addition, these structures may be anisotropic connection structures.
As the conductive particles, known conductive particles used in conductive films can be used. Examples thereof include: particles of various metals or metal alloys such as nickel, iron, copper, aluminum, tin, lead, chromium, cobalt, silver, and gold; metal particles are coated on the surfaces of particles of metal oxides, carbon, graphite, glass, ceramics, plastics and the like; and particles obtained by further performing an insulating treatment such as coating an insulating film or adhering insulating fine particles on the surfaces of these particles. From these, 2 or more species can be mixed. In the case of particles obtained by coating the surface of resin particles with a metal, the resin particles may be, for example: particles of epoxy resins, phenol resins, acrylic resins, acrylonitrile/styrene (AS) resins, benzoguanamine resins, divinylbenzene-based resins, styrene-based resins, and the like.
The average particle diameter of the conductive particles is usually 1 to 30μm, preferably 2 to 20μm, more preferably 2.5 to 15μAnd m is selected. In addition, from the viewpoint of connection reliability and insulation reliability, the average particle density of the conductive particles in the binder resin is preferably 100 to 100000 particles/mm2More preferably 500 to 80000 pieces/mm2. For example, the film may be formed into a film shape, and the observation result obtained by observing the film surface with an optical microscope or a metal microscope may be obtained by using image analysis software WinROOF (trade name, ltd.).
The conductive particles may be dispersed in the insulating resin, and in the case of a film, they may be independently present in a plan view of the film, or may be present in any arrangement. In the case of disposing the conductive particles, the number density, the distance between the conductive particles, and the like may be set according to the size or layout of the electrodes to be connected. Therefore, it is effective for improving trapping, suppressing short circuit, and the like, and cost reduction effects such as improvement in yield can also be expected.
The minimum melt viscosity of the conductive adhesive is preferably 1 to 100000 pas, and more preferably 10 to 10000 pas. The optimization of the minimum melt viscosity also depends on the compression deformation characteristics of the conductive particles, but if the minimum melt viscosity is too high, the adhesive between the conductive particles and the electrode cannot be sufficiently eliminated at the time of thermal compression, and therefore the connection resistance tends to increase. In particular, it is difficult for the conductive particles having the protrusions to sufficiently exclude the adhesive between the conductive particles and the electrode at the time of thermal compression. On the other hand, if the minimum melt viscosity is too low, the deformation of the conductive adhesive due to the load at the time of thermal compression increases, and therefore, the restoring force of the conductive adhesive is applied to the connection portion interface or the like as a force in the peeling direction at the time of releasing the pressurization. Therefore, immediately after the thermocompression bonding, the connection resistance tends to increase, or air bubbles tend to be generated in the connection portion.
The moisture permeability of the conductive adhesive having such a configuration is preferably 80g/m measured at a temperature of 40 ℃ and a relative humidity of 90% after curing224 hours or longer, more preferably 85g/m224 hours or longer, more preferably 90g/m224 hours or longer. This makes it possible to immediately discharge moisture that has entered the interior of the device bonded with the conductive adhesive, and high reliability can be obtained in HAST. The moisture permeability can be measured under the conditions of 40 ℃ and 90% relative humidity in accordance with the moisture permeability test method (cup method) for moisture-proof packaging materials according to JIS Z0208.
According to the conductive adhesive, moisture penetrating into the device can be immediately discharged, and thus excellent connection reliability can be obtained.
< 2. method for producing interconnect
Production of the connecting body according to the present embodimentThe method comprises the following steps: a disposing step of disposing a1 st electronic component and a 2 nd electronic component via an adhesive composition containing: the total of the surface areas of the true spherical particles calculated from the average particle diameter of the silicone particles per 100g of the composition is 10X 103m2The above; and a curing step of curing the adhesive composition while pressing the 2 nd electronic component onto the 1 st electronic component with the pressing tool. Here, the press tool refers to a tool that presses from the 1 st electronic component or the 2 nd electronic component, or both of them. The shape and material of the pressing tool are not particularly limited, and examples thereof include: a flat metal tool is provided with a heating mechanism. The tool may be a tool used in known hot press apparatus. Further, a mechanism for irradiating light may be provided.
Further, the connector according to the present embodiment includes: a1 st electronic component, a 2 nd electronic component, and an adhesive film having the 1 st electronic component and the 2 nd electronic component adhered thereto, wherein the adhesive film is formed by curing the adhesive composition and has a moisture permeability of 80g/m224 hours or longer, the adhesive composition comprising: silicone particles, a silane coupling agent, a polymerizable compound and a curing agent, wherein the total of the surface areas of true spherical particles calculated from the average particle diameter of the silicone particles per 100g of the composition is 10X 103m2The above.
In the connected body according to the present embodiment, since the adhesive film to which the 1 st electronic component and the 2 nd electronic component are bonded has high moisture permeability, moisture penetrating into the inside of the device can be immediately discharged, and high reliability can be obtained in HAST.
A method for producing a connected body using an adhesive film will be described below. Fig. 1 is a sectional view schematically showing an arrangement step of the method for producing a connected body according to the present embodiment. Since the adhesive composition constituting the adhesive film is the same as described above, the description thereof is omitted here.
[ disposing step (S1) ]
As shown in fig. 1, in the disposing step (S1), the adhesive film 20 containing the silicone particles 21 is disposed on the 1 st electronic component 10. The 1 st electronic component 10 includes a1 st terminal row 11. The 1 st electronic component 10 is not particularly limited and may be appropriately selected according to the purpose. Examples of the 1 st electronic component 10 include: LCD (Liquid Crystal Display) panels, Flat Panel Displays (FPD) such as organic el (oled), transparent substrates for touch panels, Printed Wiring Boards (PWB), Flexible Printed Circuits (FPC), and the like. The material of the printed wiring board is not particularly limited, and for example, glass epoxy sheet (ガラエポ, glass epoxy) such as FR-4 substrate, plastics such as thermoplastic resin, ceramics, and the like can be used. The transparent substrate is not particularly limited as long as it is a substrate having high transparency, and examples thereof include: glass substrates, plastic substrates, and the like. Among these, a ceramic substrate is preferably used from the viewpoint of heat resistance.
Further, as the 2 nd electronic component opposed to the 1 st electronic component, a plating bump such as an IC or a flexible substrate is preferably formed. The plated bumps are preferably dimpled low, or dimpled free, or preferably flat in surface. In addition, from the viewpoint of increasing the contact area at the time of press-fitting, it is preferable that the surface of the plated bump is flattened. In addition, stud bumps (stud bumps) may be formed on the wiring substrate.
Since the adhesive film 20 is a film formed by forming the adhesive composition into a film shape, a detailed description thereof will be omitted. The thickness of the adhesive film 20 is preferably 1 to 100μm, more preferably 10 to 50μAnd m is selected. The same applies to the case of a single layer or the case of forming a plurality of layers. In the case of paste, the thickness is used for connection.
[ curing step (S2) ]
In the curing step (S2), the 2 nd electronic component is placed on the adhesive film 20, and the 2 nd electronic component is pressed against the 1 st electronic component 10 by a pressing tool, and the pressing is performed while heating. In the curing step (S2), the pressing is performed using a press tool at a temperature of preferably 250 ℃ or lower, more preferably 220 ℃ or lower, and still more preferably 200 ℃ or lower. Thus, the resin is melted by the heat of the bonding tool, the 2 nd electronic component is sufficiently press-fitted by the bonding tool, and the resin is thermally cured, so that excellent adhesiveness can be obtained. In this case, although it is assumed that the heating means is attached to the bonding tool, the adhesive film 20 may be heated and cured by a method in which the heating means is not attached to the bonding tool.
The 2 nd electronic component includes a 2 nd terminal row facing the 1 st terminal row 11. The 2 nd electronic component is not particularly limited and may be appropriately selected according to the purpose. Examples of the 2 nd electronic component include: an Integrated Circuit (IC), a Flexible Printed Circuit (FPC), a Tape Carrier Package (TCP) substrate, and the like. When an IC is mounted On an FPC, the IC becomes a Chip On Film (COF).
In addition, in the curing process (S2), a buffer material may be used between the bonding tool and the 2 nd electronic component. As the buffer material, Polytetrafluoroethylene (PTFE), polyimide, glass cloth, silicone rubber, or the like can be used.
According to the method for manufacturing a connected body, since the adhesive film that bonds the 1 st electronic component and the 2 nd electronic component has high moisture permeability, moisture that has entered the inside of the device can be immediately discharged, and high reliability can be obtained in HAST.
[ modified examples ]
In the above-described embodiment, the 1 st electronic component and the 2 nd electronic component are connected by using the adhesive film, but the present invention is not limited thereto, and the 1 st electronic component and the 2 nd electronic component may be connected by using a conductive adhesive film containing conductive particles. The conductive adhesive film may have a configuration of 2 or more layers including a layer containing conductive particles (referred to as a conductive particle-containing layer for convenience) and a layer not containing conductive particles (referred to as a non-conductive particle-containing layer for convenience). In the case of paste, the same structure can be formed at the time of connection.
< 3. example >.
Examples
Hereinafter, examples of the present technology will be described. In example 1, as one embodiment of the adhesive composition, an adhesive film was produced, and a connected body was produced. Then, the moisture permeability of the cured adhesive film, the initial adhesive strength of the connected body and the adhesive strength after the reliability test, and the initial on-resistance of the connected body and the on-resistance after the reliability test were measured.
[ production of adhesive film and measurement of moisture permeability ]
Blending the materials shown in Table 1 to make a thickness of 35μm, an adhesive film. In addition, in order to measure the moisture permeability, the adhesive film was cured at a temperature of 200 ℃ to prepare a sample film. The moisture permeability is measured under the conditions of 40 ℃ and 90% relative humidity in accordance with the moisture permeability test method (cup method) for moisture-proof packaging materials according to JIS Z0208. Specifically, calcium chloride (anhydrous) was sealed in a cup, the cup covered with a sample film was allowed to stand in a constant temperature and humidity state, and the weighing operation was repeated at regular intervals to evaluate the increase in the mass of the cup as the amount of water vapor transmitted.
[ preparation of a linker ]
The bare chip (IC chip) is: a wiring (bump size: 50X 50) for measuring conduction, which had a thickness of 0.4mm, a width of 6mm and a length of 6mm (6mm X6 mm), was usedμm, spacing: 85μm (space between bumps 35)μm), metal bump height h =15μm) was measured using TEG (Test Element Group: test element group). The metal bump is an electroplating bump, and a smooth metal bump without dent is used.
The substrate of the Flexible Printed Circuits (FPC) was polyimide, and the thickness was 25 mmμm, spacing: 85μm (L/S =45/40), Top (Top): 40μm is formed with a measuring TEG for conducting a measuring wire.
Bare chips are mounted on the flexible wiring board using an adhesive film. The thermocompression bonding conditions were: the temperature is 200 ℃, the pressure is 100MPa, and the time is 10 seconds. In addition, the thickness 50 of the buffer material will be used in the hot pressingμThe teflon sheet of m is configured on the bare chip.
[ measurement of adhesive Strength ]
And stripping the flexible wiring board of the connector along the 90 ℃ direction at a stretching speed of 50 mm/second, and taking the maximum value of the stripping strength required by the stripping as the bonding strength. The initial linker and the linker after the reliability test were measured. The reliability test was carried out according to JEDEC (JESD22-A110) under conditions of a temperature of 110 ℃, a humidity of 85% and a time of 264 hours.
[ measurement of on-resistance ]
As for the connection state of the bare chip and the flexible wiring board, the on-resistance (Ω) was measured using a digital multimeter at the initial stage of connection and after a reliability test. The on-resistance value was measured by connecting a digital multimeter to the wiring of the flexible wiring board connected to the bumps of the bare chip, and measuring the on-resistance value with a 4-terminal method with a current of 1 mA. The reliability test was carried out according to JEDEC (JESD22-A110) under conditions of a temperature of 110 ℃, a humidity of 85% and a time of 264 hours.
Figure DEST_PATH_IMAGE001
Polymer (b): YP-50 (New Nippon Tekken Chemicals (strain));
epoxy curing agent: HP3941 (asahi Chemicals (ltd));
epoxy compound (c): HP4032D (DIC (strain));
rubber particles: XER-91 (JSR (strain));
rubber component (b): SG80H (tradex);
coupling agent: a-187 (Momentive Performance Materials Japan);
silicone particles a: x-52-7030 (shinyleaf Silicone strain) and an average particle diameter of 0.8μm, true specific gravity 1.01;
silicone particles B: KMP-605 (shinyless Silicone (TM)) and an average particle diameter of 2μm, true specific gravity 0.99;
silicone particles C: KMP-600 (shin-Etsu Silicone (Strain))) and an average particle diameter of 5μm, true specific gravity 0.99.
The specific surface area of the silicone particles was determined from the surface area per 1 particle calculated from the average particle diameter and the mass per 1 particle calculated from the average particle diameter and the true specific gravity.
As shown in Table 1, the composition was made of silicone based per 100g of the compositionThe total of the surface areas of the true spherical particles calculated from the average particle diameters of the particles was 10X 103m2As described above (examples 1 to 8), 80g/m was obtained2Moisture permeability of 24 hours or more. The total surface area of the true spherical particles calculated from the average particle diameter of the silicone particles per 100g of the composition was 50X 103m2As described above (examples 5 to 7), 90g/m was obtained2Moisture permeability of 24 hours or more. When the silicone particles were not blended, the moisture permeability was 75g/m224 hours (comparative example 1).
[ example 2 ]
In example 2, as one embodiment of the adhesive composition, a conductive film was produced, and a connected body was produced. Then, the moisture permeability of the cured conductive film, the initial adhesive strength of the connected body and the adhesive strength after the reliability test, and the initial on-resistance of the connected body and the on-resistance after the reliability test were measured.
[ production of conductive film and measurement of moisture permeability ]
Blending the materials shown in Table 1 to make a thickness of 35μm is a conductive film. In addition, in order to measure the moisture permeability, the conductive film was cured at a temperature of 200 ℃ to prepare a sample film. The moisture permeability is measured under the conditions of 40 ℃ and 90% relative humidity in accordance with the moisture permeability test method (cup method) for moisture-proof packaging materials according to JIS Z0208. Specifically, calcium chloride (anhydrous) was sealed in a cup, the cup covered with a sample film was allowed to stand in a constant temperature and humidity state, and the weighing operation was repeated at regular intervals to evaluate the increase in the mass of the cup as the amount of water vapor transmitted.
[ preparation of a linker ]
The bare chip (IC chip) is: a wiring (bump size: 50X 50) for measuring conduction, which had a thickness of 0.4mm, a width of 6mm and a length of 6mm (6mm X6 mm), was usedμm, spacing: 85μm (space between bumps 35)μm), metal bump height h =15μm) was measured using TEG (Test Element Group: test element group). The metal bump is an electroplating bump, and a smooth metal bump without dent is used.
Using a conductive film in the flexibilityThe wiring board has a bare chip mounted thereon. The thermocompression bonding conditions were: the temperature is 200 ℃, the pressure is 100MPa, and the time is 10 seconds. Further, the thickness 200 to be a cushioning material at the time of thermal compression bondingμm of silicone rubber are disposed on the die.
[ measurement of adhesive Strength ]
And stripping the flexible wiring board of the connector along the 90 ℃ direction at a stretching speed of 50 mm/second, and taking the maximum value of the stripping strength required by the stripping as the bonding strength. The initial connected body and the connected body after the reliability test were measured. The reliability test was carried out according to JEDEC (JESD22-A110) under conditions of a temperature of 110 ℃, a humidity of 85% and a time of 264 hours.
[ measurement of on-resistance ]
As for the connection state of the bare chip and the flexible wiring board, the on-resistance (Ω) was measured using a digital multimeter at the initial stage of connection and after a reliability test. The on-resistance value was measured by connecting a digital multimeter to the wiring of the flexible wiring board connected to the bumps of the bare chip, and measuring the on-resistance value with the current of 1mA by the 4-terminal method. The reliability test was carried out according to JEDEC (JESD22-A110) under conditions of a temperature of 110 ℃, a humidity of 85% and a time of 264 hours.
Figure 573956DEST_PATH_IMAGE002
Polymer (b): YP-50 (New Nippon Tekken Chemicals (strain));
epoxy curing agent: HP3941 (asahi Chemicals (ltd));
epoxy compound (c): HP4032D (DIC (strain));
rubber particles: XER-91 (JSR (strain));
rubber component (b): SG80H (tradex);
coupling agent: a-187 (Momentive Performance Materials Japan);
conductive particles A: Ni/Au plated acrylic resin particles having an average particle diameter of 5μm, Japan chemical (strain);
conductive particles B: Ni/Au plated acrylic resin particles having an average particle diameter of 3.5μm, Japan chemical (strain);
conductive particles C: Ni/Au plated acrylic resin particles having an average particle diameter of 3μm, Japan chemical (strain);
silicone particles a: x-52-7030 (shinyleaf Silicone strain) and an average particle diameter of 0.8μm, true specific gravity 1.01;
silicone particles B: KMP-605 (shinyless Silicone (TM)) and an average particle diameter of 2μm, true specific gravity 0.99;
silicone particles C: KMP-600 (shin-Etsu Silicone (Strain))) and an average particle diameter of 5μm, true specific gravity 0.99.
The specific surface area of the silicone particles was determined from the surface area per 1 particle calculated from the average particle diameter and the mass per 1 particle calculated from the average particle diameter and the true specific gravity.
As shown in Table 2, the average particle diameter of the silicone particles was smaller than the average particle diameter of the conductive particles, and the total of the surface areas of the true spherical particles calculated from the average particle diameter of the silicone particles per 100g of the composition was 10X 103m2As described above (examples 9 to 17), 80g/m was obtained2Moisture permeability of 24 hours or more. The total surface area of the true spherical particles calculated from the average particle diameter of the silicone particles per 100g of the composition was 50X 103m2The above で (examples 13 to 15) gave a yield of 90g/m2Moisture permeability of 24 hours or more. When the silicone particles were not blended, the moisture permeability was 75g/m224 hours (comparative example 2). When the average particle diameter of the silicone particles is equal to or larger than the average particle diameter of the conductive particles, the resistance value increases (comparative examples 3 and 4).
As in examples 9 to 17, the moisture permeability of the conductive film was set to 80g/m224 hours or more, the resistance increase after the reliability test can be suppressed. This is believed to be due to: by utilizing the high moisture permeability of the conductive film, moisture that has intruded into the device can be immediately discharged.
Description of the symbols
10: 1 st electronic component;
11: a1 st terminal row;
20: an adhesive film;
21: silicone particles.

Claims (11)

1. An adhesive composition comprising: silicone particles, a silane coupling agent, a polymerizable compound and a curing agent,
the total of the surface areas of the true spherical particles calculated from the average particle diameter of the silicone particles per 100g of the composition was 10X 103m2The above.
2. The adhesive composition according to claim 1, wherein the silicone particles have an average particle diameter of 5μm is less than or equal to m.
3. The adhesive composition according to claim 1 or 2, wherein the silicone-based particles comprise a silicone composite powder, and the silicone composite powder is a spherical powder obtained by coating the surface of a spherical silicone rubber powder with a silicone resin.
4. The adhesive composition according to any one of claims 1 to 3, wherein,
the polymerizable compound is an epoxy compound,
the curing agent is an epoxy curing agent,
the silane coupling agent is an epoxy silane coupling agent.
5. The adhesive composition according to claim 4, which has a moisture permeability of 80g/m as measured at a temperature of 40 ℃ and a relative humidity of 90% after curing224 hours or longer.
6. The adhesive composition according to any one of claims 1 to 3, further comprising conductive particles,
the silicone particles have an average particle diameter smaller than the average particle diameter of the conductive particles.
7. The adhesive composition according to any one of claims 1 to 6, which is in the form of a film.
8. A method for producing a connected body, comprising the steps of:
a disposing step of disposing a1 st electronic component and a 2 nd electronic component via the adhesive composition,
wherein the adhesive composition comprises: silicone particles, a silane coupling agent, a polymerizable compound and a curing agent,
the total of the surface areas of the true spherical particles calculated from the average particle diameter of the silicone particles per 100g of the composition was 10X 103m2The above; and
and a curing step of curing the adhesive composition while pressing the 2 nd electronic component onto the 1 st electronic component with a pressing tool.
9. The method for producing a connected body according to claim 8, wherein the adhesive composition further contains conductive particles.
10. A connector, comprising: a1 st electronic component, a 2 nd electronic component, and an adhesive film on which the 1 st electronic component and the 2 nd electronic component are adhered,
the adhesive film is formed by curing the adhesive composition and has a moisture permeability of 80g/m224 hours or longer, the adhesive composition comprising: silicone particles, a silane coupling agent, a polymerizable compound and a curing agent, wherein the total of the surface areas of true spherical particles calculated from the average particle diameter of the silicone particles per 100g of the composition is 10X 103m2The above.
11. The interconnect according to claim 10, wherein the adhesive composition further comprises conductive particles.
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