JPWO2016204182A1 - Thermosetting resin composition, cured product, resin sheet, sealing structure and manufacturing method thereof, and electronic component device and manufacturing method thereof - Google Patents

Abstract

Containing first particles having at least one selected from the group consisting of a monosulfide group, a multisulfide group and a thiol group on the surface, and second particles having an unsaturated double bond on the surface, A thermosetting resin composition in which one particle contains an inorganic material.

Description

  The present invention relates to a thermosetting resin composition, a cured product, a resin sheet, a sealing structure, a manufacturing method thereof, an electronic component device, and a manufacturing method thereof.

  In portable electronic devices such as smartphones and tablet PCs that have been increasing in recent years, lightness, thinness, and price reduction are remarkable. Electronic component devices (semiconductor devices and the like) used in such portable electronic devices are required to be reduced in size and cost as well as in size.

  Many new mounting methods have been proposed in order to reduce the size and thickness of electronic component devices (such as semiconductor devices) and reduce costs. For example, after rearranging a semiconductor element produced by dividing a semiconductor wafer into pieces having an appropriate interval, the semiconductor element is sealed with a resin sealing material (sealing resin) using a compression mold apparatus, Development of a mounting method in which a terminal for external connection is provided also in a sealing portion that is outside a semiconductor element, and a semiconductor device manufactured by this mounting method are under development. This mounting method eliminates the need for a package substrate, making it possible to reduce the thickness of the semiconductor device, increase the number of semiconductor elements to be rearranged, and reduce the cost by enlarging the area to be sealed at once. (For example, see Patent Documents 1 to 4 below).

  For example, a semiconductor element used in an electronic device is sealed by molding using a liquid or solid resin sealing material. However, in the mounting method as described above, a small amount of resin sealing material is uniformly and It is necessary to supply a large area. However, the liquid resin sealing material has high viscosity, and it is difficult to supply a small amount of resin sealing material uniformly and quickly over a large area. In addition to the above-described problems, the powdered or granular solid resin sealing material may cause contamination of the device due to dust generated from the resin sealing material.

Japanese Patent No. 3616615 JP 2001-244372 A Japanese Patent Laid-Open No. 2001-127095 US Patent Application Publication No. 2007/205513

  In the sealing step of the above-described method, an electronic component (semiconductor element or the like) is supported on the carrier using a tape or the like that can be temporarily fixed to a carrier such as stainless steel, silicon, or glass. Thereafter, the electronic component is removed from the temporarily fixable tape or the like, and a terminal for external connection is produced using a sealed body like a substrate. However, for cured products (molded products, etc.) of resin encapsulants, there is a problem that problems such as cracks occur during handling or after the sealing process, and in particular, cured products (molded products, etc.) The occurrence of such a problem is remarkable when it is thin and has a large area.

  This invention is made | formed in view of the said situation, and it aims at providing the thermosetting resin composition which can obtain the hardened | cured material which is hard to crack, and its hardened | cured material. Moreover, this invention aims at providing the resin sheet using the said thermosetting resin composition, the sealing structure, its manufacturing method, an electronic component apparatus, and its manufacturing method.

  The present inventors investigated in detail the relationship between the ease of cracking of a cured product (molded product or the like) and the filler filling amount. As a result, since it becomes easy to crack as the filling amount of the filler increases, the present inventors start from the place where the fillers are in contact with each other without the resin in the cured product (molded product, etc.). It was estimated that cracking occurred. Therefore, the inventors of the present invention have thought that by causing the fillers to be chemically bonded to each other, the crack starting point does not occur even in a portion where the fillers are in contact with each other without using a resin. As a result of intensive studies based on this point of view, the present thermosetting resin composition includes an inorganic material and at least selected from the group consisting of a monosulfide group, a multisulfide group, and a thiol group. It has been found that the above problem can be solved by using together the first particles having one kind on the surface and the second particles having an unsaturated double bond on the surface, and based on this finding, the present invention has been completed. It was.

  The present invention contains a first particle having on the surface at least one selected from the group consisting of a monosulfide group, a multisulfide group and a thiol group, and a second particle having an unsaturated double bond on the surface. And the thermosetting resin composition in which said 1st particle | grain contains an inorganic material is provided.

  According to the thermosetting resin composition according to the present invention, it is possible to obtain a cured product (molded product or the like) that is difficult to break. When the monosulfide group, multisulfide group or thiol group of the first particle reacts with the unsaturated double bond of the second particle, the first particles are chemically bonded to each other via the second particle. By bonding, it is considered that cracking of the cured product (molded product or the like) is suppressed. According to the thermosetting resin composition of the present invention, it is possible to suppress cracking of the molded product after the sealing molding of the object to be sealed.

  The first particle may have a structure derived from a silane coupling agent having at least one selected from the group consisting of a monosulfide group, a multisulfide group, and a thiol group on the surface. The silane coupling agent may contain bis (triethoxysilylpropyl) tetrasulfide, and may contain 3-mercaptopropyltriethoxysilane. The inorganic material may contain silica or alumina.

  The second particles may include a resin material having an unsaturated double bond. The resin material may contain a compound having a structure derived from at least one selected from the group consisting of butadiene and isoprene.

  The second particles include an inorganic material and may have a structure derived from a silane coupling agent having an unsaturated double bond on the surface.

  The content of the first particles is preferably 50% by volume or more based on the total amount of the first particles and the second particles.

  It is preferable that the thermosetting resin composition according to the present invention is an embodiment further containing an epoxy resin and a curing agent, or an embodiment further containing an epoxy resin, a curing agent and a curing accelerator. The total content of the epoxy resin that is liquid at 25 ° C. and the curing agent that is liquid at 25 ° C. is preferably 30 to 80% by mass based on the total amount of the epoxy resin and the curing agent.

  As the resin sealing material, a film-like insulating material can be used. The film-like resin encapsulant can supply a small amount of resin encapsulant uniformly and over a large area by adjusting the film thickness, and the film-like resin encapsulant is cut in advance to the desired dimensions. This makes it possible to supply quickly. From such a viewpoint, the thermosetting resin composition according to the present invention may be in the form of a film. The thickness of the film-like thermosetting resin composition is preferably 10 to 1000 μm. The content of the organic solvent in the film-like thermosetting resin composition is preferably 0.2 to 1.5% by mass.

  The present invention provides a cured product of the thermosetting resin composition.

  The present invention provides a resin sheet comprising a support and a thermosetting resin composition layer disposed on the support, wherein the thermosetting resin composition layer includes the thermosetting resin composition. provide.

  The present invention includes a sealed body and a sealing portion that seals at least a part of the sealed body, and the sealing portion includes the thermosetting resin composition or a cured product thereof. A sealing structure is provided. The present invention comprises a step of forming a sealing part that seals at least a part of an object to be sealed, and the sealing part includes the thermosetting resin composition or a cured product thereof. A manufacturing method is provided.

  The present invention includes a step of embedding at least a part of the electronic component in the thermosetting resin composition by pressing the thermosetting resin composition onto the electronic component under heating, and the thermosetting resin composition A method of manufacturing an electronic component device is provided, comprising: a step of curing the components. The present invention includes an electronic component and a sealing portion that seals at least a part of the electronic component, and the sealing portion includes the thermosetting resin composition or a cured product thereof. I will provide a. In the electronic component device and the manufacturing method thereof according to the present invention, the electronic component may be a semiconductor element.

  ADVANTAGE OF THE INVENTION According to this invention, the thermosetting resin composition which can obtain the hardened | cured material which is hard to break, and its hardened | cured material can be provided. Moreover, according to this invention, the resin sheet using the said thermosetting resin composition, the sealing structure, its manufacturing method, an electronic component apparatus, and its manufacturing method can be provided.

  The thermosetting resin composition according to the present invention can be suitably used for sealing a semiconductor element (device), embedding an electronic component disposed on a printed wiring board, and the like. Furthermore, the thermosetting resin composition according to the present invention can be suitably used for embedding a previously formed copper wiring or the like. Further, the thermosetting resin composition according to the present invention can be suitably used for molding methods (laminate, press, etc.) that do not require a mold in addition to being suitably used for molding.

  ADVANTAGE OF THE INVENTION According to this invention, the application of the thermosetting resin composition as a sealing material can be provided. ADVANTAGE OF THE INVENTION According to this invention, the application of the thermosetting resin composition to sealing of an electronic component can be provided. ADVANTAGE OF THE INVENTION According to this invention, the application of the thermosetting resin composition to sealing of a semiconductor element (device) can be provided. ADVANTAGE OF THE INVENTION According to this invention, the application of the thermosetting resin composition to embedding of the previously formed copper wiring etc. can be provided. ADVANTAGE OF THE INVENTION According to this invention, the application of the thermosetting resin composition to embedding of the electronic component arrange | positioned at the printed wiring board can be provided. According to the present invention, application of a thermosetting resin composition to molding can be provided. ADVANTAGE OF THE INVENTION According to this invention, the application of the thermosetting resin composition to the shaping | molding methods (laminate, press, etc.) which do not require a metal mold | die can be provided.

It is a figure for demonstrating the effect which suppresses a crack. It is a figure for demonstrating the effect which suppresses a crack.

  Hereinafter, embodiments for carrying out the present invention will be described in detail.

  In addition, in this specification, the numerical range shown using "to" shows the range which includes the numerical value described before and behind "to" as a minimum value and a maximum value, respectively. In the numerical ranges described stepwise in this specification, the upper limit value or the lower limit value of a numerical range in a certain step may be replaced with the upper limit value or the lower limit value of a numerical range in another step. In the numerical range described in this specification, the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples. Further, the amount of each component in the composition means the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition.

  In the present specification, “a compound that is liquid at 25 ° C.” (for example, a thermosetting resin that is liquid at 25 ° C. (such as an epoxy resin) and a curing agent that is liquid at 25 ° C.) is an E-type viscosity. It refers to a compound having a viscosity at 25 ° C. of 400 Pa · s or less as measured by a meter.

<Thermosetting resin composition and cured product>
The thermosetting resin composition according to this embodiment includes (A) an inorganic material, and a group consisting of a monosulfide group (monosulfide bond), a multisulfide group (multisulfide bond), and a thiol group (thiol bond). A first particle (hereinafter referred to as “component (A)” in some cases) having at least one kind (sulfide structure and thiol structure) selected from the above, and (B) a second particle having an unsaturated double bond on the surface. Particles (hereinafter referred to as “component (B)” in some cases) are contained as essential components. The thermosetting resin composition according to the present embodiment may be in a liquid form or a film form. The cured product according to the present embodiment is a cured product of the thermosetting resin composition according to the present embodiment.

  The thermosetting resin composition according to the present embodiment (for example, an epoxy resin composition containing an epoxy resin) can suppress cracking after curing (such as after molding) by having the above-described configuration, and is sealed. A body (an electronic component such as a semiconductor element) can be embedded well.

  The ease of cracking of a cured product (molded product or the like) of the thermosetting resin composition according to the present embodiment can be quantitatively evaluated by a bending test of a resin piece produced using the thermosetting resin composition. The larger the breaking energy obtained in the bending test, the harder it is to crack.

  Although it is not clear why the cracking after curing can be suppressed, the inventors presume that the cracking after curing is suppressed due to the following reason. That is, in the conventional thermosetting resin composition, as shown in FIG. 1A, there is a crack C between the filler F and the resin R due to curing shrinkage during curing, load during handling after curing, and the like. May enter. On the other hand, in the thermosetting resin composition according to the present embodiment, as shown in FIG. 1B, the particles A as the component (A) are bonded through the particles B as the component (B). In the resin R, a strong cross-linked structure is formed. Thereby, since a tough cured product can be obtained, the occurrence of cracks due to curing shrinkage during curing, load during handling after curing, and the like are suppressed.

  Particle A and particle B are bonded via a sulfur atom of a monosulfide group, a multisulfide group or a thiol group. For example, when bis (triethoxysilylpropyl) tetrasulfide is used, a structure including a tetrasulfide group is formed on the surface of the particle A as shown in FIG. During thermosetting, as shown in FIG. 2 (b), the tetrasulfide group of the particle A is cleaved, and the sulfur atom and the unsaturated double bond of the particle B react to change the sulfur atom. The particles A and the particles B are bonded to each other to form a crosslinked structure.

  The thermosetting resin composition according to the present embodiment contains first particles containing an inorganic material as the component (A). (A) component has at least 1 sort (s) chosen from the group which consists of a monosulfide group, a multisulfide group, and a thiol group on the surface. Examples of the multisulfide group include a disulfide group (disulfide bond), a trisulfide group (trisulfide bond), a tetrasulfide group (tetrasulfide bond), and other polysulfide groups (polysulfide bond).

  As particles containing inorganic material (hereinafter referred to as “inorganic particles”), conventionally known inorganic particles can be used and are not particularly limited. Examples of the constituent material of the inorganic particles include barium sulfate, barium titanate, silicon oxide (silica), talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide (alumina), aluminum hydroxide, silicon nitride, and aluminum nitride. . As a constituent material of the inorganic particles, silica is preferable from the viewpoint of easily obtaining desired physical properties of a cured product (cured film or the like) since it has a relatively small coefficient of thermal expansion. Examples of inorganic particles containing silica (silica particles) include amorphous silica, crystalline silica, fused silica, and spherical silica. As a constituent material of the inorganic particles, alumina is preferable from the viewpoint of excellent heat dissipation. Alumina has a high thermal conductivity and a low coefficient of thermal expansion. (A) A component may be used individually by 1 type and may use 2 or more types together.

  The content of the inorganic material in the component (A) may be 50% by mass or more, 90% by mass or more, 95% by mass or more, and 98% by mass or more. 99 mass% or more may be sufficient.

  As the component (A), at least one selected from the group consisting of a monosulfide group, a multisulfide group, and a thiol group is used from the viewpoint of easily forming a crosslinked structure by reacting with the unsaturated double bond of the component (B). The inorganic particle processed with the silane coupling agent which has can be used. That is, the component (A) can have a structure derived from a silane coupling agent having at least one selected from the group consisting of a monosulfide group, a multisulfide group, and a thiol group on the surface. A silane coupling agent may be used individually by 1 type, and may use 2 or more types together.

As a silane coupling agent having a sulfide group (at least one selected from the group consisting of a monosulfide group and a multisulfide group), a conventionally known silane coupling agent having a sulfide group can be used and is not particularly limited. Examples of the silane coupling agent having a sulfide group include bis (triethoxysilylpropyl) tetrasulfide and 3-octanoylthio-1-propyltriethoxysilane. A commercially available product may be used as the silane coupling agent having a sulfide group. As a commercial product of a silane coupling agent having a sulfide group, a product name “KBE-846” (bis (triethoxysilylpropyl) tetrasulfide, (C ₂ H ₅ O) ₃ SiC ₃ H, manufactured by Shin-Etsu Chemical Co., Ltd., is available. ₆ S ₄ C ₃ H ₆ Si (OC ₂ H ₅ ) ₃ ), product name “A-LINK599” (3-octanoylthio-1-propyltriethoxysilane, CH ₃ (CH ₂ ) manufactured by Momentive Performance Materials, Inc. ) ₆ C (═O) SCH ₂ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₃ )) and the like.

As a silane coupling agent which has a thiol group, the conventionally well-known silane coupling agent which has a thiol group can be used, It does not specifically limit. Examples of the silane coupling agent having a thiol group include 3-mercaptopropyltriethoxysilane. A commercially available product may be used as the silane coupling agent having a thiol group. As a commercial product of a silane coupling agent having a thiol group, a product name “Z-6920” (3-mercaptopropyltriethoxysilane, HS (CH ₂ ) ₃ Si (OCH ₂ CH ₃ ) manufactured by Toray Dow Corning Co., Ltd. ) ₃ ) and the like.

  The average particle size of the component (A) is that the aggregation of the component (A) is easily suppressed and sufficient dispersion is easy, and a thermosetting resin composition (for example, a film-like thermosetting resin composition). From the viewpoint of easily suppressing the sedimentation of particles in the varnish, the following range is preferable. (A) The minimum of the average particle diameter of a component is from a viewpoint which is easy to suppress the molding defect resulting from the viscosity at the time of shaping | molding of a thermosetting resin composition (for example, film-form thermosetting resin composition) becoming high. The thickness is preferably 0.01 μm or more, more preferably 0.1 μm or more, still more preferably 0.3 μm or more, particularly preferably 1 μm or more, and most preferably 3 μm or more. The upper limit of the average particle diameter of the component (A) is preferably 50 μm or less, more preferably 25 μm or less, still more preferably 10 μm or less, and particularly preferably 7 μm from the viewpoint of easy thin sealing. Or less, and most preferably 5 μm or less. From these viewpoints, the average particle diameter of the component (A) is preferably 0.01 to 50 μm, more preferably 0.1 to 25 μm, still more preferably 0.3 to 10 μm, and particularly preferably. It is 1-7 micrometers, Most preferably, it is 3-5 micrometers. The average particle size of the component (A) can be measured by, for example, a laser diffraction type particle size distribution meter.

  The content of the component (A) is the warpage of the sealing structure (such as an electronic component device such as a semiconductor device) due to the difference in coefficient of thermal expansion between the sealed object (such as an electronic component such as a semiconductor element) and the sealing portion. In the drying process, a crack can occur during the production of a thermosetting resin composition (for example, a film-like thermosetting resin composition such as a film-like epoxy resin composition). In view of this, and from the viewpoint of easily suppressing that the object to be sealed cannot be sufficiently sealed due to an increase in the melt viscosity of the thermosetting resin composition (for example, a film-like thermosetting resin composition). Based on the total amount of the conductive resin composition (excluding the solvent. The total amount including the liquid component excluding the solvent), the following range is preferable. The lower limit of the content of component (A) is preferably 40% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass or more, and particularly preferably 70% by mass or more. The upper limit of the content of component (A) is preferably 95% by mass or less, more preferably 90% by mass or less, and still more preferably 85% by mass or less. From these viewpoints, the content of the component (A) is preferably 40 to 95% by mass or more, more preferably 50 to 95% by mass, still more preferably 60 to 95% by mass, and particularly preferably. 60-90% by weight, very preferably 70-90% by weight, very preferably 70-85% by weight.

  By the way, although the crack of hardened | cured material tends to be reduced by reducing the filling amount of a filler, the thermal expansion coefficient or hardening shrinkage of a thermosetting resin composition (for example, a film-like thermosetting resin composition). May be reduced. On the other hand, according to the thermosetting resin composition according to the present embodiment, cracking of the cured product is suppressed without reducing the filling amount of the filler (component (A)) while suppressing the decrease in the thermal expansion coefficient and the curing shrinkage. Can be suppressed.

  The lower limit of the content of the component (A) is the sum of the components (A) and (B) from the viewpoint of further suppressing cracking of the cured product by easily obtaining chemical bonds via the component (B). It is preferably 30% by volume or more, more preferably 40% by volume or more, and still more preferably 50% by volume or more, based on the amount (total of 100% by volume of component (A) and component (B)). The upper limit of the content of the component (A) is the sum of the component (A) and the component (B) from the viewpoint of further suppressing cracking of the cured product by easily obtaining a chemical bond via the component (B). Based on the amount, it is preferably less than 100% by volume, more preferably 99% by volume or less, still more preferably 95% by volume or less, particularly preferably 90% by volume or less, and most preferably 80% by volume. Or less, very preferably 70% by volume or less, even more preferably 60% by volume or less, and even more preferably 55% by volume or less.

  The thermosetting resin composition according to the present embodiment contains second particles having an unsaturated double bond (unsaturated double bond structure) on the surface as the component (B). In addition to the surface (outermost layer), the component (B) may have an unsaturated double bond inside the particle. Component (B) may be particles obtained by surface modification with a silane coupling agent having an unsaturated double bond (particles having a structure derived from a silane coupling agent having an unsaturated double bond). A core-shell structure having core particles (for example, particles containing an inorganic material) and a shell portion (covering portion) containing a resin having an unsaturated double bond may be provided.

  As the component (B), conventionally known particles can be used and are not particularly limited. (B) As a constituent material of a component, the material (resin material etc.) which has an unsaturated double bond may be used, and the material which does not have an unsaturated double bond may be used. When a material having no unsaturated double bond is used, the unsaturated double bond can be introduced by using a silane coupling agent having an unsaturated double bond. The component (B) may include an inorganic material and may have a structure derived from a silane coupling agent having an unsaturated double bond on the surface.

  (B) As a constituent material of a component, an organic material, an inorganic material, etc. are mentioned. Examples of the organic material include resin materials such as natural rubber, styrene butadiene rubber, isoprene rubber, acrylonitrile butadiene rubber, and ethylene propylene diene rubber. Examples of the inorganic material include barium sulfate, barium titanate, silicon oxide (silica), talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide (alumina), aluminum hydroxide, silicon nitride, and aluminum nitride. (B) A component may be used individually by 1 type and may use 2 or more types together.

  Since the resin material (rubber etc.) has flexibility, when the resin material is used as the component (B), the internal stress generated by the curing shrinkage is relieved (absorbed by the component (B)). Later cracking can be further suppressed. Component (B) includes a compound having a structure derived from at least one selected from the group consisting of butadiene and isoprene as a resin material having an unsaturated double bond from the viewpoint of further suppressing cracking after curing. You may go out.

It does not specifically limit as a silane coupling agent which has an unsaturated double bond, The conventionally well-known silane coupling agent which has an unsaturated double bond can be used. Examples of the silane coupling agent having an unsaturated double bond include vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, and 3-methacryloxypropylmethyldimethoxysilane. A commercially available product may be used as the silane coupling agent having an unsaturated double bond. As a commercial item of the silane coupling agent having an unsaturated double bond, trade name “KBM-1003” (vinyltrimethoxysilane, (CH ₃ O) ₃ SiCH═CH ₂ ) manufactured by Shin-Etsu Chemical Co., Ltd., “ KBE-1003 "(vinyl _{triethoxysilane, (C 2 H 5 O)} 3 SiCH = CH 2), " KBM-1403 "(p- _{styryltrimethoxysilane, (CH 3 O) 3 Si} (C 6 H 4) _CH = CH 2), "KBM-502" (3-methacryloxy propyl methyl dimethoxy _{silane, (CH 3 O) 2 Si} (CH 3) C 3 H 6 OC (= O) C (CH 3) = CH 2 " ) And the like. A silane coupling agent may be used individually by 1 type, and may use 2 or more types together.

  The average particle size of the component (B) is such that the aggregation of the component (B) is easily suppressed and sufficient dispersion is easy, and a thermosetting resin composition (for example, a film-like thermosetting resin composition). From the viewpoint of easily suppressing the sedimentation of particles in the varnish, the following range is preferable. The lower limit of the average particle size of the component (B) is preferably 0.01 μm or more, more preferably 0.1 μm or more, still more preferably 0.3 μm or more, and particularly preferably 0.4 μm or more. Very preferably 0.5 μm or more. The upper limit of the average particle diameter of the component (B) is preferably 50 μm or less, more preferably 25 μm or less, further preferably 10 μm or less, particularly preferably 6 μm or less, and most preferably 3 μm or less. It is very preferably 1 μm or less. From these viewpoints, the average particle size of the component (B) is preferably 0.01 to 50 μm, more preferably 0.1 to 25 μm, still more preferably 0.3 to 10 μm, and particularly preferably. It is 0.4 to 6 μm, very preferably 0.5 to 3 μm, and very preferably 0.5 to 1 μm. (B) The average particle diameter of a component can be measured with particle size distribution analyzers, such as a laser diffraction type, for example.

  From the viewpoint of reducing the thermal expansion coefficient of the resin composition, when the component (B) contains an organic material, the average particle size of the component (B) is smaller than the average particle size of the component (A) (average of the component (A) It is preferable that particle diameter> (average particle diameter of component (B)). In general, particles containing an organic material have high flexibility. Since the highly flexible particles have a high coefficient of thermal expansion, the relationship between the particle diameters is that “(A) component average particle diameter> (B) component average particle diameter”. Since the component (B) easily relaxes the internal stress, the coefficient of thermal expansion of the resin composition can be lowered.

  The content of the component (B) easily suppresses that the object to be sealed cannot be sufficiently sealed due to the viewpoint that the glass transition temperature is easily maintained and the increase in the melt viscosity of the thermosetting resin composition. From the viewpoint, the following range is preferable based on the total amount of the thermosetting resin composition (excluding the solvent. The total amount including the liquid component excluding the solvent). The lower limit of the content of component (B) is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, still more preferably 0.5% by mass or more, and particularly preferably 1 It is at least mass%. (B) The upper limit of content of a component becomes like this. Preferably it is 30 mass% or less, More preferably, it is 20 mass% or less. From these viewpoints, the content of the component (B) is preferably 0.1% by mass or more, more preferably 0.1 to 30% by mass, and still more preferably 0.3 to 30% by mass. Especially preferably, it is 0.5-30 mass%, Most preferably, it is 0.5-20 mass%, Most preferably, it is 1-20 mass%.

  The thermosetting resin composition according to the present embodiment can contain (C) a thermosetting resin (hereinafter sometimes referred to as “component (C)”). In the thermosetting resin composition according to the present embodiment, in order to obtain a cured product (molded product or the like) that is difficult to break after curing (such as after molding), the component (A) and the component (B) are used in combination. Well, the kind of thermosetting resin is not limited.

  Examples of thermosetting resins include epoxy resins, phenol resins, unsaturated imide resins, cyanate resins, isocyanate resins, benzoxazine resins, oxetane resins, amino resins, unsaturated polyester resins, allyl resins, dicyclopentadiene resins, silicones. Examples include resins, triazine resins, and melamine resins. A thermosetting resin may be used individually by 1 type, and may use 2 or more types together.

  As the thermosetting resin, an epoxy resin can be preferably used from the viewpoint of excellent balance of various properties. Although it does not specifically limit as an epoxy resin, The resin which has a 2 or more glycidyl group in 1 molecule is preferable. An epoxy resin may be used individually by 1 type, and may use 2 or more types together.

  As epoxy resins, bisphenol A type epoxy resin, bisphenol AP type epoxy resin, bisphenol AF type epoxy resin, bisphenol B type epoxy resin, bisphenol BP type epoxy resin, bisphenol C type epoxy resin, bisphenol E type epoxy resin, bisphenol F type Epoxy resin, bisphenol G type epoxy resin, bisphenol M type epoxy resin, bisphenol S type epoxy resin, bisphenol P type epoxy resin, bisphenol PH type epoxy resin, bisphenol TMC type epoxy resin, bisphenol Z type epoxy resin, bisphenol S type epoxy resin (Hexanediol bisphenol S diglycidyl ether, etc.), novolac type epoxy resin (cresol novolac type epoxy resin, Enol novolac type epoxy resins, etc.), biphenyl type epoxy resins (biphenyl aralkyl type epoxy resins, etc.), naphthalene type epoxy resins, dicyclopentadiene type epoxy resins (dicyclopentadiene aralkyl type epoxy resins, etc.), bixylenol type epoxy resins (biphenyl). Xylenol diglycidyl ether), heterocyclic epoxy resins (tris (2,3-epoxypropyl) isocyanurate, etc.), hydrogenated bisphenol A type epoxy resins (hydrogenated bisphenol A glycidyl ether, etc.), dibasic acid modifications thereof Examples thereof include diglycidyl ether type epoxy resins; aliphatic epoxy resins; epoxidized products of condensates of phenols and aromatic aldehydes having a phenolic hydroxyl group.

  A commercially available product can be used as the epoxy resin. Commercially available epoxy resins include naphthalene-type epoxies such as EXA4700 (tetrafunctional naphthalene type epoxy resin) and Epicron HP-4032 manufactured by DIC Corporation; NC-7000 (naphthalene skeleton-containing polyfunctional solid epoxy resin) manufactured by Nippon Kayaku Co., Ltd. Resin; Epoxidized product (trisphenol type epoxy resin) of a condensate of phenols and aromatic aldehyde having a phenolic hydroxyl group, such as Nippon Kayaku Co., Ltd. EPPN-502H (trisphenol epoxy resin); DIC Corporation Dicyclopentadiene aralkyl epoxy resin such as Epicron HP-7200H (dicyclopentadiene skeleton-containing polyfunctional solid epoxy resin) manufactured by Nippon Kayaku Co., Ltd .; biphenyl arral such as NC-3000H (biphenyl skeleton-containing polyfunctional solid epoxy resin) Ki Type epoxy resin; cresol novolac type epoxy resin such as Epicron N660 and Epicron N690 manufactured by DIC Corporation, EOCN-104S manufactured by Nippon Kayaku Co., Ltd .; tris (2,3-epoxypropyl) isocyania such as TEPIC manufactured by Nissan Chemical Industries, Ltd. Nurate; Epicron 860 manufactured by DIC Corporation, Epicron 900-IM, Epicron EXA-4816 and Epicron EXA-4822, Araldite AER280 manufactured by Asahi Ciba Co., Ltd., Epototo YD-134 manufactured by Tohto Kasei Co., Ltd. (Nippon Steel & Sumikin Chemical Co., Ltd.) Mitsubishi Chemical Corporation JER834 and JER872, Sumitomo Chemical Co., Ltd. ELA-134, Japan Epoxy Resin Co., Ltd. (Mitsubishi Chemical Corporation) Epicoat 807, 815, 825, 827, 828, 834, 100 , 1004, 1007 and 1009, DER-330, 301 and 361 manufactured by Dow Chemical Company, and YD8125 and YDF8170 manufactured by Tohto Kasei Co., Ltd. (Nippon Steel & Sumikin Chemical Co., Ltd.); JER806 manufactured by Mitsubishi Chemical Corporation Bisphenol F type epoxy resin such as DIC; phenol novolak type epoxy resin such as Epicron N-740 manufactured by DIC Corporation; and aliphatic epoxy resin such as Nadecol DLC301 manufactured by Nagase ChemteX Corporation. These epoxy resins may be used individually by 1 type, and may use 2 or more types together.

  The epoxy resin that is liquid at 25 ° C. is preferably a resin having two or more glycidyl groups in one molecule, more preferably a resin containing a bisphenol skeleton, and bisphenol A, bisphenol B, bisphenol C, bisphenol E, bisphenol F. More preferred is a resin containing a bisphenol G or bisphenol Z skeleton. The epoxy resin that is liquid at 25 ° C. often has a low molecular weight, and when the epoxy resin does not have a phenol skeleton, the epoxy resin tends to be disadvantageous from the viewpoint of heat resistance. Good heat resistance can be obtained because it contains an excellent phenol skeleton.

  The content of the thermosetting resin (epoxy resin etc.) is in the following range based on the total amount of the thermosetting resin composition (epoxy resin composition etc.) from the viewpoint of excellent physical properties of the cured product (cured film etc.). It is preferable that The lower limit of the content of the thermosetting resin is preferably 3% by mass or more, more preferably 4% by mass or more, still more preferably 5% by mass or more, and particularly preferably 7% by mass or more. Most preferably, it is 10 mass% or more. The upper limit of the content of the thermosetting resin is preferably 30% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass or less, and particularly preferably 15% by mass or less. From these viewpoints, the content of the thermosetting resin is preferably 3 to 30% by mass, more preferably 4 to 25% by mass, still more preferably 5 to 20% by mass, and particularly preferably 7%. It is -15 mass%, Most preferably, it is 10-15 mass%.

  The thermosetting resin, if necessary, removes (D) curing agent (excluding compounds corresponding to the components (A) to (C). Hereinafter referred to as “(D) component”) and / or (E) curing acceleration. It can be used in combination with an agent (excluding compounds corresponding to the components (A) to (D), hereinafter referred to as “component (E)”). The thermosetting resin composition according to the present embodiment is a thermosetting resin composition containing (A) component, (B) component, (C) component and (D) component, or (A) component, ( B) component, (C) component, (D) component, and (E) component are preferred thermosetting resin compositions, (A) component, (B) component, epoxy resin and (D) component It is more preferable that it is an epoxy resin composition containing (A) component, (B) component, epoxy resin, (D) component and (E) component.

  At least one of the component (C) and the component (D) can contain a compound that is liquid at 25 ° C. In the thermosetting resin composition according to this embodiment, the lower limit of the total content of the thermosetting resin that is liquid at 25 ° C. and the curing agent that is liquid at 25 ° C. is the thermosetting resin and the curing agent. From the viewpoint of excellent film formability since a sufficient tack of the thermosetting resin composition is easily obtained on the basis of the total amount (total mass) of the above, it is preferably 30% by mass or more, more preferably 40% by mass. It is above, More preferably, it is 50 mass% or more. The upper limit of the total content is preferably 80% by mass or less, more preferably 70% by mass or less, from the viewpoint of excellent glass transition temperature, based on the total amount of the thermosetting resin and the curing agent. More preferably, it is 60 mass% or less. From these viewpoints, the total content is preferably 30 to 80% by mass, more preferably 40 to 70% by mass, and still more preferably based on the total amount of the thermosetting resin and the curing agent. It is 50-60 mass%.

  At least one of the epoxy resin and the curing agent may include a compound that is liquid at 25 ° C. In the thermosetting resin composition according to the present embodiment, the lower limit of the total content of the epoxy resin that is liquid at 25 ° C. and the curing agent that is liquid at 25 ° C. is the total amount of the epoxy resin and the curing agent ( From the viewpoint of excellent film formability because it is easy to obtain a sufficient tack of the thermosetting resin composition on the basis of the total mass), it is preferably 30% by mass or more, more preferably 40% by mass or more, More preferably, it is 50 mass% or more. The upper limit of the total content is preferably 80% by mass or less, more preferably 70% by mass or less, and still more preferably from the viewpoint of excellent glass transition temperature based on the total amount of the epoxy resin and the curing agent. Is 60% by mass or less. From these viewpoints, the total content is preferably 30 to 80% by mass, more preferably 40 to 70% by mass, and even more preferably 50 to 50% by mass based on the total amount of the epoxy resin and the curing agent. 60% by mass.

  Although it does not specifically limit as a hardening | curing agent which is (D) component, The compound which has 2 or more of reactive groups with a glycidyl group in 1 molecule is preferable. (D) As a component, a phenol resin, an acid anhydride, an imidazole compound, an aliphatic amine, and an alicyclic amine are mentioned, for example. (D) A component may be used individually by 1 type and may use 2 or more types together.

  The phenol resin is not particularly limited as long as it is a resin having two or more phenolic hydroxyl groups in one molecule, and a known phenol resin can be used. As phenol resins, resins obtained by condensation or co-condensation of phenols or naphthols and aldehydes under an acidic catalyst, biphenyl skeleton type phenol resins, paraxylylene modified phenol resins, metaxylylene / paraxylylene modified phenol resins, melamine modified Examples include phenol resins, terpene-modified phenol resins, dicyclopentadiene-modified phenol resins, cyclopentadiene-modified phenol resins, polycyclic aromatic ring-modified phenol resins, and xylylene-modified naphthol resins. Examples of the phenols include phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, and the like. Examples of naphthols include α-naphthol, β-naphthol, dihydroxynaphthalene and the like. Examples of aldehydes include formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde and the like. As the phenol resin, for example, a phenol novolac resin can be used.

  A commercial item can be used as a hardening | curing agent. Commercially available phenolic resins include Phenolite LF2882, Phenolite LF2822, Phenolite TD-2090, Phenolite TD-2149, Phenolite VH-4150, and Phenolite VH4170; PAPS- manufactured by Asahi Organic Materials Co., Ltd. PN2 (molecular weight distribution intensive type phenol novolak resin); Mitsui Chemicals Co., Ltd. XLC-LL and XLC-4L; Nippon Steel & Sumikin Chemical Co., Ltd. SN-100, SN-180, SN-300, SN-395 and SN-400; Examples include TrisP-HAP, TrisP-PA, TriP-PHBA, CyRS-PRD4 and MTPC manufactured by Honshu Chemical Industry Co., Ltd .; SK resin HE910-10 manufactured by Air Water Co., Ltd., and the like.

  As a curing agent that is liquid at 25 ° C., a compound having two or more functional groups that react with a glycidyl group in one molecule is preferable. For example, a phenol resin, an acid anhydride, an imidazole compound, an aliphatic amine, and an alicyclic group. Examples include amines. These curing agents may be used alone or in combination of two or more.

  As a phenol resin which is liquid at 25 ° C., a resin containing a bisphenol skeleton is preferable, for example, bisphenols such as bisphenol A, bisphenol F, bisphenol AD and bisphenol S; dihydroxybiphenyls such as 4,4′-dihydroxybiphenyl; Dihydroxyphenyl ethers such as bis (4-hydroxyphenyl) ether; linear alkyl groups, branched alkyl groups, aryl groups, hydroxyalkyl groups, allyl groups, cyclic aliphatic groups, etc. were introduced into the aromatic rings of these phenol skeletons. Resin; a polycyclic bifunctional in which a linear alkyl group, a branched alkyl group, an allyl group, an allyl group having a substituent bonded thereto, a cyclic aliphatic group, or an alkoxycarbonyl group is introduced to the carbon atom in the center of the bisphenol skeleton Phenols are mentioned.

  The content of the component (D) easily prevents the desired physical properties of the cured product (cured film, etc.) from becoming difficult to obtain due to the unreacted component (C) or component (D) remaining. From the point of view, the following range is preferable with respect to 100 parts by mass of component (C) (epoxy resin or the like). (D) Content of a component becomes like this. Preferably it is 50 mass parts or more, More preferably, it is 75 mass parts or more, More preferably, it is 100 mass parts or more. (D) Content of a component becomes like this. Preferably it is 200 mass parts or less, More preferably, it is 150 mass parts or less, More preferably, it is 125 mass parts or less. From these viewpoints, the content of the component (D) is preferably 50 to 200 parts by mass, more preferably 75 to 150 parts by mass, and still more preferably 100 to 125 parts by mass.

  Ratio of equivalent of glycidyl group of epoxy resin to equivalent of functional group reacting with glycidyl group in component (D) ([equivalent of glycidyl group of epoxy resin] / [equivalent of functional group reacting with glycidyl group in curing agent) ]) From the viewpoint of easily preventing the desired physical properties of a cured product (cured film, etc.) from being easily obtained due to the remaining unreacted epoxy resin or component (D). It is preferable that The lower limit of the equivalent ratio is preferably 0.7 or more, more preferably 0.8 or more, and further preferably 0.9 or more. The upper limit of the equivalent ratio is preferably 2.0 or less, more preferably 1.8 or less, and still more preferably 1.7 or less. From these viewpoints, the equivalent ratio is preferably 0.7 to 2.0, more preferably 0.8 to 1.8, and still more preferably 0.9 to 1.7.

  Although it does not restrict | limit especially as a hardening accelerator which is (E) component, An amine type, imidazole type, urea type, or a phosphorus type curing catalyst is preferable. Examples of the amine curing catalyst include 1,8-diazabicyclo [5.4.0] undecene-7, 1,5-diazabicyclo [4.3.0] nonene-5. Examples of the imidazole-based curing catalyst include 2-phenyl-4,5-dihydroxymethylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, and the like. Examples of urea-based curing catalysts include 3-phenyl-1,1-dimethylurea. Examples of the phosphorus-based curing catalyst include triphenylphosphine and its addition reaction product, (4-hydroxyphenyl) diphenylphosphine, bis (4-hydroxyphenyl) phenylphosphine, tris (4-hydroxyphenyl) phosphine, and the like. Among these, imidazole-based curing accelerators are particularly preferable because they are rich in derivatives and easily obtain a desired activation temperature. Examples of the imidazole-based curing accelerator include commercially available products such as 2PHZ-PW and 2P4MZ manufactured by Shikoku Kasei Kogyo Co., Ltd.

  The content of the component (E) is such that a sufficient curing accelerating effect can be easily obtained, a thermosetting resin composition (for example, a film-like thermosetting resin composition such as a film-like epoxy resin composition). It is easy to suppress the progress of curing during the production process or during storage of a thermosetting resin composition (for example, a film-like thermosetting resin composition such as a film-like epoxy resin composition). From the viewpoint of easily preventing cracking of a thermosetting resin composition (for example, a film-like thermosetting resin composition such as a film-like epoxy resin composition) and molding defects associated with an increase in melt viscosity. The total amount (total mass) of the component (C) (epoxy resin, etc.) and the component (D) is preferably in the following range. (E) Content of component becomes like this. Preferably it is 0.01 mass% or more, More preferably, it is 0.1 mass% or more, More preferably, it is 0.2 mass% or more. The content of the component (E) is preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 1.5% by mass or less, and particularly preferably 1% by mass or less. Most preferably, it is 0.5 mass% or less. From these viewpoints, the content of the component (E) is preferably 0.01 to 5% by mass, more preferably 0.1 to 3% by mass, and still more preferably 0.2 to 1.5% by mass. %, Particularly preferably 0.2 to 1% by mass, and very preferably 0.2 to 0.5% by mass.

  The thermosetting resin composition according to the present embodiment may further contain other additives (excluding compounds corresponding to the components (A) to (E)). Such additives include vulcanization accelerators, vulcanization retarders (scorch inhibitors), pigments, dyes, mold release agents, antioxidants, stress relaxation agents, coupling agents, surface tension modifiers, ion exchange. Body, colorant, flame retardant and the like. As the vulcanization accelerator, thiazoles, thioureas, thiurams, dithiocarbamic acids, guanidines and the like can be used. As the vulcanization retarder, thiophthalimides and the like can be used. By using a vulcanization accelerator or a vulcanization retarder, the reaction between the component (A) and the component (B) can be adjusted. However, an additive is not limited to these, The thermosetting resin composition which concerns on this embodiment may contain the various well-known additives in this technical field as needed.

<Film-like thermosetting resin composition and resin sheet>
The thermosetting resin composition or the cured product thereof according to the present embodiment may be in the form of a film (a film-like thermosetting resin composition or a cured product thereof). The film-like thermosetting resin composition according to the present embodiment includes the thermosetting resin composition according to the present embodiment or a cured product thereof. The film-like thermosetting resin composition according to this embodiment can be used for sealing by molding, sealing by a molding method that does not require a mold (laminate, press, etc.), and the like.

  According to the film-like thermosetting resin composition according to this embodiment, even when the encapsulated body is enlarged, it is compared with a liquid or solid (granule, powder, etc.) resin encapsulant. The resin sealing material (sealing resin) can be uniformly supplied onto the object to be sealed, and the object to be sealed can be easily and satisfactorily sealed. In addition, when a resin sealing material that is a granule or powder is used, the resin sealing material becomes a dust generation source, and the device or the clean room may be contaminated. According to the thermosetting resin composition, the size of the sealed molded product can be increased while reducing the problem of dust generation.

  In molding, since a resin sealing material (sealing resin) is molded in a mold, it is necessary to increase the size of the mold in order to increase the size of the sealed molded product. Increasing the size of the mold requires high mold accuracy, which increases the technical difficulty and may significantly increase the mold manufacturing cost. On the other hand, the film-like thermosetting resin composition according to the present embodiment is suitable not only for mold forming, which is a conventional sealing molding method, but also for molding methods that do not require a mold (laminate, press, etc.). Can be used.

  The thickness of the film-like thermosetting resin composition according to the present embodiment is preferably 10 μm or more from the viewpoint of easily preventing the film-like thermosetting resin composition (film-like epoxy resin composition or the like) from cracking, More preferably, it is 25 micrometers or more, More preferably, it is 50 micrometers or more. The thickness of the film-like thermosetting resin composition (film-like epoxy resin composition or the like) according to the present embodiment is preferably 1000 μm or less from the viewpoint of easily suppressing variation in the thickness of the film-like thermosetting resin composition. More preferably, it is 500 micrometers or less, More preferably, it is 300 micrometers or less. From these viewpoints, the thickness of the film-like thermosetting resin composition according to this embodiment is preferably 10 to 1000 μm, more preferably 10 to 500 μm, still more preferably 10 to 300 μm, and particularly preferably. Is 25 to 300 μm, very preferably 50 to 300 μm.

  The film-like thermosetting resin composition according to this embodiment can be obtained, for example, by molding the thermosetting resin composition according to this embodiment or a cured product thereof into a film shape. As a manufacturing method of a film-like thermosetting resin composition, the varnish coating method is preferable from a viewpoint which can control thickness easily. For example, the method for producing a film-like thermosetting resin composition according to the present embodiment uses a varnish obtained by dissolving and dispersing essential components and various optional components used as necessary in a solvent. And a step of obtaining a film-like thermosetting resin composition by heating and drying the coating film.

  In the film-like thermosetting resin composition according to the present embodiment, for example, each compounding component (essential components, various optional components used as necessary) is kneaded with a kneader, a two-roll, a continuous kneader or the like. It can also be obtained by extruding the solid resin composition produced in step 1 into a sheet.

  A conventionally well-known organic solvent can be used as a solvent. Examples of the organic solvent include aliphatic hydrocarbons, aromatic hydrocarbons, terpenes, halogens, esters, ketones, alcohols, aldehydes, and the like. An organic solvent may be used individually by 1 type, and may use 2 or more types together.

  The organic solvent is preferably at least one selected from the group consisting of esters, ketones, and alcohols from the viewpoints of low environmental burden and easy dissolution of the thermosetting resin. The organic solvent is preferably at least one selected from the group consisting of acetone, methyl ethyl ketone and methyl isobutyl ketone from the viewpoint of low volatility at room temperature (25 ° C.) and easy removal during drying.

  The content of the organic solvent in the varnish used for the production of the film-like thermosetting resin composition (film-like epoxy resin composition, etc.) is preferably 2 to 30% by mass, more preferably based on the total amount of the varnish. 5 to 25% by mass. When the content is within such a range, problems such as film cracking can be easily prevented, and a sufficient minimum melt viscosity can be easily obtained. In addition, it is possible to easily prevent problems such as the adhesiveness becoming too strong and the handling property being lowered, and problems such as foaming due to the volatilization of the organic solvent during heat curing.

  The content of the organic solvent in the film-like thermosetting resin composition is preferably in the following range based on the total mass of the film-like thermosetting resin composition. The lower limit of the content of the organic solvent is preferably 0.2% by mass or more, more preferably 0.5% by mass or more, and still more preferably, from the viewpoint of excellent film formability and fluidity during sealing molding. Is 0.8 mass% or more. The upper limit of the content of the organic solvent is preferably 1.5% by mass or less, more preferably 1.3% by mass or less, and still more preferably 1% by mass or less, from the viewpoint of excellent film formability and curability. It is. From these viewpoints, the content of the organic solvent is preferably 0.2 to 1.5% by mass, more preferably 0.5 to 1.3% by mass, and still more preferably 0.8 to 1% by mass. %. The content of the organic solvent in the film-like thermosetting resin composition can be measured by the amount of mass change before and after heating. The content of the organic solvent in the film-like thermosetting resin composition is the sum of the contents of the thermosetting resin that is liquid at 25 ° C. and the curing agent that is liquid at 25 ° C. In the case of 30 to 80% by mass based on the total amount of the curing agent and the curing agent, the above range is preferable. In this case, the more preferable range of the total content of the thermosetting resin that is liquid at 25 ° C. and the curing agent that is liquid at 25 ° C. is as described above.

  In the varnish coating method, a film-like thermosetting resin composition can be produced by heating and drying a coating film obtained by applying varnish to a support by hot air spraying or the like. Although it does not specifically limit as a coating method used for application | coating, A die coat, a comma coat, etc. are mentioned.

  Although it does not specifically limit as a support body, A polymer film, metal foil, etc. are mentioned. Examples of the polymer film include polyolefin films such as polyethylene film and polypropylene film; polyester films such as polyethylene terephthalate film; polyvinyl chloride film; polycarbonate film; acetylcellulose film; polyimide film; polyamide film; . Examples of the metal foil include copper foil and aluminum foil.

  Although the thickness of a support body is not specifically limited, From a viewpoint which is excellent in workability | operativity and drying property, 2-200 micrometers is preferable. With such a thickness, it is possible to easily prevent the problem that the support is cut during coating, and the problem that the support is bent during coating due to the weight of the varnish. Moreover, generation | occurrence | production of the malfunction which prevents the solvent drying in a varnish can be suppressed when using the dryer which hot air sprays from both surfaces of a coating surface and a back surface.

  As the heat drying of the coating film, the coating film can be heated at a temperature of ± 10 ° C. of the boiling point of the organic solvent for a time of 25% or more of the total drying time. Heat drying can be performed in two or more steps with different heating temperatures. In this case, heat drying may be performed from a low temperature, and the heating temperature of the next stage can be set within + 30 ° C. of the heating temperature of the previous stage.

  According to the present embodiment, a support and a thermosetting resin composition layer disposed on the support are provided, and the thermosetting resin composition layer is a thermosetting resin according to the present embodiment. A resin sheet (sealing sheet) containing the composition can be provided. The sealing sheet may further include a protective layer (such as a protective film) on the side opposite to the support side of the thermosetting resin composition layer (film-like thermosetting resin composition). That is, you may arrange | position the protective layers (protective film etc.) for the purpose of protection on the thermosetting resin composition layer (film-like thermosetting resin composition) provided on the support body. By disposing the protective layer, the handling property is further improved, and in the case of winding, it is possible to avoid the problem that the thermosetting resin composition layer (film thermosetting resin composition) sticks to the back surface of the support. it can.

  Although it does not specifically limit as a protective layer, A polymer film, metal foil, etc. are mentioned. Examples of the polymer film include polyolefin films such as polyethylene films and polypropylene films; polyester films such as polyethylene terephthalate films; polyvinyl chloride films; polycarbonate films; acetylcellulose films; Examples of the metal foil include copper foil and aluminum foil.

  The thickness of the protective layer is not particularly limited. From the viewpoint of obtaining a sufficient protective effect, and from the viewpoint of reducing the thickness when the film-like thermosetting resin composition is wound into a roll, ˜100 μm is preferred.

<Sealing structure and manufacturing method thereof>
The sealing structure according to the present embodiment includes an object to be sealed and a sealing part that seals at least a part of the object to be sealed, and the sealing part is a heat according to the embodiment. A curable resin composition or a cured product thereof is included. The manufacturing method of the sealing structure which concerns on this embodiment is equipped with the sealing process which forms the sealing part which seals at least one part of a to-be-sealed body, and the said sealing part is the heat which concerns on this embodiment. A curable resin composition or a cured product thereof is included. An electronic component device etc. are mentioned as a sealing structure. An electronic component etc. are mentioned as a to-be-sealed body.

  The sealing step includes a step of embedding at least a part of the object to be sealed in the thermosetting resin composition by pressing the thermosetting resin composition according to this embodiment against the object to be sealed under heating. You may do it. The sealing step may further include a step of curing the thermosetting resin composition. Part or all of an object to be sealed (such as an electronic component) can be embedded in the thermosetting resin composition.

  The electronic component device according to the present embodiment includes an electronic component and a sealing portion that seals at least a part of the electronic component, and the sealing portion is a thermosetting resin composition according to the present embodiment. (Epoxy resin composition or the like) or a cured product thereof. The electronic component device according to the present embodiment is formed by sealing an electronic component using a thermosetting resin composition (for example, a film-like thermosetting resin composition). A semiconductor element etc. are mentioned as an electronic component. Examples of the electronic component device including the electronic component include a semiconductor device including a semiconductor element.

  The manufacturing method of the electronic component device according to the present embodiment includes a thermosetting resin composition (for example, a film-like thermosetting resin composition) by pressing the thermosetting resin composition against the electronic component under heating, for example. ) And a step of embedding at least a part of the electronic component and a step of curing the thermosetting resin composition to obtain a sealing portion. That is, the manufacturing method of the electronic component device according to the present embodiment is, for example, thermosetting by pressing a thermosetting resin composition (for example, a film-like thermosetting resin composition) on the electronic component under heating. A step of embedding at least a part of the electronic component in the resin composition, and a step of curing the thermosetting resin composition in which the electronic component is embedded to obtain a sealing portion. The method for manufacturing a semiconductor device according to the present embodiment includes, for example, a thermosetting resin composition by pressing a thermosetting resin composition (for example, a film-like thermosetting resin composition) against a semiconductor element under heating. The step of embedding at least a part of the semiconductor element and the step of curing the thermosetting resin composition to obtain a sealing portion are provided in this order.

  As mentioned above, although embodiment of this invention was described, this invention is not limited to embodiment mentioned above, You may change suitably in the range which does not deviate from the meaning.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the scope of the present invention is not limited to these examples.

<Preparation of a film-like thermosetting resin composition>
Example 1
After putting 497.5 g of methyl isobutyl ketone in a 10 L capacity polyethylene container, inorganic particles treated with a silane coupling agent having a sulfide group (component (A), product name manufactured by Admatechs Co., Ltd .: SX-E2 ( 3475 g of particles obtained by treating untreated silica particles) with KBE-846 (product name, manufactured by Shin-Etsu Chemical Co., Ltd., bis (triethoxysilylpropyl) tetrasulfide), average particle size: 5.8 μm), And 25 g of particles having an unsaturated double bond on the surface (component (B), manufactured by JSR Corporation, product name: XSK-500, average particle size: 0.5 μm, styrene butadiene rubber particles) were added. Then, the dispersion liquid containing the silica particle disperse | distributed to methyl isobutyl ketone and the styrene butadiene rubber particle was prepared by stirring using a stirring blade. In this dispersion, bisphenol F type epoxy resin ((C) thermosetting resin, glycidyl group equivalent: 160 g / eq, viscosity (25 ° C.): 2 Pa · s) 500 g, which is liquid at 25 ° C., and 25 ° C. Stirring was performed after adding 500 g of a phenol novolak resin ((D) curing agent, manufactured by Asahi Organic Materials Co., Ltd., product name: PAPS-PN2, phenolic hydroxyl group equivalent: 104 g / eq) that was not liquid. After the bisphenol F-type epoxy resin and the phenol novolak resin are dissolved, (E) imidazole (product name: 2PHZ-PW, 2-phenyl-4,5-dihydroxymethylimidazole) 2 manufactured by Shikoku Kasei Kogyo Co., Ltd. 2 as a curing accelerator .5 g was added. Then, it stirred for 1 hour and prepared the liquid mixture. The mixture was filtered through nylon # 200 mesh (opening 75 μm). The filtrate was collected to obtain a varnish-like thermosetting resin composition. As a result of calculating the density of silica particles as 2.2 g / cm ³ and the density of styrene butadiene rubber particles as 0.94 g / cm ³ , the total amount of the component (A) and the component (B) is used as a reference. The content of was 98.3% by volume, and the content of component (B) was 1.7% by volume.

This varnish-like thermosetting resin composition is applied and dried on a support (polyethylene terephthalate film) having a thickness of 38 μm using a coating machine under the following conditions, and a film-like thermosetting property having a thickness of 100 μm. A resin composition (thermosetting resin layer) was prepared. Then, the sealing sheet was obtained by laminating | stacking a protective film (polyethylene film. Thickness: 50 micrometers) on a film-like thermosetting resin composition.
Coating head method: Comma coater Coating and drying speed: 4 m / min Drying conditions (temperature / furnace length): 110 ° C./3.3 m, 130 ° C./3.3 m, 140 ° C./3.3 m

(Example 2)
A film-like thermosetting resin composition having a thickness of 100 μm was prepared in the same manner as in Example 1 except that the amount of component (A) was changed to 3250 g and the amount of component (B) was changed to 250 g. Produced. Based on the total amount of component (A) and component (B), the content of component (A) was 82.0% by volume, and the content of component (B) was 18.0% by volume.

(Example 3)
A film-like thermosetting resin composition having a thickness of 100 μm was prepared in the same manner as in Example 1 except that the amount of component (A) was changed to 3100 g and the amount of component (B) was changed to 400 g. Produced. Based on the total amount of the component (A) and the component (B), the content of the component (A) was 69.8% by volume, and the content of the component (B) was 30.2% by volume.

Example 4
A film-like thermosetting resin composition having a thickness of 100 μm was prepared in the same manner as in Example 1 except that the amount of component (A) was changed to 2900 g and the amount of component (B) was changed to 600 g. Produced. Based on the total amount of component (A) and component (B), the content of component (A) was 51.6% by volume, and the content of component (B) was 48.4% by volume.

(Example 5)
(A) Thickness by the method similar to Example 1 except having changed the silane coupling agent of the component into Z-6920 (product name, Toray Dow Corning Co., Ltd. product, 3-mercaptopropyltriethoxysilane). A 100 μm film thermosetting resin composition was prepared.

(Example 6)
In addition to changing the amount of component (A) used to 1806 g, inorganic particles treated with a silane coupling agent having an unsaturated double bond (product name: SX-E2 manufactured by Admatechs Co., Ltd.) (Untreated silica particles) was treated with KBM-1003 (product name, manufactured by Shin-Etsu Chemical Co., Ltd., vinyltrimethoxysilane), and the particle size was changed to 1694 g (average particle size: 5.8 μm). Except for the above, a film-like thermosetting resin composition having a thickness of 100 μm was produced in the same manner as in Example 1. Based on the total amount of component (A) and component (B), the content of component (A) was 51.6% by volume, and the content of component (B) was 48.4% by volume.

(Example 7)
Component (A), inorganic particles treated with a silane coupling agent having a sulfide group (product name: DAW-50 (untreated alumina particles) manufactured by Denka Co., Ltd.) and KBE-846 (product name, Shin-Etsu Chemical Co., Ltd.) A film having a thickness of 100 μm was obtained in the same manner as in Example 1 except that the particles obtained by treatment with bis (triethoxysilylpropyl) tetrasulfide) manufactured by Co., Ltd. were changed to 6002 g (average particle size: 5 μm). A thermosetting resin composition was prepared. As a result of calculating the density of the alumina particles as 3.8 g / cm ³ , the content of the component (A) is 98.3% by volume based on the total amount of the component (A) and the component (B), and (B) The component content was 1.7% by volume.

(Comparative Example 1)
(A) Implemented except that the component was changed to inorganic particles (manufactured by Admatechs Co., Ltd., product name: SX-E2 (untreated with silane coupling), average particle size: 5.8 μm, silica particles) instead of component (A). A film-like thermosetting resin composition having a thickness of 100 μm was produced in the same manner as in Example 1.

(Comparative Example 2)
(A) Instead of component, inorganic particles treated with a silane coupling agent having an aminophenyl structure (product name: SX-E2 (untreated silica particles, average particle size: 5.8 μm, manufactured by Admatechs Co., Ltd.) ) Was changed to KBM-573 (product name, particles obtained by treatment with Shin-Etsu Chemical Co., Ltd., N-phenyl-3-aminopropyltrimethoxysilane), and the same as in Example 1 By the method, a film-like thermosetting resin composition having a thickness of 100 μm was produced.

(Comparative Example 3)
A film-like thermosetting resin composition having a thickness of 100 μm was produced in the same manner as in Example 1 except that the amount of the component (A) was changed to 3500 g without using the component (B).

<Evaluation of content of organic solvent in film-like thermosetting resin composition>
The content (volatile content, residual solvent ratio) of the organic solvent in the film-like thermosetting resin composition (thermosetting resin layer) provided on the support was calculated according to the following procedure.

  First, after cutting the sealing sheet into 5 cm square, the protective film was peeled off to obtain a sample. Subsequently, the sample was put in an aluminum cup whose weight was previously measured, and the weight was measured (Measurement A). Next, the sample was heated in an oven at 180 ° C. for 10 minutes while being placed in an aluminum cup, and then cooled to room temperature. And the weight after standing for 10 minutes at room temperature was measured (measurement B).

  A separately prepared support was cut into a 5 cm square, and the weight of the support was measured. Next, using the values of measurement A and measurement B, the weight of the support body alone and the weight of the aluminum cup were subtracted to determine the difference in weight of the film-like epoxy resin composition before and after heating. This difference in weight was obtained as the amount of organic solvent volatilized by heating (the amount of residual solvent in the film-like thermosetting resin composition). And the ratio of the quantity of the organic solvent with respect to the weight of the film-form epoxy resin composition single-piece | unit before a heating was obtained as a residual solvent rate. The measurement results are shown in Tables 1 and 2.

<Evaluation of easy cracking of film-like thermosetting resin composition>
The easiness of cracking of the film-like thermosetting resin composition was quantitatively evaluated by a bending test of a test piece prepared by the following procedure using the film-like thermosetting resin composition. It means that it is hard to crack, so that the fracture | rupture energy obtained by a bending test is large. The breaking energy of the film-like thermosetting resin composition was evaluated by the following procedure using a Tensilon universal material testing machine (RTC-1350A manufactured by Orientec Co., Ltd.).

[Method for preparing specimen]
A center part of a 3 mm thick Naflon sheet (manufactured by Nichias Corporation, product name, polytetrafluoroethylene) was cut into a length of 80 mm and a width of 80 mm to obtain a Naflon sheet having an opening. After a specified amount of a film-like thermosetting resin composition is put into the opening, the upper and lower sides are sandwiched with a 3 mm-thick Naflon sheet and pressed under vacuum (0.1 kPa) at a temperature of 110 ° C. and a pressure of 0.1 MPa for 5 minutes. did. Next, the pressure of the press was returned to normal pressure to obtain a resin plate having a thickness of 3 mm, a length of 80 mm, and a width of 80 mm (a resin plate prepared from a film-like thermosetting resin composition). Thereafter, the resin plate was cured by heating in an oven at 180 ° C. for 2 hours. And it cut | disconnected with width 10mm, length 60mm, and thickness 3mm with the precision cutter, and obtained the test piece.

[Measurement of breaking energy]
Next, the test piece was supported at two fulcrums (distance between fulcrums: 48 mm). A load was applied to the center between the fulcrums with a pressure wedge, and the load (P) when the test piece broke was measured under the following conditions. A load-deflection curve was drawn, and the breaking energy was calculated from the area of the region surrounded by the curve, the vertical axis, and the horizontal axis. The measurement results are shown in Tables 1 and 2.
Load cell: 500kgf (4.90kN)
Crosshead speed: 0.5 mm / min Measuring temperature: 25 ° C

  Tables 1 and 2 show physical property values and the like of the varnish-like thermosetting resin composition and the film-like thermosetting resin composition. The content of the epoxy resin and the curing agent that are liquid at 25 ° C. is a content based on the total amount of the epoxy resin and the curing agent. The “content of the organic solvent in the thermosetting resin layer” is a content based on the total mass of the film-like thermosetting resin composition.

  Example 1 showed a higher breaking energy than Comparative Example 1 in which the component (A) was not used. This is because the sulfide group of the (A) component reacts with the unsaturated double bond of the (B) component, and the network of the (A) component is formed via the (B) component, thereby improving the breaking energy. It is estimated to be. For the same reason, in Example 1, Comparative Example 2 using inorganic particles treated with a silane coupling agent that does not have a binding site with the (B) component, and Comparative Example 3 not using the (B) component. High fracture energy was obtained.

  In Examples 1 to 4, the proportions of the component (A) and the component (B) were different, and the breaking energy increased as the proportion of the component (B) increased. This is because the more the component (B) is, the lower the elastic modulus is because the network of the component (A) via the component (B) is more densely formed and the proportion of the component (B) increases. It is estimated to be.

  The breaking energy of Example 1 is larger than that of Example 5 and Example 6. This is presumed to be due to the difference in reactivity between the component (A) and the component (B).

  The breaking energy of Example 1 is larger than that of Example 7. This is presumed to be due to the lower elastic modulus than alumina particles by using silica particles.

  A, B ... particles, C ... cracks, F ... filler, R ... resin.

Claims (24)

A first particle having on its surface at least one selected from the group consisting of a monosulfide group, a multisulfide group and a thiol group;
A second particle having an unsaturated double bond on its surface,
A thermosetting resin composition in which the first particles include an inorganic material.   The thermosetting according to claim 1, wherein the first particle has a structure derived from a silane coupling agent having at least one selected from the group consisting of a monosulfide group, a multisulfide group, and a thiol group on the surface. Resin composition.   The thermosetting resin composition according to claim 2, wherein the silane coupling agent contains bis (triethoxysilylpropyl) tetrasulfide.   The thermosetting resin composition according to claim 2 or 3, wherein the silane coupling agent contains 3-mercaptopropyltriethoxysilane.   The thermosetting resin composition according to any one of claims 1 to 4, wherein the inorganic material contains silica.   The thermosetting resin composition according to any one of claims 1 to 5, wherein the inorganic material contains alumina.   The thermosetting resin composition according to any one of claims 1 to 6, wherein the second particles include a resin material having an unsaturated double bond.   The thermosetting resin composition according to claim 7, wherein the resin material includes a compound having a structure derived from at least one selected from the group consisting of butadiene and isoprene.   The thermosetting resin according to any one of claims 1 to 6, wherein the second particle includes an inorganic material and has a structure derived from a silane coupling agent having an unsaturated double bond on the surface. Composition.   The thermosetting according to any one of claims 1 to 9, wherein the content of the first particles is 50% by volume or more based on the total amount of the first particles and the second particles. Resin composition.   The thermosetting resin composition according to any one of claims 1 to 10, further comprising an epoxy resin and a curing agent.   The thermosetting resin composition according to claim 11, further comprising a curing accelerator.   12. The total content of an epoxy resin that is liquid at 25 ° C. and a curing agent that is liquid at 25 ° C. is 30 to 80% by mass based on the total amount of the epoxy resin and the curing agent. Or the thermosetting resin composition of 12.   The thermosetting resin composition according to any one of claims 1 to 13, which is in a film form.   The thermosetting resin composition according to claim 14, wherein the thickness is 10 to 1000 μm.   The thermosetting resin composition according to claim 14 or 15, wherein the content of the organic solvent is 0.2 to 1.5 mass%.   Hardened | cured material of the thermosetting resin composition as described in any one of Claims 1-16. A support, and a thermosetting resin composition layer disposed on the support,
The resin sheet in which the said thermosetting resin composition layer contains the thermosetting resin composition as described in any one of Claims 1-16. A sealed body, and a sealing portion that seals at least a part of the sealed body,
The sealing structure in which the said sealing part contains the thermosetting resin composition as described in any one of Claims 1-16, or its hardened | cured material. Including a step of forming a sealing portion that seals at least a part of the object to be sealed;
The manufacturing method of the sealing structure in which the said sealing part contains the thermosetting resin composition as described in any one of Claims 1-16, or its hardened | cured material. A step of embedding at least a part of the electronic component in the thermosetting resin composition by pressing the thermosetting resin composition according to any one of claims 1 to 16 onto the electronic component under heating. ,
The manufacturing method of an electronic component apparatus provided with the process of hardening the said thermosetting resin composition in this order.   The method of manufacturing an electronic component device according to claim 21, wherein the electronic component is a semiconductor element. An electronic component, and a sealing portion that seals at least a part of the electronic component,
The electronic component apparatus in which the said sealing part contains the thermosetting resin composition as described in any one of Claims 1-16, or its hardened | cured material.   The electronic component device according to claim 23, wherein the electronic component is a semiconductor element.

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