WO2018079365A1 - Anisotropic conductive film - Google Patents

Anisotropic conductive film Download PDF

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Publication number
WO2018079365A1
WO2018079365A1 PCT/JP2017/037664 JP2017037664W WO2018079365A1 WO 2018079365 A1 WO2018079365 A1 WO 2018079365A1 JP 2017037664 W JP2017037664 W JP 2017037664W WO 2018079365 A1 WO2018079365 A1 WO 2018079365A1
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WIPO (PCT)
Prior art keywords
particles
insulating
conductive
resin layer
conductive particles
Prior art date
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PCT/JP2017/037664
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French (fr)
Japanese (ja)
Inventor
三宅 健
怜司 塚尾
達朗 深谷
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デクセリアルズ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Priority claimed from JP2017160657A external-priority patent/JP6935702B2/en
Application filed by デクセリアルズ株式会社 filed Critical デクセリアルズ株式会社
Priority to KR1020197000758A priority Critical patent/KR102071047B1/en
Priority to KR1020207002129A priority patent/KR102240767B1/en
Priority to CN202110420313.2A priority patent/CN113078486B/en
Priority to US16/343,380 priority patent/US11557562B2/en
Priority to CN201780062727.4A priority patent/CN109845040B/en
Publication of WO2018079365A1 publication Critical patent/WO2018079365A1/en

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Definitions

  • the present invention relates to an anisotropic conductive film.
  • Anisotropic conductive films are widely used for mounting electronic components such as IC chips. From the viewpoint of making an anisotropic conductive film correspond to a high mounting density, in an anisotropic conductive film, conductive particles are dispersed in the insulating resin layer at a high density. However, increasing the density of the conductive particles is a cause of short circuit.
  • Patent Document 1 An anisotropic conductive film can be obtained by kneading the conductive particles with insulating particles in a binder resin using a mixer and forming a film.
  • Patent Document 1 when the conductive particles with insulating particles are kneaded using a binder resin and a mixer, the insulating particles are isolated from the conductive particles, and the original insulating properties of the conductive particles with insulating particles are obtained. It may not be possible. Therefore, there is a possibility that a short circuit may occur in a connection structure of an electronic component that is anisotropically conductively connected using an anisotropic conductive film in which conductive particles with insulating particles are dispersed in a binder resin at high density.
  • the present invention is an anisotropic conductive film using conductive particles with insulating particles, which reduces the conduction resistance of the connection structure that is anisotropically conductively connected and reliably suppresses the occurrence of short circuits.
  • An object of the present invention is to provide an anisotropic conductive film that can be used.
  • the present inventor made a film surface of the conductive particles in the conductive particles with insulating particles.
  • the number of insulating particles adhering in the direction is maintained, but if the number of insulating particles adhering in the film thickness direction of the conductive particles is reduced, an anisotropic conductive connection using an anisotropic conductive film is used.
  • the conductive particles are easily pressed against the terminal surface without using the insulating particles, so that the conduction resistance of the connection structure can be reduced, and the presence of the insulating particles between adjacent terminals is less likely to cause a short circuit.
  • the inventor came up with the present invention.
  • the present invention is an anisotropic conductive film in which conductive particles with insulating particles attached to the surface of conductive particles are dispersed in an insulating resin layer.
  • an anisotropic conductive film in which the number of insulating particles in contact with the particles in the film thickness direction is smaller than the number of insulating particles in contact with the conductive particles in the film surface direction.
  • the present invention provides a method for manufacturing a connection structure in which electronic components are anisotropically conductively connected using the above-described anisotropic conductive film, and a connection structure obtained thereby.
  • the conductive particles with the initial insulating particles in which the insulating particles adhere substantially uniformly on the entire surface of the conductive particles are in contact with the conductive particles in the film thickness direction.
  • the number of insulating particles is smaller than the number of insulating particles in contact with the conductive particles in the film surface direction. Therefore, when the anisotropic conductive film is used to anisotropically connect the terminals of the electronic component, the direct connection between the terminals and the conductive particles can be achieved as compared with the case where the initial state of the conductive particles with insulating particles is maintained. Since the contact area increases, the conduction resistance can be reduced in the connection structure. Further, according to this anisotropic conductive film, the number of insulating particles in contact with the conductive particles in the film surface direction is maintained at the initial state of the conductive particles with insulating particles. A short circuit between them can be suppressed.
  • FIG. 1A is a plan view showing the arrangement of conductive particles of an anisotropic conductive film 10A of an example.
  • FIG. 1B is a cross-sectional view of the anisotropic conductive film 10A of the example.
  • FIG. 2 is an explanatory diagram of a method for measuring the number of insulating particles in contact with the surface of the conductive particles in the film thickness direction or the film surface direction.
  • FIG. 3A is an explanatory diagram of a dent in the insulating resin layer around the conductive particles with insulating particles.
  • FIG. 3B is an explanatory diagram of a dent in the insulating resin layer on the conductive particles with insulating particles.
  • FIG. 1A is a plan view showing the arrangement of conductive particles of an anisotropic conductive film 10A of an example.
  • FIG. 1B is a cross-sectional view of the anisotropic conductive film 10A of the example.
  • FIG. 2 is an explanatory diagram of a method for measuring
  • FIG. 4A is a cross-sectional view illustrating a method for manufacturing the anisotropic conductive film 10A of the example.
  • FIG. 4B is a cross-sectional view illustrating the method for manufacturing the anisotropic conductive film 10A of the example.
  • FIG. 4C is a cross-sectional view illustrating the method for manufacturing the anisotropic conductive film 10A of the example.
  • FIG. 4D is a cross-sectional view illustrating the method for manufacturing the anisotropic conductive film 10A of the example.
  • Drawing 4E is a sectional view explaining the manufacturing method of anisotropic conductive film 10A of an example.
  • FIG. 4F is a cross-sectional view illustrating the method for manufacturing the anisotropic conductive film 10A of the example.
  • FIG. 5 is a cross-sectional view of the anisotropic conductive film 10B of the example.
  • FIG. 6 is a cross-sectional view of the anisotropic conductive film 10C of the example.
  • FIG. 7 is a cross-sectional view of the anisotropic conductive film 10D of the example.
  • FIG. 1A is a plan view for explaining the arrangement of conductive particles of an anisotropic conductive film 10A according to an embodiment of the present invention
  • FIG. 1B is a sectional view taken along line XX.
  • This anisotropic conductive film 10 ⁇ / b> A has a structure in which conductive particles 3 with insulating particles in which insulating particles 2 are in contact with or attached to the surface of conductive particles 1 are embedded on one surface of insulating resin layer 5. Yes.
  • the conductive particles 3 with insulating particles are dispersed without contacting each other, and the conductive particles 3 with insulating particles are also dispersed without overlapping each other in the film thickness direction. Further, the positions of the conductive particles 3 with insulating particles in the film thickness direction (the vertical direction of the paper surface of FIG. 1B) are aligned, and the conductive particles 3 with insulating particles are single-layered in the film surface direction (the horizontal direction of the paper surface of FIG. 1B). I am doing.
  • the arrangement of the insulating particles 2 in the conductive particles 3 with insulating particles is characteristic, and is in contact with the conductive particles 1 in the film thickness direction as described in detail below.
  • the number of insulating particles 2 is smaller than the number of insulating particles 2 in contact with the conductive particles 1 in the film surface direction.
  • the number of the conductive particles 1 in the film thickness direction of the conductive particles 1 in the conductive particles 3 with insulating particles is smaller than the number of the conductive particles 1 in the film surface direction.
  • the conductive particles 3 with insulating particles used as the raw material for producing the anisotropic conductive film 10A of the present invention it is possible to use the conductive particles 1 having the insulating particles 2 attached substantially uniformly to the entire surface of the conductive particles 1. it can.
  • the particle diameter of the conductive particles 1 is preferably 1 ⁇ m or more and 30 ⁇ m or less, more preferably 2.5 ⁇ m or more and 13 ⁇ m from the viewpoint of suppressing an increase in conduction resistance when there is a variation in wiring height and suppressing the occurrence of short circuits.
  • it is more preferably 3 ⁇ m or more and 10 ⁇ m or less.
  • the particle diameter of the insulating particles 2 is smaller than the particle diameter of the conductive particles 1.
  • the specific particle diameter of the insulating particles 2 can be determined according to the particle diameter of the conductive particles 1, the use of the anisotropic conductive film, etc., but is usually preferably 0.005 ⁇ m or more and 5 ⁇ m or less, 0.01 ⁇ m
  • the thickness is more preferably 2.5 ⁇ m or less, further preferably 1 ⁇ m or less, and particularly preferably 0.5 ⁇ m or less. This eliminates the need for excessively increasing the pressure and temperature required for anisotropic conductive connection.
  • the lower limit is preferably 0.4% or more, and 0.6% More preferably, it is more preferably 0.8% or more. If the upper limit is too large, adhesion to the conductive particles and the necessary number may be insufficient. Therefore, the upper limit is preferably 18% or less, more preferably 12% or less, and even more preferably 6% or less.
  • the particle diameters of the conductive particles 1, the insulating particles 2, and the conductive particles 3 with insulating particles are measured by spreading these particles on glass, and using an optical microscope, a metal microscope, a transmission electron microscope (TEM), or a scanning electron microscope. It can be determined by observing with (SEM) or the like. These particle sizes in the film can also be obtained from observation with a scanning electron microscope or the like. In the measurement of the particle diameter, it is desirable that the number of samples to be measured is 300 or more.
  • the transmission electron microscope can accurately measure the particle diameter of a relatively small insulating particle, and the scanning electron microscope is particularly suitable for obtaining the particle diameter of the conductive particles 3 with insulating particles.
  • the average particle diameter of single conductive particles can be measured by a general particle size distribution measuring apparatus. It may be an image type or a laser type. As an example of the image type measuring apparatus, a wet flow type particle diameter / shape analyzer FPIA-3000 (Malvern) can be mentioned.
  • the number of samples (number of conductive particles) for measuring the particle diameter D of the conductive particles with insulating particles is preferably 1000 or more.
  • the particle diameter D of the conductive particles with insulating particles in the anisotropic conductive film can be determined from observation with an electron microscope such as SEM. In this case, it is desirable that the number of samples (number of conductive particles) for measuring the particle diameter D of the conductive particles with insulating particles be 300 or more.
  • the ratio (coverage) covered with the insulating particles 2 in the entire surface of the conductive particles 1 is preferably 20 to 97%. ⁇ 95% is more preferred. If the coverage is too small, short-circuiting is likely to occur, and if it is too large, there is a concern that capturing of the conductive particles by the bumps is hindered.
  • the coverage is the ratio of the covering area (projected area) of insulating particles to the entire surface of the conductive particles with insulating particles.
  • it is obtained by observing 100 conductive particles 3 with insulating particles using a scanning electron microscope and averaging the coverage in each observation image.
  • the number of insulating particles per one conductive particle with insulating particles is measured in each observation image, the numerical value, the projected area of one conductive particle with insulating particles, and one insulating particle.
  • the coverage may be calculated from the projected area.
  • the observation image of the insulating particles partially overlaps with the circular observation image of the conductive particles, the number of the partially overlapping insulating particles may be calculated as 0.5.
  • the number of the insulating particles 2 in contact with the conductive particles 1 in the film thickness direction is the number of the insulating particles 2 in contact with the conductive particles 1 in the film surface direction. Less than the number.
  • the number of insulating particles 2 in contact with the conductive particles 1 in the film thickness direction means that the conductive particles with insulating particles in the cross section in the film thickness direction of the conductive particles 3 with insulating particles in the anisotropic conductive film 10A shown in FIG.
  • the conductive particle 1 refers to the number of insulating particles 2 existing in regions (regions along the film surface) A1 and A2 above and below 1.
  • the number of insulating particles 2 in contact with the conductive particles 1 in the film surface direction is a region (region along the film thickness direction) on the left and right of the conductive particles 1 in the four regions A1, A2, A3, and A4 described above. This refers to the number of insulating particles 2 present in A3 and A4.
  • the cross section of a film thickness direction has a several different direction with the same film (confirm the cross-sectional view of a different direction), and it is more preferable that two cross sections which are 90 degrees are included. .
  • the insulating particles 2 In obtaining the number of insulating particles 2 present in the regions A1, A2, A3, A4, the insulating particles 2 straddling both the upper and lower regions A1, A2 and the left and right regions A3, A4 of the conductive particles 1, The attribution is determined depending on which region it belongs to.
  • the present invention it is not necessary that all the conductive particles with insulating particles 3 satisfy the above inequality.
  • the number of insulating particles 2 present in the regions A1, A2, A3, and A4 in the individual conductive particles 3 with insulating particles may vary, and there are conductive particles 3 with insulating particles that do not satisfy the above inequality.
  • N A3 and N A4 are larger than N A1 and N A2 .
  • the number of the insulating particles 2 present in the regions A1, A2, A3, and A4 is measured for each conductive particle 3 with insulating particles.
  • rectangular measurement areas each having a side of 100 ⁇ m or more are separated from each other and set at a plurality of locations (preferably 5 or more, more preferably 10 or more) so that the total area is 1 mm 2 or more.
  • the extracted conductive particles 3 with insulating particles 3 were observed, and the number of insulating particles 2 existing in the regions A1 and A2 and the number of insulating particles 2 existing in the regions A3 and A4 for each conductive particle 3 with insulating particles.
  • the number (N A1 + N A2 ) of insulating particles 2 in contact with the conductive particles 1 in the film thickness direction and the conductive particles 1 with the film is obtained, and the existence of the above inequality is examined. What is necessary is just to adjust a measurement area
  • the number of insulating particles 2 in contact with the conductive particles 1 in the film thickness direction (N A1 + N A2 ) is less than the number of insulating particles 2 in contact with the conductive particles 1 in the film surface direction (N A3 + N A4 ).
  • N A1 + N A2 the number of insulating particles 2 in contact with the conductive particles 1 in the film surface direction
  • N A3 + N A4 the number of the insulating particles 2 overlapping the conductive particles 1 in the plan view of either one of the front and back surfaces of the anisotropic conductive film in the measurement region having an area of 1 mm 2 or more is It may be confirmed that the number is smaller than the number of insulating particles 2 overlapping the conductive particles 1 in a plan view of the other film surface.
  • N A3 , N A4 ⁇ N A2 > N A1 Therefore, by confirming N A2 > N A1 , the number of insulating particles 2 in contact with the conductive particles 1 in the film thickness direction (N A1 + N A2 ) is equal to the number of insulating particles 2 in contact with the conductive particles 1 in the film surface direction. It can be confirmed that the number is smaller than the number (N A3 + N A4 ).
  • the difference in the number of insulating particles 2 due to such regions A1, A2, A3, and A4 is that the conductive particles 3 with insulating particles are arranged in a predetermined arrangement in the method of manufacturing the anisotropic conductive film 10A, as will be described later. This occurs when a transfer mold is used. That is, the difference in the number of the insulating particles 2 is that the insulating particles 2 that contact the conductive particles 1 in the film thickness direction (insulation in the region A1) when the conductive particles 3 with insulating particles are transferred from the transfer mold to the insulating resin layer.
  • the particles 2 are easily detached from the conductive particles 1 due to friction with the transfer mold or friction with the pressure member and remain in the transfer mold, and also in contact with the conductive particles 1 in the film thickness direction.
  • the particles 2 may move to a position in contact with the conductive particles 1 in the film surface direction, but the insulating particles 2 in contact with the conductive particles 1 in the film surface direction are transferred from the transfer type conductive particles 3 with insulating particles to the insulating resin layer. This is caused by the fact that even when transferred onto the conductive particles 1, detachment or movement from the conductive particles 1 hardly occurs.
  • the dispersed state of the conductive particles with insulating particles in the present invention includes a state in which the conductive particles with insulating particles 3 are dispersed randomly and a state in which the conductive particles with insulating particles are dispersed in a regular arrangement.
  • the conductive particles with insulating particles are arranged in non-contact with each other, and the number ratio is preferably 95% or more, more preferably 98% or more, and further preferably 99.5% or more. .
  • the conductive particles with insulating particles that are intentionally contacted in a regular arrangement in a dispersed state are counted as one.
  • the positions in the film thickness direction are aligned.
  • the fact that the positions of the conductive particles 1 in the film thickness direction are aligned is not limited to being aligned at a single depth in the film thickness direction, but the front and back interfaces of the insulating resin layer 5 or the vicinity thereof. Each of which includes conductive particles.
  • the conductive particles with insulating particles 3 are preferably arranged regularly in a plan view of the film, and can be, for example, a square lattice arrangement as shown in FIG. 1A.
  • examples of the regular arrangement of the conductive particles with insulating particles include a lattice arrangement such as a rectangular lattice, an oblique lattice, and a hexagonal lattice.
  • the regular arrangement is not limited to the lattice arrangement, and for example, a row of particles in which conductive particles with insulating particles are arranged in a straight line at a predetermined interval may be arranged in parallel at a predetermined interval.
  • the conductive particles with insulating particles 3 By arranging the conductive particles with insulating particles 3 in a non-contact manner and in a regular arrangement such as a lattice, pressure is applied evenly to the conductive particles with insulating particles 3 during anisotropic conductive connection, Variations can be reduced.
  • the regular arrangement can be confirmed, for example, by repeating a predetermined particle arrangement in the longitudinal direction of the film.
  • the lattice axis or the array axis of the array of the conductive particles with insulating particles may be parallel to the longitudinal direction of the anisotropic conductive film, may cross the longitudinal direction of the anisotropic conductive film, It can be determined according to the terminal pitch. For example, in the case of an anisotropic conductive film for fine pitch, as shown in FIG.
  • the lattice axis A of the conductive particles with insulating particles 3 is skewed with respect to the longitudinal direction of the anisotropic conductive film 10A, so
  • the angle ⁇ formed by the longitudinal direction of the terminals 20 connected by the isotropic conductive film 10A (the short direction of the film) and the lattice axis A is preferably 6 ° to 84 °, more preferably 11 ° to 74 °.
  • the inter-particle distance of the conductive particles 3 with insulating particles is appropriately determined according to the size and terminal pitch of the terminals connected by the anisotropic conductive film. For example, when an anisotropic conductive film is made compatible with fine pitch COG (Chip On Glass), the distance between the conductive particles 1 of the closest conductive particles 3 with insulating particles from the point of preventing the occurrence of short-circuiting is provided. It is preferably larger than 0.5 times the particle diameter of the particles, more preferably larger than 0.7 times.
  • the distance between the conductive particles 1 of the closest conductive particles 3 with insulating particles is preferably 4 times or less the particle diameter of the conductive particles with insulating particles. It is more preferable to set it to double or less.
  • the number density measurement region of the conductive particles with insulating particles is arbitrarily a plurality of rectangular regions having a side of 100 ⁇ m or more in the anisotropic conductive film 10A (preferably 5 or more, more preferably 10 or more). It is preferable to set the total area of the measurement region to 2 mm 2 or more. What is necessary is just to adjust suitably the magnitude
  • a region having an area of 100 ⁇ m ⁇ 100 ⁇ m is a region where one or more bumps exist in a connection object having a space between bumps of 50 ⁇ m or less.
  • the number density is preferably 150 to 70000 pieces / mm 2 , particularly in the case of fine pitch use, preferably 6000 to 42000 pieces / mm 2 , more preferably 10,000 to 40000 pieces / mm 2 , and further preferably 15000 to 35000 pieces / mm 2 . In addition, less than 150 pieces / mm 2 is not excluded.
  • the number density of the conductive particles with insulating particles is obtained using a metal microscope as described above, and is measured using image analysis software (for example, WinROOF, Mitani Corporation) on the microscopic image of the conductive particles with insulating particles. May be.
  • image analysis software for example, WinROOF, Mitani Corporation
  • the area occupancy ratio of the conductive particles with insulating particles in a plan view of the film is an index of the thrust required for the pressing jig for thermocompression bonding of the anisotropic conductive film to the electronic component.
  • the thrust required for the pressing jig for thermocompression bonding the isotropic conductive film to the electronic component becomes excessively large, and there is a problem that the pressing is insufficient with the conventional pressing jig.
  • the thrust required for the pressing jig for thermocompression bonding of the anisotropic conductive film to the electronic component can be suppressed low.
  • the minimum melt viscosity of the insulating resin layer 5 is not particularly limited, and is appropriately determined according to the use object of the anisotropic conductive film, the method for manufacturing the anisotropic conductive film, and the like. be able to.
  • the below-mentioned dents 5b (FIG. 3A) and 5c (FIG. 3B) can be formed, it can be set to about 1000 Pa ⁇ s depending on the method for manufacturing the anisotropic conductive film.
  • the minimum melt viscosity of the insulating resin is 1100 Pa ⁇ s or higher from the viewpoint that the insulating resin layer enables film forming.
  • a dent 5b is formed around the exposed portion of the conductive particles with insulating particles 3 pushed into the insulating resin layer 5.
  • 3B from the point of forming the recess 5c directly above the conductive particles with insulating particles 3 pushed into the insulating resin layer 5, as shown in FIG. 3B, preferably 1500 Pa ⁇ s or more, more preferably 2000 Pa ⁇ s or more, The pressure is preferably 3000 to 15000 Pa ⁇ s, and more preferably 3000 to 10,000 Pa ⁇ s.
  • This minimum melt viscosity can be obtained using a rotary rheometer (manufactured by TA Instruments Inc.) as an example, kept constant at a measurement pressure of 5 g, and using a measurement plate having a diameter of 8 mm, and more specifically in the temperature range. At 30 to 200 ° C., it can be obtained by setting the temperature rising rate 10 ° C./min, the measurement frequency 10 Hz, and the load fluctuation 5 g with respect to the measurement plate.
  • the minimum melt viscosity of the insulating resin layer 5 By setting the minimum melt viscosity of the insulating resin layer 5 to a high viscosity of 1500 Pa ⁇ s or more, unnecessary movement of the conductive particles can be suppressed for pressure bonding of the anisotropic conductive film to the article. It is possible to prevent the conductive particles to be sandwiched between the terminals sometimes from being caused to flow due to the resin flow.
  • the conductive resin particles with insulating particles 3 are exposed from the insulating resin layer 5 when the conductive particles with insulating particles 3 are pushed.
  • the insulating resin layer 5 is plastically deformed and recessed into the insulating resin layer 5 around the conductive particles 3 with insulating particles (FIG. 3A), or a conductive material with insulating particles so that the conductive particle with insulating particles 3 is buried in the insulating resin layer 5 without being exposed from the insulating resin layer 5.
  • the viscosity of the insulating resin layer 5 at 60 ° C. is preferably at least 3000 Pa ⁇ s, more preferably at least 4000 Pa ⁇ s, even more preferably at least 4500 Pa ⁇ s, and the upper limit is preferably at most 20000 Pa ⁇ s. More preferably, it is 15000 Pa.s or less, More preferably, it is 10000 Pa.s or less. This measurement is performed by the same measurement method as that for the minimum melt viscosity, and can be obtained by extracting a value at a temperature of 60 ° C.
  • the specific viscosity of the insulating resin layer 5 when the conductive particles 3 with insulating particles are pushed into the insulating resin layer 5 is preferably 3000 Pa depending on the shape and depth of the recesses 5b and 5c to be formed.
  • such a viscosity is preferably obtained at 40 to 80 ° C., more preferably 50 to 60 ° C.
  • the recesses 5b are formed around the conductive particles 3 with insulating particles exposed from the insulating resin layer 5, and thus the anisotropic conductive film is produced when it is pressed onto the article.
  • the resistance received from the insulating resin against the flattening of the conductive particles 3 with insulating particles is reduced as compared with the case where there is no recess 5b. For this reason, it becomes easy for the conductive particles to be sandwiched between the terminals at the time of anisotropic conductive connection, so that the conduction performance is improved and the trapping property is improved.
  • the recess 5c (FIG. 3B) is formed on the surface of the insulating resin layer 5 immediately above the conductive particles 3 with insulating particles buried without being exposed from the insulating resin layer 5, there is no recess 5c.
  • the pressure at the time of pressure-bonding the anisotropic conductive film to the article tends to concentrate on the conductive particles 3 with insulating particles. For this reason, the trapping property is improved because the conductive particles are easily held between the terminals at the time of anisotropic conductive connection, and the conduction performance is improved.
  • the embedding rate when the conductive particles with insulating particles 3 are pushed into the insulating resin layer 5 is 100% or less, and the conductive particles with insulating particles 3 are the insulating resin layer.
  • the insulating resin layer 5 with the insulating particles is pressed into the insulating resin layer 5 after the insulating particles with the insulating particles 5 are pushed in.
  • a recess 5b (FIG. 3A) may be formed around the conductive particles 3. At this time, only insulating particles may be exposed.
  • a recess 5c may be formed on the surface of the insulating resin layer 5. The meaning of the embedding rate will be described in detail in the description of the embedded state of the conductive particles with insulating particles in the subsequent stage.
  • Such recesses 5b and 5c are formed according to the viscosity, pressing speed, temperature, and the like of the insulating resin layer 5 when the conductive particles with insulating particles 3 are pressed into the insulating resin layer 5. Although the presence or absence of the recesses 5b and 5c does not particularly affect the effect of the present invention, the recesses 5b and 5c having a large recess depth (for example, the depth of the deepest portion of the recess is the particle diameter D of the conductive particles with insulating particles). If there is a region where 10% or more of the region is locally concentrated, if such a region is bonded to the substrate, depending on the material or surface state of the substrate, the anisotropic conductive connection in that region may occur.
  • the surface of the anisotropic conductive film having such a region is heated and pressed to such an extent that it does not interfere with the anisotropic conductive connection, or the dent 5b is dispersed by spraying resin. It is preferable to make 5c shallower or flat. In this case, it is preferable that the resin to be dispersed has a lower viscosity than the resin that forms the insulating resin layer 5. The concentration of the resin to be sprayed may be diluted to such an extent that the dent of the insulating resin layer 5 can be confirmed after the spraying.
  • the anisotropic conductive film 10A has a conductive particle dispersion layer, that is, a layer in which the conductive particles with insulating particles 3 are regularly dispersed with one surface of the insulating resin layer 5 exposed (FIGS. 3A and 3B). ).
  • the conductive particles 3 with insulating particles are not in contact with each other in a plan view of the film, and the conductive particles 3 with insulating particles are regularly dispersed in the film thickness direction without overlapping each other.
  • a single-layer conductive particle layer having a uniform position in the thickness direction is formed.
  • a slope 5b is formed on the surface 5a of the insulating resin layer 5 in the vicinity of each of the conductive particles with insulating particles 3 with respect to the tangential plane 5p of the insulating resin layer 5 at the center between adjacent conductive particles with insulating particles.
  • inclination means that the flatness of the surface of the insulating resin layer is impaired in the vicinity of the conductive particles 3 with insulating particles, and a part of the insulating resin layer is missing from the tangential plane 5p. This means that the amount is decreasing. In other words, in the inclination, the surface of the insulating resin layer in the vicinity of the conductive particles with insulating particles is missing from the tangent plane.
  • “undulation” means that the surface of the insulating resin layer directly above the conductive particles with insulating particles has undulations, and the resin is reduced due to the presence of a part with a difference in elevation such as undulations. To do.
  • the resin amount of the insulating resin layer immediately above the conductive particles with insulating particles is smaller than when the surface of the insulating resin layer immediately above the conductive particles with insulating particles is in a tangential plane. Therefore, only the insulating particles may be exposed in the swell. These can be recognized by comparing a portion corresponding to the conductive particles with insulating particles and a flat surface portion (FIGS. 3A and 3B) between the conductive particles. In some cases, the starting point of undulations exists as a slope.
  • the conductive particles 3 with insulating particles at the time of anisotropic conductive connection. Since the resistance received from the insulating resin with respect to the flattening of the conductive particles 3 with insulating particles generated when the particles are sandwiched between the terminals is reduced as compared with the case where there is no inclination 5b, the conductive particles with insulating particles at the terminals As a result, the conduction performance is improved and the trapping property is improved.
  • This inclination is preferably along the outer shape of the conductive particles with insulating particles.
  • the inclination and the undulation may be partially lost by heat-pressing the insulating resin layer, and the present invention includes this.
  • the conductive particles with insulating particles may be exposed at one point on the surface of the insulating resin layer.
  • the anisotropic conductive film has a variety of electronic parts to be connected, and as long as it is tuned according to these, it is desired that the degree of freedom of design is high enough to satisfy various requirements, so the inclination or undulation is reduced. It can be used even if it disappears or partially disappears.
  • the undulations 5c are formed on the surface of the insulating resin layer 5 directly above the conductive particles 3 with insulating particles buried without being exposed from the insulating resin layer 5, the case of inclination Similarly, a pressing force from the terminal is easily applied to the conductive particles with insulating particles during anisotropic connection.
  • the amount of resin immediately above the conductive particles with insulating particles is reduced compared to when the resin is deposited flat due to undulations, the resin directly above the conductive particles with insulating particles at the time of connection is eliminated. This facilitates the contact between the terminal and the conductive particle with insulating particles, so that the trapping property of the conductive particle with insulating particles at the terminal is improved, and the conduction reliability is improved.
  • the position of the conductive particles 3 with insulating particles in the thickness direction of the insulating resin layer 5 in consideration of the viewpoint of “inclination” or “undulation” is the same as described above.
  • 5 may be exposed or may be embedded in the insulating resin layer 5 without being exposed, but the conductive with insulating particles from the tangential plane 5p in the central portion between the adjacent conductive particles with insulating particles.
  • the ratio (Lb / D) (hereinafter referred to as the embedding rate) of the distance Lb of the deepest part of the particles (hereinafter referred to as the embedding amount) to the particle diameter D of the conductive particles with insulating particles is 30% or more and 105% or less. In order to obtain the effects of the invention, it is more preferable that the ratio be 60% or more and 105% or less.
  • the embedding rate (Lb / D) is 30% or more and less than 60%, the ratio of the conductive particles with insulating particles exposed from the relatively high viscosity insulating resin layer holding the conductive particles with insulating particles becomes high. Therefore, lower temperature and low pressure mounting becomes easier.
  • the conductive particles 3 with insulating particles can be easily maintained in a predetermined particle dispersion state or a predetermined arrangement by the insulating resin layer 5. Further, since the contact area between the conductive particles with insulating particles and the resin at the time of manufacture (pushing into the film) becomes large, it can be expected that the effects of the invention can be easily obtained.
  • the resin amount of the insulating resin layer which acts so that the electrically-conductive particle between terminals may flow unnecessarily at the time of anisotropic conductive connection can be reduced.
  • the value of the embedding rate (Lb / D) is 80% or more, preferably 90% or more, more preferably 96% or more of the total number of conductive particles with insulating particles contained in the anisotropic conductive film. It means that it is a numerical value of the inclusion rate (Lb / D). Therefore, the embedding rate of 30% or more and 105% or less means that the embedding rate is 80% or more, preferably 90% or more, more preferably 96% or more of the total number of conductive particles with insulating particles contained in the anisotropic conductive film. The rate is 30% or more and 105% or less.
  • the pressing load is uniformly applied to the conductive particles with insulating particles, so that the state of trapping the conductive particles with insulating particles at the terminal is captured. Is improved and the stability of conduction is improved.
  • the embedding rate (Lb / D) was determined by arbitrarily extracting 10 or more regions having an area of 30 mm 2 or more from the anisotropic conductive film, observing a part of the film cross section with an SEM image, and totaling 50 or more insulating particles. It can be determined by measuring attached conductive particles. In order to increase the accuracy, 200 or more conductive particles with insulating particles may be measured and obtained.
  • the measurement of the embedding rate (Lb / D) can be obtained collectively for a certain number by adjusting the focus in the surface field image.
  • a laser discrimination displacement sensor manufactured by Keyence Co., Ltd. may be used for measuring the embedding rate (Lb / D).
  • the ratio (Le / D) between the maximum depth Le of the inclination 5b and the particle diameter D of the conductive particles 3 with insulating particles is preferably less than 50%, more preferably less than 30%, and even more preferably 20 to 25%.
  • the ratio (Ld / D) between the maximum diameter Ld of the slope 5b or the undulation 5c and the particle diameter D of the conductive particles 3 with insulating particles is preferably 100% or more, more preferably 100 to 150%.
  • the ratio (Lf / D) between the maximum depth Lf of 5c and the particle diameter D of the conductive particles 3 with insulating particles is greater than 0, preferably less than 10%, more preferably 5% or less.
  • the diameter Lc of the exposed (immediately above) portion of the conductive particles 3 with insulating particles in the slope 5b or the undulation 5c can be equal to or smaller than the particle diameter D of the conductive particles 3 with insulating particles, and preferably 10 to 10 times the particle diameter D. 90%.
  • the conductive particles with insulating particles 3 may be exposed at one point on the top, or the conductive particles with insulating particles 3 are completely buried in the insulating resin layer 5 so that the diameter Lc becomes zero. Good.
  • the presence of the slopes 5b and undulations 5c on the surface of the insulating resin layer 5 can be confirmed by observing the cross section of the anisotropic conductive film with a scanning electron microscope. Can also be confirmed.
  • the tilt 5b and the undulations 5c can be observed even with an optical microscope or a metal microscope.
  • size of the inclination 5b and the undulation 5c can also be confirmed by the focus adjustment at the time of image observation. The same applies even after the inclination or undulation is reduced by heat pressing as described above. This is because traces may remain.
  • the insulating resin layer 5 is preferably formed from a curable resin composition, and can be formed from, for example, a thermopolymerizable composition containing a thermopolymerizable compound and a thermal polymerization initiator. You may make a thermopolymerizable composition contain a photoinitiator as needed.
  • thermopolymerizable compound When a thermal polymerization initiator and a photopolymerization initiator are used in combination, one that also functions as a photopolymerizable compound may be used as the thermopolymerizable compound, and a photopolymerizable compound is contained separately from the thermopolymerizable compound. May be. Preferably, a photopolymerizable compound is contained separately from the thermally polymerizable compound.
  • a cationic curing initiator is used as the thermal polymerization initiator
  • an epoxy resin is used as the thermopolymerizable compound
  • a photo radical initiator is used as the photopolymerization initiator
  • an acrylate compound is used as the photopolymerizable compound.
  • the photopolymerization initiator As the photopolymerization initiator, a plurality of types that react to light having different wavelengths may be contained. Accordingly, the wavelength used for the photocuring of the resin constituting the insulating resin layer during the production of the anisotropic conductive film and the photocuring of the resin for bonding the electronic components to each other during the anisotropic conductive connection. Can be used properly.
  • all or part of the photopolymerizable compound contained in the insulating resin layer can be photocured.
  • the arrangement of the conductive particles with insulating particles 3 in the insulating resin layer 5 is maintained or fixed, and it is expected that the short circuit is suppressed and the conductive particles are captured better.
  • the blending amount of the photopolymerizable compound in the insulating resin layer is preferably 30% by mass or less, more preferably 10% by mass or less, and more preferably less than 2% by mass. This is because when the amount of the photopolymerizable compound is too large, the thrust applied to the pushing at the time of connection increases.
  • thermally polymerizable composition examples include a thermal radical polymerizable acrylate composition containing a (meth) acrylate compound and a thermal radical polymerization initiator, and a thermal cationic polymerizable epoxy system containing an epoxy compound and a thermal cationic polymerization initiator.
  • examples thereof include compositions.
  • a thermal anionic polymerizable epoxy composition containing a thermal anionic polymerization initiator may be used.
  • a plurality of types of polymerizable compositions may be used in combination as long as there is no particular problem. Examples of the combination include a combination of a cationic polymerizable compound and a radical polymerizable compound.
  • the (meth) acrylate compound a conventionally known thermal polymerization type (meth) acrylate monomer can be used.
  • a monofunctional (meth) acrylate monomer or a bifunctional or higher polyfunctional (meth) acrylate monomer can be used.
  • thermal radical polymerization initiator examples include organic peroxides and azo compounds.
  • organic peroxides that does not generate nitrogen that causes bubbles can be preferably used.
  • the amount of the thermal radical polymerization initiator used is preferably 2 to 60 parts by weight, more preferably 100 parts by weight of the (meth) acrylate compound. 5 to 40 parts by mass.
  • the epoxy compound examples include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a novolac type epoxy resin, a modified epoxy resin thereof, an alicyclic epoxy resin, and the like. it can.
  • an oxetane compound may be used in combination.
  • thermal cationic polymerization initiator those known as thermal cationic polymerization initiators for epoxy compounds can be employed.
  • thermal cationic polymerization initiators for epoxy compounds.
  • iodonium salts, sulfonium salts, phosphonium salts, ferrocenes, etc. that generate an acid by heat are used.
  • an aromatic sulfonium salt showing a good potential with respect to temperature can be preferably used.
  • the amount of the thermal cationic polymerization initiator used is preferably 2 to 60 mass relative to 100 parts by mass of the epoxy compound. Part, more preferably 5 to 40 parts by weight.
  • the thermopolymerizable composition preferably contains a film-forming resin and a silane coupling agent.
  • the film-forming resin include phenoxy resin, epoxy resin, unsaturated polyester resin, saturated polyester resin, urethane resin, butadiene resin, polyimide resin, polyamide resin, polyolefin resin, and the like. be able to.
  • a phenoxy resin can be preferably used from the viewpoint of film forming property, workability, and connection reliability.
  • the weight average molecular weight is preferably 10,000 or more.
  • the silane coupling agent include an epoxy silane coupling agent and an acrylic silane coupling agent. These silane coupling agents are mainly alkoxysilane derivatives.
  • the thermally polymerizable composition may contain an insulating filler separately from the conductive particles with insulating particles 3 described above.
  • examples of this include silica powder and alumina powder.
  • a fine filler having an insulating filler particle size of 20 to 1000 nm is preferable, and the blending amount is preferably 5 to 50 parts by mass with respect to 100 parts by mass of a thermally polymerizable compound (photopolymerizable compound) such as an epoxy compound. .
  • the anisotropic conductive film of the present invention contains a filler, softener, accelerator, anti-aging agent, colorant (pigment, dye), organic solvent, ion catcher agent, etc. in addition to the above-mentioned insulating filler. You may let them.
  • the ratio (La / D) between the layer thickness La of the insulating resin layer 5 and the particle diameter D of the conductive particles with insulating particles 3 is 0.3 or more because of the reason described later.
  • the upper limit can be made 10 or less. Therefore, the ratio is preferably 0.3 to 10, more preferably 0.6 to 8, and still more preferably 0.6 to 6.
  • the particle diameter D of the conductive particles 3 with insulating particles means the average particle diameter.
  • the ratio (La / D) is preferably 0.3 or more, and the insulating resin layer 5 ensures that the predetermined particle dispersion state or the predetermined arrangement is reliably maintained by 0.6.
  • the above is more preferable.
  • the ratio (La / D) between the layer thickness La of the insulating resin layer 5 and the particle diameter D of the conductive particles 3 with insulating particles is preferably 0.8-2. is there.
  • the burying rate is 30% or more and 105% or less.
  • the conductive particles 3 with insulating particles can be maintained in a predetermined particle dispersion state or a predetermined arrangement by the insulating resin layer 5.
  • the embedding rate it is possible to reduce the amount of resin in the insulating resin layer that acts to cause the conductive particles with insulating particles to flow unnecessarily during anisotropic conductive connection.
  • the embedding rate is the surface 5a of the insulating resin layer 5 in which the conductive particles 3 with insulating particles are embedded (the surface on which the conductive particles 3 with insulating particles are unevenly distributed in the insulating resin layer 5). ) And the deepest portion of the conductive particles with insulating particles 3 embedded in the insulating resin layer 5 with respect to the surface 5a is the embedded amount Lb, with respect to the particle diameter D of the conductive particles with insulating particles 3 It is the ratio (Lb / D) of the embedding amount Lb (FIG. 1B).
  • the value of the embedding rate (Lb / D) is 80% or more, preferably 90% or more, more preferably 96% or more of the total number of conductive particles with insulating particles contained in the anisotropic conductive film.
  • the embedding rate of 30% or more and 105% or less means that the embedding rate is 80% or more, preferably 90% or more, more preferably 96% or more of the total number of conductive particles with insulating particles contained in the anisotropic conductive film.
  • the rate is 30% or more and 105% or less.
  • the embedding rate (Lb / D) of the conductive particles with all insulating particles is uniform, the load of pressing is uniformly applied to the conductive particles, so that the state of capturing the conductive particles at the terminals is improved and the conduction is improved. Improves stability.
  • the embedding rate (Lb / D) was determined by arbitrarily extracting 10 or more regions having an area of 30 mm 2 or more from the anisotropic conductive film, observing a part of the film cross section with an SEM image, and totaling 50 or more conductive particles. Can be obtained by measuring In order to increase accuracy, 200 or more conductive particles may be measured and obtained.
  • the measurement of the embedding rate (Lb / D) can be obtained collectively for a certain number by adjusting the focus in the surface field image.
  • a laser discrimination displacement sensor manufactured by Keyence Co., Ltd. may be used for measuring the embedding rate (Lb / D).
  • the recesses 31 of the transfer mold 30 are filled with the conductive particles with insulating particles 3 (FIG. 4A).
  • the recesses 31 are formed in the same arrangement as the conductive particles 3 with insulating particles in the anisotropic conductive film.
  • a transfer mold 30 for example, an inorganic material such as silicon, various ceramics, glass, stainless steel, or the like, or an organic material such as various resins may be formed by a known opening forming method such as a photolithographic method. What formed the recessed part 31 can be used. Further, the transfer mold can take a plate shape, a roll shape or the like.
  • the insulating resin layer 5 is formed in a film shape on the release film 7, and the insulating resin layer 5 is put on the conductive particles 3 with insulating particles filled in the transfer mold 30 (FIG. 4C).
  • the insulating particles 2 are removed from the conductive particles 1 by bringing the flat plate 32 into contact with the conductive particles with insulating particles 3 filled in the transfer mold 30. Then, the insulating resin layer 5 may be covered (FIG. 4C).
  • the insulating resin layer 5 is peeled from the transfer mold 30 to obtain the insulating resin layer 5 to which the conductive particles with insulating particles 3 are transferred (FIG. 4D).
  • the transfer mold 30 and the insulating particles 2 are rubbed, so that the insulating particles 2 that are in contact with the bottom surface of the recess 31 of the transfer mold 30 (the ones that become the insulating particles 2 in the region A1). Is easily detached from the conductive particles 3 with insulating particles. Further, when the insulating resin layer 5 is placed on the conductive particles 3 with insulating particles in the transfer mold 30, a large force is applied to the insulating particles 2 that first contact the insulating resin layer 5. The particles 2 (those that become the insulating particles 2 in the region A2) may also be detached. For this reason, the insulating particles 2 may be present (dotted) on the film.
  • the insulating particles 2 in the film surface direction are maintained on the insulating resin layer 5 without being detached from the insulating resin layer 5 even after the insulating resin layer 5 is peeled off from the transfer mold 30.
  • the conductive particles 3 with insulating particles after being transferred to the insulating resin layer 5 are in contact with the conductive particles 1 in the film thickness direction among the insulating particles 2 constituting the conductive particles 3 with insulating particles as compared to before the transfer.
  • the number of insulating particles 2 is reduced as compared with the number of insulating particles 2 in contact with the conductive particles 1 in the film surface direction.
  • the conductive particles with insulating particles 3 transferred to the insulating resin layer 5 are pushed in with a flat plate or a roller 33 (FIG. 4E).
  • the insulating particles 2 that have formed the conductive particles 3 with insulating particles at the time of pressing, and the insulating particles 2 (insulating particles 2 to be the region A1) on the flat plate or roller 33 side are in contact with the flat plate or roller 33. Is relatively detached from the conductive particles 1.
  • the indentation rate (Lb / D) is preferably 30% or more and 105% or less, more preferably 60, when the conductive particles 3 with insulating particles transferred to the insulating resin layer 5 are pressed with a flat plate or roller 33. It is preferable to adjust so that it may become more than% and below 105%, and it is preferable to determine according to the thrust etc. which are required for a pressing jig for pushing.
  • an anisotropic conductive film 10A in which the number of insulating particles 2 in contact with the conductive particles 1 in the thickness direction of the anisotropic conductive film among the number of insulating particles 2 in the conductive particles 3 with insulating particles is reduced can be obtained. Yes (FIG. 4F).
  • the number of the insulating particles 2 detached from the initial conductive particles 3 with insulating particles depends on the temperature and viscosity of the insulating resin layer 5 and the embedding rate (Lb / D) or the like.
  • the anisotropic conductive film of the present invention has an insulating resin layer 5 in which the conductive particles with insulating particles 3 are embedded, as in the anisotropic conductive film 10B shown in FIG.
  • a low viscosity insulating resin layer 6 having a low minimum melt viscosity may be laminated.
  • the minimum melt viscosity ratio between the insulating resin layer 5 and the low-viscosity insulating resin layer 6 is preferably 2 or more, more preferably 5 or more, still more preferably 8 or more, and practically 15 or less.
  • the more specific minimum melt viscosity of the low-viscosity insulating resin layer 6 is 3000 Pa ⁇ s or less, more preferably 2000 Pa ⁇ s or less, and particularly preferably 1000 to 2000 Pa ⁇ s.
  • the amount is relatively small, and the conductive particles with insulating particles 3 between the terminals are less likely to flow due to resin flow. Therefore, the adhesiveness between the electronic components can be improved without impairing the trapping property of the conductive particles 3 with insulating particles during anisotropic conductive connection.
  • the minimum melt viscosity of the entire anisotropic conductive film 10B including the insulating resin layer 5 and the low-viscosity insulating resin layer 6 is preferably 200 to 4000 Pa ⁇ s.
  • the low-viscosity insulating resin layer 6 can be formed by adjusting the viscosity in the same resin composition as the insulating resin layer 5.
  • the layer thickness of the low-viscosity insulating resin layer 6 is preferably 4 to 20 ⁇ m. Alternatively, it is preferably 1 to 8 times the particle diameter D of the conductive particles with insulating particles.
  • the anisotropic conductive film 10C may be used as the anisotropic conductive film 10C (FIG. 6) after the insulating resin layer 5 is peeled from the transfer mold 30 and before the conductive particles 3 with insulating particles are pushed.
  • the laminated conductive resin layer 6 may be an anisotropic conductive film 10D (FIG. 7).
  • the conductive particles with insulating particles may exist between the insulating resin layer and the low-viscosity insulating resin layer.
  • the number of insulating particles on the conductive particles in a plan view of the low viscosity insulating resin layer side film surface is smaller than the number of insulating particles on the conductive particles in a plan view of the insulating resin layer side film surface.
  • a plurality of conductive particles 3 with insulating particles may be provided at different positions in the film thickness direction. These deformation modes can be appropriately combined.
  • the anisotropic conductive film of the present invention anisotropically conducts first electronic components such as IC chips, IC modules, and FPCs and second electronic components such as FPCs, glass substrates, plastic substrates, rigid substrates, and ceramic substrates. It can be preferably used when connecting. IC chips and wafers may be stacked to be multilayered.
  • the electronic component connected with the anisotropic conductive film of this invention is not limited to the above-mentioned electronic component. It can be used for various electronic parts that have been diversified in recent years.
  • the present invention provides a method for manufacturing a connection structure for anisotropically conductively connecting electronic components using the anisotropic conductive film of the present invention, and the connection structure obtained by this manufacturing method, that is, facing the connection structure.
  • the terminal of the electronic component is a connection structure in which the conductive particles with insulating particles and the insulating resin layer are anisotropically conductively connected, and the conductive particles with insulating particles that are not sandwiched between opposing terminals are connected to each other.
  • a connection structure including conductive particles with insulating particles having an insulating particle missing region facing in the opposite direction is provided.
  • the conductive particles with insulating particles are also included in the conductive particles with insulating particles sandwiched between the opposing terminals and have insulating particle missing regions facing the opposing direction of the terminals.
  • the opposing direction of the terminals corresponds to the film thickness direction of the anisotropic conductive film of the present invention used for the production of the connection structure
  • the connection surface direction of the terminals is the anisotropic conductive film.
  • the insulating particle missing region refers to a region where a part of the surface of the conductive particle with insulating particles has a lower surface density of the insulating particles than the outer annular portion.
  • the conductive particles with insulating particles sandwiched between the opposing terminals correspond to the region A1 or A2 in which the number of insulating particles is reduced in the anisotropic conductive film described above. It can be said that the number of insulating particles in contact with the conductive particles in the opposing direction between them is smaller than the number of insulating particles in contact with the conductive particles in the connecting surface direction of the terminals (direction orthogonal to the opposing direction of the terminals).
  • Such conductive particles with insulating particles are held by the insulating resin until the direction of the insulating particle missing region of the conductive particles with insulating particles that are not sandwiched between the opposing terminals is just sandwiched between the terminals.
  • the conductive particles with insulating particles sandwiched between the opposing terminals are preferable in terms of conduction stability because the insulating particle missing region is in contact with at least one of the opposing terminals. More preferably, both are in contact.
  • connection structure the conductive particles with insulating particles in which the region lacking the insulating particles faces the opposing direction of the terminals, as described above, the region A1 or A2 in which the number of insulating particles is reduced in the anisotropic conductive film. Therefore , the relationship of (N A3 + N A4 )> (N A1 + N A2 ) in the anisotropic conductive film is satisfied.
  • a partial region of the surface of the sphere corresponding to a central angle of 45 ° is This can be said to be a partial region of the surface of the sphere corresponding to the central angle 45 ° when the surface density of the insulating particles is lower than the annular region corresponding to the outer central angle 45 ° to 135 °.
  • connection structure conductive particles with insulating particles that are not sandwiched between opposing terminals are sandwiched between non-formation regions of the terminal rows in the electronic component, out of the connection surfaces of the opposing electronic component.
  • the conductive particles with insulating particles in this case are, for example, when the opposing electronic parts are the first electronic part and the second electronic part, the terminal row non-formation region in the first electronic component and the terminal row in the second electronic component It is the electroconductive particle with an insulating particle pinched
  • the conductive particles with insulating particles that are not sandwiched between the opposing terminals are the inter-terminal spaces of the opposing electronic components when the terminal rows are formed on the electronic components with the predetermined inter-terminal spaces. Including conductive particles with insulating particles between them.
  • the conductive particles with insulating particles that are not sandwiched between opposing terminals mean the majority of conductive particles with insulating particles that do not contribute to connection in the connection structure.
  • the conductive particles with insulating particles that are not sandwiched between the opposing terminals are those that have moved relative to the state before the heating and pressurization due to the heating and pressurization during the anisotropic conductive connection. Some are included and have changed orientation. The degree of change in direction varies depending on the position of the conductive particles with insulating particles with respect to the terminals, the viscosity of the insulating resin layer, the heating and pressing conditions, etc. This includes those that maintain their orientation. Therefore, when the anisotropic conductive film used in the manufacture of the connection structure is the anisotropic conductive film of the present invention, at least some of the conductive particles with insulating particles that are not sandwiched between opposing terminals include insulating particles.
  • the missing region includes those facing the opposing direction of the opposing terminals, which is the connection structure of the present invention.
  • the connection structure is the connection structure of the present invention. It is easy to see that
  • An anisotropic conductive film may be cut to approximately the same size as one outer shape of an electronic component, but is generally cut to be larger than one outer shape of an electronic component. That is, it may include a region that does not contribute to the connection (separately away from the tool). Therefore, there may be a region lacking insulating particles facing the opposing direction of the terminals in the outer anisotropic conductive film between the opposing electronic components, and from here also confirm the characteristics of the connection structure of the present invention. Can do.
  • the conductive particles with insulating particles are regularly arranged in the anisotropic conductive film used for manufacturing the connection structure, the conductive particles with insulation particles that are not sandwiched between opposing terminals in the connection structure are also arranged. Maintenance of regularity may be found. In this case, in the conductive particles with insulating particles in which the regularity of the arrangement is found, it can be easily confirmed that the insulating particle missing region is facing the facing direction of the terminals. Moreover, ( NA3 + NA4 )> ( NA1 + NA2 ) can be easily confirmed about the anisotropic conductive film used for the manufacture.
  • connection structure of the present invention it is a structure in the manufacturing process of the connection structure of the present invention, and the anisotropic conductive film of the present invention is attached to one electronic component, but the other electronic component is not yet connected
  • the conductive particles with insulating particles in the anisotropic conductive film are the insulating particles in the connection structure described above (the intermediate product in the connection process, in other words, the anisotropic conductive film-attached electronic component). It has the same characteristics as the attached conductive particles.
  • the resin layer of the anisotropic conductive film is a single layer of the insulating resin layer 5, it is anisotropic to the second electronic component such as various substrates.
  • the conductive particles with insulating particles 3 of the conductive conductive film are temporarily pressure-bonded from the side embedded in the surface, and the IC chips or the like are provided on the side of the anisotropically conductive film 3 with the insulating particles with insulating particles embedded therein that are not embedded in the surface.
  • the insulating resin layer of the anisotropic conductive film contains not only a thermal polymerization initiator and a thermal polymerizable compound, but also a photopolymerization initiator and a photopolymerizable compound (may be the same as the thermal polymerizable compound), A pressure bonding method using both light and heat may be used. In this way, unnecessary movement of the conductive particles with insulating particles can be minimized. Further, the side on which the conductive particles with insulating particles 3 are not embedded may be temporarily attached to the second electronic component for use. Note that the anisotropic conductive film may be temporarily attached to the first electronic component instead of the second electronic component.
  • the insulating resin layer 5 is used as a second electronic component such as various substrates.
  • the first electronic component such as an IC chip is aligned and placed on the low-viscosity insulating resin layer 6 of the anisotropic conductive film that has been temporarily attached and temporarily bonded, and then subjected to thermocompression bonding.
  • the low-viscosity insulating resin layer 6 side of the anisotropic conductive film may be temporarily attached to the first electronic component for use.
  • the resin composition for forming the insulating resin layer is applied onto a PET film having a film thickness of 50 ⁇ m with a bar coater, dried in an oven at 80 ° C. for 5 minutes, and the insulating resin layer having the thickness shown in Table 2 is formed on the PET film. Formed. Similarly, low-viscosity insulating resin layers were formed on PET films with the thicknesses shown in Table 2, respectively.
  • the conductive particles with insulating particles have a square lattice arrangement shown in FIG. 1A in plan view, and the mold is set so that the distance between particles is equal to the particle diameter of the conductive particles with insulating particles and the number density is 28000 / mm 2.
  • the convex pattern of the mold (number density 28000 pieces / mm 2 ) is a square lattice arrangement, the pitch of the convex portions on the lattice axis is twice the average particle diameter, and the short of the lattice axis and the anisotropic conductive film.
  • a mold having an angle ⁇ of 15 ° with the hand direction is manufactured, and a known transparent resin pellet is melted and poured into the mold, cooled and solidified, whereby the recesses are arranged as shown in FIG. 1A.
  • a resin mold of the pattern was formed.
  • the mold of the convex portion pattern (number density 28000 pieces / mm 2) to create a material obtained by randomly recess using the mold to form a resin mold as a random pattern.
  • the distance between the conductive particles of adjacent conductive particles with insulating particles was set to be 0.5 times or more the average diameter of the conductive particles.
  • insulating fine particles (average particle size of 0) are formed on the surface of metal-coated resin particles (Sekisui Chemical Co., Ltd., AUL703, average particle size of 3 ⁇ m) according to the description in JP-A No. 2014-132567. .3 ⁇ m) was prepared, and the conductive particles with insulating particles were filled in the resin-shaped recesses, and the above-mentioned insulating resin layer was covered thereon.
  • the insulating resin layer was pressed at 60 ° C. and 0.5 MPa, and the insulating resin layer was peeled off from the resin mold to transfer the conductive particles with insulating particles to the insulating resin layer. .
  • the embedding rate (Lb / D) of the conductive particles with insulating particles in the insulating resin layer was 30% in cross-sectional observation by SEM.
  • there was no dent around the conductive particles with insulating particles on the surface of the insulating resin layer to which the conductive particles with insulating particles were transferred (see FIG. 2).
  • Example 7 to 10 the conductive particles with insulating particles were transferred to the insulating resin layer in the same manner as in Examples 1 to 2, but the dents were formed in the insulating resin layer around the conductive particles with insulating particles after transfer.
  • the temperature when pressing the conductive particles with insulating particles against the insulating resin layer was made lower than 60 ° C.
  • Example 3 to 10 the conductive particles with insulating particles were pressed into the insulating resin layer at a pressing rate (Lb / D) of 100% by pressing the conductive particles with insulating particles on the insulating resin layer.
  • the temperature and pressure at the time of pressing were the same as those described above when the conductive particles with insulating particles were transferred from the resin mold to the insulating resin layer.
  • there is no dent in the insulating resin layer around the conductive particles with insulative particles after being pushed in and in Examples 7 to 10 the insulating resin layer around the conductive particles with insulative particles after being pushed in The dent was formed in (refer FIG. 3A).
  • Examples 5 to 10 the low-viscosity insulating resin layer was not laminated.
  • a depression was formed in the insulating resin layer around the conductive particles with insulating particles in a state where the conductive particles with insulating particles were pressed into the insulating resin layer.
  • No. 10 eliminated the dent by heating and pressing the insulating resin layer having a dent under the condition that the anisotropic conductive connection was not hindered.
  • Comparative Examples 1 to 4 In Comparative Examples 1 to 4, insulating coated conductive particles (coated film thickness: 0.1 to 0.5 ⁇ m) in which an insulating coating is applied to the entire surface of metal-coated resin particles (Sekisui Chemical Co., Ltd., AUL703, average particle diameter of 3 ⁇ m) Is used in place of the conductive particles with insulating particles of the above-mentioned embodiment, the above-mentioned resin mold is filled so that the insulating coated conductive particles are arranged or arranged as shown in Table 2, and the insulating resin layer is insulated with the insulating coated conductive material.
  • metal-coated resin particles Sekisui Chemical Co., Ltd., AUL703, average particle diameter of 3 ⁇ m
  • the particles were transferred (indentation rate 30%), and in Comparative Examples 3 and 4, the insulating coated conductive particles transferred to the insulating resin layer were pressed into the insulating resin layer so that the indentation rate was 100%. And the low-viscosity insulating resin layer was laminated
  • the insulating particle coverage of the conductive particles with insulating particles (conductive particles with insulating particles before embedding in the insulating resin layer) used in the production of the anisotropic conductive film of the example was determined. .
  • the insulating particle coverage is measured by observing 100 conductive particles with insulating particles using a scanning electron microscope (SEM) and measuring the number of insulating particles per conductive particle for each conductive particle with insulating particles. The calculated number was calculated from the area in plan view of one conductive particle with insulating particles and the area in plan view of one insulating particle.
  • SEM scanning electron microscope
  • the IC for evaluation and the glass substrate correspond to their terminal patterns, and the sizes are as follows. Further, when connecting the evaluation IC and the glass substrate, the longitudinal direction of the anisotropic conductive film and the short direction of the bump were matched.
  • the measured incidence of short circuit was evaluated according to the following criteria. A: Less than 50 ppm B: 50 ppm or more and 200 ppm or less C: Above 200 ppm, there is no practical problem if it is evaluated as B.
  • Examples 5 and 6 in which the insulating resin layer around the conductive particles with insulating particles does not have a dent, and Examples 7 and 8 in which the insulating resin layer around the conductive particles with insulating particles have a dent also have dents.
  • Examples 9 and 10 which were eliminated by heating and pressing the initial conduction resistance, conduction reliability, short-circuit occurrence rate, and conductive particle capturing property were also good. From this, it can be seen that in this example, the conductive particles with insulating particles did not move unnecessarily due to the resin flow regardless of the presence or absence of dents.

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Abstract

This anisotropic conductive film, which is capable of reliably inhibiting the occurrence of a short circuit, while reducing the conduction resistance of a connection structure that is anisotropically conductively connected, has a structure wherein conductive particles 3 with insulating particles, each of which is obtained by having insulating particles 2 adhere to the surface of a conductive particle 1, are dispersed in an insulating resin layer 5. With respect to the conductive particles 3 with insulating particles in this anisotropic conductive film, the number of insulating particles 2 in contact with a conductive particle 1 in the film thickness direction is smaller than the number of insulating particles 2 in contact with the conductive particle 1 in the film surface direction. The number of insulating particles overlapping conductive particles in a plan view of one of the front and back surfaces of this anisotropic conductive film is preferably smaller than the number of insulating particles overlapping conductive particles in a plan view of the other surface.

Description

異方性導電フィルムAnisotropic conductive film
 本発明は、異方性導電フィルムに関する。 The present invention relates to an anisotropic conductive film.
 ICチップなどの電子部品の実装に異方性導電フィルムは広く使用されている。異方性導電フィルムを高実装密度に対応させる観点から、異方性導電フィルムでは、その絶縁性樹脂層に導電粒子を高密度に分散させることが行われている。しかしながら、導電粒子の密度を高めることはショートの発生要因となる。 Anisotropic conductive films are widely used for mounting electronic components such as IC chips. From the viewpoint of making an anisotropic conductive film correspond to a high mounting density, in an anisotropic conductive film, conductive particles are dispersed in the insulating resin layer at a high density. However, increasing the density of the conductive particles is a cause of short circuit.
 これに対し、従前の導電粒子に代えて、導電粒子の表面に絶縁粒子を付着させた絶縁粒子付導電粒子を使用することが提案されている(特許文献1)。この絶縁粒子付導電粒子をバインダー樹脂にミキサーを用いて混練りし、フィルム化することにより異方性導電フィルムを得ることができる。 In contrast, it has been proposed to use conductive particles with insulating particles in which insulating particles are attached to the surface of the conductive particles instead of the conventional conductive particles (Patent Document 1). An anisotropic conductive film can be obtained by kneading the conductive particles with insulating particles in a binder resin using a mixer and forming a film.
特開2014-132567号公報JP 2014-132567 A
 しかしながら、特許文献1に記載のように絶縁粒子付導電粒子をバインダー樹脂とミキサーを用いて混練りすると、絶縁粒子が導電粒子から単離してしまい、絶縁粒子付導電粒子の本来の絶縁性を得られない場合がある。そのため、絶縁粒子付導電粒子をバインダー樹脂に高密度に分散させた異方性導電フィルムを用いて異方性導電接続した電子部品の接続構造体ではショートが発生する虞がある。 However, as described in Patent Document 1, when the conductive particles with insulating particles are kneaded using a binder resin and a mixer, the insulating particles are isolated from the conductive particles, and the original insulating properties of the conductive particles with insulating particles are obtained. It may not be possible. Therefore, there is a possibility that a short circuit may occur in a connection structure of an electronic component that is anisotropically conductively connected using an anisotropic conductive film in which conductive particles with insulating particles are dispersed in a binder resin at high density.
 また、この異方性導電フィルムを用いた異方性導電接続では、絶縁粒子付導電粒子が電子部品の端子に押し付けられるとき、導電粒子だけでなく、絶縁粒子が端子に押し付けられることになるので、接続構造体の導通抵抗が高くなり易いという問題もある。 Further, in the anisotropic conductive connection using this anisotropic conductive film, when the conductive particles with insulating particles are pressed against the terminals of the electronic component, not only the conductive particles but also the insulating particles are pressed against the terminals. There is also a problem that the conduction resistance of the connection structure tends to be high.
 これに対し、本発明は、絶縁粒子付導電粒子を使用した異方性導電フィルムであって、異方性導電接続した接続構造体の導通抵抗を低減させ、かつショートの発生を確実に抑制することのできる異方性導電フィルムの提供を課題とする。 In contrast, the present invention is an anisotropic conductive film using conductive particles with insulating particles, which reduces the conduction resistance of the connection structure that is anisotropically conductively connected and reliably suppresses the occurrence of short circuits. An object of the present invention is to provide an anisotropic conductive film that can be used.
 本発明者は、絶縁粒子が導電粒子の全表面に略均等に付着している絶縁粒子付導電粒子を用いて異方性導電フィルムを製造するにあたり、絶縁粒子付導電粒子において導電粒子のフィルム面方向に付着している絶縁粒子の数は維持されるが、導電粒子のフィルム厚方向に付着している絶縁粒子の数は低減するようにすると、異方性導電フィルムを用いる異方性導電接続において、導電粒子が絶縁粒子を介さず直接的に端子面に押圧されやすくなるので接続構造体の導通抵抗を低減でき、また、隣接する端子間では絶縁粒子の存在によりショートが引き起こされにくいことを見出し、本発明を想到した。 In producing an anisotropic conductive film using conductive particles with insulating particles in which the insulating particles are adhered substantially evenly to the entire surface of the conductive particles, the present inventor made a film surface of the conductive particles in the conductive particles with insulating particles. The number of insulating particles adhering in the direction is maintained, but if the number of insulating particles adhering in the film thickness direction of the conductive particles is reduced, an anisotropic conductive connection using an anisotropic conductive film is used. In this case, the conductive particles are easily pressed against the terminal surface without using the insulating particles, so that the conduction resistance of the connection structure can be reduced, and the presence of the insulating particles between adjacent terminals is less likely to cause a short circuit. The inventor came up with the present invention.
 即ち、本発明は、導電粒子の表面に絶縁粒子が付着している絶縁粒子付導電粒子が絶縁性樹脂層に分散している異方性導電フィルムであって、絶縁粒子付導電粒子において、導電粒子とフィルム厚方向で接する絶縁粒子数が、導電粒子とフィルム面方向で接する絶縁粒子数よりも少ない異方性導電フィルムを提供する。 That is, the present invention is an anisotropic conductive film in which conductive particles with insulating particles attached to the surface of conductive particles are dispersed in an insulating resin layer. Provided is an anisotropic conductive film in which the number of insulating particles in contact with the particles in the film thickness direction is smaller than the number of insulating particles in contact with the conductive particles in the film surface direction.
 また、本発明は、上述の異方性導電フィルムを用いて電子部品同士を異方性導電接続する接続構造体の製造方法や、それにより得られた接続構造体を提供する。 Also, the present invention provides a method for manufacturing a connection structure in which electronic components are anisotropically conductively connected using the above-described anisotropic conductive film, and a connection structure obtained thereby.
 本発明の異方性導電フィルムによれば、導電粒子の全表面に絶縁粒子が略均等に付着している当初の絶縁粒子付導電粒子に対し、導電粒子に対してフィルム厚方向で接している絶縁粒子数が、導電粒子に対してフィルム面方向で接している絶縁粒子数よりも少ない。したがって、この異方性導電フィルムを用いて電子部品の端子を異方性導電接続すると、当初の絶縁粒子付導電粒子の状態が維持されている場合に比して端子と導電粒子との直接的な接触面積が増加するので、接続構造体において導通抵抗を低減させることができる。また、この異方性導電フィルムによれば、フィルム面方向で導電粒子と接する絶縁粒子数については、当初の絶縁粒子付導電粒子の状態が維持されているので、接続構造体において、隣接する端子間のショートを抑制することができる。 According to the anisotropic conductive film of the present invention, the conductive particles with the initial insulating particles in which the insulating particles adhere substantially uniformly on the entire surface of the conductive particles are in contact with the conductive particles in the film thickness direction. The number of insulating particles is smaller than the number of insulating particles in contact with the conductive particles in the film surface direction. Therefore, when the anisotropic conductive film is used to anisotropically connect the terminals of the electronic component, the direct connection between the terminals and the conductive particles can be achieved as compared with the case where the initial state of the conductive particles with insulating particles is maintained. Since the contact area increases, the conduction resistance can be reduced in the connection structure. Further, according to this anisotropic conductive film, the number of insulating particles in contact with the conductive particles in the film surface direction is maintained at the initial state of the conductive particles with insulating particles. A short circuit between them can be suppressed.
図1Aは、実施例の異方性導電フィルム10Aの導電粒子の配置を示す平面図である。FIG. 1A is a plan view showing the arrangement of conductive particles of an anisotropic conductive film 10A of an example. 図1Bは、実施例の異方性導電フィルム10Aの断面図である。FIG. 1B is a cross-sectional view of the anisotropic conductive film 10A of the example. 図2は、導電粒子の表面にフィルム厚方向又はフィルム面方向で接している絶縁粒子の個数の計測方法の説明図である。FIG. 2 is an explanatory diagram of a method for measuring the number of insulating particles in contact with the surface of the conductive particles in the film thickness direction or the film surface direction. 図3Aは、絶縁粒子付導電粒子の周囲の絶縁性樹脂層の凹みの説明図である。FIG. 3A is an explanatory diagram of a dent in the insulating resin layer around the conductive particles with insulating particles. 図3Bは、絶縁粒子付導電粒子上の絶縁性樹脂層の凹みの説明図である。FIG. 3B is an explanatory diagram of a dent in the insulating resin layer on the conductive particles with insulating particles. 図4Aは、実施例の異方性導電フィルム10Aの製造方法を説明する断面図である。FIG. 4A is a cross-sectional view illustrating a method for manufacturing the anisotropic conductive film 10A of the example. 図4Bは、実施例の異方性導電フィルム10Aの製造方法を説明する断面図である。FIG. 4B is a cross-sectional view illustrating the method for manufacturing the anisotropic conductive film 10A of the example. 図4Cは、実施例の異方性導電フィルム10Aの製造方法を説明する断面図である。FIG. 4C is a cross-sectional view illustrating the method for manufacturing the anisotropic conductive film 10A of the example. 図4Dは、実施例の異方性導電フィルム10Aの製造方法を説明する断面図である。FIG. 4D is a cross-sectional view illustrating the method for manufacturing the anisotropic conductive film 10A of the example. 図4Eは、実施例の異方性導電フィルム10Aの製造方法を説明する断面図である。Drawing 4E is a sectional view explaining the manufacturing method of anisotropic conductive film 10A of an example. 図4Fは、実施例の異方性導電フィルム10Aの製造方法を説明する断面図である。FIG. 4F is a cross-sectional view illustrating the method for manufacturing the anisotropic conductive film 10A of the example. 図5は、実施例の異方性導電フィルム10Bの断面図である。FIG. 5 is a cross-sectional view of the anisotropic conductive film 10B of the example. 図6は、実施例の異方性導電フィルム10Cの断面図である。FIG. 6 is a cross-sectional view of the anisotropic conductive film 10C of the example. 図7は、実施例の異方性導電フィルム10Dの断面図である。FIG. 7 is a cross-sectional view of the anisotropic conductive film 10D of the example.
 以下、本発明の異方性導電フィルムの一例を、図面を参照しつつ詳細に説明する。なお、各図中、同一符号は、同一又は同等の構成要素を表している。 Hereinafter, an example of the anisotropic conductive film of the present invention will be described in detail with reference to the drawings. In addition, in each figure, the same code | symbol represents the same or equivalent component.
<異方性導電フィルムの全体構成>
 図1Aは、本発明の一実施例の異方性導電フィルム10Aの導電粒子の配置を説明する平面図であり、図1BはそのX-X断面図である。
<Overall structure of anisotropic conductive film>
FIG. 1A is a plan view for explaining the arrangement of conductive particles of an anisotropic conductive film 10A according to an embodiment of the present invention, and FIG. 1B is a sectional view taken along line XX.
 この異方性導電フィルム10Aでは、導電粒子1の表面に絶縁粒子2が接している又は付着している絶縁粒子付導電粒子3が絶縁性樹脂層5の片面に埋め込まれた構造を有している。フィルムの平面視にて絶縁粒子付導電粒子3は互いに接触することなく分散しており、フィルム厚方向にも絶縁粒子付導電粒子3は互いに重なることなく分散している。また、絶縁粒子付導電粒子3のフィルム厚方向(図1Bの紙面の縦方向)の位置が揃っており、絶縁粒子付導電粒子3はフィルム面方向(図1Bの紙面の横方向)に単層をなしている。 This anisotropic conductive film 10 </ b> A has a structure in which conductive particles 3 with insulating particles in which insulating particles 2 are in contact with or attached to the surface of conductive particles 1 are embedded on one surface of insulating resin layer 5. Yes. In the plan view of the film, the conductive particles 3 with insulating particles are dispersed without contacting each other, and the conductive particles 3 with insulating particles are also dispersed without overlapping each other in the film thickness direction. Further, the positions of the conductive particles 3 with insulating particles in the film thickness direction (the vertical direction of the paper surface of FIG. 1B) are aligned, and the conductive particles 3 with insulating particles are single-layered in the film surface direction (the horizontal direction of the paper surface of FIG. 1B). I am doing.
 本発明の異方性導電フィルム10Aでは、絶縁粒子付導電粒子3における絶縁粒子2の配置が特徴的となっており、以下に詳述するように、導電粒子1にフィルム厚方向で接している絶縁粒子2の個数が、導電粒子1にフィルム面方向で接している絶縁粒子2の個数よりも少なくなっている。 In the anisotropic conductive film 10A of the present invention, the arrangement of the insulating particles 2 in the conductive particles 3 with insulating particles is characteristic, and is in contact with the conductive particles 1 in the film thickness direction as described in detail below. The number of insulating particles 2 is smaller than the number of insulating particles 2 in contact with the conductive particles 1 in the film surface direction.
<絶縁粒子付導電粒子>
 本発明の異方性導電フィルム10Aにおいて、絶縁粒子付導電粒子3における絶縁粒子2は、導電粒子1のフィルム厚方向にあるものの個数が、導電粒子のフィルム面方向にあるものの個数よりも少なくなっているが、本発明の異方性導電フィルム10Aの製造原料として使用する絶縁粒子付導電粒子3としては、導電粒子1の全表面に絶縁粒子2が略均等に付着したものを使用することができる。
<Conductive particles with insulating particles>
In the anisotropic conductive film 10A of the present invention, the number of the conductive particles 1 in the film thickness direction of the conductive particles 1 in the conductive particles 3 with insulating particles is smaller than the number of the conductive particles 1 in the film surface direction. However, as the conductive particles 3 with insulating particles used as the raw material for producing the anisotropic conductive film 10A of the present invention, it is possible to use the conductive particles 1 having the insulating particles 2 attached substantially uniformly to the entire surface of the conductive particles 1. it can.
 このような絶縁粒子付導電粒子としては、特開2009-280790号公報、特開2014-132567号公報等に記載されているものを使用することができる。 As such conductive particles with insulating particles, those described in JP2009-280790A, JP2014-132567A, and the like can be used.
 導電粒子1の粒子径は、配線高さにばらつきがある場合の導通抵抗の上昇を抑制し、且つショートの発生を抑制する点から、好ましくは1μm以上30μm以下、より好ましくは2.5μm以上13μm以下、更に好ましくは3μm以上10μm以下である。 The particle diameter of the conductive particles 1 is preferably 1 μm or more and 30 μm or less, more preferably 2.5 μm or more and 13 μm from the viewpoint of suppressing an increase in conduction resistance when there is a variation in wiring height and suppressing the occurrence of short circuits. Hereinafter, it is more preferably 3 μm or more and 10 μm or less.
 絶縁粒子2の粒子径は導電粒子1の粒子径よりも小さい。絶縁粒子2の具体的な粒子径は、導電粒子1の粒子径、異方性導電フィルムの用途等に応じて定めることができるが、通常は、0.005μm以上5μm以下が好ましく、0.01μm以上2.5μm以下がより好ましく、更に好ましくは1μm以下、特に0.5μm以下である。これにより異方性導電接続時に必要な圧力や温度を過度にあげることが不要となる。一例として、絶縁粒子の粒子径は導電粒子の粒子径に対して、小さすぎると絶縁性を付与することが困難になることから下限は0.4%以上とすることが好ましく、0.6%以上とすることがより好ましく、0.8%以上が更により好ましい。また上限は大きすぎると導電粒子への付着や必要な個数が不足する虞があることから、18%以下とすることが好ましく、12%以下がより好ましく、6%以下が更により好ましい。 The particle diameter of the insulating particles 2 is smaller than the particle diameter of the conductive particles 1. The specific particle diameter of the insulating particles 2 can be determined according to the particle diameter of the conductive particles 1, the use of the anisotropic conductive film, etc., but is usually preferably 0.005 μm or more and 5 μm or less, 0.01 μm The thickness is more preferably 2.5 μm or less, further preferably 1 μm or less, and particularly preferably 0.5 μm or less. This eliminates the need for excessively increasing the pressure and temperature required for anisotropic conductive connection. As an example, if the particle diameter of the insulating particles is too small relative to the particle diameter of the conductive particles, it is difficult to impart insulation, so the lower limit is preferably 0.4% or more, and 0.6% More preferably, it is more preferably 0.8% or more. If the upper limit is too large, adhesion to the conductive particles and the necessary number may be insufficient. Therefore, the upper limit is preferably 18% or less, more preferably 12% or less, and even more preferably 6% or less.
 導電粒子1、絶縁粒子2及び絶縁粒子付導電粒子3の粒子径の測定は、これらの粒子をガラス上に散布し、光学顕微鏡、金属顕微鏡、透過型電子顕微鏡(TEM)、又は走査型電子顕微鏡(SEM)などで観察することにより求めることができる。フィルム中のこれらの粒子径も走査型電子顕微鏡等による観察から求めることができる。粒子径の計測では、測定するサンプル数を300以上とすることが望ましい。透過型電子顕微鏡では比較的小さい絶縁粒子単体の粒子径を正確に測定することができ、走査型電子顕微鏡は、特に絶縁粒子付導電粒子3の粒子径を求めるのに適している。 The particle diameters of the conductive particles 1, the insulating particles 2, and the conductive particles 3 with insulating particles are measured by spreading these particles on glass, and using an optical microscope, a metal microscope, a transmission electron microscope (TEM), or a scanning electron microscope. It can be determined by observing with (SEM) or the like. These particle sizes in the film can also be obtained from observation with a scanning electron microscope or the like. In the measurement of the particle diameter, it is desirable that the number of samples to be measured is 300 or more. The transmission electron microscope can accurately measure the particle diameter of a relatively small insulating particle, and the scanning electron microscope is particularly suitable for obtaining the particle diameter of the conductive particles 3 with insulating particles.
 単体の導電粒子の平均粒子径は、一般的な粒度分布測定装置により測定することもできる。画像型でもレーザー型であってもよい。画像型の測定装置としては、一例として湿式フロー式粒子径・形状分析装置FPIA-3000(マルバーン社)を挙げることができる。絶縁粒子付導電粒子の粒子径Dを測定するサンプル数(導電粒子個数)は1000個以上が好ましい。異方性導電フィルムにおける絶縁粒子付導電粒子の粒子径Dは、SEMなどの電子顕微鏡観察から求めることができる。この場合、絶縁粒子付導電粒子の粒子径Dを測定するサンプル数(導電粒子個数)を300個以上とすることが望ましい。 The average particle diameter of single conductive particles can be measured by a general particle size distribution measuring apparatus. It may be an image type or a laser type. As an example of the image type measuring apparatus, a wet flow type particle diameter / shape analyzer FPIA-3000 (Malvern) can be mentioned. The number of samples (number of conductive particles) for measuring the particle diameter D of the conductive particles with insulating particles is preferably 1000 or more. The particle diameter D of the conductive particles with insulating particles in the anisotropic conductive film can be determined from observation with an electron microscope such as SEM. In this case, it is desirable that the number of samples (number of conductive particles) for measuring the particle diameter D of the conductive particles with insulating particles be 300 or more.
 異方性導電フィルム10Aの製造原料として使用する絶縁粒子付導電粒子3において、導電粒子1の全表面のうち絶縁粒子2で被覆されている割合(被覆率)が20~97%が好ましく、40~95%がより好ましい。被覆率が少なすぎるとショートが生じ易くなり、大きすぎるとバンプによる導電粒子の捕捉が阻害される懸念が生じる。 In the conductive particles with insulating particles 3 used as a raw material for manufacturing the anisotropic conductive film 10A, the ratio (coverage) covered with the insulating particles 2 in the entire surface of the conductive particles 1 is preferably 20 to 97%. ~ 95% is more preferred. If the coverage is too small, short-circuiting is likely to occur, and if it is too large, there is a concern that capturing of the conductive particles by the bumps is hindered.
 なお被覆率は、絶縁粒子付導電粒子の表面全体に占める絶縁粒子の被覆面積(投影面積)の割合である。この具体的な求め方としては、走査型電子顕微鏡を用いて100個の絶縁粒子付導電粒子3を観察し、各観察画像における被覆率を平均することにより得られる。被覆率の簡便な求め方としては、各観察画像において絶縁粒子付導電粒子1個あたりの絶縁粒子の個数を計測し、その数値と、絶縁粒子付導電粒子1個の投影面積と絶縁粒子1個の投影面積から被覆率を算出してもよい。ここで、導電粒子の円形の観察像に、絶縁粒子の観察像が部分的に重なっている場合、その部分的に重なっている絶縁粒子は0.5個として計算してもよい。 The coverage is the ratio of the covering area (projected area) of insulating particles to the entire surface of the conductive particles with insulating particles. As a specific method for obtaining this, it is obtained by observing 100 conductive particles 3 with insulating particles using a scanning electron microscope and averaging the coverage in each observation image. As a simple method for obtaining the coverage, the number of insulating particles per one conductive particle with insulating particles is measured in each observation image, the numerical value, the projected area of one conductive particle with insulating particles, and one insulating particle. The coverage may be calculated from the projected area. Here, when the observation image of the insulating particles partially overlaps with the circular observation image of the conductive particles, the number of the partially overlapping insulating particles may be calculated as 0.5.
 一方、異方性導電フィルム10Aを現に構成する絶縁粒子付導電粒子3においては、導電粒子1にフィルム厚方向で接する絶縁粒子2の個数が、導電粒子1にフィルム面方向で接する絶縁粒子2の個数よりも少ない。ここで、導電粒子1にフィルム厚方向で接する絶縁粒子2の個数とは、図2に示す、異方性導電フィルム10Aにおける絶縁粒子付導電粒子3のフィルム厚方向の断面において、絶縁粒子付導電粒子3を、導電粒子1の中心を通る、フィルム厚方向に対してプラス45°傾いた直線及びマイナス45°傾いた直線で4つの領域A1、A2、A3、A4に分割した場合に、導電粒子1の上下にある領域(フィルム面に沿った領域)A1、A2に存在する絶縁粒子2の個数をいう。また、導電粒子1にフィルム面方向で接する絶縁粒子2の個数とは、上述の4つの領域A1、A2、A3、A4のうち導電粒子1の左右にある領域(フィルム厚方向に沿った領域)A3、A4に存在する絶縁粒子2の個数をいう。したがって、領域A1、A2、A3、A4に存在する絶縁粒子2の個数をNA1、NA2、NA3、NA4とすると、本発明においては、(NA3+NA4)>(NA1+NA2)となる。なお、フィルム厚方向の断面は、同じフィルムで複数の異なる方向がある(異なる方向の断面視を確認する)ことが好ましく、90°になっている2つの断面が含まれていることがより好ましい。 On the other hand, in the conductive particles with insulating particles 3 that actually constitute the anisotropic conductive film 10A, the number of the insulating particles 2 in contact with the conductive particles 1 in the film thickness direction is the number of the insulating particles 2 in contact with the conductive particles 1 in the film surface direction. Less than the number. Here, the number of insulating particles 2 in contact with the conductive particles 1 in the film thickness direction means that the conductive particles with insulating particles in the cross section in the film thickness direction of the conductive particles 3 with insulating particles in the anisotropic conductive film 10A shown in FIG. When the particle 3 is divided into four regions A1, A2, A3, and A4 along a straight line that passes through the center of the conductive particle 1 and is inclined by + 45 ° with respect to the film thickness direction and a straight line that is inclined by minus 45 °, the conductive particle 1 refers to the number of insulating particles 2 existing in regions (regions along the film surface) A1 and A2 above and below 1. In addition, the number of insulating particles 2 in contact with the conductive particles 1 in the film surface direction is a region (region along the film thickness direction) on the left and right of the conductive particles 1 in the four regions A1, A2, A3, and A4 described above. This refers to the number of insulating particles 2 present in A3 and A4. Accordingly, if the number of insulating particles 2 existing in the regions A1, A2, A3, A4 is N A1 , N A2 , N A3 , N A4 , in the present invention, (N A3 + N A4 )> (N A1 + N A2 ). In addition, it is preferable that the cross section of a film thickness direction has a several different direction with the same film (confirm the cross-sectional view of a different direction), and it is more preferable that two cross sections which are 90 degrees are included. .
 なお、領域A1、A2、A3、A4に存在する絶縁粒子2の個数を求めるにあたり、導電粒子1の上下の領域A1、A2と左右の領域A3、A4の双方に跨がる絶縁粒子2は、いずれの領域に大きく属するかで帰属を決定する。 In obtaining the number of insulating particles 2 present in the regions A1, A2, A3, A4, the insulating particles 2 straddling both the upper and lower regions A1, A2 and the left and right regions A3, A4 of the conductive particles 1, The attribution is determined depending on which region it belongs to.
 また、本発明において、全ての絶縁粒子付導電粒子3が上述の不等式を満たす必要はない。個々の絶縁粒子付導電粒子3において領域A1、A2、A3、A4に存在する絶縁粒子2の個数にはバラツキがあってよく、上述の不等式が成立しない絶縁粒子付導電粒子3が存在していてもよいが、異方性導電フィルムに含まれる全ての絶縁粒子付導電粒子3について平均すると上述の不等式が成立し、NA3、NA4がNA1、NA2より多くなる。 In the present invention, it is not necessary that all the conductive particles with insulating particles 3 satisfy the above inequality. The number of insulating particles 2 present in the regions A1, A2, A3, and A4 in the individual conductive particles 3 with insulating particles may vary, and there are conductive particles 3 with insulating particles that do not satisfy the above inequality. However, when all the conductive particles 3 with insulating particles contained in the anisotropic conductive film are averaged, the above inequality is established, and N A3 and N A4 are larger than N A1 and N A2 .
 なお、異方性導電フィルムに含まれる全ての絶縁粒子付導電粒子3について上述の不等式が成立することを確認することは現実的ではない。そこで、以下に示すように領域A1、A2、A3、A4に存在する絶縁粒子2の個数を計測して上述の不等式が成立する場合には、全ての絶縁粒子付導電粒子の平均において上述の不等式の関係が成立すると見なしてもよい。 In addition, it is not realistic to confirm that the above-mentioned inequality holds for all the conductive particles with insulating particles 3 included in the anisotropic conductive film. Therefore, when the above inequality is satisfied by measuring the number of insulating particles 2 present in the regions A1, A2, A3, and A4 as shown below, the above inequality is obtained in the average of all the conductive particles with insulating particles. It may be considered that the relationship is established.
 即ち、個々の絶縁粒子付導電粒子3について、領域A1、A2、A3、A4に存在する絶縁粒子2の個数を、異方性導電フィルム10Aの断面を走査型電子顕微鏡を用いて観察することにより計測するにあたり、1辺が100μm以上の矩形の計測領域を互いに離間させて複数箇所(好ましくは5箇所以上、より好ましくは10箇所以上)設定して合計面積を1mm以上とし、各計測領域から抜き取った100個の絶縁粒子付導電粒子3を観察し、それぞれの絶縁粒子付導電粒子3について領域A1及びA2に存在する絶縁粒子2の個数と、領域A3及びA4に存在する絶縁粒子2の個数を求め、100個の絶縁粒子付導電粒子の平均として、導電粒子1にフィルム厚方向で接する絶縁粒子2の個数(NA1+NA2)と、導電粒子1にフィルム面方向で接する絶縁粒子2の個数(NA3+NA4)を求め、上述の不等式の成立の有無を調べる。計測領域は導電粒子の大きさによって、適宜調整すればよい。 That is, by observing the cross section of the anisotropic conductive film 10A using a scanning electron microscope, the number of the insulating particles 2 present in the regions A1, A2, A3, and A4 is measured for each conductive particle 3 with insulating particles. In measurement, rectangular measurement areas each having a side of 100 μm or more are separated from each other and set at a plurality of locations (preferably 5 or more, more preferably 10 or more) so that the total area is 1 mm 2 or more. The extracted conductive particles 3 with insulating particles 3 were observed, and the number of insulating particles 2 existing in the regions A1 and A2 and the number of insulating particles 2 existing in the regions A3 and A4 for each conductive particle 3 with insulating particles. As the average of 100 conductive particles with insulating particles, the number (N A1 + N A2 ) of insulating particles 2 in contact with the conductive particles 1 in the film thickness direction and the conductive particles 1 with the film The number (N A3 + N A4 ) of the insulating particles 2 in contact in the plane direction is obtained, and the existence of the above inequality is examined. What is necessary is just to adjust a measurement area | region suitably with the magnitude | size of an electrically-conductive particle.
 また、導電粒子1にフィルム厚方向で接する絶縁粒子2の個数(NA1+NA2)が、導電粒子1にフィルム面方向で接する絶縁粒子2の個数(NA3+NA4)よりも少ないことを簡便に確認する方法としては、面積1mm以上の計測領域において、異方性導電フィルムの表裏のいずれか一方のフィルム面の平面視において導電粒子1と重なっている絶縁粒子2の個数が、表裏の他方のフィルム面の平面視において導電粒子1と重なっている絶縁粒子2の個数よりも少ないことを確認してもよい。後述するように本発明の異方性導電フィルムの製造工程において絶縁性樹脂層に絶縁粒子付導電粒子を押し込んだ場合には
A3,NA4 ≧NA2 >NA1
となるため、NA2 >NA1を確認することにより、導電粒子1にフィルム厚方向で接する絶縁粒子2の個数(NA1+NA2)が、導電粒子1にフィルム面方向で接する絶縁粒子2の個数(NA3+NA4)よりも少ないことを確認することができる。
In addition, the number of insulating particles 2 in contact with the conductive particles 1 in the film thickness direction (N A1 + N A2 ) is less than the number of insulating particles 2 in contact with the conductive particles 1 in the film surface direction (N A3 + N A4 ). As a method for confirming, the number of the insulating particles 2 overlapping the conductive particles 1 in the plan view of either one of the front and back surfaces of the anisotropic conductive film in the measurement region having an area of 1 mm 2 or more is It may be confirmed that the number is smaller than the number of insulating particles 2 overlapping the conductive particles 1 in a plan view of the other film surface. As will be described later, when conductive particles with insulating particles are pressed into the insulating resin layer in the manufacturing process of the anisotropic conductive film of the present invention, N A3 , N A4 ≧ N A2 > N A1
Therefore, by confirming N A2 > N A1 , the number of insulating particles 2 in contact with the conductive particles 1 in the film thickness direction (N A1 + N A2 ) is equal to the number of insulating particles 2 in contact with the conductive particles 1 in the film surface direction. It can be confirmed that the number is smaller than the number (N A3 + N A4 ).
 なお、このような領域A1、A2、A3、A4による絶縁粒子2の個数差は、後述するように、異方性導電フィルム10Aの製造方法において絶縁粒子付導電粒子3を所定の配列に配置するために転写型を使用した場合に生じる。即ち、このような絶縁粒子2の個数差は、絶縁粒子付導電粒子3を転写型から絶縁性樹脂層に転写した場合に、導電粒子1にフィルム厚方向で接する絶縁粒子2(領域A1の絶縁粒子2)が、転写型との摩擦により又は加圧部材との摩擦により、導電粒子1から脱離して該転写型に残り易い、ということにより、また、導電粒子1にフィルム厚方向で接する絶縁粒子2は、導電粒子1にフィルム面方向で接する位置に移動する場合があるが、導電粒子1にフィルム面方向で接する絶縁粒子2は、絶縁粒子付導電粒子3を転写型から絶縁性樹脂層に転写させても導電粒子1からの脱離や、移動が生じにくい、ということにより生じる。 The difference in the number of insulating particles 2 due to such regions A1, A2, A3, and A4 is that the conductive particles 3 with insulating particles are arranged in a predetermined arrangement in the method of manufacturing the anisotropic conductive film 10A, as will be described later. This occurs when a transfer mold is used. That is, the difference in the number of the insulating particles 2 is that the insulating particles 2 that contact the conductive particles 1 in the film thickness direction (insulation in the region A1) when the conductive particles 3 with insulating particles are transferred from the transfer mold to the insulating resin layer. Insulating that the particles 2) are easily detached from the conductive particles 1 due to friction with the transfer mold or friction with the pressure member and remain in the transfer mold, and also in contact with the conductive particles 1 in the film thickness direction. The particles 2 may move to a position in contact with the conductive particles 1 in the film surface direction, but the insulating particles 2 in contact with the conductive particles 1 in the film surface direction are transferred from the transfer type conductive particles 3 with insulating particles to the insulating resin layer. This is caused by the fact that even when transferred onto the conductive particles 1, detachment or movement from the conductive particles 1 hardly occurs.
<絶縁粒子付導電粒子の分散状態>
 本発明における絶縁粒子付導電粒子の分散状態には、絶縁粒子付導電粒子3がランダムに分散している状態も規則的な配置に分散している状態も含まれる。この分散状態において、絶縁粒子付導電粒子が互いに非接触で配置されていることが好ましく、その個数割合は好ましくは95%以上、より好ましくは98%以上、更に好ましくは99.5%以上である。この個数割合に関し、分散状態における規則的な配置において、意図的に接触させている絶縁粒子付導電粒子は、1個としてカウントする。後述するフィルム平面視における絶縁粒子付導電粒子の占有面積率の求め方と同様に、N=200以上で求めることができる。どちらの場合においても、フィルム厚方向の位置が揃っていることが捕捉安定性の点から好ましい。ここで、フィルム厚方向の導電粒子1の位置が揃っているとは、フィルム厚方向の単一の深さに揃っていることに限定されず、絶縁性樹脂層5の表裏の界面又はその近傍のそれぞれに導電粒子が存在している態様を含む。
<Dispersed state of conductive particles with insulating particles>
The dispersed state of the conductive particles with insulating particles in the present invention includes a state in which the conductive particles with insulating particles 3 are dispersed randomly and a state in which the conductive particles with insulating particles are dispersed in a regular arrangement. In this dispersed state, it is preferable that the conductive particles with insulating particles are arranged in non-contact with each other, and the number ratio is preferably 95% or more, more preferably 98% or more, and further preferably 99.5% or more. . Regarding this number ratio, the conductive particles with insulating particles that are intentionally contacted in a regular arrangement in a dispersed state are counted as one. Similar to the method of obtaining the occupation area ratio of the conductive particles with insulating particles in the film plan view described later, it can be obtained at N = 200 or more. In either case, it is preferable from the viewpoint of capture stability that the positions in the film thickness direction are aligned. Here, the fact that the positions of the conductive particles 1 in the film thickness direction are aligned is not limited to being aligned at a single depth in the film thickness direction, but the front and back interfaces of the insulating resin layer 5 or the vicinity thereof. Each of which includes conductive particles.
 本発明において、前述したように、絶縁粒子付導電粒子3はフィルムの平面視にて規則的に配列していることが好ましく、例えば、図1Aに示したように正方格子配列とすることができる。この他、絶縁粒子付導電粒子の規則的な配列態様としては、長方格子、斜方格子、6方格子等の格子配列を挙げることができる。規則的な配列は格子配列に限定されるものではなく、例えば、絶縁粒子付導電粒子が所定間隔で直線状に並んだ粒子列を所定の間隔で並列させてもよい。絶縁粒子付導電粒子3を互いに非接触で配置し、格子状等の規則的な配列にすることにより、異方性導電接続時に各絶縁粒子付導電粒子3に圧力を均等に加え、導通抵抗のばらつきを低減させることができる。規則的な配列は、例えばフィルムの長手方向に所定の粒子配置が繰り返されていることにより確認できる。 In the present invention, as described above, the conductive particles with insulating particles 3 are preferably arranged regularly in a plan view of the film, and can be, for example, a square lattice arrangement as shown in FIG. 1A. . In addition, examples of the regular arrangement of the conductive particles with insulating particles include a lattice arrangement such as a rectangular lattice, an oblique lattice, and a hexagonal lattice. The regular arrangement is not limited to the lattice arrangement, and for example, a row of particles in which conductive particles with insulating particles are arranged in a straight line at a predetermined interval may be arranged in parallel at a predetermined interval. By arranging the conductive particles with insulating particles 3 in a non-contact manner and in a regular arrangement such as a lattice, pressure is applied evenly to the conductive particles with insulating particles 3 during anisotropic conductive connection, Variations can be reduced. The regular arrangement can be confirmed, for example, by repeating a predetermined particle arrangement in the longitudinal direction of the film.
 絶縁粒子付導電粒子の配列の格子軸又は配列軸は、異方性導電フィルムの長手方向に対して平行でもよく、異方性導電フィルムの長手方向と交叉してもよく、接続する端子幅、端子ピッチなどに応じて定めることができる。例えば、ファインピッチ用の異方性導電フィルムとする場合、図1Aに示したように絶縁粒子付導電粒子3の格子軸Aを異方性導電フィルム10Aの長手方向に対して斜行させ、異方性導電フィルム10Aで接続する端子20の長手方向(フィルムの短手方向)と格子軸Aとのなす角度θを6°~84°、好ましくは11°~74°にすることが好ましい。 The lattice axis or the array axis of the array of the conductive particles with insulating particles may be parallel to the longitudinal direction of the anisotropic conductive film, may cross the longitudinal direction of the anisotropic conductive film, It can be determined according to the terminal pitch. For example, in the case of an anisotropic conductive film for fine pitch, as shown in FIG. 1A, the lattice axis A of the conductive particles with insulating particles 3 is skewed with respect to the longitudinal direction of the anisotropic conductive film 10A, so The angle θ formed by the longitudinal direction of the terminals 20 connected by the isotropic conductive film 10A (the short direction of the film) and the lattice axis A is preferably 6 ° to 84 °, more preferably 11 ° to 74 °.
 絶縁粒子付導電粒子3の粒子間距離は、異方性導電フィルムで接続する端子の大きさや端子ピッチに応じて適宜定める。例えば、異方性導電フィルムをファインピッチのCOG(Chip On Glass)に対応させる場合、ショートの発生を防止する点から最近接した絶縁粒子付導電粒子3の導電粒子1間距離を絶縁粒子付導電粒子の粒子径の0.5倍より大きくすることが好ましく、0.7倍より大きくすることがより好ましい。一方、絶縁粒子付導電粒子3の捕捉性の点から、最近接した絶縁粒子付導電粒子3の導電粒子1間距離を絶縁粒子付導電粒子の粒子径の4倍以下とすることが好ましく、3倍以下とすることがより好ましい。 The inter-particle distance of the conductive particles 3 with insulating particles is appropriately determined according to the size and terminal pitch of the terminals connected by the anisotropic conductive film. For example, when an anisotropic conductive film is made compatible with fine pitch COG (Chip On Glass), the distance between the conductive particles 1 of the closest conductive particles 3 with insulating particles from the point of preventing the occurrence of short-circuiting is provided. It is preferably larger than 0.5 times the particle diameter of the particles, more preferably larger than 0.7 times. On the other hand, from the viewpoint of capturing properties of the conductive particles 3 with insulating particles, the distance between the conductive particles 1 of the closest conductive particles 3 with insulating particles is preferably 4 times or less the particle diameter of the conductive particles with insulating particles. It is more preferable to set it to double or less.
 また、絶縁粒子付導電粒子の面積占有率が35%以下、好ましくは0.3~30%となるように定める。ここで、面積占有率は、
[平面視における絶縁粒子付導電粒子の個数密度]×[絶縁粒子付導電粒子の1個の平面視面積の平均]×100
により算出される。
Further, the area occupation ratio of the conductive particles with insulating particles is determined to be 35% or less, preferably 0.3 to 30%. Here, the area occupancy is
[Number density of conductive particles with insulating particles in plan view] × [average of one planar view area of conductive particles with insulating particles] × 100
Is calculated by
 式中、絶縁粒子付導電粒子の個数密度の測定領域は、異方性導電フィルム10Aにおいて1辺が100μm以上の矩形領域を任意に複数箇所(好ましくは5箇所以上、より好ましくは10箇所以上)設定し、測定領域の合計面積を2mm以上とすることが好ましい。個々の領域の大きさや数は、個数密度の状態によって適宜調整すればよい。ファインピッチ用途の比較的個数密度が大きい場合の一例として、異方性導電フィルム10Aから任意に選択した面積100μm×100μmの領域の200箇所(2mm)について、金属顕微鏡などによる観測画像を用いて個数密度を測定し、それを平均することにより上述の式の「平面視における絶縁粒子付導電粒子の個数密度」を得ることができる。面積100μm×100μmの領域は、バンプ間スペース50μm以下の接続対象物において1個以上のバンプが存在する領域になる。 In the formula, the number density measurement region of the conductive particles with insulating particles is arbitrarily a plurality of rectangular regions having a side of 100 μm or more in the anisotropic conductive film 10A (preferably 5 or more, more preferably 10 or more). It is preferable to set the total area of the measurement region to 2 mm 2 or more. What is necessary is just to adjust suitably the magnitude | size and number of each area | region according to the state of number density. As an example of a relatively large number density for fine pitch applications, 200 observation points (2 mm 2 ) in an area of 100 μm × 100 μm area arbitrarily selected from the anisotropic conductive film 10A are used by using observation images with a metal microscope or the like. By measuring the number density and averaging it, it is possible to obtain the “number density of conductive particles with insulating particles in plan view” of the above formula. A region having an area of 100 μm × 100 μm is a region where one or more bumps exist in a connection object having a space between bumps of 50 μm or less.
 個数密度は、好ましくは150~70000個/mmであり、特にファインピッチ用途の場合には好ましくは6000~42000個/mm、より好ましくは10000~40000個/mm、更に好ましくは15000~35000個/mmである。なお、150個/mm未満を除外するものではない。 The number density is preferably 150 to 70000 pieces / mm 2 , particularly in the case of fine pitch use, preferably 6000 to 42000 pieces / mm 2 , more preferably 10,000 to 40000 pieces / mm 2 , and further preferably 15000 to 35000 pieces / mm 2 . In addition, less than 150 pieces / mm 2 is not excluded.
 絶縁粒子付導電粒子の個数密度は、上述のように金属顕微鏡を用いて求める他、絶縁粒子付導電粒子の顕微鏡画像に対して画像解析ソフト(例えば、WinROOF、三谷商事株式会社等)用いて計測してもよい。 The number density of the conductive particles with insulating particles is obtained using a metal microscope as described above, and is measured using image analysis software (for example, WinROOF, Mitani Corporation) on the microscopic image of the conductive particles with insulating particles. May be.
 また、絶縁粒子付導電粒子1個当りのフィルム平面視面積の平均は、フィルム面の金属顕微鏡などによる観測画像から計測により求められる。上述のように画像解析ソフトを用いてもよい。N=300以上であることが好ましい。 In addition, the average of the film plan view area per one conductive particle with insulating particles can be obtained by measurement from an observation image of the film surface with a metal microscope or the like. Image analysis software may be used as described above. It is preferable that N = 300 or more.
 絶縁粒子付導電粒子のフィルム平面視における面積占有率は、異方性導電フィルムを電子部品に熱圧着するために押圧治具に必要とされる推力の指標となる。従来、異方性導電フィルムをファインピッチに対応させるために、ショートを発生させない限りで導電粒子の粒子間距離を狭め、個数密度が高められてきたが、そのように個数密度を高めると、異方性導電フィルムを電子部品に熱圧着するために押圧治具に必要とされる推力が過度に大きくなり、従前の押圧治具では押圧が不十分になるという問題が起こる。これに対し、面積占有率を上述の範囲とすることにより、異方性導電フィルムを電子部品に熱圧着するために押圧治具に必要とされる推力を低く抑えることができる。 The area occupancy ratio of the conductive particles with insulating particles in a plan view of the film is an index of the thrust required for the pressing jig for thermocompression bonding of the anisotropic conductive film to the electronic component. Conventionally, in order to make an anisotropic conductive film correspond to a fine pitch, the distance between particles of the conductive particles has been reduced and the number density has been increased as long as no short-circuit occurs. The thrust required for the pressing jig for thermocompression bonding the isotropic conductive film to the electronic component becomes excessively large, and there is a problem that the pressing is insufficient with the conventional pressing jig. On the other hand, by setting the area occupancy to the above-described range, the thrust required for the pressing jig for thermocompression bonding of the anisotropic conductive film to the electronic component can be suppressed low.
<絶縁性樹脂層>
(絶縁性樹脂層の最低溶融粘度)
 本発明の異方性導電フィルムにおいて、絶縁性樹脂層5の最低溶融粘度は、特に制限はなく、異方性導電フィルムの使用対象や、異方性導電フィルムの製造方法等に応じて適宜定めることができる。例えば、後述の凹み5b(図3A)、5c(図3B)を形成できる限り、異方性導電フィルムの製造方法によっては1000Pa・s程度とすることもできる。一方、異方性導電フィルムの製造方法として、絶縁粒子付導電粒子を絶縁性樹脂層の表面に所定の配置で保持させ、その絶縁粒子付導電粒子を絶縁性樹脂層に押し込む方法を行うとき、絶縁性樹脂層がフィルム成形を可能とする点から絶縁性樹脂の最低溶融粘度を1100Pa・s以上とすることが好ましい。
<Insulating resin layer>
(Minimum melt viscosity of insulating resin layer)
In the anisotropic conductive film of the present invention, the minimum melt viscosity of the insulating resin layer 5 is not particularly limited, and is appropriately determined according to the use object of the anisotropic conductive film, the method for manufacturing the anisotropic conductive film, and the like. be able to. For example, as long as the below-mentioned dents 5b (FIG. 3A) and 5c (FIG. 3B) can be formed, it can be set to about 1000 Pa · s depending on the method for manufacturing the anisotropic conductive film. On the other hand, as a method for producing an anisotropic conductive film, when conducting a method of holding the conductive particles with insulating particles in a predetermined arrangement on the surface of the insulating resin layer and pushing the conductive particles with insulating particles into the insulating resin layer, It is preferable that the minimum melt viscosity of the insulating resin is 1100 Pa · s or higher from the viewpoint that the insulating resin layer enables film forming.
 また、後述の異方性導電フィルムの製造方法で説明するように、図3Aに示すように絶縁性樹脂層5に押し込んだ絶縁粒子付導電粒子3の露出部分の周りに凹み5bを形成したり、図3Bに示すように絶縁性樹脂層5に押し込んだ絶縁粒子付導電粒子3の直上に凹み5cを形成したりする点から、好ましくは1500Pa・s以上、より好ましくは2000Pa・s以上、さらに好ましくは3000~15000Pa・s、さらにより好ましくは3000~10000Pa・sである。この最低溶融粘度は、一例として回転式レオメータ(TA instruments社製)を用い、測定圧力5gで一定に保持し、直径8mmの測定プレートを使用し求めることができ、より具体的には、温度範囲30~200℃において、昇温速度10℃/分、測定周波数10Hz、前記測定プレートに対する荷重変動5gとすることにより求めることができる。 Further, as described in the method for manufacturing an anisotropic conductive film described later, as shown in FIG. 3A, a dent 5b is formed around the exposed portion of the conductive particles with insulating particles 3 pushed into the insulating resin layer 5. 3B, from the point of forming the recess 5c directly above the conductive particles with insulating particles 3 pushed into the insulating resin layer 5, as shown in FIG. 3B, preferably 1500 Pa · s or more, more preferably 2000 Pa · s or more, The pressure is preferably 3000 to 15000 Pa · s, and more preferably 3000 to 10,000 Pa · s. This minimum melt viscosity can be obtained using a rotary rheometer (manufactured by TA Instruments Inc.) as an example, kept constant at a measurement pressure of 5 g, and using a measurement plate having a diameter of 8 mm, and more specifically in the temperature range. At 30 to 200 ° C., it can be obtained by setting the temperature rising rate 10 ° C./min, the measurement frequency 10 Hz, and the load fluctuation 5 g with respect to the measurement plate.
 絶縁性樹脂層5の最低溶融粘度を1500Pa・s以上の高粘度とすることにより、異方性導電フィルムの物品への圧着に導電粒子の無用な移動を抑制でき、特に、異方性導電接続時に端子間で挟持されるべき導電粒子が樹脂流動により流されてしまうことを防止できる。 By setting the minimum melt viscosity of the insulating resin layer 5 to a high viscosity of 1500 Pa · s or more, unnecessary movement of the conductive particles can be suppressed for pressure bonding of the anisotropic conductive film to the article. It is possible to prevent the conductive particles to be sandwiched between the terminals sometimes from being caused to flow due to the resin flow.
 また、絶縁性樹脂層5に絶縁粒子付導電粒子3を押し込む場合において、絶縁粒子付導電粒子3を押し込むときの絶縁性樹脂層5は、絶縁粒子付導電粒子3が絶縁性樹脂層5から露出するように絶縁粒子付導電粒子3を絶縁性樹脂層5に押し込んだときに、絶縁性樹脂層5が塑性変形して絶縁粒子付導電粒子3の周囲の絶縁性樹脂層5に凹み5b(図3A)が形成されるような高粘度な粘性体とするか、あるいは、絶縁粒子付導電粒子3が絶縁性樹脂層5から露出することなく絶縁性樹脂層5に埋まるように絶縁粒子付導電粒子3を押し込んだときに、絶縁粒子付導電粒子3の直上の絶縁性樹脂層5の表面に凹み5c(図3B)が形成されるような高粘度な粘性体とする。そのため、絶縁性樹脂層5の60℃における粘度は、下限は好ましくは3000Pa・s以上、より好ましくは4000Pa・s以上、さらに好ましくは4500Pa・s以上であり、上限は、好ましくは20000Pa・s以下、より好ましくは15000Pa・s以下、さらに好ましくは10000Pa・s以下である。この測定は最低溶融粘度と同様の測定方法で行い、温度が60℃の値を抽出して求めることができる。 Further, when the conductive particles with insulating particles 3 are pushed into the insulating resin layer 5, the conductive resin particles with insulating particles 3 are exposed from the insulating resin layer 5 when the conductive particles with insulating particles 3 are pushed. Thus, when the conductive particles 3 with insulating particles are pushed into the insulating resin layer 5, the insulating resin layer 5 is plastically deformed and recessed into the insulating resin layer 5 around the conductive particles 3 with insulating particles (FIG. 3A), or a conductive material with insulating particles so that the conductive particle with insulating particles 3 is buried in the insulating resin layer 5 without being exposed from the insulating resin layer 5. When the 3 is pushed in, a highly viscous viscous material is formed in which a recess 5c (FIG. 3B) is formed on the surface of the insulating resin layer 5 immediately above the conductive particles 3 with insulating particles. Therefore, the viscosity of the insulating resin layer 5 at 60 ° C. is preferably at least 3000 Pa · s, more preferably at least 4000 Pa · s, even more preferably at least 4500 Pa · s, and the upper limit is preferably at most 20000 Pa · s. More preferably, it is 15000 Pa.s or less, More preferably, it is 10000 Pa.s or less. This measurement is performed by the same measurement method as that for the minimum melt viscosity, and can be obtained by extracting a value at a temperature of 60 ° C.
 絶縁性樹脂層5に絶縁粒子付導電粒子3を押し込むときの該絶縁性樹脂層5の具体的な粘度は、形成する凹み5b、5cの形状や深さなどに応じて、下限は好ましくは3000Pa・s以上、より好ましくは4000Pa・s以上、さらに好ましくは4500Pa・s以上であり、上限は、好ましくは20000Pa・s以下、より好ましくは15000Pa・s以下、さらに好ましくは10000Pa・s以下である。また、このような粘度を好ましくは40~80℃、より好ましくは50~60℃で得られるようにする。 The specific viscosity of the insulating resin layer 5 when the conductive particles 3 with insulating particles are pushed into the insulating resin layer 5 is preferably 3000 Pa depending on the shape and depth of the recesses 5b and 5c to be formed. · S or more, more preferably 4000 Pa · s or more, further preferably 4500 Pa · s or more, and the upper limit is preferably 20000 Pa · s or less, more preferably 15000 Pa · s or less, and still more preferably 10000 Pa · s or less. Further, such a viscosity is preferably obtained at 40 to 80 ° C., more preferably 50 to 60 ° C.
 上述したように、絶縁性樹脂層5から露出している絶縁粒子付導電粒子3の周囲に凹み5b(図3A)が形成されていることにより、異方性導電フィルムの物品への圧着時に生じる絶縁粒子付導電粒子3の扁平化に対して絶縁性樹脂から受ける抵抗が、凹み5bが無い場合に比して低減する。このため、異方性導電接続時に端子で導電粒子が挟持され易くなることで導通性能が向上し、また捕捉性が向上する。 As described above, the recesses 5b (FIG. 3A) are formed around the conductive particles 3 with insulating particles exposed from the insulating resin layer 5, and thus the anisotropic conductive film is produced when it is pressed onto the article. The resistance received from the insulating resin against the flattening of the conductive particles 3 with insulating particles is reduced as compared with the case where there is no recess 5b. For this reason, it becomes easy for the conductive particles to be sandwiched between the terminals at the time of anisotropic conductive connection, so that the conduction performance is improved and the trapping property is improved.
 また、絶縁性樹脂層5から露出することなく埋まっている絶縁粒子付導電粒子3の直上の絶縁性樹脂層5の表面に凹み5c(図3B)が形成されていることにより、凹み5cが無い場合に比して異方性導電フィルムの物品への圧着時の圧力が絶縁粒子付導電粒子3に集中し易くなる。このため、異方性導電接続時に端子で導電粒子が挟持され易くなることで捕捉性が向上し、また導通性能が向上する。 Further, since the recess 5c (FIG. 3B) is formed on the surface of the insulating resin layer 5 immediately above the conductive particles 3 with insulating particles buried without being exposed from the insulating resin layer 5, there is no recess 5c. As compared with the case, the pressure at the time of pressure-bonding the anisotropic conductive film to the article tends to concentrate on the conductive particles 3 with insulating particles. For this reason, the trapping property is improved because the conductive particles are easily held between the terminals at the time of anisotropic conductive connection, and the conduction performance is improved.
 なお、後述する異方性導電フィルムの製造方法において、絶縁性樹脂層5に絶縁粒子付導電粒子3を押し込むときの埋込率を100%以下とし、絶縁粒子付導電粒子3が絶縁性樹脂層5から露出するようにする場合に、絶縁性樹脂層5の60℃の粘度が上述の範囲であると、絶縁粒子付導電粒子3が押し込まれた後の絶縁性樹脂層5には絶縁粒子付導電粒子3の周囲に凹み5b(図3A)が形成されることがある。この際、絶縁粒子のみが露出する場合もある。また、埋込率を100%超とし、絶縁粒子付導電粒子3が絶縁性樹脂層5から露出せず、絶縁性樹脂層5に埋まるようにした場合には、絶縁粒子付導電粒子3の直上の絶縁性樹脂層5の表面に凹み5c(図3B)が形成されることがある。なお、埋込率の意味については、後段の絶縁粒子付導電粒子の埋込状態の説明において詳述する。 In the anisotropic conductive film manufacturing method to be described later, the embedding rate when the conductive particles with insulating particles 3 are pushed into the insulating resin layer 5 is 100% or less, and the conductive particles with insulating particles 3 are the insulating resin layer. 5, when the insulating resin layer 5 has a viscosity of 60 ° C. within the above range, the insulating resin layer 5 with the insulating particles is pressed into the insulating resin layer 5 after the insulating particles with the insulating particles 5 are pushed in. A recess 5b (FIG. 3A) may be formed around the conductive particles 3. At this time, only insulating particles may be exposed. When the embedding rate is over 100% and the conductive particles 3 with insulating particles are not exposed from the insulating resin layer 5 and are embedded in the insulating resin layer 5, the conductive particles 3 with insulating particles are directly above the conductive particles 3. A recess 5c (FIG. 3B) may be formed on the surface of the insulating resin layer 5. The meaning of the embedding rate will be described in detail in the description of the embedded state of the conductive particles with insulating particles in the subsequent stage.
 このような凹み5b、5cは、絶縁粒子付導電粒子3を絶縁性樹脂層5に押し込むときの絶縁性樹脂層5の粘度、押込速度、温度などに応じて形成される。凹み5b、5cの有無が本発明の効果に格別影響するものではないが、凹みの深さが大きい凹み5b、5c(例えば、凹みの最深部の深さが絶縁粒子付導電粒子の粒子径Dの10%以上)が局所的に集中した領域が存在する場合に、そのような領域を基板に向けて貼り合わせると、基板の材質や表面状態などによっては、その領域で異方性導電接続後に浮き等が生じ、実用上の問題はなくとも外観が劣る場合がある。これに対しては、そのような領域のある異方性導電フィルムの表面を、異方性導電接続に支障を来たさない程度に加熱押圧したり、樹脂を散布するなどして凹み5b、5cを浅くするか、又は平坦にすることが好ましい。この場合、散布する樹脂は、絶縁性樹脂層5を形成する樹脂よりも低粘度であることが好ましい。散布する樹脂の濃度は、散布後に絶縁性樹脂層5の凹みが確認できる程度に希釈されていてもよい。 Such recesses 5b and 5c are formed according to the viscosity, pressing speed, temperature, and the like of the insulating resin layer 5 when the conductive particles with insulating particles 3 are pressed into the insulating resin layer 5. Although the presence or absence of the recesses 5b and 5c does not particularly affect the effect of the present invention, the recesses 5b and 5c having a large recess depth (for example, the depth of the deepest portion of the recess is the particle diameter D of the conductive particles with insulating particles). If there is a region where 10% or more of the region is locally concentrated, if such a region is bonded to the substrate, depending on the material or surface state of the substrate, the anisotropic conductive connection in that region may occur. Occurrence may occur and the appearance may be inferior even if there is no practical problem. For this, the surface of the anisotropic conductive film having such a region is heated and pressed to such an extent that it does not interfere with the anisotropic conductive connection, or the dent 5b is dispersed by spraying resin. It is preferable to make 5c shallower or flat. In this case, it is preferable that the resin to be dispersed has a lower viscosity than the resin that forms the insulating resin layer 5. The concentration of the resin to be sprayed may be diluted to such an extent that the dent of the insulating resin layer 5 can be confirmed after the spraying.
<凹みに代わる“傾斜”もしくは“起伏”>
 図3A、3Bに示すような異方性導電フィルムの 「凹み」5b、5cは、「傾斜」もしくは「起伏」という観点から説明することもできる。以下に、図面を参照しながら説明する。
<"Inclination" or "undulation" instead of dents>
The “dents” 5b and 5c of the anisotropic conductive film as shown in FIGS. 3A and 3B can also be described from the viewpoint of “inclination” or “undulation”. Hereinafter, description will be given with reference to the drawings.
 異方性導電フィルム10Aは、導電粒子分散層、即ち、絶縁性樹脂層5の片面に絶縁粒子付導電粒子3が露出した状態で規則的に分散している層を有する(図3A、図3B)。フィルムの平面視にて絶縁粒子付導電粒子3は互いに接触しておらず、フィルム厚方向にも絶縁粒子付導電粒子3が互いに重なることなく規則的に分散し、絶縁粒子付導電粒子3のフィルム厚方向の位置が揃った単層の導電粒子層を構成している。 The anisotropic conductive film 10A has a conductive particle dispersion layer, that is, a layer in which the conductive particles with insulating particles 3 are regularly dispersed with one surface of the insulating resin layer 5 exposed (FIGS. 3A and 3B). ). The conductive particles 3 with insulating particles are not in contact with each other in a plan view of the film, and the conductive particles 3 with insulating particles are regularly dispersed in the film thickness direction without overlapping each other. A single-layer conductive particle layer having a uniform position in the thickness direction is formed.
 個々の絶縁粒子付導電粒子3の近傍の絶縁性樹脂層5の表面5aには、隣接する絶縁粒子付導電粒子間の中央部における絶縁性樹脂層5の接平面5pに対して傾斜5bが形成されている。なお後述するように、本発明の異方性導電フィルムでは、絶縁性樹脂層5に埋め込まれた絶縁粒子付導電粒子3の直上の絶縁性樹脂層5の表面に起伏5cが形成されていてもよい(図3B)。 A slope 5b is formed on the surface 5a of the insulating resin layer 5 in the vicinity of each of the conductive particles with insulating particles 3 with respect to the tangential plane 5p of the insulating resin layer 5 at the center between adjacent conductive particles with insulating particles. Has been. As will be described later, in the anisotropic conductive film of the present invention, even when the undulations 5c are formed on the surface of the insulating resin layer 5 immediately above the conductive particles with insulating particles 3 embedded in the insulating resin layer 5. Good (FIG. 3B).
 本発明において、「傾斜」とは、絶縁粒子付導電粒子3の近傍で絶縁性樹脂層の表面の平坦性が損なわれ、前記接平面5pに対して絶縁性樹脂層の一部が欠けて樹脂量が低減している状態を意味する。換言すれば、傾斜では、絶縁粒子付導電粒子の近傍の絶縁性樹脂層の表面が接平面に対して欠けていることになる。一方、「起伏」とは、絶縁粒子付導電粒子の直上の絶縁性樹脂層の表面にうねりがあり、うねりのように高低差がある部分が存在することで樹脂が低減している状態を意味する。換言すれば、絶縁粒子付導電粒子直上の絶縁性樹脂層の樹脂量が、絶縁粒子付導電粒子直上の絶縁性樹脂層の表面が接平面にあるとしたときに比して少なくなる。そのため、うねりにおいて絶縁粒子のみが露出する場合もある。これらは、絶縁粒子付導電粒子の直上に相当する部位と導電粒子間の平坦な表面部分(図3A、3B)とを対比して認識することができる。なお、起伏の開始点が傾斜として存在する場合もある。 In the present invention, “inclination” means that the flatness of the surface of the insulating resin layer is impaired in the vicinity of the conductive particles 3 with insulating particles, and a part of the insulating resin layer is missing from the tangential plane 5p. This means that the amount is decreasing. In other words, in the inclination, the surface of the insulating resin layer in the vicinity of the conductive particles with insulating particles is missing from the tangent plane. On the other hand, “undulation” means that the surface of the insulating resin layer directly above the conductive particles with insulating particles has undulations, and the resin is reduced due to the presence of a part with a difference in elevation such as undulations. To do. In other words, the resin amount of the insulating resin layer immediately above the conductive particles with insulating particles is smaller than when the surface of the insulating resin layer immediately above the conductive particles with insulating particles is in a tangential plane. Therefore, only the insulating particles may be exposed in the swell. These can be recognized by comparing a portion corresponding to the conductive particles with insulating particles and a flat surface portion (FIGS. 3A and 3B) between the conductive particles. In some cases, the starting point of undulations exists as a slope.
 上述したように、絶縁性樹脂層5から露出している絶縁粒子付導電粒子3の周囲に傾斜5b(図3A)が形成されていることにより、異方性導電接続時に絶縁粒子付導電粒子3が端子間で挟持される際に生じる絶縁粒子付導電粒子3の扁平化に対して絶縁性樹脂から受ける抵抗が、傾斜5bが無い場合に比して低減するため、端子における絶縁粒子付導電粒子の挟持がされ易くなることで導通性能が向上し、また捕捉性が向上する。この傾斜は、絶縁粒子付導電粒子の外形に沿っていることが好ましい。接続における効果がより発現しやすくなる以外に、絶縁粒子付導電粒子を認識し易くなることで、異方性導電フィルムの製造における検査などが行い易くなるからである。また、この傾斜および起伏は絶縁性樹脂層にヒートプレスするなどにより、その一部が消失してしまう場合があるが、本発明はこれを包含する。この場合、絶縁粒子付導電粒子は絶縁性樹脂層の表面に1点で露出する場合がある。なお、異方性導電フィルムは、接続する電子部品が多様であり、これらに合わせてチューニングする以上、種々の要件を満たせるように設計の自由度が高いことが望まれるので、傾斜もしくは起伏を低減させても部分的に消失させても用いることができる。 As described above, by forming the slope 5b (FIG. 3A) around the conductive particles 3 with insulating particles exposed from the insulating resin layer 5, the conductive particles 3 with insulating particles at the time of anisotropic conductive connection. Since the resistance received from the insulating resin with respect to the flattening of the conductive particles 3 with insulating particles generated when the particles are sandwiched between the terminals is reduced as compared with the case where there is no inclination 5b, the conductive particles with insulating particles at the terminals As a result, the conduction performance is improved and the trapping property is improved. This inclination is preferably along the outer shape of the conductive particles with insulating particles. This is because, in addition to the effect of connection being more easily manifested, it is easier to recognize the conductive particles with insulating particles, thereby facilitating inspections in the production of anisotropic conductive films. In addition, the inclination and the undulation may be partially lost by heat-pressing the insulating resin layer, and the present invention includes this. In this case, the conductive particles with insulating particles may be exposed at one point on the surface of the insulating resin layer. In addition, the anisotropic conductive film has a variety of electronic parts to be connected, and as long as it is tuned according to these, it is desired that the degree of freedom of design is high enough to satisfy various requirements, so the inclination or undulation is reduced. It can be used even if it disappears or partially disappears.
 また、絶縁性樹脂層5から露出することなく埋まっている絶縁粒子付導電粒子3の直上の絶縁性樹脂層5の表面に起伏5c(図3B)が形成されていることにより、傾斜の場合と同様に、異方性接続時に端子からの押圧力が絶縁粒子付導電粒子にかかりやすくなる。また、起伏があることにより樹脂が平坦に堆積している場合よりも絶縁粒子付導電粒子の直上の樹脂量が低減しているため、接続時の絶縁粒子付導電粒子直上の樹脂の排除が生じやすくなり、端子と絶縁粒子付導電粒子とが接触し易くなることから、端子における絶縁粒子付導電粒子の捕捉性が向上し、導通信頼性が向上する。 In addition, since the undulations 5c (FIG. 3B) are formed on the surface of the insulating resin layer 5 directly above the conductive particles 3 with insulating particles buried without being exposed from the insulating resin layer 5, the case of inclination Similarly, a pressing force from the terminal is easily applied to the conductive particles with insulating particles during anisotropic connection. In addition, since the amount of resin immediately above the conductive particles with insulating particles is reduced compared to when the resin is deposited flat due to undulations, the resin directly above the conductive particles with insulating particles at the time of connection is eliminated. This facilitates the contact between the terminal and the conductive particle with insulating particles, so that the trapping property of the conductive particle with insulating particles at the terminal is improved, and the conduction reliability is improved.
(絶縁性樹脂層の厚さ方向における絶縁粒子付導電粒子の位置)
 「傾斜」もしくは「起伏」という観点を考慮した場合の絶縁性樹脂層5の厚さ方向における絶縁粒子付導電粒子3の位置は、前述と同様に、絶縁粒子付導電粒子3が絶縁性樹脂層5から露出していてもよく、露出することなく、絶縁性樹脂層5内に埋め込まれていても良いが、隣接する絶縁粒子付導電粒子間の中央部における接平面5pからの絶縁粒子付導電粒子の最深部の距離(以下、埋込量という)Lbと、絶縁粒子付導電粒子の粒子径Dとの比(Lb/D)(以下、埋込率という)が30%以上105%以下であることが好ましく、60%以上105%以下とすることが発明の効果を得るためにはより好ましい。
(Position of conductive particles with insulating particles in the thickness direction of the insulating resin layer)
The position of the conductive particles 3 with insulating particles in the thickness direction of the insulating resin layer 5 in consideration of the viewpoint of “inclination” or “undulation” is the same as described above. 5 may be exposed or may be embedded in the insulating resin layer 5 without being exposed, but the conductive with insulating particles from the tangential plane 5p in the central portion between the adjacent conductive particles with insulating particles. The ratio (Lb / D) (hereinafter referred to as the embedding rate) of the distance Lb of the deepest part of the particles (hereinafter referred to as the embedding amount) to the particle diameter D of the conductive particles with insulating particles is 30% or more and 105% or less. In order to obtain the effects of the invention, it is more preferable that the ratio be 60% or more and 105% or less.
 埋込率(Lb/D)を30%以上60%未満とすると、絶縁粒子付導電粒子を保持する比較的高粘度の絶縁性樹脂層から絶縁粒子付導電粒子が露出している比率が高くなることから、より低温低圧実装が容易になる。60%以上とすることにより、絶縁粒子付導電粒子3を絶縁性樹脂層5によって所定の粒子分散状態あるいは所定の配列に維持し易くなる。また、製造(フィルムへの押し込み)時の絶縁粒子付導電粒子と樹脂との接触面積が大きくなることから、発明の効果が得られ易くなることが期待できる。また、105%以下とすることにより、異方性導電接続時に端子間の導電粒子を無用に流動させるように作用する絶縁性樹脂層の樹脂量を低減させることができる。 When the embedding rate (Lb / D) is 30% or more and less than 60%, the ratio of the conductive particles with insulating particles exposed from the relatively high viscosity insulating resin layer holding the conductive particles with insulating particles becomes high. Therefore, lower temperature and low pressure mounting becomes easier. By setting it to 60% or more, the conductive particles 3 with insulating particles can be easily maintained in a predetermined particle dispersion state or a predetermined arrangement by the insulating resin layer 5. Further, since the contact area between the conductive particles with insulating particles and the resin at the time of manufacture (pushing into the film) becomes large, it can be expected that the effects of the invention can be easily obtained. Moreover, by setting it as 105% or less, the resin amount of the insulating resin layer which acts so that the electrically-conductive particle between terminals may flow unnecessarily at the time of anisotropic conductive connection can be reduced.
 なお、埋込率(Lb/D)の数値は、異方性導電フィルムに含まれる全絶縁粒子付導電粒子数の80%以上、好ましくは90%以上、より好ましくは96%以上が、当該埋込率(Lb/D)の数値になっていることをいう。したがって、埋込率が30%以上105%以下とは、異方性導電フィルムに含まれる全絶縁粒子付導電粒子数の80%以上、好ましくは90%以上、より好ましくは96%以上の埋込率が30%以上105%以下であることをいう。このように全絶縁粒子付導電粒子の埋込率(Lb/D)が揃っていることにより、押圧の加重が絶縁粒子付導電粒子に均一にかかるので、端子における絶縁粒子付導電粒子の捕捉状態が良好になり、導通の安定性が向上する。 The value of the embedding rate (Lb / D) is 80% or more, preferably 90% or more, more preferably 96% or more of the total number of conductive particles with insulating particles contained in the anisotropic conductive film. It means that it is a numerical value of the inclusion rate (Lb / D). Therefore, the embedding rate of 30% or more and 105% or less means that the embedding rate is 80% or more, preferably 90% or more, more preferably 96% or more of the total number of conductive particles with insulating particles contained in the anisotropic conductive film. The rate is 30% or more and 105% or less. Thus, since the embedding rate (Lb / D) of all the conductive particles with insulating particles is uniform, the pressing load is uniformly applied to the conductive particles with insulating particles, so that the state of trapping the conductive particles with insulating particles at the terminal is captured. Is improved and the stability of conduction is improved.
 埋込率(Lb/D)は、異方性導電フィルムから面積30mm以上の領域を任意に10箇所以上抜き取り、そのフィルム断面の一部をSEM画像で観察し、合計50個以上の絶縁粒子付導電粒子を計測することにより求めることができる。より精度を上げるため、200個以上の絶縁粒子付導電粒子を計測して求めてもよい。 The embedding rate (Lb / D) was determined by arbitrarily extracting 10 or more regions having an area of 30 mm 2 or more from the anisotropic conductive film, observing a part of the film cross section with an SEM image, and totaling 50 or more insulating particles. It can be determined by measuring attached conductive particles. In order to increase the accuracy, 200 or more conductive particles with insulating particles may be measured and obtained.
 また、埋込率(Lb/D)の計測は、面視野画像において焦点調整することにより、ある程度の個数について一括して求めることができる。もしくは埋込率(Lb/D)の計測にレーザー式判別変位センサ((株)キーエンス製など)を用いてもよい。 Further, the measurement of the embedding rate (Lb / D) can be obtained collectively for a certain number by adjusting the focus in the surface field image. Alternatively, a laser discrimination displacement sensor (manufactured by Keyence Co., Ltd.) may be used for measuring the embedding rate (Lb / D).
 上述した絶縁粒子付導電粒子の周りの絶縁性樹脂層5の傾斜5b(図3A)や、絶縁粒子付導電粒子の直上の絶縁性樹脂層の起伏5c(図3B)の効果を得易くする点から、傾斜5bの最大深さLeと絶縁粒子付導電粒子3の粒子径Dとの比(Le/D)は、好ましくは50%未満、より好ましくは30%未満、さらに好ましくは20~25%であり、傾斜5bや起伏5cの最大径Ldと絶縁粒子付導電粒子3の粒子径Dとの比(Ld/D)は、好ましくは100%以上、より好ましくは100~150%であり、起伏5cの最大深さLfと絶縁粒子付導電粒子3の粒子径Dとの比(Lf/D)は、0より大きく、好ましくは10%未満、より好ましくは5%以下である。 The point which makes it easy to obtain the effect of the slope 5b (FIG. 3A) of the insulating resin layer 5 around the conductive particles with insulating particles and the undulation 5c (FIG. 3B) of the insulating resin layer immediately above the conductive particles with insulating particles. From the above, the ratio (Le / D) between the maximum depth Le of the inclination 5b and the particle diameter D of the conductive particles 3 with insulating particles is preferably less than 50%, more preferably less than 30%, and even more preferably 20 to 25%. The ratio (Ld / D) between the maximum diameter Ld of the slope 5b or the undulation 5c and the particle diameter D of the conductive particles 3 with insulating particles is preferably 100% or more, more preferably 100 to 150%. The ratio (Lf / D) between the maximum depth Lf of 5c and the particle diameter D of the conductive particles 3 with insulating particles is greater than 0, preferably less than 10%, more preferably 5% or less.
 なお、傾斜5b又は起伏5cにおける絶縁粒子付導電粒子3の露出(直上)部分の径Lcは、絶縁粒子付導電粒子3の粒子径D以下とすることができ、好ましくは粒子径Dの10~90%である。なお、絶縁粒子付導電粒子3の頂部の1点で露出するようにしてもよく、絶縁粒子付導電粒子3が絶縁性樹脂層5内に完全に埋まり、径Lcがゼロとなるようにしてもよい。 Note that the diameter Lc of the exposed (immediately above) portion of the conductive particles 3 with insulating particles in the slope 5b or the undulation 5c can be equal to or smaller than the particle diameter D of the conductive particles 3 with insulating particles, and preferably 10 to 10 times the particle diameter D. 90%. The conductive particles with insulating particles 3 may be exposed at one point on the top, or the conductive particles with insulating particles 3 are completely buried in the insulating resin layer 5 so that the diameter Lc becomes zero. Good.
 このような本発明において、絶縁性樹脂層5の表面の傾斜5b、起伏5cの存在は、異方性導電フィルムの断面を走査型電子顕微鏡で観察することにより確認することができ、面視野観察においても確認できる。光学顕微鏡、金属顕微鏡でも傾斜5b、起伏5cの観察は可能である。また、傾斜5b、起伏5cの大きさは画像観察時の焦点調整などで確認することもできる。上述のようにヒートプレスにより傾斜もしくは起伏を減少させた後であっても、同様である。痕跡が残る場合があるからである。 In the present invention, the presence of the slopes 5b and undulations 5c on the surface of the insulating resin layer 5 can be confirmed by observing the cross section of the anisotropic conductive film with a scanning electron microscope. Can also be confirmed. The tilt 5b and the undulations 5c can be observed even with an optical microscope or a metal microscope. Moreover, the magnitude | size of the inclination 5b and the undulation 5c can also be confirmed by the focus adjustment at the time of image observation. The same applies even after the inclination or undulation is reduced by heat pressing as described above. This is because traces may remain.
(絶縁性樹脂層の組成)
 絶縁性樹脂層5は、硬化性樹脂組成物から形成することが好ましく、例えば、熱重合性化合物と熱重合開始剤とを含有する熱重合性組成物から形成することができる。熱重合性組成物には必要に応じて光重合開始剤を含有させてもよい。
(Composition of insulating resin layer)
The insulating resin layer 5 is preferably formed from a curable resin composition, and can be formed from, for example, a thermopolymerizable composition containing a thermopolymerizable compound and a thermal polymerization initiator. You may make a thermopolymerizable composition contain a photoinitiator as needed.
 熱重合開始剤と光重合開始剤を併用する場合に、熱重合性化合物として光重合性化合物としても機能するものを使用してもよく、熱重合性化合物とは別に光重合性化合物を含有させてもよい。好ましくは、熱重合性化合物とは別に光重合性化合物を含有させる。例えば、熱重合開始剤としてカチオン系硬化開始剤、熱重合性化合物としてエポキシ樹脂を使用し、光重合開始剤として光ラジカル開始剤、光重合性化合物としてアクリレート化合物を使用する。 When a thermal polymerization initiator and a photopolymerization initiator are used in combination, one that also functions as a photopolymerizable compound may be used as the thermopolymerizable compound, and a photopolymerizable compound is contained separately from the thermopolymerizable compound. May be. Preferably, a photopolymerizable compound is contained separately from the thermally polymerizable compound. For example, a cationic curing initiator is used as the thermal polymerization initiator, an epoxy resin is used as the thermopolymerizable compound, a photo radical initiator is used as the photopolymerization initiator, and an acrylate compound is used as the photopolymerizable compound.
 光重合開始剤として、波長の異なる光に反応する複数種類を含有させてもよい。これにより、異方性導電フィルムの製造時における、絶縁性樹脂層を構成する樹脂の光硬化と、異方性導電接続時に電子部品同士を接着するための樹脂の光硬化とで使用する波長を使い分けることができる。 As the photopolymerization initiator, a plurality of types that react to light having different wavelengths may be contained. Accordingly, the wavelength used for the photocuring of the resin constituting the insulating resin layer during the production of the anisotropic conductive film and the photocuring of the resin for bonding the electronic components to each other during the anisotropic conductive connection. Can be used properly.
 異方性導電フィルムの製造時の光硬化では、絶縁性樹脂層に含まれる光重合性化合物の全部又は一部を光硬化させることができる。この光硬化により、絶縁性樹脂層5における絶縁粒子付導電粒子3の配置が保持乃至固定化され、ショートの抑制と導電粒子の捕捉の向上が見込まれる。また、この光硬化により、異方性導電フィルムの製造工程における絶縁性樹脂層の粘度を適宜調整してもよい。 In photocuring during the production of the anisotropic conductive film, all or part of the photopolymerizable compound contained in the insulating resin layer can be photocured. By this photocuring, the arrangement of the conductive particles with insulating particles 3 in the insulating resin layer 5 is maintained or fixed, and it is expected that the short circuit is suppressed and the conductive particles are captured better. Moreover, you may adjust suitably the viscosity of the insulating resin layer in the manufacturing process of an anisotropic conductive film by this photocuring.
 絶縁性樹脂層における光重合性化合物の配合量は30質量%以下が好ましく、10質量%以下がより好ましく、2質量%未満がより好ましい。光重合性化合物が多すぎると接続時の押し込みにかかる推力が増加するためである。 The blending amount of the photopolymerizable compound in the insulating resin layer is preferably 30% by mass or less, more preferably 10% by mass or less, and more preferably less than 2% by mass. This is because when the amount of the photopolymerizable compound is too large, the thrust applied to the pushing at the time of connection increases.
 熱重合性組成物の例としては、(メタ)アクリレート化合物と熱ラジカル重合開始剤とを含む熱ラジカル重合性アクリレート系組成物、エポキシ化合物と熱カチオン重合開始剤とを含む熱カチオン重合性エポキシ系組成物等が挙げられる。熱カチオン重合開始剤を含む熱カチオン重合性エポキシ系組成物に代えて、熱アニオン重合開始剤を含む熱アニオン重合性エポキシ系組成物を使用してもよい。また、特に支障を来たさなければ、複数種の重合性組成物を併用してもよい。併用例としては、カチオン重合性化合物とラジカル重合性化合物の併用などが挙げられる。 Examples of the thermally polymerizable composition include a thermal radical polymerizable acrylate composition containing a (meth) acrylate compound and a thermal radical polymerization initiator, and a thermal cationic polymerizable epoxy system containing an epoxy compound and a thermal cationic polymerization initiator. Examples thereof include compositions. Instead of the thermal cationic polymerizable epoxy composition containing a thermal cationic polymerization initiator, a thermal anionic polymerizable epoxy composition containing a thermal anionic polymerization initiator may be used. In addition, a plurality of types of polymerizable compositions may be used in combination as long as there is no particular problem. Examples of the combination include a combination of a cationic polymerizable compound and a radical polymerizable compound.
 ここで、(メタ)アクリレート化合物としては、従来公知の熱重合型(メタ)アクリレートモノマーを使用することができる。例えば、単官能(メタ)アクリレート系モノマー、二官能以上の多官能(メタ)アクリレート系モノマーを使用することができる。 Here, as the (meth) acrylate compound, a conventionally known thermal polymerization type (meth) acrylate monomer can be used. For example, a monofunctional (meth) acrylate monomer or a bifunctional or higher polyfunctional (meth) acrylate monomer can be used.
 熱ラジカル重合開始剤としては、例えば、有機過酸化物、アゾ系化合物等を挙げることができる。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。 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.
 熱ラジカル重合開始剤の使用量は、少なすぎると硬化不良となり、多すぎると製品ライフの低下となるので、(メタ)アクリレート化合物100質量部に対し、好ましくは2~60質量部、より好ましくは5~40質量部である。 If the amount of the thermal radical polymerization initiator used is too small, curing will be poor, and if it is too large, the product life will be reduced. Therefore, it is preferably 2 to 60 parts by weight, more preferably 100 parts by weight of the (meth) acrylate compound. 5 to 40 parts by mass.
 エポキシ化合物としては、ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、ノボラック型エポキシ樹脂、それらの変性エポキシ樹脂、脂環式エポキシ樹脂などを挙げることができ、これらの2種以上を併用することができる。また、エポキシ化合物に加えてオキセタン化合物を併用してもよい。 Examples of the epoxy compound include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a novolac type epoxy resin, a modified epoxy resin thereof, an alicyclic epoxy resin, and the like. it can. In addition to the epoxy compound, an oxetane compound may be used in combination.
 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。 As the thermal cationic polymerization initiator, those known as thermal cationic polymerization initiators for epoxy compounds can be employed. For example, iodonium salts, sulfonium salts, phosphonium salts, ferrocenes, etc. that generate an acid by heat are used. In particular, an aromatic sulfonium salt showing a good potential with respect to temperature can be preferably used.
 熱カチオン重合開始剤の使用量は、少なすぎても硬化不良となる傾向があり、多すぎても製品ライフが低下する傾向があるので、エポキシ化合物100質量部に対し、好ましくは2~60質量部、より好ましくは5~40質量部である。 If the amount of the thermal cationic polymerization initiator used is too small, curing tends to be poor, and if it is too much, the product life tends to decrease. Therefore, the amount is preferably 2 to 60 mass relative to 100 parts by mass of the epoxy compound. Part, more preferably 5 to 40 parts by weight.
 熱重合性組成物は、膜形成樹脂やシランカップリング剤を含有することが好ましい。膜形成樹脂としては、フェノキシ樹脂、エポキシ樹脂、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等を挙げることができ、これらの2種以上を併用することができる。これらの中でも、製膜性、加工性、接続信頼性の観点から、フェノキシ樹脂を好ましく使用することができる。重量平均分子量は10000以上であることが好ましい。また、シランカップリング剤としては、エポキシ系シランカップリング剤、アクリル系シランカップリング剤等を挙げることができる。これらのシランカップリング剤は、主としてアルコキシシラン誘導体である。 The thermopolymerizable composition preferably contains a film-forming resin and a silane coupling agent. Examples of the film-forming resin include phenoxy resin, epoxy resin, unsaturated polyester resin, saturated polyester resin, urethane resin, butadiene resin, polyimide resin, polyamide resin, polyolefin resin, and the like. be able to. Among these, a phenoxy resin can be preferably used from the viewpoint of film forming property, workability, and connection reliability. The weight average molecular weight is preferably 10,000 or more. Examples of the silane coupling agent include an epoxy silane coupling agent and an acrylic silane coupling agent. These silane coupling agents are mainly alkoxysilane derivatives.
 熱重合性組成物には、溶融粘度調整のために、上述の絶縁粒子付導電粒子3とは別に絶縁性フィラーを含有させてもよい。これはシリカ粉やアルミナ粉などが挙げられる。絶縁性フィラー粒径20~1000nmの微小なフィラーが好ましく、また、配合量はエポキシ化合物等の熱重合性化合物(光重合性化合物)100質量部に対して5~50質量部とすることが好ましい。 In order to adjust the melt viscosity, the thermally polymerizable composition may contain an insulating filler separately from the conductive particles with insulating particles 3 described above. Examples of this include silica powder and alumina powder. A fine filler having an insulating filler particle size of 20 to 1000 nm is preferable, and the blending amount is preferably 5 to 50 parts by mass with respect to 100 parts by mass of a thermally polymerizable compound (photopolymerizable compound) such as an epoxy compound. .
 本発明の異方性導電フィルムには、上述の絶縁性のフィラーとは別に充填剤、軟化剤、促進剤、老化防止剤、着色剤(顔料、染料)、有機溶剤、イオンキャッチャー剤などを含有させてもよい。 The anisotropic conductive film of the present invention contains a filler, softener, accelerator, anti-aging agent, colorant (pigment, dye), organic solvent, ion catcher agent, etc. in addition to the above-mentioned insulating filler. You may let them.
(絶縁性樹脂層の層厚)
 本発明の異方性導電フィルムでは、絶縁性樹脂層5の層厚Laと絶縁粒子付導電粒子3の粒子径Dとの比(La/D)が後述の理由から下限を0.3以上とすることができ、上限を10以下することができる。従って、その比は0.3~10が好ましく、0.6~8がより好ましく、0.6~6が更に好ましい。ここで、絶縁粒子付導電粒子3の粒子径Dは、その平均粒子径を意味する。絶縁性樹脂層5の層厚Laが大き過ぎると異方性導電接続時に絶縁粒子付導電粒子3が樹脂流動により位置ズレしやすくなり、端子における絶縁粒子付導電粒子3の捕捉性が低下する。この傾向はこの比(La/D)が10を超えると顕著であるため、8以下がより好ましく、6以下が更に好ましい。反対に絶縁性樹脂層5の層厚Laが小さすぎてこの比(La/D)が0.3未満となると、絶縁粒子付導電粒子3を絶縁性樹脂層5によって所定の粒子分散状態あるいは所定の配列に維持することが困難となるので比(La/D)は0.3以上が好ましく、絶縁性樹脂層5によって所定の粒子分散状態あるいは所定の配列を確実に維持する点から0.6以上がより好ましい。また、接続する端子が高密度COGの場合、絶縁性樹脂層5の層厚Laと絶縁粒子付導電粒子3の粒子径Dとの比(La/D)は、好ましくは0.8~2である。
(Insulating resin layer thickness)
In the anisotropic conductive film of the present invention, the ratio (La / D) between the layer thickness La of the insulating resin layer 5 and the particle diameter D of the conductive particles with insulating particles 3 is 0.3 or more because of the reason described later. The upper limit can be made 10 or less. Therefore, the ratio is preferably 0.3 to 10, more preferably 0.6 to 8, and still more preferably 0.6 to 6. Here, the particle diameter D of the conductive particles 3 with insulating particles means the average particle diameter. If the layer thickness La of the insulating resin layer 5 is too large, the conductive particles with insulating particles 3 are likely to be displaced due to resin flow during anisotropic conductive connection, and the trapping property of the conductive particles with insulating particles 3 at the terminals is lowered. Since this tendency is remarkable when this ratio (La / D) exceeds 10, 8 or less is more preferable, and 6 or less is still more preferable. On the contrary, if the layer thickness La of the insulating resin layer 5 is too small and this ratio (La / D) is less than 0.3, the conductive particles 3 with insulating particles are dispersed in a predetermined particle state or a predetermined state by the insulating resin layer 5. Therefore, the ratio (La / D) is preferably 0.3 or more, and the insulating resin layer 5 ensures that the predetermined particle dispersion state or the predetermined arrangement is reliably maintained by 0.6. The above is more preferable. When the terminal to be connected is high density COG, the ratio (La / D) between the layer thickness La of the insulating resin layer 5 and the particle diameter D of the conductive particles 3 with insulating particles is preferably 0.8-2. is there.
<絶縁性樹脂層における絶縁粒子付導電粒子の埋込状態>
 絶縁性樹脂層5における絶縁粒子付導電粒子3の埋込状態は、埋込率を30%以上105%以下とすることが好ましい。埋込率30%以上、好ましくは60%以上とすることにより、絶縁粒子付導電粒子3を絶縁性樹脂層5によって所定の粒子分散状態あるいは所定の配列に維持させることができる。また、埋込率105%以下とすることにより、異方性導電接続時に絶縁粒子付導電粒子を無用に流動させるように作用する絶縁性樹脂層の樹脂量を低減させることができる。
<Embedded state of conductive particles with insulating particles in insulating resin layer>
In the embedded state of the conductive particles 3 with insulating particles in the insulating resin layer 5, it is preferable that the burying rate is 30% or more and 105% or less. By setting the embedding rate to 30% or more, preferably 60% or more, the conductive particles 3 with insulating particles can be maintained in a predetermined particle dispersion state or a predetermined arrangement by the insulating resin layer 5. In addition, by setting the embedding rate to 105% or less, it is possible to reduce the amount of resin in the insulating resin layer that acts to cause the conductive particles with insulating particles to flow unnecessarily during anisotropic conductive connection.
 ここで、埋込率とは、絶縁粒子付導電粒子3が埋め込まれている絶縁性樹脂層5の表面5a(絶縁性樹脂層5において、絶縁粒子付導電粒子3が偏在している方の表面)と、絶縁性樹脂層5に埋め込まれている絶縁粒子付導電粒子3の前記表面5aに対する最深部との距離を埋込量Lbとした場合に、絶縁粒子付導電粒子3の粒子径Dに対する埋込量Lbの比率(Lb/D)である(図1B)。 Here, the embedding rate is the surface 5a of the insulating resin layer 5 in which the conductive particles 3 with insulating particles are embedded (the surface on which the conductive particles 3 with insulating particles are unevenly distributed in the insulating resin layer 5). ) And the deepest portion of the conductive particles with insulating particles 3 embedded in the insulating resin layer 5 with respect to the surface 5a is the embedded amount Lb, with respect to the particle diameter D of the conductive particles with insulating particles 3 It is the ratio (Lb / D) of the embedding amount Lb (FIG. 1B).
 なお、本発明において、埋込率(Lb/D)の数値は、異方性導電フィルムに含まれる全絶縁粒子付導電粒子数の80%以上、好ましくは90%以上、より好ましくは96%以上が、当該埋込率(Lb/D)の数値になっていることをいう。したがって、埋込率が30%以上105%以下とは、異方性導電フィルムに含まれる全絶縁粒子付導電粒子数の80%以上、好ましくは90%以上、より好ましくは96%以上の埋込率が30%以上105%以下であることをいう。このように全絶縁粒子付導電粒子の埋込率(Lb/D)が揃っていることにより、押圧の加重が導電粒子に均一にかかるので、端子における導電粒子の捕捉状態が良好になり、導通の安定性が向上する。 In the present invention, the value of the embedding rate (Lb / D) is 80% or more, preferably 90% or more, more preferably 96% or more of the total number of conductive particles with insulating particles contained in the anisotropic conductive film. Is the numerical value of the embedding rate (Lb / D). Therefore, the embedding rate of 30% or more and 105% or less means that the embedding rate is 80% or more, preferably 90% or more, more preferably 96% or more of the total number of conductive particles with insulating particles contained in the anisotropic conductive film. The rate is 30% or more and 105% or less. Thus, since the embedding rate (Lb / D) of the conductive particles with all insulating particles is uniform, the load of pressing is uniformly applied to the conductive particles, so that the state of capturing the conductive particles at the terminals is improved and the conduction is improved. Improves stability.
 埋込率(Lb/D)は、異方性導電フィルムから面積30mm以上の領域を任意に10箇所以上抜き取り、そのフィルム断面の一部をSEM画像で観察し、合計50個以上の導電粒子を計測することにより求めることができる。より精度を上げるため、200個以上の導電粒子を計測して求めてもよい。 The embedding rate (Lb / D) was determined by arbitrarily extracting 10 or more regions having an area of 30 mm 2 or more from the anisotropic conductive film, observing a part of the film cross section with an SEM image, and totaling 50 or more conductive particles. Can be obtained by measuring In order to increase accuracy, 200 or more conductive particles may be measured and obtained.
 また、埋込率(Lb/D)の計測は、面視野画像において焦点調整することにより、ある程度の個数について一括して求めることもできる。もしくは埋込率(Lb/D)の計測にレーザー式判別変位センサ((株)キーエンス製など)を用いてもよい。 Further, the measurement of the embedding rate (Lb / D) can be obtained collectively for a certain number by adjusting the focus in the surface field image. Alternatively, a laser discrimination displacement sensor (manufactured by Keyence Co., Ltd.) may be used for measuring the embedding rate (Lb / D).
<異方性導電フィルムの製造方法>
 図1A、図1Bに示した異方性導電フィルム10Aの製造方法の一例においては、転写型30の凹部31に絶縁粒子付導電粒子3を充填する(図4A)。この凹部31は、異方性導電フィルムにおける絶縁粒子付導電粒子3と同様の配列に形成されている。
<Method for producing anisotropic conductive film>
In an example of the method for manufacturing the anisotropic conductive film 10A shown in FIGS. 1A and 1B, the recesses 31 of the transfer mold 30 are filled with the conductive particles with insulating particles 3 (FIG. 4A). The recesses 31 are formed in the same arrangement as the conductive particles 3 with insulating particles in the anisotropic conductive film.
 このような転写型30としては、例えば、シリコン、各種セラミックス、ガラス、ステンレススチールなどの金属等の無機材料や、各種樹脂等の有機材料などに対し、フォトリソグラフ法等の公知の開口形成方法によって凹部31を形成したものを使用することができる。また、転写型は、板状、ロール状等の形状をとることができる。 As such a transfer mold 30, for example, an inorganic material such as silicon, various ceramics, glass, stainless steel, or the like, or an organic material such as various resins may be formed by a known opening forming method such as a photolithographic method. What formed the recessed part 31 can be used. Further, the transfer mold can take a plate shape, a roll shape or the like.
 一方、剥離フィルム7上に絶縁性樹脂層5をフィルム状に形成しておき、転写型30に充填した絶縁粒子付導電粒子3上に絶縁性樹脂層5を被せる(図4C)。あるいは、絶縁粒子付導電粒子3上に絶縁性樹脂層5を被せる前に、転写型30に充填した絶縁粒子付導電粒子3に平板32を接触させるなどにより、絶縁粒子2を導電粒子1から脱離させ(図4B)、その後、絶縁性樹脂層5を被せてもよい(図4C)。次に、転写型30から絶縁性樹脂層5を剥離し、絶縁粒子付導電粒子3が転写した絶縁性樹脂層5を得る(図4D)。この絶縁粒子付導電粒子3の転写工程では、転写型30と絶縁粒子2が擦れるために、転写型30の凹部31の底面と接していた絶縁粒子2(領域A1の絶縁粒子2となるもの)が絶縁粒子付導電粒子3から脱離しやすい。また、転写型30内の絶縁粒子付導電粒子3に絶縁性樹脂層5を被せたときに、絶縁性樹脂層5と最初に接触する絶縁粒子2には大きな力がかかるため、この領域の絶縁粒子2(領域A2の絶縁粒子2となるもの)も脱離することがある。このため、フィルム上に絶縁粒子2が存在(点在)していることがある。 On the other hand, the insulating resin layer 5 is formed in a film shape on the release film 7, and the insulating resin layer 5 is put on the conductive particles 3 with insulating particles filled in the transfer mold 30 (FIG. 4C). Alternatively, before covering the insulating resin layer 5 on the conductive particles with insulating particles 3, the insulating particles 2 are removed from the conductive particles 1 by bringing the flat plate 32 into contact with the conductive particles with insulating particles 3 filled in the transfer mold 30. Then, the insulating resin layer 5 may be covered (FIG. 4C). Next, the insulating resin layer 5 is peeled from the transfer mold 30 to obtain the insulating resin layer 5 to which the conductive particles with insulating particles 3 are transferred (FIG. 4D). In the transfer process of the conductive particles 3 with insulating particles, the transfer mold 30 and the insulating particles 2 are rubbed, so that the insulating particles 2 that are in contact with the bottom surface of the recess 31 of the transfer mold 30 (the ones that become the insulating particles 2 in the region A1). Is easily detached from the conductive particles 3 with insulating particles. Further, when the insulating resin layer 5 is placed on the conductive particles 3 with insulating particles in the transfer mold 30, a large force is applied to the insulating particles 2 that first contact the insulating resin layer 5. The particles 2 (those that become the insulating particles 2 in the region A2) may also be detached. For this reason, the insulating particles 2 may be present (dotted) on the film.
 一方、フィルム面方向の絶縁粒子2は、絶縁性樹脂層5を転写型30から剥離した後も絶縁性樹脂層5から脱離することなく、絶縁性樹脂層5に維持されている。 On the other hand, the insulating particles 2 in the film surface direction are maintained on the insulating resin layer 5 without being detached from the insulating resin layer 5 even after the insulating resin layer 5 is peeled off from the transfer mold 30.
 したがって、絶縁性樹脂層5に転写した後の絶縁粒子付導電粒子3では、転写前に比して、絶縁粒子付導電粒子3を構成する絶縁粒子2のうち導電粒子1とフィルム厚方向で接する絶縁粒子2の個数が、導電粒子1とフィルム面方向で接する絶縁粒子2の個数に比して低減する。 Accordingly, the conductive particles 3 with insulating particles after being transferred to the insulating resin layer 5 are in contact with the conductive particles 1 in the film thickness direction among the insulating particles 2 constituting the conductive particles 3 with insulating particles as compared to before the transfer. The number of insulating particles 2 is reduced as compared with the number of insulating particles 2 in contact with the conductive particles 1 in the film surface direction.
 次に、必要に応じて、絶縁性樹脂層5に転写した絶縁粒子付導電粒子3を平板又はローラー33で押し込む(図4E)。この押し込み時に、絶縁粒子付導電粒子3を形成していた絶縁粒子2であって、平板又はローラー33側にあった絶縁粒子2(領域A1となる絶縁粒子2)は平板又はローラー33との接触により導電粒子1から比較的脱離する。 Next, if necessary, the conductive particles with insulating particles 3 transferred to the insulating resin layer 5 are pushed in with a flat plate or a roller 33 (FIG. 4E). The insulating particles 2 that have formed the conductive particles 3 with insulating particles at the time of pressing, and the insulating particles 2 (insulating particles 2 to be the region A1) on the flat plate or roller 33 side are in contact with the flat plate or roller 33. Is relatively detached from the conductive particles 1.
 絶縁性樹脂層5に転写した絶縁粒子付導電粒子3を平板又はローラー33で押し込むときの押込量Lbは、埋込率(Lb/D)が好ましくは30%以上105%以下、より好ましくは60%以上105%以下となるように調整することが好ましく、また押し込みに押圧治具に必要とされる推力等に応じて定めることが好ましい。 The indentation rate (Lb / D) is preferably 30% or more and 105% or less, more preferably 60, when the conductive particles 3 with insulating particles transferred to the insulating resin layer 5 are pressed with a flat plate or roller 33. It is preferable to adjust so that it may become more than% and below 105%, and it is preferable to determine according to the thrust etc. which are required for a pressing jig for pushing.
 こうして、絶縁粒子付導電粒子3における絶縁粒子2の個数のうち、異方性導電フィルムのフィルム厚方向で導電粒子1と接する絶縁粒子2の個数が低減した異方性導電フィルム10Aを得ることができる(図4F)。 Thus, an anisotropic conductive film 10A in which the number of insulating particles 2 in contact with the conductive particles 1 in the thickness direction of the anisotropic conductive film among the number of insulating particles 2 in the conductive particles 3 with insulating particles is reduced can be obtained. Yes (FIG. 4F).
 また、上述した異方性導電フィルム10Aの製造方法において、当初の絶縁粒子付導電粒子3から脱離する絶縁粒子2の個数は、絶縁性樹脂層5の温度及び粘度、並びに埋込率(Lb/D)等により調整することができる。 Moreover, in the manufacturing method of the anisotropic conductive film 10A described above, the number of the insulating particles 2 detached from the initial conductive particles 3 with insulating particles depends on the temperature and viscosity of the insulating resin layer 5 and the embedding rate (Lb / D) or the like.
<異方性導電フィルムの変形態様>
 本発明の異方性導電フィルムは、図5に示す異方性導電フィルム10Bのように、絶縁粒子付導電粒子3が埋め込まれている絶縁性樹脂層5に、該絶縁性樹脂層5よりも最低溶融粘度が低い低粘度絶縁性樹脂層6を積層してもよい。低粘度絶縁性樹脂層6の積層により、異方性導電フィルムを用いて電子部品を異方性導電接続するときに、電子部品の電極やバンプによって形成される空間を充填し、接着性を向上させることができる。
<Deformation aspect of anisotropic conductive film>
The anisotropic conductive film of the present invention has an insulating resin layer 5 in which the conductive particles with insulating particles 3 are embedded, as in the anisotropic conductive film 10B shown in FIG. A low viscosity insulating resin layer 6 having a low minimum melt viscosity may be laminated. By laminating the low-viscosity insulating resin layer 6, when an anisotropic conductive film is used to anisotropically connect an electronic component, the space formed by the electrodes and bumps of the electronic component is filled to improve adhesion. Can be made.
 絶縁性樹脂層5と低粘度絶縁性樹脂層6との最低溶融粘度比は、好ましくは2以上、より好ましくは5以上、さらに好ましくは8以上、実用上15以下である。低粘度絶縁性樹脂層6のより具体的な最低溶融粘度は3000Pa・s以下、より好ましくは2000Pa・s以下であり、特に1000~2000Pa・sであることが好ましい。このように低粘度絶縁性樹脂層6を低粘度とすることにより、電子部品の電極やバンプによって形成される空間が低粘度絶縁性樹脂層で充填されやすくなるので、絶縁性樹脂層5の移動量が相対的に少なくなり、端子間の絶縁粒子付導電粒子3が樹脂流動により流されにくくなる。よって、異方性導電接続時に絶縁粒子付導電粒子3の捕捉性を損なうことなく、電子部品同士の接着性を向上させることができる。 The minimum melt viscosity ratio between the insulating resin layer 5 and the low-viscosity insulating resin layer 6 is preferably 2 or more, more preferably 5 or more, still more preferably 8 or more, and practically 15 or less. The more specific minimum melt viscosity of the low-viscosity insulating resin layer 6 is 3000 Pa · s or less, more preferably 2000 Pa · s or less, and particularly preferably 1000 to 2000 Pa · s. By making the low-viscosity insulating resin layer 6 low in this way, the space formed by the electrodes and bumps of the electronic component can be easily filled with the low-viscosity insulating resin layer. The amount is relatively small, and the conductive particles with insulating particles 3 between the terminals are less likely to flow due to resin flow. Therefore, the adhesiveness between the electronic components can be improved without impairing the trapping property of the conductive particles 3 with insulating particles during anisotropic conductive connection.
 また、絶縁性樹脂層5と低粘度絶縁性樹脂層6を合わせた異方性導電フィルム10B全体の最低溶融粘度は、好ましくは、200~4000Pa・sである。 The minimum melt viscosity of the entire anisotropic conductive film 10B including the insulating resin layer 5 and the low-viscosity insulating resin layer 6 is preferably 200 to 4000 Pa · s.
 なお、低粘度絶縁性樹脂層6は、絶縁性樹脂層5と同様の樹脂組成物において、粘度を調整することにより形成することができる。 The low-viscosity insulating resin layer 6 can be formed by adjusting the viscosity in the same resin composition as the insulating resin layer 5.
 また、異方性導電フィルム10Bにおいて、低粘度絶縁性樹脂層6の層厚は、好ましくは4~20μmである。もしくは、絶縁粒子付導電粒子の粒子径Dに対して、好ましくは1~8倍である。 In the anisotropic conductive film 10B, the layer thickness of the low-viscosity insulating resin layer 6 is preferably 4 to 20 μm. Alternatively, it is preferably 1 to 8 times the particle diameter D of the conductive particles with insulating particles.
 本発明においては、転写型30から絶縁性樹脂層5を剥離した後、絶縁粒子付導電粒子3を押し込む前のものを異方性導電フィルム10C(図6)としてもよく、これに低粘度絶縁性樹脂層6を積層したものを異方性導電フィルム10Dとしてもよい(図7)。この場合、絶縁粒子付導電粒子が、絶縁性樹脂層と低粘度絶縁性樹脂層の間に存在させてもよい。また、低粘度絶縁性樹脂層側フィルム面の平面視における導電粒子上の絶縁粒子数が、絶縁性樹脂層側フィルム面の平面視における導電粒子上の絶縁粒子数よりも少なくすることが好ましい。さらに、必要に応じて、低粘度絶縁性樹脂層6の反対側の絶縁性樹脂層5上にさらに低粘度絶縁性樹脂層を積層してもよい。 In the present invention, the anisotropic conductive film 10C (FIG. 6) may be used as the anisotropic conductive film 10C (FIG. 6) after the insulating resin layer 5 is peeled from the transfer mold 30 and before the conductive particles 3 with insulating particles are pushed. The laminated conductive resin layer 6 may be an anisotropic conductive film 10D (FIG. 7). In this case, the conductive particles with insulating particles may exist between the insulating resin layer and the low-viscosity insulating resin layer. Moreover, it is preferable that the number of insulating particles on the conductive particles in a plan view of the low viscosity insulating resin layer side film surface is smaller than the number of insulating particles on the conductive particles in a plan view of the insulating resin layer side film surface. Furthermore, you may laminate | stack a low-viscosity insulating resin layer further on the insulating resin layer 5 on the opposite side of the low-viscosity insulating resin layer 6 as needed.
 また、絶縁粒子付導電粒子3を、フィルム厚方向の異なる位置に複数層設けてもよい。これらの変形態様は、適宜組み合わせることができる。 Moreover, a plurality of conductive particles 3 with insulating particles may be provided at different positions in the film thickness direction. These deformation modes can be appropriately combined.
<異方性導電フィルムで接続する電子部品>
 本発明の異方性導電フィルムは、ICチップ、ICモジュール、FPCなどの第1電子部品と、FPC、ガラス基板、プラスチック基板、リジッド基板、セラミック基板などの第2電子部品とを異方性導電接続する際に好ましく使用することができる。ICチップやウェーハーをスタックして多層化させてもよい。なお、本発明の異方性導電フィルムで接続する電子部品は、上述の電子部品に限定されるものではない。近年、多様化している種々の電子部品に使用することができる。
<Electronic components connected with anisotropic conductive film>
The anisotropic conductive film of the present invention anisotropically conducts first electronic components such as IC chips, IC modules, and FPCs and second electronic components such as FPCs, glass substrates, plastic substrates, rigid substrates, and ceramic substrates. It can be preferably used when connecting. IC chips and wafers may be stacked to be multilayered. In addition, the electronic component connected with the anisotropic conductive film of this invention is not limited to the above-mentioned electronic component. It can be used for various electronic parts that have been diversified in recent years.
<異方性導電フィルムを用いた接続方法及び接続構造体>
 本発明は、本発明の異方性導電フィルムを用いて電子部品同士を異方性導電接続する接続構造体の製造方法を提供し、この製造方法により得られた接続構造体、即ち、対向する電子部品の端子同士が、絶縁粒子付導電粒子と絶縁性樹脂層により異方性導電接続されている接続構造体であって、対向する端子に挟持されていない絶縁粒子付導電粒子に、端子同士の対向方向を向いた絶縁粒子欠落領域を有する絶縁粒子付導電粒子が含まれている接続構造体を提供する。
<Connection method and connection structure using anisotropic conductive film>
The present invention provides a method for manufacturing a connection structure for anisotropically conductively connecting electronic components using the anisotropic conductive film of the present invention, and the connection structure obtained by this manufacturing method, that is, facing the connection structure. The terminal of the electronic component is a connection structure in which the conductive particles with insulating particles and the insulating resin layer are anisotropically conductively connected, and the conductive particles with insulating particles that are not sandwiched between opposing terminals are connected to each other. A connection structure including conductive particles with insulating particles having an insulating particle missing region facing in the opposite direction is provided.
 この接続構造体には、対向する端子に挟持されている絶縁粒子付導電粒子にも、端子同士の対向方向を向いた絶縁粒子欠落領域を有する絶縁粒子付導電粒子が含まれている。この接続構造体において、端子同士の対向方向は、接続構造体の製造に使用した本発明の異方性導電フィルムのフィルム厚方向に対応し、端子の接続面方向は、異方性導電フィルムのフィルム面方向に対応する。また、絶縁粒子欠落領域とは、絶縁粒子付導電粒子の表面の一部分が、その外側の環状部分に比して絶縁粒子の面密度が低くなっている領域をいう。したがって、この接続構造体において、対向する端子に挟持されている絶縁粒子付導電粒子は、前述した異方性導電フィルムにおいて絶縁粒子数が低減している領域A1又はA2に対応しており、端子同士の対向方向で導電粒子と接する絶縁粒子数が、端子の接続面方向(端子同士の対向方向と直交する方向)で導電粒子と接する絶縁粒子数よりも少ない絶縁粒子付導電粒子と言える。このような絶縁粒子付導電粒子は、上述の対向する端子に挟持されていない絶縁粒子付導電粒子の絶縁粒子欠落領域の向きが、端子に挟持される直前まで絶縁性樹脂によって保持され、端子に挟持された後もその向きが保持されたものと推察される。対向する端子に挟持されている絶縁粒子付導電粒子は、絶縁粒子欠落領域が対向する端子の少なくとも一方と接触しているため、導通安定性の上では好ましく、絶縁粒子欠落領域が対向する端子の双方と接触していることがより好ましい。 In this connection structure, the conductive particles with insulating particles are also included in the conductive particles with insulating particles sandwiched between the opposing terminals and have insulating particle missing regions facing the opposing direction of the terminals. In this connection structure, the opposing direction of the terminals corresponds to the film thickness direction of the anisotropic conductive film of the present invention used for the production of the connection structure, and the connection surface direction of the terminals is the anisotropic conductive film. Corresponds to the film surface direction. In addition, the insulating particle missing region refers to a region where a part of the surface of the conductive particle with insulating particles has a lower surface density of the insulating particles than the outer annular portion. Therefore, in this connection structure, the conductive particles with insulating particles sandwiched between the opposing terminals correspond to the region A1 or A2 in which the number of insulating particles is reduced in the anisotropic conductive film described above. It can be said that the number of insulating particles in contact with the conductive particles in the opposing direction between them is smaller than the number of insulating particles in contact with the conductive particles in the connecting surface direction of the terminals (direction orthogonal to the opposing direction of the terminals). Such conductive particles with insulating particles are held by the insulating resin until the direction of the insulating particle missing region of the conductive particles with insulating particles that are not sandwiched between the opposing terminals is just sandwiched between the terminals. It is presumed that the orientation was maintained even after being pinched. The conductive particles with insulating particles sandwiched between the opposing terminals are preferable in terms of conduction stability because the insulating particle missing region is in contact with at least one of the opposing terminals. More preferably, both are in contact.
 また、この接続構造体において絶縁粒子欠落領域が端子同士の対向方向を向いた絶縁粒子付導電粒子は、上述のように、異方性導電フィルムにおいて絶縁粒子数が低減している領域A1又はA2を有する絶縁粒子付導電粒子に対応するから、異方性導電フィルムにおける前述の(NA3+NA4)>(NA1+NA2)の関係を満たしている。 Further, in this connection structure, the conductive particles with insulating particles in which the region lacking the insulating particles faces the opposing direction of the terminals, as described above, the region A1 or A2 in which the number of insulating particles is reduced in the anisotropic conductive film. Therefore , the relationship of (N A3 + N A4 )> (N A1 + N A2 ) in the anisotropic conductive film is satisfied.
 接続構造体における絶縁粒子欠落領域の絶縁粒子付導電粒子を概念的に説明すると、絶縁粒子付導電粒子を球とした場合に、中心角45°に対応する球の表面の一部領域が、その外側の中心角45°~135°に対応する環状領域よりも絶縁粒子の面密度が低くなっている場合の当該中心角45°に対応する球の表面の一部領域といえる。 When the conductive particles with insulating particles in the insulating particle missing region in the connection structure are conceptually described, when the conductive particles with insulating particles are spheres, a partial region of the surface of the sphere corresponding to a central angle of 45 ° is This can be said to be a partial region of the surface of the sphere corresponding to the central angle 45 ° when the surface density of the insulating particles is lower than the annular region corresponding to the outer central angle 45 ° to 135 °.
 この接続構造体において、対向する端子に挟持されていない絶縁粒子付導電粒子は、対向する電子部品の接続面のうち、電子部品における端子列の非形成領域で挟まれている、対向する電子部品間の絶縁粒子付導電粒子を含む。この場合の絶縁粒子付導電粒子は、例えば、対向する電子部品を第1電子部品と第2電子部品とした場合に、第1電子部品における端子列の非形成領域と第2電子部品における端子列の非形成領域により電子部品の対向方向で挟まれている絶縁粒子付導電粒子のことである。 In this connection structure, conductive particles with insulating particles that are not sandwiched between opposing terminals are sandwiched between non-formation regions of the terminal rows in the electronic component, out of the connection surfaces of the opposing electronic component. Including conductive particles with insulating particles in between. The conductive particles with insulating particles in this case are, for example, when the opposing electronic parts are the first electronic part and the second electronic part, the terminal row non-formation region in the first electronic component and the terminal row in the second electronic component It is the electroconductive particle with an insulating particle pinched | interposed by the non-formation area | region of the electronic component in the opposing direction.
 また、この接続構造体において、対向する端子に挟持されていない絶縁粒子付導電粒子は、電子部品に端子列が所定の端子間スペースで形成されている場合の、対向する電子部品の端子間スペース同士の間にある絶縁粒子付導電粒子を含む。 Further, in this connection structure, the conductive particles with insulating particles that are not sandwiched between the opposing terminals are the inter-terminal spaces of the opposing electronic components when the terminal rows are formed on the electronic components with the predetermined inter-terminal spaces. Including conductive particles with insulating particles between them.
 言い換えると、対向する端子に挟持されていない絶縁粒子付導電粒子とは、接続構造体において、接続に寄与していない大多数の絶縁粒子付導電粒子を意味する。 In other words, the conductive particles with insulating particles that are not sandwiched between opposing terminals mean the majority of conductive particles with insulating particles that do not contribute to connection in the connection structure.
 一般に、接続構造体において、対向する端子に挟持されていない絶縁粒子付導電粒子には、異方性導電接続時の加熱加圧により、加熱加圧前の状態に対して移動しているものが含まれ、向きが変わっているものもある。向きの変わる程度は、当該絶縁粒子付導電粒子の端子に対する位置、絶縁性樹脂層の粘度、加熱加圧条件等によって異なるが、接続構造体の絶縁粒子付導電粒子には、加熱加圧前の向きを維持しているものも含まれる。したがって、接続構造体の製造に使用した異方性導電フィルムが本発明の異方性導電フィルムであると、対向する端子に挟持されていない絶縁粒子付導電粒子の少なくとも一部には、絶縁粒子欠落領域が、対向する端子の対向方向を向いたものが含まれることとなり、本発明の接続構造体であることがわかる。特に、接続構造体において導電粒子欠落領域が、対向する端子の対向方向を向いた絶縁粒子付導電粒子が、ある領域に集まって存在していると、その接続構造体は本発明の接続構造体であることが容易にわかる。 In general, in the connection structure, the conductive particles with insulating particles that are not sandwiched between the opposing terminals are those that have moved relative to the state before the heating and pressurization due to the heating and pressurization during the anisotropic conductive connection. Some are included and have changed orientation. The degree of change in direction varies depending on the position of the conductive particles with insulating particles with respect to the terminals, the viscosity of the insulating resin layer, the heating and pressing conditions, etc. This includes those that maintain their orientation. Therefore, when the anisotropic conductive film used in the manufacture of the connection structure is the anisotropic conductive film of the present invention, at least some of the conductive particles with insulating particles that are not sandwiched between opposing terminals include insulating particles. It can be seen that the missing region includes those facing the opposing direction of the opposing terminals, which is the connection structure of the present invention. In particular, when the conductive particle missing region in the connection structure has the conductive particles with insulating particles facing the opposing direction of the opposing terminals gathered in a certain region, the connection structure is the connection structure of the present invention. It is easy to see that
 異方性導電フィルムは電子部品の一方の外形にほぼ同じ大きさに裁断されて使用されることもあるが、一般には電子部品の一方の外形よりも大きく裁断されて使用される。つまり、接続に寄与しない(ツールから十分に離れている)領域を含む場合がある。そのため、対向した電子部品間の外側の異方性導電フィルムに端子同士の対向方向を向いた絶縁粒子欠落領域が存在する場合もあり、ここからも本発明の接続構造体の特徴を確認することができる。 An anisotropic conductive film may be cut to approximately the same size as one outer shape of an electronic component, but is generally cut to be larger than one outer shape of an electronic component. That is, it may include a region that does not contribute to the connection (separately away from the tool). Therefore, there may be a region lacking insulating particles facing the opposing direction of the terminals in the outer anisotropic conductive film between the opposing electronic components, and from here also confirm the characteristics of the connection structure of the present invention. Can do.
 また、接続構造体の製造に用いた異方性導電フィルムにおいて絶縁粒子付導電粒子が規則配列している場合、接続構造体において、対向する端子に挟持されていない絶縁粒子付導電粒子にも配列の規則性の維持が見出されることもある。この場合には、この配列の規則性が見出された絶縁粒子付導電粒子において、絶縁粒子欠落領域が端子同士の対向方向を向いていることを容易に確認することができる。また、その製造に使用した異方性導電フィルムについて、容易に(NA3+NA4)>(NA1+NA2)を確認することができる。 In addition, when the conductive particles with insulating particles are regularly arranged in the anisotropic conductive film used for manufacturing the connection structure, the conductive particles with insulation particles that are not sandwiched between opposing terminals in the connection structure are also arranged. Maintenance of regularity may be found. In this case, in the conductive particles with insulating particles in which the regularity of the arrangement is found, it can be easily confirmed that the insulating particle missing region is facing the facing direction of the terminals. Moreover, ( NA3 + NA4 )> ( NA1 + NA2 ) can be easily confirmed about the anisotropic conductive film used for the manufacture.
 なお、本発明の接続構造体の製造過程の構造体であって、本発明の異方性導電フィルムが一方の電子部品に貼着されているが、他方の電子部品はまだ接続されていない状態の構造体(接続工程における中間品であり、換言すれば異方性導電フィルム貼着電子部品)でも、その異方性導電フィルム中の絶縁粒子付導電粒子は、上述の接続構造体における絶縁粒子付導電粒子と同様の特徴を有する。 In addition, it is a structure in the manufacturing process of the connection structure of the present invention, and the anisotropic conductive film of the present invention is attached to one electronic component, but the other electronic component is not yet connected The conductive particles with insulating particles in the anisotropic conductive film are the insulating particles in the connection structure described above (the intermediate product in the connection process, in other words, the anisotropic conductive film-attached electronic component). It has the same characteristics as the attached conductive particles.
 異方性導電フィルムを用いた電子部品の接続方法としては、異方性導電フィルムの樹脂層が絶縁性樹脂層5の単層からなる場合、各種基板などの第2電子部品に対し、異方性導電フィルムの絶縁粒子付導電粒子3が表面に埋め込まれている側から仮圧着し、仮圧着した異方性導電フィルムの絶縁粒子付導電粒子3が表面に埋め込まれていない側にICチップ等の第1電子部品を合わせ、熱圧着することにより製造することができる。異方性導電フィルムの絶縁性樹脂層に熱重合開始剤と熱重合性化合物だけでなく、光重合開始剤と光重合性化合物(熱重合性化合物と同一でもよい)が含まれている場合、光と熱を併用した圧着方法でもよい。このようにすれば、絶縁粒子付導電粒子の無用な移動を最小限に抑えることができる。また、絶縁粒子付導電粒子3が埋め込まれていない側を第2電子部品に仮貼りして使用してもよい。尚、第2電子部品ではなく、第1電子部品に異方性導電フィルムを仮貼りして使用することもできる。 As a method for connecting an electronic component using an anisotropic conductive film, when the resin layer of the anisotropic conductive film is a single layer of the insulating resin layer 5, it is anisotropic to the second electronic component such as various substrates. The conductive particles with insulating particles 3 of the conductive conductive film are temporarily pressure-bonded from the side embedded in the surface, and the IC chips or the like are provided on the side of the anisotropically conductive film 3 with the insulating particles with insulating particles embedded therein that are not embedded in the surface. These first electronic components can be combined and thermocompression bonded. When the insulating resin layer of the anisotropic conductive film contains not only a thermal polymerization initiator and a thermal polymerizable compound, but also a photopolymerization initiator and a photopolymerizable compound (may be the same as the thermal polymerizable compound), A pressure bonding method using both light and heat may be used. In this way, unnecessary movement of the conductive particles with insulating particles can be minimized. Further, the side on which the conductive particles with insulating particles 3 are not embedded may be temporarily attached to the second electronic component for use. Note that the anisotropic conductive film may be temporarily attached to the first electronic component instead of the second electronic component.
 また、異方性導電フィルムの樹脂層が、絶縁性樹脂層5と低粘度絶縁性樹脂層6の積層体から形成されている場合、絶縁性樹脂層5を各種基板などの第2電子部品に仮貼りして仮圧着し、仮圧着した異方性導電フィルムの低粘度絶縁性樹脂層6にICチップ等の第1電子部品をアライメントして載置し、熱圧着する。異方性導電フィルムの低粘度絶縁性樹脂層6側を第1電子部品に仮貼りして使用してもよい。 Further, when the resin layer of the anisotropic conductive film is formed of a laminate of the insulating resin layer 5 and the low-viscosity insulating resin layer 6, the insulating resin layer 5 is used as a second electronic component such as various substrates. The first electronic component such as an IC chip is aligned and placed on the low-viscosity insulating resin layer 6 of the anisotropic conductive film that has been temporarily attached and temporarily bonded, and then subjected to thermocompression bonding. The low-viscosity insulating resin layer 6 side of the anisotropic conductive film may be temporarily attached to the first electronic component for use.
 以下、本発明を実施例により具体的に説明する。
 実施例1~10
(1)異方性導電フィルムの製造
 表1に示した配合で、絶縁性樹脂層及び低粘度絶縁性樹脂層を形成する樹脂組成物をそれぞれ調製した。
Hereinafter, the present invention will be specifically described by way of examples.
Examples 1 to 10
(1) Manufacture of anisotropic conductive film The resin composition which forms an insulating resin layer and a low-viscosity insulating resin layer with the formulation shown in Table 1 was prepared.
 絶縁性樹脂層を形成する樹脂組成物をバーコータ-でフィルム厚50μmのPETフィルム上に塗布し、80℃のオーブンにて5分間乾燥させ、PETフィルム上に表2に示す厚みの絶縁性樹脂層を形成した。同様にして、低粘度絶縁性樹脂層を、それぞれ表2に示す厚みでPETフィルム上に形成した。 The resin composition for forming the insulating resin layer is applied onto a PET film having a film thickness of 50 μm with a bar coater, dried in an oven at 80 ° C. for 5 minutes, and the insulating resin layer having the thickness shown in Table 2 is formed on the PET film. Formed. Similarly, low-viscosity insulating resin layers were formed on PET films with the thicknesses shown in Table 2, respectively.
 一方、絶縁粒子付導電粒子が平面視で図1Aに示す正方格子配列で、粒子間距離が絶縁粒子付導電粒子の粒子径と等しくなり、個数密度28000個/mm2となるように金型を作製した。即ち、金型の凸部パターン(個数密度28000個/mm2 )が正方格子配列で、格子軸における凸部のピッチが平均粒子径の2倍であり、格子軸と異方性導電フィルムの短手方向とのなす角度θが15°となる金型を作製し、公知の透明性樹脂のペレットを溶融させた状態で該金型に流し込み、冷やして固めることで、凹部が図1Aに示す配列パターンの樹脂型を形成した。 On the other hand, the conductive particles with insulating particles have a square lattice arrangement shown in FIG. 1A in plan view, and the mold is set so that the distance between particles is equal to the particle diameter of the conductive particles with insulating particles and the number density is 28000 / mm 2. Produced. That is, the convex pattern of the mold (number density 28000 pieces / mm 2 ) is a square lattice arrangement, the pitch of the convex portions on the lattice axis is twice the average particle diameter, and the short of the lattice axis and the anisotropic conductive film. A mold having an angle θ of 15 ° with the hand direction is manufactured, and a known transparent resin pellet is melted and poured into the mold, cooled and solidified, whereby the recesses are arranged as shown in FIG. 1A. A resin mold of the pattern was formed.
 また、金型の凸部パターン(個数密度28000個/mm2 )をランダムにしたものを作成し、その金型を用いて凹部がランダムパターンとなる樹脂型を形成した。このとき、隣接する絶縁粒子付導電粒子の導電粒子間の距離が導電粒子の平均径の0.5倍以上になるように設定した。 Further, the mold of the convex portion pattern (number density 28000 pieces / mm 2) to create a material obtained by randomly recess using the mold to form a resin mold as a random pattern. At this time, the distance between the conductive particles of adjacent conductive particles with insulating particles was set to be 0.5 times or more the average diameter of the conductive particles.
 絶縁粒子付導電粒子として、金属被覆樹脂粒子(積水化学工業(株)、AUL703、平均粒子径3μm)の表面に、特開2014-132567号公報の記載に準じて絶縁性微粒子(平均粒子径0.3μm)を付着させたものを用意し、この絶縁粒子付導電粒子を樹脂型の凹部に充填し、その上に上述の絶縁性樹脂層を被せた。 As the conductive particles with insulating particles, insulating fine particles (average particle size of 0) are formed on the surface of metal-coated resin particles (Sekisui Chemical Co., Ltd., AUL703, average particle size of 3 μm) according to the description in JP-A No. 2014-132567. .3 μm) was prepared, and the conductive particles with insulating particles were filled in the resin-shaped recesses, and the above-mentioned insulating resin layer was covered thereon.
 実施例1~2では、この絶縁性樹脂層を60℃、0.5MPaで押圧し、樹脂型から絶縁性樹脂層を剥離することで絶縁粒子付導電粒子を絶縁性樹脂層に転着させた。この時の絶縁粒子付導電粒子の絶縁性樹脂層への埋込率(Lb/D)は、SEMによる断面観察で30%であった。また、絶縁粒子付導電粒子が転着した絶縁性樹脂層の表面の該絶縁粒子付導電粒子の周囲に凹みはなかった(図2参照)。実施例7~10では、実施例1~2と同様に絶縁粒子付導電粒子を絶縁性樹脂層に転着させたが、転着後の絶縁粒子付導電粒子の周囲の絶縁性樹脂層に凹みができるように、絶縁粒子付導電粒子を絶縁性樹脂層に押圧するときの温度を60℃よりも低くした。 In Examples 1 and 2, the insulating resin layer was pressed at 60 ° C. and 0.5 MPa, and the insulating resin layer was peeled off from the resin mold to transfer the conductive particles with insulating particles to the insulating resin layer. . At this time, the embedding rate (Lb / D) of the conductive particles with insulating particles in the insulating resin layer was 30% in cross-sectional observation by SEM. Moreover, there was no dent around the conductive particles with insulating particles on the surface of the insulating resin layer to which the conductive particles with insulating particles were transferred (see FIG. 2). In Examples 7 to 10, the conductive particles with insulating particles were transferred to the insulating resin layer in the same manner as in Examples 1 to 2, but the dents were formed in the insulating resin layer around the conductive particles with insulating particles after transfer. The temperature when pressing the conductive particles with insulating particles against the insulating resin layer was made lower than 60 ° C.
 次に、実施例3~10では、絶縁性樹脂層上の絶縁粒子付導電粒子を押圧することで絶縁粒子付導電粒子を絶縁性樹脂層に押込率(Lb/D)100%で押し込んだ。この押し込み時の温度及び圧力は、絶縁粒子付導電粒子を樹脂型から絶縁性樹脂層へ転着させるときの前述の温度及び圧力と同様とした。その結果、実施例3~6では押し込み後の絶縁粒子付導電粒子の周囲の絶縁性樹脂層に凹みはなく、実施例7~10では押し込み後の絶縁粒子付導電粒子の周囲の絶縁性樹脂層に凹みが形成されていた(図3A参照)。 Next, in Examples 3 to 10, the conductive particles with insulating particles were pressed into the insulating resin layer at a pressing rate (Lb / D) of 100% by pressing the conductive particles with insulating particles on the insulating resin layer. The temperature and pressure at the time of pressing were the same as those described above when the conductive particles with insulating particles were transferred from the resin mold to the insulating resin layer. As a result, in Examples 3 to 6, there is no dent in the insulating resin layer around the conductive particles with insulative particles after being pushed in, and in Examples 7 to 10 the insulating resin layer around the conductive particles with insulative particles after being pushed in The dent was formed in (refer FIG. 3A).
 実施例1、2(埋込率30%)、及び実施例3、4(埋込率100%)では、絶縁性樹脂層の、絶縁粒子付導電粒子の転着面に低粘度絶縁性樹脂層を積層し、これを異方性導電フィルムとした(図5参照)。 In Examples 1 and 2 (embedding rate 30%) and Examples 3 and 4 (embedding rate 100%), a low-viscosity insulating resin layer on the transfer surface of the conductive particles with insulating particles of the insulating resin layer Was laminated to make an anisotropic conductive film (see FIG. 5).
 一方、実施例5~10(埋込率100%)では低粘度絶縁性樹脂層を積層しなかった。このうち、実施例7~10では絶縁粒子付導電粒子を絶縁性樹脂層に押し込んだ状態で、絶縁粒子付導電粒子の周囲の絶縁性樹脂層に凹みが形成されていたが、実施例9、10は凹みのある絶縁性樹脂層を、異方性導電接続に支障をきたさない条件で加熱押圧することにより凹みをなくした。 On the other hand, in Examples 5 to 10 (embedding rate 100%), the low-viscosity insulating resin layer was not laminated. Among these, in Examples 7 to 10, a depression was formed in the insulating resin layer around the conductive particles with insulating particles in a state where the conductive particles with insulating particles were pressed into the insulating resin layer. No. 10 eliminated the dent by heating and pressing the insulating resin layer having a dent under the condition that the anisotropic conductive connection was not hindered.
 比較例1~4
 比較例1~4では、金属被覆樹脂粒子(積水化学工業(株)、AUL703、平均粒子径3μm)の全面に絶縁コートを施した絶縁コート導電粒子(コート膜厚0.1~0.5μm)を上述の実施例の絶縁粒子付導電粒子に代えて使用し、絶縁コート導電粒子が表2に示した配列又は配置となるように上述の樹脂型に充填し、絶縁性樹脂層に絶縁コート導電粒子を転着し(押込率30%)、さらに、比較例3、4では絶縁性樹脂層に転着した絶縁コート導電粒子を押込率100%となるように絶縁性樹脂層に押し込んだ。そして、絶縁コート導電粒子の転着面又は押し込み面に低粘度絶縁性樹脂層を積層した。
Comparative Examples 1 to 4
In Comparative Examples 1 to 4, insulating coated conductive particles (coated film thickness: 0.1 to 0.5 μm) in which an insulating coating is applied to the entire surface of metal-coated resin particles (Sekisui Chemical Co., Ltd., AUL703, average particle diameter of 3 μm) Is used in place of the conductive particles with insulating particles of the above-mentioned embodiment, the above-mentioned resin mold is filled so that the insulating coated conductive particles are arranged or arranged as shown in Table 2, and the insulating resin layer is insulated with the insulating coated conductive material. The particles were transferred (indentation rate 30%), and in Comparative Examples 3 and 4, the insulating coated conductive particles transferred to the insulating resin layer were pressed into the insulating resin layer so that the indentation rate was 100%. And the low-viscosity insulating resin layer was laminated | stacked on the transfer surface or pushing surface of the insulation coat electrically-conductive particle.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
(2)粒子の配置状態
(2-1)独立粒子個数割合
 走査型電子顕微鏡(SEM)を用いて、各実施例及び比較例の異方性導電フィルムの表裏のフィルム面(低粘度絶縁性樹脂層を積層したものについては、低粘度絶縁性樹脂層側表面とその反対面)のそれぞれについて100個の絶縁粒子付導電粒子又は絶縁コート導電粒子を観察し、互いに接触していない絶縁粒子付導電粒子又は絶縁コート導電粒子の個数を計測し、その個数の全数に対する割合(即ち、独立粒子個数割合)を求めた。その結果、各実施例及び比較例において、独立粒子個数割合は99%を上回っていた。
(2) Particle arrangement state
(2-1) Number ratio of independent particles Using a scanning electron microscope (SEM), the front and back film surfaces of the anisotropic conductive films of the examples and comparative examples (for the laminated low viscosity insulating resin layers) 100 conductive particles with insulating particles or insulating coated conductive particles are observed for each of the low-viscosity insulating resin layer side surface and the opposite surface), and the conductive particles with insulating particles or insulating coated conductive particles that are not in contact with each other. The number was measured, and the ratio of the number to the total number (that is, the number ratio of independent particles) was obtained. As a result, in each Example and Comparative Example, the number ratio of independent particles exceeded 99%.
(2-2)絶縁粒子被覆率
 実施例の異方性導電フィルムの製造に使用した絶縁粒子付導電粒子(絶縁性樹脂層に埋め込む前の絶縁粒子付導電粒子)における絶縁粒子被覆率を求めた。絶縁粒子被覆率は、走査型電子顕微鏡(SEM)を用いて、絶縁粒子付導電粒子100個を観察し、各絶縁粒子付導電粒子について導電粒子1個当たりの絶縁粒子の個数を計測し、計測された個数と、絶縁粒子付導電粒子1個の平面視における面積と、絶縁粒子1個の平面視における面積から算出した。その結果、異方性導電フィルムの製造に使用した絶縁粒子付導電粒子における絶縁粒子被覆率は67%であった。
(2-2) Insulating particle coverage The insulating particle coverage of the conductive particles with insulating particles (conductive particles with insulating particles before embedding in the insulating resin layer) used in the production of the anisotropic conductive film of the example was determined. . The insulating particle coverage is measured by observing 100 conductive particles with insulating particles using a scanning electron microscope (SEM) and measuring the number of insulating particles per conductive particle for each conductive particle with insulating particles. The calculated number was calculated from the area in plan view of one conductive particle with insulating particles and the area in plan view of one insulating particle. As a result, the insulating particle coverage in the conductive particles with insulating particles used for the production of the anisotropic conductive film was 67%.
(2-3)異方性導電フィルム作製後の絶縁粒子の被覆状態
 実施例の異方性導電フィルムに分散している絶縁粒子付導電粒子における絶縁粒子の被覆状態を走査型電子顕微鏡(SEM)による断面観察により求めた。この断面観察で、絶縁粒子付導電粒子100個を計測し、図2に示した領域A1、A2、A3、A4における絶縁粒子の個数、NA1、NA2、NA3、NA4の大小関係を調べた。その結果、各実施例において領域A3と領域A4における絶縁粒子の個数に格別の差異はなかった。また、実施例3~10では実施例1に比して、領域A1にある絶縁粒子の個数が、領域A2にある絶縁粒子の個数に比して著しく低減していた。
(2-3) Covering state of insulating particles after production of anisotropic conductive film Scanning electron microscope (SEM) shows the covering state of insulating particles in conductive particles with insulating particles dispersed in the anisotropic conductive film of Example It was determined by cross-sectional observation. In this cross-sectional observation, 100 conductive particles with insulating particles were measured, and the number of insulating particles in the regions A1, A2, A3, and A4 shown in FIG. 2 and the magnitude relationship of N A1 , N A2 , N A3 , and N A4 Examined. As a result, there was no particular difference in the number of insulating particles in the regions A3 and A4 in each example. In Examples 3 to 10, as compared with Example 1, the number of insulating particles in region A1 was significantly reduced compared to the number of insulating particles in region A2.
(3)評価
 各実施例及び比較例の異方性導電フィルムを、接続および評価に十分な面積で裁断した後、裁断した異方性導電フィルムを使用し、以下に説明するように、(a)初期導通抵抗、(b)導通信頼性、(c)ショート発生率、(d)導電粒子捕捉性、を測定ないし評価した。結果を表2に示す。
(3) Evaluation After the anisotropic conductive film of each Example and Comparative Example was cut in an area sufficient for connection and evaluation, the cut anisotropic conductive film was used, as described below (a ) Initial conduction resistance, (b) conduction reliability, (c) short-circuit occurrence rate, and (d) conductive particle trapping property were measured or evaluated. The results are shown in Table 2.
(a)初期導通抵抗 
 各実施例及び比較例の異方性導電フィルムを、導通特性の評価用ICとガラス基板との間に挟み、加熱加圧(180℃、60MPa、5秒)して各評価用接続物を得、得られた評価用接続物の導通抵抗を測定し、測定された初期導通抵抗を次の基準で評価した。
 A:0.3Ω以下
 B:0.3Ω超、0.4Ω以下
 C:0.4Ω超
B評価であれば実用上問題はない。A評価であれば、より好ましい。
(A) Initial conduction resistance
The anisotropic conductive film of each Example and Comparative Example was sandwiched between an IC for conducting property evaluation and a glass substrate, and heated and pressurized (180 ° C., 60 MPa, 5 seconds) to obtain a connected object for evaluation. The conduction resistance of the obtained connection for evaluation was measured, and the measured initial conduction resistance was evaluated according to the following criteria.
A: 0.3Ω or less B: More than 0.3Ω, 0.4Ω or less C: More than 0.4Ω There is no practical problem if B is evaluated. If it is A evaluation, it is more preferable.
 ここで、評価用ICとガラス基板は、それらの端子パターンが対応しており、サイズは次の通りである。また、評価用ICとガラス基板を接続する際には、異方性導電フィルムの長手方向とバンプの短手方向を合わせた。 Here, the IC for evaluation and the glass substrate correspond to their terminal patterns, and the sizes are as follows. Further, when connecting the evaluation IC and the glass substrate, the longitudinal direction of the anisotropic conductive film and the short direction of the bump were matched.
導通特性の評価用IC
 外形 1.8×20.0mm
 厚み 0.5mm
 バンプ仕様 サイズ30×85μm、バンプ間距離50μm、バンプ高さ15μm
IC for evaluating conduction characteristics
Outline 1.8 × 20.0mm
Thickness 0.5mm
Bump specifications Size 30 × 85μm, distance between bumps 50μm, bump height 15μm
ガラス基板
 ガラス材質 コーニング社製1737F
 外径 30×50mm
 厚み 0.5mm
 電極 ITO配線 
Glass substrate Glass material 1737F made by Corning
Outer diameter 30 × 50mm
Thickness 0.5mm
Electrode ITO wiring
(b)導通信頼性
 (a)で作製した評価用接続物を、温度85℃、湿度85%RHの恒温槽に500時間おいた後の導通抵抗を、初期導通抵抗と同様に測定し、測定された導通抵抗を次の基準で評価した。
(B) Conduction reliability Conductivity after the connected object for evaluation prepared in (a) is placed in a thermostatic chamber at 85 ° C. and humidity 85% RH for 500 hours is measured and measured in the same manner as the initial conduction resistance. The conducted resistance was evaluated according to the following criteria.
 S:3.0Ω以下
 A:3.0Ω超、4.0Ω以下
 B:4.0Ω超、6.0Ω以下
 C:6.0Ω超
B評価であれば実用上問題はない。A評価以上であれば、より好ましい。
S: 3.0Ω or less A: More than 3.0Ω, 4.0Ω or less B: More than 4.0Ω, 6.0Ω or less C: More than 6.0Ω There is no practical problem if it is evaluated as B. If it is more than A evaluation, it is more preferable.
(c)ショート発生率
 各実施例及び比較例の異方性導電フィルムを、絶縁性試験評価用IC(7.5μmスペースの櫛歯TEG(test element group))と、端子パターンが対応するガラス基板との間に挟み、初期導通抵抗と同様に加熱加圧して評価用接続物を得、得られた評価用接続物におけるショート発生率をデジタルマルチメーター(デジタルマルチメーター7561、横河メータ&インスツルメンツ(株))で測定した。この絶縁性試験評価用ICの仕様を以下に示す。
(C) Short-circuit occurrence rate An anisotropic conductive film of each of the examples and comparative examples was obtained by using an insulating test evaluation IC (7.5 μm space comb tooth TEG (test element group)) and a glass substrate corresponding to a terminal pattern. In the same manner as in the initial conduction resistance, the connection object for evaluation is obtained by heating and pressurizing, and the short circuit occurrence rate in the obtained connection object for evaluation is digital multimeter (digital multimeter 7561, Yokogawa meter & instruments ( Co.)). The specification of this insulation test evaluation IC is shown below.
絶縁性試験評価用IC
 外形 1.5×13mm
 厚み 0.5mm
 バンプ仕様 金メッキ、サイズ25×140μm、バンプ間距離7.5μm、バンプ高さ15μm
Insulation test evaluation IC
External dimensions 1.5 x 13 mm
Thickness 0.5mm
Bump specifications Gold plating, size 25 × 140μm, distance between bumps 7.5μm, bump height 15μm
 測定されたショート発生率を次の基準で評価した。
 A:50ppm未満 
 B:50ppm以上200ppm以下
 C:200ppm超
B評価であれば実用上問題はない。
The measured incidence of short circuit was evaluated according to the following criteria.
A: Less than 50 ppm
B: 50 ppm or more and 200 ppm or less C: Above 200 ppm, there is no practical problem if it is evaluated as B.
(d)導電粒子捕捉性
 導電粒子捕捉性の評価用ICを使用し、この評価用ICと、端子パターンが対応するITOコーティング基板とを、アライメントを6μmずらして加熱加圧(180℃、60MPa、5秒)し、評価用ICのバンプと基板の端子とが重なる6μm×66.6μmの領域の100個について導電粒子の捕捉数を計測し、最低捕捉数を求め、次の基準で評価した。
(D) Conductive particle trapping property Using an evaluation IC for conductive particle trapping property, this evaluation IC and the ITO coated substrate corresponding to the terminal pattern are heated and pressurized (180 ° C., 60 MPa, 5 seconds), the number of trapped conductive particles was measured with respect to 100 regions of 6 μm × 66.6 μm where the bumps of the IC for evaluation overlapped with the terminals of the substrate, and the minimum number of traps was determined and evaluated according to the following criteria.
 導電粒子捕捉性の評価用IC
 外形 1.6×29.8mm
 厚み 0.3mm
 バンプ仕様 サイズ12×66.6μm、バンプピッチ22μm(L/S=12μm/10μm)、バンプ高さ12μm
IC for evaluating conductive particle trapping property
Outline 1.6 × 29.8mm
Thickness 0.3mm
Bump specifications Size 12 × 66.6μm, bump pitch 22μm (L / S = 12μm / 10μm), bump height 12μm
 導電粒子捕捉性評価基準
 OK:3個以上
 NG:3個未満
Conductive particle scavenging evaluation criteria OK: 3 or more NG: Less than 3
 表2から、実施例1~10の異方性導電フィルムでは、絶縁粒子付導電粒子における絶縁粒子の個数密度が領域A3、A4よりも領域A2、A1が低く、特に、異方性導電フィルムの製造時に絶縁粒子付導電粒子を絶縁性樹脂層に押し込んだ実施例3~10では、絶縁粒子の個数密度が領域A2よりも領域A1で顕著に低かった。その結果、導電粒子にフィルム厚方向で接する領域A2、A1の絶縁粒子2の個数密度が、導電粒子1にフィルム面方向で接する領域A3、A4の絶縁粒子2の個数よりもさらに少なくなり、実施例3、4は、実施例1、2に比して導通信頼性が優れていることがわかる。これに対し、樹脂コート導電粒子を用いた比較例1~4では導通信頼性が劣っていた。 From Table 2, in the anisotropic conductive films of Examples 1 to 10, the number density of the insulating particles in the conductive particles with insulating particles is lower in the regions A2 and A1 than in the regions A3 and A4. In Examples 3 to 10 in which the conductive particles with insulating particles were pushed into the insulating resin layer during production, the number density of the insulating particles was significantly lower in the region A1 than in the region A2. As a result, the number density of the insulating particles 2 in the regions A2 and A1 in contact with the conductive particles in the film thickness direction is further smaller than the number of insulating particles 2 in the regions A3 and A4 in contact with the conductive particles 1 in the film surface direction. It can be seen that Examples 3 and 4 have better conduction reliability than Examples 1 and 2. In contrast, Comparative Examples 1 to 4 using resin-coated conductive particles were inferior in conduction reliability.
 また、表2の結果では、実施例1と2の対比、実施例3と4の対比、実施例5と6の対比、実施例7と8の対比、実施例9と10の対比、比較例1と2の対比、比較例3と4の対比により、絶縁粒子付導電粒子を正方格子に配列させた場合とランダムに配置した場合や、絶縁コート導電粒子を正方格子に配列させた場合とランダムに配置した場合とで導通抵抗、ショート発生率、導電粒子捕捉性について差異が見られないが、捕捉性の評価において、絶縁粒子付導電粒子又は絶縁コート導電粒子を正方格子に配列させた方がランダムに配置した場合より圧痕を確認しやすかった。 Further, in the results of Table 2, the comparison between Examples 1 and 2, the comparison between Examples 3 and 4, the comparison between Examples 5 and 6, the comparison between Examples 7 and 8, the comparison between Examples 9 and 10, and the comparative example According to the comparison between 1 and 2, and the comparison between Comparative Examples 3 and 4, the case where the conductive particles with insulating particles are arranged in a square lattice and the case where the conductive particles with insulating coat are arranged in a square lattice are random. Although there is no difference in conduction resistance, short-circuit occurrence rate, and conductive particle trapping property when arranged in the above, in the evaluation of trapping property, it is better to arrange the conductive particles with insulating particles or insulating coated conductive particles in a square lattice Indentation was easier to check than when placed randomly.
 なお、絶縁粒子付導電粒子の周囲の絶縁性樹脂層に凹みが無い実施例5、6も、絶縁粒子付導電粒子の周囲の絶縁性樹脂層に凹みがある実施例7、8も、その凹みを加熱押圧して解消した実施例9、10も、初期導通抵抗、導通信頼性、ショート発生率及び導電粒子捕捉性の評価は良好であった。このことから、本実施例では、凹みの有無によらず、絶縁粒子付導電粒子が樹脂流動によって無用に移動しなかったことがわかる。 In addition, Examples 5 and 6 in which the insulating resin layer around the conductive particles with insulating particles does not have a dent, and Examples 7 and 8 in which the insulating resin layer around the conductive particles with insulating particles have a dent also have dents. In Examples 9 and 10, which were eliminated by heating and pressing, the initial conduction resistance, conduction reliability, short-circuit occurrence rate, and conductive particle capturing property were also good. From this, it can be seen that in this example, the conductive particles with insulating particles did not move unnecessarily due to the resin flow regardless of the presence or absence of dents.
 1 導電粒子
 2 絶縁粒子
 3 絶縁粒子付導電粒子
 5 絶縁性樹脂層
 5a 絶縁性樹脂層の表面
 5b 凹み(傾斜)
 5c 凹み(起伏)
 5p 接平面
 6 低粘度絶縁性樹脂層
 7 剥離フィルム
10A、10B、10C、10D 異方性導電フィルム
30 転写型
31 凹部
32 平板
33 平板又はローラー
 A 格子軸
 A1、A2、A3、A4 領域
 D 絶縁粒子付導電粒子の粒子径
 La 絶縁性樹脂層の層厚
 Lb 絶縁粒子付導電粒子と近接している面から絶縁粒子付導電粒子の最深部までの距離
 Lc 傾斜又は起伏における絶縁粒子付導電粒子の露出(直上)部分の径
 Ld 絶縁粒子付導電粒子の周り又は直上の絶縁性樹脂層の傾斜又は起伏の最大径
 Le 絶縁粒子付導電粒子の周りの絶縁性樹脂層における傾斜の最大深さ
 Lf 絶縁粒子付導電粒子の直上の絶縁性樹脂層における起伏の最大深さ
 NA1、NA2、NA3、NA4 領域に存在する絶縁粒子の個数
 θ 端子の長手方向と格子軸とのなす角度
DESCRIPTION OF SYMBOLS 1 Conductive particle 2 Insulating particle 3 Conductive particle with insulating particle 5 Insulating resin layer 5a Surface of insulating resin layer 5b Recess (inclination)
5c Dent (undulation)
5p Tangent plane 6 Low-viscosity insulating resin layer 7 Release film 10A, 10B, 10C, 10D Anisotropic conductive film 30 Transfer mold 31 Recess 32 Flat plate 33 Flat plate or roller A Grid axis A1, A2, A3, A4 Region D Insulating particle Particle diameter of conductive particles La Layer thickness of insulating resin layer Lb Distance from surface close to conductive particles with insulating particles to deepest part of conductive particles with insulating particles Lc Exposure of conductive particles with insulating particles in inclination or undulation (Directly above) Diameter of the portion Ld Maximum diameter of the inclination or undulation of the insulating resin layer around or directly above the conductive particles with insulating particles Le Maximum depth of inclination in the insulating resin layer around the conductive particles with insulating particles Lf Insulating particles It the longitudinal and the lattice axis of the undulations of the maximum depth N A1, N A2, N A3 , the number of insulating particles present in N A4 region θ terminal in the insulating resin layer just above the Tsukeshirubeden particles Angle

Claims (12)

  1.  導電粒子の表面に絶縁粒子が付着している絶縁粒子付導電粒子が絶縁性樹脂層に分散している異方性導電フィルムであって、絶縁粒子付導電粒子において、導電粒子とフィルム厚方向で接する絶縁粒子数が、導電粒子とフィルム面方向で接する絶縁粒子数よりも少ない異方性導電フィルム。 An anisotropic conductive film in which conductive particles with insulating particles attached to the surface of the conductive particles are dispersed in an insulating resin layer, wherein the conductive particles with insulating particles An anisotropic conductive film in which the number of insulating particles in contact is smaller than the number of insulating particles in contact with conductive particles in the film surface direction.
  2.  異方導電性フィルムの表裏の一方のフィルム面の平面視において導電粒子と重なっている絶縁粒子の個数が、他方のフィルム面の平面視において導電粒子と重なっている絶縁粒子の個数よりも少ない請求項1記載の異方性導電フィルム。 The number of insulating particles overlapping with the conductive particles in plan view of one film surface on the front and back of the anisotropic conductive film is less than the number of insulating particles overlapping with the conductive particles in plan view of the other film surface Item 10. An anisotropic conductive film according to Item 1.
  3.  絶縁粒子付導電粒子が互いに非接触で配置している請求項1又は2記載の異方性導電フィルム。 The anisotropic conductive film according to claim 1 or 2, wherein the conductive particles with insulating particles are arranged in non-contact with each other.
  4.  絶縁性樹脂層に、該絶縁性樹脂層よりも最低溶融粘度が低い低粘度絶縁性樹脂層が積層されている請求項1~3のいずれかに記載の異方性導電フィルム。 The anisotropic conductive film according to any one of claims 1 to 3, wherein a low-viscosity insulating resin layer having a minimum melt viscosity lower than that of the insulating resin layer is laminated on the insulating resin layer.
  5.  絶縁粒子付導電粒子が、絶縁性樹脂層と低粘度絶縁性樹脂層の間に存在する請求項4記載の異方性導電フィルム。 The anisotropic conductive film according to claim 4, wherein the conductive particles with insulating particles are present between the insulating resin layer and the low-viscosity insulating resin layer.
  6.  低粘度絶縁性樹脂層側フィルム面の平面視における導電粒子上の絶縁粒子数が、絶縁性樹脂層側フィルム面の平面視における導電粒子上の絶縁粒子数よりも少ない請求項5記載の異方性導電フィルム。 The anisotropic structure according to claim 5, wherein the number of insulating particles on the conductive particles in a plan view of the low viscosity insulating resin layer side film surface is smaller than the number of insulating particles on the conductive particles in a plan view of the insulating resin layer side film surface. Conductive film.
  7.  絶縁性樹脂層の表裏の面のうち、絶縁粒子付導電粒子が近接している面から絶縁粒子付導電粒子の最深部までの距離Lbと絶縁粒子付導電粒子の粒子径Dとの比(Lb/D)が30~105%である請求項1~6のいずれかに記載の異方性導電フィルム。 Of the front and back surfaces of the insulating resin layer, the ratio of the distance Lb from the surface where the conductive particles with insulating particles are close to the deepest part of the conductive particles with insulating particles to the particle diameter D of the conductive particles with insulating particles (Lb 7. The anisotropic conductive film according to claim 1, wherein / D) is 30 to 105%.
  8.  絶縁粒子付導電粒子近傍の絶縁性樹脂層の表面が、隣接する絶縁粒子付導電粒子間の中央部における絶縁性樹脂層の接平面に対して傾斜もしくは起伏を有する請求項1~7のいずれかに記載の異方性導電フィルム。 The surface of the insulating resin layer in the vicinity of the conductive particles with insulating particles has an inclination or undulation with respect to the tangential plane of the insulating resin layer at the center between adjacent conductive particles with insulating particles. An anisotropic conductive film as described in 1.
  9.  前記傾斜では、絶縁粒子付導電粒子の近傍の絶縁性樹脂層の表面が、前記接平面に対して欠けており、前記起伏では、絶縁粒子付導電粒子の直上の絶縁性樹脂層の樹脂量が、前記絶縁粒子付導電粒子の直上の絶縁性樹脂層の表面が該接平面にあるとしたときに比して少ない請求項8記載の異方性導電フィルム。 In the inclination, the surface of the insulating resin layer in the vicinity of the conductive particles with insulating particles is chipped with respect to the tangential plane, and in the undulation, the resin amount of the insulating resin layer immediately above the conductive particles with insulating particles is The anisotropic conductive film according to claim 8, wherein the anisotropic conductive film is less than when the surface of the insulating resin layer immediately above the conductive particles with insulating particles is on the tangent plane.
  10.  請求項1~9のいずれかに記載の異方性導電フィルムを使用して電子部品同士を異方性導電接続する接続構造体の製造方法。 A method for producing a connection structure in which electronic parts are anisotropically conductively connected using the anisotropic conductive film according to any one of claims 1 to 9.
  11.  請求項1~9のいずれかに記載の異方性導電フィルムにより電子部品同士が異方性導電接続されている接続構造体。 A connection structure in which electronic components are anisotropically conductively connected by the anisotropic conductive film according to any one of claims 1 to 9.
  12.  対向する電子部品の端子同士が、絶縁粒子付導電粒子と絶縁性樹脂層により異方性導電接続されている接続構造体であって、対向する端子に挟持されていない絶縁粒子付導電粒子に、端子同士の対向方向を向いた絶縁粒子欠落領域を有する絶縁粒子付導電粒子が含まれている接続構造体。 Terminals of opposing electronic components are connected to each other in an anisotropic conductive connection with conductive particles with insulating particles and an insulating resin layer, and the conductive particles with insulating particles that are not sandwiched between the opposing terminals, A connection structure including conductive particles with insulating particles having an insulating particle missing region facing the opposing direction of the terminals.
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US16/343,380 US11557562B2 (en) 2016-10-24 2017-10-18 Anisotropic conductive film
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024195546A1 (en) * 2023-03-23 2024-09-26 デクセリアルズ株式会社 Filler-containing film, connection structure, and production method for same

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0371570A (en) * 1989-08-10 1991-03-27 Casio Comput Co Ltd Binder for conduction and conductive connection structure
JPH03112011A (en) * 1989-09-26 1991-05-13 Catalysts & Chem Ind Co Ltd Anisotropic conductive material, anisotropic adhesive, electrically connecting method of the adhesive applied electrode, and electric circuit substrate formed thereby
JPH0613432A (en) * 1992-06-26 1994-01-21 Citizen Watch Co Ltd Connecting method for semiconductor integrated circuit device
JP2016131082A (en) * 2015-01-13 2016-07-21 デクセリアルズ株式会社 Anisotropically conductive film, method for manufacturing the same and connection structure

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4999460A (en) * 1989-08-10 1991-03-12 Casio Computer Co., Ltd. Conductive connecting structure
KR100597391B1 (en) * 2004-05-12 2006-07-06 제일모직주식회사 Insulated Conductive Particles and an Anisotropic Conductive Adhesive Film containing the Particles
KR101240155B1 (en) * 2006-04-27 2013-03-11 아사히 가세이 일렉트로닉스 가부시끼가이샤 Electroconductive particle placement sheet and anisotropic electroconductive film
KR100861010B1 (en) * 2006-12-22 2008-09-30 제일모직주식회사 Insulated Conductive Particles for Anisotropic Conduction and Anisotropic Conductive Film Using Same
JP2008186761A (en) * 2007-01-31 2008-08-14 Tokai Rubber Ind Ltd Method for manufacturing particle transfer film and particle retention film, and anisotropic conductive film
CN102047347B (en) * 2008-07-01 2012-11-28 日立化成工业株式会社 Circuit connection material and circuit connection structure
JP2010033793A (en) * 2008-07-28 2010-02-12 Tokai Rubber Ind Ltd Method for manufacturing particle transfer film
JP5476168B2 (en) * 2010-03-09 2014-04-23 積水化学工業株式会社 Conductive particles, anisotropic conductive materials, and connection structures
JP5484265B2 (en) * 2010-09-02 2014-05-07 積水化学工業株式会社 Conductive particles, conductive particles with insulating particles, anisotropic conductive material, and connection structure
JP5672022B2 (en) 2011-01-25 2015-02-18 日立化成株式会社 Insulating coated conductive particles, anisotropic conductive material, and connection structure
JP2012160546A (en) * 2011-01-31 2012-08-23 Hitachi Chem Co Ltd Adhesive film for circuit connection and circuit connection structure
JP6079425B2 (en) * 2012-05-16 2017-02-15 日立化成株式会社 Conductive particles, anisotropic conductive adhesive film, and connection structure
JP6024621B2 (en) * 2012-08-24 2016-11-16 デクセリアルズ株式会社 Method for producing anisotropic conductive film and anisotropic conductive film
CN107189562B (en) * 2012-08-29 2021-01-19 迪睿合电子材料有限公司 Anisotropic conductive film and method for producing same
WO2015016207A1 (en) * 2013-07-31 2015-02-05 デクセリアルズ株式会社 Anisotropically conductive film and manufacturing method therefor
US20170110806A1 (en) 2014-03-20 2017-04-20 Dexerials Corporation Anisotropic conductive film and production method of the same
CN106415938B (en) * 2014-03-31 2019-09-06 迪睿合株式会社 Anisotropic conductive film and preparation method thereof
JP6935702B2 (en) * 2016-10-24 2021-09-15 デクセリアルズ株式会社 Anisotropic conductive film

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0371570A (en) * 1989-08-10 1991-03-27 Casio Comput Co Ltd Binder for conduction and conductive connection structure
JPH03112011A (en) * 1989-09-26 1991-05-13 Catalysts & Chem Ind Co Ltd Anisotropic conductive material, anisotropic adhesive, electrically connecting method of the adhesive applied electrode, and electric circuit substrate formed thereby
JPH0613432A (en) * 1992-06-26 1994-01-21 Citizen Watch Co Ltd Connecting method for semiconductor integrated circuit device
JP2016131082A (en) * 2015-01-13 2016-07-21 デクセリアルズ株式会社 Anisotropically conductive film, method for manufacturing the same and connection structure

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024195546A1 (en) * 2023-03-23 2024-09-26 デクセリアルズ株式会社 Filler-containing film, connection structure, and production method for same

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