JPWO2011024720A1 - Method for manufacturing connection structure - Google Patents

Abstract

Provided is a connection structure manufacturing method capable of improving conduction reliability when electrodes of connection target members are electrically connected. In the method for manufacturing a connection structure 1 according to the present invention, the anisotropic conductive material layer 3A is formed by applying an anisotropic conductive material containing conductive particles to the upper surface 2a of the first connection target member 2. And by irradiating the anisotropic conductive material layer 3A with light, the curing of the anisotropic conductive material layer 3A proceeds to make the anisotropic conductive material layer 3A B-stage; The second connection target member 4 is further laminated on the upper surface 3a of the anisotropic conductive material layer 3B, and heat is applied to the B-staged anisotropic conductive material layer 3B, thereby forming the B stage. Curing the anisotropic conductive material layer 3B.

Description

  The present invention is a method of manufacturing a connection structure using an anisotropic conductive material including a plurality of conductive particles, and more specifically, various connections such as a flexible printed circuit board, a glass substrate, and a semiconductor chip. The present invention relates to a method for manufacturing a connection structure in which electrodes of a target member are electrically connected via conductive particles.

  Anisotropic conductive materials such as anisotropic conductive paste, anisotropic conductive ink, and anisotropic conductive adhesive are widely known. In these anisotropic conductive materials, a plurality of conductive particles are dispersed in paste, ink, or resin.

  The anisotropic conductive material is, for example, a connection between a flexible printed circuit board and a glass substrate (FOG (Film on Glass)), a connection between a semiconductor chip and a flexible printed circuit board (COF (Chip on Film)), or a semiconductor chip. It is used for connection with a glass substrate (COG (Chip on Glass)) and the like.

  As an example of the anisotropic conductive material, the following Patent Document 1 describes an anisotropic conductive material as an epoxy resin, rubber-like polymer particles, a thermally active latent epoxy curing agent, and high softening point polymer particles. An anisotropic conductive material containing conductive particles is disclosed. For example, when the electrode of the semiconductor chip and the electrode of the glass substrate are electrically connected by this anisotropic conductive material, an anisotropic conductive material containing conductive particles is applied on the glass substrate. Next, the semiconductor chips are stacked, and heated and pressurized. As a result, the anisotropic conductive material is cured, and the electrodes are electrically connected via the conductive particles to obtain a connection structure.

JP 2000-345010 A

  During the electrical connection between the electrodes, the anisotropic conductive material applied on the glass substrate and the conductive particles contained in the anisotropic conductive material may flow greatly before curing. . For this reason, the hardened | cured material layer and electroconductive particle formed with the anisotropic electrically-conductive material may not be arrange | positioned to a specific area | region. Furthermore, the conductive particles may not be disposed between the upper and lower electrodes to be connected, or adjacent electrodes that should not be connected may be electrically connected via a plurality of conductive particles. For this reason, the conduction | electrical_connection reliability of the obtained connection structure may be low.

  In addition, the anisotropic conductive material applied by the dispenser may spread beyond the coating width due to liquid dripping, and the anisotropic conductive material may protrude unintentionally outside a specific region.

  The objective of this invention is providing the manufacturing method of the connection structure which can improve conduction | electrical_connection reliability, when the electrodes of a connection object member are electrically connected.

  According to a wide aspect of the present invention, an anisotropic conductive material layer containing conductive particles is applied to the upper surface of the first connection target member to form an anisotropic conductive material layer, and the anisotropic conductive material is formed. The step of curing the anisotropic conductive material layer by irradiating the material layer with light to make the anisotropic conductive material layer into a B stage, and the anisotropic conductive material that has been B staged A second connection target member is further laminated on the upper surface of the layer, and heat is applied to the B-staged anisotropic conductive material layer, whereby the B-staged anisotropic conductive material layer is formed. The manufacturing method of a connection structure provided with the process to harden is provided.

  In a specific aspect of the method for manufacturing a connection structure according to the present invention, in the step of forming the anisotropic conductive material layer and the step of forming the anisotropic conductive material layer into a B-stage, the anisotropy is performed. While applying the conductive material, the anisotropic conductive material layer is irradiated with light.

  In another specific aspect of the method for manufacturing a connection structure according to the present invention, the anisotropic process includes the step of forming the anisotropic conductive material layer and the step of forming the anisotropic conductive material layer into a B-stage. The anisotropic conductive material layer is irradiated with light simultaneously with the application of the conductive conductive material or immediately after the application.

  In still another specific aspect of the method for manufacturing a connection structure according to the present invention, in the step of forming the anisotropic conductive material layer and the step of converting the anisotropic conductive material layer into a B-stage, The time from application of the isotropic conductive material to irradiation with light is in the range of 0 to 3 seconds.

  In another specific aspect of the method for manufacturing a connection structure according to the present invention, the anisotropic conductive material includes a curable compound, a thermosetting agent, a photocuring initiator, and conductive particles. Conductive material is used.

  In still another specific aspect of the method for manufacturing a connection structure according to the present invention, in the step of forming the anisotropic conductive material layer and the step of converting the anisotropic conductive material layer into a B-stage, a dispenser and And a light emitting device connected to the dispenser is used.

  In the manufacturing method of the connection structure according to the present invention, the anisotropic conductive material layer is cured by irradiating the anisotropic conductive material layer with light, and the anisotropic conductive material layer is moved to the B stage. Then, heat is applied to the B-staged anisotropic conductive material layer, so that the flow of the anisotropic conductive material layer and the conductive particles contained in the anisotropic conductive material layer can be suppressed. Therefore, the hardened | cured material layer and electroconductive particle formed with the anisotropic electrically-conductive material can be arrange | positioned in a specific area | region. For this reason, conduction | electrical_connection reliability can be improved when the electrodes of the 1st, 2nd connection object member are electrically connected. For example, the upper and lower electrodes to be connected can be easily connected with conductive particles, and adjacent electrodes that should not be connected can be prevented from being connected via a plurality of conductive particles. In addition, since the anisotropic conductive material applied with the dispenser is cured before dripping, it is harder to spread than the coating width, preventing the anisotropic conductive material from unintentionally protruding outside the specific area. it can.

FIG. 1 is a partially cutaway front sectional view schematically showing a connection structure obtained by a method for manufacturing a connection structure according to an embodiment of the present invention. 2 (a) to 2 (c) are partially cutaway front cross-sectional views for explaining each step of the method for manufacturing a connection structure according to one embodiment of the present invention. 3 (a) and 3 (b) show a B-stage anisotropic conductive process using a composite device including a dispenser and a light irradiation device in a method for manufacturing a connection structure according to an embodiment of the present invention. It is a typical front view for demonstrating the method of forming a material layer. FIGS. 4A and 4B are schematic front views for explaining a modification of the method of forming the B-staged anisotropic conductive material layer.

  Hereinafter, the present invention will be clarified by describing specific embodiments of the present invention with reference to the drawings.

  In FIG. 1, an example of the connection structure obtained by the manufacturing method of the connection structure which concerns on one Embodiment of this invention is typically shown with a partial notch front sectional drawing.

  A connection structure 1 shown in FIG. 1 has a structure in which a second connection target member 4 is connected to an upper surface 2 a of a first connection target member 2 via a cured product layer 3. The cured product layer 3 is formed by curing an anisotropic conductive material including a plurality of conductive particles 5. A plurality of electrodes 2 b are provided on the upper surface 2 a of the first connection target member 2. A plurality of electrodes 4 b are provided on the lower surface 4 a of the second connection target member 4. The electrode 2b and the electrode 4b are electrically connected by one or a plurality of conductive particles 5.

  In the connection structure 1, a glass substrate is used as the first connection target member 2, and a semiconductor chip is used as the second connection target member 4. The first and second connection target members are not particularly limited. Specific examples of the first and second connection target members include electronic components such as semiconductor chips, capacitors, and diodes, and circuit boards such as printed boards, flexible printed boards, and glass boards.

  The connection structure 1 shown in FIG. 1 can be obtained as follows, for example.

  As shown to Fig.2 (a), the 1st connection object member 2 which has the electrode 2b on the upper surface 2a is prepared. Next, an anisotropic conductive material including a plurality of conductive particles 5 is applied to the upper surface 2a of the first connection target member 2, and the anisotropic conductive material layer 3A is applied to the upper surface 2a of the first connection target member 2. Form. At this time, it is preferable that one or a plurality of conductive particles 5 be disposed on the electrode 2b.

  Next, as shown in FIG. 2B, the anisotropic conductive material layer 3A is cured by irradiating the anisotropic conductive material layer 3A with light. By curing the anisotropic conductive material layer 3A, the anisotropic conductive material layer 3A is B-staged. A B-staged anisotropic conductive material layer 3B is formed on the upper surface 2a of the first connection target member 2.

  It is preferable to irradiate the anisotropic conductive material layer 3 </ b> A with light while applying the anisotropic conductive material to the upper surface 2 a of the first connection target member 2. Furthermore, it is also preferable to irradiate the anisotropic conductive material layer 3 </ b> A simultaneously with the application of the anisotropic conductive material to the upper surface 2 a of the first connection target member 2 or immediately after the application. When application and light irradiation are performed as described above, the flow of the anisotropic conductive material layer can be further suppressed. For this reason, the conduction | electrical_connection reliability of the obtained connection structure 1 can be improved further. The time from the application of the anisotropic conductive material to the upper surface 2a of the first connection target member 2 to the irradiation of light is preferably within a range of 0 to 3 seconds, and within a range of 0 to 2 seconds. It is more preferable that It is preferable that the time from when the anisotropic conductive material comes into contact with the upper surface 2a of the first connection target member 2 until irradiation with light satisfies the above range.

In order to appropriately cure the anisotropic conductive material layer 3A, the light irradiation intensity at the time of light irradiation is preferably in the range of 0.1 to 100 mW / cm ² . The light source used when irradiating light is not specifically limited. Examples of the light source include a light source having a sufficient light emission distribution at a wavelength of 420 nm or less. Specific examples of the light source include, for example, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, a black light lamp, a microwave excitation mercury lamp, and a metal halide lamp.

  Next, as shown in FIG. 2C, the second connection target member 4 is laminated on the upper surface 3a of the B-staged anisotropic conductive material layer 3B. The second connection target member 4 is laminated so that the electrode 2b on the upper surface 2a of the first connection target member 2 and the electrode 4b on the lower surface 4a of the second connection target member 4 face each other.

  Further, when the second connection target member 4 is laminated, the anisotropic conductive material layer 3B is further cured by applying heat to the anisotropic conductive material layer 3B to form the cured product layer 3. However, heat may be applied to the anisotropic conductive material layer 3B before the second connection target member 4 is laminated. Furthermore, heat may be applied to the anisotropic conductive material layer 3B after the second connection target member 4 is laminated.

  The preferable lower limit of the heating temperature when the anisotropic conductive material layer 3B is cured by applying heat is 160 ° C, the preferable upper limit is 250 ° C, and the more preferable upper limit is 200 ° C.

  It is preferable to apply pressure when the anisotropic conductive material layer 3B is cured. By compressing the conductive particles 5 with the electrodes 2b and 4b by pressurization, the contact area between the electrodes 2b and 4b and the conductive particles 5 can be increased. For this reason, conduction reliability can be improved.

  By curing the anisotropic conductive material layer 3 </ b> B, the first connection target member 2 and the second connection target member 4 are connected via the cured product layer 3. Further, the electrode 2 b and the electrode 4 b are electrically connected through the conductive particles 5. In this way, the connection structure 1 shown in FIG. 1 can be obtained. In this embodiment, since photocuring and thermosetting are used together, the anisotropic conductive material can be cured in a short time.

  In the present embodiment, when the anisotropic conductive material layer 3A is formed and the anisotropic conductive material layer 3A is B-staged, the composite apparatus shown in FIG. 3A is preferably used.

  The composite device 11 shown in FIG. 3A includes a dispenser 12 and a light irradiation device 13 connected to the dispenser 12. The dispenser 12 includes a syringe 12a for filling the inside with an anisotropic conductive material, and a grip portion 12b that grips the outer peripheral surface of the syringe 12a. The light irradiation device 13 includes a light irradiation device main body 13a and a light irradiation unit 13b. In the composite apparatus 11, the grip part 12b and the light irradiation apparatus main body 13a are connected. Therefore, the distance between the dispenser 12 and the light irradiation device 13 can be reduced, that is, the distance between the discharge part of the dispenser 12 and the light irradiation part 13b can be reduced. Furthermore, the dispenser 12 and the light irradiation device 13 can be easily moved at the same speed. In addition, the syringe 12a and the light irradiation apparatus main body 13a may be directly connected.

  As shown in FIG. 3A, when applying and irradiating light, while moving the composite device 11 in the direction of arrow A, the syringe 12a is anisotropically moved from the syringe 12a to the upper surface 2a of the first connection target member 2. A conductive conductive material is applied to form the anisotropic conductive material layer 3A. Further, the anisotropic conductive material layer 3 </ b> A is irradiated with light from the light irradiation unit 13 b of the light irradiation device 13 connected to the dispenser 12 as indicated by an arrow B while being applied.

  From the viewpoint of further suppressing the flow of the anisotropic conductive material layer 3A formed on the upper surface 2a of the first connection target member 2 and the conductive particles 5 contained in the anisotropic conductive material layer 3A, It is preferable that application and light irradiation are performed while moving the dispenser 12 and the light irradiation device 13. Furthermore, it is preferable that the dispenser 12 and the light irradiation device 13 are moved at the same speed from the viewpoint of controlling the time until the light irradiation with high accuracy. However, the table 31 may be moved in the direction of the arrow A without moving the composite apparatus 11.

  As shown in FIG. 4A, a dispenser 12 and a light irradiation device 21 that is not connected to the dispenser 12 may be used. Similar to the light irradiation device 13, the light irradiation device 21 includes a light irradiation device main body 21 a and a light irradiation unit 21 b. The light irradiation device 21 is configured to irradiate light over a wider area than the light irradiation device 13.

  When using the dispenser 12 and the light irradiation device 21 not connected to the dispenser 12, for example, as shown in FIG. 4A, the light irradiation device 21 is placed above the first connection target member 2. Deploy. Next, while the dispenser 12 is moved in the direction of the arrow A between the first connection target member 2 and the light irradiation device 21, anisotropic conduction is performed from the syringe 12 a to the upper surface 2 a of the first connection target member 2. The material is applied to form the anisotropic conductive material layer 3A. Next, as shown in FIG. 4 (b), after the application of the anisotropic conductive material is completed, the light irradiation unit 21b of the light irradiation device 21 disposed above the first connection target member 2 is different from the first irradiation target member 2. The isotropic conductive material layer 3A is irradiated with light. The light irradiation is performed, for example, simultaneously with the application of the anisotropic conductive material or immediately after the application.

  The light irradiation device 21 is preferably disposed above the first connection target member 2 during application. In this case, light can be irradiated quickly after application. After the application, it is preferable to irradiate the entire region of the anisotropic conductive material layer 3A all together. In this case, the anisotropic conductive material layer 3A can be made B-stage even more uniformly.

  By using the apparatus shown in FIG. 3 (a) or FIG. 4 (a), the anisotropic conductive material is applied simultaneously or immediately after the application of the anisotropic conductive material to the upper surface 2a of the first connection target member 2. The material layer 3A can be easily irradiated with light.

  The anisotropic conductive material used in the method for manufacturing a connection structure according to the present invention is not particularly limited. From the viewpoint of further suppressing the flow of the anisotropic conductive material applied to the upper surface 2a of the first connection target member 2 or the conductive particles contained in the anisotropic conductive material, the anisotropic conductive material is used. The material preferably contains a curable compound, a thermosetting agent, a photocuring initiator, and conductive particles.

  The viscosity of the anisotropic conductive material before coating at 25 ° C. and 2.5 rpm is preferably in the range of 20 to 200 Pa · s. In this case, for example, after the anisotropic conductive material is applied to the upper surface 2a of the first connection target member 2, the flow of the anisotropic conductive material before curing can be further suppressed. Furthermore, the resin component between the electrode and the conductive particles can be easily removed, and the contact area between the electrode and the conductive particles can be increased. Furthermore, when the surface of the first connection target member is uneven, the surface of the unevenness can be sufficiently filled with an anisotropic conductive material, and voids hardly occur after curing. Further, it becomes difficult for the conductive particles to settle in the anisotropic conductive material, and the dispersibility of the conductive particles can be improved.

  The manufacturing method of the said anisotropic conductive material is not specifically limited. Examples of the method for producing the anisotropic conductive material include the curable compound, the thermosetting agent, the photocuring initiator, the conductive particles, and other components added as necessary. And a sufficient production method using a planetary stirrer or the like.

  The connection structure manufacturing method according to the present invention includes, for example, a connection between a flexible printed circuit board and a glass substrate (FOG (Film on Glass)), a connection between a semiconductor chip and a flexible printed circuit board (COF (Chip on Film)), Or it can use for the connection (COG (Chip on Glass)) etc. of a semiconductor chip and a glass substrate. Especially, the manufacturing method of the connection structure concerning the present invention is suitable for COG use. The method for manufacturing a connection structure according to the present invention is suitably used for connection between a semiconductor chip and a glass substrate. However, the use of the method for manufacturing a connection structure according to the present invention is not limited to the above-described application.

  In COG applications, in particular, it is often difficult to reliably connect the electrodes of the semiconductor chip and the glass substrate with conductive particles of an anisotropic conductive material. For example, in the case of COG use, the distance between adjacent electrodes of a semiconductor chip and the distance between adjacent electrodes of a glass substrate may be about 10 to 20 μm, and fine wiring is often formed. Even if fine wiring is formed, the connection structure body manufacturing method according to the present invention can connect the electrodes of the semiconductor chip and the glass substrate with high accuracy, and can improve conduction reliability.

  Hereinafter, the detail of each component contained in the said anisotropic conductive material is demonstrated.

(Curable compound)
A conventionally known curable compound can be used as the curable compound, and is not particularly limited. As for the said sclerosing | hardenable compound, only 1 type may be used and 2 or more types may be used together.

  Examples of the curable compound include light and thermosetting compounds, photocurable compounds, and thermosetting compounds. The light and thermosetting compounds have photocuring properties and thermosetting properties. The said photocurable compound has photocurability, for example, and does not have thermosetting. The said thermosetting compound does not have photocurability, for example, and has thermosetting.

  The curable compound includes light and a thermosetting compound, or includes a photocurable compound and a thermosetting compound. When the curable compound includes the light and the thermosetting compound, the curable compound may not include at least one of the photocurable compound and the thermosetting compound. In addition to the thermosetting compound, at least one of a photocurable compound and a thermosetting compound may be further included. When the said curable compound does not contain the said light and a thermosetting compound, the said curable compound contains a photocurable compound and a thermosetting compound.

  From the viewpoint of easily controlling the curing of the anisotropic conductive material, the curable compound includes the light and the thermosetting compound, and at least one of the photocurable compound and the thermosetting compound, Or it is preferable that a photocurable compound and a thermosetting compound are included. More preferably, the curable compound includes a photocurable compound and a thermosetting compound.

The curable compound is not particularly limited. Examples of the curable compound include epoxy compounds, episulfide compounds, (meth) acrylic compounds, phenolic compounds, amino compounds, unsaturated polyester compounds, polyurethane compounds, silicone compounds, and polyimide compounds. The (meth) acryl means acryl or methacryl.
When a photocurable compound and a thermosetting compound are used in combination, the usage amount of the photocurable compound and the thermosetting compound is appropriately adjusted according to the types of the photocurable compound and the thermosetting compound. The The anisotropic conductive material preferably contains a photocurable compound and a thermosetting compound in a weight ratio of 1:99 to 90:10, more preferably 5:95 to 60:40, More preferably, it is included at 20:80 to 40:60.

[Thermosetting compound]
From the viewpoint of easily controlling the curing of the anisotropic conductive material and further enhancing the conduction reliability of the connection structure, the curable compound is an epoxy compound or an episulfide compound (thiirane group-containing compound). It is preferable that at least one of these is included, and it is more preferable that an episulfide compound is included. From the viewpoint of enhancing the curability of the anisotropic conductive material, in 100 parts by weight of the curable compound, the preferred lower limit of the content of the episulfide compound is 10 parts by weight, the more preferred lower limit is 20 parts by weight, and the preferred upper limit is 50 parts by weight. Parts, more preferred upper limit is 40 parts by weight.

  Each of the epoxy compound and the episulfide compound preferably has an aromatic ring. Examples of the aromatic ring include a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, tetracene ring, chrysene ring, triphenylene ring, tetraphen ring, pyrene ring, pentacene ring, picene ring, and perylene ring. Especially, it is preferable that the said aromatic ring is a benzene ring, a naphthalene ring, or an anthracene ring, and it is more preferable that it is a benzene ring or a naphthalene ring.

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

  From the viewpoint of curing more rapidly at a low temperature, the episulfide compound preferably has a structure represented by the following formula (1), (2), (5), (7) or (8). It is more preferable to have a structure represented by the formula (1) or (2).

  In the above formula (1), R1 and R2 each represent an alkylene group having 1 to 5 carbon atoms, 2 to 4 groups out of 4 groups of R3, R4, R5 and R6 represent hydrogen, and R3 , R4, R5 and R6 which are not hydrogen represent a group represented by the following formula (3).

  All four groups of R3, R4, R5 and R6 in the above formula (1) may be hydrogen. One or two of the four groups of R3, R4, R5 and R6 are groups represented by the following formula (3), and among the four groups of R3, R4, R5 and R6 The group that is not a group represented by the following formula (3) may be hydrogen.

上記式（３）中、Ｒ７は炭素数１〜５のアルキレン基を表す。

In said formula (3), R7 represents a C1-C5 alkylene group.

  In the above formula (2), R51 and R52 each represent an alkylene group having 1 to 5 carbon atoms, and 4 to 6 groups out of 6 groups of R53, R54, R55, R56, R57 and R58 are hydrogen. The group which is not hydrogen among R53, R54, R55, R56, R57 and R58 represents a group represented by the following formula (4).

  All of the six groups of R53, R54, R55, R56, R57 and R58 in the above formula (2) may be hydrogen. One or two of the six groups of R53, R54, R55, R56, R57 and R58 are groups represented by the following formula (4), and R53, R54, R55, R56, R57 and R58. Of these, the group that is not a group represented by the following formula (4) may be hydrogen.

  In said formula (4), R59 represents a C1-C5 alkylene group.

  In said formula (5), R101 and R102 represent a C1-C5 alkylene group, respectively. Six to eight groups out of the eight groups of R103, R104, R105, R106, R107, R108, R109 and R110 represent hydrogen.

  The group which is not hydrogen among R103, R104, R105, R106, R107, R108, R109 and R110 in the above formula (5) represents a group represented by the following formula (6). All of the eight groups of R103, R104, R105, R106, R107, R108, R109 and R110 may be hydrogen. One or two of the eight groups of R103, R104, R105, R106, R107, R108, R109 and R110 are groups represented by the following formula (6), and R103, R104, R105, R106 , R107, R108, R109 and R110, which is not a group represented by the following formula (6), may be hydrogen.

上記式（６）中、Ｒ１１１は炭素数１〜５のアルキレン基を表す。

In said formula (6), R111 represents a C1-C5 alkylene group.

上記式（７）中、Ｒ１及びＲ２はそれぞれ炭素数１〜５のアルキレン基を表す。

In said formula (7), R1 and R2 represent a C1-C5 alkylene group, respectively.

  In said formula (8), R3 and R4 represent a C1-C5 alkylene group, respectively.

  The episulfide compound having a structure represented by the above formula (1) or (2) has at least two thiirane groups (episulfide groups). In addition, a group having a thiirane group is bonded to a benzene ring or a naphthalene ring. Since it has such a structure, the anisotropic conductive material can be rapidly cured at a low temperature by heating the anisotropic conductive material. In this specification, low temperature means a temperature of 200 ° C. or lower.

  The episulfide compound having the structure represented by the above formula (1), (2), (5), (7) or (8) is represented by the above formula (1), (2), (5), (7) or The reactivity is high compared with the compound whose thiirane group in (8) is an epoxy group. This is because a thiirane group is easier to open a ring and has higher reactivity than an epoxy group. Since the episulfide compound having the structure represented by the above formula (1), (2), (5), (7) or (8) has high reactivity, the anisotropic conductive material is rapidly cured at a low temperature. Can do. In particular, since an episulfide compound having a structure represented by the above formula (1) or (2) has a considerably high reactivity, an anisotropic conductive material can be rapidly cured at a low temperature.

  R1 and R2 in the above formula (1), R51 and R52 in the above formula (2), R7 in the above formula (3), R59 in the above formula (4), R101 in the above formula (5) and R102, R111 in the above formula (6), R1 and R2 in the above formula (7), R3 and R4 in the above formula (8) are alkylene groups having 1 to 5 carbon atoms. If the alkylene group has more than 5 carbon atoms, the curing rate of the episulfide compound tends to be slow.

  R1 and R2 in the above formula (1), R51 and R52 in the above formula (2), R7 in the above formula (3), R59 in the above formula (4), R101 in the above formula (5) and R102, R111 in the above formula (6), R1 and R2 in the above formula (7), and R3 and R4 in the above formula (8) are each preferably an alkylene group having 1 to 3 carbon atoms. More preferably, it is a group. The alkylene group may be an alkylene group having a straight chain structure or an alkylene group having a branched structure.

  The structure represented by (1) is preferably a structure represented by the following formula (1A). An episulfide compound having a structure represented by the following formula (1A) is excellent in curability.

  In said formula (1A), R1 and R2 represent a C1-C5 alkylene group, respectively.

  The structure represented by the above formula (1) is more preferably a structure represented by the following formula (1B). An episulfide compound having a structure represented by the following formula (1B) is more excellent in curability.

  The structure represented by the above (2) is preferably a structure represented by the following formula (2A). An episulfide compound having a structure represented by the following formula (2A) is excellent in curability.

  In said formula (2A), R51 and R52 represent a C1-C5 alkylene group, respectively.

  The structure represented by the above formula (2) is more preferably a structure represented by the following formula (2B). An episulfide compound having a structure represented by the following formula (2B) is more excellent in curability.

  The epoxy compound is not particularly limited. A conventionally well-known epoxy compound can be used as an epoxy compound. As for the said epoxy compound, only 1 type may be used and 2 or more types may be used together.

  Examples of the epoxy compound include phenoxy resin having an epoxy group, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, biphenol type epoxy resin, naphthalene type epoxy resin, fluorene type epoxy resin, phenol aralkyl type epoxy. Examples thereof include a resin, a naphthol aralkyl type epoxy resin, a dicyclopentadiene type epoxy resin, an anthracene type epoxy resin, an epoxy resin having an adamantane skeleton, an epoxy resin having a tricyclodecane skeleton, and an epoxy resin having a triazine nucleus in the skeleton.

  Specific examples of the epoxy compound include, for example, epichlorohydrin and bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol D type epoxy resin and the like, bisphenol type epoxy resin, and epichlorohydrin and phenol novolac or cresol novolak. And epoxy novolac resins derived from Various epoxy compounds having two or more oxirane groups in one molecule such as glycidylamine, glycidyl ester, and alicyclic or heterocyclic may be used.

  The curable compound includes an epoxy compound having a structure in which the thiirane group in the structure represented by the formula (1), (2), (5), (7) or (8) is replaced with an epoxy group. Also good. In this case, the structures represented by the above formulas (3), (4) and (6) are also preferably structures in which the thiirane group is replaced with an epoxy group. The said curable compound may contain the epoxy compound represented by following formula (11) or (12). The curable compound preferably contains an episulfide compound represented by the above formula (1) or (2) and an epoxy compound represented by the following formula (11) or (12).

  In said formula (11), R11 and R12 represent a C1-C5 alkylene group, respectively, 2-4 groups among four groups of R13, R14, R15, and R16 represent hydrogen, R13 , R14, R15 and R16, which are not hydrogen, represent a group represented by the following formula (13).

  All four groups of R13, R14, R15 and R16 in the above formula (11) may be hydrogen. One or two of the four groups of R13, R14, R15 and R16 is a group represented by the following formula (13), and among the four groups of R13, R14, R15 and R16 The group that is not a group represented by the following formula (13) may be hydrogen.

上記式（１３）中、Ｒ１７は炭素数１〜５のアルキレン基を表す。

In said formula (13), R17 represents a C1-C5 alkylene group.

  In the above formula (12), R61 and R62 each represent an alkylene group having 1 to 5 carbon atoms, and 4 to 6 groups out of 6 groups of R63, R64, R65, R66, R67 and R68 are hydrogen. The group which is not hydrogen among R63, R64, R65, R66, R67 and R68 represents a group represented by the following formula (14).

  All of the six groups of R63, R64, R65, R66, R67 and R68 in the above formula (12) may be hydrogen. One or two of the six groups R63, R64, R65, R66, R67 and R68 are groups represented by the following formula (14), and R63, R64, R65, R66, R67 and R68. Of these six groups, a group that is not a group represented by the following formula (14) may be hydrogen.

  In said formula (14), R69 represents a C1-C5 alkylene group.

  R11 and R12 in the formula (11), R61 and R62 in the formula (12), R17 in the formula (13), and R69 in the formula (14) are alkylene groups having 1 to 5 carbon atoms. It is. If the alkylene group has more than 5 carbon atoms, the curing rate of the epoxy compound represented by the above formula (11) or (12) tends to be slow.

  R11 and R12 in the above formula (11), R61 and R62 in the above formula (12), R17 in the above formula (13), and R69 in the above formula (14) are each an alkylene having 1 to 3 carbon atoms. It is preferably a group, more preferably a methylene group. The alkylene group may be an alkylene group having a straight chain structure or an alkylene group having a branched structure.

  The structure represented by (11) is preferably a structure represented by the following formula (11A). An epoxy compound having a structure represented by the following formula (11A) is commercially available and can be easily obtained.

  In said formula (11A), R11 and R12 represent a C1-C5 alkylene group, respectively.

  The structure represented by the above formula (11) is more preferably a structure represented by the following formula (11B). The epoxy compound having a structure represented by the following formula (11B) is resorcinol diglycidyl ether. Resorcinol diglycidyl ether is commercially available and can be easily obtained.

  The structure represented by (12) is preferably a structure represented by the following formula (12A). An epoxy compound having a structure represented by the following formula (12A) can be easily obtained.

  In said formula (12A), R61 and R62 represent a C1-C5 alkylene group, respectively.

  The structure represented by the above formula (12) is more preferably a structure represented by the following formula (12B). An epoxy compound having a structure represented by the following formula (12B) can be easily obtained.

  A mixture of an episulfide compound having a structure represented by the above formula (1) or (2) and an epoxy compound represented by the above formula (11) or (12) (hereinafter sometimes abbreviated as “mixture A”) In which the content of the episulfide compound having the structure represented by the formula (1) or (2) is 10 to 50% by weight, and the epoxy represented by the formula (11) or (12) The content of the compound is preferably 90 to 50% by weight, the content of the episulfide compound having a structure represented by the above formula (1) or (2) is 20 to 30% by weight, and the above formula (11) Or it is more preferable that content of the epoxy compound represented by (12) is 80 to 70 weight%.

  When there is too little content of the episulfide compound which has a structure represented by the said Formula (1) or (2), there exists a tendency for the hardening rate of the said mixture A to become slow. When there is too much content of the episulfide compound which has a structure represented by the said Formula (1) or (2), the viscosity of the said mixture A will become high too much, or the said mixture A may become a solid.

  The method for producing the mixture A is not particularly limited. Examples of the production method include a production method in which an epoxy compound represented by the above formula (11) or (12) is prepared and a part of the epoxy group of the epoxy compound is converted into a thiirane group.

  In the method for producing the mixture A, the epoxy compound represented by the above formula (11) or (12) or the solution containing the epoxy compound is continuously or intermittently added to the first solution containing the sulfurizing agent. A method in which the second solution containing the sulfurizing agent is further added continuously or intermittently is preferable. By this method, some epoxy groups of the epoxy compound can be converted into thiirane groups. As a result, the mixture A can be obtained. Examples of the sulfurizing agent include thiocyanates, thioureas, phosphine sulfide, dimethylthioformamide, N-methylbenzothiazol-2-thione, and the like. Examples of the thiocyanates include sodium thiocyanate, potassium thiocyanate, and sodium thiocyanate.

  The curable compound is a monomer of an epoxy compound having a structure represented by the following formula (21), a multimer in which at least two epoxy compounds are bonded, or a mixture of the monomer and the multimer. May be included.

  In said formula (21), R1 represents a C1-C5 alkylene group, R2 represents a C1-C5 alkylene group, R3 is a hydrogen atom, a C1-C5 alkyl group, or following formula ( 22), R4 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a structure represented by the following formula (23).

  In said formula (22), R5 represents a C1-C5 alkylene group.

  In said formula (23), R6 represents a C1-C5 alkylene group.

  The epoxy compound having the structure represented by the above formula (21) has an unsaturated double bond and at least two epoxy groups. By using an epoxy compound having a structure represented by the above formula (21), the anisotropic conductive material can be rapidly cured at a low temperature.

  The curable compound includes a monomer having a structure represented by the following formula (31), a multimer in which at least two of the compounds are bonded, or a mixture of the monomer and the multimer. You may go out.

  In the above formula (31), R1 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a structure represented by the following formula (32), R2 represents an alkylene group having 1 to 5 carbon atoms, and R3 represents carbon. X 1 represents an oxygen atom or a sulfur atom, and X 2 represents an oxygen atom or a sulfur atom.

  In said formula (32), R4 represents a C1-C5 alkylene group, X3 represents an oxygen atom or a sulfur atom.

  The epoxy compound corresponding to the compound having the structure represented by the above formula (31) can be synthesized, for example, as follows.

  A raw material compound, a fluorene compound having a hydroxyl group, epichlorohydrin, sodium hydroxide, and methanol are mixed, cooled, and reacted. Thereafter, an aqueous sodium hydroxide solution is dropped. After dripping, it is further reacted to obtain a reaction solution. Next, water and toluene are added to the reaction solution, and the toluene layer is taken out. The toluene layer is washed with water and then dried to remove water and the solvent. In this way, an epoxy compound corresponding to the compound having the structure represented by the formula (31) can be easily obtained. In addition, the fluorene compound which has a hydroxyl group which is a raw material compound is marketed, for example from JFE Chemical Company etc., for example.

  Further, the thiirane group-containing compound corresponding to the compound having the structure represented by the above formula (31) has the epoxy group of the epoxy compound corresponding to the compound having the structure represented by the above formula (31) as a thiirane group. It can be synthesized by conversion. For example, an epoxy compound as a raw material compound or a solution containing the epoxy compound is added to the solution containing the sulfurizing agent, and then the solution containing the sulfurizing agent is further added to easily convert the epoxy group to a thiirane group. it can.

  The said curable compound may contain the epoxy compound which has a heterocyclic ring containing a nitrogen atom. The epoxy compound having a heterocyclic ring containing a nitrogen atom is preferably an epoxy compound represented by the following formula (41) or an epoxy compound represented by the following formula (42). By using such a curable compound, the curing rate of the anisotropic conductive material can be further increased, and the heat resistance of the cured product of the anisotropic conductive material can be further enhanced.

  In said formula (41), R1-R3 represents a C1-C5 alkylene group, respectively, Z represents an epoxy group or a hydroxymethyl group. R21 to R23 may be the same or different.

  In the above formula (42), R1 to R3 each represent an alkylene group having 1 to 5 carbon atoms, p, q and r each represents an integer of 1 to 5, and R4 to R6 each represent an alkylene having 1 to 5 carbon atoms. Represents a group. R1 to R3 may be the same or different. p, q and r may be the same or different. R4-6 may be the same or different.

  The epoxy compound having a heterocyclic ring containing a nitrogen atom is preferably triglycidyl isocyanurate or trishydroxyethyl isocyanurate triglycidyl ether. By using these curable compounds, the curing rate of the anisotropic conductive material can be further increased.

  The curable compound preferably includes an epoxy compound having an aromatic ring. By using an epoxy compound having an aromatic ring, the curing rate of the anisotropic conductive material can be further increased and the anisotropic conductive material can be easily applied. From the viewpoint of further improving the applicability of the anisotropic conductive material, the aromatic ring is preferably a benzene ring, a naphthalene ring or an anthracene ring. Examples of the epoxy compound having an aromatic ring include resorcinol diglycidyl ether or 1,6-naphthalenediglycidyl ether. Among these, resorcinol diglycidyl ether having a structure represented by the above formula (11B) is particularly preferable. By using resorcinol diglycidyl ether, the curing rate of the anisotropic conductive material can be increased and the anisotropic conductive material can be easily applied.

[Photocurable compound]
The curable compound according to the present invention may contain a photocurable compound so as to be cured by light irradiation. The curable compound can be semi-cured by light irradiation, and the fluidity of the curable compound can be reduced.

  It does not specifically limit as said photocurable compound, (meth) acrylic resin, cyclic ether group containing resin, etc. are mentioned.

  Examples of the (meth) acrylic resin include an ester compound obtained by reacting (meth) acrylic acid and a compound having a hydroxyl group, and an epoxy (meth) acrylate obtained by reacting (meth) acrylic acid and an epoxy compound. Urethane (meth) acrylate obtained by reacting a (meth) acrylic acid derivative having a hydroxyl group with isocyanate is preferably used.

  When a photocurable compound other than the photocurable compounds described above is included, the photocurable compound may be a crosslinkable compound or a non-crosslinkable compound.

  Specific examples of the crosslinkable compound include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, (poly ) Ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, glycerol methacrylate acrylate, pentaerythritol tri (meth) acrylate, tri Examples include methylolpropane trimethacrylate, allyl (meth) acrylate, vinyl (meth) acrylate, divinylbenzene, polyester (meth) acrylate, and urethane (meth) acrylate.

  Specific examples of the non-crosslinkable compound include ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) ) Acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, decyl (Meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, and the like.

[Light and thermosetting compounds]
In the case where the curable compound contains, for example, a thermosetting compound and a photopolymerizable compound, from the viewpoint of easily controlling the curing of the anisotropic conductive material or further improving the conduction reliability of the connection structure. The curable compound preferably contains a light and thermosetting compound having at least one of an epoxy group and a thiirane group and a (meth) acryloyl group. It is preferable that the said curable compound contains the light and thermosetting compound (henceforth a partial (meth) acrylated epoxy resin) which has an epoxy group and a (meth) acryloyl group. The (meth) acrylate means acrylate or methacrylate.

  The partially (meth) acrylated epoxy resin can be obtained, for example, by reacting an epoxy resin and (meth) acrylic acid in the presence of a basic catalyst according to a conventional method. It is preferable that 20% or more of the epoxy groups are converted to (meth) acryloyl groups (conversion rate) and partially (meth) acrylated. More preferably, 50% of the epoxy groups are converted to (meth) acryloyl groups.

  From the viewpoint of increasing the curability of the anisotropic conductive material, the preferable lower limit of the content of the partially (meth) acrylated epoxy resin is 0.1% by weight and the more preferable lower limit is 0 in 100% by weight of the curable compound. 0.5 wt%, the preferred upper limit is 2 wt%, and the more preferred upper limit is 1.5 wt%.

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

(Thermosetting agent)
The said thermosetting agent is not specifically limited. A conventionally known thermosetting agent can be used as the thermosetting agent. Examples of the thermosetting agent include imidazole curing agents, amine curing agents, phenol curing agents, polythiol curing agents, and acid anhydrides. As for the said thermosetting agent, only 1 type may be used and 2 or more types may be used together.

  Since the anisotropic conductive material can be cured more rapidly at a low temperature, the thermosetting agent is preferably an imidazole curing agent, a polythiol curing agent, or an amine curing agent. In addition, a latent curing agent is preferable because the storage stability of the anisotropic conductive material can be improved. The latent curing agent is preferably a latent imidazole curing agent, a latent polythiol curing agent or a latent amine curing agent. The thermosetting agent may be coated with a polymer material such as polyurethane resin or polyester resin.

  The imidazole curing agent is not particularly limited, and 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2, 4-Diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine and 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s- Examples include triazine isocyanuric acid adducts.

  The polythiol curing agent is not particularly limited, and examples include trimethylolpropane tris-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, and dipentaerythritol hexa-3-mercaptopropionate. .

  The amine curing agent is not particularly limited, and hexamethylene diamine, octamethylene diamine, decamethylene diamine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraspiro [5.5]. Examples include undecane, bis (4-aminocyclohexyl) methane, metaphenylenediamine, and diaminodiphenylsulfone.

  The content of the thermosetting agent is not particularly limited. A preferable lower limit of the content of the thermosetting agent is 5 parts by weight, a more preferable lower limit is 10 parts by weight, a preferable upper limit is 30 parts by weight, and a more preferable upper limit is 20 parts by weight with respect to a total of 100 parts by weight of the curable compound. It is. If content of the said thermosetting agent satisfy | fills the said preferable minimum and upper limit, an anisotropic conductive material can fully be thermosetted.

(Photocuring initiator)
The photocuring initiator is not particularly limited. A conventionally known photocuring initiator can be used as the photocuring initiator. As for the said photocuring initiator, only 1 type may be used and 2 or more types may be used together.

  The photocuring initiator is not particularly limited, and examples thereof include acetophenone photocuring initiator, benzophenone photocuring initiator, thioxanthone, ketal photocuring initiator, halogenated ketone, acyl phosphinoxide, and acyl phosphonate. .

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

  The content of the photocuring initiator is not particularly limited. The preferable lower limit of the content of the photocuring initiator is 0.1 parts by weight, the more preferable lower limit is 0.2 parts by weight, and the preferable upper limit is 2 parts by weight with respect to the total of 100 parts by weight of the curable compound. The upper limit is 1 part by weight. If content of the said photocuring initiator satisfy | fills the said preferable minimum and upper limit, an anisotropic conductive material can be photocured moderately. By irradiating the anisotropic conductive material with light to form a B stage, the flow of the anisotropic conductive material can be suppressed.

(Conductive particles)
As the conductive particles contained in the anisotropic conductive material, for example, conventionally known conductive particles capable of electrically connecting the electrodes are used. The conductive particles are preferably particles having a conductive layer on the outer surface. The conductive particles may have insulating particles attached to the surface of the conductive layer, or the surface of the conductive layer may be covered with an insulating layer. In this case, the insulating particles or the insulating layer is removed by pressurization when the electrodes are connected.

  Examples of the conductive particles include organic particles, inorganic particles, organic-inorganic hybrid particles, or conductive particles whose surfaces are covered with a conductive layer, and metal particles that are substantially composed of only metal. Is mentioned. The conductive layer is not particularly limited. Examples of the conductive layer include a gold layer, a silver layer, a copper layer, a nickel layer, a palladium layer, or a conductive layer containing tin.

  In 100% by weight of the anisotropic conductive material, the content of the conductive particles is preferably in the range of 1 to 25% by weight. The more preferable lower limit of the content of the conductive particles is 5% by weight, the more preferable upper limit is 19% by weight, the still more preferable upper limit is 15% by weight, and the most preferable upper limit is 10% by weight. When the content of the conductive particles is within the above range, the conductive particles can be easily arranged between the upper and lower electrodes to be connected. Furthermore, it becomes difficult to electrically connect adjacent electrodes that should not be connected via a plurality of conductive particles. That is, a short circuit between adjacent electrodes can be prevented.

(Other ingredients)
The anisotropic conductive material may contain a solvent. For example, when the curable compound is solid, the dispersibility of the curable compound can be increased by adding a solvent to the solid curable compound and dissolving it. Examples of the solvent include ethyl acetate, methyl cellosolve, toluene, acetone, methyl ethyl ketone, cyclohexane, n-hexane, tetrahydrofuran, and diethyl ether.

  Since the adhesive force of the cured product of the anisotropic conductive material can be increased, the anisotropic conductive material preferably contains an adhesive strength adjusting agent. From the viewpoint of further increasing the adhesive strength, the adhesive strength modifier is preferably a silane coupling agent.

  The anisotropic conductive material preferably contains a filler. By using the filler, latent heat expansion of the cured product of the anisotropic conductive material can be suppressed. The filler is not particularly limited. Examples of the filler include silica, aluminum nitride, and alumina. As for the said filler, only 1 type may be used and 2 or more types may be used together.

  The content of the filler is not particularly limited. The preferable lower limit of the filler content is 5 parts by weight, the more preferable lower limit is 15 parts by weight, the preferable upper limit is 70 parts by weight, and the more preferable upper limit is 50 parts by weight with respect to the total of 100 parts by weight of the curable compound. . When content of the said filler satisfy | fills the said preferable minimum and upper limit, the latent thermal expansion of the cured | curing material of an anisotropic conductive material can fully be suppressed, and also a filler can fully be disperse | distributed in an anisotropic conductive material.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. The present invention is not limited only to the following examples.

Example 1
(1) Preparation of episulfide compound-containing mixture In a 2 L vessel equipped with a stirrer, a cooler and a thermometer, ethanol 250 mL, pure water 250 mL, and potassium thiocyanate 20 g were added to dissolve potassium thiocyanate, One solution was prepared. Thereafter, the temperature in the container was kept in the range of 20 to 25 ° C. Next, 160 g of resorcinol diglycidyl ether was dropped into the first solution at a rate of 5 mL / min while stirring the first solution in the container maintained at 20 to 25 ° C. After dropping, the mixture was further stirred for 30 minutes to obtain an epoxy compound-containing mixed solution.

  Next, a second solution in which 20 g of potassium thiocyanate was dissolved in a solution containing 100 mL of pure water and 100 mL of ethanol was prepared. The obtained second solution was added to the obtained epoxy group-containing mixed solution at a rate of 5 mL / min, and then stirred for 30 minutes. After stirring, a second solution in which 20 g of potassium thiocyanate is dissolved in a solution containing 100 mL of pure water and 100 mL of ethanol is further prepared, and the second solution is further added to the container at a rate of 5 mL / min. And stirred for 30 minutes. Thereafter, the temperature in the container was cooled to 10 ° C., and stirred for 2 hours to be reacted.

  Next, 100 mL of saturated saline was added to the container and stirred for 10 minutes. After stirring, 300 mL of toluene was further added to the container and stirred for 10 minutes. Thereafter, the solution in the container was transferred to a separating funnel and allowed to stand for 2 hours to separate the solution. The lower solution in the separatory funnel was discharged, and the supernatant was taken out. 100 mL of toluene was added to the removed supernatant, stirred, and allowed to stand for 2 hours. Further, 100 mL of toluene was further added, stirred and allowed to stand for 2 hours.

  Next, 50 g of magnesium sulfate was added to the supernatant liquid to which toluene was added and stirred for 5 minutes. After stirring, magnesium sulfate was removed with a filter paper to separate the solution. The remaining solvent was removed by drying the separated solution under reduced pressure at 80 ° C. using a vacuum dryer. In this way, an episulfide compound-containing mixture was obtained.

¹ H-NMR measurement of the obtained episulfide compound-containing mixture was performed using chloroform as a solvent. As a result, the signal in the region of 6.5 to 7.5 ppm indicating the presence of the epoxy group decreased, and the signal appeared in the region of 2.0 to 3.0 ppm indicating the presence of the episulfide group. This confirmed that some epoxy groups of resorcinol diglycidyl ether were converted into episulfide groups. Moreover, from the integral value of the measurement result of ¹ H-NMR, the episulfide compound-containing mixture contains 70% by weight of resorcinol diglycidyl ether and 30% by weight of the episulfide compound having a structure represented by the above formula (1B). It was confirmed.

(2) Preparation of anisotropic conductive paste 30 parts by weight of the resulting episulfide compound-containing mixture, 5 parts by weight of an amine adduct (“PN-23J” manufactured by Ajinomoto Fine Techno Co.) as a thermosetting agent, and a photocurable compound 5 parts by weight of epoxy acrylate ("EBECRYL 3702" manufactured by Daicel-Cytec), 0.1 parts by weight of acylphosphine oxide compound ("DAROCUR TPO" manufactured by Ciba Japan) as a photopolymerization initiator, and curing acceleration 1 part by weight of 2-ethyl-4-methylimidazole as an agent, 20 parts by weight of silica having an average particle diameter of 0.25 μm and 20 parts by weight of alumina having an average particle diameter of 0.5 μm are blended, and further average particles Conductive particles having a diameter of 3 μm were added so that the content in 100% by weight of the composition was 10% by weight. , By stirring for 5 minutes at 2000rpm using a planetary mixing machine to obtain a formulation.

  The conductive particles used are conductive particles having a metal layer in which a nickel plating layer is formed on the surface of divinylbenzene resin particles and a gold plating layer is formed on the surface of the nickel plating layer. is there.

  The obtained blend was filtered using a nylon filter paper (pore diameter: 10 μm) to obtain an anisotropic conductive paste having a conductive particle content of 10% by weight.

(3) Production of connection structure A transparent glass substrate having an ITO electrode pattern with L / S of 30 μm / 30 μm formed on the upper surface was prepared. Further, a semiconductor chip was prepared in which a copper electrode pattern having L / S of 30 μm / 30 μm was formed on the lower surface.

  Moreover, the composite apparatus provided with the dispenser as shown to Fig.3 (a) and the ultraviolet irradiation lamp as a light irradiation apparatus connected to this dispenser was prepared.

While moving the composite apparatus, the anisotropic conductive paste obtained was applied from the syringe of the dispenser to the upper surface of the transparent glass substrate so as to have a thickness of 30 μm to form an anisotropic conductive paste layer. Further, while moving the composite device and applying the anisotropic conductive paste, using the ultraviolet irradiation lamp on the anisotropic conductive paste layer, the ultraviolet irradiation of 420 nm is irradiated so that the light irradiation intensity becomes 50 mW / cm ^2. Then, the anisotropic conductive paste layer was B-staged by photopolymerization. The time T from the time when the anisotropic conductive paste was applied to the transparent glass substrate to the time when the anisotropic conductive paste layer was irradiated with light was 0.5 seconds. .

  Next, the semiconductor chip was stacked on the upper surface of the B-staged anisotropic conductive paste layer so that the electrodes face each other. Then, while adjusting the temperature of the head so that the temperature of the anisotropic conductive paste layer becomes 185 ° C., a pressure heating head is placed on the upper surface of the semiconductor chip, and a pressure of 3 MPa is applied to make the B-staged different The isotropic conductive paste layer was completely cured at 185 ° C. to obtain a connection structure.

(Example 2)
An anisotropic conductive paste was obtained in the same manner as in Example 1 except that the epoxy acrylate was changed to urethane acrylate ("EBECRYL8804" manufactured by Daicel-Cytec Co., Ltd.) during the preparation of the anisotropic conductive paste. A connection structure was obtained in the same manner as in Example 1 except that the obtained anisotropic conductive paste was used.

(Example 3)
An anisotropic conductive paste is applied using a dispenser shown in FIG. 4A and an ultraviolet irradiation lamp as a light irradiation device not connected to the dispenser, instead of the composite device shown in FIG. A connection structure was obtained in the same manner as in Example 1 except that the light was irradiated immediately after the completion of. The time T from application to irradiation with light was 2 seconds.

Example 4
A connection structure was obtained in the same manner as in Example 3 except that the time T from application to light irradiation was changed to 3 seconds.

(Example 5)
An anisotropic conductive paste was obtained in the same manner as in Example 3 except that the epoxy acrylate was changed to urethane acrylate ("EBECRYL8804" manufactured by Daicel-Cytec Co., Ltd.) when preparing the anisotropic conductive paste. A connection structure was obtained in the same manner as in Example 3 except that the obtained anisotropic conductive paste was used.

(Reference Example 1)
An anisotropic conductive paste was obtained in the same manner as in Example 1 except that the acylphosphine oxide compound as a photopolymerization initiator was not used in the production of the anisotropic conductive paste.

  A transparent glass substrate having an ITO electrode pattern with an L / S of 30 μm / 30 μm formed on the upper surface was prepared. Further, a semiconductor chip was prepared in which a copper electrode pattern having L / S of 30 μm / 30 μm was formed on the lower surface.

  On the upper surface of the transparent glass substrate, the obtained anisotropic conductive paste was applied from a syringe of a dispenser to a thickness of 30 μm to form an anisotropic conductive paste layer. No light was applied during and after application.

  Next, the semiconductor chip was laminated on the upper surface of the anisotropic conductive paste layer so that the electrodes face each other. Then, while adjusting the temperature of the head so that the temperature of the anisotropic conductive paste layer becomes 185 ° C., a pressure heating head is placed on the upper surface of the semiconductor chip and a pressure of 3 MPa is applied to form the anisotropic conductive paste layer. Completely cured at 185 ° C. to obtain a connection structure.

(Evaluation)
(1) Viscosity of anisotropic conductive paste before application Using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.), the viscosity was measured at 25 ° C. and 2.5 rpm.

(2) Leak Evaluation Using the obtained connection structure, it was measured with a tester whether or not a leak occurred in 20 adjacent electrodes.

(3) Presence / absence of voids In the obtained connection structure, whether or not voids were generated in the cured product layer formed of the anisotropic conductive paste layer was visually observed from the lower surface side of the transparent glass substrate.

  The results are shown in Table 1 below.

  In Examples 1 to 5, since the anisotropic conductive material applied with the dispenser is cured before dripping, the anisotropic conductive material does not spread beyond the coating width and is not intended outside the specific region. It did not protrude.

DESCRIPTION OF SYMBOLS 1 ... Connection structure 2 ... 1st connection object member 2a ... Upper surface 2b ... Electrode 3 ... Hardened | cured material layer 3a ... Upper surface 3A ... Anisotropic conductive material layer 3B ... An anisotropic conductive material layer made into B stage 4 ... 2nd connection object member 4a ... lower surface 4b ... electrode 5 ... electroconductive particle 11 ... composite apparatus 12 ... dispenser 12a ... syringe 12b ... grip part 13 ... light irradiation apparatus 13a ... light irradiation apparatus main body 13b ... light irradiation part 21 ... light Irradiation device 21a ... Light irradiation device body 21b ... Light irradiation unit 31 ... Stand

According to a wide aspect of the present invention, an anisotropic conductive material containing conductive particles (an anisotropic conductive material containing a photobase generator that generates a base by light irradiation) is formed on the upper surface of the first connection target member. The anisotropic conductive material layer is applied to the anisotropic conductive material layer, and the anisotropic conductive material layer is cured by irradiating the anisotropic conductive material layer with light. A step of forming a conductive conductive material layer into a B-stage, and a second connection target member is further laminated on the upper surface of the anisotropic conductive material layer that has been converted into a B-stage, thereby forming the B-staged anisotropic conductive material. And a step of curing the B-staged anisotropic conductive material layer by applying heat to the material layer.

According to a wide aspect of the present invention, there is provided a method for manufacturing a connection structure for connecting a semiconductor chip and a glass substrate , wherein a curable compound, a thermosetting agent, and a photocuring initiator are formed on the upper surface of the first connection target member. anisotropic conductive material is coated, and a step of forming an anisotropic conductive material layer, by irradiating light to the anisotropic conductive material layer, the anisotropic conductive material containing conductive particles and A step of curing the layer to form a B-stage of the anisotropic conductive material layer, and further laminating a second connection target member on the upper surface of the B-staged anisotropic conductive material layer Curing the B-staged anisotropic conductive material layer by applying heat to the B-staged anisotropic conductive material layer, and the second connection target member and the step as a first connection object member, Ru with the semiconductor chip and the glass substrate Method for producing a connection structure is provided.

Claims (9)

Applying an anisotropic conductive material containing conductive particles to the upper surface of the first connection target member to form an anisotropic conductive material layer;
Irradiating the anisotropic conductive material layer with light to advance the curing of the anisotropic conductive material layer and forming the anisotropic conductive material layer into a B-stage;
A second connection target member is further laminated on the upper surface of the B-staged anisotropic conductive material layer, and heat is applied to the B-staged anisotropic conductive material layer, thereby providing the B-staged anisotropic conductive material layer. And a step of curing the staged anisotropic conductive material layer. In the step of forming the anisotropic conductive material layer and the step of converting the anisotropic conductive material layer into a B-stage,
The method for manufacturing a connection structure according to claim 1, wherein the time from application of the anisotropic conductive material to irradiation with light is within a range of 0 to 3 seconds. In the step of forming the anisotropic conductive material layer and the step of converting the anisotropic conductive material layer into a B-stage,
The manufacturing method of the connection structure of Claim 1 which irradiates light to the said anisotropic conductive material layer, apply | coating the said anisotropic conductive material. In the step of forming the anisotropic conductive material layer and the step of converting the anisotropic conductive material layer into a B-stage,
The manufacturing method of the connection structure of Claim 3 which is within the range for 0 to 3 second after apply | coating the said anisotropic conductive material and irradiating light. In the step of forming the anisotropic conductive material layer and the step of converting the anisotropic conductive material layer into a B-stage,
The manufacturing method of the connection structure of Claim 1 which irradiates light to the said anisotropic conductive material layer simultaneously with application | coating of the said anisotropic conductive material, or immediately after application | coating. In the step of forming the anisotropic conductive material layer and the step of converting the anisotropic conductive material layer into a B-stage,
The method for manufacturing a connection structure according to claim 5, wherein the time from application of the anisotropic conductive material to irradiation with light is within a range of 0 to 3 seconds.   The anisotropic conductive material containing a curable compound, a thermosetting agent, a photocuring initiator, and conductive particles is used as the anisotropic conductive material. Method for manufacturing the connection structure of the present invention. In the step of forming the anisotropic conductive material layer and the step of converting the anisotropic conductive material layer into a B-stage,
The manufacturing method of the connection structure of any one of Claims 1-6 using a composite apparatus provided with a dispenser and the light irradiation apparatus connected to this dispenser. In the step of forming the anisotropic conductive material layer and the step of converting the anisotropic conductive material layer into a B-stage,
The manufacturing method of the connection structure of Claim 7 using the composite apparatus provided with a dispenser and the light irradiation apparatus connected to this dispenser.

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