JP6717005B2 - Resin composition, cured product, resin film, sealing material and sealing structure - Google Patents

Description

The present invention relates to a resin composition, a cured product, a resin film, a sealing material and a sealing structure.

As electronic devices become lighter, thinner, shorter, and smaller, semiconductor devices are becoming smaller and thinner. A form in which a semiconductor device having almost the same size as a semiconductor element is used, or a form in which a semiconductor device is stacked on a semiconductor device (package on package) is actively used. It is expected that the thickness will be further reduced.

As the miniaturization of semiconductor elements progresses and the number of terminals increases, it becomes difficult to provide all external connection terminals (terminals for external connection) on the semiconductor element. For example, when the external connection terminals are forcibly provided on the semiconductor element, the pitch between the terminals becomes narrow and the terminal height becomes low, which makes it difficult to secure the connection reliability after mounting the semiconductor device. Therefore, many new mounting methods have been proposed in order to realize a smaller and thinner semiconductor device.

For example, a semiconductor element manufactured by dividing a semiconductor wafer into pieces is rearranged so as to have an appropriate interval, and then the semiconductor element is sealed with a liquid or solid resin composition to seal the semiconductor element. A mounting method in which an external connection terminal is further provided on the sealing portion and a semiconductor device manufactured by using the mounting method have been proposed (for example, see Patent Documents 1 to 4 below).

Japanese Patent No. 3616615 JP, 2001-244372, A JP 2001-127095 A U.S. Patent Application Publication No. 2007/205513

However, when an object to be sealed is sealed with a cured product of the resin composition using a conventional resin composition, cracks may occur in the cured product. Therefore, it is required for the resin composition for sealing the object to be sealed to suppress the generation of cracks after curing.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a resin composition capable of suppressing the occurrence of cracks after curing and a cured product thereof. Another object of the present invention is to provide a resin film containing the resin composition or the cured product, and a sealing material provided with the resin film. Furthermore, this invention aims at providing the sealing structure provided with the sealing part containing the said resin composition, the said hardened|cured material, or the said resin film.

The resin composition according to the first embodiment of the present invention contains a thermosetting component, an inorganic filler, and a silane compound having an acid anhydride group.

The resin composition according to the second embodiment of the present invention contains a thermosetting component and an inorganic filler surface-treated with a silane compound having an acid anhydride group.

According to the resin composition of the present invention, it is possible to suppress the occurrence of cracks after curing, cracks in the sealing structure obtained by sealing the sealed object using the resin composition Can be suppressed.

Molding of a liquid or solid resin composition with a mold may be performed to seal the sealed object (electronic component or the like). For example, transfer molding may be used in which a pellet-shaped resin composition is melted and the resin composition is poured into a mold for sealing. However, in transfer molding, since a molten resin composition is poured and molded, an unfilled portion may occur when a large area is to be sealed. Therefore, in recent years, compression molding has begun to be used in which a resin composition is previously supplied to a mold or an object to be sealed (electronic parts or the like) and then molding is performed. In the compression molding, since the resin composition is directly supplied to the mold or the object to be sealed, there is an advantage that an unfilled portion is unlikely to occur even when sealing a large area. In the compression molding, a liquid or solid resin composition is used as in the transfer molding.

On the other hand, in recent years, by using a resin film (film-shaped resin encapsulant) instead of a liquid or solid resin composition, a molding method (laminating, pressing, etc.) that does not require a mold is used for encapsulation. Sealing the body is being considered. However, when the sealed body is obtained by sealing the sealed body using the conventional resin film, cracks may occur in the sealed structure. On the other hand, according to the resin composition of the present invention, it is possible to obtain a resin film capable of suppressing the occurrence of cracks after curing, and to seal the sealed object using the resin film. It is possible to suppress the occurrence of cracks in the obtained sealing structure.

Further, when a conventional resin film is used to seal an object to be sealed, the resin film may be damaged during handling and it may be difficult to perform sealing. On the other hand, according to the resin composition of the present invention, it is possible to obtain a resin film having excellent handleability (flexibility, etc.), and it is possible to easily prevent the resin film from being damaged during handling. ..

The thermosetting component may include an epoxy resin. In this case, moldability and adhesiveness can be further improved.

The thermosetting component preferably contains an epoxy resin that is liquid at 25°C. In this case, since it is possible to impart flexibility to the resin film, the handleability (flexibility etc.) of the resin film can be further improved.

［式中、Ｒ^１は、単結合又は炭素数１〜１８の炭化水素基を示し、Ｒ^２及びＲ^３は、それぞれ独立に炭素数１〜１８の炭化水素基を示し、ｋは、１〜３の整数であり、ｌは、０〜２の整数であり、ｍは、１〜３の整数であり、ｋ＋ｌ＋ｍ＝４である。］ The silane compound preferably contains a compound represented by the following general formula (1). In this case, the dispersibility of the inorganic filler during mixing can be further improved.

[In the formula, R ¹ represents a single bond or a hydrocarbon group having 1 to 18 carbon atoms, R ² and R ³ each independently represent a hydrocarbon group having 1 to 18 carbon atoms, and k represents 1 to It is an integer of 3, l is an integer of 0 to 2, m is an integer of 1 to 3, and k+l+m=4. ]

The silane compound preferably contains 3-trimethoxysilylpropyl succinic anhydride. In this case, the dispersibility of the inorganic filler and the resin can be further improved.

The average particle size of the inorganic filler may be 0.01 to 50 μm. In this case, aggregation of the inorganic filler can be easily suppressed and the inorganic filler can be easily dispersed, and sedimentation of the inorganic filler in the varnish in the production of the resin film can be easily suppressed.

The resin composition according to the present invention may be used for sealing electronic components.

The cured product according to the present invention is a cured product of the resin composition.

The resin film according to the present invention contains the resin composition or the cured product.

The encapsulating material according to the present invention includes a support and the resin film, and the resin film is arranged on the support.

The sealing structure according to the present invention includes an object to be sealed and a sealing part that seals the object to be sealed, wherein the sealing part is the resin composition, the cured product, or the resin. Including film. In the sealed structure according to the present invention, the sealed object may be an electronic component.

According to the present invention, it is possible to obtain a resin film having excellent handleability (flexibility, etc.), and to provide a resin composition capable of suppressing the occurrence of cracks after curing and a cured product thereof. can do. Moreover, according to this invention, the resin film containing the said resin composition or the said cured material, and the sealing material provided with the said resin film can be provided. Furthermore, according to this invention, the sealing structure provided with the sealing part containing the said resin composition, the said hardened|cured material, or the said resin film can be provided.

INDUSTRIAL APPLICABILITY The present invention can be suitably used for sealing electronic components (semiconductor devices, etc.) (including, for example, embedding electronic components arranged on a printed wiring board). Further, the present invention can be suitably used not only for molding but also for a molding method (laminating, pressing, etc.) which does not require a mold.

According to the present invention, it is possible to provide an application of the resin composition, the resin film, or the encapsulant to the encapsulation of the object. According to the present invention, it is possible to provide application of a resin composition, a resin film, or an encapsulant to encapsulation of electronic components. According to the present invention, it is possible to provide application of a resin composition, a resin film, or a sealing material to embedding an electronic component arranged on a printed wiring board. According to the present invention, it is possible to provide application of a resin composition, a resin film or a sealing material to molding. According to the present invention, it is possible to provide application of the resin composition, the resin film, or the encapsulant to a molding method (laminating, pressing, etc.) that does not require a mold.

It is a top view which shows the test piece used for manufacture of the sample for evaluation of crack resistance. It is a figure which shows the evaluation method of crack resistance. It is a figure which shows the relationship between breaking energy and SP value of a silane compound.

Hereinafter, embodiments of the present invention will be described. However, the present invention is not limited to the following embodiments.

In the present specification, the numerical range indicated by using "to" indicates a range including the numerical values before and after "to" as the minimum value and the maximum value, respectively. In the numerical ranges described stepwise in the present specification, the upper limit value or the lower limit value of the numerical range of a certain stage may be replaced with the upper limit value or the lower limit value of the numerical range of another stage. In the numerical ranges described in the present specification, the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples. “A or B” may include either A or B, or may include both. Unless otherwise specified, the materials exemplified in this specification can be used alone or in combination of two or more kinds. In the present specification, the content of each component in the composition is the total of the plurality of substances present in the composition, unless a plurality of substances corresponding to each component are present in the composition. Means quantity.

<Resin composition>
The resin composition according to the present embodiment (the first embodiment and the second embodiment) contains (A) a thermosetting component and (B) an inorganic filler. The resin composition according to the first embodiment further contains (C) a silane compound having an acid anhydride group. In the resin composition according to the second embodiment, the component (B) is an inorganic filler (C) surface-treated with a silane compound having an acid anhydride group. In the present embodiment, the resin composition further contains a silane compound having an acid anhydride group (C), and the inorganic filler (B) is surface-treated with a silane compound having an acid anhydride group (C). May be.

The silane compound having an acid anhydride group (C) for surface-treating the inorganic filler (B) may maintain the state before the surface treatment on the surface of the inorganic filler (B), and It may be modified by the reaction with the filler. The silane compound having an acid anhydride group (C) may be contained in the resin composition without contacting with the inorganic filler (B).

According to the resin composition of the present embodiment, it is possible to obtain a resin film having excellent handleability (flexibility, etc.) and suppress the occurrence of cracks after curing. Due to the fact that the silane compound has an acid anhydride group, the resin composition containing the inorganic filler has a high affinity for the thermosetting component and the silane compound having an acid anhydride group. It is presumed that the above effect can be obtained.

Examples of the form of the resin composition according to the present embodiment include film form, liquid form, solid form (granule, powder, etc.).

The resin composition according to the present embodiment can be used for sealing by molding, sealing by a molding method (laminating, pressing, etc.) that does not require a mold. The resin composition according to this embodiment can be used for sealing electronic components. Examples of electronic components include semiconductor elements, semiconductor wafers, integrated circuits, semiconductor devices, filters such as SAW filters, and passive components such as sensors.

Hereinafter, constituent components and the like of the resin composition according to the present embodiment will be described.

(Component (A): thermosetting component)
Examples of the component (A) include thermosetting resins, curing agents, curing accelerators (excluding compounds corresponding to curing agents), and the like. Examples of the thermosetting resin include epoxy resin, phenoxy resin, cyanate resin, thermosetting polyimide, melamine resin, urea resin, unsaturated polyester, alkyd resin, phenol resin and polyurethane. The component (A) contains, for example, an epoxy resin and a curing agent.

[Epoxy resin]
The epoxy resin may be a compound having two or more glycidyl groups in one molecule and is not particularly limited. Examples of the epoxy resin include novolac type epoxy resins such as phenol novolac type epoxy resin and orthocresol novolac type epoxy resin; bisphenol A, bisphenol F, bisphenol S, alkyl-substituted or unsubstituted biphenol, diglycidyl ethers such as stilbene type phenols. (Bisphenol type epoxy resin, biphenyl type epoxy resin, stilbene type epoxy resin, etc.); Butanediol, polyethylene glycol, polypropylene glycol, and other alcohol glycidyl ethers; Carboxylic acids (phthalic acid, isophthalic acid, tetrahydrophthalic acid, etc.) Glycidyl ester (glycidyl ester-type epoxy resin); glycidyl-type or methylglycidyl-type epoxy resin such as compounds in which active hydrogen bonded to nitrogen atom such as aniline and isocyanuric acid is substituted with glycidyl group; olefin bond in molecule is epoxy Vinylcyclohexene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy) Alicyclic epoxy resin such as cyclohexane-m-dioxane; glycidyl ether of paraxylylene and/or metaxylylene modified phenolic resin; glycidyl ether of terpene modified phenolic resin; glycidyl ether of dicyclopentadiene modified phenolic resin; glycidyl of cyclopentadiene modified phenolic resin Ether; glycidyl ether of polycyclic aromatic ring-modified phenol resin; glycidyl ether of naphthalene ring-containing phenol resin; halogenated phenol novolac type epoxy resin; hydroquinone type epoxy resin; trimethylolpropane type epoxy resin; olefin bond peracid (peracetic acid) Etc.) obtained by oxidation with a linear aliphatic epoxy resin; diphenylmethane type epoxy resin; epoxidized aralkyl type phenol resin (phenol/aralkyl resin, naphthol aralkyl resin, etc.); sulfur atom-containing epoxy resin; naphthalene type epoxy resin, etc. Is mentioned. As the novolac type epoxy resin, for example, at least one selected from the group consisting of phenols and naphthols and a compound having an aldehyde group are condensed or co-condensed under an acidic catalyst to epoxidize a novolac resin. The resin obtained by the above is mentioned. Examples of phenols include phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F and the like. Examples of naphthols include α-naphthol, β-naphthol, dihydroxynaphthalene and the like. Examples of the compound having an aldehyde group include formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and hydroxybenzaldehyde. The epoxy resins may be used alone or in combination of two or more.

The component (A) is an epoxy resin that is liquid at 25° C. (hereinafter, referred to as “the It is preferable to include at least one type of liquid epoxy resin). Here, the “liquid epoxy resin at 25° C.” means that the viscosity of the epoxy resin held at 25° C. is 400 Pa·s or less measured by using an E-type viscometer or a B-type viscometer. Indicates an epoxy resin.

The liquid epoxy resin preferably contains at least one selected from the group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type and biphenyl type epoxy resin. .. The liquid epoxy resins may be used alone or in combination of two or more.

A commercial item may be used as the epoxy resin. Commercially available liquid epoxy resins include trade name "jER825" (bisphenol A type epoxy resin, epoxy equivalent: 175) manufactured by Mitsubishi Chemical Corporation, trade name "jER806" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Corporation. , Epoxy equivalent: 160), a trade name "HP-4032D" (bifunctional naphthalene type epoxy resin) manufactured by DIC Corporation, and the like. Commercially available products of other epoxy resins include trade names "HP-4750" and "HP-4710" manufactured by DIC Corporation; trade names "EPPN-500" series manufactured by Nippon Kayaku Co., Ltd., and the like.

Even if the SP value of the epoxy resin (liquid epoxy resin, etc.) is 8 or more, from the viewpoint of obtaining a resin film having more excellent handleability (flexibility etc.) and further suppressing the occurrence of cracks after curing. It may be 9 or more, or 10 or more. Even if the SP value of the epoxy resin (liquid epoxy resin, etc.) is 12 or less from the viewpoint of obtaining a resin film having more excellent handleability (flexibility etc.) and further suppressing the occurrence of cracks after curing. It may be 11 or less. In addition, in this specification, "SP value" means the theoretical solubility parameter calculated by the calculation method devised by Fedors, "Journal of the Japan Adhesive Society" (1986, Vol. 22, No. 10, 566-567). Page). The unit of SP value is (cal/cm ³ ) ^0.5 .

The content of the epoxy resin may be 40% by mass or more, 45% by mass or more, or 50% by mass, based on the total mass of the component (A), from the viewpoint of excellent handleability of the resin film. % Or more. The content of the epoxy resin is 70% by mass or less based on the total mass of the component (A), from the viewpoint that the release property of the protective film in the encapsulating material (encapsulating sheet) including the protective film is good. May be 65% by mass or less, or 63% by mass or less. From these viewpoints, the content of the epoxy resin may be 40 to 70 mass% or 45 to 65 mass% based on the total mass of the component (A).

The content of the liquid epoxy resin may be 32% by mass or more based on the total amount of the thermosetting resin component and the curing agent from the viewpoint of obtaining further excellent handleability (flexibility, etc.), and may be 35% by mass. % Or more, 40% by mass or more, or 45% by mass or more. The content of the liquid epoxy resin is 60% by mass or less based on the total amount of the thermosetting resin component and the curing agent from the viewpoint that the peelability of the protective layer is good when the encapsulating material including the protective layer is used. Or may be 55% by mass or less. From these viewpoints, the content of the liquid epoxy resin may be 32 to 60 mass% or 35 to 55 mass% based on the total amount of the thermosetting resin component and the curing agent.

The content of the liquid epoxy resin may be 32% by mass or more, or 35% by mass or more, based on the total amount of the epoxy resin and the curing agent, from the viewpoint of obtaining further excellent handleability (flexibility, etc.). It may be present, may be 40% by mass or more, and may be 45% by mass or more. The content of the liquid epoxy resin is 60% by mass or less, based on the total amount of the epoxy resin and the curing agent, from the viewpoint that the peelability of the protective layer is good when the encapsulating material including the protective layer is used. Or may be 55 mass% or less. From these viewpoints, the content of the liquid epoxy resin may be 32 to 60 mass% or 35 to 55 mass% based on the total amount of the epoxy resin and the curing agent.

The content of the liquid epoxy resin may be 60% by mass or more, or 65% by mass or more, based on the total mass of the epoxy resin, from the viewpoint of obtaining further excellent handleability (flexibility, etc.). Well, it may be 70% by mass or more. The content of the liquid epoxy resin may be 100% by mass or less, or 95% by mass or less, based on the total mass of the epoxy resin, from the viewpoint of obtaining further excellent handleability (flexibility and the like). It may be 90% by mass or less. From these viewpoints, the content of the liquid epoxy resin may be 60 to 100% by mass, 65 to 95% by mass, or 70 to 90% by mass, based on the total mass of the epoxy resin. It may be.

[Curing agent]
The curing agent is not particularly limited, and examples thereof include a phenol type curing agent, an acid anhydride type curing agent, an active ester type curing agent, and a cyanate ester type curing agent. The curing agents may be used alone or in combination of two or more.

The phenol-based curing agent is not particularly limited, but it is a novolac-type curing agent, phenol/aralkyl resin, biphenyl-type curing agent, naphthol-type curing agent, naphthalene-type curing agent, dicyclopentadiene-type curing agent, naphthylene. Examples thereof include ether type curing agents and triazine skeleton-containing phenolic curing agents.

Commercially available phenol-based curing agents include Asahi Organic Materials Co., Ltd., trade name "PAPS-PN2" (novolac type phenolic resin); Air Water Co., Ltd., trade name "SK Resin HE200C-7" (biphenyl). Aralkyl-type phenol resin) and trade name "HE910-10" (trisphenylmethane-type phenol resin); "MEH-7000", "DL-92", "H-4" and "HF-1M" manufactured by Meiwa Kasei Co., Ltd. (Both are trade names); "LVR-8210DL", "ELP series" and "NC series" (both are trade names) manufactured by Gunei Chemical Industry Co., Ltd.; "SN-180" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. , "SN-395", "SN-475" and "SN-485" (all are trade names); "LA3018", "LA7052", "LA7054" and "LA1356" manufactured by DIC Corporation (triazine skeleton-containing phenol). Systematic curing agents, all trade names); trade name "HPM-J3" manufactured by Hitachi Chemical Co., Ltd., and the like. The phenol-based curing agents may be used alone or in combination of two or more.

The acid anhydride-based curing agent is not particularly limited, but is phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylnadic anhydride. , Monomeric acid anhydrides such as, nadic anhydride, glutaric anhydride, dimethyl glutaric anhydride, diethyl glutaric anhydride, succinic anhydride, methyl hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride; polymeric acid anhydrides And so on.

The active ester-based curing agent is not particularly limited, but an ester group having high reaction activity such as phenol ester, thiophenol ester, N-hydroxyamine ester, and ester of heterocyclic hydroxy compound may be used. Examples thereof include compounds having two or more in one molecule.

The cyanate ester-based curing agent is not particularly limited, but it is a novolac type (phenol novolac type, alkylphenol novolac type, etc.) cyanate ester type curing agent, a dicyclopentadiene type cyanate ester type curing agent, a bisphenol type (bisphenol A Type, bisphenol F type, bisphenol S type, etc.) cyanate ester type curing agents, and prepolymers in which these are partially triazine-ized.

From the viewpoint of excellent heat resistance, the content of the curing agent may be 17 to 50% by mass, 20 to 45% by mass, or 20 to 42% by mass based on the total mass of the component (A). It may be% by mass.

Ratio (equivalent of glycidyl group of epoxy resin/equivalent of curing agent) of equivalent of glycidyl group of epoxy resin (epoxy equivalent) to equivalent of functional group (eg phenolic hydroxyl group) that reacts with glycidyl group of curing agent (eg hydroxyl equivalent) The equivalent of the functional group that reacts with the glycidyl group) may be 0.7 or more, may be 0.8 or more, and may be 0.9 or more, from the viewpoint of reducing the residual amount of the unreacted curing agent. May be The ratio may be 2.0 or less, 1.8 or less, or 1.7 or less from the viewpoint of reducing the amount of unreacted epoxy resin remaining. From these viewpoints, the ratio may be 0.7 to 2.0, 0.8 to 1.8, or 0.9 to 1.7.

[Curing accelerator]
The curing accelerator is not particularly limited. The curing accelerator may be, for example, at least one selected from the group consisting of an amine curing accelerator, an imidazole curing accelerator, a urea curing accelerator, and a phosphorus curing accelerator. .. Examples of the amine-based curing accelerator include 1,8-diazabicyclo[5.4.0]-7-undecene and 1,5-diazabicyclo[4.3.0]-5-nonene. Examples of the imidazole-based curing accelerator include 2-phenyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole and the like. Examples of the urea-based curing accelerator include 3-phenyl-1,1-dimethylurea. Examples of phosphorus-based curing accelerators include triphenylphosphine and its addition reaction product, (4-hydroxyphenyl)diphenylphosphine, bis(4-hydroxyphenyl)phenylphosphine, and tris(4-hydroxyphenyl)phosphine.

The curing accelerator may be an imidazole-based curing accelerator from the viewpoint that it has a wide variety of derivatives and that a desired activation temperature can be easily obtained. A commercially available product may be used as the imidazole-based curing accelerator. Examples of commercially available imidazole curing accelerators include trade names “CUREZOL 2PHZ-PW” and “CUREZOL 2P4MZ” manufactured by Shikoku Chemicals Co., Ltd. The curing accelerator may be used alone or in combination of two or more.

The content of the curing accelerator is 0.01% by mass or more based on the total amount of the thermosetting resin (epoxy resin or the like) and the curing agent from the viewpoint that a sufficient curing acceleration effect can be easily obtained. The amount may be 0.1% by mass or more, or 0.3% by mass or more. The content of the curing accelerator can suppress the progress of curing during the steps of manufacturing the resin film (for example, the coating step and the drying step), or during the storage of the resin film, and also the cracking of the resin film. And, from the viewpoint of easily preventing a molding defect due to an increase in melt viscosity, it may be 5% by mass or less based on the total amount of the thermosetting resin (epoxy resin etc.) and the curing agent, and may be 3% by mass. It may be less than or equal to 1.5% by mass. From these viewpoints, the content of the curing accelerator may be 0.01 to 5 mass% based on the total amount of the thermosetting resin (epoxy resin or the like) and the curing agent, It may be 3% by mass or 0.3 to 1.5% by mass.

The content of the component (A) may be 14% by mass or more based on the total mass of the resin composition (excluding solvents such as organic solvents) from the viewpoint of imparting flexibility to the resin film, 15 It may be at least mass% or may be at least 16 mass%. The content of the component (A) may be 22% by mass or less, or 21% by mass or less, based on the total mass of the resin composition (excluding solvents such as organic solvents) from the viewpoint of excellent heat resistance. It may be present or may be 20% by mass or less. From these viewpoints, the content of the component (A) may be 14 to 22% by mass, or 15 to 21% by mass, based on the total mass of the resin composition (excluding solvents such as organic solvents). It may be present or may be 16 to 20% by mass. The content of the component (A) is the total amount of the thermosetting components such as the thermosetting resin, the curing agent and the curing accelerator.

(Component (B): inorganic filler)
As the inorganic filler, conventionally known inorganic fillers can be used and are not particularly limited. Examples of the inorganic filler include silicas (amorphous silica, crystalline silica, fused silica, spherical silica, synthetic silica, hollow silica, etc.), barium sulfate, barium titanate, talc, clay, mica powder, magnesium carbonate, calcium carbonate. , Aluminum oxide, aluminum hydroxide, magnesium oxide, magnesium hydroxide, silicon nitride, aluminum nitride, aluminum borate, boron nitride, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide. , Barium zirconate, calcium zirconate and the like. Due to surface modification (for example, surface treatment with silane compound), the effect of improving dispersibility in the resin composition and the effect of suppressing sedimentation in the varnish are easily obtained, and the coefficient of thermal expansion is relatively small. From the viewpoint of easily obtaining the desired cured film characteristics due to the presence of the above, silicas are preferable. Alumina is preferable from the viewpoint of obtaining high thermal conductivity. Examples of commercially available inorganic fillers include trade name "SO-C2" manufactured by Admatechs Co., Ltd. The inorganic fillers may be used alone or in combination of two or more.

The component (B) may contain an inorganic filler surface-treated with the component (C). The component (B) may have a group derived from the component (C) on its surface. The group derived from the component (C) is, for example, a group obtained by subjecting a functional group (alkoxy group or the like) of the component (C) to hydrolysis and then performing a condensation reaction with a functional group (hydroxyl group or the like) on the surface of the inorganic filler. Are listed.

Further, the component (B) may contain an inorganic filler which is not surface-treated, an inorganic filler which is surface-treated with a component other than the component (C), and the like. A known coupling agent can be used as a component other than the component (C) for surface-treating the inorganic filler. Examples of the coupling agent include various silane compounds such as epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureidosilane, and vinylsilane; titanium compounds; aluminum chelates; aluminum/zirconium compounds.

In the surface treatment of the inorganic filler, for example, the surface treatment agent ((C) component, the coupling agent, etc.) can be immobilized on the surface of part or all of the inorganic filler by a chemical reaction or adsorption. Examples of the surface treatment method include a method of mixing a mixture of the surface treatment agent and the inorganic filler for several tens of minutes to several days using a mixing device (high speed mixer, ball mill, mix rotor, etc.). The surface treatment agent can be mixed with the inorganic filler in a state of being dissolved or dispersed in a suitable solvent such as water or alcohol.

The average particle size of the component (B) may be 0.01 μm or more, or 0.1 μm or more, from the viewpoint that the aggregation of the inorganic filler is easily suppressed and the inorganic filler is easily dispersed. Or may be 0.3 μm or more. The average particle size of the component (B) may be 50 μm or less, 25 μm or less, or 10 μm from the viewpoint of easily suppressing the sedimentation of the inorganic filler in the varnish during the production of the resin film. It may be the following. From these viewpoints, the average particle size of the component (B) may be 0.01 to 50 μm, 0.1 to 25 μm, or 0.3 to 10 μm.

The average particle size of the component (B) can be measured by a laser diffraction/scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the component (B) can be created on a volume basis using a laser diffraction/scattering particle size distribution measuring device, and the median diameter can be used as the average particle diameter for measurement. As the measurement sample, those in which the component (B) is dispersed in water by ultrasonic waves can be preferably used. “MT3300EX II” manufactured by Nikkiso Co., Ltd. can be used as the laser diffraction/scattering type particle size distribution measuring apparatus.

The content of the component (B) depends on the difference in the coefficient of thermal expansion between the object to be sealed (electronic parts such as semiconductor elements) and the sealing portion, and the content of the sealing structure (for example, electronic part devices such as semiconductor devices). From the viewpoint that the warp can be easily prevented from increasing, it may be 50% by mass or more, or 55% by mass or more, based on the total mass of the resin composition (excluding solvents such as organic solvents). Well, it may be 60% by mass or more. The content of the component (B) is the total mass of the resin composition (solvent such as an organic solvent) from the viewpoint that it is possible to easily suppress the problem that the sealed object cannot be sufficiently sealed due to an increase in melt viscosity of the resin film. Excluding) may be 95% by mass or less, 93% by mass or less, or 90% by mass or less. From these viewpoints, the content of the component (B) may be 50 to 95% by mass, or 55 to 93% by mass, based on the total mass of the resin composition (excluding solvents such as organic solvents). It may be present, or may be 60 to 90 mass %.

The content of the inorganic filler surface-treated with the component (C) is such that the cracking of the resin film can be easily suppressed in the drying step during the production of the resin film, and the melt viscosity of the resin film increases, so that the resin film is sealed. From the viewpoint of easily suppressing the problem that the stopper cannot be sufficiently sealed, it may be 50% by mass or more, based on the total mass of the resin composition (excluding solvents such as organic solvents), 55% by mass It may be more than 60% by mass. The content of the inorganic filler surface-treated with the component (C) is such that the cracking of the resin film can be easily suppressed in the drying step during the production of the resin film, and the melt viscosity of the resin film increases, so that the resin film is sealed. From the viewpoint of easily suppressing the problem that the stopper cannot be sufficiently sealed, it may be 95% by mass or less, based on the total mass of the resin composition (excluding solvents such as organic solvents), and 90% by mass. It may be the following. From these viewpoints, the content of the inorganic filler surface-treated with the component (C) may be 50% by mass or more based on the total mass of the resin composition (excluding solvents such as organic solvents). It may be 55 to 95 mass %, or 60 to 90 mass %.

The content of the inorganic filler that has not been surface-treated with the component (C) depends on the difference in the coefficient of thermal expansion between the object to be sealed (electronic components such as semiconductor elements) and the sealing portion (for example, From the viewpoint of easily increasing the warpage of electronic component devices such as semiconductor devices), it may be 50% by mass or more based on the total mass of the resin composition (excluding solvents such as organic solvents). , 55 mass% or more, or 60 mass% or more. The content of the inorganic filler that has not been surface-treated with the component (C) can be easily controlled from the viewpoint of easily suppressing the problem that the sealed body cannot be sufficiently sealed due to an increase in melt viscosity of the resin film. It may be 95% by mass or less, or 90% by mass or less, based on the total mass (excluding solvents such as organic solvents). From these viewpoints, the content of the inorganic filler not surface-treated with the component (C) is 50% by mass or more based on the total mass of the resin composition (excluding solvents such as organic solvents). It may be 55 to 95% by mass, or 60 to 90% by mass.

(Component (C): Silane Compound Having Acid Anhydride Group)
In the resin composition according to the present embodiment, the component (C) may be adsorbed on the surface of the component (B) or may be contained in the resin composition without adsorbing the component (B). ..

The component (C) is not particularly limited, but preferably contains an alkoxysilane compound having an acid anhydride group. Among them, the component (C) preferably contains a compound represented by the following general formula (1).

［式中、Ｒ^１は、単結合又は炭素数１〜１８の炭化水素基を示す。Ｒ^２及びＲ^３は、それぞれ独立に炭素数１〜１８の炭化水素基を示す。ｋは、１〜３の整数であり、ｌは、０〜２の整数であり、ｍは、１〜３の整数であり、ｋ＋ｌ＋ｍ＝４である。Ｒ^１、Ｒ^２及びＲ^３がそれぞれ複数存在する場合、互いに同一でも異なっていてもよい。］

[In the formula, R ¹ represents a single bond or a hydrocarbon group having 1 to 18 carbon atoms. R ² and R ³ each independently represent a hydrocarbon group having 1 to 18 carbon atoms. k is an integer of 1 to 3, l is an integer of 0 to 2, m is an integer of 1 to 3, and k+l+m=4. When a plurality of R ¹ , R ² and R ³ are present, they may be the same or different from each other. ]

The hydrocarbon group in R ¹ has 1 to 18 carbon atoms, may be 1 to 10 carbon atoms, and may be 1 to 5 carbon atoms. The hydrocarbon group may be a substituted or unsubstituted hydrocarbon group. The hydrocarbon group may be a linear or branched hydrocarbon group. The hydrocarbon group may be a saturated or unsaturated hydrocarbon group. An alkylene group etc. are mentioned as said hydrocarbon group.

The hydrocarbon group in R ² and R ³ has 1 to 18 carbon atoms, may be 1 to 5 carbon atoms, and may be 1 to 3 carbon atoms. The hydrocarbon group may be a substituted or unsubstituted hydrocarbon group. The hydrocarbon group may be a linear or branched hydrocarbon group. The hydrocarbon group may be a saturated or unsaturated hydrocarbon group. An alkyl group etc. are mentioned as said hydrocarbon group.

Examples of the compound represented by the formula (1) include 3-trimethoxysilylpropyl succinic anhydride. The component (C) preferably contains 3-trimethoxysilylpropyl succinic anhydride. 3-trimethoxysilylpropyl succinic anhydride is a compound represented by the following formula (2). Examples of commercially available products of the compound represented by the formula (2) include trade name “X-12-967C” manufactured by Shin-Etsu Chemical Co., Ltd. and the like.

The SP value of the component (C) may be 8.0 or more from the viewpoint of obtaining a resin film having further excellent handleability (flexibility, etc.) and further suppressing the occurrence of cracks after curing. It may be 9.0 or higher, or 9.5 or higher. The SP value of the component (C) may be 11.0 or less from the viewpoint of obtaining a resin film having further excellent handleability (flexibility and the like) and further suppressing the occurrence of cracks after curing, It may be 10.8 or less, or 10.5 or less.

The present inventor uses an epoxy resin (a liquid epoxy resin or the like) and a component (C) having a small SP value difference as a constituent component of a resin composition containing an inorganic filler, whereby a cured product of the resin composition is obtained. It has been found that the breaking energy of is easily improved and the generation of cracks after curing can be further suppressed. Since the difference in SP value between the epoxy resin (liquid epoxy resin and the like) and the component (C) is small, a higher affinity between the epoxy resin (liquid epoxy resin and the like) and the component (C) can be obtained. It is presumed that the generation of cracks can be further suppressed. The difference in SP value between the epoxy resin (liquid epoxy resin and the like) and the component (C) may be 1.2 or less, or 0.9 or less, from the viewpoint of further suppressing the occurrence of cracks after curing. Good.

The content of the component (C) is, from the viewpoint of obtaining a resin film having more excellent handleability (flexibility, etc.) and further suppressing the occurrence of cracks after curing, with respect to 100 parts by mass of the inorganic filler, It may be 0.02 parts by mass or more, 0.05 parts by mass or more, and 0.2 parts by mass or more. The content of the component (C) may be 5.0 parts by mass or less and may be 3.0 parts by mass or less with respect to 100 parts by mass of the inorganic filler from the viewpoint of easily obtaining sufficient curability. Or 1.0 parts by mass or less. From these viewpoints, the content of the component (C) may be 0.02 to 5.0 parts by mass, or 0.05 to 3.0 parts by mass with respect to 100 parts by mass of the inorganic filler. Or may be 0.2 to 1.0 part by mass. The content of the component (C) includes the amount of the component (C) fixed on the surface of the component (B).

The compounding method of the component (C) is not particularly limited, and includes, for example, an integral blending method in which it is directly mixed with other constituent materials; a dry treatment method in which it is mixed with an inorganic filler in advance and then mixed with other constituent materials; Wet treatment method; masterbatch method of previously mixing with thermosetting resin (epoxy resin etc.) and/or curing agent and then mixing with other constituent materials; pretreatment method of preliminarily surface-treating the inorganic filler. To be

The amount of the component (C) used when surface-treating the inorganic filler with the component (C) is such that a resin film having more excellent handleability (flexibility, etc.) is obtained and cracks are not generated after curing. From the viewpoint of further suppressing, with respect to 100 parts by mass of the inorganic filler, 0.02 parts by mass or more, 0.05 parts by mass or more, or 0.2 parts by mass or more may be used. Good. The amount of the component (C) used may be 5.0 parts by mass or less, or 3.0 parts by mass or less, based on 100 parts by mass of the inorganic filler, from the viewpoint of easily obtaining sufficient curability. It may be present or may be 1.0 part by mass or less. From these viewpoints, the amount of the component (C) used may be 0.02 to 5.0 parts by mass, or 0.05 to 3.0 parts by mass with respect to 100 parts by mass of the inorganic filler. It may be present, or may be 0.2 to 1.0 part by mass.

(Organic solvent)
The resin composition according to this embodiment may contain an organic solvent. A conventionally known organic solvent can be used as the organic solvent. As the organic solvent, a solvent that can dissolve components other than the component (B) can be used. Examples of the organic solvent include aliphatic hydrocarbons, aromatic hydrocarbons, terpenes, halogens, esters, ketones, alcohols and aldehydes. The organic solvent may be used alone or in combination of two or more.

The organic solvent is at least one selected from the group consisting of esters, ketones, and alcohols from the viewpoint of low environmental load and from the viewpoint of easily dissolving a thermosetting resin (epoxy resin etc.) and a curing agent. May be. As the organic solvent, ketones may be used from the viewpoint of easily dissolving the thermosetting resin (epoxy resin or the like) and the curing agent. The organic solvent may be 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.

(Other ingredients)
The resin composition according to the present embodiment may contain other additives. Examples of such additives include pigments, dyes, release agents, antioxidants, stress relaxation agents, coupling agents (excluding the component (C)), surface tension adjusting agents, ion exchangers, coloring agents, flame retardants. Etc. can be mentioned. However, the additives are not limited to these, and the resin composition according to the present embodiment may contain various additives well known in the art, if necessary.

As the coupling agent, various silane compounds such as epoxy silane, mercapto silane, amino silane, alkyl silane, ureido silane and vinyl silane; titanium compounds; aluminum chelates; known coupling agents such as aluminum/zirconium compounds. Can be mentioned.

<Cured product, resin film and sealing material>
The cured product according to this embodiment is a cured product of the resin composition. The resin film according to this embodiment includes the resin composition or the cured product according to this embodiment. The encapsulating material (encapsulating sheet) according to the present embodiment includes a support and the resin film according to the present embodiment, and the resin film is arranged on the support. The resin film and the encapsulant according to this embodiment can be used for encapsulation by molding, encapsulation by a molding method (laminating, pressing, etc.) that does not require a mold.

According to the resin film and the encapsulant according to the present embodiment, even when the object to be encapsulated is large, compared with a liquid or solid (granule, powder, etc.) resin composition, It is possible to uniformly supply the resin composition onto the stopper, and it is possible to easily and favorably seal the sealed body. Further, when a granular or powdery resin composition is used, the resin composition may serve as a dust source and contaminate the device or the clean room. According to the material, it is possible to increase the size of the sealing molded body while reducing the problem of dust generation.

In molding, since the resin composition is molded in the mold, it is necessary to increase the size of the mold in order to increase the size of the sealing structure. However, increasing the size of the mold may increase the difficulty in terms of technology because high mold accuracy is required, and the manufacturing cost of the mold may increase significantly. On the other hand, the resin film and the encapsulant according to the present embodiment are preferably used not only in the conventional encapsulation molding method such as molding, but also in a molding method that does not require a mold (lamination, pressing, etc.) be able to.

The thickness of the resin film may be 25 μm or more, or may be 50 μm or more, from the viewpoint of easily preventing the resin film from cracking. The thickness of the resin film may be 500 μm or less, or may be 300 μm or less, from the viewpoint of easily suppressing variation in thickness during production of the resin film.

The resin film according to this embodiment can be obtained, for example, by molding the resin composition according to this embodiment or a cured product thereof into a film shape. The encapsulant according to this embodiment can be obtained by disposing a resin film on a support.

The method for producing the resin film may be a varnish coating method. For example, a coating film is formed on a support using a varnish (varnish-like resin composition) containing the components (A) and (B). And a step of heating and drying the coating film to obtain a resin film. Further, the method for producing the resin film may be a method including a step of molding a solid resin composition containing the component (A), the component (B) and the like into a sheet to obtain a resin film. The varnish coating method may be used from the viewpoint of easily controlling the thickness of the resin film.

The resin film according to the present embodiment can be produced, for example, by mixing essential components (component (A), component (B), etc.) and various optional components used as necessary. The mixing method is not particularly limited as long as each compounding component can be dispersed and mixed, but a mill, a mixer, a stirring blade or the like can be used. If necessary, a film can be formed by a varnish coating method using a varnish obtained by dissolving each component in an organic solvent or the like. Further, the resin film according to the present embodiment is obtained by extruding a solid resin composition produced by kneading each compounding component with a kneader, two rolls, a continuous kneading device or the like into a sheet to form a film. You can also

The content of the organic solvent in the varnish used for producing the resin film may be 2 to 30 mass% or 5 to 25 mass% based on the total mass of the varnish. 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 the problem that the tackiness becomes too strong and the handleability is deteriorated, and the problem such as foaming caused by the volatilization of the organic solvent during the thermosetting of the resin composition.

The content of the organic solvent in the resin film is preferably 0.2 to 1.5% by mass, more preferably 0.3 to 1% by mass, based on the total mass of the resin composition (including a solvent such as an organic solvent). preferable. When the content of the organic solvent is 0.2% by mass or more, the resin composition becomes brittle to cause problems such as cracking of the resin, and the minimum melt viscosity becomes high, so that the sealing property of the object to be sealed (embedding) Properties) can be prevented from decreasing. When the content of the organic solvent is 1.5 mass% or less, the tackiness of the resin composition becomes too strong and the handleability is deteriorated, and foaming is caused by volatilization of the organic solvent during thermosetting of the resin layer. It is possible to easily prevent such problems.

In the varnish coating method, a resin film can be prepared by heating and drying a coating film obtained by coating the support with varnish by hot air blowing or the like. The coating method used for coating is not particularly limited, and examples thereof include die coating and comma coating.

The support is not particularly limited, and examples thereof include a polymer film and a metal foil. 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; acetyl cellulose film; polyimide film; polyamide film; tetrafluoroethylene film and the like. .. Examples of the metal foil include copper foil and aluminum foil.

The thickness of the support is not particularly limited, but may be 2 to 200 μm from the viewpoint of excellent workability and dryness. 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 bends during coating due to the weight of the varnish. Further, when using a dryer in which hot air is blown from both the coated surface and the back surface at the time of drying, it is possible to easily prevent the problem that the solvent in the varnish is prevented from drying.

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

The encapsulating material according to the present embodiment may include a protective layer (for example, a protective film) for protection on the resin film provided on the support. That is, the encapsulant according to this embodiment may include a protective layer on the side of the resin film opposite to the support. By using the protective layer, the handleability is further improved, and it is possible to easily avoid the problem that the resin film sticks to the back surface of the support when wound up.

The protective layer is not particularly limited, but examples thereof include a polymer film and a metal foil. 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; acetyl cellulose film; tetrafluoroethylene film and the like. Examples of the metal foil include copper foil and aluminum foil.

The thickness of the protective layer is not particularly limited, but from the viewpoint of obtaining a sufficient protective effect and from the viewpoint of reducing the thickness when the resin film is wound into a roll, it is 12 to 100 μm. May be.

<Sealing structure>
The sealing structure according to the present embodiment includes an object to be sealed and a sealing portion that seals the object to be sealed, and the sealing portion is a resin composition according to the present embodiment, and is cured. Including objects or resin films. The sealing structure according to the present invention is, for example, an electronic component device including an electronic component as the sealed object. The electronic component device according to the present embodiment includes an electronic component and a sealing portion that seals the electronic component, and the sealing portion includes the resin composition, the cured product, or the resin film according to the present embodiment. .. Examples of the electronic component device include a semiconductor device including a semiconductor element.

The method for manufacturing a sealing structure according to the present embodiment includes a sealing step of sealing an object to be sealed with the resin composition according to the present embodiment, and a step of curing the resin composition to obtain a sealing portion. And The sealing step is a step of sealing an object to be sealed (for example, an object to be sealed provided on a substrate) by pressing the resin composition under heating. The method for manufacturing the sealed structure according to the present embodiment includes, for example, a step of pressing the resin film against the sealed object under heating to seal the sealed object with the resin composition, and Curing the resin composition in which the body is sealed to obtain the sealed portion.

Although the embodiments of the present invention have been described above, the present invention is not limited to the above-described embodiments, and various modifications may be made without departing from the spirit of the present invention.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited to these Examples.

<Preparation of resin film constituents>
The components shown in Table 1 were prepared as the constituent components of the resin film. Details of each component are shown below.

(Component (A): thermosetting component)
[Thermosetting resin]
A11: Bisphenol F type epoxy resin (epoxy resin which is liquid at 25° C., epoxy equivalent: 160, manufactured by Mitsubishi Chemical Corporation, trade name “jER806”, SP value: 10.8)
A12: Trifunctional naphthalene type epoxy resin (epoxy equivalent: 182, manufactured by DIC Corporation, trade name "HP-4750")

［式中、ｎ８は０〜１０の整数を示す。］
Ａ２２：ノボラック型フェノール樹脂（水酸基当量：１０４、旭有機材工業株式会社製、商品名「ＰＡＰＳ−ＰＮ２」） [Curing agent]
A21: Compound represented by the following formula (hydroxyl equivalent: 110, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name "SN-395")

[In formula, n8 shows the integer of 0-10. ]
A22: Novolac-type phenol resin (hydroxyl equivalent: 104, manufactured by Asahi Organic Materials Co., Ltd., trade name "PAPS-PN2")

[Curing accelerator]
A3: Shikoku Chemical Industry Co., Ltd., trade name "Curesol 2P4MZ"

(Component (B): inorganic filler)
[Inorganic filler surface-treated with a silane compound having an acid anhydride group]
B11: 100 parts by mass of spherical silica (“SO-C2” manufactured by Admatechs Co., Ltd., average particle diameter 0.5 μm) was used as a silane compound having an acid anhydride group (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “X-12”). -967C", SP value of silane compound: 9.98).
B12: 100 parts by mass of spherical silica (“SO-C2” manufactured by Admatechs Co., Ltd., average particle size 0.5 μm) was used as a silane compound having an acid anhydride group (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “X-12”). -967C", SP value of silane compound: 9.98) An inorganic filler surface-treated with 1.0 part by mass.
B13: 100 parts by mass of spherical silica (“SO-C2” manufactured by Admatechs Co., Ltd., average particle diameter 0.5 μm) was used as a silane compound having an acid anhydride group (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “X-12”). -967C", SP value of silane compound: 9.98) An inorganic filler surface-treated with 1.5 parts by mass.

[Inorganic filler not surface-treated with a silane compound having an acid anhydride group]
B21: Spherical silica (no surface treatment, manufactured by Admatechs Co., Ltd., trade name “SO-C2”, average particle size 0.5 μm).
B22: 100 parts by mass of spherical silica (manufactured by Admatechs Co., Ltd., trade name “SO-C2”, average particle size 0.5 μm) was used as a silane compound having a vinyl group (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBM-”). 1003", SP value of silane compound: 7.49) An inorganic filler surface-treated with 1.0 part by mass.
B23: Spherical silica (manufactured by Admatechs Co., Ltd., trade name “SO-C2”, average particle size 0.5 μm), 100 parts by mass of a silane compound having an epoxy group (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBM-”). 403", SP value of silane compound: 8.49) An inorganic filler surface-treated with 1.0 part by mass.
B24: 100 parts by mass of spherical silica (manufactured by Admatechs Co., Ltd., trade name “SO-C2”, average particle size 0.5 μm) was used as a silane compound having an aminophenyl group (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBM”). -573", SP value of silane compound: 9.15) An inorganic filler surface-treated with 1.0 part by mass.
B25: 100 parts by mass of spherical silica (manufactured by Admatechs Co., Ltd., trade name “SO-C2”, average particle size 0.5 μm) was used as a silane compound having an isocyanate group (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBM-”). 9007", SP value of silane compound: 9.17) An inorganic filler surface-treated with 1.0 part by mass.

(Component (C): Silane Compound Having Acid Anhydride Group)
C1: manufactured by Shin-Etsu Chemical Co., Ltd., product name "X-12-967C"

(Organic solvent)
D1: Methyl ethyl ketone (manufactured by Gordo Co., Ltd.)

<Production of resin film>
Each component was charged in a 1 L polyethylene container at the blending amount (unit: parts by mass) shown in Table 1, and then stirred and dispersed for 3 hours to obtain a mixed liquid. This mixed solution was filtered through nylon #200 mesh (opening diameter: 75 μm), and the filtrate was collected as a varnish resin composition. Next, using a coating machine, the varnish-shaped resin composition was applied onto a support (polyethylene terephthalate, manufactured by Oji Ftex Co., Ltd., thickness: 38 μm), and then the varnish-shaped resin composition was dried. As a result, a laminate having a resin film laminated on the support (total thickness: 188 μm, thickness of layer comprising resin film: 150 μm) was produced. The conditions for applying and drying the varnish resin composition are as follows.
・Coating method: Comma coat ・Drying speed: 1 m/min ・Drying conditions (temperature/furnace length): 110°C/3.3 m, 130°C/3.3 m, 140°C/3.3 m

<Evaluation>
The following evaluation was performed using the said laminated body.

(Evaluation of handleability (flexibility))
The handleability of the resin film was evaluated by the flexibility. Flexibility was evaluated by the following procedure using a bending tester. As a testing machine, a bending tester (JIS type 1, cylindrical mandrel method) manufactured by Yoshimitsu Seiki Co., Ltd. was prepared. A test piece was prepared by cutting the laminated body into 5 cm square pieces. The support side of the test piece was brought into contact with a cylindrical mandrel having a diameter of 2 mm, and the presence or absence of cracks in the resin film when the test piece was bent 180° was evaluated. Table 1 shows the evaluation results of handleability (flexibility). The case where no cracking occurred was regarded as good in flexibility, and indicated as "A" in the table. The case where cracking occurred was regarded as inferior in flexibility and was represented by "B" in the table.

(Evaluation of crack resistance)
[Preparation of evaluation sample]
A Naflon sheet (trade name: TOMBO 9000-S, "Naflon" is a registered trademark) manufactured by Nichias Corporation having a length of 200 mm x a width of 200 mm x a thickness of 0.5 mm was prepared. The center portion of the Naflon sheet was cut into a length of 40 mm, a width of 25 mm, and a thickness of 0.5 mm to obtain a test piece 10 having an opening 10a as shown in FIG. Next, four resin films having a thickness of 150 μm (films cut into a length of 50 mm and a width of 35 mm) were placed on the test piece 10 so as to cover the entire surface of the opening 10a. A laminate of the four resin films and the test piece 10 was pressed under vacuum (0.1 kPa) at a temperature of 110° C. and a pressure of 0.1 MPa for 5 minutes. Next, the pressure of the press was returned to normal pressure, the resin film was heated in an oven at 140° C. for 2 hours to cure, and then naturally cooled to 25° C. Then, a cured product of the resin composition (length 40 mm x width 25 mm x thickness 0.5 mm) formed in the opening 10a of the test piece 10 was obtained as an evaluation sample.

[Evaluation of crack resistance]
The crack resistance was evaluated using the evaluation sample. The evaluation method will be described with reference to FIG. FIG. 2A is a diagram showing an evaluation sample, and FIG. 2B is a diagram for explaining an evaluation method. The evaluation was performed by a three-point support type bending test using TENSILON manufactured by Orientec Co., Ltd. (type RTM-100). Specifically, as shown in FIG. 2B, one surface of the evaluation sample is supported by two fulcrums F arranged at intervals of 20 mm, and two fulcrums F on the other surface of the evaluation sample are supported. A load W was applied to the center position between them and the breaking energy was measured. The evaluation conditions are as follows. The evaluation results are shown in Table 1. When the breaking energy was 50 N·mm or more, the crack resistance was evaluated as good.
-Size of evaluation sample: length 40 mm x width 25 mm x thickness 0.5 mm
・Tensilon head speed (load speed): 1.0 mm/min ・Span (distance between fulcrums): 20 mm

FIG. 3 shows the relationship between the obtained breaking energy and the SP value of the silane compounds used in Example 2 and Comparative Examples 2-5. The vertical axis of FIG. 3 represents the breaking energy (unit: N·mm). The horizontal axis of FIG. 3 shows the SP value of the silane compound. In FIG. 3, A shows Example 2, B shows Comparative Example 4, C shows Comparative Example 5, D shows Comparative Example 3, and E shows Comparative Example 2.

From the results of Table 1, the resin compositions of the examples were good in both handleability and crack resistance. On the other hand, in the comparative example, handleability and crack resistance were poor.

10... test piece, 10a... opening, F... fulcrum, W... load.

Claims (6)

A resin film comprising a resin composition or a cured product thereof,
The resin composition,
Contains a thermosetting component, an inorganic filler surface-treated with a silane compound having an acid anhydride group ,
The thermosetting component includes an epoxy resin and a curing agent,
The epoxy resin includes an epoxy resin that is liquid at 25° C.,
The epoxy resin which is liquid at 25° C. is a bisphenol F type epoxy resin having an SP value of 8 or more and 12 or less,
The content of the epoxy resin that is liquid at 25° C. is 70 to 90 mass% based on the total mass of the epoxy resin,
The silane compound includes a compound represented by the following general formula (1),

[In the formula, R ¹ represents a single bond or a hydrocarbon group having 1 to 18 carbon atoms, R ² and R ³ each independently represent a hydrocarbon group having 1 to 18 carbon atoms, and k represents 1 to It is an integer of 3, l is an integer of 0 to 2, m is an integer of 1 to 3, and k+l+m=4. ]
The content of the silane compound is 0.2 to 1.0 parts by mass with respect to 100 parts by mass of the inorganic filler,
The average particle size of the inorganic filler is 0.01 to 50 μm,
The resin film, wherein the content of the inorganic filler is 50 to 95 mass% based on the total mass of the resin composition. The resin film according to claim 1, wherein the silane compound comprises 3-trimethoxysilylpropyl succinic anhydride. Used for sealing electronic parts, a resin film according to claim 1 or 2. A support and the resin film according to any one of claims 1 to 3 ,
A sealing material, in which the resin film is disposed on the support. An object to be sealed, and a sealing part for sealing the object to be sealed,
The sealing portion comprises a resin film according to any one of 請 Motomeko 1-3, sealing structure. The sealed structure according to claim 5 , wherein the sealed object is an electronic component.

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