TW201406921A - Anisotropic electroconductive adhesive and method for manufacturing connected structure using the anisotropic electroconductive adhesive - Google Patents

Abstract

Disclosed is an anisotropic electroconductive adhesive that, even when a heating tool is contacted and pressed at a slow speed, can realize high electrical connection reliability. The anisotropic electroconductive adhesive comprises an insulating adhesive component and electroconductive particles dispersed in the insulating adhesive component. The insulating adhesive component comprises a radical polymerizable compound, a radical initiator, and a film forming resin. The lowest melt viscosity of the anisotropic electroconductive adhesive is in the range of 100 to 800 Pas, and the temperature at which the adhesive exhibits the lowest melt viscosity is in the range of 90 to 115 DEG C.

Description

Anisotropic conductive adhesive and method of manufacturing the same using the same

The present invention relates to an anisotropic conductive adhesive which is formed by dispersing conductive particles in an insulating adhesive component, and a method for producing a bonded structure using the same.

Conventionally, in FOG (Film on Glass) bonding in which a glass substrate and a flexible printed wiring board (FPC) are bonded, the connection terminals of the terminal electrode of the glass substrate and the flexible printed wiring board are transmitted. When the anisotropic conductive adhesive is opposed to each other and the anisotropic conductive adhesive is heat-hardened by using a heating tool, the terminal electrodes are pressed to electrically connect the two terminal electrodes (Patent Document 1).

However, the linear expansion coefficient (10 to 40 × 10 ^-6 / ° C) of a polyimide resin which is generally used as a substrate of a flexible printed wiring board is larger than the linear expansion coefficient of glass (about 8.5 × 10 ^-6 /°C), the flexible printed wiring board has a greater degree of expansion (expansion) than the glass substrate due to the heat of the heating tool during FOG bonding, so the terminal electrodes of the two substrates may vary in size. In this case, if the terminal electrode pitch is small, there is a tendency that it is difficult to sufficiently electrically connect.

Therefore, in practice, the design interval of the terminal electrodes of the flexible printed wiring board is formed to be narrower than the design interval (sometimes referred to as a predetermined interval) of the terminal electrodes of the corresponding glass substrate. When the anisotropic conductive adhesive is heat-hardened, the heat of the heating tool can be expanded to a predetermined interval to suppress the size difference between the glass substrate and the terminal electrodes of the flexible printed wiring board.

Patent Document 1: Japanese Patent No. 3477367

However, the design interval of the terminal electrodes of the flexible printed wiring board is formed to be narrower than the predetermined interval, and the operating conditions of the heating tool at the time of FOG bonding are slightly different with individual FOG bonding, or due to manufacturing requirements. When the operating conditions of the heating tool are slightly changed, the anisotropic conductive adhesive may not be able to achieve a good electrical connection.

At this time, in order to prevent or suppress the anisotropic conductive adhesive from being hardened before the terminal of the printed wiring board reaches the terminal of the glass substrate, thereby achieving between the two terminal electrodes of the glass substrate and the flexible printed substrate and the conductive particles With sufficient connection, it has been proposed to contact and press the heating tool at a relatively fast speed for the flexible printed wiring board, but there is a possibility that the flexible printed wiring board to be formed to be narrower cannot be secured. The time required for the interval between the terminal electrodes to expand to the interval between the terminal electrodes of the glass substrate is a concern.

Therefore, it has been proposed to contact and press the heating tool at a relatively slow speed for the flexible printed wiring board. In this way, it is necessary to secure the necessary time for expanding the interval of the terminal electrodes of the narrowly formed flexible printed wiring board to the interval of the terminal electrodes of the glass substrate. However, in this case, since the anisotropic conductive adhesive is thermally hardened before being sufficiently extruded, there is a fear that the two terminal electrodes of the glass substrate and the flexible printed circuit board and the conductive particles cannot be sufficiently connected.

Further, when the heating tool is brought into contact with and pressed against the flexible printed wiring board, the flexible printed wiring board generates internal stress due to cooling shrinkage after the pressing of the heating tool is completed regardless of the speed. In particular, since the distance between the terminal electrodes is as large as that of the flexible printed circuit board which is sufficiently expanded, the internal stress is also increased, so that the connection reliability is lowered. Therefore, it is expected that an anisotropic conductive adhesive having high stress relaxation ability can be developed.

The object of the present invention is to solve the above problems, and to provide an anisotropic conductive adhesive which can achieve high electrical connection reliability even in the case of contact and pressing under conditions of a slow heating tool; and provide a use A method of producing a bonded structure of the anisotropic conductive adhesive.

As a result of intensive research, the present inventors have found that the radically polymerizable compound is used as the main hardening component of the anisotropic conductive adhesive, and on the other hand, the lowest melt viscosity is in the range of 100 to 800 Pa. The range of s and the temperature reaching the lowest melt viscosity are in a very narrow range of 90 to 115 ° C, and even if the speed of the heating tool is slow, a good anisotropic conductive connection can be achieved, thereby completing the present invention.

In other words, the present invention provides an anisotropic conductive adhesive, which is characterized in that conductive particles are dispersed in an insulating adhesive component containing a radical polymerizable compound, a radical initiator, and a film-forming resin. It is: the lowest melt viscosity is located at 100~800Pa. The range of s shows that the temperature of the lowest melt viscosity is in the range of 90 to 115 °C.

Further, the present invention provides a method of manufacturing a connection structure in which a glass substrate having terminal electrodes formed at regular intervals and a terminal electrode having a narrower interval than the predetermined interval are formed using an anisotropic conductive adhesive. The printed wiring board is connected, and has the following steps (A) and (B): (A) a configuration step of disposing the anisotropic conductive adhesive of the first application of the patent range on the terminal electrode of the glass substrate (B) a step of connecting from the side of the flexible printed wiring board using a heating tool, and performing heating and pressing at a temperature higher than the minimum melt viscosity The electrical connection between the terminal electrodes is made.

The anisotropic conductive adhesive of the invention has the following characteristics: the lowest melt viscosity is 100~800Pa. s, and the temperature showing the lowest melt viscosity is 90-115 °C. Therefore, when the glass substrate in which the terminal electrode is formed at a predetermined interval and the flexible printed wiring board in which the terminal electrode is formed at a narrow interval from the predetermined interval is used, the anisotropic conductive adhesive of the present invention can be used. The terminal electrode interval of the flexible printed wiring board is sufficiently expanded, and on the other hand, it is ensured that the anisotropic conductive adhesive maintains high fluidity even when it is held between the glass substrate and the flexible printed wiring board. As a result, it is possible to provide a joint structure which has high connection reliability even if the extrusion speed of the heating tool is slightly different in manufacturing or the extrusion speed is low.

1‧‧‧ glass substrate

2‧‧‧ Anisotropic conductive adhesive

3‧‧‧Flexible printed wiring board

11,31‧‧‧terminal electrode

Fig. 1A is an explanatory view showing a method of joining a glass substrate and a flexible printed wiring board.

Fig. 1B is an explanatory view showing a method of joining a glass substrate and a flexible printed wiring board, with reference to Fig. 1A.

Hereinafter, one embodiment of the present invention will be described with reference to the drawings. In addition, unless otherwise indicated in this specification, the numerical range "X~Y" means the meaning of X≦ and ≦Y.

The anisotropic conductive adhesive of the present invention is characterized in that the conductive particles are dispersed in an insulating adhesive component containing a radical polymerizable compound, a radical initiator, and a film-forming resin, and are characterized by a minimum melt viscosity. Located at 100~800Pa. The range of s is preferably between 100 and 400 Pa. The range of s; and the temperature showing the lowest melt viscosity is in the range of 90 to 115 ° C, preferably 95 to 110 Pa. The scope of s.

In the present invention, the lowest melt viscosity is set to 100 to 800 Pa. The reason for s is that If the lowest melt viscosity is 100Pa. Above s, excessive flow of the anisotropic conductive adhesive during heat pressing can be avoided, and as a result, the required amount of the bonding between the terminal electrodes can be ensured. In addition, if the lowest melt viscosity exceeds 800Pa. In s, the fluidity at the time of heating and pressing of the anisotropic conductive adhesive is lowered, and then the thickness becomes larger than the diameter of the conductive particles, and as a result, the connection reliability is lowered.

Further, the reason why the temperature at which the lowest melt viscosity is shown is set to 90 to 115 ° C will be described below. First, the anisotropic conductive adhesive having a minimum melting temperature of less than 90 °C causes the melt viscosity to reach the rising region earlier due to the subsequent heating and pressing, resulting in a rapid decrease in fluidity, so that the interval is narrower than the predetermined interval. The flexible printed wiring board forming the terminal electrode, before the interval is sufficiently expanded, most of the anisotropic conductive adhesive is hardened, and the terminal electrode and the conductive particles of the substrate of the glass substrate and the flexible printed wiring board are made. The contact between them becomes insufficient.

On the other hand, an anisotropic conductive adhesive having a minimum melting temperature of more than 115 ° C, at the end of a predetermined time of heating and pressing by a heating tool, the curing reaction itself is still insufficiently performed, which may result in a glass substrate and The contact between the terminal electrodes of the two substrates of the flexible printed wiring board and the conductive particles is insufficient.

As described above, in the present invention, the lowest melt viscosity is located at 100 to 800 Pa. The range of s shows that the temperature of the lowest melt viscosity is in the range of 90-115 ° C, so the lowest melt viscosity is divided by the value of the temperature showing the lowest melt viscosity [(the lowest melt viscosity) / (the temperature showing the lowest melt viscosity)] The range is from 0.88 to 8.8.

In addition, the value of [(minimum melt viscosity) / (the temperature showing the lowest melt viscosity)] is at least the best among the "lowest melt viscosity" and "the lowest melt viscosity". Outside the range, it will be the cause of poor connection.

In the conductive particles of the anisotropic conductive adhesive of the present invention, for example, metal particles such as nickel, gold, or copper, gold plating on the resin particles, and the like, and the outermost layer of the particles coated with the resin particles may be used for insulation. Covered by others. Here, the average particle diameter of the conductive particles is preferably from 1 to 20 μm, more preferably from 2 to 10 μm, from the viewpoint of conduction reliability. In addition, the content of the conductive particles in the insulating adhesive component is preferably from 2 to 50% by mass, more preferably from 3 to 20% by mass, from the viewpoints of conduction reliability and insulation reliability.

As described above, the insulating adhesive component contains at least a radical polymerizable compound, a radical polymerization initiator, and a film-forming resin.

As the radical polymerizable compound, (meth) acrylate monomer such as dicyclopentenyl (meth) acrylate or phosphorus (meth) acrylate; and methic acid (meth) acrylate may be used. (meth) acrylate oligomers such as esters and (meth)acrylic polyesters. Further, at least one of the dicyclopentenyl (meth)acrylate monomer and the (meth)acrylic acid urethane oligomer is preferably used because it can appropriately take into consideration the melt viscosity and the hardening speed. . Further, other radical polymerizable compounds which are free-radically polymerizable with the monomers and oligomers may be used in combination within a range not impairing the effects of the present invention.

As the radical initiator, a known radical polymerization initiator can be used, and among them, a peroxide radical initiator is preferably used. Specific examples of the peroxide-based radical initiator include dioxane peroxides such as benzamidine peroxide; tertiary amyl peroxide isobutyrate; and tertiary butyl peroxybenzoate; Peroxyalkyl ketones; peroxy ketals such as 1,1-di(tri-butylperoxy)cyclohexane. In addition, as a commercial item, NYPER BW (dimercapto peroxide, Nippon Oil Co., Ltd.), NYPER BMT-K40 (dimercapto peroxide, Nippon Oil Co., Ltd.), NYPER BO (second 醯) can be used. Base peroxide, Nippon Oil Co., Ltd.), NYPER FF (two 醯Base Peroxide, Nippon Oil Co., Ltd.), NYPER BS (dimercapto-based peroxide, Nippon Oil Co., Ltd.), NYPER E (dimercapto-based peroxide, Nippon Oil Co., Ltd.), NYPER NS ( Dimercapto-based peroxide, Nippon Oil Co., Ltd.), PERHEXYL O (peroxy ester, Nippon Oil Co., Ltd.), PERBUTYL O (peroxyester, Nippon Oil Co., Ltd.), PERTETRA A (peroxide ketal, Nippon Oil Co., Ltd.), PERHEXA C-80(S) (peroxy ketal, Nippon Oil Co., Ltd.), PERHEXA C-75 (EB) (peroxy ketal, Nippon Oil Co., Ltd.), PERHEXA C ( C) (peroxide ketal, Nippon Oil Co., Ltd.), PERHEXA C (S) (peroxy ketal, Nippon Oil Co., Ltd.), PERHEXA C-40 (peroxy ketal, Nippon Oil Co., Ltd.), PERHEXA C-40MB(S) (peroxide ketal, Nippon Oil Co., Ltd.), PERHEXYL I (peroxy ester, Nippon Oil Co., Ltd.). These polymeric starters may be used singly or in combination.

The film-forming resin imparts film-forming properties to the insulating adhesive component containing the radical polymerizable compound and the anisotropic conductive adhesive which is a component thereof, and is easily formed into a film, and the anisotropic conductive adhesive as a whole is further provided. Increased cohesion. As the film-forming resin, at least one of a phenoxy resin or a mixed resin of a phenoxy resin and an epoxy resin which are produced in the production process of a phenoxy resin can be preferably used. The weight average molecular weight of the phenoxy resin or the mixed resin is preferably from 20,000 to 60,000, more preferably from 20,000 to 40,000, in view of film strength and fluidity of the anisotropic conductive adhesive. The reason for this is that if the weight average molecular weight is 20,000 or more, excessive flow during heating of the anisotropic conductive adhesive can be avoided, and if the weight average molecular weight is 60,000 or less, fluidity will be insufficient.

In the present invention, it is preferred that the insulating adhesive component contains a stress relieving agent. The strength of the internal stress generated by the interface portion between the anisotropic conductive adhesive and the glass substrate can be alleviated by the inclusion of the stress relieving agent.

As the stress relieving agent, a rubber-based elastic material can be preferably used, and it is preferably used in the form of particles. Examples of the rubber-based elastic material include butadiene rubber (BR) composed of polybutadiene, acrylic rubber (ACR), and nitrile rubber (NBR). Among them, the butadiene rubber (BR) composed of polybutadiene has a higher resilience than acrylic rubber (ACR), nitrile rubber (NBR), etc., and thus it is preferable to absorb a large amount of internal stress. Therefore, it is particularly preferable to use polybutadiene particles as the stress relieving agent in the present invention.

The polybutadiene particles used in the present invention are preferably ones having a smaller modulus of elasticity than the anisotropic conductive adhesive having a higher modulus of elasticity, but if the modulus of elasticity is too small, the endurance is lowered. If the modulus of elasticity is too high, the internal stress of the cured product of the anisotropic conductive adhesive may not be sufficiently reduced. Therefore, it is preferred to use an elastic modulus of 1 × 10 ⁸ to 1 × 10 ¹⁰ dyn/cm ² . .

Further, as an element for sufficiently ensuring electrical connection between the conductive particles and the connection electrode, the average particle diameter of the polybutadiene particles is preferably smaller than the average of the conductive particles from the viewpoint of an important average particle diameter. Particle size. If the average particle diameter of the butadiene particles is too small, the internal stress cannot be completely absorbed. If the average particle diameter of the butadiene particles is too large, there is a concern that the conductive particles and the contact electrode are not sufficiently electrically connected, so the average particle The diameter is preferably 0.01 to 0.5 μm.

The content of the polybutadiene particles as described above in the anisotropic conductive adhesive is preferably from 10 to 30 parts by mass, more preferably from 15 to 30 parts by mass, based on the total of the radically polymerizable compound and the film-forming resin. ~25 parts by mass. When the content is 10 parts by mass or more, the internal stress generated in the anisotropic conductive adhesive can be sufficiently reduced; if it is 30 parts by mass or less, the formation of the anisotropic conductive adhesive is not good. In addition, it is possible to avoid a decrease in heat resistance.

Next, an example of the method for producing the anisotropic conductive adhesive of the present invention is Line description.

First, a radical polymerizable compound and a film-forming resin are dissolved in a solvent, and then a predetermined amount of a radical initiator and conductive particles are added, and then a stress relieving agent (preferably a polybutadiene particle) is added as needed. ) Mix and stir. The mixed solution is applied onto a release film such as a polyester film, and after drying, a cover film is laminated thereon, whereby a film-forming anisotropic conductive adhesive can be obtained.

The anisotropic conductive adhesive of the present invention described above can be preferably used for anisotropic conductive connection between a glass substrate such as a liquid crystal panel and a flexible printed wiring board to produce a bonded structure. The method of manufacturing the above-described connection structure will be described below with reference to FIGS. 1A and 1B (an explanatory view of a method of joining a glass substrate and a flexible printed wiring board).

In the method for producing a connection structure according to the present invention, the glass substrate having the terminal electrodes formed at predetermined intervals is connected to the flexible printed wiring board having the terminal electrodes at a predetermined interval therebetween by using an anisotropic conductive adhesive. It has the following steps (A) and (B).

Step (A) <Configuration Step>

First, the anisotropic conductive adhesive of the present invention described above is disposed between the terminal electrode of the glass substrate and the terminal electrode of the flexible printed wiring board. In this configuration step, in addition to the use of the anisotropic conductive adhesive of the present invention, a conventionally known method can be used.

As shown in FIG. 1A, the terminal electrode 11 formed at a predetermined interval A is formed on the glass substrate 1, and the flexible printed wiring board 3 is formed with an interval B which is narrower than the predetermined interval A of the glass substrate 1. Terminal electrode 31.

As the glass substrate 1, a glass substrate of a display panel such as a liquid crystal panel is preferable. The predetermined interval A refers to the pitch of the terminal electrode 11 formed of an ITO electrode or the like, basically It does not refer to the space between adjacent electrodes, but the space can also be set as a reference. It is usually 20 to 200 μm, and particularly the effect of the present invention may be 20 to 60 μm.

On the other hand, as the flexible printed wiring board 3, a flexible substrate in which a copper foil is laminated on a polyimide film substrate (the copper foil is formed by etching or the like to form the terminal electrode 31) is preferable. The interval B which is narrower than the predetermined interval A means the pitch of the terminal electrodes 31, and basically does not refer to the space between the adjacent electrodes, but the space can be set as a reference.

Further, although the interval B is narrower than the predetermined interval A, the degree of the narrowness varies depending on the linear expansion coefficient, the heating temperature, the heating rate, the extrusion strength, and the like of the glass substrate 1 or the flexible printed wiring board 3, and is usually set to It is reduced by 0.01~1%, preferably by 0.1~0.3%, compared with the predetermined interval A.

Contact step (B) <connection step>

Next, a heating tool (not shown) is pressed from the side of the flexible printed wiring board 3, and is heated and pressed at a temperature equal to or higher than the lowest melt viscosity to cure the anisotropic conductive adhesive 2, thereby making the glass substrate 1 is electrically connected to the two terminal electrodes of the flexible printed wiring board 3. That is, in the connecting step, the flexible printed wiring board 3 is expanded by heating, and as shown in FIG. 1B, the interval B' of the terminal electrode 31 of the flexible printed wiring board 3 and the terminal electrode 11 of the glass substrate 1 The interval A is substantially equal, and the terminal electrodes 11 and 31 are electrically connected by the cured product of the anisotropic conductive adhesive. Thereby, a connection structure can be produced.

As a preferable heating and pressing condition in the step (B), the heating condition is adjusted such that the temperature of the anisotropic conductive adhesive reaches 150 to 200 ° C after 4 seconds, and the heating tool is used. After the flexible printed wiring board is abutted at a speed of 1 to 50 mm/sec, preferably 1 to 10 mm/sec, it is heated at this speed for 4 seconds or more. Specifically, The following conditions: the heating tool of 150~200 °C is used for the pressing speed of the relative anisotropic conductive adhesive 2 of 1~50mm/sec, especially when the low speed is used, the pressing speed of 1~10mm/sec is heated. Press for more than 4 seconds, preferably 4 to 6 seconds. In this condition, the temperature range (90 to 115 ° C) of the lowest melt viscosity of the anisotropic conductive adhesive 2 is shown to be higher than the temperature at the start of heating (for example, room temperature), and is used to harden the anisotropic conductivity. The heating temperature of the agent 2 (150 to 200 ° C) is low. Therefore, under the above heating conditions, the anisotropic conductive adhesive 2 has a viscosity which lowers after the start of heating, passes through the lowest melt viscosity (100 to 800 Pa.s), and then increases hardening. By the above-described viscosity change, the glass substrate and the flexible printed wiring board can be connected with high reliability.

Further, the reason why the pressing speed of the heating tool is 1 to 50 mm/sec is that if the pressing speed is slow, the interval between the terminal electrodes of the flexible printed wiring board can be expanded to a predetermined interval, but on the other hand, The anisotropic conductive adhesive hardens before it is sufficiently pressed, and as a result, there is a concern that a good anisotropic conductive connection cannot be achieved. Conversely, if the pressing speed is high, there is a concern that the anisotropic conductive adhesive hardens before the interval between the terminal electrodes of the flexible printed wiring board expands to a predetermined interval.

Example

Hereinafter, the present invention will be specifically described by way of examples. Among them, the components used in the examples or comparative examples are as follows.

<Radical polymerizable compound>

Dicyclopentadienyl dimethacrylate (DCP, Xinzhongcun Chemical Industry Co., Ltd.)

Methyl methacrylate (M-1600, East Asia Synthetic (Shares))

Phosphorus-containing methacrylate (PM2, Nippon Kayaku Co., Ltd.)

<Free radical polymerization initiator>

Peroxide dicarbonate initiator (PERROYL L, Nippon Oil Co., Ltd.)

Dimercapto-based peroxide initiator (NYPER BW, Nippon Oil Co., Ltd.)

Peroxyketal-based initiator (PERTETRA A, Nippon Oil Co., Ltd.)

Dialkyl peroxide initiator (PERCUMYL D, Nippon Oil Co., Ltd.)

<Film Forming Resin>

Bisphenol A/bisphenol F mixed phenoxy resin (Bis-A/Bis-F mixed phenoxy resin: weight average molecular weight 60000) (YP-50, Dongdu Huacheng (share))

Bisphenol A/bisphenol F mixed phenoxy resin (Bis-A/Bis-F mixed phenoxy resin: weight average molecular weight 30000) (jER-4110, Japan epoxy resin)

Bisphenol F type phenoxy resin (Bis-F phenoxy resin: weight average molecular weight 20000) (jER-4007P, Japan epoxy resin (share))

<stress mitigator>

Acrylic rubber (weight average molecular weight 1200000) (SG-600LB, Nagase ChemteX (share))

Polybutadiene particles (average particle size 0.1 μm)

<decane coupling agent>

Decane coupling agent (KBM-503, Shin-Etsu Chemical Industry Co., Ltd.)

<Electrically conductive particles>

Benzene particles coated with conductive particles of a nickel-gold plating layer (average particle size 5 μm, Nippon Chemical Industry Co., Ltd.)

Examples 1 to 7 and Comparative Examples 1 to 4

Among the components shown in Table 1, a radical polymerizable compound, a radical initiator, a film-forming resin, and a decane coupling agent are dissolved in toluene as a solvent to prepare an insulating component. Solution.

Then, 3 parts by mass of conductive particles were added to the insulating adhesive component solution (100 parts by mass of the component other than toluene) to prepare an anisotropic conductive adhesive liquid.

Then, the anisotropic conductive adhesive liquid was applied onto the peeled polyester film and dried to a thickness of 25 μm, and dried at 80 ° C for 5 minutes to obtain anisotropic film formation. Conductive adhesive. The anisotropic conductive adhesive was cut into a strip shape having a width of 2 mm to obtain the anisotropic conductive film samples of Examples 1 to 7 and Comparative Examples 1 to 4.

(Evaluation)

For each of the anisotropic conductive film samples of Examples 1 to 7 and Comparative Examples 1 to 4, "on-resistance value", "connection reliability", "minimum melt viscosity", and "maximum arrival" were as follows. The temperature of the melt viscosity and the "space gap between the terminals" generated by the connection were measured and evaluated. The results obtained are shown in Table 2.

<(1) On-resistance value>

The sample of the anisotropic conductive film was heated and pressed at 180 ° C, a pressure of 3.5 MPa, and a pressing time of 4 seconds using a heating tool of a stainless steel block to form a connection structure, and the on-resistance of the connection structure was measured. value. Further, the speed of the heating tool was measured at five speeds of 50, 30, 10, 1.0, and 0.1 mm/sec, and the on-resistance values of the heating tools of the different speeds were measured.

<(2) Connection reliability>

The connection structure after measuring the on-resistance value as described above was subjected to an aging treatment for 500 hours under the conditions of a temperature of 85 ° C and a relative humidity of 85%, and then the on-resistance was measured.

<(3) Minimum melt viscosity and temperature showing the lowest melt viscosity>

The anisotropic conductive adhesive liquid was removed without curing to remove toluene, and the cured person was loaded on a rotary viscometer, and the melt viscosity was measured while raising temperature at a predetermined temperature increase rate (10 ° C/min).

<(4) Clearance between terminals>

The connection structure in which the anisotropic conductive film samples were connected was visually observed from the glass substrate side using an optical microscope, and the presence or absence of voids was observed.

(Evaluation results)

From the results of Table 1 and Table 2, it is understood that the sample having the anisotropic conductive adhesive prepared by the combination of Examples 1 to 7 has a minimum melt viscosity of 100 to 800 Pa. s, the heating tool speed of the connection structure using the sample of the examples is in the range of 1.0 to 50 mm/sec, and the on-resistance values are all 1 Ω or less, and the initial connection state is good. Further, it is also known that the electric resistance values of the embodiments do not rise more than 5 Ω even after a predetermined aging treatment, and the connection reliability is high.

On the other hand, the connection structure using the sample of Comparative Example 1 showed a low on-resistance value when the speed of the heating tool was relatively fast, but it was 10 Ω at 1.0 mm/sec. Although the temperature of the sample of Comparative Example 1 reached the lowest melt viscosity, the lowest melt viscosity itself was 1000 Pa. The high level of s is a poor mobility. The above situation is considered to be that the heating tool is fast and stylish, but if the heating tool is at a low speed, the spacing of the terminal electrodes of the flexible printed wiring board is anisotropically conductive before the predetermined interval of the terminal electrodes on the glass substrate is expanded. The film has reached the rising region of the melt viscosity by the lowest melt viscosity, and the contact between the terminal electrodes of the glass substrate and the flexible printed wiring board and the conductive particles is insufficient, and the electrical connection of the connection structure is poor.

Using the joint structure of the sample of Comparative Example 2, no void occurred at any of the heating tool speeds. The occurrence of voids does not directly cause electrical connection failure of the connection structure, but it is still a cause of poor connection. The sample of Comparative Example 2 is suitable for the temperature at which it reaches the lowest melt viscosity, but the lowest melt viscosity itself is 70 Pa. s is low, so the reason for excessive flow is considered to cause voids.

The connection structure of the sample of Comparative Example 3 was used, and the speed of the heating tool was located. In any of the ranges of 1.0 to 50 mm/sec, the on-resistance value is 1 Ω or less, and the initial connection state is good. However, the on-resistance value is greatly increased due to the predetermined aging treatment. The sample of Comparative Example 3 had a minimum melt viscosity of 250 Pa. Although s is appropriate, the temperature at which the lowest melt viscosity is reached is 120 ° C. Therefore, it takes time to finally cure, and hardening failure occurs, and as a result, it is considered that the electrical connection of the connection structure is poor.

When the connection structure of the sample of Comparative Example 4 was used, the on-resistance value increased when the heating tool speed was a low speed region of 10 mm/sec. The sample of Comparative Example 4 had a minimum melt viscosity of 900 Pa. s is higher, and the temperature at which the lowest melt viscosity is reached is 88 ° C. Therefore, it is considered that the anisotropic conductive adhesive has reached the rising region of the melt viscosity by the lowest melt viscosity, so if the heating tool speed is in the low speed region, the contact between the two terminals and the conductive particles may be insufficient, and the result is considered to be connected. Poor electrical connection to the structure.

<Flexibility of flexible printed wiring board>

In the connection structure of the anisotropic conductive film samples of Examples 1 to 7, the expansion ratio of the flexible printed wiring board in the connection structure was measured for Example 2 and Example 3. The results obtained are shown in Table 3.

The above-described expansion ratio was calculated by measuring the length of the flexible printed wiring board before and after the heat pressing using a two-dimensional length measuring machine. Further, the glass substrate (trade name: Corning 1737F, manufactured by Corning Co., Ltd.) used in the connection structure and the polyimide (Kapton-EN, manufactured by Dupont-Toray Co., Ltd.) which is a substrate of the flexible printed wiring board have thermal expansion coefficients, respectively. It is 3.7 × 10 ^-6 / ° C and 16 × 10 ^-6 / ° C.

[table 3]

As is apparent from Table 3, among the temperature, pressure, and time of the heating tool used in the embodiment, the expansion ratio of the flexible printed wiring board was large in the case where the speed of the heating tool was relatively slow. Therefore, it is understood that even if the same structure is used, the amount of expansion and contraction must be considered in the case where the heating is performed under the condition that the heating tool is slow.

The expansion ratio is generally related to the temperature of the heating tool, the speed of the heating tool, the linear expansion coefficient and the thickness of the polyimide of the flexible printed wiring board, and is in the low speed region (1.0 to 10 mm/sec). 3 It can be seen that the range of the expansion ratio is 0.1 to 0.25%.

Industrial availability

The anisotropic conductive adhesive of the present invention can achieve high electrical connection reliability even in the case where contact or pressing is performed under conditions in which the heating tool is slow. Therefore, it can be used for an anisotropic conductive connection between a glass substrate of a display element such as a liquid crystal panel and a flexible printed wiring board.

1‧‧‧ glass substrate

2‧‧‧ Anisotropic conductive adhesive

3‧‧‧Flexible printed wiring board

11,31‧‧‧terminal electrode

A, B‧‧ ‧ interval

Claims (12)

An anisotropic conductive adhesive consisting of a conductive particle dispersed in an insulating adhesive component containing a radical polymerizable compound, a radical initiator, and a film-forming resin, wherein the lowest melt viscosity is 100 ~800Pa. The range of s shows that the temperature of the lowest melt viscosity is in the range of 90 to 115 °C. For example, the anisotropic conductive adhesive of claim 1 wherein the (minimum melt viscosity) / (the temperature showing the lowest melt viscosity) has a value of 0.88 to 8.8. The anisotropic conductive adhesive of claim 1 or 2, further comprising a stress relieving agent. An anisotropic conductive adhesive according to claim 3, wherein the stress relieving agent is a polybutadiene particle. The anisotropic conductive adhesive according to the fourth aspect of the invention, wherein the polybutadiene particles are contained in an amount of 10 to 30 parts by mass based on 75 parts by mass of the total of the radical polymerizable compound and the film-forming resin. An anisotropic conductive adhesive according to claim 4 or 5, wherein the polybutadiene particles have an elastic modulus of from 1 × 10 ⁸ to 1 × 10 ¹⁰ dyn/cm ² . The anisotropic conductive adhesive according to any one of claims 4 to 6, wherein the polybutadiene particles have an average particle diameter of 0.01 to 5 μm. The anisotropic conductive adhesive according to any one of claims 1 to 7, wherein the film-forming resin comprises a phenoxy resin having a weight average molecular weight of 20,000 to 60,000 or a phenoxy resin and an epoxy resin. At least a mixed resin having a weight average molecular weight of 20,000 to 60,000 One. The anisotropic conductive adhesive according to any one of claims 1 to 8, wherein the radically polymerizable compound contains a dicyclopentenyl (meth)acrylate monomer and an (meth)acrylic acid amine. At least one of the carboxylic acid ester oligomers. In a method of manufacturing a connection structure, a glass substrate having terminal electrodes formed at predetermined intervals is connected to a flexible printed wiring board having terminal electrodes formed at a predetermined interval therebetween by using an anisotropic conductive adhesive. It is characterized in that it has the following steps (A) and (B): (A) a step of disposing an anisotropic conductive adhesive of the first application of the patent scope on a terminal electrode of the glass substrate and the flexibility (B) a step of connecting from the side of the flexible printed wiring board using a heating tool, and heating and pressing at a temperature higher than the minimum melt viscosity to the terminal electrode Make electrical connections between them. The method for manufacturing a connection structure according to claim 10, wherein in the step (B), the heating tool is adjusted such that the temperature of the anisotropic conductive adhesive reaches 150 to 200 ° C after 4 seconds. After the heating tool abuts the flexible printed wiring board at a speed of 1 to 50 mm/sec, the heating is pressed at the speed for 4 seconds or more. The method for manufacturing a connection structure according to claim 10, wherein in the step (B), the heating tool is adjusted such that the temperature of the anisotropic conductive adhesive reaches 150 to 200 ° C after 4 seconds. After the heating tool abuts the flexible printed wiring board at a speed of 1 to 10 mm/sec, the heating is pressed at the speed for 4 seconds or more.