WO2020203295A1

WO2020203295A1 - Adhesive composition

Info

Publication number: WO2020203295A1
Application number: PCT/JP2020/011982
Authority: WO
Inventors: 佐藤　大祐; 明史樋口
Original assignee: デクセリアルズ株式会社
Priority date: 2019-03-29
Filing date: 2020-03-18
Publication date: 2020-10-08
Also published as: KR20210129169A; CN113785027B; JP2020164722A; CN113785027A

Abstract

Provided is an adhesive composition that can achieve high reliability. An adhesive composition that 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.

Description

Adhesive composition

The present technology relates to, for example, an adhesive composition for connecting an IC (Integrated Circuit) chip and a flexible wiring board. This application claims priority on the basis of Japanese Patent Application No. Japanese Patent Application No. 2019-068612 filed on March 29, 2019 in Japan, and this application is referred to in this application. It will be used.

Conventionally, for example, in a device in which an LCD (Liquid Crystal Display) driver IC is connected to a flexible wiring board, when the device is heated, the moisture that has entered the inside of the device may rapidly expand and destroy the device.

To solve this problem, Patent Document 1, drawn from the interior of the display panel, proposed to use the exposed wiring, moisture permeability 5 ~ 6g / m 2 · ^24h or less sealing material Has been done.

Further, in Patent Document 2, a moisture permeation preventive material is provided on the base film of the electrode connection portion of the flexible wiring board, and a lead electrode is formed on the base film, and the lead electrode is formed on the electrode connection portion of the flexible wiring board. such as in the form of coating between the lead electrodes in moisture proof material is described, as a moisture permeation prevention member, moisture permeability has been proposed to use the following: 10g / m 2 · ^24h.

Japanese Unexamined Patent Publication No. 2000-090840 Japanese Unexamined Patent Publication No. 2004-327873

The method described in the above-mentioned Patent Documents 1 and 2 is to improve the moisture resistance by using a sealing resin having a low moisture permeability for the wiring (outer lead). However, the use of a sealing resin with low moisture permeability causes an increase in the number of materials and a limit in material selection. Therefore, in HAST (Highly Accelerated Temperature and Humidity Stress Test), which is one of the test methods for evaluating moisture resistance, , It is difficult to obtain high reliability.

This technology solves the above-mentioned problems and provides an adhesive composition that can obtain high reliability.

The present inventor has proceeded with research on the formulation of an adhesive composition that can obtain high moisture permeability in order to immediately discharge the moisture that has entered the inside of the device. As a result, the present technology has been completed based on the finding that the moisture permeability is improved by blending a predetermined amount of silicone particles and a silane coupling agent.

That is, the adhesive composition according to the present technology contains silicone-based particles, a silane coupling agent, a polymerizable compound, and a curing agent, and is a true spherical particle calculated from the average particle size of the silicone-based particles. The total surface area of the composition is 10 × 10 ³ m ² or more per 100 g of the composition.

Further, the method for producing a connector according to the present technology contains silicone-based particles, a silane coupling agent, a polymerizable compound, and a curing agent, and is a true sphere calculated from the average particle size of the silicone-based particles. By the placement step of arranging the first electronic component and the second electronic component via the adhesive composition in which the total surface area of the particles is 10 × 10 ³ m ² or more per 100 g of the composition, and the crimping tool. It has a curing step of crimping the second electronic component to the first electronic component and curing the adhesive composition.

Further, the connector according to the present technology includes the first electronic component, the second electronic component, and the adhesive film to which the first electronic component and the second electronic component are adhered, and the adhesion is provided. The film contains silicone-based particles, a silane coupling agent, a polymerizable compound, and a curing agent, and the total surface area of spherical particles calculated from the average particle size of the silicone-based particles is the composition. 10 × ¹⁰ 3 ^m adhesive composition is ^two or more per 100g is cured, is moisture permeability ^{80 g} / m 2 · 24 hr or more.

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.

FIG. 1 is a cross-sectional view schematically showing an arrangement process of a connecting body manufacturing method according to the present embodiment.

Hereinafter, embodiments of the present technology will be described in detail in the following order with reference to the drawings.
1. 1. Adhesive composition 2. Method of manufacturing the connector 3. Example

<1. Adhesive composition>
The adhesive composition according to the present embodiment contains silicone-based particles, a silane coupling agent, a polymerizable compound, and a curing agent, and is a true sphere particle calculated from the average particle size of the silicone-based particles. The total surface area is 10 × 10 ³ m ² or more per 100 g of the composition. As a result, the moisture permeability is improved, and high reliability can be obtained in HAST (Highly Accelerated Temperature and Humidity Stress Test), which is one of the test methods for evaluating the moisture resistance.

The adhesive composition may be in the form of a film or a paste. From the viewpoint of ease of handling, it is preferably in the form of a film, and from the viewpoint of cost, it is preferably in the form of a paste. Further, examples of the curing type of the adhesive composition include a thermosetting type, a photocuring type, and a photocuring type that is combined with light heat, and can be appropriately selected depending on the intended use.

Hereinafter, a thermosetting adhesive composition will be described as an example. As the thermosetting type, for example, a cation curing type, an anion curing type, a radical curing type, or a combination thereof can be used. Examples of the polymerizable compound include an epoxy compound having an ionic polymerization group (cationic polymerization, anionic polymerization), an oxetane compound, a (meth) acrylic compound having a radical polymerization group, and the like, and these are used alone or in combination of two or more. be able to. In addition, examples of the silane coupling agent include silane coupling agents having a functional group such as an epoxy group, a (meth) acrylic group, and a vinyl group, which can be appropriately selected depending on the type of the polymerizable compound.

As a specific example of the thermosetting type, an anion curing type epoxy resin composition is shown. The adhesive composition shown as a specific example contains silicone-based particles, an epoxy-based silane coupling agent, an epoxy compound, and an epoxy curing agent. Thereby, an epoxy-based adhesive having high moisture permeability can be obtained.

Examples of the silicone-based particles include a silicone rubber powder having a structure in which organopolysiloxane is crosslinked, a silicone resin powder having a structure in which the siloxane bond is represented by (RSiO _3/2 ) _n in a three-dimensional network, and a spherical shape. Examples thereof include silicone composite powder, which is a spherical powder in which the surface of the silicone rubber powder is coated with silicone resin, and one of these can be used alone or in combination of two or more. Among these, from the viewpoint of dispersibility, the silicone-based particles preferably contain a silicone composite powder. Specific examples of the silicone composite powder available on the market include the trade names "KMP-600", "KMP-605", and "X-52-7030" of Shin-Etsu Chemical Co., Ltd.

The average particle size of the silicone-based particles is preferably 5 μm or less, more preferably 3 μm or less, still more preferably 1 μm or less. This makes it possible to increase the total surface area of the true sphere particles calculated from the average particle size of the silicone-based particles in the adhesive composition.

The total surface area of the true sphere particles calculated from the average particle size of the silicone-based particles is 10 × 10 ³ m ² or more per 100 g of the composition, more preferably 25 × 10 ³ m ² or more per 100 g of the composition 150 × 10 ³ It is m ² or less, more preferably 50 × 10 ³ m ² or more and 150 × 10 ³ m ² or less per 100 g of the composition. As the total surface area of the true sphere particles calculated from the average particle size of the silicone-based particles increases, the moisture permeability tends to increase, but the adhesive strength tends to decrease.

The total surface area of the true sphere particles calculated from the average particle size of the silicone-based particles in the adhesive composition can be calculated from, for example, the specific surface area of the silicone-based particles and the amount of the silicone-based particles added. it can. Further, the specific surface area of the silicone-based particles can be obtained from, for example, the surface area per particle calculated from the average particle size and the mass per particle calculated from the average particle size and the true specific gravity.

The blending amount of the silicone-based particles is, for example, preferably 1 to 30 parts by mass, more preferably 5 to 30 parts by mass, and 10 to 30 parts by mass with respect to 100 parts by mass of the adhesive composition excluding the silicone-based particles. It is more preferable to use parts by mass. When conductive particles are blended in the adhesive composition, it is in the range of parts by mass with respect to 100 parts by mass of the adhesive composition excluding the conductive particles.

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 and the epoxy resin which is a matrix resin to improve dispersibility.

Examples of the epoxy-based silane coupling agent include silane compounds having an epoxy structure such as 3-glycidoxypropyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Specific examples of epoxy-based silane coupling agents available on the market include "A-187" from Momentive Performance Materials Japan (Go).

The blending amount of the epoxy-based silane coupling agent is preferably, for example, 0.1 to 10 parts by mass, and 0.1 to 5 parts by mass, based on 100 parts by mass of the adhesive composition excluding the silicone-based particles. Is more preferable, and 0.5 to 1 part by mass is further preferable.

The epoxy compound is not particularly limited, and is a naphthalene type epoxy compound, a glycidyl ether type epoxy compound, a glycidyl ester type epoxy compound, an alicyclic epoxy compound, a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, and a dicyclopentadiene type epoxy. Examples include compounds, novolak phenol-type epoxy compounds, and biphenyl-type epoxy compounds, and one of these can be used alone or in combination of two or more. Specific examples of the naphthalene-type bifunctional epoxy resin available on the market include "HP4032D" of DIC Corporation.

The blending amount of the epoxy compound is, for example, preferably 1 to 30 parts by mass, more preferably 1 to 20 parts by mass, and 1 to 10 parts by mass with respect to 100 parts by mass of the adhesive composition excluding the silicone-based particles. It is more preferable to use a part.

Examples of the epoxy curing agent include imidazoles, polyhydric phenols, acid anhydrides, amines, hydrazides, polyethercaptans, and Lewis acid-amine complexes, and one of these may be used alone or 2 Seeds and above can be used in combination. Among these, from the viewpoint of storage stability and heat resistance of the cured product, the epoxy curing agent more preferably contains imidazoles. Further, from the viewpoint of storage stability and pot life, it is preferable to use a microcapsule type latent curing agent in which an epoxy curing agent is coated with a polyurethane-based or polyester-based polymer substance and microencapsulated. Examples of the imidazole-based latent curing agent available on the market include "HP3941" of Asahi Kasei Chemicals Co., Ltd.

The blending amount of the epoxy curing agent is, for example, preferably 5 to 70 parts by mass, more preferably 10 to 60 parts by mass, and 20 to 50 parts by mass with respect to 100 parts by mass of the adhesive composition excluding the silicone-based particles. It is more preferable to use parts by mass.

Further, the adhesive composition shown as a specific example preferably contains a polymer and a rubber component.

Examples of the polymer 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, polycarbonate and the like. It 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 and the like. Phenoxy resin is a polyhydroxypolyether synthesized from bisphenols and epichlorohydrin. Specific examples of the phenoxy resin available on the market include the trade name "YP-50" of Nippon Steel & Sumikin Chemical Co., Ltd.

The amount of the polymer to be blended is preferably, for example, 10 to 60 parts by mass, more preferably 20 to 50 parts by mass, based on 100 parts by mass of the adhesive composition excluding the silicone-based particles. Is even more preferable.

Examples of the rubber component include acrylic rubber (ACR), butadiene rubber (BR), nitrile rubber (NBR), etc., 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 and the like. Specific examples of acrylic rubber available on the market include the trade name "SG80H" of Nagase Chemtex Co., Ltd.

Further, it is preferable to contain elastic particles as a rubber component. The elastic particles can absorb internal stress and do not cause hardening inhibition, so that high connection reliability can be provided. Examples of the elastic particles include crosslinked acrylonitrile-butadiene rubber particles, crosslinked styrene-butadiene rubber particles, acrylic rubber particles, and silicone particles. Specific examples of the crosslinked acrylonitrile butadiene rubber particles available on the market include XER-91 (average particle diameter 0.5 μm, manufactured by JSR Corporation).

The amount of the rubber component to be blended is preferably, for example, 1 to 30 parts by mass, more preferably 5 to 25 parts by mass, and 10 to 20 parts by mass with respect to 100 parts by mass of the adhesive composition excluding the silicone-based particles. It is more preferable to use a part.

The minimum melt viscosity of the adhesive composition is preferably 1 to 100,000 Pa · s, and more preferably 10 to 10000 Pa · s. If the minimum melt viscosity is too high, the binder between the electrodes cannot be sufficiently removed during thermocompression bonding, and 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 during thermocompression bonding becomes large, so that the restoring force of the adhesive composition is applied to the interface of the connecting portion as a force in the peeling direction when the pressure is released. .. For this reason, the connection resistance tends to increase immediately after thermocompression bonding, and bubbles tend to be generated at the connection portion.

The adhesive composition of such a construction is the moisture permeability measured under conditions of temperature and 90% relative humidity 40 ° C. after curing, preferably ^80g / m 2 · 24hr or more, more preferably 85 g / m ² · 24 hr or more, and more preferably ^90g / m 2 · 24hr or more. As a result, the moisture that has entered the inside 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 ° C. and 90% relative humidity in accordance with the moisture permeability test method (cup method) of the moisture-proof packaging material of JIS Z 0208.

According to such an adhesive composition, the moisture that has entered the inside of the device can be immediately discharged, so that excellent connection reliability can be obtained. If water resistance is provided, the infiltrated water will stay. In other words, it can be said that, instead of allowing a certain amount of water to enter, it does not allow the retention of water that causes excessive deterioration of adhesiveness. The ability to adjust the required water resistance conditions has the effect of expanding the selectivity of the design conditions of the device and the equipment in which it is incorporated. For example, in addition to mobile terminals and wearable terminals that require weather resistance, motorcycles and automobiles that are expected to require higher weather resistance, flying devices (drones, airplanes, etc.), moving objects such as ships, and electrical equipment for vehicles. There are advantages that can be used for.

Further, the adhesive composition may be a conductive adhesive further containing conductive particles having an average particle diameter larger than the average particle diameter of the silicone-based particles. When conductive particles are contained, the average particle size of the conductive particles is preferably larger than the average particle size of the solid composition other than the conductive particles so as not to hinder the sandwiching. 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, still more preferably 3.5 or more. The value should be large so that the silicone-based particles do not hinder the compression and flattening of the conductive particles. On the other hand, when the conductive particles are sandwiched between the electrodes, it is preferable to sandwich the silicone-based particles together with the compressed or flattened conductive particles in order to assist in breaking through the oxides on the electrodes. Therefore, it may be better to have a small number. It is preferably 1.1 or less, more preferably 1.07 or less, and even more preferably 1.05 or less. These may be appropriately adjusted according to the purpose.

The conductive adhesive may be either a film-like conductive film or a paste-like conductive paste. A conductive film is preferable from the viewpoint of ease of handling, and a conductive paste is preferable from the viewpoint of cost. Further, the conductive adhesive and the conductive film can also be used as the anisotropic conductive adhesive and the anisotropic conductive film. Further, these structures may be anisotropic connection structures.

As the conductive particles, known conductive particles used in the conductive film can be used. For example, on the surface of particles of various metals and metal alloys such as nickel, iron, copper, aluminum, tin, lead, chromium, cobalt, silver and gold, and particles of metal oxides, carbon, graphite, glass, ceramics and plastics. Examples thereof include those coated with metal, those coated with an insulating thin film on the surface of these particles, and those subjected to an insulating treatment such as adhering insulating fine particles. Two or more of these may be mixed. When the surface of the resin particles is coated with metal, the resin particles include, for example, epoxy resin, phenol resin, acrylic resin, acrylonitrile-styrene (AS) resin, benzoguanamine resin, divinylbenzene resin, styrene resin and the like. Particles can be used.

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. The average particle density of the conductive particles in the binder resin, connected in terms of reliability and insulation reliability, and preferably from 100 to 100,000 / mm ^2, more preferably from 500 to 80,000 pieces / mm ^2. For example, the observation result obtained by forming a film and forming the film surface with an optical microscope or a metallurgical microscope can be obtained by the image analysis software WinROOF (Mitani Shoji Co., Ltd.).

Further, the conductive particles may be dispersed in the insulating resin, and in the case of a film, they may be individually independent in the plan view of the film, or may be arbitrarily arranged and present. When the conductive particles are arranged, the number density, the distance between the conductive particles, and the like can be set according to the size and layout of the connected electrodes. For this reason, it is effective in improving capture and suppressing short circuits, and is expected to have cost reduction effects such as improvement in yield.

The minimum melt viscosity of the conductive adhesive is preferably 1 to 100,000 Pa · s, and more preferably 10 to 10000 Pa · s. The optimization of the minimum melt viscosity also depends on the compressive deformation characteristics of the conductive particles, but if the minimum melt viscosity is too high, the binder between the conductive particles and the electrodes cannot be sufficiently removed during thermocompression bonding, resulting in connection resistance. It tends to rise. In particular, the conductive particles having protrusions make it difficult to sufficiently remove the binder between the conductive particles and the electrodes during thermocompression bonding. On the other hand, if the minimum melt viscosity is too low, the deformation of the conductive adhesive due to the load during thermocompression bonding becomes large, so that the restoring force of the conductive adhesive is applied to the interface of the connection portion as a force in the peeling direction when the pressure is released. .. For this reason, the connection resistance tends to increase immediately after thermocompression bonding, and bubbles tend to be generated at the connection portion.

Such configuration of the conductive adhesive, moisture permeability is measured under the conditions of temperature and 90% relative humidity 40 ° C. after curing, preferably 80g / m 2 ^· 24hr or more, more preferably 85 g / m ² · 24 hr or more, and more preferably ^90g / m 2 · 24hr or more. As a result, the moisture that has entered the inside of the device adhered with the conductive adhesive can be immediately discharged, and high reliability can be obtained in HAST. The moisture permeability can be measured under the conditions of 40 ° C. and 90% relative humidity in accordance with the moisture permeability test method (cup method) of the moisture-proof packaging material of JIS Z 0208.

With such a conductive adhesive, the moisture that has entered the inside of the device can be immediately discharged, so that excellent connection reliability can be obtained.

<2. Manufacturing method of connector>
The method for producing a connector according to the present embodiment contains silicone-based particles, a silane coupling agent, a polymerizable compound, and a curing agent, and is a true spherical particle calculated from the average particle size of the silicone-based particles. The first electronic component and the second electronic component are arranged via the adhesive composition having a total surface area of 10 × 10 ³ m ² or more per 100 g of the composition, and the second by the crimping tool. It has a curing step of crimping the electronic component of No. 1 to the first electronic component and curing the adhesive composition. Here, the crimping tool refers to a tool that pressurizes from a first electronic component, a second electronic component, or both. The shape and material of the crimping tool are not particularly limited, but an example thereof is a flat metal having a heating mechanism. This may be used in known thermocompression bonding devices. Further, a mechanism for irradiating light may be provided.

Further, the connector according to the present embodiment includes an adhesive film in which the first electronic component, the second electronic component, and the first electronic component and the second electronic component are adhered to each other. Contains silicone particles, a silane coupling agent, a polymerizable compound, and a curing agent, and the total surface area of true sphere particles calculated from the average particle size of the silicone particles is per 100 g of the composition. the adhesive composition is ¹⁰ × 10 3 ^{m 2} or more is cured, is moisture permeability ^80g / m 2 · 24hr or more.

In the connecting body according to the present embodiment, since the adhesive film in which the first electronic component and the second electronic component are bonded has high moisture permeability, the moisture that has entered the inside of the device can be immediately discharged. It can be done, and high reliability can be obtained in HAST.

Hereinafter, a method for manufacturing a connector using an adhesive film will be described. FIG. 1 is a cross-sectional view schematically showing an arrangement process of a connecting body manufacturing method according to the present embodiment. Since the adhesive composition constituting the adhesive film is the same as described above, description thereof will be omitted here.

[Arrangement step (S1)]
As shown in FIG. 1, in the arrangement step (S1), the adhesive film 20 containing the silicone-based particles 21 is arranged on the first electronic component 10. The first electronic component 10 includes a first terminal row 11. The first electronic component 10 is not particularly limited and may be appropriately selected depending on the intended purpose. The first electronic component 10 includes, for example, an LCD (Liquid Crystal Display) panel, a flat panel display (FPD) application such as an organic EL (OLED), a transparent substrate for a touch panel application, a printed wiring board (PWB), and a flexible substrate. (FPC: Flexible Printed Circuits) and the like. The material of the printed wiring board is not particularly limited, and for example, a glass epoxy such as a FR-4 base material may be used, and plastic such as a thermoplastic resin, ceramic or the like can also be used. The transparent substrate is not particularly limited as long as it has high transparency, and examples thereof include a glass substrate and a plastic substrate. Among these, a ceramic substrate is preferably used from the viewpoint of heat resistance.

Further, as the second electronic component facing the first electronic component, it is preferable that a plated bump such as an IC or a flexible substrate is formed. The plated bumps preferably have low or no dimples, or preferably have a flat surface. Further, the surface of the plated bump is preferably leveled from the viewpoint of increasing the contact area at the time of crimping. Further, stud bumps may be formed on the wiring board.

Since the adhesive film 20 is made by forming the above-mentioned adhesive composition into a film, detailed description thereof will be omitted here. The thickness of the adhesive film 20 is preferably 1 to 100 μm, more preferably 10 to 50 μm. This range is the same regardless of whether it is a single layer or a multi-layer structure. In the case of a paste, it refers to the thickness when used for connection.

[Curing step (S2)]
In the curing step (S2), the second electronic component is placed on the adhesive film 20, and the second electronic component is pressed against the first electronic component 10 by a crimping tool to be crimped while applying heat. Further, in the curing step (S2), pressing is performed using a crimping tool at a temperature of preferably 250 ° C. or lower, more preferably 220 ° C. or lower, and further preferably 200 ° C. or lower. As a result, the resin is melted by the heat of the crimping tool, the second electronic component is sufficiently pushed by the crimping tool, and the resin is thermoset, so that excellent adhesiveness can be obtained. In this case, although it is assumed that the crimping tool incorporates a heating mechanism, the adhesive film 20 may be heated and cured by a method in which the crimping tool does not incorporate a heating mechanism.

The second electronic component includes a second terminal row facing the first terminal row 11. The second electronic component is not particularly limited and may be appropriately selected depending on the intended purpose. Examples of the second electronic component include an IC (Integrated Circuit), a flexible printed circuit board (FPC: Flexible Printed Circuits), a tape carrier package (TCP) board, and the like. When the IC is mounted on the FPC, it becomes COF (Chip On Film).

Further, in the curing step (S2), a cushioning material may be used between the crimping tool and the second electronic component. As the cushioning material, polytetrafluoroethylene (PTFE: polytetrafluoroethylene), polyimide, glass cloth, silicon rubber or the like can be used.

According to the method for manufacturing such a connector, the adhesive film that adheres the first electronic component and the second electronic component has high moisture permeability, so that the moisture that has entered the inside of the device can be immediately removed. It can be discharged, and high reliability can be obtained in HAST.

[Modification example]
In the above-described embodiment, the first electronic component and the second electronic component are connected by using an adhesive film, but the present invention is not limited to this, and the conductive adhesive film containing conductive particles. May be used to connect the first electronic component and the second electronic component. Further, the conductive adhesive film is composed of a layer containing conductive particles (for convenience, a layer containing conductive particles) and a layer not containing conductive particles (for convenience, a layer containing no conductive particles). It may have a structure of layers or more. Further, even in the case of a paste, the same configuration can be taken at the time of connection.
<3. Example>

Hereinafter, examples of this technology will be described. In the first embodiment, an adhesive film was produced as one form of the adhesive composition, and a connector was produced. Then, the moisture permeability of the adhesive film after curing, the initial adhesive strength of the connector, the adhesive strength after the reliability test, the initial conduction resistance of the connector, and the conduction resistance after the reliability test were measured.

[Preparation of adhesive film and measurement of moisture permeability]
The materials shown in Table 1 were blended to prepare an adhesive film having a thickness of 35 μm. Further, in order 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 under the conditions of 40 ° C. and 90% relative humidity in accordance with the moisture permeability test method (cup method) of the moisture-proof packaging material of JIS Z 0208. Specifically, calcium chloride (anhydrous) is sealed in the cup, the cup covered with the sample film is allowed to stand in a constant temperature and humidity state, and the weighing operation is repeated at regular intervals to permeate the mass increase of the cup with water vapor. Evaluated as a quantity.

[Making a connector]
The bare chip (IC chip) has a thickness of 0.4 mm, a width of 6 mm, and a length of 6 mm (6 mm × 6 mm), and is a wiring for continuity measurement (bump size: 50 × 50 μm, pitch: 85 μm (space between bumps 35 μm), gold bump. A TEG (Test Element Group) for measurement having a height h = 15 μm) was used. The gold bump was a plated bump and was smooth without dimples.

The flexible wiring board (FPC: Flexible Printed Circuits) is for measurement in which the base material is polyimide, the thickness is 25 μm, the pitch is 85 μm (L / S = 45/40), and the Top: 40 μm. TEG was used.

A 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 10 sec. Further, at the time of thermocompression bonding, a polytetrafluoroethylene sheet having a thickness of 50 μm was placed on the bare chip as a cushioning material.

[Measurement of adhesive strength]
The flexible wiring board of the connecting body was peeled off in the 90 ° direction at a pulling speed of 50 mm / sec, and the maximum value of the peel strength required for the peeling was defined as the adhesive strength. The initial connection and the connection after the reliability test were measured. The reliability test was based on JEDEC (JEDEC22-A110), and the conditions were a temperature of 110 ° C., a humidity of 85%, and a time of 264 hr.

[Measurement of conduction resistance]
Regarding the connection state between the bare chip and the flexible wiring board, the conduction resistance (Ω) was measured at the initial stage of connection and after the reliability test using a digital multimeter. To measure the conduction resistance value, a digital multimeter was connected to the wiring of the flexible wiring board connected to the bump of the bare chip, and a current of 1 mA was passed by the 4-terminal method to measure the conduction resistance value. The reliability test was based on JEDEC (JEDEC22-A110), and the conditions were a temperature of 110 ° C., a humidity of 85%, and a time of 264 hr.

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

The specific surface area of the silicone-based particles was determined from the surface area per particle calculated from the average particle size and the mass per particle calculated from the average particle size and the true specific gravity.

As shown in Table 1, the total surface area of the true sphere particles calculated from the average particle size of the silicone-based particles is 10 × 10 ³ m ² or more per 100 g of the composition (Examples 1 to 8). It could be obtained 80g ^/ m 2 · 24hr or more moisture permeability. Further, the total surface area of the true sphere particles calculated from the average particle size of the silicone-based particles is 50 × 10 ³ m ² or more per 100 g of the composition (Examples 5 to 7), so that 90 g / m ² ·. A moisture permeability of 24 hr or more could be obtained. If not blended silicone particles, moisture permeability became ^75g / m 2 · 24hr (Comparative Example 1).

[Second Example]
In the second embodiment, a conductive film was prepared as one form of the adhesive composition, and a connector was prepared. Then, the moisture permeability of the conductive film after curing, the initial adhesive strength of the connector, the adhesive strength after the reliability test, the initial conduction resistance of the connector, and the conduction resistance after the reliability test were measured. ..

[Preparation of conductive film and measurement of moisture permeability]
The materials shown in Table 1 were blended to prepare a conductive film having a thickness of 35 μm. Further, in order to measure the moisture permeability, a conductive film was cured at a temperature of 200 ° C. to prepare a sample film. The moisture permeability was measured under the conditions of 40 ° C. and 90% relative humidity in accordance with the moisture permeability test method (cup method) of the moisture-proof packaging material of JIS Z 0208. Specifically, calcium chloride (anhydrous) is sealed in the cup, the cup covered with the sample film is allowed to stand in a constant temperature and humidity state, and the weighing operation is repeated at regular intervals to permeate the mass increase of the cup with water vapor. Evaluated as a quantity.

A 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 10 sec. Further, at the time of thermocompression bonding, a silicon rubber having a thickness of 200 μm was placed on the bare chip as a cushioning material.

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

As shown in Table 2, the average particle size of the silicone-based particles is smaller than the average particle size of the conductive particles, and the total surface area of the true sphere particles calculated from the average particle size of the silicone-based particles is per 100 g of the composition. by at ¹⁰ × 10 3 ^{m 2} or more (examples 9-17), it was possible to obtain a more moisture permeability ^80g / m 2 · 24hr. The total surface area of a sphere particles is calculated from an average particle size of the silicone-based particles, (Examples 13-15) by at 50 × ¹⁰ 3 ^{m 2} or more per 100g, ^90g / m 2 · 24hr or more I was able to obtain the moisture permeability of. If not blended silicone particles, moisture permeability became ^75g / m 2 · 24hr (Comparative Example 2). Further, when the average particle size of the silicone-based particles was equal to or larger than the average particle size of the conductive particles, the resistance value became high (Comparative Examples 3 and 4).

The moisture permeability of the conductive film as in Examples 9-17 by a 80g / m 2 ^· 24hr or more, it was possible to suppress the increase in resistance after reliability testing. It is considered that this is because the high humidity permeability of the conductive film made it possible to immediately discharge the moisture that had entered the inside of the device.

10 1st electronic component, 11 1st terminal row, 20 adhesive film, 21 silicone particles,

Claims

Contains silicone particles, a silane coupling agent, a polymerizable compound, and a curing agent.
An adhesive composition in which the total surface area of true spherical particles calculated from the average particle size of the silicone-based particles is 10 × 10 3 m 2 or more per 100 g of the composition.
The adhesive composition according to claim 1, wherein the average particle size of the silicone-based particles is 5 μm or less.
The adhesive composition according to claim 1 or 2, wherein the silicone-based particles contain 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.
The polymerizable compound is an epoxy compound,
The curing agent is an epoxy curing agent.
The adhesive composition according to any one of claims 1 to 3, wherein the silane coupling agent is an epoxy-based silane coupling agent.
Moisture permeability as measured under conditions of 40 ° C. temperature and 90% relative humidity after curing of the composition, according to claim 4 An adhesive composition according is 80g / m 2 · 24hr or more.
Contains more conductive particles
The adhesive composition according to any one of claims 1 to 3, wherein the average particle size of the silicone-based particles is smaller than the average particle size of the conductive particles.
The adhesive composition according to any one of claims 1 to 6, which is in the form of a film.
Contains silicone particles, a silane coupling agent, a polymerizable compound, and a curing agent.
The total surface area of the true spherical particles calculated from the average particle size of the silicone-based particles is 10 × 10 3 m 2 or more per 100 g of the composition. The placement process for arranging the electronic components of
A method for manufacturing a connector, which comprises a curing step of crimping the second electronic component to the first electronic component with a crimping tool and curing the adhesive composition.
The method for producing a connector according to claim 8, wherein the adhesive composition further contains conductive particles.
A first electronic component, a second electronic component, and an adhesive film to which the first electronic component and the second electronic component are bonded are provided.
The adhesive film contains silicone-based particles, a silane coupling agent, a polymerizable compound, and a curing agent, and the total surface area of true sphere particles calculated from the average particle size of the silicone-based particles is the said. the adhesive composition is the composition 100g per 10 × 10 3 m 2 or more is cured, is moisture permeability 80g / m 2 · 24hr or more connectors.
The connector according to claim 10, wherein the adhesive composition further contains conductive particles.