adhesive composition

Abstract

To provide an adhesive composition that can achieve high reliability.SOLUTION: The adhesive composition contains silicone particles, a silane coupling agent, a polymerizable compound, and a curing agent. The total surface area of perfectly spherical particles as calculated from the average particle size of the silicone particles is at least 10×103 m2 per 100 g of the composition. The adhesive composition can thereby improve moisture permeability and achieve high reliability.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present technology relates to an adhesive composition for connecting, for example, an IC (Integrated Circuit) chip and a flexible wiring board. [Background technology]

[0002] In the past, when a device in which an LCD (Liquid Crystal Display) driver IC is connected to a flexible wiring board is heated, moisture that has entered the device can suddenly expand and destroy the device.

[0003] To solve this problem, Patent Document 1 describes a method for setting a moisture permeability of 5 to 6 g / m for exposed wiring drawn out from inside the display panel. 2 It is suggested to use a sealant for 24 hours or less.

[0004] Patent Document 2 also describes a configuration in which a moisture permeation prevention material is provided on a base film of an electrode connection portion of a flexible wiring board, and a lead electrode is formed thereon, and a configuration in which the space between lead electrodes formed on the electrode connection portion of a flexible wiring board is covered with a moisture permeation prevention material, and the moisture permeation prevention material has a moisture permeation rate of 10 g / m 2 It is suggested to use 24 hours or less. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2000-090840 [Patent Document 2] Japanese Patent Application Laid-Open No. 2004-327873 Summary of the Invention [Problem to be solved by the invention]

[0006] The methods described in the aforementioned Patent Documents 1 and 2 improve moisture resistance by using a sealing resin with low moisture permeability for the wiring (outer lead). However, using a sealing resin with low moisture permeability increases the number of materials required and places limitations on material selection, making it difficult to achieve high reliability in the Highly Accelerated Temperature and Humidity Stress Test (HAST), one of the test methods for evaluating moisture resistance.

[0007] The present technology solves the above-mentioned problems and provides an adhesive composition that can provide high reliability. [Means for solving the problem]

[0008] The present inventors have conducted research into the formulation of adhesive compositions that can achieve high moisture permeability in order to quickly expel moisture that has penetrated into the device, and have completed this technology based on the discovery that moisture permeability can be improved by blending a specific amount of silicone particles and a silane coupling agent.

[0009] That is, the adhesive composition according to the present technology comprises silicone particles, an epoxy-based silane coupling agent, and Other than the above epoxy-based silane coupling agents The composition contains an epoxy compound, an epoxy curing agent, and two or more rubber components other than the silicone-based particles, and the total surface area of ​​spherical particles calculated from the average particle size of the silicone-based particles is 90.7 x10 3 m 2 The rubber component contains elastic particles, and the composition A 35 μm thick film was prepared from the above and cured at 200°C. The moisture permeability measured at a temperature of 40°C and a relative humidity of 90% is 90 g / m 2 - 24 hours or more.

[0010] Further, the method for producing a connector according to the present technology includes: a silicone-based particle; an epoxy-based silane coupling agent; Other than the above epoxy-based silane coupling agentsThe composition contains an epoxy compound, an epoxy curing agent, and two or more rubber components other than the silicone-based particles, and the total surface area of ​​spherical particles calculated from the average particle size of the silicone-based particles is 90.7 x10 3 m 2 The rubber component contains elastic particles, and the composition A 35 μm thick film was prepared from the above and cured at 200°C. The moisture permeability measured at a temperature of 40°C and a relative humidity of 90% is 90 g / m 2 The method includes a placement step of placing a first electronic component and a second electronic component via an adhesive composition having a durability of 24 hours or more, and a curing step of crimping the second electronic component to the first electronic component with a crimping tool and curing the adhesive composition.

[0011] In addition, a connection body according to the present technology includes a first electronic component, a second electronic component, and an adhesive film to which the first electronic component and the second electronic component are adhered, the adhesive film including silicone particles, an epoxy-based silane coupling agent, and Other than the above epoxy-based silane coupling agents The composition contains an epoxy compound, an epoxy curing agent, and two or more rubber components other than the silicone-based particles, and the total surface area of ​​spherical particles calculated from the average particle size of the silicone-based particles is 90.7 x10 3 m 2 The rubber component contains elastic particles, and the composition A 35 μm thick film was prepared from the above and cured at 200°C. The moisture permeability measured at a temperature of 40°C and a relative humidity of 90% is 90 g / m 2 The adhesive composition is cured for 24 hours or more. [Effects of the Invention]

[0012] According to this technology, by blending a predetermined amount of silicone particles and a silane coupling agent, moisture permeability is improved and high reliability can be obtained. [Brief explanation of the drawings]

[0013] [Figure 1]FIG. 1 is a cross-sectional view that schematically shows an arrangement step in a method for manufacturing a connector according to the present embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0014] Hereinafter, embodiments of the present technology will be described in detail in the following order with reference to the drawings. 1. Adhesive composition 2. Manufacturing method of connector 3. Working Example

[0015] <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, and the total surface area of ​​the spherical particles calculated from the average particle diameter of the silicone particles is 10×10 per 100 g of the composition. 3 m 2 This improves moisture permeability and makes it possible to obtain high reliability in the HAST (Highly Accelerated Temperature and Humidity Stress Test), which is one of the testing methods for evaluating moisture resistance.

[0016] The adhesive composition may be in the form of either a film or a paste. A film is preferred from the viewpoint of ease of handling, and a paste is preferred from the viewpoint of cost. The curing type of the adhesive composition may include a heat-curing type, a photo-curing type, and a combined photo-thermal and photo-curing type, and can be appropriately selected depending on the application.

[0017] The following description will be given taking a thermosetting adhesive composition as an example. Examples of thermosetting adhesives include cationic curing, anionic curing, and radical curing, as well as a combination of these. Polymerizable compounds include epoxy compounds having ionic polymerization groups (cationic polymerization, anionic polymerization), oxetane compounds, and (meth)acrylic compounds having radical polymerization groups, which can be used alone or in combination of two or more. Silane coupling agents include those having functional groups such as epoxy groups, (meth)acrylic groups, and vinyl groups, and can be selected appropriately depending on the type of polymerizable compound.

[0018] As a specific example of a thermosetting adhesive, an anionically curable epoxy resin composition is shown. The specific adhesive composition contains silicone particles, an epoxy silane coupling agent, an epoxy compound, and an epoxy curing agent. This allows for the production of an epoxy adhesive with high moisture permeability.

[0019] Examples of silicone particles include silicone rubber powder having a crosslinked structure of organopolysiloxane, and silicone rubber powder having a siloxane bond (RSiO 3 / 2 ) n Examples of suitable silicone particles include silicone resin powders having a three-dimensional network-like crosslinked structure represented by the formula (I), and silicone composite powders, which are spherical powders in which the surface of spherical silicone rubber powders is coated with silicone resin. One of these may be used alone, or two or more may be used in combination. Among these, from the viewpoint of dispersibility, it is preferable that the silicone particles include silicone composite powders. Specific examples of commercially available silicone composite powders include those available from Shin-Etsu Chemical Co., Ltd. under the trade names "KMP-600," "KMP-605," and "X-52-7030."

[0020] The average particle size of the silicone particles is preferably 5 μm or less, more preferably 3 μm or less, and even more preferably 1 μm or less, which makes it possible to increase the total surface area of ​​the spherical particles calculated from the average particle size of the silicone particles in the adhesive composition.

[0021] The total surface area of ​​the spherical particles calculated from the average particle size of the silicone particles is 10 × 10 per 100 g of the composition. 3 m 2 or more, more preferably 25 x 10 per 100 g of the composition 3 m 2 Over 150 x 10 3 m 2 or less, more preferably 50 x 10 per 100 g of the composition 3 m 2 Over 150 x 10 3 m 2 The larger the total surface area of ​​the spherical particles calculated from the average particle size of the silicone particles, the higher the moisture permeability, but the lower the adhesive strength tends to be.

[0022] The total surface area of ​​the spherical particles calculated from the average particle diameter of the silicone-based particles in the adhesive composition can be calculated, for example, from the specific surface area of ​​the silicone-based particles and the amount of silicone-based particles added. The specific surface area of ​​the silicone-based particles can be determined, for example, from the surface area per particle calculated from the average particle diameter and the mass per particle calculated from the average particle diameter and true specific gravity.

[0023] The amount of silicone particles blended is, for example, preferably 1 to 30 parts by mass, more preferably 5 to 30 parts by mass, and even more preferably 10 to 30 parts by mass, per 100 parts by mass of the adhesive composition excluding the silicone particles. When conductive particles are blended into the adhesive composition, the amount is in the range of parts by mass per 100 parts by mass of the adhesive composition excluding the conductive particles.

[0024] The epoxy-based silane coupling agent is an organosilicon compound having both an epoxy group and a hydrolyzable group, and chemically bonds the silicone-based particles with the epoxy resin matrix resin, improving dispersibility.

[0025] Examples of epoxy silane coupling agents include silane compounds with an epoxy structure, such as 3-glycidoxypropyltrimethoxysilane and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. A commercially available example of an epoxy silane coupling agent is Momentive Performance Materials Japan's "A-187."

[0026] 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 even more preferably 0.5 to 1 part by mass, per 100 parts by mass of the adhesive composition excluding the silicone particles.

[0027] The epoxy compound is not particularly limited, and examples thereof include 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 phenol-type epoxy compounds, and biphenyl-type epoxy compounds. One of these can be used alone, or two or more can be used in combination. A specific example of a commercially available naphthalene-type bifunctional epoxy resin is "HP4032D" manufactured by DIC Corporation.

[0028] The amount of the epoxy compound blended is, for example, preferably 1 to 30 parts by mass, more preferably 1 to 20 parts by mass, and even more preferably 1 to 10 parts by mass, per 100 parts by mass of the adhesive composition excluding the silicone-based particles.

[0029] Examples of epoxy curing agents include imidazoles, polyhydric phenols, acid anhydrides, amines, hydrazides, polymercaptans, and Lewis acid-amine complexes. These can be used singly or in combination. Among these, from the viewpoints of storage stability and heat resistance of the cured product, it is more preferable for the epoxy curing agent to contain imidazoles. Furthermore, from the viewpoints of storage stability and usable life, it is preferable to use a microencapsulated latent curing agent in which the epoxy curing agent is microencapsulated by coating it with a polyurethane-based or polyester-based polymeric substance. Commercially available imidazole-based latent curing agents include "HP3941" from Asahi Kasei Chemicals Corporation.

[0030] The amount of epoxy curing agent blended is, for example, preferably 5 to 70 parts by mass, more preferably 10 to 60 parts by mass, and even more preferably 20 to 50 parts by mass, per 100 parts by mass of the adhesive composition excluding the silicone-based particles.

[0031] The adhesive composition shown as a specific example preferably contains a polymer and a rubber component.

[0032] Examples of polymers include bisphenol A-type phenoxy resin, bisphenol F-type phenoxy resin, bisphenol S-type phenoxy resin, phenoxy resin having a fluorene skeleton, polystyrene, polyacrylonitrile, polyphenylene sulfide, polytetrafluoroethylene, and polycarbonate, which can be used alone or in combination of two or more. Among these, bisphenol A-type phenoxy resin is preferably used from the viewpoint of film formation state, connection reliability, etc. Phenoxy resin is a polyhydroxy polyether synthesized from bisphenols and epichlorohydrin. A specific example of a commercially available phenoxy resin is "YP-50" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.

[0033] The blend amount of the polymer is, for example, preferably parts by mass, more preferably 10 to 60 parts by mass, and even more preferably 20 to 50 parts by mass, per 100 parts by mass of the adhesive composition excluding the silicone-based particles.

[0034] Examples of rubber components include acrylic rubber (ACR), butadiene rubber (BR), and nitrile rubber (NBR), which can be used alone or in combination of two or more. Among these, acrylic rubber is preferably used from the viewpoint of film formation state, connection reliability, etc. A specific example of commercially available acrylic rubber is "SG80H" manufactured by Nagase Chemtex Corporation.

[0035] It is also preferable to contain elastic particles as the rubber component. The elastic particles can absorb internal stress and do not inhibit curing, thereby providing high connection reliability. Examples of elastic particles include cross-linked acrylonitrile butadiene rubber particles, cross-linked styrene butadiene rubber particles, acrylic rubber particles, and silicone particles. A specific example of commercially available cross-linked acrylonitrile butadiene rubber particles is XER-91 (average particle size 0.5 μm, manufactured by JSR Corporation).

[0036] The amount of the rubber component is, for example, preferably 1 to 30 parts by mass, more preferably 5 to 25 parts by mass, and even more preferably 10 to 20 parts by mass, per 100 parts by mass of the adhesive composition excluding the silicone-based particles.

[0037] The minimum melt viscosity of the adhesive composition is preferably 1 to 100,000 Pa·s, and more preferably 10 to 10,000 Pa·s. If the minimum melt viscosity is too high, the binder between the electrodes cannot be sufficiently removed during thermocompression bonding, which tends to increase the connection resistance. On the other hand, if the minimum melt viscosity is too low, the adhesive composition undergoes significant deformation due to the load applied during thermocompression bonding, and the restoring force of the adhesive composition is applied to the connection interface, etc., as a force in the peel direction when the pressure is released. This tends to increase the connection resistance immediately after thermocompression bonding, and air bubbles tend to form in the connection.

[0038] The adhesive composition having such a constitution has a moisture permeability of preferably 80 g / m 2 or less when measured at a temperature of 40° C. and a relative humidity of 90% after curing. 2 24 hours or more, preferably 85g / m 2 24 hours or more, preferably 90 g / m 2 24 hours or more. This allows moisture that has penetrated into the inside of a device bonded with the adhesive composition to be immediately expelled, resulting in high reliability in HAST. The moisture permeability can be measured in accordance with JIS Z 0208, the moisture permeability test method for moisture-proof packaging materials (cup method), under conditions of 40°C and a relative humidity of 90%.

[0039] Such an adhesive composition can instantly expel moisture that has penetrated into the device, thereby achieving excellent connection reliability. If the adhesive composition were water-resistant, the infiltrated moisture would remain. In other words, this aspect of the present invention can be said to tolerate a certain amount of moisture penetration, but not allow moisture retention, which would excessively accelerate deterioration of adhesiveness. The ability to adjust the required water resistance conditions has the effect of broadening the options for design conditions for devices and the equipment into which they are incorporated. For example, in addition to mobile devices and wearable devices that require weather resistance, the adhesive composition can be advantageously used in electrical equipment for moving objects and vehicles, such as motorcycles, automobiles, flying devices (drones, airplanes, etc.), and ships, which are expected to require even higher weather resistance.

[0040] The adhesive composition may also be a conductive adhesive further containing conductive particles having an average particle size larger than that of the silicone-based particles. From the viewpoint of conductivity, the ratio of the average particle size of the conductive particles to the average particle size of the silicone particles is preferably 1.5 or more, more preferably 2.0 or more, and even more preferably 3.5 or more. A larger value is preferable so that the silicone-based particles do not hinder the compression or flattening of the conductive particles. On the other hand, when the conductive particles are sandwiched between electrodes, it may be preferable to sandwich the silicone-based particles together with the compressed or flattened conductive particles to help break through oxides on the electrodes, so a smaller value may be preferable. The ratio is preferably 1.1 or less, more preferably 1.07 or less, and even more preferably 1.05 or less. These ratios may be adjusted appropriately depending on the purpose.

[0041] The conductive adhesive may be either a film-like conductive film or a paste-like conductive paste. A conductive film is preferred from the viewpoint of ease of handling, and a conductive paste is preferred from the viewpoint of cost. The conductive adhesive and the conductive film may also be used as an anisotropic conductive adhesive and an anisotropic conductive film. These structures may also be an anisotropic connection structure.

[0042] The conductive particles can be any known conductive particles used in conductive films. Examples include particles of various metals and metal alloys such as nickel, iron, copper, aluminum, tin, lead, chromium, cobalt, silver, and gold; particles of metal oxides, carbon, graphite, glass, ceramics, and plastics coated with metal; and particles that have been further insulated by coating the surface of an insulating thin film or by attaching insulating fine particles. Two or more of these may be mixed. In the case of resin particles coated with metal, examples of the resin particles that can be used include particles of epoxy resin, phenolic resin, acrylic resin, acrylonitrile-styrene (AS) resin, benzoguanamine resin, divinylbenzene resin, and styrene resin.

[0043] The average particle size of the conductive particles is usually 1 to 30 μm, preferably 2 to 20 μm, and more preferably 2.5 to 15 μm. 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 100,000 particles / mm 2 , more preferably 500 to 80,000 pieces / mm 2 For example, the results of observation of the film surface obtained by forming it into a film and using an optical microscope or a metallurgical microscope can be obtained using image analysis software WinROOF (Mitani Corporation).

[0044] The conductive particles may be dispersed in the insulating resin, and in the case of a film, they may be individually independent in a planar view of the film, or may be arbitrarily arranged. When the conductive particles are arranged, the number density and the distance between the conductive particles can be set according to the size and layout of the electrodes to be connected. This is effective in improving capture and preventing short circuits, and is also expected to reduce costs by improving yield.

[0045] The minimum melt viscosity of the conductive adhesive is preferably 1 to 100,000 Pa·s, and more preferably 10 to 10,000 Pa·s. While optimizing the minimum melt viscosity depends on the compressive deformation characteristics of the conductive particles, if the minimum melt viscosity is too high, the binder between the conductive particles and the electrode cannot be sufficiently removed during thermocompression bonding, resulting in increased connection resistance. In particular, conductive particles with protrusions make it difficult to fully remove the binder between the conductive particles and the electrode during thermocompression bonding. On the other hand, if the minimum melt viscosity is too low, the conductive adhesive will deform significantly due to the load applied during thermocompression bonding, and the restoring force of the conductive adhesive will be applied to the connection interface, etc., as a peeling force when the pressure is released. This tends to increase connection resistance and cause bubbles to form in the connection immediately after thermocompression bonding.

[0046] The conductive adhesive having such a structure preferably has a moisture permeability of 80 g / m 2 or less when measured at a temperature of 40° C. and a relative humidity of 90% after curing. 2 24 hours or more, preferably 85g / m 224 hours or more, preferably 90 g / m 2 -24 hours or more. This allows moisture that has entered the device bonded with the conductive adhesive to be immediately expelled, achieving high reliability in HAST. The moisture permeability can be measured at 40°C and a relative humidity of 90%, in accordance with the JIS Z 0208 moisture permeability test method (cup method) for moisture-proof packaging materials.

[0047] Such a conductive adhesive can immediately expel moisture that has entered the device, thereby achieving excellent connection reliability.

[0048] <2. Method for manufacturing connector> The method for producing a connector according to the present embodiment is a method for producing a connector comprising: a silicone-based particle, a silane coupling agent, a polymerizable compound, and a curing agent; and a method for producing a connector comprising producing a silicone-based particle having a spherical particle whose total surface area calculated from the average particle diameter of the silicone-based particle is 10×10 per 100 g of the composition. 3 m 2 The method includes a placement step of placing a first electronic component and a second electronic component via the adhesive composition described above, and a curing step of using a crimping tool to crimp the second electronic component onto the first electronic component and curing the adhesive composition. The crimping tool refers to a tool that applies pressure from either the first electronic component, the second electronic component, or both. The shape and material of the crimping tool are not particularly limited, but an example is a flat metal tool equipped with a heating mechanism. This tool may be one used in a known thermocompression bonding device. It may also be equipped with a light irradiation mechanism.

[0049] Furthermore, a connecting body according to the present embodiment includes a first electronic component, a second electronic component, and an adhesive film that bonds the first electronic component and the second electronic component, the adhesive film containing silicone particles, a silane coupling agent, a polymerizable compound, and a curing agent, and the total surface area of ​​the spherical particles calculated from the average particle diameter of the silicone particles is 10×10 per 100 g of the composition. 3 m 2 The adhesive composition is cured and has a moisture permeability of 80 g / m2 - 24 hours or more.

[0050] In the connection body of this embodiment, the adhesive film that bonds the first electronic component and the second electronic component has high moisture permeability, so that moisture that has entered the device can be immediately expelled, thereby achieving high reliability in HAST.

[0051] A method for manufacturing a connection body using an adhesive film will be described below. Fig. 1 is a cross-sectional view schematically showing the arrangement step of the method for manufacturing a connection body according to this embodiment. The adhesive composition constituting the adhesive film is the same as that described above, and therefore will not be described here.

[0052] [Placement process (S1)] As shown in FIG. 1 , in the placement step (S1), an adhesive film 20 containing silicone-based particles 21 is placed on a first electronic component 10. The first electronic component 10 has a first terminal row 11. The first electronic component 10 is not particularly limited and can be appropriately selected depending on the purpose. Examples of the first electronic component 10 include transparent substrates for flat panel displays (FPDs) such as LCD (Liquid Crystal Display) panels and organic light-emitting diodes (OLEDs), touch panels, printed wiring boards (PWBs), and flexible printed circuits (FPCs). The material of the printed wiring board is not particularly limited, and may be, for example, a glass epoxy such as an FR-4 substrate, or a plastic such as a thermoplastic resin, or ceramic. The transparent substrate is not particularly limited as long as it is highly transparent, and examples include a glass substrate and a plastic substrate. Among these, a ceramic substrate is preferably used from the viewpoint of heat resistance.

[0053] Furthermore, the second electronic component facing the first electronic component preferably has plated bumps formed thereon, such as an IC or flexible substrate. The plated bumps preferably have low or no dimples, or a flat surface. The surface of the plated bumps is preferably leveled to increase the contact area during compression bonding. Stud bumps may also be formed on the wiring substrate.

[0054] The adhesive film 20 is a film of the adhesive composition described above, and so a detailed description will be omitted here. The thickness of the adhesive film 20 is preferably 1 to 100 μm, and more preferably 10 to 50 μm. This range is the same whether it is a single layer or a multilayer. In the case of a paste, the thickness refers to the thickness when used for connection.

[0055] [Curing process (S2)] In the curing step (S2), a second electronic component is placed on the adhesive film 20, and the second electronic component is pressed against the first electronic component 10 using a crimping tool to bond them together while applying heat. Furthermore, in the curing step (S2), the crimping tool is used to press the second electronic component at a temperature of preferably 250°C or lower, more preferably 220°C or lower, and even more preferably 200°C or lower. This melts the resin due to the heat from the crimping tool, and the second electronic component is sufficiently pressed into the crimping tool, causing the resin to thermally cure, resulting in excellent adhesiveness. While this assumes that a heating mechanism is incorporated into the crimping tool, the adhesive film 20 may also be heated and cured by a method in which a heating mechanism is not incorporated into the crimping tool.

[0056] The second electronic component has a second terminal row facing the first terminal row 11. There are no particular limitations on the second electronic component, and it can be appropriately selected depending on the purpose. Examples of the second electronic component include an integrated circuit (IC), a flexible printed circuit (FPC), and a tape carrier package (TCP) board. When an IC is mounted on an FPC, it becomes a chip on film (COF).

[0057] In the curing step (S2), a buffer material may be used between the crimping tool and the second electronic component. Examples of the buffer material that can be used include polytetrafluoroethylene (PTFE), polyimide, glass cloth, and silicone rubber.

[0058] According to this method for manufacturing a connection body, the adhesive film that bonds the first electronic component and the second electronic component has high moisture permeability, so that moisture that has entered the device can be immediately expelled, thereby achieving high reliability in HAST.

[0059] [Variations] In the above-described embodiment, the first electronic component and the second electronic component are connected using an adhesive film, but the present invention is not limited to this. The first electronic component and the second electronic component may be connected using a conductive adhesive film containing conductive particles. The conductive adhesive film may also have a two-layer structure consisting of a layer containing conductive particles (for convenience, referred to as a conductive particle-containing layer) and a layer not containing conductive particles (for convenience, referred to as a conductive particle-free layer). A similar structure can also be used when connecting in a paste form. <3. Example> [Example]

[0060] Examples of the present technology will be described below. In the first example, an adhesive film was prepared as one form of the adhesive composition, and a connection was made. The moisture permeability of the adhesive film after curing, the initial adhesive strength of the connection, and the adhesive strength after a reliability test were measured, as well as the initial conduction resistance of the connection, and the conduction resistance after a reliability test.

[0061] [Preparation of adhesive film and measurement of moisture permeability] An adhesive film 35 μm thick was prepared by blending the materials shown in Table 1. Furthermore, to measure the moisture permeability, the adhesive film was cured at a temperature of 200°C to prepare a sample film. The moisture permeability was measured at 40°C and a relative humidity of 90% in accordance with the moisture permeability test method for moisture-proof packaging materials (cup method) of JIS Z 0208. Specifically, calcium chloride (anhydrous) was sealed in a cup, and the cup, covered with the sample film, was allowed to stand at a constant temperature and humidity. The cup was repeatedly weighed at regular intervals, and the increase in the mass of the cup was evaluated as the amount of water vapor transmitted through it.

[0062] [Creating a connector] The bare chip (IC chip) was 0.4 mm thick, 6 mm wide, and 6 mm long (6 mm x 6 mm), and a measurement TEG (Test Element Group) was used, which had wiring for measuring conductivity (bump size: 50 x 50 μm, pitch: 85 μm (space between bumps: 35 μm), gold bump height h = 15 μm). The gold bumps were plated bumps, and were smooth and free of dimples.

[0063] The flexible printed circuit board (FPC: Flexible Printed Circuits) used was a measurement TEG with a polyimide substrate, a thickness of 25 μm, a pitch of 85 μm (L / S=45 / 40), and a top of 40 μm, on which wiring for measuring conductivity was formed.

[0064] The bare chip was mounted on a flexible wiring board using an adhesive film. The thermocompression bonding conditions were a temperature of 200°C, a pressure of 100 MPa, and a time of 10 seconds. During the thermocompression bonding, a 50 μm-thick polytetrafluoroethylene sheet was placed on the bare chip as a buffer material.

[0065] [Adhesion strength measurement] The flexible wiring board of the connection was peeled off in a 90° direction at a pulling speed of 50 mm / sec, and the maximum peel strength required for the peel was taken as the adhesive strength. Measurements were taken for the initial connection and the connection after reliability testing. The reliability test was conducted in accordance with JEDEC (JESD22-A110) under conditions of a temperature of 110°C, humidity of 85%, and a duration of 264 hours.

[0066] [Measurement of conduction resistance] Regarding the connection state between the bare chip and the flexible wiring board, a digital multimeter was used to measure the conduction resistance (Ω) at the initial connection and after the reliability test. The conduction resistance value was measured by connecting the digital multimeter to the wiring of the flexible wiring board connected to the bumps of the bare chip, and passing a current of 1 mA using the four-terminal method. The reliability test was conducted in accordance with JEDEC (JESD22-A110), under conditions of a temperature of 110°C, humidity of 85%, and for 264 hours.

[0067] [Table 1] Polymer: YP-50 (Nippon Steel & Sumikin Chemical Co., Ltd.) Epoxy hardener: HP3941 (Asahi Kasei Chemicals Corporation) Epoxy compound: HP4032D (DIC Corporation) Rubber particles: XER-91 (JSR Corporation) Rubber component: SG80H (Nagase ChemteX Corporation) Coupling agent: A-187 (Momentive Performance Materials Japan, Ltd.) Silicone particles A: X-52-7030 (Shin-Etsu Silicone Co., Ltd.), average particle size 0.8 μm, true specific gravity 1.01 Silicone particles B: KMP-605 (Shin-Etsu Silicone Co., Ltd.), average particle size 2 μm, true specific gravity 0.99 Silicone particles C: KMP-600 (Shin-Etsu Silicone Co., Ltd.), average particle size 5 μm, true specific gravity 0.99

[0068] The specific surface area of ​​the silicone particles was determined from the surface area per particle calculated from the average particle diameter and the mass per particle calculated from the average particle diameter and true specific gravity.

[0069] As shown in Table 1, the total surface area of ​​the spherical particles calculated from the average particle diameter of the silicone-based particles is 10 × 10 per 100 g of the composition. 3 m 2 By this (Examples 1 to 8), 80 g / m 2 The total surface area of ​​the spherical particles calculated from the average particle diameter of the silicone particles was 50 x 10 per 100 g of the composition. 3 m 2 By being equal to or greater than this (Examples 5 to 7), 2 -Moisture permeability of over 24 hours was achieved. Without silicone particles, the moisture permeability was 75 g / m 2 24 hours (Comparative Example 1).

[0070] [Second Example] In the second example, a conductive film was prepared as a form of the adhesive composition, and a connection was then prepared. The moisture permeability of the cured conductive film, the initial adhesive strength of the connection, and the adhesive strength after a reliability test were then measured, as well as the initial conduction resistance of the connection, and the conduction resistance after a reliability test.

[0071] [Preparation of conductive film and measurement of moisture permeability] A 35 μm-thick conductive film was prepared by blending the materials shown in Table 1. Furthermore, to measure the moisture permeability, the conductive film was cured at a temperature of 200°C to prepare a sample film. The moisture permeability was measured at 40°C and a relative humidity of 90% in accordance with the JIS Z 0208 moisture permeability test method for moisture-proof packaging materials (cup method). Specifically, calcium chloride (anhydrous) was sealed in a cup, and the cup, covered with the sample film, was left to stand at a constant temperature and humidity. The cup was repeatedly weighed at regular intervals, and the increase in mass of the cup was evaluated as the amount of water vapor transmitted through it.

[0072] [Creating a connector] The bare chip (IC chip) was 0.4 mm thick, 6 mm wide, and 6 mm long (6 mm x 6 mm), and a measurement TEG (Test Element Group) was used, which had wiring for measuring conductivity (bump size: 50 x 50 μm, pitch: 85 μm (space between bumps: 35 μm), gold bump height h = 15 μm). The gold bumps were plated bumps, and were smooth and free of dimples.

[0073] The bare chip was mounted on a flexible wiring board using a conductive film. The thermocompression bonding conditions were a temperature of 200°C, a pressure of 100 MPa, and a time of 10 seconds. During the thermocompression bonding, a 200 μm thick silicone rubber was placed on the bare chip as a buffer material.

[0074] [Adhesion strength measurement] The flexible wiring board of the connection was peeled off in a 90° direction at a pulling speed of 50 mm / sec, and the maximum peel strength required for the peel was taken as the adhesive strength. Measurements were taken for the initial connection and the connection after reliability testing. The reliability test was conducted in accordance with JEDEC (JESD22-A110) under conditions of a temperature of 110°C, humidity of 85%, and a duration of 264 hours.

[0075] [Measurement of conduction resistance] Regarding the connection state between the bare chip and the flexible wiring board, a digital multimeter was used to measure the conduction resistance (Ω) at the initial connection and after the reliability test. The conduction resistance value was measured by connecting the digital multimeter to the wiring of the flexible wiring board connected to the bumps of the bare chip, and passing a current of 1 mA using the four-terminal method. The reliability test was conducted in accordance with JEDEC (JESD22-A110), under conditions of a temperature of 110°C, humidity of 85%, and for 264 hours.

[0076] [Table 2] Polymer: YP-50 (Nippon Steel & Sumikin Chemical Co., Ltd.) Epoxy hardener: HP3941 (Asahi Kasei Chemicals Corporation) Epoxy compound: HP4032D (DIC Corporation) Rubber particles: XER-91 (JSR Corporation) Rubber component: SG80H (Nagase ChemteX Corporation) Coupling agent: A-187 (Momentive Performance Materials Japan, Ltd.) Conductive particles A: Ni / Au plated acrylic resin particles, average particle diameter 5 μm, Nippon Chemical Co., Ltd. Conductive particles B: Ni / Au plated acrylic resin particles, average particle size 3.5 μm, Nippon Chemical Co., Ltd. Conductive particles C: Ni / Au plated acrylic resin particles, average particle size 3 μm, Nippon Chemical Co., Ltd. Silicone particles A: X-52-7030 (Shin-Etsu Silicone Co., Ltd.), average particle size 0.8 μm, true specific gravity 1.01 Silicone particles B: KMP-605 (Shin-Etsu Silicone Co., Ltd.), average particle size 2 μm, true specific gravity 0.99 Silicone particles C: KMP-600 (Shin-Etsu Silicone Co., Ltd.), average particle size 5 μm, true specific gravity 0.99

[0077] The specific surface area of ​​the silicone particles was determined from the surface area per particle calculated from the average particle diameter and the mass per particle calculated from the average particle diameter and true specific gravity.

[0078] As shown in Table 2, the average particle size of the silicone particles is smaller than the average particle size of the conductive particles, and the total surface area of ​​the spherical particles calculated from the average particle size of the silicone particles is 10 × 10 per 100 g of the composition. 3 m 2 By this (Examples 9 to 17), 80 g / m 2 The moisture permeability was more than 24 hours. In addition, the total surface area of ​​the spherical particles calculated from the average particle diameter of the silicone particles was 50 x 10 per 100 g. 3 m 2 By this (Examples 13 to 15), 90 g / m 2-Moisture permeability of over 24 hours was achieved. Without silicone particles, the moisture permeability was 75 g / m 2 24 hours (Comparative Example 2). Furthermore, when the average particle size of the silicone particles was equal to or larger than the average particle size of the conductive particles, the resistance value increased (Comparative Examples 3 and 4).

[0079] As in Examples 9 to 17, the moisture permeability of the conductive film was set to 80 g / m 2 By setting the test time to 24 hours or more, it was possible to suppress the increase in resistance after the reliability test. This is thought to be because the high moisture permeability of the conductive film allowed moisture that had entered the device to be immediately expelled. [Explanation of symbols]

[0080] 10 first electronic component, 11 first terminal row, 20 adhesive film, 21 silicone particles

Claims

1. The rubber composition contains silicone particles, an epoxy silane coupling agent, an epoxy compound other than the epoxy silane coupling agent, an epoxy curing agent, and two or more rubber components other than the silicone particles, The total surface area of ​​the spherical particles calculated from the average particle diameter of the silicone-based particles is 90.7 × 10 per 100 g of the composition. ３ m ２ That's all, The rubber component contains elastic particles, A film having a thickness of 35 μm was prepared from the composition and cured at 200°C. The moisture permeability of the cured product measured at a temperature of 40°C and a relative humidity of 90% was 90 g / m ２ - An adhesive composition having a durability of 24 hours or more.

2. 2. The adhesive composition according to claim 1, wherein the rubber component comprises an acrylic rubber and elastic particles.

3. 3. The adhesive composition according to claim 1, wherein the amount of the rubber component is 1 to 30 parts by mass per 100 parts by mass of the adhesive composition.

4. 4. The adhesive composition according to claim 1, wherein the silicone particles have an average particle size of 5 [mu]m or less.

5. 5. The adhesive composition according to claim 1, wherein the silicone particles comprise a silicone composite powder, which is a spherical powder in which the surface of a spherical silicone rubber powder is coated with a silicone resin.

6. Further containing conductive particles, The adhesive composition according to claim 1 , wherein the average particle size of the silicone-based particles is smaller than the average particle size 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. The rubber composition contains silicone particles, an epoxy silane coupling agent, an epoxy compound other than the epoxy silane coupling agent, an epoxy curing agent, and two or more rubber components other than the silicone particles, The total surface area of ​​the spherical particles calculated from the average particle diameter of the silicone-based particles is 90.7 × 10 per 100 g of the composition. ３ m ２ or more, the rubber component contains elastic particles, and a film having a thickness of 35 μm is produced from the composition and cured at 200° C. The moisture permeability of the cured product measured at a temperature of 40° C. and a relative humidity of 90% is 90 g / m ２ a placement step of placing a first electronic component and a second electronic component via an adhesive composition having a shelf life of 24 hours or more; a curing step of pressing the second electronic component to the first electronic component with a pressing tool and curing the adhesive composition; A method for manufacturing a connector having the above structure.

9. 9. The method for producing a connector according to claim 8, wherein the rubber component contains acrylic rubber and elastic particles.

10. 10. The method for producing a connector according to claim 8, wherein the amount of the rubber component is 1 to 30 parts by mass per 100 parts by mass of the composition.

11. the adhesive composition further contains conductive particles, The method for producing a connection body according to any one of claims 8 to 10, wherein the average particle size of the silicone-based particles is smaller than the average particle size of the conductive particles.

12. a first electronic component, a second electronic component, and an adhesive film that bonds the first electronic component and the second electronic component together; The adhesive film contains silicone particles, an epoxy silane coupling agent, an epoxy compound other than the epoxy silane coupling agent, an epoxy curing agent, and two or more rubber components other than the silicone particles, and the total surface area of ​​spherical particles calculated from the average particle diameter of the silicone particles is 90.7 × 10 per 100 g of the composition. ３ m ２ or more, the rubber component contains elastic particles, and a film having a thickness of 35 μm is produced from the composition and cured at 200° C. The moisture permeability of the cured product measured at a temperature of 40° C. and a relative humidity of 90% is 90 g / m ２ A connection body formed by curing an adhesive composition for 24 hours or more.

13. 13. The connector according to claim 12, wherein the rubber component contains acrylic rubber and elastic particles.

14. 14. The connector according to claim 12, wherein the amount of the rubber component is 1 to 30 parts by mass per 100 parts by mass of the composition.

15. the adhesive composition further contains conductive particles, 15. The connector according to claim 12, wherein the average particle size of the silicone-based particles is smaller than the average particle size of the conductive particles.

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