JP2020084168A - Anisotropic film - Google Patents

Abstract

To provide an anisotropic film with high reliability by electrically connecting circuit electrodes having a fine pattern together.SOLUTION: An anisotropic film contains an insulating resin and particle groups, in which the particle groups are groups of particles consisting of a plurality of particles bound together with a binder, and the particle groups are regularly arranged with an interval of 1-1,000 μm.SELECTED DRAWING: Figure 1

Description

The present invention relates to an anisotropic film, particularly an anisotropic conductive film.

2. Description of the Related Art In recent years, when connecting flat panel displays such as liquid crystal displays (LCD) and electronic components of precision equipment, an anisotropic conductive film (ACF) is used instead of solder. There is. The anisotropic conductive film is made of an insulating resin containing conductive particles, and is placed between circuit electrodes, so that the circuits can be electrically connected by pressure bonding and pressure bonding.

As a general method for producing an anisotropic conductive film, there is a method in which an insulating resin and conductive particles are mixed and coated. In Patent Document 1, an anisotropic conductive film is manufactured by applying a mixture of a polyvinyl butyral resin and an epoxy resin containing tin-lead solder particles having an average particle size of 10 μm and a maximum particle size of 15 μm. In Patent Document 2, nickel particles having an average particle diameter of 2 μm are mixed with a phenoxy resin, and an anisotropic conductive film is manufactured using a coating device. In Patent Document 3, an anisotropic conductive film is manufactured by mixing silver-plated resin particles having an average particle diameter of 20 μm with an insulating resin and applying the mixture.

However, since it is difficult to uniformly disperse the particles in these anisotropic conductive films due to agglomeration of particles with each other, it is possible to maintain the insulating property in the plane direction of the anisotropic conductive film while maintaining the desired property. Retaining conductive areas is difficult. If the particle concentration is reduced to prevent the particles from aggregating, it is difficult to maintain the conductivity in the cross-sectional direction of the anisotropic conductive film. Therefore, the circuit electrodes having a fine pattern could not be electrically connected to each other.

Patent Document 4 reports an anisotropic conductive film in which conductive particles are regularly arranged by adsorbing and transferring the conductive particles on a porous plate having pores smaller than the particle diameter of the conductive particles. Patent Document 5 reports an anisotropic conductive film in which conductive particles are regularly arranged by transferring and transferring the conductive particles in a mold.

However, since the circuit electrode is connected to the conductive particles at a point, the circuit electrode may become non-conductive due to repeated thermal shocks such as low temperature and high temperature.

JP-A-5-154857 JP, 2008-112713, A JP, 2005-147832, A JP, 2005-209454, A JP, 2008-090768, A

The present invention has been made in view of the above problems, and an object of the present invention is to electrically connect circuit electrodes having fine patterns to each other to provide a highly reliable anisotropic conductive film. Further, the present invention is not limited to the case of being electrically conductive, and an object of the present invention is to provide an anisotropic film having a fine and accurate pattern of particle groups.

In order to achieve the above object, the present invention is an anisotropic film containing an insulating resin and a particle group, wherein the particle group is a group of particles in which a plurality of particles are bound by a binder, In addition, the particle group is regularly arranged, and an anisotropic film having a distance between 1 μm and 1,000 μm is provided.

Such an anisotropic film makes it possible to more stably connect circuit electrodes having a fine pattern, or fine electronic parts or elements. Further, since it is an anisotropic film having a fine and precise pattern due to the particle group, it can be applied to various uses.

Further, it is preferable that the difference in linear expansion coefficient between the insulating resin and the particle group in the range of −50° C. to 200° C. is 1 to 200 ppm/K.

Such a difference in linear expansion coefficient makes it more difficult for the electronic component to separate from the anisotropic film even when the temperature changes.

Furthermore, the binder may be a resin composition having the same composition as the insulating resin.

When the same kind of resin is used, the binder and the insulating resin are compatible with each other, and the strength of the anisotropic film can be increased.

Further, the binder may be a resin composition having a composition different from that of the insulating resin.

It is preferable to use different resins because even if the composition (mixture of binder and particles) contains particles, the linear expansion coefficient of the composition and the insulating resin can be matched.

Further, the particles may be conductive particles, and the particle group may be conductive particle groups.

When the particles are such particles, the anisotropic film of the present invention can be electrically connected to circuit electrodes having fine patterns and can be made into a highly reliable anisotropic conductive film.

Further, the particles may be heat conductive particles, and the particle group may be heat conductive particle groups.

When the particles have such a shape, the anisotropic film of the present invention can be used as an anisotropic heat conductive film.

Further, the particles may be a phosphor and the particle group may be a phosphor particle group.

When the particles have such a shape, the anisotropic film of the present invention can be used as an anisotropic phosphor film.

Further, the particles may be magnetic particles, and the particle group may be a magnetic particle group.

When the particles have such a shape, the anisotropic film of the present invention can be used as an anisotropic magnetic film.

Further, the particles may be an electromagnetic wave absorbing filler, and the particle group may be an electromagnetic wave absorbing filler particle group.

By using such particles as the particles, the anisotropic film of the present invention can be used as an anisotropic electromagnetic wave absorbing film.

The thickness of the anisotropic film is preferably 1 μm to 2000 μm.

With such an anisotropic film, the influence of the difference in coefficient of thermal expansion (CTE) between the insulating resin portion and the particle group is small, so that the electronic component is less likely to be separated from the anisotropic film.

The average particle size of the particles is preferably 0.01 to 100 μm as a median diameter measured by a laser diffraction type particle size distribution measuring device.

Within this range, the particles can be highly filled.

Further, it is preferable that the particle group has a width of 1 to 1000 μm.

Within this range, the respective advantages of the insulating resin and the particle group can be utilized, which is preferable.

Further, it is preferable that the width of the particle group is 5 times or more the average particle diameter of the particles.

Within this range, the function of the particles as a particle group can be exhibited more reliably, which is preferable.

Further, it is preferable that the theoretical average number of particles in the particle group is 50 to 1×10 ⁹ .

Within this range, the particle group can be formed into a columnar shape, which is preferable.

The shape of the particle group is preferably cylindrical or prismatic.

Within this range, anisotropy is likely to be exhibited as the function of the particle group, which is preferable.

The ratio of the area of the lower surface to the area of the upper surface of the particle group is preferably 0.5 to 10.

Within this range, anisotropy is likely to be exhibited as a function of the particle group, and production is facilitated, which is preferable.

The thickness of the particle group is preferably 50% or more of the thickness of the anisotropic film.

In this case, for example, when the electrode is pressed from above the finished anisotropic conductive film, it becomes easy to secure the conduction.

Further, it is preferable that the particle group is exposed on at least one surface of the anisotropic film.

For example, since the conductive particle group is exposed on at least one surface of the anisotropic conductive film, conduction can be secured without thermocompression bonding the anisotropic conductive film with a large force.

Further, the area ratio of the exposed particle group on the at least one surface is preferably 20 to 90%.

Within this range, the anisotropic film can reliably exhibit its intended function while maintaining high flexibility.

Further, it is preferable that the insulating resin is a plastic solid or semi-solid state at 25° C. in an uncured state.

When the insulating resin has such a property, it can be deformed, for example, when the electronic component is pressure-bonded, and a good adhesive force can be obtained by completely curing it.

Further, it is preferable that the particles include metal particles.

In the present invention, such particles can be preferably used. In particular, metal particles are preferably used because they have low electric resistance and can be sintered at high temperature.

Further, it is preferable that the insulating resin contains insulating inorganic particles.

By containing the insulating inorganic particles, the thermal expansion coefficient of the cured product of the insulating resin can be reduced.

At this time, the insulating inorganic particles may be a white pigment.

When the insulating inorganic particles are such, the anisotropic film of the present invention can be used as a reflector film, for example.

Further, the insulating resin may contain hollow particles.

By containing the hollow particles, the anisotropic film of the present invention can be made into a hollow film.

Further, it is preferable that the cured product of the insulating resin has a relative dielectric constant of 3.5 or less at 10 GHz.

With such a cured product, for example, the transmission loss of the circuit device can be reduced.

Further, the anisotropic film may be any one of a conductive film, a heat conductive film, a phosphor film, a magnetic film, an electromagnetic wave absorption film, a reflector film, and a hollow film.

The anisotropic film of the present invention can be used for such applications.

As described above, the present invention is applicable to various applications because it is an anisotropic film having a fine and accurate pattern of particle groups. In particular, the present invention is capable of electrically connecting circuit electrodes having extremely fine patterns to each other, thereby achieving downsizing, thinning, and weight reduction of electronic devices, and high reliability that can withstand thermal shock and the like. An anisotropic conductive film is provided.

It is an image figure which shows an example of the anisotropic conductive film of this invention. 3 is a top view of an anisotropic conductive film having a pattern of a film having a thickness of 30 μm, a silver particle group width of 30 μm, a thickness of 30 μm, and an interval of 30 μm, which is manufactured in Example 1. FIG. 3 is a cross-sectional view after transferring a group of silver particles in the film manufactured in Example 1. FIG. FIG. 3 is a cross-sectional view of the film manufactured in Example 1 after being hot pressed to press a group of silver particles into the film. 5 is an enlarged view of a part of the cross-sectional view of FIG. 4. 5 is a top view of an anisotropic conductive film having a pattern of a film having a thickness of 200 μm, a copper particle group width of 80 μm, a thickness of 100 μm, and a gap of 80 μm, which is manufactured in Example 2. FIG. 7 is a top view of an anisotropic conductive film having a pattern of a film having a thickness of 10 μm, a silver particle group width of 5 μm, a thickness of 5 μm, and an interval of 5 μm, which is manufactured in Example 3. FIG. 7 is a top view of an anisotropic conductive film having a pattern of a film having a thickness of 100 μm, a silver particle group width of 80 μm, a thickness of 80 μm, and a gap of 80 μm, which is manufactured in Example 4. FIG. 7 is a top view of an anisotropic conductive film having a pattern of a film having a thickness of 3 μm, a silver particle group width of 1 μm, a thickness of 2 μm, and a gap of 1.5 μm, which is manufactured in Example 5. FIG. 7 is a top view of an anisotropic conductive film having a pattern of a film having a thickness of 500 μm, a copper particle group width of 1,000 μm, a thickness of 500 μm, and a spacing of 1,000 μm, which is manufactured in Example 6. FIG. 7 is a top view of an anisotropic conductive film having a pattern of a film having a thickness of 600 μm, a silver particle group width of 500 μm, a thickness of 500 μm, and a spacing of 500 μm, which is manufactured in Example 7. FIG. 9 is a top view of an anisotropic conductive film having a pattern of a film having a thickness of 20 μm, a copper particle group width of 5 μm, a thickness of 5 μm, and an interval of 5 μm, which is manufactured in Example 8. FIG. 9 is a top view of an anisotropic heat conductive film having a pattern of a film having a thickness of 500 μm, a heat conductive particle group having a width of 500 μm, a thickness of 500 μm, and an interval of 50 μm, which is manufactured in Example 9. FIG. FIG. 9 is a top view of an anisotropic phosphor film having a pattern of a film having a thickness of 40 μm, a phosphor particle group width of 40 μm, a thickness of 40 μm, and an interval of 40 μm, manufactured in Example 10; 8 is a top view of an anisotropic phosphor film having a pattern of a film having a thickness of 30 μm, a phosphor particle group width of 30 μm, a thickness of 30 μm, and an interval of 30 μm, manufactured in Example 11. FIG. 9 is a top view of an anisotropic magnetic film having a pattern of a film having a thickness of 2000 μm, a magnetic particle group width of 800 μm, a thickness of 1500 μm, and a spacing of 100 μm, which is manufactured in Example 12. FIG. FIG. 7 is a top view of an anisotropic electromagnetic wave absorbing film having a pattern of a film having a thickness of 100 μm, an electromagnetic wave absorbing particle group width of 200 μm, a thickness of 100 μm, and an interval of 40 μm, which is manufactured in Example 13; FIG. 8 is a top view of a film produced in Comparative Example 1 having a thickness of 8 μm and conductive particles sparsely present. FIG. 8 is a top view of a film produced in Comparative Example 2 having a thickness of 30 μm and silver particles sparsely present. FIG. 8 is a top view of a film produced in Comparative Example 3 having a thickness of 2 μm and silver particles attached to each other. FIG. 7 is a top view of an anisotropic conductive film having a pattern in which the film manufactured in Comparative Example 4 has a thickness of 200 μm, a silver particle group width of 1,200 μm, a thickness of 200 μm, and a spacing of 1,200 μm.

As described above, there has been a demand for the development of a highly reliable anisotropic conductive film that electrically connects circuit electrodes having fine patterns to each other. Further, it is not limited to the case of being conductive, and there has been a demand for the development of an anisotropic film having a fine and accurate pattern of particle groups.

As a result of intensive investigations by the inventors to achieve the above-mentioned object, an anisotropic conductive film containing an insulating resin and conductive particle groups, wherein the conductive particle groups are bound by a binder If the anisotropic conductive film containing particles and the conductive particle groups are regularly arranged and the interval thereof is 1 μm to 1,000 μm, circuit electrodes having a fine pattern are short-circuited. The inventors have found that they can be electrically connected to each other, and have completed the present invention.

That is, the present invention is an anisotropic film containing an insulating resin and a particle group, wherein the particle group is a group of particles in which a plurality of particles are bound by a binder, and the particle group is It is an anisotropic film that is regularly arranged and has a distance of 1 μm to 1,000 μm. Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.

In the following description, an example will be described in which the particles are conductive particles, the particles are conductive particles, and the anisotropic film is an anisotropic conductive film. However, the present embodiment can be similarly applied to the case where the particles are heat conductive particles, phosphors, magnetic particles, electromagnetic wave absorbing fillers, or the like.

FIG. 1 is an image diagram showing an example of the anisotropic conductive film of the present invention. The anisotropic conductive film 10 of the present invention contains an insulating resin 1 and a conductive particle group 2. The conductive particle group 2 includes conductive particles 4 bound by a binder 3 and is regularly arranged, and the distance A is 1 μm to 1,000 μm.
Hereinafter, each component of the anisotropic conductive film 10 of the present invention will be described in detail.

[Insulating resin]
The insulating resin 1 used in the present invention is not particularly limited, and is a thermoplastic resin such as acrylic resin, polyester resin, polyethylene resin, cellulose resin, styrene resin, polyamide resin, polyimide resin, melamine resin, silicone resin, Thermosetting resins such as epoxy resin, silicone/epoxy resin, maleimide resin, phenol resin, and perfluoropolyether resin can be mentioned. Considering heat resistance and light resistance, silicone resin, epoxy resin, maleimide resin, etc. Thermosetting resins are preferred.

Further, the insulating resin 1 is preferably a plastic solid or semisolid at 25° C. in a semi-cured state called uncured or B stage, and is a plastic solid or semi-solid at 25° C. in an uncured state. Is more preferable. With such properties, the electronic component can be deformed when it is pressure-bonded, and a good adhesive force can be obtained by completely curing it.

In the present specification, the term “semi-solid” refers to a state of a substance that has plasticity and can retain the shape for at least 1 hour, preferably 8 hours or more when molded into a specific shape. Thus, for example, a flowable substance having a very high viscosity at 25° C. is essentially flowable, but due to the very high viscosity, changes to the given shape in a short time of at least 1 hour (ie, A material is said to be in a semi-solid state when no collapse is visible to the naked eye.

The insulating resin 1 may include insulating inorganic particles. The insulating inorganic particles are not particularly limited, for example, silica, calcium carbonate, potassium titanate, glass fiber, silica balloon, glass balloon, aluminum oxide, aluminum nitride, boron nitride, beryllium oxide, barium titanate, barium sulfate. , Zinc oxide, titanium oxide, magnesium oxide, antimony oxide, aluminum hydroxide, magnesium hydroxide and the like, preferably silica, aluminum oxide, aluminum nitride, boron nitride and zinc oxide. By containing these insulating inorganic particles, the thermal expansion coefficient of the cured product of the insulating resin 1 can be reduced.

The particle diameter of the insulating inorganic particles is not particularly limited, but the median diameter measured by a laser diffraction particle size distribution measuring device is preferably 0.05 to 10 μm, more preferably 0.1 to 8 μm, and 0.5 to 5 μm is more preferable. Within this range, it is easy to disperse the resin uniformly in the insulating resin and it does not settle over time, which is preferable. Furthermore, the particle size of the insulating inorganic particles is preferably 50% or less with respect to the thickness T of the anisotropic conductive film 10. When the particle diameter is 50% or less with respect to the thickness T of the anisotropic conductive film 10, it is easy to uniformly disperse the insulating inorganic particles in the insulating resin 1, and further, the anisotropic conductive film. It is preferable to apply 10 evenly because it is easy.

The content of the insulating inorganic particles is not particularly limited, but is preferably 30 to 95 mass% of the mass of the insulating resin 1, more preferably 40 to 90 mass%, and further preferably 50 to 85 mass%. Within this range, the coefficient of thermal expansion of the insulating resin 1 can be effectively reduced, and the film does not become brittle after being formed into a film and completely cured, which is preferable.

Further, the insulating resin 1 used in the present invention preferably has a relative dielectric constant of 3.5 or less at 10 GHz of the cured product. With such a cured product, transmission loss can be reduced. Here, as for the relative dielectric constant, the insulating resin 1 was completely cured at 180° C. for 2 hours, and the cured product was used as a test piece having a length of 30 mm×a width of 40 mm and a thickness of 100 μm, and a network analyzer (E5063- 2D5) and a strip line (manufactured by Keycom Co., Ltd.) are connected to indicate a value measured.

Hereinafter, specific examples of the insulating resin and the insulating inorganic particles used in the present invention will be described. Among the above-mentioned resins, the insulating resin particularly preferably used in the present invention is a silicone resin, an epoxy resin, or a maleimide resin. Insulating inorganic particles that are particularly preferably used are white pigments and hollow particles among those described above. Hereinafter, these will be described in more detail. However, the hollow particles are not limited to inorganic particles.

<Silicone resin>
The silicone resin that can be used as the insulating resin in the present invention is not particularly limited, and examples thereof include addition-curable silicone resins and condensation-curable silicone resins.

Examples of the addition-curable silicone resin include (A) an organosilicon compound having a non-conjugated double bond (for example, an alkenyl group-containing diorganopolysiloxane), (B) an organohydrogenpolysiloxane, and (C) a platinum-based compound. A composition containing a catalyst as an essential component is particularly preferable. Hereinafter, these components (A) to (C) will be described.

Component (A): Organosilicon Compound Having Non-Conjugated Double Bonds As the organosilicon compound having a non-conjugated double bond of the component (A), both ends of the molecular chain represented by the following general formula (1) are aliphatic. Examples are organopolysiloxanes such as linear diorganopolysiloxanes capped with unsaturated group-containing triorganosiloxy groups.
(In the formula, R ¹¹ represents a non-conjugated double bond-containing monovalent hydrocarbon group, R ^{12 to} R ¹⁷ each represent the same or different monovalent hydrocarbon group, and a and b are 0≦a≦500, (An integer that satisfies 0≦b≦250 and 0≦a+b≦500.)

In the general formula (1), R ¹¹ is a non-conjugated double bond-containing monovalent hydrocarbon group, preferably an aliphatic group represented by an alkenyl group having 2 to 8 carbon atoms, and particularly preferably 2 to 6 carbon atoms. It is a non-conjugated double bond-containing monovalent hydrocarbon group having an unsaturated bond. R ^{12 to} R ¹⁷ are the same or different monovalent hydrocarbon groups, preferably having 1 to 20 carbon atoms, and particularly preferably having 1 to 10 carbon atoms, an alkyl group, an alkenyl group, an aryl group, an aralkyl group and the like. Is mentioned. Of these, R ^{14 to} R ¹⁷ are more preferably a monovalent hydrocarbon group excluding an aliphatic unsaturated bond, and particularly preferably an alkyl group having no aliphatic unsaturated bond such as an alkenyl group, an aryl group, An aralkyl group and the like can be mentioned. Further, among these, R ¹⁶ and R ¹⁷ are preferably aromatic monovalent hydrocarbon groups, and particularly preferably aryl groups having 6 to 12 carbon atoms such as phenyl groups and tolyl groups.

In the general formula (1), a and b are integers satisfying 0≦a≦500, 0≦b≦250, and 0≦a+b≦500, and a is preferably 10≦a≦500, and b Is preferably 0≦b≦150, and a+b preferably satisfies 10≦a+b≦500.

Examples of the organopolysiloxane represented by the general formula (1) include cyclic diorganopolysiloxanes such as cyclic diphenylpolysiloxane and cyclic methylphenylpolysiloxane, and diphenyltetravinyldisiloxane and divinyltetraphenyldisiloxane that form terminal groups. It can be obtained by an alkaline equilibration reaction with disiloxane such as siloxane. In this case, however, in the equilibration reaction with an alkali catalyst (especially a strong alkali such as KOH), the polymerization proceeds by an irreversible reaction even with a small amount of the catalyst. Since only the ring-opening polymerization quantitatively proceeds and the terminal blocking rate is high, the silanol group and the chloro component are not usually contained.

Specific examples of the organopolysiloxane represented by the above general formula (1) include the following.
(In the above formula, k and m are integers satisfying 0≦k≦500, 0≦m≦250, and 0≦k+m≦500, preferably 5≦k+m≦250 and 0≦m/(k+m). It is an integer that satisfies ≦0.5.)

The component (A) includes an organopolysiloxane having a linear structure represented by the general formula (1), a trifunctional siloxane unit represented by the following general formula (2), a tetrafunctional siloxane unit, and the like. It is also possible to use an organopolysiloxane having a three-dimensional network structure. Such organosilicon compounds having a non-conjugated double bond may be used alone or in combination of two or more.
(In the formula, R ⁸ is each independently a group selected from a saturated hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, and an alkenyl group having 2 to 10 carbon atoms, However, at least two of the groups represented by R ⁸ are alkenyl groups, r is an integer of 0 to 100, s is an integer of 0 to 300, t is an integer of 0 to 200, and u is an integer of 0 to 200. 1≦t+u≦400, 2≦r+s+t+u≦800, where r, s, t and u are values in which the organopolysiloxane has at least two alkenyl groups in one molecule.)

The organopolysiloxane having a linear structure represented by the general formula (1) and the organopolysiloxane having a network structure represented by the general formula (2) may be used alone or in combination.

Amount of the group having a non-conjugated double bond (for example, a monovalent hydrocarbon group having a double bond such as an alkenyl group bonded to a Si atom) in the organosilicon compound having a non-conjugated double bond of the component (A). Is preferably 0.1 to 20 mol% of all monovalent hydrocarbon groups (all monovalent hydrocarbon groups bonded to Si atoms), more preferably 0.2 to 10 mol%, and particularly preferably. Is 0.2 to 5 mol %. If the amount of the group having a non-conjugated double bond is 0.1 mol% or more, a good cured product can be obtained when it is cured, and if it is 20 mol% or less, mechanical properties when cured Is preferable and is preferable.

In addition, the organosilicon compound having a non-conjugated double bond of the component (A) preferably has an aromatic monovalent hydrocarbon group (aromatic monovalent hydrocarbon group bonded to Si atom). The content of hydrogen groups is preferably 0 to 95 mol% of all monovalent hydrocarbon groups (all monovalent hydrocarbon groups bonded to Si atoms), more preferably 10 to 90 mol%, and particularly preferably. Is 20 to 80 mol %. When the aromatic monovalent hydrocarbon group is contained in the resin in an appropriate amount, it has an advantage that it has good mechanical properties when cured and is easy to manufacture.

Component (B): Organohydrogenpolysiloxane As the component (B), an organohydrogenpolysiloxane having two or more hydrogen atoms bonded to silicon atoms (hereinafter referred to as “SiH groups”) in one molecule is preferable. .. If the organohydrogenpolysiloxane has two or more SiH groups in one molecule, it acts as a cross-linking agent, and the SiH group in the component (B), the vinyl group in the component (A), and other alkenyl groups such as A cured product can be formed by an addition reaction with the conjugated double bond-containing group.

Further, the organohydrogenpolysiloxane as the component (B) preferably has an aromatic monovalent hydrocarbon group. Thus, the organohydrogenpolysiloxane having an aromatic monovalent hydrocarbon group can enhance the compatibility with the component (A). Such organohydrogenpolysiloxanes may be used alone or in combination of two or more. For example, an organohydrogenpolysiloxane having an aromatic hydrocarbon group may be used as a part of the component (B). Or it can be included as a whole.

The organohydrogenpolysiloxane as the component (B) is not particularly limited, but examples thereof include 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, and tris(dimethylhydrogen). Gensiloxy)methylsilane, tris(dimethylhydrogensiloxy)phenylsilane, 1-glycidoxypropyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,5-glycidoxypropyl-1,3,5 ,7-Tetramethylcyclotetrasiloxane, 1-glycidoxypropyl-5-trimethoxysilylethyl-1,3,5,7-tetramethylcyclotetrasiloxane, both ends trimethylsiloxy group-blocked methylhydrogenpolysiloxane, both Dimethyl siloxane/methyl hydrogen siloxane copolymer with trimethylsiloxy terminal block, dimethylpolysiloxane with dimethyl hydrogen siloxy group with both terminals dimethylpolysiloxane, dimethyl siloxane/methyl hydrogen siloxane copolymer with both dimethyl hydrogen siloxy group blocked, trimethyl both terminals Siloxy group-blocked methylhydrogensiloxane/diphenylsiloxane copolymer, trimethylsiloxy group-blocked methylhydrogensiloxane/diphenylsiloxane/dimethylsiloxane copolymer at both ends, trimethoxysilane polymer, (CH ₃ ) ₂ HSiO _1/2 unit And a copolymer of SiO _4/2 units, a copolymer of (CH ₃ )HSiO _2/2 units, (CH ₃ ) ₂ SiO _2/2 and (C ₆ H ₅ )SiO _3/2 units. , A copolymer of (CH ₃ ) ₂ HSiO _1/2 units, SiO _4/2 units, and (C ₆ H ₅ )SiO _3/2 units.

Further, compounds represented by the following structures, or organohydrogenpolysiloxanes obtained by using these compounds as materials can also be used.

The molecular structure of the organohydrogenpolysiloxane as the component (B) may be linear, cyclic, branched, or three-dimensional network structure, and may be the number of silicon atoms in one molecule (or in the case of a polymer). Is preferably 2 or more, more preferably 3 to 500, particularly preferably 4 to 300.

The blending amount of the organohydrogenpolysiloxane as the component (B) is such that the SiH group in the component (B) is 0.7 to 3. per one group having a non-conjugated double bond such as an alkenyl group of the component (A). The amount is preferably 0, and particularly preferably 1.0 to 2.0.

Component (C): Platinum-based catalyst Examples of the platinum-based catalyst as the component (C) include chloroplatinic acid, alcohol-modified chloroplatinic acid, and a platinum complex having a chelate structure. These can be used alone or in combination of two or more.

The amount of the platinum-based catalyst as the component (C) may be a curing effective amount (so-called catalytic amount), and is usually the mass conversion of the platinum group metal per 100 parts by mass of the total mass of the components (A) and (B). Is preferably 0.1 to 500 ppm, and particularly preferably 0.5 to 100 ppm.

Examples of the condensation-curable silicone resin include (A-1) the following average composition formula (3):
(In the formula, R ¹ is independently an alkyl group having 1 to 12 carbon atoms, an alkenyl group, an aryl group or a halogen substituent thereof, or a hydrogen atom, and X is independently —Si(R ² R ³ R ⁴ ) (R ² , R ³ and R ⁴ are an alkyl group, an alkenyl group, an aryl group or a halogen substituent thereof, or a hydrogen atom), an alkyl group having 1 to 6 carbon atoms, an alkenyl group, It is an alkoxyalkyl group, an acyl group or a hydrogen atom, a is a number from 1.00 to 1.50, b is a number satisfying 0<b<2, provided that 1.00<a+b<2.00. It is.)
An organopolysiloxane having a maximum polystyrene-equivalent weight average molecular weight of 1×10 ⁴ or more,
And (A-2) a composition containing a condensation catalyst as a curing agent. Hereinafter, the preferable composition will be described in detail.

[(A-1) Organopolysiloxane]
The component (A-1) is an organopolysiloxane represented by the above average composition formula (3) and having a maximum polystyrene-equivalent weight average molecular weight of 1×10 ⁴ or more.

In the above formula (3), examples of the alkyl group represented by R ¹ include a methyl group, an ethyl group, a propyl group and a butyl group. Examples of the alkenyl group include a vinyl group. Examples of the aryl group include a phenyl group and the like. Of these, a methyl group or a phenyl group is preferable as R ¹ . Examples of the halogen substituent include a trichloromethyl group, a trifluoropropyl group, a 3,3,4,4,5,5,6,6,6-nonafluorohexyl group and the like.

In the above formula (3), —Si(R ² R ³ R ⁴ ) represented by X is a silyl group of a hydroxyl group in a hydrolyzed organopolysiloxane, which will be described later. R ² , R ³ and R ⁴ are non-reactive substituted or unsubstituted monovalent hydrocarbon groups, such as alkyl groups such as methyl group, ethyl group and propyl group, alkenyl groups such as vinyl group, phenyl group, etc. And the halogen-substituted organic group thereof are exemplified. Examples of the halogen substituent include a trichloromethyl group, a trifluoropropyl group, a 3,3,4,4,5,5,6,6,6-nonafluorohexyl group and the like.

Further, in the above formula (3), examples of the alkyl group represented by X include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and the like. Examples of the alkenyl group include a vinyl group. Examples of the alkoxyalkyl group include a methoxyethyl group, an ethoxyethyl group, a butoxyethyl group and the like. Examples of the acyl group include an acetyl group and a propionyl group.

In the above formula (3), a is preferably a number of 1.00 to 1.50, b is 0<b<2, particularly 0.01≦b≦1.0, and particularly 0.05≦b≦. It is preferably a number satisfying 0.7. When a is 1.00 or more, there is no risk of cracks in the film obtained by curing the composition sheet obtained, and when it is 1.50 or less, the toughness of the film is poor and the film becomes brittle. There is no fear. When b is larger than 0, the adhesiveness to the substrate is sufficient, and when it is less than 2, a cured film is surely obtained. Further, a+b is preferably 1.00≦a+b≦1.50, and more preferably 1.10≦a+b≦1.30.

The organopolysiloxane of this component can be obtained, for example, by the following general formula (4) or (5):
(Wherein, ^{R 5} is independently the same as ^{R 1} as defined above, ^{R 6} is independently as excluding ^{-Si (R 2 R 3 R 4} ) of X as defined above It is the same and c is an integer of 1 to 3.)
The silane compound represented by the formula (4) or (5) and the silane compound represented by the following general formula (4) or (5) are hydrolyzed and condensed:
(In the formula, R ⁶ is independently the same as X defined above except for -Si(R ² R ³ R ⁴ ).)
Obtained by co-hydrolytic condensation with an alkyl silicate represented by and/or a polycondensation product of the alkyl silicate (alkyl polysilicate) (both together, also referred to as “alkyl (poly)silicate”). Be done. These silane compounds and alkyl(poly)silicates may be used alone or in combination of two or more. The method for synthesizing the organopolysiloxane of this component is not limited to this.

Examples of the silane compound represented by the above formula (4) or (5) include, for example, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, Dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, methyldimethoxysilane, ethyldimethoxysilane, phenyldimethoxysilane, methyltrichlorosilane, ethyltrichlorosilane, phenyl Trichlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, methylphenyldichlorosilane, methyldichlorosilane, ethyldichlorosilane, phenyldichlorosilane and the like can be mentioned, preferably methyltrimethoxysilane, methyldimethoxysilane, phenyltrimethoxysilane, methyltrichlorosilane. These are chlorosilane, methyldichlorosilane and phenyltrichlorosilane. These silane compounds may be used alone or in combination of two or more.

Examples of the alkyl silicate represented by the above formula (6) include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, and tetraisopropyloxysilane. As the polycondensate of the alkylsilicate (alkylpolysilicate), Examples include methyl polysilicate and ethyl polysilicate. These alkyl (poly)silicates may be used alone or in combination of two or more.

Among these, since the resulting cured product is more excellent in crack resistance and heat resistance, organopolysiloxane of this component is methyltrimethoxysilane, phenyltrimethoxysilane, methyltrichlorosilane, phenyltrichlorosilane, etc. Of 20 to 75 mol% of trialkoxysilane and trichlorosilane, and 80 to 25 mol% of dialkoxysilane such as dimethyldimethoxysilane and dimethyldichlorosilane, and preferably 25 to 65 mol of trialkoxysilane and trichlorosilane. % And dialkoxysilane and dichlorosilane 75 to 35 mol% are more preferable.

In a preferred embodiment of the present invention, the organopolysiloxane of this component is obtained by subjecting the silane compound represented by the above formula (4) to a two-step hydrolysis and condensation reaction of primary hydrolysis and secondary hydrolysis, Alternatively, it can be obtained by subjecting the silane compound and alkyl(poly)silicate to a two-step hydrolysis and condensation reaction of primary hydrolysis and secondary hydrolysis, and the following conditions can be applied, for example.

The silane compound and alkyl(poly)silicate represented by the above formula (4) are usually preferably dissolved in an organic solvent such as alcohols, ketones, esters, cellosolves and aromatic compounds before use. .. Specific examples of the organic solvent used here include alcohol-based solvents such as methanol, ethanol, isopropyl alcohol, isobutyl alcohol, n-butanol, and 2-butanol. Isobutyl alcohol is more preferable because it has excellent toughness.

Furthermore, the silane compound represented by the above formula (4) and the alkyl (poly)silicate may be hydrolyzed and condensed by using an acid catalyst such as acetic acid, hydrochloric acid or sulfuric acid as a primary hydrolysis catalyst. preferable. The amount of water added during the primary hydrolysis-condensation is usually 0.9 to 1. per mol of the silane compound or the total amount of the silane compound and the alkoxy group in the alkyl (poly)silicate. It is 5 mol, preferably 1.0 to 1.2 mol. When the blending amount satisfies the range of 0.9 to 1.5 mol, the workability of the obtained composition is excellent, and the cured product is excellent in toughness.

The maximum value of the polystyrene equivalent weight average molecular weight of the organopolysiloxane that is the primary hydrolysis/condensation product is preferably 5×10 ^{3 to} 6×10 ⁴ , and particularly preferably 1×10 ⁴ to 4×10 ⁴ .

The weight average molecular weight herein means the weight average molecular weight measured by gel permeation chromatography (GPC) under the following conditions, using polystyrene as a standard substance.
[Measurement condition]
・Developing solvent: THF
・Flow rate: 0.6 mL/min
・Detector: Differential refractive index detector (RI)
・Column: TSK GuardcollomSuperH-L
-TSKgel Super H4000 (6.0 mm ID x 15 cm x 1)
-TSKgel Super H3000 (6.0 mm ID x 15 cm x 1)
-TSKgel Super H2000 (6.0 mm ID x 15 cm x 2)
(All made by Tosoh Corporation)
・Column temperature: 40℃
・Sample injection amount: 20 μL (THF solution with a concentration of 0.5% by weight)

If necessary, secondary hydrolysis and condensation reaction may be performed. The secondary hydrolysis/condensation reaction is to produce a high molecular weight organopolysiloxane by using a secondary hydrolysis/condensation catalyst of the organopolysiloxane obtained by the primary hydrolysis/condensation reaction.

As the secondary hydrolysis/condensation catalyst, a polystyrene type anion exchange resin is used as an anion exchange resin. As the polystyrene-based anion exchange resin, DIAION (manufactured by Mitsubishi Chemical Co., Ltd.) is preferably used, and as the product name, DIAION SA series (SA10A, SA11A, SA12A, NSA100, SA20A, SA21A), DIAION PA series (PA308, PA312, PA316, PA406, PA412, PA418), DIAION HPA series (HPA25), DIAION WA series (WA10, WA20, WA21J, WA30) and the like can be mentioned.

Of these, SA10A represented by the following structural formula (8) is particularly preferably used. SA10A is a water-containing polystyrene-based anion exchange resin, and the water content in SA10A causes the reaction to proceed due to the catalytic effect of the basic ion exchange resin SA10A.

The catalyst amount of the secondary hydrolysis is 1% by mass to 50% by mass, preferably 5% by mass to 30% by mass, relative to the nonvolatile content (150° C./1 hour dried) of the primary hydrolyzate polysiloxane. is there. If it is 1% by mass or more, the reaction for increasing the molecular weight proceeds at a sufficient rate, and if it is 50% by mass or less, there is no possibility of gelation. The secondary hydrolysis catalyst may be used alone or in combination of two or more.

The temperature of this secondary hydrolysis reaction is preferably 0°C to 40°C, and particularly 15°C to 30°C, the reaction proceeds well. When the temperature is 0°C or higher, the reaction proceeds at a sufficient speed, and when the temperature is 40°C or lower, gelation does not occur.

Further, this secondary hydrolysis reaction is preferably carried out in a solvent, and the solid content concentration is preferably 50% by mass to 95% by mass, and particularly preferably 65% by mass to 90% by mass. When the solid content concentration is 50% by mass or more, the reaction proceeds at a sufficient speed, and when the solid content concentration is 95% by mass or less, there is no fear that the reaction will be rapid and gelation will occur.

The solvent used for the secondary hydrolysis is not particularly limited, but those having a boiling point of 60° C. or higher are preferable, and examples thereof include hydrocarbon solvents such as benzene, toluene and xylene; tetrahydrofuran, 1,4-dioxane and the like. Ether-based solvent; ketone-based solvent such as methyl ethyl ketone; halogenated hydrocarbon-based solvent such as 1,2-dichloroethane; alcohol-based solvent such as methanol, ethanol, isopropyl alcohol, isobutyl alcohol; octamethylcyclotetrasiloxane, hexamethyldisiloxane Etc., and organic solvents having a boiling point of 150° C. or higher such as cellosolve acetate, cyclohexanone, butyrocellosolve, methyl carbitol, carbitol, butyl carbitol, diethyl carbitol, cyclohexanol, diglyme, and triglyme may be used. it can. These organic solvents can be used alone or in combination of two or more. As the solvent, xylene, isobutyl alcohol, diglyme and triglyme are preferable, and isobutyl alcohol is particularly preferable.

The maximum value of the polystyrene equivalent weight average molecular weight of the organopolysiloxane that is the secondary hydrolysis/condensation product is 1×10 ⁴ or more, and particularly preferably 3×10 ⁴ to 4×10 ⁵ . When the maximum value of the weight average molecular weight is 1×10 ⁴ or more, the cured film is likely to be cracked, and there is no fear that it becomes difficult to obtain a film having a thickness of 50 μm or more.

Since the high molecular weight organopolysiloxane obtained by the secondary hydrolysis has a high molecular weight, there is a problem that it easily gels due to condensation of residual hydroxyl groups. The problem of gelation can be solved by silylating the remaining hydroxyl groups to obtain a stable high molecular weight organopolysiloxane.

Examples of the silylation method using a silyl group having a non-reactive substituent of the remaining hydroxyl group in the organopolysiloxane include a method of reacting with trialkylhalosilane, hexaalkyldisilazane, N,N-diethylaminotrialkylsilane, N -(Trialkylsilyl)acetamide, N-methyl(trialkylsilyl)acetamide, N,O-bis(trialkylsilyl)acetamide, N,O-bis(trialkylsilyl)carbamate, N-trialkylsilylimidazole, etc. Examples thereof include a method using a nitrogen-containing silylating agent, a method of reacting with a trialkylsilanol, and a method of reacting with a hexaalkyldisiloxane under weak acidity. When using a trialkylhalosilane, a hydrogen halide produced as a by-product may be neutralized in the presence of a base. When using a nitrogen-containing silylating agent, a catalyst such as trimethylchlorosilane or ammonium sulfate may be added. Specifically, a method in which trimethylchlorosilane is used as a silylating agent in the presence of triethylamine is suitable.

The silylation reaction can be carried out in a solvent, but the solvent can be omitted. Suitable solvents include aromatic hydrocarbon solvents such as benzene, toluene and xylene, aliphatic hydrocarbon solvents such as hexane and heptane, ether solvents such as diethyl ether and tetrahydrofuran, ketone solvents such as acetone and methyl ethyl ketone, acetic acid. Examples thereof include ester solvents such as ethyl and butyl acetate, halogenated hydrocarbon solvents such as chloroform, trichloroethylene and carbon tetrachloride, and dimethylformamide and dimethylsulfoxide. The reaction temperature for such silylation is suitably 0°C to 150°C, preferably 0°C to 60°C.

Since the high molecular weight organopolysiloxane of the component (A-1) obtained by the above production method is used, the cured film has high strength, good flexibility, and good adhesiveness. It has excellent characteristics capable of forming a thick film sheet having a thickness of 50 μm or more.

[(A-2) Condensation catalyst]
The condensation catalyst as the component (A-2) is a component required to cure the organopolysiloxane as the component (A-1). The condensation catalyst is not particularly limited, but an organometallic catalyst is usually used because it is excellent in stability of the organopolysiloxane, hardness of the obtained cured product, non-yellowing property and the like. Examples of the organometallic catalyst include those containing atoms such as zinc, aluminum, titanium, tin, and cobalt, preferably zinc, aluminum, and those containing titanium atoms, and specifically, Organic acid zinc, Lewis acid catalyst, aluminum compound, organic titanium compound and the like are preferably used, and specifically, zinc octylate, zinc benzoate, zinc p-tert-butylbenzoate, zinc laurate, zinc stearate, Aluminum chloride, aluminum perchlorate, aluminum phosphate, aluminum triisopropoxide, aluminum acetylacetonate, aluminum butoxybisethyl acetoacetate, tetrabutyl titanate, tetraisopropyl titanate, tin octylate, cobalt naphthenate, tin naphthenate, etc. Among these, specifically, aluminum acetylacetonate and Acetope Al-MX3 (manufactured by Hope Pharmaceutical Co., Ltd.) are preferably used. These condensation catalysts may be used alone or in combination of two or more.

The addition amount of the condensation catalyst of the component (A-2) is 0.05 to 10 parts by mass, particularly 0.1 to 5 parts by mass, relative to 100 parts by mass of the organopolysiloxane of the component (A-1). When the addition amount is 0.05 parts by mass or more, the curability may not be poor, and when it is 10 parts by mass or less, gelation may not occur.

<Epoxy resin>
The epoxy resin that can be used as the insulating resin in the present invention is not particularly limited, and examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, 3,3′,5,5′-tetramethyl-4, Biphenol type epoxy resin such as 4'-biphenol type epoxy resin or 4,4'-biphenol type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, naphthalene diol type epoxy resin , Trisphenylol methane type epoxy resin, tetrakis phenylol ethane type epoxy resin, and phenol dicyclopentadiene novolac type epoxy resin hydrogenated epoxy ring, alicyclic epoxy resin, etc. An epoxy resin can be used. Further, if necessary, a certain amount of epoxy resin other than the above can be used in combination depending on the purpose.

The epoxy resin may be an insulating resin composition containing an epoxy resin, and the composition may include a curing agent for the epoxy resin. As such a curing agent, a phenol novolac resin, various amine derivatives, an acid anhydride or a compound obtained by partially opening the acid anhydride group to generate a carboxylic acid can be used. Above all, it is preferable to use a phenol novolac resin. Particularly, it is preferable to mix the epoxy resin and the phenol novolac resin so that the ratio of the epoxy group and the phenolic hydroxyl group is 1:0.8 to 1.3.

Further, in order to promote the reaction between the epoxy resin and the curing agent, a metal compound such as an imidazole derivative, a phosphine derivative, an amine derivative or an organic aluminum compound may be used as a reaction accelerator (catalyst).

The insulating resin composition containing an epoxy resin may further contain various additives, if necessary. For example, various thermoplastic resins, thermoplastic elastomers, organic synthetic rubbers, low-stress agents such as silicones, waxes, and additives such as halogen trap agents are appropriately added and blended according to the purpose for the purpose of improving the properties of the resin. can do.

<Maleimide resin>
Examples of the maleimide resin preferably used as the insulating resin of the present invention include maleimide compounds represented by the following general formula (9).

In formula (9), A independently represents a tetravalent organic group containing a cyclic structure. B is independently an alkylene group having 6 or more carbon atoms which may contain a divalent hetero atom. Q is independently an arylene group having 6 or more carbon atoms which may contain a divalent hetero atom. W is the same as B or Q. n is 0-100 and m represents the number of 0-100.

A in the general formula (9) represents a tetravalent organic group containing a cyclic structure, and it is particularly preferably any of the tetravalent organic groups represented by the following structural formulas.
(Note that the bond in the above structural formula to which the substituent is not bonded is a bond to the carbonyl carbon forming the cyclic imide structure in the general formula (9).)

B in the general formula (9) is independently an alkylene group having 6 or more carbon atoms which may contain a divalent hetero atom, and preferably an alkylene group having 8 or more carbon atoms. B in the general formula (9) is more preferably an alkylene group having an aliphatic ring represented by the following structural formula.
(Note that the bond in the above structural formula to which the substituent is not bonded is a bond to the nitrogen atom forming the cyclic imide structure in the general formula (9).)

Q is independently an arylene group having 6 or more carbon atoms, which may contain a divalent hetero atom, and preferably an arylene group having 8 or more carbon atoms. It is more preferable that Q in the formula (9) is any of the arylene groups having an aromatic ring represented by the following structural formula.

N in the general formula (9) is a number of 0 to 100, preferably 0 to 70. M in the general formula (9) is a number of 0 to 100, preferably 0 to 70. However, at least one of n and m is a positive number.

As the high molecular weight maleimide, commercially available products such as BMI-2500, BMI-2560, BMI-3000, BMI-5000, BMI-6000, BMI-6100 (above, Designer Molecule Inc.) can be used. The cyclic imide compounds may be used alone or in combination of two or more.

The composition may contain a reaction initiator to cure the maleimide resin. The reaction initiator is not particularly limited, and examples thereof include a thermal radical polymerization initiator, a thermal cationic polymerization initiator, a thermal anionic polymerization initiator, and a photopolymerization initiator.

Examples of the thermal radical polymerization initiator include methyl ethyl ketone peroxide, methyl cyclohexanone peroxide, methyl acetoacetate peroxide, acetylacetone peroxide, 1,1-bis(t-butylperoxy)3,3,5-trimethylcyclohexane, 1 ,1-bis(t-hexylperoxy)cyclohexane, 1,1-bis(t-hexylperoxy)3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 2, 2-bis(4,4-di-t-butylperoxycyclohexyl)propane, 1,1-bis(t-butylperoxy)cyclododecane, n-butyl 4,4-bis(t-butylperoxy)valerate , 2,2-bis(t-butylperoxy)butane, 1,1-bis(t-butylperoxy)-2-methylcyclohexane, t-butylhydroperoxide, p-menthane hydroperoxide, 1,1 ,3,3-Tetramethylbutyl hydroperoxide, t-hexyl hydroperoxide, dicumyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, α,α′-bis (T-Butylperoxy)diisopropylbenzene, t-butylcumyl peroxide, di-t-butylperoxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne-3, isobutyrylper Oxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, cinnamic acid peroxide, m-toluoyl peroxide, benzoyl peroxide, diisopropyl peroxydicarbonate, bis(4-t -Butylcyclohexyl)peroxydicarbonate, di-3-methoxybutylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, di-sec-butylperoxydicarbonate, di(3-methyl-3-methoxybutyl) ) Peroxydicarbonate, di(4-t-butylcyclohexyl)peroxydicarbonate, α,α′-bis(neodecanoylperoxy)diisopropylbenzene, cumylperoxy neodecanoate, 1,1,3, 3,-Tetramethylbutylperoxy neodecanoate, 1-Cyclohexyl-1-methylethylperoxy neodecanoate, t-hexyl peroxy neodecanoate Canoate, t-butylperoxy neodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate , T-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t-butylperoxymaleic acid, t-butylperoxylaurate, t-butylperoxy-3,5. 5-trimethylhexanoate, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexylmonocarbonate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, t-butylpercarbonate Oxyacetate, t-hexylperoxybenzoate, t-butylperoxy-m-toluoylbenzoate, t-butylperoxybenzoate, bis(t-butylperoxy)isophthalate, t-butylperoxyallylmonocarbonate, 3 ,3',4,4'-Tetra(t-butylperoxycarbonyl)benzophenone and other organic peroxides, 2,2'-azobis(N-butyl-2-methylpropionamide), 2,2'-azobis (N-cyclohexyl-2-methylpropionamide), 2,2′-azobis[N-(2-methylpropyl)-2-methylpropionamide], 2,2′-azobis[N-(2-methylethyl) 2-Methylpropionamide], 2,2′-azobis(N-hexyl-2-methylpropionamide), 2,2′-azobis(N-propyl-2-methylpropionamide), 2,2′-azobis (N-ethyl-2-methylpropionamide), 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 2,2'-azobis[N-(2-propenyl)- 2-Methylpropionamide], 2,2′-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide}, 2,2′-azobis[N-( 2-propenyl)-2-methylpropionamide], azo such as dimethyl-1,1′-azobis(1-cyclohexanecarboxylate) Examples thereof include dicumyl peroxide, di-t-butyl peroxide, isobutyryl peroxide, 2,2′-azobis(N-butyl-2-methylpropionamide), 2,2′-azobis[ N-(2-methylethyl)-2-methylpropionamide], and more preferably dicumyl peroxide, di-t-butyl peroxide and isobutyryl peroxide.

Examples of the thermal cationic polymerization initiator include (4-methylphenyl)[4-(2-methylpropyl)phenyl]iodonium cation, (4-methylphenyl)(4-isopropylphenyl)iodonium cation, (4-methylphenyl). (4-isobutyl)iodonium cation, bis(4-tert-butyl)iodonium cation, bis(4-dodecylphenyl)iodonium cation, (2,4,6-trimethylphenyl)[4-(1-methylacetic acid ethyl ether) Aromatic iodonium salts such as phenyl]iodonium cations, aromatic sulfonium salts such as diphenyl[4-(phenylthio)phenyl]sulfonium cations, triphenylsulfonium cations, alkyltriphenylsulfonium cations, etc., and preferably (4-methylphenyl ) [4-(2-Methylpropyl)phenyl]iodonium cation, (4-methylphenyl)(4-isopropylphenyl)iodonium cation, triphenylsulfonium cation, alkyltriphenylsulfonium cation, and more preferably (4-methyl). Phenyl)[4-(2-methylpropyl)phenyl]iodonium cation and (4-methylphenyl)(4-isopropylphenyl)iodonium cation.

Examples of the thermal anionic polymerization initiator include 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methyl. Imidazoles such as imidazole, triethylamine, triethylenediamine, 2-(dimethylaminomethyl)phenol, 1,8-diaza-bicyclo(5,4,0)undecene-7, tris(dimethylaminomethyl)phenol, benzyldimethylamine, etc. Amines, triphenylphosphine, tributylphosphine, trioctylphosphine and other phosphines, and preferably 2-methylimidazole, 2-ethyl-4-methylimidazole, triethylamine, triethylenediamine, 1,8-diaza-bicyclo. (5,4,0)undecene-7, triphenylphosphine and tributylphosphine, more preferably 2-ethyl-4-methylimidazole, 1,8-diaza-bicyclo(5,4,0)undecene-7, It is triphenylphosphine.

The photopolymerization initiator is not particularly limited, but a benzoyl compound (or phenylketone compound) such as benzophenone, particularly 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, A benzoyl compound (or a phenylketone compound) having a hydroxy group on the carbon atom at the α-position of a carbonyl group such as 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one; 2-methyl -1-(4-Methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-dimethylamino-2- Α-alkylaminophenone compounds such as (4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, Acylphosphine oxide compounds such as bisacyl monoorganophosphine oxide and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide; benzoin ether compounds such as isobutyl benzoin ether; acetophenone diethyl ketal Ketal compound; thioxanthone compound; acetophenone compound. In particular, since the radiation emitted from the UV-LED has a single wavelength, when the UV-LED is used as a light source, the light of the α-alkylaminophenone compound or the acylphosphine oxide compound having the peak of the absorption spectrum in the region of 340 to 400 nm is used. It is effective to use a polymerization initiator.

These initiator components may be used alone or in combination of two or more.
The content of the initiator component is not particularly limited, but is 0.01 to 10 parts by mass, preferably 0.05 to 8 parts by mass, and more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the maleimide resin component. is there. Within this range, the insulating resin composition can be sufficiently cured.

<White pigment>
The white pigment is mixed in order to increase the whiteness required for applications such as reflectors. Examples of the white pigment include titanium dioxide, rare earth oxides represented by yttrium oxide, zinc sulfate, zinc oxide, magnesium oxide, and the like, and these can be used alone or in combination of several kinds.

Above all, it is preferable to use titanium dioxide in order to further increase the whiteness. The unit cell of titanium dioxide includes rutile type, anatase type and brookite type, and any of them can be used, but it is preferable to use the rutile type from the viewpoint of whiteness and photocatalytic ability of titanium dioxide.

Further, the average particle size and shape of titanium dioxide are not limited, but the average particle size is preferably 0.05 to 5.0 μm, more preferably 1.0 μm or less, and further preferably 0.30 μm or less. ..

The titanium dioxide is preferably surface-treated in order to enhance the wettability and compatibility with the insulating resin and the dispersibility and fluidity, and silica, alumina, zirconia, a polyol, and an organosilicon compound are used. It is more preferable that the surface treatment is carried out with at least one selected from the treatment agents, and particularly two or more types of treatment agents.

In addition, titanium dioxide treated with an organosilicon compound is preferable in order to improve the initial reflectance and the fluidity of the insulating resin containing a white pigment. Examples of the organosilicon compound include chlorosilane, silazane, monomer organosilicon compounds such as silane coupling agents having a reactive functional group such as epoxy group and amino group, and organopolysiloxanes such as silicone oil and silicone resin. Can be mentioned. It should be noted that other treatment agents that are usually used for surface treatment of titanium dioxide, such as organic acids such as stearic acid, may be used. It doesn't matter.

<Hollow particles>
Examples of the hollow particles include inorganic hollow particles or unexpanded or already expanded fine hollow particles made of an organic resin, which can be expanded by heat, already expanded hollow particles, and thermally expandable microcapsules. Examples of the inorganic hollow particles include silica balloons, carbon balloons, alumina balloons, aluminosilicate balloons and zirconia balloons, which are inflatable by heat and are not expanded or have already been expanded. Resin-made fine hollow particles, expanded hollow particles. Examples include phenol resin balloons and plastic balloons, and the thermally expandable microcapsules include vinylidene chloride, acrylonitrile, methacrylonitrile, polymers of monomers selected from acrylic acid esters and methacrylic acid esters, or two types of the above monomers. It has an outer shell made of an organic resin formed by the above copolymer, and is constituted by encapsulating a volatile substance or a low boiling point substance such as a hydrocarbon solvent such as isobutane or isopentane. ..

[Conductive particle group]
The conductive particle group 2 of the present invention is an assembly in which the conductive particles 4 are bound by the binder 3 and is a portion in which two or more conductive particles 4 are in contact with each other (FIG. 1 ).

<Conductive particles>
The conductive particles 4 are appropriately selected depending on the intended purpose without any limitation, and examples thereof include metal particles, metal-coated particles, and conductive polymer particles.

Examples of the metal particles include gold, silver, copper, palladium, aluminum, nickel, iron, titanium, manganese, zinc, tungsten, platinum, lead, tin, and other simple metals, or solder, steel, stainless steel, and other alloys. Is mentioned. Each of these may be used alone or in combination of two or more.

Examples of the metal-coated particles may include resin particles such as acrylic resin and epoxy resin whose surfaces are coated with a metal, and inorganic particles such as glass and ceramics whose surfaces are coated with a metal. The method for coating the metal surface of the particles is not particularly limited, and examples thereof include electroless plating and sputtering.

Here, examples of the metal that coats the surface of the particles include gold, silver, copper, iron, nickel, and aluminum.

Examples of the conductive polymer particles include carbon, polyacetylene nanoparticles, polypyrrole nanoparticles, and the like.

Among these conductive particles, metal particles are preferably used because they have low electric resistance and can be sintered at high temperature.

The conductive particles 4 may have conductivity when electrically connected to the circuit electrodes. For example, even a particle having an insulating coating on its surface is a conductive particle as long as the particle is deformed when electrically connected and the metal particle is exposed.

For the above reason, as the conductive particles 4, those which have been treated with a surface treatment agent such as a silane coupling agent may be used for the purpose of improving the kneading property with the binder 3, the affinity and the like.

The average particle diameter of the conductive particles 4 is not particularly limited, but the median diameter measured by a laser diffraction particle size distribution analyzer is preferably 0.01 to 100 μm, and more preferably 0.01 to 50 μm. More preferably, 0.05 to 30 μm is still more preferable, and 0.1 to 10 μm is extremely preferable. Within this range, the conductive particles can be highly filled. Further, two or more kinds of conductive particles 4 having different particle sizes may be used in combination.

The binder 3 of the conductive particle group 2 of the present invention is for binding the conductive particles 4 to each other. The binder 3 is not particularly limited, but examples thereof include a thermosetting resin and a thermoplastic resin. The thermosetting resin is highly reliable because it can be cured in a state in which electric conduction is secured when it is thermocompression bonded. If it is a thermoplastic resin, it is possible to maintain a state in which electricity is secured by cooling to room temperature after thermocompression bonding.

The type of the resin used as the binder 3 may be the same as the type of the insulating resin 1 used in the film-shaped insulating resin composition (which forms the base material of the anisotropic conductive film 10) described later, but may be different. May be. It is preferable to use the same type of resin because the binder 3 and the film-shaped insulating resin 1 can be compatible with each other, and the strength of the anisotropic conductive film 10 can be increased. If different types of resins are used, the conductive composition (the binder 3 and the conductive type) can be used. Even if the (mixture of particles 4) contains the conductive particles 4, the linear expansion coefficient of the conductive composition and the film-shaped insulating resin 1 can be matched, which is preferable.

Examples of the thermosetting resin include silicone resin, epoxy resin, acrylic resin, silicone-epoxy resin, maleimide resin, phenol resin, thermosetting polyimide resin, unsaturated polyester resin, and the like, and as the thermoplastic resin, Examples thereof include perfluoropolyether resin, polyester resin, polyethylene resin, cellulose resin, styrene resin, polyamide resin, polyimide resin, and melamine resin. Considering heat resistance and light resistance, silicone resin, epoxy resin, maleimide Thermosetting resins such as resins are preferred.

Further, the thermosetting resin is preferably a plastic solid or semi-solid at 25° C. in a semi-cured state called uncured or B stage, and a solid or semi-solid plastic at 25° C. in an uncured state. Is more preferable. With such properties, the electronic component can be deformed when pressure-bonded, and by being completely cured, a good adhesive force with the conductive particles 4 can be obtained.
The conductive particle group 2 includes 60 to 98% by mass of the conductive particles 4 and 2 to 40% by mass of the binder 3 according to the conductive particles 4, and a commercially available stirrer (THINKY CONDITIONING MIXER (manufactured by Shinky Co., Ltd.)). Etc.) and stir for about 1 to 5 minutes, or uniformly mix using a three-roll mill (manufactured by Inoue Seisakusho Co., Ltd.).

Here, the particle group is a portion (functional portion) for exhibiting its function in a so-called functional film. When the functional part is formed of one particle, the shape of the one particle is spherical or hemispherical, and the element and the like that come into contact with the film are contacted at only one point. That is, the connection stability is not sufficient. In addition, in the shape of one particle itself, there may be chipping or variation in shape, and when the functional part is formed by one particle, the lacking or shape variation is reflected in the functional part. , After all, it adversely affects the connection stability. Furthermore, in the case of one particle, if one is missing, the function of that part is completely lost, so one particle must be arranged at the target location, which is also disadvantageous in terms of cost. On the other hand, in the anisotropic film of the present invention, since the functional portion is a particle group composed of a plurality of particles bound by a binder, it can be in contact with the element at a plurality of points or planes, so You can secure a stable connection. In addition, since the particle group is composed of a plurality of particles, the chipping or variation in shape of each particle does not affect the shape of the functional portion (that is, the particle group), and in this respect also A stable connection can be secured, and the shape of the particle group can be changed according to the shape of the electrode portion of the device.

The width of the particle group is preferably 1 to 1,000 μm, more preferably 3 to 800 μm, still more preferably 5 to 500 μm, and particularly preferably 10 to 100 μm. Within this range, the respective advantages of the insulating resin and the particle group can be utilized, which is preferable. The width of the particle group is the maximum interparticle distance of particles belonging to one particle group.

The width of the particle group must be larger than that of the particles, and is preferably 5 times or more, more preferably 10 times or more and 1,000 times or less. Within this range, the function of the particles as a particle group can be sufficiently exhibited, which is preferable.

The theoretical average number of particles in the particle group is preferably 50 to 1×10 ⁹ particles, more preferably 100 to 1×10 ⁸ particles, and even more preferably 200 to 1×10 ⁷ particles. Within this range, the particle group can be easily formed into a columnar shape, which is preferable.

Here, the theoretical average number of particles is a parameter corresponding to the density (volume density) of particles included in the particle group, and can be calculated as follows. First, all particles constituting the particle group are regarded as spheres, and the average volume of the particles is calculated from the average particle diameter of the particles. Then, a value obtained by dividing the volume of the particle group by the average volume is set as a theoretical average number of particles in the particle group. When two or more types of particles having different average particle sizes are used in combination, the weighted average value of the average particle size of each particle is set as the average particle size of the particles constituting the particle group.

The present inventors have found that the number of particles in the particle group, that is, the particle density, is important for the particle group to exhibit the characteristics of the particle. However, it is very difficult and unrealistic to measure the number of particles in the particle group. As a result of investigations, the inventors have found that the theoretical average particle number shown below is useful as an alternative parameter of particle density.

Further, the shape of the particle group is preferably cylindrical or prismatic. The prismatic shape includes a triangular prism, a quadrangular prism, a pentagonal prism, a hexagonal prism, and the like. The upper bottom surface and the lower bottom surface may have the same shape or different shapes.

The ratio of the area of the lower surface to the area of the upper surface of the particle group is preferably 0.5 to 10, more preferably 0.6 to 5, and even more preferably 0.8 to 2. Within this range, anisotropy is likely to be exhibited as the function of the particle group, which is preferable.

Further, the particle group can have various functions depending on the type of particles included in the particle group. For example, the particles may be conductive particles, heat conductive particles, phosphors, magnetic particles, electromagnetic wave absorbing fillers, in which case the particle groups are respectively conductive particle groups, heat conductive particle groups, and phosphors. It becomes a particle group, a magnetic particle group, and an electromagnetic wave absorbing filler particle group. Hereinafter, the heat conductive particles, the phosphor, the magnetic particles, and the electromagnetic wave absorbing filler that can be used in the particle group of the present invention will be described in detail.

<Thermally conductive particles>
The heat conductive particles are not particularly limited, but at least one selected from metal particles, boron nitride, aluminum nitride, silicon nitride, beryllium oxide, magnesium oxide, zinc oxide, and aluminum oxide in view of the heat conductivity. Of these, metal particles, boron nitride, aluminum nitride, aluminum oxide, and magnesium oxide are preferable.

Examples of the metal particles include gold, silver, copper, palladium, aluminum, nickel, iron, titanium, manganese, zinc, tungsten, platinum, lead, tin, and other simple metals, or solder, steel, stainless steel, and other alloys. And preferably silver, copper, aluminum, nickel, iron, titanium, tungsten, solder, steel, and stainless steel. Each of these may be used alone or in combination of two or more.

The shape of the heat conductive particles is not particularly limited, and examples thereof include spheres, scales, flakes, needles, rods, and ellipses, among which spherical, scales, ellipses, rods are preferable, and spheres, Scale-like and elliptical shapes are more preferable.

<Phosphor>
Either an inorganic phosphor or an organic phosphor can be used as the phosphor, and a complexed organic phosphor can also be used as the organic phosphor. An inorganic phosphor is preferable from the viewpoint of reliability such as heat resistance of the phosphor.

As the inorganic phosphor, it is possible to use, for example, one that absorbs light from a semiconductor light emitting diode having a nitride-based semiconductor as a light emitting layer and converts the light into light of a different wavelength. Examples of such inorganic phosphors include nitride phosphors and oxynitride phosphors that are mainly activated by lanthanoid-based elements such as Eu and Ce; lanthanoid-based elements such as Eu and transition metals such as Mn. Alkaline earth metal halogen apatite phosphors, alkaline earth metal borate halogen phosphors, alkaline earth metal aluminate phosphors, alkaline earth metal silicate phosphors, alkaline earth metals which are mainly activated by system elements Metal sulfide phosphors, rare earth sulfide phosphors, alkaline earth metal thiogallate phosphors, alkaline earth metal silicon nitride phosphors, germanate phosphors; rare earth aluminates mainly activated by lanthanoid series elements such as Ce Examples thereof include salt phosphors, rare earth silicate phosphors, and Ca—Al—Si—O—N oxynitride glass phosphors that are mainly activated by lanthanoid elements such as Eu. These inorganic phosphors may be used alone or in combination of two or more. The following inorganic phosphors can be given as specific examples, but the invention is not limited thereto.

Nitride-based phosphors that are mainly activated by lanthanoid-based elements such as Eu and Ce include M ₂ Si ₅ N ₈ :Eu, MSi ₇ N ₁₀ :Eu, M _1.8 Si ₅ O _0.2 N ₈ :Eu, M _0.9 Si ₇ O _0.1 N ₁₀ :Eu (M is at least one selected from Sr, Ca, Ba, Mg, and Zn) and the like.

As the oxynitride-based phosphor that is mainly activated by lanthanoid-based elements such as Eu and Ce, MSi ₂ O ₂ N ₂ :Eu (M is one selected from Sr, Ca, Ba, Mg, and Zn) These are the above) and the like.

As an alkaline earth metal halogen apatite phosphor mainly activated by a lanthanoid-based element such as Eu and a transition metal-based element such as Mn, M ₅ (PO ₄ ) ₃ X:Z (M is Sr, Ca, Ba) , And Mg, X is at least one selected from F, Cl, Br, and I, and Z is at least one selected from Eu, Mn, and Eu and Mn. There is) and the like.

Examples of the alkaline earth metal borate halogen phosphor that is mainly activated by a lanthanoid element such as Eu and a transition metal element such as Mn include M ₂ B ₅ O ₉ X:Z (M is Sr, Ca, Ba). , And Mg, X is at least one selected from F, Cl, Br, and I, and Z is at least one selected from Eu, Mn, and Eu and Mn. There is) and the like.

Lanthanoid element such as Eu, alkaline earth metal aluminate phosphor which is mainly activated by transition metal elements such as Mn _{is, SrAl 2 O 4: Z,} Sr 4 Al 14 O 25: Z, CaAl 2 _{O 4: Z, BaMg 2 Al} 16 O 27: Z, BaMg 2 Al 16 O 12: Z, BaMgAl 10 O 17: Z (Z is Eu, Mn, and one or more selected from Eu and Mn) Can be exemplified.

Alkaline earth metal silicate phosphors mainly activated by lanthanoid elements such as Eu and transition metal elements such as Mn include (BaMg)Si ₂ O ₅ :Eu and (BaSrCa) ₂ SiO ₄ :Eu. , Etc. can be illustrated.

Examples of the alkaline earth metal sulfide phosphor that is mainly activated by a lanthanoid-based element such as Eu and a transition metal-based element such as Mn include (Ba, Sr, Ca)(Al, Ga)2S4; Eu and the like. ..

La ₂ O ₂ S:Eu, Y ₂ O ₂ S:Eu, Gd ₂ O ₂ S: are rare earth sulfide phosphors mainly activated by lanthanoid elements such as Eu and transition metal elements such as Mn. Examples thereof include Eu.

Examples of alkaline earth metal thiogallate phosphors that are mainly activated by lanthanoid elements such as Eu and transition metal elements such as Mn include MGa ₂ S ₄ :Eu (M is Sr, Ca, Ba, Mg, Zn). And the like).

Alkaline earth metal silicon nitride phosphors mainly activated by lanthanoid elements such as Eu and transition metal elements such as Mn include (Ca,Sr,Ba)AlSiN3:Eu,(Ca,Sr,Ba)2Si5N8. :Eu, SrAlSi4N7:Eu, etc. can be exemplified.

Examples of the germanate phosphor that is mainly activated by a lanthanoid-based element such as Eu and a transition-metal-based element such as Mn include Zn ₂ GeO ₄ :Mn.

Examples of rare earth aluminate phosphors that are mainly activated by lanthanoid elements such as Ce include Y ₃ Al ₅ O ₁₂ :Ce, (Y _0.8 Gd _0.2 ) ₃ Al ₅ O ₁₂ :Ce, Y _{3 (Al 0.8 Ga 0.2) 5 O} 12: Ce, (Y, Gd) 3 (Al, Ga) etc. _{5 O 12,} etc. YAG phosphor of the exemplified. Further, Tb ₃ Al ₅ O ₁₂ :Ce, Lu ₃ Al ₅ O ₁₂ :Ce, etc., in which part or all of Y is substituted with Tb, Lu, etc., can also be used.

Examples of rare earth silicate phosphors that are mainly activated by lanthanoid elements such as Ce include Y ₂ SiO ₅ :Ce, Tb.

The Ca-Al-SiO-N-based oxynitride glass phosphor, by mol%, 20-50 mol% in terms of CaCO ₃ to CaO, the _Al 2 _{O 3} 0 to 30 mol%, SiO As the base material of oxynitride glass containing 25 to 60 mol% of AlN, 5 to 50 mol% of AlN, 0.1 to 20 mol% of rare earth oxide or transition metal oxide, and 100 mol% of five components in total. It is a phosphor. The phosphor containing oxynitride glass as a base material preferably has a nitrogen content of 15% by mass or less. Further, in addition to the rare earth oxide ion, it is preferable to contain other rare earth element ion serving as a sensitizer in the state of the rare earth oxide, and the phosphor is co-activated with a content in the range of 0.1 to 10 mol %. It is preferable to include it as an agent.

Other examples of the inorganic phosphor include ZnS:Eu. Examples of silicate-based phosphors other than the above include (BaSrMg) ₃ Si ₂ O ₇ :Pb, (BaMgSrZnCa) ₃ Si ₂ O ₇ :Pb, Zn ₂ SiO ₄ :Mn, and BaSi ₂ O ₅ :Pb. Be done.

In addition, in the above inorganic phosphor, instead of Eu or in addition to Eu, one or more selected from Tb, Cu, Ag, Au, Cr, Nd, Dy, Co, Ni, and Ti is included. Can also be used.

Further, phosphors other than the above-mentioned inorganic phosphors can be used as the particles of the present invention as long as they have the same performance and effect as those described above.

The property of the above-mentioned inorganic phosphor is not particularly limited, and powdery one can be used, for example. Further, the shape of the inorganic phosphor powder is not particularly limited, and examples thereof include spherical, scale-like, flake-like, needle-like, rod-like, and elliptical shapes, among which spherical, scale-like, and flake-like are preferable, The spherical shape and the flake shape are more preferable.

As the organic phosphor, for example, an organic phosphor or an organic complex phosphor that is mainly activated by a lanthanoid-based element such as Eu can be used, and a 9,10-diarylanthracene derivative, pyrene, coronene, and perylene can be used. , Rubrene, 1,1,4,4-tetraphenylbutadiene, tris(8-quinolinolato)aluminum complex, tris(4-methyl-8-quinolinolato)aluminum complex, bis(8-quinolinolato)zinc complex, tris(4- Methyl-5-trifluoromethyl-8-quinolinolato) aluminum complex, tris(4-methyl-5-cyano-8-quinolinolato)aluminum complex, bis(2-methyl-5-trifluoromethyl-8-quinolinolato) [4 -(4-Cyanophenyl)phenolate]aluminum complex, bis(2-methyl-5-cyano-8-quinolinolato)[4-(4-cyanophenyl)phenolato]aluminum complex, tris(8-quinolinolato)scandium complex, bis [8-(para-tosyl)aminoquinoline]zinc complex and cadmium complex, 1,2,3,4-tetraphenylcyclopentadiene, pentaphenylcyclopentadiene, poly[2,5-diheptyloxy-p-phenylenevinylene] , Coumarin-based phosphor, perylene-based phosphor, pyran-based phosphor, anthuron-based phosphor, porphyrin-based phosphor, quinacridone-based phosphor, N,N'-dialkyl-substituted quinacridone-based phosphor, naphthalimide-based phosphor, N , N′-diaryl-substituted pyrrolopyrrole-based phosphors, phosphorescent luminescent materials such as Ir complexes, and the like can be used.

<Magnetic particles>
As magnetic particles, simple ferromagnetic metals such as iron, cobalt and nickel, stainless steel, magnetic stainless steel (Fe-Cr-Al-Si alloy), sendust (Fe-Si-Al alloy), permalloy (Fe-Ni alloy), Silicon copper (Fe-Cu-Si alloy), Fe-Si alloy, Fe-Si-B (-Cu-Nb) alloy, Fe-Si-Cr-Ni alloy, Fe-Si-Cr alloy, Fe-Si-Al Magnetic metal alloys such as —Ni—Cr alloys, metal oxides such as hematite (Fe ₂ O ₃ ), magnetite (Fe ₃ O ₄ ), Mn—Zn ferrites, Ni—Zn ferrites, Mg—Mn ferrites, Ferrites such as Zr-Mn-based ferrite, Ti-Mn-based ferrite, Mn-Zn-Cu-based ferrite, barium ferrite, and strontium ferrite are preferably used.

The shape of the magnetic particles is not particularly limited, and examples thereof include spherical shape, scale shape, flake shape needle shape, rod shape, elliptical shape, and porous shape, among which spherical shape, scale shape, elliptical shape, flake shape, and porous shape. Are preferred, and spherical, scale-like, flake-like, and porous are more preferable.

In the case of obtaining porous magnetic particles, it can be obtained by adding a pore adjusting agent such as calcium carbonate during granulation, granulating and firing. Further, a complicated void can be formed inside the ferrite by adding a material that inhibits particle growth during the ferrite formation reaction. Examples of such a material include tantalum oxide and zirconium oxide.

<Electromagnetic wave absorption filler>
As the electromagnetic wave absorbing filler, conductive loss, dielectric loss electromagnetic wave absorbing material typified by carbon particles, ferrite, and magnetic loss electromagnetic wave absorbing material typified by soft magnetic metal powder can be applied.

As the conductive particles, metal particles, conductive metal oxide particles, particles made of a conductive polymer, particles coated with a metal and the like can be used.

Examples of metal particles include gold, silver, copper, palladium, aluminum, nickel, iron, titanium, manganese, zinc, tungsten, platinum, lead, tin, and other simple metals, or solder, steel, stainless steel, and other alloys. Can be mentioned. Each of these may be used alone or in combination of two or more.

As the metal oxide-based particles, particles made of conductive metal oxides such as zinc oxide, indium oxide, and tin oxide can be used. Each of these may be used alone or in combination of two or more.

Examples of particles made of a conductive polymer include polyacetylene particles, polythiophene particles, polyacetylene particles, polypyrrole particles, and particles having their surfaces coated.

As an example of the metal-coated particles, resin particles such as acrylic resin or epoxy resin whose surface is coated with metal, or inorganic particles such as glass or ceramic whose surface is coated with metal may be used. The metal coating method on the surface is not particularly limited, and examples thereof include electroless plating and sputtering.

Here, examples of the metal that coats the surface of the particles include gold, silver, copper, iron, nickel, and aluminum.

As the dielectric loss electromagnetic wave absorber, carbon black, acetylene black, Ketjen black, graphite, carbon nanotube, graphene, fullerene, carbon nanocoil, carbon microcoil, carbon fiber and the like can be used.

As the soft magnetic alloy powder, those containing an iron element are preferable from the viewpoints of supply stability, price, etc., and particularly those containing 15 mass% or more of an iron element are preferable. Examples of such soft magnetic alloy powder include carbonyl iron, electrolytic iron, Fe-Cr alloy, Fe-Si alloy, Fe-Ni alloy, Fe-Al alloy, Fe-Co alloy, Fe- alloy. Examples include, but are not limited to, Al-Si alloys, Fe-Cr-Si alloys, Fe-Cr-Al alloys, Fe-Si-Ni alloys, and Fe-Si-Cr-Ni alloys. Not a thing. These soft magnetic metal powders may be used alone or in combination of two or more. The shape of the soft magnetic alloy powder may be either a flat shape or a particle shape, or both may be used in combination.

Specific examples of the ferrite powder include spinel type ferrites such as Mg—Zn based ferrite, Ni—Zn based ferrite, and Mn—Zn based ferrite, Ba ₂ Co ₂ Fe ₁₂ O ₂₂ , Ba ₂ Ni ₂ Fe ₁₂ O ₂₂ , _{Ba 2 Zn 2 Fe 12 O 22} , Ba 2 Mn 2 Fe 12 O 22, Ba 2 Mg 2 Fe 12 O 22, Ba 2 Cu 2 Fe 12 O 22, Ba 3 ferro box planar, such as Co _{2 Fe} 24 _{O 41} ( (Y type, Z type) type hexagonal ferrite, BaFe ₁₂ O ₁₉ , SrFe ₁₂ O ₁₉ and/or BaFe ₁₂ O ₁₉ , SrFe ₁₂ O ₁₉ Fe elements are Ti, Co, Mn, Cu, Zn, Ni and Mg. A magneplanbite (M type) type hexagonal ferrite having a basic composition of a substituted one can be used, but the present invention is not limited thereto. These ferrite powders may be used alone or in combination of two or more.

[Anisotropic film]
Further, the anisotropic film of the present invention, as described above, by selecting the type of particles contained in the particle group, for example, a conductive film, a heat conductive film, a phosphor film, a magnetic film, an electromagnetic wave absorption film, It can be a reflector film or a hollow film. Hereinafter, the anisotropic film of the present invention will be described in detail with respect to an embodiment of an anisotropic conductive film. This embodiment includes a heat conductive film, a phosphor film, a magnetic film, an electromagnetic wave absorbing film, a reflector film, and a hollow. It can also be applied to films and the like.

[Anisotropic conductive film]
In the anisotropic conductive film 10 of the present invention, the conductive particle groups 2 are regularly arranged, and the interval A thereof is 1 μm to 1,000 μm, preferably 3 to 800 μm, more preferably 5 to 500 μm, and further preferably Is 10 to 100 μm. If they are not arranged at the intervals A in this range, it becomes difficult to secure the electrical conductivity in the thickness direction T and the insulating property in the surface direction without any defects.

The thickness T of the anisotropic conductive film 10 is preferably 1 μm to 2000 μm, more preferably 1 μm to 500 μm, and further preferably 10 μm to 300 μm. Within this range, the influence of the difference in CTE between the insulating resin 1 portion and the conductive particle group 2 is small, and the chip does not easily come off, which is preferable.

In addition, the thickness of the conductive particle group 2 is determined by the thickness T of the anisotropic conductive film 10, and the thickness of the conductive particle group 2 with respect to the thickness T of the anisotropic conductive film 10. Is preferably 50% to 150%, and more preferably 70% to 100%. When the thickness of the conductive particle group 2 is in this range, it becomes easy to secure electric conduction when the electrode is pressed from above the completed anisotropic conductive film 10.

Further, the conductive particle group 2 is preferably exposed on at least one surface of the anisotropic conductive film 10. The thickness of the conductive particle group 2 is 100% of the thickness T of the anisotropic conductive film 10, which means that the conductive particle group 2 is exposed on both surfaces of the anisotropic conductive film 10. That is, it means that it penetrates. By exposing the conductive particle group 2 on at least one surface, conduction can be secured without thermocompression-bonding the anisotropic conductive film 10 with a large force, which is preferable. The conductive particle group 2 is an anisotropic conductive film. More preferably, it penetrates 10.

At this time, the area ratio of the exposed particle group on at least one surface is more preferably 20 to 90%. Within this range, the anisotropic film can reliably exhibit its intended function while maintaining high flexibility.

Further, it is preferable that the difference in linear expansion coefficient between the insulating resin and the particle group in the range of -50°C to 200°C is 1 to 200 ppm/K.

Such a difference in linear expansion coefficient makes it more difficult for the electronic component to separate from the anisotropic film even when the temperature changes.

Further, the anisotropic conductive film 10 of the present invention may be provided with a resin film having releasability with respect to the insulating resin 1. The resin film having releasability is optimized depending on the type of the insulating resin 1, but specifically, a fluorine resin-coated PET (polyethylene terephthalate) film, a silicone resin-coated PET film, and a PTFE (polytetrafluoroethylene) film. Examples thereof include fluororesin films such as fluoroethylene), ETFE (ethylene-tetrafluoroethylene), and CTFE (chlorotrifluoroethylene). The resin film having the releasability facilitates the handling of the anisotropic conductive film 10 and prevents foreign matter such as dust from adhering thereto.

As a method for producing the anisotropic conductive film 10 of the present invention, for example, after the binder 3 and the conductive particles 4 are uniformly mixed to prepare a conductive composition, an uneven pattern is formed as in Examples described later. A conductive particle group 2 is formed by filling a mold such as a silicon wafer substrate thus prepared with this conductive composition. Then, the conductive particle group 2 is transferred and pressed onto the film-shaped insulating resin 1. In this way, the anisotropic conductive film 10 can be manufactured.

Since the step of burying the particle group in the insulating resin is included, the hardness of the particle group is preferably equal to or higher than the hardness of the insulating resin. Thereby, the particle group can be embedded in the insulating film while maintaining its shape. The hardness of the particle group measured in accordance with the method described in JIS K 6253-3:2012 in the embedding step is preferably durometer type A20 or more, and more preferably durometer type A40 to type D50. preferable. The hardness of the insulating resin at this time is preferably durometer type E60 or more, and more preferably durometer type E80 to type D30.

In addition, the hardness measured according to the method described in JIS K 6253-3:2012 after curing (that is, when using an anisotropic film) is preferably in the following range. That is, the hardness of the binder is preferably durometer type A30 or more, and more preferably durometer type D40 to D95. The hardness of the particle group is preferably durometer type A30 or more, and more preferably durometer type D40 to D95. The hardness of the insulating resin is preferably durometer type A20 or more, and more preferably durometer type D30 to D90.

In addition, as a method of using the anisotropic conductive film 10 of the present invention, when a resin film having releasability is disposed, it is peeled off, and then, between the wiring board electrode portion and the semiconductor electrode portion. Anisotropic conductivity can be obtained by sandwiching the anisotropic conductive film 10 and thermocompression bonding. The temperature for heating is preferably 100°C to 300°C, more preferably 120°C to 250°C, and further preferably 150°C to 200°C. The pressure at the time of pressure bonding is preferably 0.01 MPa to 100 MPa, more preferably 0.05 MPa to 80 MPa, and further preferably 0.1 MPa to 50 MPa.

The storage elastic modulus of the conductive particle group 2 at the thermocompression bonding temperature is preferably 0.7 times or more, and more preferably 1.0 times or more the storage elastic modulus of the anisotropic conductive film 10. Within this range, the viscosity of the insulating resin 1 is reduced by heating, and it becomes easy to press the electrode portion of the semiconductor against the electrode portion of the wiring board by applying pressure. In the case of the conductive particles 4 that can be sintered at a low temperature, the conductive particles 4 are sintered by heating, and stable conduction can be obtained.

After obtaining the conductive state, the insulating resin 1 of the anisotropic conductive film 10 is cured by further heating and curing. As the curing conditions, heating at 100 to 300°C for 0.5 to 5 hours is preferable, and heating at 150 to 250°C for 1 to 4 hours is more preferable.

Hereinafter, the present invention will be described in more detail by showing synthetic examples, examples and comparative examples, but the present invention is not limited to the following examples.

In the following examples, the weight average molecular weight is a weight average molecular weight using polystyrene as a standard substance by gel permeation chromatography (GPC) measured under the following conditions. In the following synthesis example, Me is a methyl group, Ph is a phenyl group, and Vi is a vinyl group.

[Measurement condition]
Developing solvent: THF (tetrahydrofuran)
Flow rate: 0.6 mL/min
Detector: Differential refractive index detector (RI)
Column: TSK Guardcollom SuperH-L
TSKgel Super H4000 (6.0 mm ID x 15 cm x 1)
TSKgel Super H3000 (6.0 mm ID x 15 cm x 1)
TSKgel Super H2000 (6.0 mm ID x 15 cm x 2)
(All made by Tosoh Corporation)
Column temperature: 40°C
Sample injection volume: 20 μL (THF solution with a concentration of 0.5% by mass)

Synthesis of insulating resin [Synthesis example 1]
Synthesis of alkenyl group-containing organopolysiloxane 1142.1 g (87.1 mol%) phenyltrichlorosilane, 529 g (3.2 mol%) ClMe ₂ SiO(Me ₂ SiO) ₃₃ SiMe ₂ Cl, and 72.4 g (9 mol) dimethylvinylchlorosilane. 0.7 mol%) was dissolved in a toluene solvent, dropped into water, cohydrolyzed, further neutralized by washing with water and alkali, dehydrated, and then the solvent was distilled off under reduced pressure to give a solid at 25° C. and a softening point of 45. Thus, a phenyl group-containing vinyl silicone resin A1 having a temperature of ℃ was obtained. The weight average molecular weight was 63,000. As a result of analyzing the obtained silicone resin A1, the following structural formula was obtained.
(In the formula, dimethylsiloxy units are shown to have a continuous block structure)
It was found to be a silicone resin represented by.

[Synthesis example 2]
Synthesis of organohydrogenpolysiloxane 1142.1 g (87.1 mol%) of phenyltrichlorosilane, 529 g (3.2 mol%) of ClMe ₂ SiO(Me ₂ SiO) ₃₃ SiMe ₂ Cl, and 69 g (9.7 mol%) of methyldichlorosilane. ) Is dissolved in a toluene solvent, added dropwise to water, co-hydrolyzed, further washed with water, neutralized by alkali washing, dehydrated, and then the solvent is distilled off under reduced pressure to give a solid at 25° C. A group-containing hydrogen silicone resin A2 was obtained. The weight average molecular weight was 58,000. As a result of analyzing the obtained silicone resin A2, the following structural formula was obtained.
(In the formula, dimethylsiloxy units are shown to have a continuous block structure)
It was found to be a silicone resin represented by.

[Synthesis example 3]
Synthesis of Bismaleimide To 196 g of acetone, 144 g (1.0 mol) of 1,8-diaminooctane and 196 g (2.0 mol) of maleic anhydride were added and stirred at room temperature for 3 hours. Acetone was distilled off under reduced pressure from the resulting solution at 50° C., 82 g (1.0 mol) of sodium acetate and 204 g (2.0 mol) of acetic anhydride were added, and the mixture was stirred at 80° C. for 1 hour. Then, after adding 500 g of toluene, further washing with water and dehydration, the solvent was distilled off under reduced pressure to obtain α,ω-bismaleimide octane A3 having a softening point of 25° C. and a softening point of 80° C.

Preparation of composition (paste) [Preparation Example 1]
10 g of the vinyl silicone resin A1 synthesized in Synthesis Example 1, 10 g of the hydrogen silicone resin A2 synthesized in Synthesis Example 2, platinum (0)-1,3-divinyltetramethyldisiloxane complex (platinum concentration 1% by mass) 0 0.2 mg, ethynylcyclohexanol 60 mg, toluene 10 g, and silver filler (average particle size 1.5 μm) 120 g were mixed to prepare a silver paste 1.

[Preparation Example 2]
A copper paste was prepared by mixing 10 g of α,ω-bismaleimide octane A3 synthesized in Synthesis Example 3, 5 g of toluene, and 100 g of a copper filler (average particle size 1.5 μm).

[Preparation Example 3]
Epoxy resin (jER-1256, manufactured by Mitsubishi Chemical Corporation) 10 g, cyclohexanone 20 g, and silver nanofiller (average particle size 20 nm) 30 g were mixed to prepare silver paste 2.

[Preparation Example 4]
Epoxy resin (jER-1256, manufactured by Mitsubishi Chemical Corporation) 10 g, cyclohexanone 20 g, silver filler (average particle size 5 μm) 80 g, and silver nanofiller (average particle size 20 nm) 10 g were mixed to prepare silver paste 3.

[Preparation Example 5]
BMI-1500 (Designer Molecules Inc.) 10 g, toluene 5 g, and aluminum nitride (average particle size 2 μm) 80 g were mixed to prepare a heat conductive particle paste.

[Preparation Example 6]
10 g of the vinyl silicone resin A1 synthesized in Synthesis Example 1, 10 g of the hydrogen silicone resin A2 synthesized in Synthesis Example 2, platinum (0)-1,3-divinyltetramethyldisiloxane complex (platinum concentration 1% by mass) 0 .2 mg, ethynylcyclohexanol 60 mg, toluene 10 g, and yellow phosphor YAG (manufactured by Mitsubishi Chemical Corporation, average particle diameter 2 μm) were mixed to prepare a yellow phosphor paste.

[Preparation Example 7]
10 g of the vinyl silicone resin A1 synthesized in Synthesis Example 1, 10 g of the hydrogen silicone resin A2 synthesized in Synthesis Example 2, platinum (0)-1,3-divinyltetramethyldisiloxane complex (platinum concentration 1% by mass) 0 .2 mg, ethynylcyclohexanol 60 mg, toluene 10 g, and red phosphor CASN (manufactured by Mitsubishi Chemical Corporation, average particle diameter 2 μm) 20 g were mixed to prepare a red phosphor paste. Further, a green phosphor paste was prepared by changing the CASN to a green phosphor β-SIALON (manufactured by Mitsubishi Chemical Corporation, average particle diameter 3 μm). Furthermore, the blue phosphor paste was prepared by changing the CASN to the blue phosphor SBCA (manufactured by Mitsubishi Chemical Corporation, average particle size 2 μm).

[Preparation Example 8]
BMI-3000 (manufactured by Designer Moleculars Inc.) 10 g, toluene 5 g, and Fe-Cr-Al-Si alloy (average particle size 4 μm) 80 g were mixed to prepare a magnetic particle paste.

[Preparation Example 9]
BMI-5000 (manufactured by Designer Molecules Inc.) 10 g, toluene 5 g, and Ba ₂ Co ₂ Fe ₁₂ O ₂₂ ferrite (average particle size 6 μm) 80 g were mixed to prepare an electromagnetic wave absorbing particle paste.

Production of anisotropic conductive film [Example 1]
100 g of the vinyl silicone resin A1 synthesized in Synthesis Example 1, 100 g of the hydrogen silicone resin A2 synthesized in Synthesis Example 2, platinum (0)-1,3-divinyltetramethyldisiloxane complex (platinum concentration 1% by mass) 2 mg , 600 mg of ethynylcyclohexanol and 100 g of toluene were mixed to prepare an organopolysiloxane composition. Using an automatic coating device PI-1210 (manufactured by Tester Sangyo Co., Ltd.), the organopolysiloxane composition was applied onto an ETFE (ethylene-tetrafluoroethylene) film, and the length was 150 mm×width 150 mm and thickness 40 μm. Was formed into a film having Then, toluene was volatilized by heating at 100° C. for 30 minutes to prepare a solid uncured silicone resin film having a length of 150 mm×a width of 150 mm and a thickness of 30 μm at 25° C. In addition, an oxide film is formed on a silicon wafer base material, and by using a well-known photolithography method, a concavo-convex pattern in which one side of a square convex pattern has a length of 30 μm, a height of 30 μm, and an interval of 30 μm is formed. Molding silicone rubber KE-12 (manufactured by Shin-Etsu Chemical Co., Ltd.) is poured and cured, and a concave pattern opposite to the silicon wafer base material has a side length of 30 μm, a height of 30 μm, and an interval of 30 μm. A patterned silicone mold was made. The silver paste 1 prepared in Preparation Example 1 was squeegeeed in a silicone mold recess and dried to form silver particle groups, which were transferred onto the uncured silicone resin film at 60° C. (FIG. 3). Then, the uncured silicone resin film is hot-pressed at 100° C. for 5 minutes to press the silver particle group into the uncured silicone resin film (FIG. 4), the film thickness is 30 μm, and the silver particle group is one side long. An uncured anisotropic conductive film regularly arranged with a thickness of 30 μm, a thickness of 30 μm, and an interval of 30 μm was manufactured (FIG. 2). The theoretical average number of particles was about 1900, the particle group was a quadrangular prism, and the area ratio of the lower surface to the area of the upper surface was about 1. It should be noted that FIG. 4-2 is an enlarged view of FIG. 4, but it can be seen that the manufactured anisotropic conductive film is embedded in the insulating film while the conductive particle group maintains its shape. ..

[Example 2]
By the same method as in Example 1, the organopolysiloxane composition was formed into a film having a length of 150 mm×a width of 150 mm and a thickness of 300 μm. Then, toluene was volatilized by heating at 100° C. for 30 minutes to prepare a solid uncured silicone resin film having a length of 150 mm×a width of 150 mm×a thickness of 200 μm at 25° C. In the same manner as in Example 1, a silicone mold having a concave-convex pattern with one side having a length of 80 μm, a height of 100 μm, and an interval of 80 μm was produced. The copper paste prepared in Preparation Example 2 was squeegeeed in the recesses of the silicone mold and dried to form copper particle groups, which were transferred onto the uncured silicone resin film at 60°C. Then, the uncured silicone resin film is hot pressed at 100° C. for 5 minutes to push the copper particle group into the uncured silicone resin film, the film thickness is 200 μm, the copper particle group has a side length of 80 μm, and a thickness of 80 μm. An uncured anisotropic conductive film regularly arranged with a length of 100 μm and an interval of 80 μm was manufactured (FIG. 5). The theoretical average number of particles was about 45,000, the particle group was a quadrangular prism, and the area ratio of the lower surface to the area of the upper surface was about 1.

[Example 3]
A maleimide resin composition was prepared by mixing 100 g of α,ω-bismaleimide octane A3 synthesized in Synthesis Example 3, 1 g of t-butylbenzoyl peroxide and 100 g of xylene. In the same manner as in Example 1, the maleimide resin composition was formed into a film having a length of 150 mm×width of 150 mm×thickness of 20 μm. Then, xylene was volatilized by heating at 110° C. for 30 minutes, and a solid uncured maleimide resin film having a length of 150 mm×a width of 150 mm×a thickness of 10 μm was prepared at 25° C. In the same manner as in Example 1, a silicone mold having a concave-convex pattern with one side having a length of 5 μm, a height of 5 μm, and an interval of 5 μm was produced. The silver paste 2 prepared in Preparation Example 3 was squeegeeed in the silicone-type recesses and dried to form silver particle groups, which were transferred onto the uncured maleimide resin film at 80°C. Then, by pressing the uncured maleimide resin film at 100° C. for 5 minutes, the silver particle groups are pushed into the uncured maleimide resin film, the film thickness is 10 μm, and the silver particle groups have a side length of 5 μm. An uncured anisotropic conductive film regularly arranged with a thickness of 5 μm and a spacing of 5 μm was produced (FIG. 6). The theoretical average number of particles was about 4×10 ⁶ , the particle group was a quadrangular prism, and the area ratio of the lower surface to the area of the upper surface was about 1.

[Example 4]
Epoxy resin jER-1256B40 (Mitsubishi Chemical Co., Ltd., 40 mass% methyl ethyl ketone [MEK] solution) 100 g, jER-828EL (Mitsubishi Chemical Co., Ltd.) 40 g, 2-ethyl-4-methylimidazole 0.8 g, MEK 40 g Were mixed to prepare an epoxy resin composition. By the same method as in Example 1, the epoxy resin composition was molded into a film having a length of 150 mm, a width of 150 mm, and a thickness of 200 μm. Then, MEK was volatilized by heating at 40° C. for 30 minutes, and a solid uncured epoxy resin film having a length of 150 mm×a width of 150 mm×a thickness of 100 μm was prepared at 25° C. In the same manner as in Example 1, a silicone mold having a concavo-convex pattern in which one side of the concave pattern had a length of 80 μm, a height of 80 μm, and an interval of 80 μm was produced. The silver paste 3 prepared in Preparation Example 4 was squeegeeed in the concave portion of the silicone mold and dried to form a group of silver particles, which was transferred onto the uncured epoxy resin film at 30°C. Then, by pressing the uncured epoxy resin film at 50° C. for 5 minutes, the silver particle group is pushed into the uncured epoxy resin film, the film thickness is 100 μm, and the silver particle group has a side length of 80 μm. An uncured anisotropic conductive film regularly arranged with a thickness of 80 μm and a gap of 80 μm was manufactured (FIG. 7). The theoretical average number of particles was about 1000, the particle group was a quadrangular prism, and the area ratio of the lower surface to the area of the upper surface was about 1.

[Example 5]
Epoxy resin jER-1256B40 (Mitsubishi Chemical Co., Ltd., 40 mass% methyl ethyl ketone [MEK] solution) 100 g, jER-828EL (Mitsubishi Chemical Co., Ltd.) 40 g, 2-ethyl-4-methylimidazole 0.8 g, MEK 100 g Were mixed to prepare an epoxy resin composition. The epoxy resin composition was formed into a film having a length of 150 mm×a width of 150 mm×a thickness of 10 μm by the same method as in Example 1. After that, MEK was volatilized by heating at 40° C. for 30 minutes, and a solid uncured epoxy resin film having a length of 150 mm×a width of 150 mm×a thickness of 3 μm was prepared at 25° C. In the same manner as in Example 1, a silicone mold having a concave-convex pattern with one side of the concave pattern having a length of 1 μm, a height of 2 μm, and an interval of 1.5 μm was produced. The silver paste 2 prepared in Preparation Example 3 was squeegeeed in the concave portion of the silicone mold and dried to form a group of silver particles, which was transferred onto the uncured epoxy resin film at 30°C. Then, by pressing the uncured epoxy resin film at 50° C. for 5 minutes, the silver particle group is pushed into the uncured epoxy resin film, the film thickness is 3 μm, and the silver particle group has a side length of 1 μm. An uncured anisotropic conductive film regularly arranged with a thickness of 2 μm and an interval of 1.5 μm was manufactured (FIG. 8). The theoretical average number of particles was about 60,000, and the particle group was a quadrangular prism, and the area ratio of the lower surface to the area of the upper surface was about 1.

[Example 6]
A maleimide resin composition was prepared by mixing 100 g of α,ω-bismaleimide octane A3 synthesized in Synthesis Example 3 and 1 g of t-butylbenzoyl peroxide while heating at 50°C. In the same manner as in Example 1, while heating the maleimide resin composition at 50° C., it was formed into a film having a length of 150 mm×width of 150 mm×thickness of 500 μm and cooled to give a solid uncured solid at 25° C. A maleimide resin film was produced. In the same manner as in Example 1, a silicone mold having a concave-convex pattern with one side having a length of 1,000 μm, a height of 500 μm, and an interval of 1,000 μm was produced. The copper paste prepared in Preparation Example 2 was squeegeeed in the concave portion of the silicone mold and dried to form copper particle groups, which were transferred onto the uncured maleimide resin film at 80°C. Thereafter, the uncured maleimide resin film is hot pressed at 100° C. for 5 minutes to push the copper particle group into the uncured maleimide resin film, the film thickness is 500 μm, and the copper particle group has a side length of 1 An uncured anisotropic conductive film regularly arranged with a thickness of 1,000 μm, a thickness of 500 μm, and a distance of 1,000 μm was manufactured (FIG. 9). The theoretical average number of particles was about 3×10 ⁷ , the particle group was a quadrangular prism, and the area ratio of the lower surface to the area of the upper surface was about 1.

[Example 7]
By the same method as in Example 1, the organopolysiloxane composition was formed into a film having a length of 150 mm×width of 150 mm and a thickness of 900 μm. Then, the toluene was volatilized by heating at 100° C. for 30 minutes, and a solid uncured silicone resin film having a length of 150 mm×a width of 150 mm×a thickness of 600 μm was prepared at 25° C. In the same manner as in Example 1, a silicone mold having a concave-convex pattern with one side having a length of 500 μm, a height of 500 μm, and an interval of 500 μm was produced. The silver paste 1 prepared in Preparation Example 1 was squeegeeed in the concave portion of the silicone mold and dried to form a silver particle group, which was transferred onto the uncured silicone resin film at 60°C. Then, the uncured silicone resin film is hot-pressed at 100° C. for 5 minutes to press the silver particle group into the uncured silicone resin film, the film thickness is 600 μm, the silver particle group has a side length of 500 μm, and a thickness of 500 μm. An uncured anisotropic conductive film regularly arranged with a length of 500 μm and a spacing of 500 μm was manufactured (FIG. 10). The theoretical average number of particles was about 9×10 ⁶ , the particle group was a quadrangular prism, and the area ratio of the lower surface to the area of the upper surface was about 1.

[Example 8]
A maleimide resin composition was prepared by mixing 80 g of α,ω-bismaleimide octane A3 synthesized in Synthesis Example 3, 1 g of t-butylbenzoyl peroxide and 100 g of xylene. By the same method as in Example 1, the maleimide resin composition was formed into a film having a length of 150 mm×width of 150 mm×thickness of 50 μm. Then, xylene was volatilized by heating at 110° C. for 30 minutes to prepare a solid uncured maleimide resin film having a length of 150 mm×a width of 150 mm×a thickness of 20 μm at 25° C. In the same manner as in Example 1, a silicone mold having a concave-convex pattern with one side having a length of 5 μm, a height of 5 μm, and an interval of 5 μm was produced. The silver paste 2 prepared in Preparation Example 3 was squeegeeed in the silicone-type recesses and dried to form silver particle groups, which were transferred onto the uncured maleimide resin film at 80°C. Then, the film is hot-pressed at 100° C. for 5 minutes to push the silver particle group into the uncured maleimide resin film, the film thickness is 20 μm, the silver particle group has a side length of 5 μm, and a thickness of 5 μm. An uncured anisotropic conductive film having a regular arrangement of 5 μm and a spacing of 5 μm was produced (FIG. 11). The theoretical average number of particles was about 4×10 ⁶ , the particle group was a quadrangular prism, and the area ratio of the lower surface to the area of the upper surface was about 1.

[Example 9]
A maleimide resin composition was prepared by mixing 100 g of BMI-3000J (manufactured by Designer Moleculars Inc.), 1 g of dicumyl peroxide and 100 g of xylene. By the same method as in Example 1, the maleimide resin composition was formed into a film having a length of 150 mm×a width of 150 mm×a thickness of 600 μm. Then, xylene was volatilized by heating at 110° C. for 30 minutes, and a solid uncured maleimide resin film having a length of 150 mm×a width of 150 mm×a thickness of 500 μm was prepared at 25° C. In the same manner as in Example 1, a silicone mold having a concavo-convex pattern in which the longest diagonal of the hexagonal concave pattern was 500 μm, the height was 500 μm, and the interval was 50 μm was produced. The heat conductive particle paste prepared in Preparation Example 5 was squeegeeed in the silicone-type recesses and dried to form heat conductive particle groups, which were transferred onto the uncured maleimide resin film at 80°C. Then, the film is heat-pressed at 100° C. for 5 minutes to push the thermally conductive particle group into the uncured maleimide resin film, the film thickness is 500 μm, and the longest particle of the hexagonal thermally conductive particle group is An uncured anisotropic heat conductive film having a length of 500 μm, a thickness of 500 μm, and a regular arrangement of 50 μm was manufactured (FIG. 12). The theoretical average number of particles was about 2×10 ⁶ , the particle group was hexagonal columnar, and the area ratio of the lower surface to the area of the upper surface was about 1.

[Example 10]
100 g of vinyl silicone resin A1 synthesized in Synthesis Example 1, 100 g of hydrogen silicone resin A2 synthesized in Synthesis Example 2, 200 g of titanium dioxide PF-691 (manufactured by Ishihara Sangyo Co., Ltd.), platinum (0)-1, 2 mg of 3-divinyltetramethyldisiloxane complex (platinum concentration 1% by mass), 600 mg of ethynylcyclohexanol, and 100 g of toluene were mixed to prepare an organopolysiloxane composition. In the same manner as in Example 1, the organopolysiloxane composition was formed into a film having a length of 150 mm×width of 150 mm and a thickness of 50 μm. Then, toluene was volatilized by heating at 100° C. for 30 minutes to prepare a solid uncured silicone resin film having a length of 150 mm×a width of 150 mm×a thickness of 40 μm at 25° C. In the same manner as in Example 1, a silicone mold having a concavo-convex pattern in which one side of the concave pattern had a length of 40 μm, a height of 40 μm, and an interval of 40 μm was produced. The yellow phosphor paste prepared in Preparation Example 6 was squeegeeed in the recesses of the silicone mold and dried to form phosphor particle groups, which were transferred onto the uncured silicone resin film at 60°C. Then, the uncured silicone resin film is hot pressed at 100° C. for 5 minutes to push the phosphor particle group into the uncured silicone resin film, the film thickness is 40 μm, and the side length of the phosphor particle group is 40 μm. An uncured anisotropic phosphor film with a reflector was regularly arranged with a thickness of 40 μm and a spacing of 40 μm (FIG. 13). The theoretical average number of particles was about 1900, the particle group was a quadrangular prism, and the area ratio of the lower surface to the area of the upper surface was about 1.

[Example 11]
A maleimide resin composition was prepared by mixing 100 g of BMI-3000J (manufactured by Designer Moleculars Inc.), 1 g of dicumyl peroxide and 100 g of xylene. In the same manner as in Example 1, the maleimide resin composition was formed into a film having a length of 150 mm×width of 150 mm×thickness of 40 μm. Then, xylene was volatilized by heating at 110° C. for 30 minutes, and a solid uncured maleimide resin film having a length of 150 mm×a width of 150 mm×a thickness of 30 μm was prepared at 25° C. In the same manner as in Example 1, a silicone mold having a concave/convex pattern with one side having a length of 30 μm, a height of 30 μm, and an interval of 150 μm was produced. The red phosphor paste prepared in Preparation Example 7 was squeegeeed in the silicone mold recesses and dried to form red phosphor particle groups, which were transferred onto the uncured maleimide resin film at 80°C. After that, the red phosphor particle group was pressed into the uncured maleimide resin film by hot pressing the film at 100° C. for 5 minutes. Next, the green phosphor paste prepared in Preparation Example 7 is squeegeeed in the silicone-type concave portion and dried to form a green phosphor particle group, which is displaced by 30 μm from the red phosphor particle group, and the uncured maleimide resin is heated at 80° C. Transferred onto film. Then, the green phosphor particle group was pushed into the uncured maleimide resin film by hot pressing the film at 100° C. for 5 minutes. Similarly, the blue phosphor paste prepared in Preparation Example 7 was also shifted by 30 μm and transferred, and was pressed into an uncured maleimide resin film to have a film thickness of 30 μm, a side length of the phosphor particle group of 30 μm, and a thickness. An uncured anisotropic RGB phosphor film in which 30 μm and a phosphor particle group spacing of 30 μm were regularly arranged was manufactured (FIG. 14). The theoretical average number of particles was about 450, the particle group was a quadrangular prism, and the area ratio of the lower surface to the area of the upper surface was about 1.

[Example 12]
A maleimide resin composition was prepared by mixing 100 g of BMI-3000J (manufactured by Designer Moleculars Inc.) and 1 g of dicumyl peroxide. Using the automatic coating device PI-1210 (manufactured by Tester Sangyo Co., Ltd.), the maleimide resin composition was applied onto an ETFE (ethylene-tetrafluoroethylene) film while heating at 100° C., and the length was 150 mm×width. A solid uncured maleimide resin film having a thickness of 150 mm and a thickness of 2000 μm at 25° C. was prepared. In the same manner as in Example 1, a silicone mold having a concavo-convex pattern with a circular concave pattern having a diameter length of 800 μm, a height of 1500 μm, and an interval of 100 μm was produced. The magnetic particle paste prepared in Preparation Example 8 was squeegeeed in the silicone-type recesses and dried to form a group of magnetic particles, which were transferred onto the uncured maleimide resin film at 80°C. Then, the film is hot pressed at 100° C. for 5 minutes to push the magnetic particle group into the uncured maleimide resin film, the film thickness is 2000 μm, the diameter of the magnetic particle group is 800 μm, and the thickness is 1500 μm. An uncured anisotropic magnetic film regularly arrayed at intervals of 100 μm was manufactured (FIG. 15). The theoretical average number of particles was about 3×10 ⁶ , the particle group was columnar, and the area ratio of the lower surface to the area of the upper surface was about 1.

[Example 13]
BMI-3000J (manufactured by Designer Molecules Inc.) 100 g, dicumyl peroxide 1 g, hollow particles Silinax (manufactured by Nittetsu Mining Co., Ltd., particle size 80 to 130 nm) 50 g, xylene 100 g are mixed, and a maleimide resin composition is mixed. The thing was prepared. By the same method as in Example 1, the maleimide resin composition was formed into a film having a length of 150 mm×a width of 150 mm×a thickness of 120 μm. Then, xylene was volatilized by heating at 110° C. for 30 minutes to prepare a solid uncured maleimide resin film having a length of 150 mm×a width of 150 mm×a thickness of 100 μm at 25° C. In the same manner as in Example 1, a silicone mold having a concavo-convex pattern in which the longest diagonal of the hexagonal concave pattern was 200 μm, the height was 100 μm, and the interval was 40 μm was produced. The electromagnetic wave absorbing particle paste prepared in Preparation Example 9 was squeegeeed in the concave portion of the silicone mold and dried to form an electromagnetic wave absorbing particle group, which was transferred onto the uncured maleimide resin film at 80°C. Then, the film is hot pressed at 100° C. for 5 minutes to push the electromagnetic wave absorbing particle group into the uncured maleimide resin film, the film thickness is 100 μm, and the longest interparticle distance of the electromagnetic wave absorbing particle group is long. An uncured hollow particle-containing anisotropic electromagnetic wave absorption film regularly arranged at a thickness of 200 μm, a thickness of 100 μm, and an interval of 40 μm was produced (FIG. 16). The theoretical average number of particles was about 2900, the particle group was hexagonal columnar, and the area ratio of the lower surface to the area of the upper surface was about 1.

[Comparative Example 1]
20 g of the vinyl silicone resin A1 synthesized in Synthesis Example 1, 20 g of the hydrogen silicone resin A2 synthesized in Synthesis Example 2, platinum (0)-1,3-divinyltetramethyldisiloxane complex (platinum concentration 1% by mass) 0 0.2 mg, ethynylcyclohexanol 60 mg, toluene 10 g, and gold-plated conductive fine particles (trade name: Micropearl AU, manufactured by Sekisui Chemical Co., Ltd., average particle size 7.25 μm) 1 g were mixed to give an organopolysiloxane composition. It was made. In the same manner as in Example 1, the organopolysiloxane composition was formed into a film having a length of 150 mm, a width of 150 mm, and a thickness of 10 μm. After that, it is heated at 100° C. for 30 minutes to volatilize the toluene, and is 150 mm long×150 mm wide×8 μm thick, uncured solid at 25° C., the conductive particles do not form conductive particle groups, and are sparse. The uncured conductive film present in Figure 3 was produced (Figure 17).

[Comparative example 2]
10 g of a silver filler (average particle diameter 3 μm) and 3 g of cyclopentanone were mixed to prepare a silver paste containing no binder. In the same manner as in Example 3, an uncured solid maleimide resin film having a length of 150 mm×a width of 150 mm×a thickness of 30 μm was prepared at 25° C. In the same manner as in Example 1, a silicone mold having a concavo-convex pattern in which one side of the concave pattern had a length of 30 μm, a height of 30 μm, and an interval of 30 μm was produced. When the silver paste was squeegeeed in a concave portion of a silicone mold and dried to form a silver particle group and transferred onto the uncured maleimide resin film at 80° C., the silver particle group was transferred in a collapsed state. .. Then, the uncured maleimide resin film is hot pressed at 100° C. for 5 minutes to push the silver particle groups into the uncured maleimide resin film, the film thickness is 30 μm, and the uncured silver particle groups are sparsely present. The electroconductive film of was manufactured (FIG. 18).

[Comparative Example 3]
Epoxy resin jER-1256B40 (manufactured by Mitsubishi Chemical Corporation, 40 mass% methyl ethyl ketone [MEK] solution) 100 g, jER-828EL (manufactured by Mitsubishi Chemical Corporation) 40 g, 2-ethyl-4-methylimidazole 0.8 g, MEK 200 g Were mixed to prepare an epoxy resin composition. By the same method as in Example 1, the epoxy resin composition was formed into a film having a length of 150 mm×a width of 150 mm×a thickness of 5 μm. Then, MEK was volatilized by heating at 40° C. for 30 minutes, and a solid uncured epoxy resin film having a length of 150 mm×a width of 150 mm×a thickness of 2 μm was prepared at 25° C. In the same manner as in Example 1, a silicone mold having a concave-convex pattern with one side having a length of 1 μm, a height of 1 μm, and an interval of 0.5 μm was produced. The silver paste 3 prepared in Preparation Example 4 was squeegeeed in the concave portion of the silicone mold and dried to form a silver particle group, which was transferred onto the uncured epoxy resin film at 30° C. It has stuck (Fig. 19).

[Comparative Example 4]
By the same method as in Example 1, the organopolysiloxane composition was formed into a film having a length of 150 mm×a width of 150 mm and a thickness of 300 μm. Then, toluene was volatilized by heating at 100° C. for 30 minutes to prepare a solid uncured silicone resin film having a length of 150 mm×a width of 150 mm×a thickness of 200 μm at 25° C. In the same manner as in Example 1, a silicone mold having a concavo-convex pattern in which one side of the concave pattern had a length of 1,200 μm, a height of 200 μm, and an interval of 1,200 μm was produced. The silver paste 1 prepared in Preparation Example 1 was squeegeeed in the concave portion of the silicone mold and dried to form a silver particle group, which was transferred onto the uncured silicone resin film at 60°C. Then, the uncured silicone resin film is hot pressed at 100° C. for 5 minutes to press the silver particle group into the uncured silicone resin film, the film thickness is 200 μm, and the silver particle group has a side length of 1,200 μm. An uncured anisotropic conductive film having a thickness of 200 μm and a regular interval of 1,200 μm was manufactured (FIG. 20). The theoretical average number of particles was about 2×10 ⁷ , the particle group was a quadrangular prism, and the area ratio of the lower surface to the area of the upper surface was about 1.

[Electrical test]
The uncured anisotropic conductive films produced in Examples 1 to 8 and Comparative Examples 1 to 4 were attached to the electrodes of the substrate, and 200 μm in Examples 1, 2, 4 and Comparative Examples 1 and 2 thereon. Flip-chip LEDs of ×200 μm and thickness of 50 μm, 20 μm×50 μm and flip-chip LEDs of thickness of 10 μm in Examples 3, 5, 8 and Comparative Example 3, and 2,000 μm in Examples 6, 7 and Comparative Example 4. A flip-chip LED having a size of 3,000 μm and a thickness of 300 μm was pressed by a pick-and-place method, and main curing was performed at 180° C. for 2 hours to prepare a test body. The test body was energized and the number of lights was measured. The results are shown in Table 1.

[Thermal shock test]
Twenty of the test pieces after the energization test were subjected to a thermal shock test at -40°C to 120°C 1,000 times, and then the energization test was performed again to count the number of lights. The results are shown in Table 1.

As shown in Table 1, the anisotropic conductive film of the present invention, unlike the conventional anisotropic conductive film, can ensure electric conduction without causing a short even to a semiconductor device having fine electrodes, Further, it is possible to secure the electricity even after the thermal shock test.

Unlike Comparative Examples 1 and 2, in the anisotropic conductive films of Examples 1 to 8, conductive particle groups containing conductive particles bound with a binder are formed. Further, unlike Comparative Examples 3 and 4, these conductive particle groups are regularly arranged within a range of 1 μm to 1,000 μm.
From the above, it has been clarified that the anisotropic conductive film of the present invention having the above characteristics can electrically connect circuit electrodes having extremely fine patterns to each other and has high reliability.
Furthermore, since it is an anisotropic film having a fine pattern due to particle groups, as shown in Examples 9 to 13, an anisotropic heat conductive film, an anisotropic phosphor film, an anisotropic magnetic film, an anisotropic film. It can be seen that it is applicable to various applications such as a strong electromagnetic wave absorption film.

The present invention is not limited to the above embodiment. The above-described embodiment is merely an example, and the invention having substantially the same configuration as the technical idea described in the scope of claims of the present invention and exhibiting the same action and effect is the present invention It is included in the technical scope of.

1... Insulating resin, 2... Conductive particle group, 3... Binder, 4... Conductive particle,
1a... uncured silicone film, 2a... silver particle group,
5... ETFE (ethylene-tetrafluoroethylene) film 10... Anisotropic conductive film, A... Interval between adjacent conductive particle groups,
T... Thickness of anisotropic conductive film.

Claims (26)

An anisotropic film containing an insulating resin and a particle group, wherein the particle group is a group of particles in which a plurality of particles are bound by a binder, and the particle group is regularly arranged. And an interval thereof is 1 μm to 1,000 μm. The anisotropic film according to claim 1, wherein the difference in linear expansion coefficient between the insulating resin and the particle group in the range of -50°C to 200°C is 1 to 200 ppm/K. The anisotropic film according to claim 1, wherein the binder is a resin composition having the same composition as the insulating resin. The anisotropic film according to claim 1 or 2, wherein the binder is a resin composition having a composition different from that of the insulating resin. The said particle|grain is a conductive particle, and the said particle group is a conductive particle group, The anisotropic film as described in any one of Claim 1 to 4 characterized by the above-mentioned. The anisotropic film according to claim 1, wherein the particles are heat conductive particles, and the particle group is a heat conductive particle group. The said particle|grain is a fluorescent substance, and the said particle group is a fluorescent substance particle group, The anisotropic film as described in any one of Claim 1 to 4 characterized by the above-mentioned. The anisotropic film according to any one of claims 1 to 4, wherein the particles are magnetic particles and the particle group is a magnetic particle group. The said particle|grains are electromagnetic wave absorption fillers, and the said particle group is an electromagnetic wave absorption filler particle group, The anisotropic film as described in any one of Claim 1 to 4 characterized by the above-mentioned. The anisotropic film according to any one of claims 1 to 9, wherein the anisotropic film has a thickness of 1 µm to 2000 µm. The average particle diameter of the particles is 0.01 to 100 μm as a median diameter measured by a laser diffraction type particle size distribution measuring device. Anisotropic film. The anisotropic film according to any one of claims 1 to 11, wherein the particle group has a width of 1 to 1000 µm. 13. The anisotropic film according to claim 1, wherein the width of the particle group is 5 times or more the average particle size of the particles. The anisotropic film according to any one of claims 1 to 13, wherein the theoretical average particle number of the particle group is 50 to 1 × 10 ⁹ . The anisotropic film according to any one of claims 1 to 14, wherein the shape of the particle group is columnar or prismatic. The anisotropic film according to any one of claims 1 to 15, wherein the ratio of the area of the lower surface to the area of the upper surface of the particle group is 0.5 to 10. The thickness of the said particle group is 50% or more of the thickness of the said anisotropic film, The anisotropic film as described in any one of Claim 1 to 16 characterized by the above-mentioned. The anisotropic film according to any one of claims 1 to 17, wherein the particle group is exposed on at least one surface of the anisotropic film. The anisotropic film according to claim 18, wherein an area ratio of the exposed particle groups on the at least one surface is 20 to 90%. The anisotropic film according to any one of claims 1 to 19, wherein the insulating resin has a plastic solid or semi-solid state at 25°C in an uncured state. The anisotropic film according to any one of claims 1 to 20, wherein the particles include metal particles. 22. The anisotropic film according to claim 1, wherein the insulating resin contains insulating inorganic particles. The anisotropic film according to claim 22, wherein the insulating inorganic particles are white pigments. The anisotropic film according to any one of claims 1 to 23, wherein the insulating resin contains hollow particles. The anisotropic film according to any one of claims 1 to 24, wherein the cured product of the insulating resin has a relative dielectric constant of 3.5 or less at 10 GHz. 26. The anisotropic film is any one of a conductive film, a heat conductive film, a phosphor film, a magnetic film, an electromagnetic wave absorption film, a reflector film, and a hollow film. An anisotropic film according to any one of 1.