WO2015119131A1 - 異方性導電フィルム及びその製造方法 - Google Patents
異方性導電フィルム及びその製造方法 Download PDFInfo
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- WO2015119131A1 WO2015119131A1 PCT/JP2015/053040 JP2015053040W WO2015119131A1 WO 2015119131 A1 WO2015119131 A1 WO 2015119131A1 JP 2015053040 W JP2015053040 W JP 2015053040W WO 2015119131 A1 WO2015119131 A1 WO 2015119131A1
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- resin layer
- insulating resin
- anisotropic conductive
- conductive film
- thermal
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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Definitions
- the present invention relates to an anisotropic conductive film and a method for producing the same.
- Anisotropic conductive films are widely used for mounting electronic components such as IC chips, and in recent years, from the viewpoint of application to high mounting density, improved connection reliability and insulation, improved conductive particle capture rate,
- Patent Document an anisotropic conductive film formed of conductive particles for anisotropic conductive connection arranged in a single layer and an insulating resin layer having a two-layer structure has been proposed (Patent Document). 1).
- conductive particles are arranged in a single layer and densely in an adhesive layer, and the adhesive layer is biaxially stretched to form a sheet in which conductive particles are arranged.
- Another insulating resin layer that contains a thermosetting resin but does not contain a latent curing agent on the conductive particles transferred to the insulating resin layer containing the thermosetting resin and the latent curing agent.
- the anisotropic conductive film of Patent Document 1 uses an insulating resin layer that does not contain a latent curing agent, it contains a latent curing agent by heating during anisotropic conductive connection. Since a relatively large resin flow easily occurs in the insulating resin layer that is not formed, and the conductive particles easily flow along the flow, the conductive particles are arranged at equal intervals in a single layer by biaxial stretching. Therefore, problems such as a decrease in the capture rate of conductive particles and occurrence of short circuits occur.
- the object of the present invention is to solve the above-mentioned problems of the prior art, in an anisotropic conductive film having a multilayer structure having conductive particles arranged in a single layer, good conductive particle capture rate, good connection It is to realize reliability and reduction of occurrence of short circuit.
- the inventor arranges the conductive particles as a single layer on one side of the photopolymerizable resin layer, fixes the conductive particles to the photopolymerization resin by irradiating with ultraviolet rays, and further heat or light on the fixed conductive particles.
- an anisotropic conductive film in which two polymerizable resin layers that are polymerized by the above are laminated, or around the fixed conductive particles, an intermediate insulating resin layer is provided as a stress relaxation layer applied to the conductive particles.
- the object of the present invention can be achieved by forming an anisotropic conductive film in which a polymerizable resin layer that is polymerized by heat or light is laminated, and the present invention has been completed.
- the present invention is an anisotropic conductive film in which a first insulating resin layer, a second insulating resin layer, and a third insulating resin layer are sequentially laminated,
- the first insulating resin layer is formed of a photopolymerization resin;
- the second insulating resin layer and the third insulating resin layer are each formed of a thermal cation or thermal anion polymerizable resin, a photo cation or photo anion polymerizable resin, a thermal radical polymerizable resin, or a photo radical polymerizable resin,
- an anisotropic conductive film in which conductive particles for anisotropic conductive connection are arranged in a single layer on the surface of the first insulating resin layer on the second insulating resin layer side.
- this anisotropic conductive film is referred to as a first anisotropic conductive film.
- the second insulating resin layer and the third insulating resin layer are preferably thermopolymerizable resin layers using a thermal polymerization initiator that initiates a polymerization reaction by heating.
- a photopolymerizable resin layer using a photopolymerization initiator that initiates a polymerization reaction by light may be used.
- a thermal / photopolymerizable resin layer in which a thermal polymerization initiator and a photopolymerization initiator are used in combination may be used.
- the present invention also provides a method for producing the first anisotropic conductive film described above, wherein the following steps (A) to (D): Step (A) Arranging the conductive particles in a single layer on the photopolymerizable resin layer; Process (B) A step of causing a photopolymerization reaction by irradiating the photopolymerizable resin layer in which the conductive particles are arranged with ultraviolet rays to form a first insulating resin layer having the conductive particles fixed on the surface; Process (C) Second insulation formed on the surface of the first insulating resin layer on the conductive particle side with a thermal cation or thermal anion polymerizable resin, a photo cation or photo anion polymerizable resin, a thermal radical polymerizable resin, or a photo radical polymerizable resin.
- Process (D) A third insulating resin layer formed of a thermal cation or thermal anion polymerizable resin, a photo cation or photo anion polymerizable resin, a thermal radical polymerizable resin, or a photo radical polymerizable resin on one surface of the second insulating resin layer Laminating the layers; Have The manufacturing method of the anisotropic conductive film which performs a process (D) before or after a process (C) is provided.
- the present invention provides a connection structure in which the first electronic component is anisotropically conductively connected to the second electronic component using the first anisotropic conductive film described above.
- the present invention is an anisotropic conductive film in which a first insulating resin layer, an intermediate insulating resin layer, and a second insulating resin layer are sequentially laminated,
- the first insulating resin layer is formed of a photopolymerization resin;
- the second insulating resin layer is formed of a thermal cation or thermal anion polymerizable resin, a photo cation or photo anion polymerizable resin, a thermal radical polymerizable resin, or a photo radical polymerizable resin,
- the intermediate insulating resin layer is formed of a resin not containing a polymerization initiator, Conductive particles for anisotropic conductive connection are arranged as a single layer on the second insulating resin layer side surface of the first insulating resin layer, and the conductive particles are in contact with the intermediate insulating resin layer.
- this anisotropic conductive film is referred to as a second anisotropic conductive film.
- the second insulating resin layer is preferably a heat-polymerizable resin layer using a heat-polymerization initiator that starts a polymerization reaction by heating. It may be a photopolymerizable resin layer using a photopolymerization initiator that starts. A thermal / photopolymerizable resin layer in which a thermal polymerization initiator and a photopolymerization initiator are used in combination may be used.
- the present invention also provides a method for producing the above-described second anisotropic conductive film, which comprises the following steps [A] to [D]: Process [A] Arranging the conductive particles in a single layer on the photopolymerizable resin layer; Process [B] A step of causing a photopolymerization reaction by irradiating the photopolymerizable resin layer in which the conductive particles are arranged with ultraviolet rays to form a first insulating resin layer having the conductive particles fixed on the surface; Process [C] Forming a second insulating resin layer formed of a thermal cation or thermal anion polymerizable resin, a photo cation or photo anion polymerizable resin, a thermal radical polymerizable resin, or a photo radical polymerizable resin; Process [D] Forming an intermediate insulating resin layer formed of a resin not containing a polymerization initiator on the conductive particle side surface of the first insulating resin layer; Have (i) Step [D] is performed after step
- the present invention provides a connection structure in which the first electronic component is anisotropically conductively connected to the second electronic component by the above-described second anisotropic conductive film.
- the first anisotropic conductive film and the second anisotropic conductive film of the present invention were laminated on a first insulating resin layer (photopolymerized resin) obtained by photopolymerization of a photopolymerizable resin layer, It has a second insulating resin layer that is polymerized by heat or light, and further, conductive particles for anisotropic conductive connection are formed in a single layer on the surface of the first insulating resin layer on the second insulating resin layer side. Is arranged in. Therefore, the conductive particles can be firmly fixed by the photopolymerized first insulating resin layer.
- the photopolymerizable resin when the photopolymerizable resin is photopolymerized when the first insulating resin layer is formed, if the ultraviolet ray is irradiated from the conductive particle side, the photopolymerizable resin below the conductive particle (back side) is affected by the conductive particle. Therefore, the ultraviolet rays are not sufficiently irradiated. For this reason, in the photopolymerized resin formed by irradiation, the area shaded by the conductive particles has a lower curing rate than the area that was not shaded, and the conductive particles are better at the time of anisotropic conductive connection. Pushed in. Therefore, the first anisotropic conductive film and the second anisotropic conductive film of the present invention can achieve good conduction reliability and insulation (low occurrence rate of short circuit).
- the first anisotropic conductive film of the present invention not only the second insulating resin layer but also the third insulating resin layer is laminated on the first insulating resin layer on which the conductive particles are arranged. Therefore, the stress at the time of using the anisotropic conductive film of this invention for anisotropic conductive connection can be relieve
- the anisotropic conductive film in the second anisotropic conductive film, an intermediate insulating resin layer is provided around the conductive particles, and this intermediate insulating resin layer is used for winding and unwinding the anisotropic conductive film.
- the stress applied to the conductive particles is alleviated at the time of conveyance, at the time of drawing the film in the anisotropic conductive connection step, and the like. Therefore, the anisotropic conductive film of the present invention can achieve a good conductive particle capture rate, conduction reliability, and a low short-circuit occurrence rate.
- the photopolymerizable resin is conductive when irradiated with ultraviolet rays from the opposite side or both sides of the conductive particles. Immobilization of the particles is promoted, and stable quality can be ensured in the production line for the anisotropic conductive film.
- an anisotropic conductive film is subjected to unnecessary external stress in the process of winding the anisotropic conductive film on a reel after it is manufactured or pulling out the film from the reel during anisotropic conductive connection, The influence of external stress is less likely to affect the arrangement of the conductive particles before the conductive conductive connection.
- the second insulating resin layer or the third insulating resin layer is formed of a polymerizable resin that reacts with heat, and in the second anisotropic conductive film,
- the anisotropic conductive connection of the electronic component using the anisotropic conductive film is the same as the connection method using the normal anisotropic conductive film. It can be carried out.
- the anisotropic conductive connection between the first electronic component and the second electronic component using the anisotropic conductive film is pushed by a connection tool. May be performed until the photoreaction is completed.
- the connection tool or the like may be heated to promote resin flow or particle pushing.
- the photoreaction is completed in the same manner as described above.
- the connection tool may be pressed and heated.
- the light transmitting property is used. Light may be irradiated from the electronic component side having
- FIG. 1 is a cross-sectional view of the first anisotropic conductive film of the present invention.
- Drawing 2 is an explanatory view of the process (A) in the manufacturing method of the 1st anisotropic conductive film of the present invention.
- FIG. 3A is an explanatory diagram of the step (B) in the method for producing the first anisotropic conductive film of the present invention.
- FIG. 3B is an explanatory diagram of the step (B) in the method for producing the first anisotropic conductive film of the present invention.
- FIG. 4A is explanatory drawing of the process (C) in the manufacturing method of the 1st anisotropic conductive film of this invention.
- FIG. 4B is explanatory drawing of the process (C) in the manufacturing method of the 1st anisotropic conductive film of this invention.
- FIG. 5 is an explanatory diagram of the step (D) in the method for producing the first anisotropic conductive film of the present invention. It is sectional drawing of the 1st anisotropic conductive film of this invention.
- FIG. 6 is an explanatory diagram of the step (D) in the method for producing the first anisotropic conductive film of the present invention.
- FIG. 7A is a cross-sectional view of the second anisotropic conductive film of the present invention.
- FIG. 7B is a cross-sectional view of a modified embodiment of the second anisotropic conductive film of the present invention.
- FIG. 7C is a cross-sectional view of a modified embodiment of the second anisotropic conductive film of the present invention.
- FIG. 8 is an explanatory diagram of the step [A] in the method for producing the second anisotropic conductive film of the present invention.
- FIG. 9A is explanatory drawing of process [B] in the manufacturing method of the 2nd anisotropic conductive film of this invention.
- FIG. 9B is explanatory drawing of process [B] in the manufacturing method of the 2nd anisotropic conductive film of this invention.
- FIG. 10 is an explanatory diagram of the step [C] in the method for producing the second anisotropic conductive film of the present invention.
- FIG. 11 is an explanatory diagram when step [D] is performed by method (i) in the method for producing a second anisotropic conductive film of the present invention.
- FIG. 12 is an explanatory diagram of a subsequent step of the step [D] performed by the method (i).
- FIG. 13 is sectional drawing of the 2nd anisotropic conductive film obtained by the post process of process [D] performed by method (i).
- FIG. 14 is an explanatory view when the step [D] is performed by the method (ii) in the production of the second anisotropic conductive film of the present invention.
- FIG. 15 is an explanatory diagram of the subsequent step of the step [D] performed by the method (ii).
- FIG. 16 is a cross-sectional view of the anisotropic conductive film obtained in the subsequent step of the step [D] performed by the method (ii).
- FIG. 1 is a cross-sectional view of a first anisotropic conductive film 1A according to an embodiment of the present invention.
- the first anisotropic conductive film 1 ⁇ / b> A the first insulating resin layer 2, the second insulating resin layer 3, and the third insulating resin layer 4 are sequentially laminated, and the second insulation of the first insulating resin layer 2.
- Conductive particles 10 for anisotropic conductive connection are arranged in a single layer on the surface 2 a on the side of the conductive resin layer 3.
- the first insulating resin layer 2 constituting the first anisotropic conductive film 1A is formed of a photopolymerization resin. More specifically, for example, it is formed by photo radical polymerization of a photo radical polymerizable resin layer containing an acrylate compound and a photo radical polymerization initiator. Since the first insulating resin layer 2 is photopolymerized, the conductive particles 10 can be appropriately fixed. That is, even if the anisotropic conductive film 1A is heated at the time of anisotropic conductive connection, the first insulating resin layer 2 is difficult to flow. Therefore, the conductive particles 10 are caused to flow unnecessarily due to the resin flow. Can be suppressed.
- the region 2X in which the conductive particles 10 exist on the second insulating resin layer 3 side in the first insulating resin layer 2 (that is, the conductive particles 10 and the first conductive film 10).
- the region located between the outer surface 2b of the insulating resin layer 2) and the curing rate of the region 2Y where the conductive particles 10 are not present in the first insulating resin layer 2 are preferably lower.
- the acrylate compound and the photo radical polymerization initiator that have not been photocured may remain.
- the insulating resin in the region 2 ⁇ / b> X is easily excluded at the time of anisotropic conductive connection, so that the conductive particles 10 are formed on the first insulating resin layer 2. Although it is difficult to move in the plane direction, it is pushed in well in the thickness direction. Therefore, the conductive particle capture rate can be improved, and the connection reliability and insulation can be improved.
- the curing rate is a numerical value defined as a vinyl group reduction ratio
- the curing rate of the region 2X of the first insulating resin layer is preferably 40 to 80%
- the curing rate of the region 2Y is preferably 70%. ⁇ 100%.
- the difference in the curing rate between the region 2X and the region 2Y is adjusted by the balance between the improvement of the conductive particle capture rate and the stability of the product quality.
- a conventionally well-known photopolymerizable acrylate can be used as an acrylate compound used as an acrylate unit.
- monofunctional (meth) acrylate here, (meth) acrylate includes acrylate and methacrylate
- bifunctional or more polyfunctional (meth) acrylate can be used.
- polyfunctional (meth) acrylate it is preferable to use polyfunctional (meth) acrylate as at least a part of the acrylic monomer so that the insulating resin layer can be thermally cured at the time of anisotropic conductive connection.
- the amount is preferably 2 to 70% by mass, more preferably 10 to 50% by mass.
- Polymerization initiator As a photoinitiator used for formation of the 1st insulating resin layer, it can select suitably from well-known radical photopolymerization initiators etc., for example. More specifically, an acetophenone photopolymerization initiator, a benzyl ketal photopolymerization initiator, a phosphorus photopolymerization initiator, and the like can be given. In addition to the photoradical polymerization initiator, a thermal radical polymerization initiator may be used. Examples of the thermal radical polymerization initiator include organic peroxides and azo compounds. In particular, an organic peroxide that does not generate nitrogen that causes bubbles can be preferably used.
- the photopolymerization initiator used is too small relative to 100 parts by weight of the acrylate compound, the photopolymerization will not proceed sufficiently, and if it is too large, it will cause a decrease in rigidity. More preferably, it is 0.5 to 15 parts by mass.
- the first insulating resin layer 2 may contain an epoxy compound and a thermal cation or a thermal anion polymerization initiator or a photo cation or a photoanion polymerization initiator, if necessary. Thereby, delamination strength can be improved.
- the polymerization initiator used together with the epoxy compound will be described in the second insulating resin layer 3.
- the first insulating resin layer 2 is further used in combination with a film forming resin such as a phenoxy resin, an unsaturated polyester resin, a saturated polyester resin, a urethane resin, a butadiene resin, a polyimide resin, a polyamide resin, or a polyolefin resin. be able to.
- the thickness is preferably 1.0 to 6.0 ⁇ m.
- the thickness is preferably 2.0 to 5.0 ⁇ m.
- the first insulating resin layer 2 is formed, for example, on a photopolymerizable resin layer containing a photoradical polymerizable resin and a photoradical polymerization initiator, by a film transfer method, a mold transfer method, an ink jet method, or electrostatic adhesion. It can be carried out by adhering conductive particles to a single layer by a method such as a method, and irradiating ultraviolet rays from the conductive particle side to perform photopolymerization.
- the curing rate of the region 2X of the first insulating resin layer can be suppressed relatively low with respect to the curing rate of the region 2Y, and the capture rate of the conductive particles can be improved. it can.
- the ultraviolet rays to the photopolymerizable resin forming the first insulating resin layer 2 may be performed from the side opposite to the conductive particles 10.
- the difference in the curing rate between the region 2X and the region 2Y is substantially eliminated in the first insulating resin layer. That is, photocuring of the 1st insulating resin layer 2 advances, and stable quality can be ensured with the production line of an anisotropic conductive film.
- the anisotropic conductive film is formed long and wound on a reel, the pressure applied to the conductive particles 10 from the start to the end of winding can be made substantially the same, and the disorder of the arrangement of the conductive particles 10 can be prevented. can do.
- the photopolymerization may be performed in one step (that is, one light irradiation) or may be performed in two steps (that is, two light irradiations).
- irradiating ultraviolet rays only from the conductive particle side causes the curing rate of the region 2X of the first insulating resin layer to be relatively lower than the curing rate of the region 2Y. 10 is preferable from the viewpoint of improving the capture rate.
- the first-stage light irradiation may be performed from the conductive particle 10 side, and the second-stage light irradiation may be performed from the opposite side to the first stage in order to stabilize the quality.
- the first insulating resin layer 2 is irradiated in the oxygen-containing atmosphere (in the air). You may carry out from the other side.
- This second-stage light irradiation may be performed by adjusting the irradiation intensity so that the curing rate of the region 2X is lower than the curing rate of the region 2Y or by using a mask.
- the curing rate in the first stage of the region 2X of the first insulating resin layer is preferably 10 to 50%, and the curing rate in the second stage is preferably 40 to 80%.
- the curing rate in the first stage of the region 2Y is preferably 30 to 90%, and the curing rate in the second stage is preferably 70 to 100%.
- the minimum melt viscosity of the first insulating resin layer 2 after the photopolymerization is preferably higher than the minimum melt viscosity of the second insulating resin layer 3, and specifically measured by a rheometer [first insulating resin layer
- the minimum melt viscosity (mPa ⁇ s) 2 / [the minimum melt viscosity (mPa ⁇ s) of the second insulating resin layer 3] is preferably 1 to 1000, more preferably 4 to 400.
- the preferred minimum melt viscosity for each of the first insulating resin layers 2 is 100 to 100,000 mPa ⁇ s, more preferably 500 to 50,000 mPa ⁇ s.
- the second insulating resin layer 3 is preferably 0.1 to 10000 mPa ⁇ s, more preferably 0.5 to 1000 mPa ⁇ s.
- the conductive particles 10 can be appropriately selected from those used in conventionally known anisotropic conductive films.
- metal particles such as nickel, cobalt, silver, copper, gold, and palladium, metal-coated resin particles, and the like can be given. Two or more kinds can be used in combination.
- the average particle diameter of the conductive particles is too small, the variation in the height of the wiring cannot be absorbed and the resistance tends to be high, and if it is too large, it tends to cause a short circuit. More preferably, it is 2 to 6 ⁇ m.
- the number is preferably 50 to 50000 per square mm, more preferably 200 to 30000.
- the position of the conductive particles 10 in the thickness direction of the first insulating resin layer 2 is not embedded in the first insulating resin layer 2 but bites into the second insulating resin layer 3. It is preferable.
- the conductive particles 10 are buried in the first insulating resin layer 2, the conductive particles are not uniformly pushed into the anisotropic conductive connection, and the conduction resistance of the connection structure in which the electronic component is anisotropically conductively connected is high. This is because there is concern about becoming.
- the degree of biting is preferably 10 to 90%, more preferably 20 to 80%, of the average particle diameter of the conductive particles 10 from the balance between the conductive particle capture rate and the conduction resistance.
- the second insulating resin layer 3 and the third insulating resin layer 4 are respectively a thermal cation or thermal anion polymerizable resin, a photo cation or photo anion polymerizable resin, a thermal radical polymerizable resin, or a photo radical polymerizable resin. It is formed. More specifically, it contains an epoxy compound, a thermal cation or thermal anion polymerization initiator or a photo cation or photoanion polymerization initiator, a polymerizable resin layer that polymerizes by heat or light, or an acrylate compound, and a thermal radical. Alternatively, it comprises a polymerizable resin layer that undergoes radical polymerization by heat or light containing a photo radical polymerization initiator.
- the amount of the polymerizable resin in the second insulating resin layer 3 is larger than that in the third insulating resin layer 4.
- the 3rd insulating resin layer 4 may contain an additive within 10 mass%.
- epoxy compound As an epoxy compound which forms the 2nd insulating resin layer 3 or the 3rd insulating resin layer 4, the compound or resin which has a 2 or more epoxy group in a molecule
- numerator is mentioned preferably. These may be liquid or solid.
- thermal cationic polymerization initiator As the thermal cationic polymerization initiator for forming the second insulating resin layer 3 or the third insulating resin layer 4, known thermal cationic polymerization initiators for epoxy compounds can be employed. Iodonium salts, sulfonium salts, phosphonium salts, ferrocenes, and the like that generate water can be used, and in particular, aromatic sulfonium salts that exhibit good potential with respect to temperature can be preferably used.
- the amount of the thermal cationic polymerization initiator is preferably 2 to 60 masses per 100 mass parts of the epoxy compound. Part, more preferably 5 to 40 parts by weight.
- thermal anionic polymerization initiator As the thermal anionic polymerization initiator for forming the second insulating resin layer 3 or the third insulating resin layer 4, known thermal anionic polymerization initiators for epoxy compounds can be employed. Use aliphatic amine compounds, aromatic amine compounds, secondary or tertiary amine compounds, imidazole compounds, polymercaptan compounds, boron trifluoride-amine complexes, dicyandiamide, organic acid hydrazides, etc. In particular, an encapsulated imidazole compound showing a good potential with respect to temperature can be preferably used.
- the amount of the thermal anionic polymerization initiator is preferably 2 to 60 masses per 100 mass parts of the epoxy compound. Part, more preferably 5 to 40 parts by weight.
- Photocationic polymerization initiator and photoanionic polymerization initiator A well-known thing can be used suitably as a photocationic polymerization initiator or photoanion polymerization initiator for epoxy compounds.
- the acrylate compound that forms the second insulating resin layer 3 or the third insulating resin layer 4 can be used by appropriately selecting from the acrylate compounds described for the first insulating resin layer 2.
- the thermal radical polymerization initiator used together with the acrylate compound is the heat described with respect to the first insulating resin layer 2. It can be used by appropriately selecting from radical polymerization initiators.
- the amount of the thermal radical polymerization initiator used is preferably 2 to 60 parts by weight, more preferably 5 to 40 parts per 100 parts by weight of the acrylate compound. Part by mass.
- Photo radical polymerization initiator As a radical photopolymerization initiator for the acrylate compound, a known radical photopolymerization initiator can be used.
- the amount of the radical photopolymerization initiator used is preferably 2 to 60 parts by weight, more preferably 5 to 40 parts per 100 parts by weight of the acrylate compound. Part by mass.
- the layer thickness of the second insulating resin layer 3 is preferably 3 to 20 ⁇ m, more preferably 5 to 15 ⁇ m, from the viewpoint of capturing conductive particles after anisotropic connection.
- the layer thickness of the third insulating resin layer 4 is preferably 1 ⁇ 2 or less of the layer thickness of the second insulating resin layer 3 in order to make it easy to control the pressing.
- the first anisotropic conductive film can be manufactured by performing the following steps (A) to (D).
- Step (A) As shown in FIG. 2, the conductive particles 10 are arranged in a single layer on the photopolymerizable resin layer 20 formed on the release film 30 as necessary.
- positioning the electrically-conductive particle 10 in the photopolymerizable resin layer 20 with a single layer Biaxial stretching operation of the resin film which fixed the electrically-conductive particle of Example 1 of the patent 478938 with the adhesive was carried out. It is possible to adopt a method of using, a method of using a mold disclosed in JP 2010-33793 A, or the like.
- the conductive particles 10 are preferably arranged at predetermined intervals in the vertical and horizontal directions. In consideration of the size of the connection target, conduction reliability, insulation, conductive particle trapping rate, etc., the two-dimensional closest interparticle distance is preferably about 1 to 100 ⁇ m.
- the photopolymerizable resin layer 20 on which the conductive particles 10 are arranged is subjected to a photopolymerization reaction by irradiating ultraviolet rays (UV) from the conductive particle 10 side, so that the conductive particles are formed on the surface.
- the first insulating resin layer 2 on which 10 is fixed is formed.
- the curing rate of the first insulating resin layer in the region located between the surface 2b and the conductive particles 10) is set to be lower than the curing rate of the region 2Y in the first insulating resin layer 2 where the conductive particles 10 are not present. Can do. Therefore, it becomes easy to push in the conductive particles 10 at the time of anisotropic conductive connection, and the flow of the conductive particles 10 in the connection plane direction can be suppressed.
- a thermal cation or thermal anion polymerizable resin, a photo cation or photo anion polymerizable resin, a thermal radical polymerizable resin, or A second insulating resin layer 3 formed of a photo radical polymerizable resin is laminated. More specifically, for example, the second insulating resin layer 3 formed on the release film 31 by a conventional method is placed on the surface of the first insulating resin layer 2 on the conductive particle 10 side, and excessive thermal polymerization does not occur. Thermocompression bonded to. And the anisotropic conductive film of FIG. 4B can be obtained by removing the peeling film 31.
- a process (D) is performed before a process (C). That is, the laminate 5 of the second insulating resin layer 3 and the third insulating resin layer 4 is formed on the release film 31 in advance, and the second insulating resin layer 3 of the laminate 5 is formed into the first insulating property.
- the first anisotropic conductive film 1A of FIG. 1 may be obtained by laminating on the surface of the resin layer 2 on the conductive particle 10 side and removing the release films 30 and 31. ⁇ Second anisotropic conductive film >>
- FIG. 7A is a cross-sectional view of a second anisotropic conductive film 1B according to an embodiment of the present invention.
- the first insulating resin layer 2, the intermediate insulating resin layer 6 and the second insulating resin layer 3 are sequentially laminated, and the conductive particles 10 for anisotropic conductive connection are
- the single insulating resin layer 2 is disposed on the surface 2a on the second insulating resin layer 3 side as a single layer so as to penetrate at least the surface of the intermediate insulating resin layer 6 on the first insulating resin layer 2 side. It is in contact with the insulating resin layer 6.
- the first insulating resin layer 2 constituting the second anisotropic conductive film 1B is formed of a photopolymerization resin similar to the first insulating resin layer 2 of the first anisotropic conductive film 1A, and is electrically conductive.
- the particles 10 are appropriately fixed.
- the region 2X in which the conductive particles 10 exist on the second insulating resin layer 3 side in the first insulating resin layer 2 (that is, the first anisotropic conductive film 1A).
- the curing rate of the region located between the conductive particle 10 and the outer surface 2b of the first insulating resin layer 2) is compared with the curing rate of the region 2Y in the first insulating resin layer 2 where the conductive particle 10 is not present. Therefore, it is preferable to make it low.
- region 2Y can be suppressed, or the difference of a hardening rate can be eliminated substantially.
- the difference in the curing rate between the region 2X and the region 2Y is adjusted by the balance between the improvement of the conductive particle capture rate and the stability of the product quality.
- conductive particles 10 constituting the second anisotropic conductive film 1B similarly to the first anisotropic conductive film 1A, metal particles such as nickel, cobalt, silver, copper, gold, palladium, metal-coated resin particles, etc. Is mentioned. Two or more kinds can be used in combination.
- the average particle diameter of the conductive particles 10 and the amount of particles in the first insulating resin layer 2 are the same as those of the first anisotropic conductive film 1A.
- the position of the conductive particles 10 in the thickness direction of the first insulating resin layer 2 penetrates the intermediate insulating resin layer 6 without being embedded in the first insulating resin layer 2, and the second It is preferable to bite into the insulating resin layer 3. That is, in this case, the conductive particles 10 straddle the first insulating resin layer 2 and the second insulating resin layer 3. Since the conductive particles 10 penetrate the intermediate insulating resin layer 6, deformation of the conductive particles 10 at the time of anisotropic conductive connection can be made uniform, and unnecessary particle deviation can be prevented.
- the degree of biting into the surface is preferably 10 to 90% of the average particle diameter of the conductive particles 10 from the balance between the conductive particle capture rate and the conductive resistance, and more Preferably it is 20 to 80%.
- the portion of the conductive particle 10 protruding from the first insulating resin layer 2 may be covered with the intermediate insulating resin layer 6.
- the first insulating resin layer 2 and the intermediate insulating resin layer 6 may be straddled without penetrating the insulating resin layer 6.
- the portion of the conductive particles 10 protruding to the first insulating resin layer 2 side is preferably 20% or less, more preferably 10% or less of the particle diameter of the conductive particles.
- the portion of the conductive particle 10 protruding from the first insulating resin layer 2 is covered with the intermediate insulating resin layer 6, as shown in FIG. 7C
- the portion protruding from the first insulating resin layer 2 is used.
- the conductive particles 10 may be covered along the ridges of the conductive particles 10 by the intermediate insulating resin layer 6 having a thickness smaller than the conductive particle diameter.
- the intermediate insulating resin layer 6 is provided following the shape of the conductive particles 10, the deformation inhibition of the conductive particles 10 when the anisotropic conductive connection is pushed in can be controlled more precisely.
- the intermediate insulating resin layer 6 is a layer that relieves stress applied to the conductive particles 10 when the second anisotropic conductive film 1B is wound, unwound, transported, pulled out in the anisotropic conductive connection step, and the like. Is provided.
- the intermediate insulating resin layer 6 is provided around the conductive particles 10 and the stress accumulated in the conductive particles 10 is relaxed, the conductive particles generated by resin flow or compression of the conductive particles 10 during anisotropic conductive connection. The positional deviation in the connection plane direction can be suppressed. Therefore, the 2nd anisotropic conductive film 1B of this invention can implement
- the thickness of the intermediate insulating resin layer 6 is preferably 1.2 times or less, more preferably 1 time or less, and even more preferably 0.7 times or less the particle diameter of the conductive particles 10. If it is in this range, problems in quality stability such as non-uniform deformation and difficulty in capturing the conductive particles at the bump ends are less likely to occur when the conductive particles 10 are pushed in the anisotropic conductive connection. In addition, when a long anisotropic conductive film is wound on a reel or the like, the pressure applied to the conductive particles can be homogenized, and disorder of the arrangement of the conductive particles can be prevented. In addition, in order to make manufacturing conditions easier, the intermediate insulating resin layer 6 may have substantially the same thickness as the conductive particles 10.
- the intermediate insulating resin layer 6 is formed from a resin that does not contain a polymerization initiator.
- the resin forming the intermediate insulating resin layer 6 preferably has an elastic modulus comparable to that of the resin component of the other layers, and may be a polymerizable resin.
- phenoxy resin, epoxy resin, polyolefin resin, polyurethane resin, acrylic resin, or the like can be used.
- the intermediate insulating resin layer 6 contains a filler such as silica in order to effectively suppress the flow of unnecessary conductive particles 10 at the time of anisotropic conductive connection.
- the filler content in the intermediate insulating resin layer 6 is preferably 0.5 to 20% by mass.
- the second insulating resin layer 3 of the second anisotropic conductive film 1B is a thermal cation or thermal anion polymerizable resin, photo cation or light similar to the second insulating resin layer 3 of the first anisotropic conductive film 1A. It is formed of an anion polymerizable resin, a thermal radical polymerizable resin, or a photo radical polymerizable resin.
- the layer thickness of the second insulating resin layer 3 is preferably 3 to 20 ⁇ m, more preferably 5 to 15 ⁇ m, from the viewpoint of capturing conductive particles during anisotropic conductive connection.
- the second anisotropic conductive film 1B can be manufactured by performing the following steps [A] to [D].
- the conductive particles 10 are arranged in a single layer on the photopolymerizable resin layer 20 formed on the release film 30 as necessary.
- positioning the electrically-conductive particle 10 in the photopolymerizable resin layer 20 with a single layer Biaxial stretching operation of the resin film which fixed the electrically-conductive particle of Example 1 of the patent 478938 with the adhesive was carried out. It is possible to adopt a method of using, a method of using a mold disclosed in JP 2010-33793 A, or the like.
- the conductive particles 10 are preferably arranged at predetermined intervals in the vertical and horizontal directions. In consideration of the size of the connection target, conduction reliability, insulation, conductive particle trapping rate, etc., the two-dimensional closest interparticle distance is preferably about 1 to 100 ⁇ m.
- the photopolymerizable resin layer 20 in which the conductive particles 10 are arranged is subjected to a photopolymerization reaction by irradiating with ultraviolet rays (UV), and the first insulating resin layer 2 having the conductive particles 10 fixed on the surface thereof is formed.
- UV ultraviolet rays
- the first insulating resin layer 2 having the conductive particles 10 fixed on the surface thereof is formed.
- FIG. 9A ultraviolet rays (UV) are irradiated from the conductive particle 10 side.
- FIG. 9B in the first insulating resin layer 2, the conductive particles 10 are present on the second insulating resin layer 3 side 2X (the surface 2b of the first insulating resin layer 2 on the peeling film 30 side).
- first insulating resin layer in the region located between the conductive particles 10 and the conductive particles 10 can be made lower than the curing rate of the region 2Y where the conductive particles 10 do not exist in the first insulating resin layer 2. . Therefore, it becomes easy to push in the conductive particles 10 at the time of anisotropic conductive connection, and the flow of the conductive particles 10 in the connection plane direction can be suppressed.
- the insulating resin layer 3 is formed by a conventional method.
- the intermediate insulating resin layer 6 is formed on the conductive particle 10 side surface of the first insulating resin layer 2 to which the conductive particles 10 are fixed in the step [B].
- This step [D] can be carried out by the following method (i) or (ii).
- the intermediate insulating resin layer 6 is formed on the surface of the first insulating resin layer 2 to which the conductive particles 10 are fixed in the step [B] on the conductive particle 10 side. More specifically, it contains at least one resin selected from a phenoxy resin, an epoxy resin, a polyolefin resin, a polyurethane resin, and an acrylic resin, preferably containing a filler such as silica, without containing a polymerization initiator.
- the intermediate insulating resin layer 6 is formed by applying or spraying the coating liquid for forming the resin layer on the surface of the first insulating resin layer 2 on the conductive particle 10 side. Thereafter, as shown in FIG.
- Method (ii) As shown in FIG. 14, the second insulating resin layer 3 formed in the step [C] is coated or sprayed with the same coating liquid for forming an intermediate insulating resin layer as that shown in FIG. An intermediate insulating resin layer 6 is formed on the insulating resin layer 3.
- the intermediate insulating resin layer 6 and the conductive particles 10 on the first insulating resin layer 2 formed in the step [B] are opposed to each other and thermocompression bonded as shown in FIG. .
- the conductive particles 10 do not penetrate the intermediate insulating resin layer 6.
- the second anisotropic conductive film 1B shown in FIG. 7C can be obtained.
- the first anisotropic conductive film 1A and the second anisotropic conductive film 1B of the present invention are different from the first electronic component such as an IC chip and an IC module and the second electronic component such as a flexible substrate and a glass substrate. This can be preferably applied when conducting conductive connection.
- the connection structure thus obtained is also part of the present invention.
- the first insulating resin layer 2 side of the first anisotropic conductive film 1A and the second anisotropic conductive film 1B is arranged on a second electronic component such as a flexible substrate, and the third insulating resin on the opposite side thereof. It is preferable to arrange the layer 4 side or the second insulating resin layer 3 on a first electronic component such as an IC chip from the viewpoint of improving connection reliability.
- Examples 1 to 6 (first anisotropic conductive film), Comparative Example 1 Conductive particles are arranged in a single layer according to the operation of Example 1 of Japanese Patent No. 4778938, and a first insulating resin layer and a second insulating resin layer formed according to the composition (parts by mass) shown in Table 1
- the first anisotropic conductive film of Examples 1 to 6 having the anisotropic conductive film of Comparative Example 1 having a third insulating resin was also prepared.
- a mixed solution of an acrylate compound, a radical photopolymerization initiator, and the like was prepared with ethyl acetate or toluene so that the solid content was 50% by mass.
- This mixed liquid is applied to a polyethylene terephthalate film having a thickness of 50 ⁇ m so as to have a dry thickness of 3 ⁇ m, and is dried in an oven at 80 ° C. for 5 minutes, whereby light that is a precursor layer of the first insulating resin layer A radical polymerizable resin layer was formed.
- conductive particles Ni / Au plated resin particles, AUL 704, Sekisui Chemical Co., Ltd. having an average particle diameter of 4 ⁇ m are placed on the surface of the obtained radical photopolymerizable resin layer, and the closest distance between the conductive particles is The single layer was arranged in a lattice shape so as to be 4 ⁇ m.
- a first insulating resin layer having conductive particles fixed on the surface was formed.
- thermosetting resin A liquid mixture of a thermosetting resin and a polymerization initiator was prepared with ethyl acetate or toluene so that the solid content was 50% by mass. This mixed solution was applied to a polyethylene terephthalate film having a thickness of 50 ⁇ m so that the dry thickness was 12 ⁇ m, and dried in an oven at 80 ° C. for 5 minutes to form a second insulating resin layer. A third insulating resin layer was formed.
- the anisotropic conductive film of Comparative Example 1 was obtained by laminating the first insulating resin layer and the second insulating resin layer thus obtained so that the conductive particles were inside. Further, by laminating the third insulating resin layer on the surface of the second insulating resin layer of the laminate of the first insulating resin layer and the second insulating resin layer, the first anisotropy of Examples 1 to 6 is achieved. A conductive film was obtained.
- Example 7 A first anisotropic conductive film was obtained in the same manner as in Example 1 except that the photo-radical polymerizable resin layer was irradiated with ultraviolet rays from the conductive particle side and the side opposite to the conductive particle by an integrated light amount of 2000 mJ / cm 2. It was.
- connection structure sample was tested and evaluated for “warpage”, “initial continuity”, “conduction reliability”, and “short-circuit occurrence rate” as described below. The results are shown in Table 1.
- warp Regarding the warpage of the connection body, on the surface of the glass substrate on which the IC chip is not mounted, a warp with a width of 20 mm corresponding to the back side of the IC chip is used with a commercially available three-dimensional side length machine (Keyence Co., Ltd.). It was measured.
- the warp is preferably less than 15 ⁇ m for practical use.
- connection structure sample The conduction resistance of the connection structure sample was measured, and when it was 0.5 ⁇ or less, it was evaluated as OK.
- connection reliability The connection resistance after the connection structure sample was left in a high-temperature and high-humidity environment of 85 ° C. and 85% RH for 500 hours was measured in the same manner as the initial conductivity. From the viewpoint of practical conduction stability of the connected electronic component, this conduction resistance was evaluated as OK when it was 5 ⁇ or less, and NG when it was larger than 5 ⁇ .
- a short-circuit occurrence rate of the connected body was calculated by “number of short-circuits / total number of 7.5 ⁇ m spaces”. Since the short-circuit occurrence rate is desirably 100 ppm or less for practical use, it was evaluated as OK when it was 100 ppm or less, and NG when it was larger than 100 ppm.
- the warpage of the first anisotropic conductive films of Examples 1 to 6 was less than 15 ⁇ m.
- the first anisotropic conductive films of Examples 1 to 6 all have an initial conductivity of 0.5 ⁇ , a conduction reliability of 4 ⁇ , and a short-circuit occurrence rate of 50 ppm, and practically preferable results for all evaluation items. showed that.
- the conduction reliability was slightly inferior to that in Example 1, but there was no problem in practical use, and the results of practically preferable results were obtained for warpage, initial conductivity, and occurrence rate of short circuit as in Example 1. It was.
- the anisotropic conductive film of Comparative Example 1 had a large warp because there was no third insulating resin layer.
- Examples 8 to 17 (second anisotropic conductive film)
- the conductive particles are arranged in a single layer.
- the first insulating resin layer, the intermediate insulating resin layer, and the first insulating resin layer formed according to the formulation (parts by mass) shown in Table 2
- a first insulating resin layer having conductive particles fixed on the surface was formed in the same manner as in Example 1.
- an intermediate insulating resin layer was formed by preparing an intermediate insulating resin layer coating material with the formulation shown in Table 2 and applying it to the first insulating resin layer to which the conductive particles are fixed.
- thermosetting resin e.g., polyethylene terephthalate film having a thickness of 50 ⁇ m so as to have a dry thickness of 12 ⁇ m, and dried in an oven at 80 ° C. for 5 minutes to form a second insulating resin layer.
- Example 18 A second anisotropic conductive film was obtained in the same manner as in Example 9 except that the photo-radical polymerization type resin layer was irradiated with ultraviolet rays from the conductive particle side and the side opposite to the conductive particle by an integrated light amount of 2000 mJ / cm 2. It was.
- Example 19 A second anisotropic conductive film was obtained in the same manner as in Example 9 except that the thickness of the intermediate insulating resin layer was 5 ⁇ m. In the second anisotropic conductive film, the conductive particles do not penetrate the intermediate insulating resin layer.
- Example 20 A second anisotropic conductive film was obtained in the same manner as in Example 18 except that the thickness of the intermediate insulating resin layer was 5 ⁇ m. In the second anisotropic conductive film, the conductive particles do not penetrate the intermediate insulating resin layer.
- connection structure sample and the connection structure sample using the anisotropic conductive film of Comparative Example 1 described above were evaluated.
- the results are shown in Table 1.
- “Mounting particle capture efficiency” “The number of conductive particles actually captured on the bump of the connection structure sample after heating / pressing” against “the number of conductive particles present on the bump of the connection structure sample before heating / pressing” The percentage (%) of was obtained by the following formula and was defined as the mounting particle trapping efficiency.
- the number of conductive particles present on the bumps of the connection structure sample before heating and pressing is determined from the number density of the conductive particles and the bump area of the anisotropic conductive film before heating and pressing of the anisotropic conductive connection.
- the number of conductive particles present on the bumps of the connection structure sample after calculation and heating and pressing was determined by observation with an optical microscope. Practically, it is preferably 50% or more.
- connection reliability Similarly to Example 1, when the connection structure sample was left in a high temperature and high humidity environment of 85 ° C. and 85% RH for 500 hours, the conduction resistance was measured. Rated as NG.
- the second anisotropic conductive films of Examples 8 to 17 had a mounting particle capturing efficiency of more than 70% and a warpage of less than 15 ⁇ m.
- the second anisotropic conductive films of Examples 8 to 17 all have an initial conductivity of 0.2 ⁇ , a conduction reliability of 4 ⁇ , and a short-circuit occurrence rate of 50 ppm, and practically preferable results for all evaluation items. showed that.
- the connection structures of Examples 18 and 20 were slightly inferior in mounting particle trapping efficiency compared to Example 9, but there was no practical problem, with regard to initial conductivity, conduction reliability, warpage, and short-circuit occurrence rate. Similar to Example 9, favorable results were shown.
- connection structure of Example 19 the shape of the conductive particles connected to the bumps by microscopic observation was slightly non-uniform compared to Example 9, but the mounting particle trapping efficiency, initial conductivity, conduction Practically preferable results were shown for all evaluation items of reliability, warpage, and occurrence rate of short circuit.
- the first anisotropic conductive film and the second anisotropic conductive film of the present invention include a first insulating resin layer obtained by photo radical polymerization of a photo radical polymerizable resin layer, a thermal cation or thermal anion polymerizable resin, light A second insulating resin layer formed of a cation or photoanion polymerizable resin, a thermal radical polymerizable resin, or a photo radical polymerizable resin is laminated, and the second insulating resin layer side surface of the first insulating resin layer is laminated. Since the conductive particles are arranged in a single layer, excellent initial conductivity, conduction reliability, and insulation (low occurrence rate of short circuit) due to a good conductive particle capture rate are exhibited.
- the anisotropic conductive film since the third insulating resin layer is laminated on the second insulating resin layer, the anisotropic conductive film is used for anisotropic conductive connection.
- the stress is relaxed, and the occurrence of warpage in the connection body obtained by anisotropic conductive connection is suppressed.
- the intermediate insulating resin layer is laminated between the first insulating resin layer and the second insulating resin layer so as to surround the conductive particles. Such stress is relaxed, and the conductive particle trapping rate at the time of anisotropic conductive connection is further improved.
- the 1st anisotropic conductive film and 2nd anisotropic conductive film of this invention are useful for the anisotropic conductive connection to the wiring board of electronic components, such as an IC chip.
- the wiring of electronic components is becoming narrower, and the present invention is particularly useful when the narrowed electronic components are anisotropically conductively connected.
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Abstract
Description
第1絶縁性樹脂層が、光重合樹脂で形成され、
第2絶縁性樹脂層及び第3絶縁性樹脂層が、それぞれ熱カチオン若しくは熱アニオン重合性樹脂、光カチオン若しくは光アニオン重合性樹脂、熱ラジカル重合性樹脂、又は光ラジカル重合性樹脂で形成され、
第1絶縁性樹脂層の第2絶縁性樹脂層側表面に、異方性導電接続用の導電粒子が単層で配置されている異方性導電フィルムを提供する。以下、この異方性導電フィルムを第1異方性導電フィルムという。
工程(A)
光重合性樹脂層に、導電粒子を単層で配置する工程;
工程(B)
導電粒子を配置した光重合性樹脂層に対して紫外線を照射することにより光重合反応させ、表面に導電粒子が固定化された第1絶縁性樹脂層を形成する工程;
工程(C)
第1絶縁性樹脂層の導電粒子側表面に、熱カチオン若しくは熱アニオン重合性樹脂、光カチオン若しくは光アニオン重合性樹脂、熱ラジカル重合性樹脂、又は光ラジカル重合性樹脂で形成された第2絶縁性樹脂層を積層する工程;
工程(D)
第2絶縁性樹脂層の片面に、熱カチオン若しくは熱アニオン重合性樹脂、光カチオン若しくは光アニオン重合性樹脂、熱ラジカル重合性樹脂、又は光ラジカル重合性樹脂で形成された第3絶縁性樹脂層を積層する工程;
を有し、
工程(D)を、工程(C)の前又は後に行う異方性導電フィルムの製造方法を提供する。
第1絶縁性樹脂層が、光重合樹脂で形成され、
第2絶縁性樹脂層が、熱カチオン若しくは熱アニオン重合性樹脂、光カチオン若しくは光アニオン重合性樹脂、熱ラジカル重合性樹脂、又は光ラジカル重合性樹脂で形成され、
中間絶縁性樹脂層が重合開始剤を含まない樹脂で形成され、
第1絶縁性樹脂層の第2絶縁性樹脂層側表面に、異方性導電接続用の導電粒子が単層で配置され、該導電粒子が中間絶縁性樹脂層と接している異方性導電フィルムを提供する。
以下、この異方性導電フィルムを第2異方性導電フィルムという。
工程[A]
光重合性樹脂層に、導電粒子を単層で配置する工程;
工程[B]
導電粒子を配置した光重合性樹脂層に対して紫外線を照射することにより光重合反応させ、表面に導電粒子が固定化された第1絶縁性樹脂層を形成する工程;
工程[C]
熱カチオン若しくは熱アニオン重合性樹脂、光カチオン若しくは光アニオン重合性樹脂、熱ラジカル重合性樹脂、又は光ラジカル重合性樹脂で形成された第2絶縁性樹脂層を形成する工程;
工程[D]
重合開始剤を含まない樹脂で形成された中間絶縁性樹脂層を、第1絶縁性樹脂層の導電粒子側表面に形成する工程;
を有し、
(i)工程[D]を工程[B]の後に行うことにより第1絶縁性樹脂層の導電粒子側表面に中間絶縁性樹脂層を形成し、次いで該中間絶縁性樹脂層と工程[C]で形成した第2絶縁性樹脂層を積層するか、又は
(ii)工程[C]で形成した第2絶縁性樹脂層上に、重合開始剤を含まない樹脂で形成された中間絶縁性樹脂層を形成し、次いで該中間絶縁性樹脂層を、工程[B]で形成した第1絶縁性樹脂層の導電粒子側表面に積層する製造方法を提供する。
<<第1異方性導電フィルム>>
第1異方性導電フィルム1Aを構成する第1絶縁性樹脂層2は、光重合樹脂で形成されている。より具体的には、例えば、アクリレート化合物と光ラジカル重合開始剤とを含む光ラジカル重合性樹脂層を光ラジカル重合させたもので形成される。第1絶縁性樹脂層2が光重合していることにより、導電粒子10を適度に固定化できる。即ち、異方性導電接続時に異方性導電フィルム1Aが加熱されても第1絶縁性樹脂層2は流れ難いので、樹脂流れにより導電粒子10が不用に流されてショートが発生することを大きく抑制することができる。
アクリレート単位となるアクリレート化合物としては、従来公知の光重合性アクリレートを使用することができる。例えば、単官能(メタ)アクリレート(ここで、(メタ)アクリレートにはアクリレートとメタクリレートとが包含される)、二官能以上の多官能(メタ)アクリレートを使用することができる。本発明においては、異方性導電接続時に絶縁性樹脂層を熱硬化できるように、アクリル系モノマーの少なくとも一部に多官能(メタ)アクリレートを使用することが好ましい。
第1絶縁性樹脂層の形成に使用する光重合開始剤としては、例えば、公知の光ラジカル重合開始剤等の中から適宜選択して使用することができる。より具体的には、アセトフェノン系光重合開始剤、ベンジルケタール系光重合開始剤、リン系光重合開始剤等が挙げられる。
また、光ラジカル重合開始剤に加えて、熱ラジカル重合開始剤を使用してもよい。熱ラジカル重合開始剤としては、例えば、有機過酸化物やアゾ系化合物等をあげる事ができる。特に、気泡の原因となる窒素を発生しない有機過酸化物を好ましく使用することができる。
第1絶縁性樹脂層2には、必要に応じて、エポキシ化合物と、熱カチオン若しくは熱アニオン重合開始剤又は光カチオン若しくは光アニオン重合開始剤を含有させてもよい。これにより、層間剥離強度を向上させることができる。エポキシ化合物と共に使用する重合開始剤については、第2絶縁性樹脂層3で説明する。第1絶縁性樹脂層2には、必要に応じて、更にフェノキシ樹脂、不飽和ポリエステル樹脂、飽和ポリエステル樹脂、ウレタン樹脂、ブタジエン樹脂、ポリイミド樹脂、ポリアミド樹脂、ポリオレフィン樹脂などの膜形成樹脂を併用することができる。
第1絶縁性樹脂層2の層厚は、薄すぎると導電粒子捕捉率が低下する傾向があり、厚すぎると導通抵抗が高くなる傾向があるので、好ましくは1.0~6.0μm、より好ましくは2.0~5.0μmである。
第1絶縁性樹脂層2の形成は、例えば、光ラジカル重合性樹脂と光ラジカル重合開始剤とを含有する光重合性樹脂層に、フィルム転写法、金型転写法、インクジェット法、静電付着法等の手法により導電粒子を単層に付着させ、紫外線を導電粒子側から照射して光重合することにより行うことができる。紫外線を導電粒子側から照射することにより、第1絶縁性樹脂層の領域2Xの硬化率を、領域2Yの硬化率に対して相対的に低く抑制し、導電粒子の捕捉率を向上させることができる。
導電粒子10としては、従来公知の異方性導電フィルムに用いられているものの中から適宜選択して使用することができる。例えばニッケル、コバルト、銀、銅、金、パラジウムなどの金属粒子、金属被覆樹脂粒子などが挙げられる。2種以上を併用することもできる。
第2絶縁性樹脂層3および第3絶縁性樹脂層4は、それぞれ、熱カチオン若しくは熱アニオン重合性樹脂、光カチオン若しくは光アニオン重合性樹脂、熱ラジカル重合性樹脂、又は光ラジカル重合性樹脂で形成される。より具体的には、エポキシ化合物と、熱カチオン若しくは熱アニオン重合開始剤又は光カチオン若しくは光アニオン重合開始剤とを含有する、熱又は光により重合する重合性樹脂層、又はアクリレート化合物と、熱ラジカル又は光ラジカル重合開始剤とを含有する熱又は光によりラジカル重合する重合性樹脂層からなるものである。
第2絶縁性樹脂層3又は第3絶縁性樹脂層4を形成するエポキシ化合物としては、分子内に2つ以上のエポキシ基を有する化合物もしくは樹脂が好ましく挙げられる。これらは液状であっても、固体状であってもよい。
第2絶縁性樹脂層3又は第3絶縁性樹脂層4を形成する熱カチオン重合開始剤としては、エポキシ化合物の熱カチオン重合開始剤として公知のものを採用することができ、例えば、熱により酸を発生するヨードニウム塩、スルホニウム塩、ホスホニウム塩、フェロセン類等を用いることができ、特に、温度に対して良好な潜在性を示す芳香族スルホニウム塩を好ましく使用することができる。
第2絶縁性樹脂層3又は第3絶縁性樹脂層4を形成する熱アニオン重合開始剤としては、エポキシ化合物の熱アニオン重合開始剤として公知のものを採用することができ、例えば、熱により塩基を発生する脂肪族アミン系化合物、芳香族アミン系化合物、二級又は三級アミン系化合物、イミダゾール系化合物、ポリメルカプタン系化合物、三フッ化ホウ素-アミン錯体、ジシアンジアミド、有機酸ヒドラジッド等を用いることができ、特に温度に対して良好な潜在性を示すカプセル化イミダゾール系化合物を好ましく使用することができる。
エポキシ化合物用の光カチオン重合開始剤又は光アニオン重合開始剤としては、公知のものを適宜使用することができる。
第2絶縁性樹脂層3又は第3絶縁性樹脂層4を形成するアクリレート化合物は、第1絶縁性樹脂層2に関して説明したアクリレート化合物の中から適宜選択して使用することができる。
また、第2絶縁性樹脂層3又は第3絶縁性樹脂層4にアクリレート化合物を含有させる場合に、アクリレート化合物と共に使用する熱ラジカル重合開始剤としては、第1絶縁性樹脂層2に関して説明した熱ラジカル重合開始剤の中から適宜選択して使用することができる。
アクリレート化合物用の光ラジカル重合開始剤としては、公知の光ラジカル重合開始剤を使用することができる。
第2絶縁性樹脂層3の層厚は、異方性接続後の導電粒子捕捉性の点から、好ましくは3~20μm、より好ましくは5~15μmである。
また、第3絶縁性樹脂層4の層厚は、押圧を制御しやすくするために、第2絶縁性樹脂層3の層厚の1/2以下とすることが好ましい。
第1異方性導電フィルムは、次の工程(A)~(D)を行い、製造することができる。
図2に示すように、必要に応じて剥離フィルム30上に形成した光重合性樹脂層20に、導電粒子10を単層で配置する。導電粒子10を単層で光重合性樹脂層20に配置する方法としては、特に制限はなく、特許第4789738号の実施例1の導電粒子を粘着剤で固定した樹脂フィルムの2軸延伸操作を利用する方法や、特開2010-33793号公報の金型を使用する方法等を採用することができる。なお、導電粒子10の配置としては、縦横に所定間隔で配列させることが好ましい。また、接続対象のサイズ、導通信頼性、絶縁性、導電粒子捕捉率等を考慮し、2次元的な最近接粒子間距離を1~100μm程度とすることが好ましい。
次に、図3Aに示すように、導電粒子10が配置された光重合性樹脂層20に対して、導電粒子10側から紫外線(UV)を照射することにより光重合反応させ、表面に導電粒子10が固定化された第1絶縁性樹脂層2を形成する。これにより、図3Bに示すように、第1絶縁性樹脂層2において、導電性粒子10が第2絶縁性樹脂層3側に存在する領域2X(第1絶縁性樹脂層2の剥離フィルム30側表面2bと導電粒子10との間に位置する領域)の第1絶縁性樹脂層の硬化率を、第1絶縁性樹脂層2において導電粒子10が存在しない領域2Yの硬化率よりも低くすることができる。したがって異方性導電接続時の導電粒子10の押し込みが容易になり、且つ導電粒子10の接続平面方向の流動を抑制することもできる。
次に、図4Aに示すように、第1絶縁性樹脂層2の導電粒子10側表面に、熱カチオン若しくは熱アニオン重合性樹脂、光カチオン若しくは光アニオン重合性樹脂、熱ラジカル重合性樹脂、又は光ラジカル重合性樹脂で形成された第2絶縁性樹脂層3を積層する。より具体的には、例えば、剥離フィルム31に常法により形成した第2絶縁性樹脂層3を、第1絶縁性樹脂層2の導電粒子10側表面に載せ、過大な熱重合が生じない程度に熱圧着する。そして剥離フィルム31を取り除くことにより図4Bの異方性導電フィルムを得ることができる。
次に、図5に示すように、第2絶縁性樹脂層3の片面(即ち、第1絶縁性樹脂層2と反対側の面)に、熱カチオン若しくは熱アニオン重合性樹脂、光カチオン若しくは光アニオン重合性樹脂、熱ラジカル重合性樹脂、又は光ラジカル重合性樹脂で形成された第3絶縁性樹脂層4を積層し、剥離フィルム30を除去する。これにより図1の第1異方性導電フィルム1Aを得ることができる。
<<第2異方性導電フィルム>>
第2異方性導電フィルム1Bを構成する第1絶縁性樹脂層2は、前述の第1異方性導電フィルム1Aの第1絶縁性樹脂層2と同様の光重合樹脂で形成されて、導電粒子10を適度に固定化する。
第2異方性導電フィルム1Bを構成する導電粒子10としては、第1異方性導電フィルム1Aと同様に、ニッケル、コバルト、銀、銅、金、パラジウムなどの金属粒子、金属被覆樹脂粒子などが挙げられる。2種以上を併用することもできる。
中間絶縁性樹脂層6は、第2異方性導電フィルム1Bの巻き取り時、巻出時、搬送時、異方性導電接続工程の引き出し時等に導電粒子10に加わる応力を緩和する層として設けられている。中間絶縁性樹脂層6が導電粒子10の周囲に設けられ、導電粒子10に蓄積された応力が緩和されていると、異方性導電接続時に、樹脂流動や導電粒子10の圧縮で生じる導電粒子の接続平面方向の位置ズレを抑制することができる。したがって、本発明の第2異方性導電フィルム1Bは、良好な導電粒子捕捉率、導通信頼性、低いショート発生率を実現することができる。
第2異方性導電フィルム1Bの第2絶縁性樹脂層3は、第1異方性導電フィルム1Aの第2絶縁性樹脂層3と同様の熱カチオン若しくは熱アニオン重合性樹脂、光カチオン若しくは光アニオン重合性樹脂、熱ラジカル重合性樹脂、又は光ラジカル重合性樹脂で形成される。
第2異方性導電フィルム1Bは、次の工程[A]~[D]を行い、製造することができる。
図8に示すように、必要に応じて剥離フィルム30上に形成した光重合性樹脂層20に、導電粒子10を単層で配置する。導電粒子10を単層で光重合性樹脂層20に配置する方法としては、特に制限はなく、特許第4789738号の実施例1の導電粒子を粘着剤で固定した樹脂フィルムの2軸延伸操作を利用する方法や、特開2010-33793号公報の金型を使用する方法等を採用することができる。なお、導電粒子10の配置としては、縦横に所定間隔で配列させることが好ましい。また、接続対象のサイズ、導通信頼性、絶縁性、導電粒子捕捉率等を考慮し、2次元的な最近接粒子間距離を1~100μm程度とすることが好ましい。
次に、導電粒子10が配列した光重合性樹脂層20に対して紫外線(UV)を照射することにより光重合反応させ、表面に導電粒子10が固定化された第1絶縁性樹脂層2を形成する。この場合、好ましくは図9Aに示すように、導電粒子10側から紫外線(UV)を照射する。これにより、図9Bに示すように、第1絶縁性樹脂層2において導電粒子10が第2絶縁性樹脂層3側に存在する領域2X(第1絶縁性樹脂層2の剥離フィルム30側表面2bと導電粒子10との間に位置する領域)の第1絶縁性樹脂層の硬化率を、第1絶縁性樹脂層2において導電粒子10が存在しない領域2Yの硬化率よりも低くすることができる。したがって異方性導電接続時の導電粒子10の押し込みが容易になり、且つ導電粒子10の接続平面方向の流動を抑制することもできる。
一方、図10に示すように剥離フィルム31上に、熱カチオン若しくは熱アニオン重合性樹脂、光カチオン若しくは光アニオン重合性樹脂、熱ラジカル重合性樹脂、又は光ラジカル重合性樹脂で形成された第2絶縁性樹脂層3を常法により形成する。
工程[B]で導電粒子10を固定した第1絶縁性樹脂層2の、導電粒子10側表面に中間絶縁性樹脂層6を形成する。
この工程[D]は次の(i)又は(ii)の方法で行うことができる。
図11に示すように、工程[B]で導電粒子10を固定した第1絶縁性樹脂層2の、導電粒子10側表面に中間絶縁性樹脂層6を形成する。より具体的には、重合開始剤を含まず、フェノキシ樹脂、エポキシ樹脂、ポリオレフィン樹脂、ポリウレタン樹脂、アクリル樹脂から選ばれる少なくとも一種の樹脂を含有し、好ましくはシリカ等のフィラーを含有する中間絶縁性樹脂層形成用塗液を第1絶縁性樹脂層2の導電粒子10側表面に塗布又は噴霧し、中間絶縁性樹脂層6を形成する。
その後、図12に示すように、中間絶縁性樹脂層6と工程[C]で形成した第2絶縁性樹脂層3を対向させ、図13に示すように熱圧着する。この場合、熱圧着により過大な熱重合が生じないようにする。そして剥離フィルム30、31を取り除くことにより図7Aの第2異方性導電フィルム1Bを得ることができる。
工程[C]で形成した第2絶縁性樹脂層3の表面に、(i)と同様の中間絶縁性樹脂層形成用塗液を塗布又は噴霧することにより、図14に示すように、第2絶縁性樹脂層3上に中間絶縁性樹脂層6を形成する。次いで、図15に示すように、中間絶縁性樹脂層6と、工程[B]で形成した第1絶縁性樹脂層2上の導電粒子10とを対向させ、図16に示すように熱圧着する。なお、図16では、導電粒子10が中間絶縁性樹脂層6を貫通していない態様を示した。剥離フィルム30、31を取り除くことにより図7Cに示した第2異方性導電フィルム1Bを得ることができる。
本発明の第1異方性導電フィルム1A及び第2異方性導電フィルム1Bは、ICチップ、ICモジュールなどの第1電子部品と、フレキシブル基板、ガラス基板などの第2電子部品とを異方性導電接続する際に好ましく適用することができる。このようにして得られる接続構造体も本発明の一部である。なお、第1異方性導電フィルム1A及び第2異方性導電フィルム1Bの第1絶縁性樹脂層2側をフレキシブル基板等の第2電子部品に配し、それと反対側の第3絶縁性樹脂層4側又は第2絶縁性樹脂層3をICチップなどの第1電子部品に配することが、接続信頼性を高める点から好ましい。
特許第4789738号の実施例1の操作に準じて導電粒子が単層に配列しており、表1に示す配合(質量部)に従って形成した第1絶縁性樹脂層と第2絶縁性樹脂層を有する比較例1の異方性導電フィルム、さらに第3絶縁性樹脂も有する実施例1~6の第1異方性導電フィルムを作製した。
光ラジカル重合性樹脂層への紫外線照射を、導電粒子側と、導電粒子と反対側から、積算光量2000mJ/cm2ずつ行う以外は実施例1と同様にして第1異方性導電フィルムを得た。
実施例1~7及び比較例1の第1異方性導電フィルムを用いて、0.5×1.8×20.0mmの大きさのICチップ(バンプサイズ30×85μm、バンプ高さ15μm、バンプピッチ50μm)を、0.5×50×30mmの大きさのコーニング社製のガラス配線基板(1737F)に180℃、80MPa、5秒という条件で実装して接続構造体サンプルを得た。
接続体の反りについては、ICチップが実装されていない側のガラス基板表面において、ICチップの裏側に相当する巾20mmの反りを、市販の三次元側長機((株)キーエンス)を用いて測定した。
反りは、実用上15μm未満であることが好ましい。
接続構造体サンプルの導通抵抗を測定し、0.5Ω以下の場合にOK、0.5Ωより大きい場合にNGと評価した。
接続構造体サンプルを、85℃、85%RHの高温高湿環境下に500時間放置した後の導通抵抗を、初期導通性と同様に測定した。この導通抵抗は、接続した電子部品の実用的な導通安定性の点から、5Ω以下の場合にOK、5Ωより大きい場合にNGと評価した。
ショート発生率の評価用ICとして、7.5μmスペースの櫛歯TEGパターンのIC(外径1.5×13mm、厚み0.5mm、Bump仕様:金メッキ、高さ15μm、サイズ25×140μm、Bump間Gap7.5μm)を用意し、各実施例及び比較例の異方性導電フィルムを、ショート発生率の評価用ICと、それに対応したパターンのガラス基板との間に挟み、初期導通性と同様の条件で加熱加圧して接続体を得た。そして、その接続体のショート発生率を、「ショート発生数/7.5μmスペース総数」により算出した。ショート発生率は、実用上、100ppm以下であることが望ましいので、100ppm以下の場合にOK、100ppmより大きい場合にNGと評価した。
特許第4789738号の実施例1の操作に準じて導電粒子が単層に配列しており、表2に示す配合(質量部)に従って形成した第1絶縁性樹脂層と中間絶縁性樹脂層と第2絶縁性樹脂層を有する異方性導電フィルムであって、導電粒子が図7Aに示すように中間絶縁性樹脂層を突き抜けている実施例8~17の第2異方性導電フィルムを作製した。
一方、表2に示した配合で中間絶縁性樹脂層用塗料を調製し、これを導電粒子が固定されている第1絶縁性樹脂層に塗布することにより、中間絶縁性樹脂層を形成した。
光ラジカル重合型樹脂層への紫外線照射を、導電粒子側と、導電粒子と反対側から、積算光量2000mJ/cm2ずつ行う以外は実施例9と同様にして第2異方性導電フィルムを得た。
中間絶縁性樹脂層の厚みを5μmとする以外は実施例9と同様にして第2異方性導電フィルムを得た。この第2異方性導電フィルムでは、導電粒子が中間絶縁性樹脂層を突き抜けていない。
中間絶縁性樹脂層の厚みを5μmとする以外は実施例18と同様にして第2異方性導電フィルムを得た。この第2異方性導電フィルムでは、導電粒子が中間絶縁性樹脂層を突き抜けていない。
実施例8~20第2異方性導電フィルムを用いて、0.5×1.8×20.0mmの大きさのICチップ(バンプサイズ30×85μm、バンプ高さ15μm、バンプピッチ50μm)を、0.5×50×30mmの大きさのコーニング社製のガラス配線基板(1737F)に180℃、80MPa、5秒という条件で実装して接続構造体サンプルを得た。
結果を表1に示す。
“加熱・加圧前の接続構造体サンプルのバンプ上に存在する導電粒子の数”に対する、“加熱・加圧後の接続構造体サンプルのバンプ上で実際に捕捉されている導電粒子の数”の割合(%)を以下の式により求め、実装粒子捕捉効率とした。
なお、加熱加圧前の接続構造体サンプルのバンプ上に存在する導電粒子の数は、異方性導電接続の加熱・加圧前における異方性導電フィルムの導電粒子の個数密度とバンプ面積から算出し、加熱加圧後の接続構造体サンプルのバンプ上に存在する導電粒子の数は光学顕微鏡の観察により求めた。
実用上、50%以上であることが好ましい。
実施例1と同様に、接続構造体サンプルの導通抵抗を測定し、0.5Ω以下の場合にOK、0.5Ωより大きい場合にNGと評価した。
実施例1と同様に、接続構造体サンプルを、85℃、85%RHの高温高湿環境下に500時間放置した後の導通抵抗を測定し、5Ω以下の場合にOK、5Ωより大きい場合にNGと評価した。
実施例1と同様にガラス配線基板の反りを測定した。
実施例1と同様にショート発生率の評価用ICとガラス基板との接続体のショート発生率を算出し、100ppm以下の場合にOK、100ppmより大きい場合にNGと評価した。
実施例18、20の接続構造体は、実施例9に対して実装粒子補捉効率がやや劣っていたが、実用上問題はなく、初期導通性、導通信頼性、反り、ショート発生率については実施例9と同様に好ましい結果を示した。
また、実施例19の接続構造体では、顕微鏡観察によりバンプに接続している導電粒子の形状が、実施例9に比べるとやや不均一であったが、実装粒子捕捉効率、初期導通性、導通信頼性、反り、ショート発生率の全ての評価項目について実用上好ましい結果を示した。
さらに、第1異方性導電フィルムでは、第2絶縁性樹脂層上には、第3絶縁性樹脂層が積層されているため、異方性導電フィルムを異方性導電接続に使用した場合の応力が緩和され、異方性導電接続により得られた接続体における反りの発生が抑制される。また、第2異方性導電フィルムでは、第1絶縁性樹脂層と第2絶縁性樹脂層の間には、中間絶縁性樹脂層が導電粒子を囲むように積層されているため、導電粒子にかかる応力が緩和され、異方性導電接続時の導電粒子捕捉率が一層向上する。
よって、本発明の第1異方性導電フィルム及び第2異方性導電フィルムは、ICチップなどの電子部品の配線基板への異方性導電接続に有用である。電子部品の配線は狭小化が進んでおり、本発明は、狭小化した電子部品を異方性導電接続する場合に特に有用となる。
1B 第2異方性導電フィルム
2 第1絶縁性樹脂層
2a 第1絶縁性樹脂層の表面
2b 第1絶縁性樹脂層の表面
2X 第1絶縁性樹脂層において、第2絶縁性樹脂層側に導電粒子が存在する領域
2Y 第1絶縁性樹脂層において、導電粒子が存在しない領域
3 第2絶縁性樹脂層
4 第3絶縁性樹脂層
5 積層体
6 中間絶縁性樹脂層
10 導電粒子
20 光重合性樹脂層
30 剥離フィルム
31 剥離フィルム
Claims (40)
- 第1絶縁性樹脂層、第2絶縁性樹脂層、第3絶縁性樹脂層が順次積層している異方性導電フィルムであって、
第1絶縁性樹脂層が、光重合樹脂で形成され、
第2絶縁性樹脂層及び第3絶縁性樹脂層が、それぞれ熱カチオン若しくは熱アニオン重合性樹脂、光カチオン若しくは光アニオン重合性樹脂、熱ラジカル重合性樹脂、又は光ラジカル重合性樹脂で形成され、
第1絶縁性樹脂層の第2絶縁性樹脂層側表面に、異方性導電接続用の導電粒子が単層で配置されている異方性導電フィルム。 - 第1絶縁性樹脂層において、導電粒子が第2絶縁性樹脂層側に存在する領域の硬化率が、導電粒子が第2絶縁性樹脂層側に存在しない領域の硬化率に対して低い請求項1記載の異方性導電フィルム。
- 第1絶縁性樹脂層が、アクリレート化合物と光ラジカル重合開始剤とを含む光ラジカル重合性樹脂層を光ラジカル重合させたものである請求項1又は2記載の異方性導電フィルム。
- 第1絶縁性樹脂層に、アクリレート化合物と光ラジカル重合開始剤が残存している請求項3記載の異方性導電フィルム。
- 第1絶縁性樹脂層が、アクリレート化合物と熱ラジカル重合開始剤を含有する請求項1~4のいずれかに記載の異方性導電フィルム。
- 第1絶縁性樹脂層が、エポキシ化合物と、熱カチオン若しくは熱アニオン重合開始剤又は光カチオン若しくは光アニオン重合開始剤を含有する請求項1~5のいずれかに記載の異方性導電フィルム。
- 第2絶縁性樹脂層が、エポキシ化合物と、熱カチオン若しくは熱アニオン重合開始剤又は光カチオン若しくは光アニオン重合開始剤を含有する重合性樹脂、又はアクリレート化合物と、熱ラジカル若しくは光ラジカル重合開始剤を含有する重合性樹脂で形成されている請求項1~6のいずれかに記載の異方性導電フィルム。
- 第3絶縁性樹脂層が、エポキシ化合物と、熱カチオン若しくは熱アニオン重合開始剤又は光カチオン若しくは光アニオン重合開始剤を含有する重合性樹脂、又はアクリレート化合物と熱ラジカル若しくは光ラジカル重合開始剤を含有する重合性樹脂で形成されている請求項1~7のいずれかに記載の異方性導電フィルム。
- 第3絶縁性樹脂層の厚みが、第2絶縁性樹脂層の厚みの1/2以下である請求項1~8のいずれかに記載の異方性導電フィルム。
- 請求項1記載の異方性導電フィルムの製造方法であって、以下の工程(A)~(D):
工程(A)
光重合性樹脂層に、導電粒子を単層で配置する工程;
工程(B)
導電粒子を配置した光重合性樹脂層に対して紫外線を照射することにより光重合反応させ、表面に導電粒子が固定化された第1絶縁性樹脂層を形成する工程;
工程(C)
第1絶縁性樹脂層の導電粒子側表面に、熱カチオン若しくは熱アニオン重合性樹脂、光カチオン若しくは光アニオン重合性樹脂、熱ラジカル重合性樹脂、又は光ラジカル重合性樹脂で形成された第2絶縁性樹脂層を積層する工程;
工程(D)
第2絶縁性樹脂層の片面に、熱カチオン若しくは熱アニオン重合性樹脂、光カチオン若しくは光アニオン重合性樹脂、熱ラジカル重合性樹脂、又は光ラジカル重合性樹脂で形成された第3絶縁性樹脂層を積層する工程;
を有し、
工程(D)を、工程(C)の前又は後に行う異方性導電フィルムの製造方法。 - 工程(B)において、紫外線を導電粒子側から照射する請求項10記載の異方性導電フィルムの製造方法。
- 第1絶縁性樹脂層を形成する光重合性樹脂が、アクリレート化合物と光ラジカル重合開始剤を含む請求項10又は11記載の異方性導電フィルムの製造方法。
- 第1絶縁性樹脂層を形成する光重合性樹脂が、熱ラジカル重合開始剤を含有する請求項10~12のいずれかに記載の異方性導電フィルムの製造方法。
- 第1絶縁性樹脂層を形成する光重合性樹脂が、エポキシ化合物と、熱カチオン若しくは熱アニオン重合開始剤又は光カチオン若しくは光アニオン重合開始剤を含有する請求項10~13のいずれかに記載の異方性導電フィルムの製造方法。
- 第2絶縁性樹脂層が、エポキシ化合物と、熱カチオン若しくは熱アニオン重合開始剤又は光カチオン若しくは光アニオン重合開始剤を含有する重合性樹脂、又はアクリレート化合物と熱ラジカル若しくは光ラジカル重合開始剤を含有する重合性樹脂で形成されている請求項10~14のいずれかに記載の異方性導電フィルムの製造方法。
- 第3絶縁性樹脂層が、エポキシ化合物と、熱カチオン若しくは熱アニオン重合開始剤又は光カチオン若しくは光アニオン重合開始剤を含有する重合性樹脂、又はアクリレート化合物と熱ラジカル若しくは光ラジカル重合開始剤を含有する重合性樹脂で形成されている請求項10~15のいずれかに記載の異方性導電フィルムの製造方法。
- 第3絶縁性樹脂層の厚みが、第2絶縁性樹脂層の厚みの1/2以下である請求項10~16のいずれかに記載の異方性導電フィルムの製造方法。
- 請求項1~9のいずれかに記載の異方性導電フィルムで第1電子部品を第2電子部品に異方性導電接続した接続構造体。
- 第1絶縁性樹脂層、中間絶縁性樹脂層及び第2絶縁性樹脂層が順次積層している異方性導電フィルムであって、
第1絶縁性樹脂層が、光重合樹脂で形成され、
第2絶縁性樹脂層が、熱カチオン若しくは熱アニオン重合性樹脂、光カチオン若しくは光アニオン重合性樹脂、熱ラジカル重合性樹脂、又は光ラジカル重合性樹脂で形成され、
中間絶縁性樹脂層が重合開始剤を含まない樹脂で形成され、
第1絶縁性樹脂層の第2絶縁性樹脂層側表面に、異方性導電接続用の導電粒子が単層で配置され、該導電粒子が中間絶縁性樹脂層と接している異方性導電フィルム。 - 中間絶縁性樹脂層の厚さが導電粒子の粒子径の1.2倍以下である請求項19記載の異方性導電フィルム。
- 導電粒子が中間絶縁性樹脂層を貫通している請求項19又は20記載の異方性導電フィルム。
- 中間絶縁性樹脂層がフィラーを含有する請求項19~21のいずれかに記載の異方性導電フィルム。
- 中間絶縁性樹脂層が、フェノキシ樹脂、エポキシ樹脂、ポリオレフィン樹脂、ポリウレタン樹脂及びアクリル樹脂から選ばれる少なくとも一種を含有する請求項19~22のいずれかに記載の異方性導電フィルム。
- 第1絶縁性樹脂層において、導電粒子が第2絶縁性樹脂層側に存在する領域の硬化率が、導電粒子が第2絶縁性樹脂層側に存在しない領域の硬化率に対して低い請求項19~23のいずれかに記載の異方性導電フィルム。
- 第1絶縁性樹脂層が、アクリレート化合物と光ラジカル重合開始剤とを含む光ラジカル重合性樹脂層を光ラジカル重合させたものである請求項19~24のいずれかに記載の異方性導電フィルム。
- 第1絶縁性樹脂層に、アクリレート化合物と光ラジカル重合開始剤が残存している請求項25記載の異方性導電フィルム。
- 第1絶縁性樹脂層が、アクリレート化合物と熱ラジカル重合開始剤を含有する請求項19~26のいずれかに記載の異方性導電フィルム。
- 第1絶縁性樹脂層が、エポキシ化合物と、熱カチオン若しくは熱アニオン重合開始剤又は光カチオン若しくは光アニオン重合開始剤を含有する請求項19~27のいずれかに記載の異方性導電フィルム。
- 第2絶縁性樹脂層が、エポキシ化合物と、熱カチオン若しくは熱アニオン重合開始剤又は光カチオン若しくは光アニオン重合開始剤を含有する重合性樹脂、又はアクリレート化合物と、熱ラジカル若しくは光ラジカル重合開始剤を含有する重合性樹脂で形成されている請求項19~28のいずれかに記載の異方性導電フィルム。
- 請求項19記載の異方性導電フィルムの製造方法であって、以下の工程[A]~[D]:
工程[A]
光重合性樹脂層に、導電粒子を単層で配置する工程;
工程[B]
導電粒子を配置した光重合性樹脂層に対して紫外線を照射することにより光重合反応させ、表面に導電粒子が固定化された第1絶縁性樹脂層を形成する工程;
工程[C]
熱カチオン若しくは熱アニオン重合性樹脂、光カチオン若しくは光アニオン重合性樹脂、熱ラジカル重合性樹脂、又は光ラジカル重合性樹脂で形成された第2絶縁性樹脂層を形成する工程;
工程[D]
重合開始剤を含まない樹脂で形成された中間絶縁性樹脂層を、第1絶縁性樹脂層の導電粒子側表面に形成する工程;
を有し、
(i)工程[D]を工程[B]の後に行うことにより第1絶縁性樹脂層の導電粒子側表面に中間絶縁性樹脂層を形成し、次いで該中間絶縁性樹脂層と工程[C]で形成した第2絶縁性樹脂層を積層するか、又は
(ii)工程[C]で形成した第2絶縁性樹脂層上に、重合開始剤を含まない樹脂で形成された中間絶縁性樹脂層を形成し、次いで該中間絶縁性樹脂層を、工程[B]で形成した第1絶縁性樹脂層の導電粒子側表面に積層する製造方法。 - 中間絶縁性樹脂層の厚みが、導電粒子の粒子径の1.2倍以下である請求項30記載の異方性導電フィルムの製造方法。
- 中間絶縁性樹脂層がフィラーを含有する請求項30又は31に記載の異方性導電フィルムの製造方法。
- 中間絶縁性樹脂層が、フェノキシ樹脂、エポキシ樹脂、ポリオレフィン樹脂、ポリウレタン樹脂及びアクリル樹脂から選ばれる少なくとも一種を含有する請求項30~32のいずれかに記載の異方性導電フィルムの製造方法。
- 工程[B]において、光重合性樹脂層に対して紫外線を導電粒子側から照射する請求項30~33のいずれかに記載の異方性導電フィルムの製造方法。
- 第1絶縁性樹脂層を形成する光重合性樹脂が、アクリレート化合物と光ラジカル重合開始剤を含む請求項30~34のいずれかに記載の異方性導電フィルムの製造方法。
- 第1絶縁性樹脂層を形成する光重合性樹脂が、さらに熱ラジカル重合開始剤を含有する請求項30~35のいずれかに記載の異方性導電フィルムの製造方法。
- 第1絶縁性樹脂層を形成する光重合性樹脂が、エポキシ化合物と、光カチオン又は光アニオン重合開始剤を含有する請求項30~36のいずれかに記載の異方性導電フィルムの製造方法。
- 第1絶縁性樹脂層が、さらに熱カチオン又は熱アニオン重合開始剤を含有する請求項30~37のいずれかに記載の異方性導電フィルムの製造方法。
- 第2絶縁性樹脂層が、エポキシ化合物と、熱カチオン若しくは熱アニオン重合開始剤又は光カチオン若しくは光アニオン重合開始剤を含有する重合性樹脂、又はアクリレート化合物と熱ラジカル若しくは光ラジカル重合開始剤を含有する重合性樹脂で形成されている請求項30~38のいずれかに記載の異方性導電フィルムの製造方法。
- 請求項19~29のいずれかに記載の異方性導電フィルムで第1電子部品を第2電子部品に異方性導電接続した接続構造体。
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WO2017191772A1 (ja) * | 2016-05-05 | 2017-11-09 | デクセリアルズ株式会社 | フィラー配置フィルム |
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JP7062389B2 (ja) * | 2017-08-23 | 2022-05-06 | デクセリアルズ株式会社 | 異方性導電フィルム |
TWI645973B (zh) * | 2017-12-15 | 2019-01-01 | 律勝科技股份有限公司 | 聚醯亞胺薄化軟性基板及其製造方法 |
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TWI777304B (zh) | 2022-09-11 |
TW202111733A (zh) | 2021-03-16 |
TWI722980B (zh) | 2021-04-01 |
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