JP2018032783A - Sealing sheet and manufacturing method of the same, and sealing structure and manufacturing method of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sealing sheet capable of obtaining a sealing portion excellent in adhesion to a metal layer and a manufacturing method of the same.SOLUTION: The sealing sheet has a resin layer having a surface having an arithmetic average roughness (Ra) of 0.1 μm or more. The method for manufacturing a sealing sheet includes a transfer step of bringing a metal member having irregularities into contact with the resin layer to transfer the irregularities to the surface of the resin layer. An arithmetic average roughness (Ra) of the surface of the resin layer after the transfer step is 0.1 μm or more.SELECTED DRAWING: None

Description

  The present invention relates to a sealing sheet and a manufacturing method thereof, and a sealing structure and a manufacturing method thereof.

  In recent years, there is a demand for downsizing, high performance, miniaturization and high density of electronic devices. In a semiconductor package, it has been required to form a metal layer on a sealing layer for the purpose of producing a wiring on the sealing layer and forming an electromagnetic wave shielding layer, which has not been performed so far. For forming a metal layer on the sealing layer, a sputtering method or a plating method after forming a primer layer excellent in adhesion to plating is used (for example, see Patent Document 1 below). This is because it is difficult to obtain a practical plating adhesive force on the sealing layer formed of the sealing resin composition.

JP 2009-290217 A

  However, the sputtering method requires a vacuum device and is difficult to apply to a large semiconductor package and takes a long time to form a metal layer. There are problems such as an increase in the process and a decrease in the characteristics of the semiconductor package due to a primer composition different from the sealing resin composition.

  This invention is made | formed in view of the said subject, and it aims at providing the sealing sheet which can obtain the sealing part which is excellent in adhesiveness with a metal layer, and its manufacturing method. Moreover, an object of this invention is to provide the sealing structure using the said sealing sheet, and its manufacturing method.

  The sealing sheet which concerns on this invention is equipped with the resin layer which has the surface whose arithmetic mean roughness (Ra) is 0.1 micrometer or more. The sealing sheet which concerns on this invention may further be equipped with the metal layer arrange | positioned on the said surface of the said resin layer.

  The manufacturing method of the sealing sheet which concerns on this invention is equipped with the transfer process which makes the metal member which has an unevenness | corrugation contact a resin layer, and transfers the said unevenness | corrugation to the surface of the said resin layer, The said resin layer after the said transfer process The arithmetic average roughness (Ra) of the surface is 0.1 μm or more. The manufacturing method of the sealing sheet which concerns on this invention may further comprise the process of removing the said metal member from the laminated body obtained by making the said metal member contact the said resin layer.

  The sealing structure which concerns on this invention is equipped with the to-be-sealed body and the sealing part which seals the said to-be-sealed body, and the said sealing part is the sealing sheet which concerns on this invention, or this It is the said resin layer of the sealing sheet obtained by the manufacturing method of the sealing sheet which concerns on invention, or its hardened | cured material. The sealing structure which concerns on this invention may further be equipped with the metal layer arrange | positioned on the said sealing part. The sealed object may be an electronic component.

  The manufacturing method of the sealing structure which concerns on this invention is the said resin layer of the sealing sheet obtained by the sealing sheet which concerns on this invention, or the sealing sheet which concerns on this invention, or its hardened | cured material. A step of sealing the object to be sealed by the sealing portion; The manufacturing method of the sealing structure according to the present invention may further include a step of forming a metal layer on the sealing portion. The sealed object may be an electronic component.

  ADVANTAGE OF THE INVENTION According to this invention, a sealing sheet provided with the resin layer which has the unevenness | corrugation which can form a conductor layer can be provided. According to the present invention, by forming a metal layer on a surface (uneven surface) having an arithmetic average roughness (Ra) of 0.1 μm or more, it is possible to obtain a sealing portion with excellent adhesion to the metal layer. it can.

  In addition, according to the present invention, after the object to be sealed is sealed, the metal layer is formed on the sealing portion, so that the metal layer can be directly used for wiring formation, thereby simplifying the wiring formation process. Can do. Furthermore, even when the metal layer is removed by etching, the conductive layer can be formed on the uneven surface by a semi-additive process method or the like because the unevenness is formed on the upper surface of the sealing sheet. The encapsulating sheet according to the present invention can be suitably used for encapsulating semiconductor devices, embedding electronic components arranged on a printed wiring board, and the like.

  Hereinafter, embodiments for carrying out the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

  In this specification, the arithmetic average roughness (Ra) is determined using, for example, a non-contact three-dimensional surface shape roughness measurement system (“Wyko NT9100” manufactured by Bruker Ax Co., Ltd.), a VSI contact mode, and a 50 × lens. Measured under the condition of a measurement range of 121 μm × 92 μm, it can be obtained as an average value of 10 points selected at random.

<Sealing sheet>
The sealing sheet which concerns on this embodiment is equipped with the resin layer (resin layer for sealing) which has the surface (uneven | corrugated surface) whose arithmetic mean roughness (Ra) is 0.1 micrometer or more. The sealing sheet which concerns on this embodiment is equipped with the resin layer which has the unevenness | corrugation which can form a conductor layer. According to the sealing sheet which concerns on this embodiment, a to-be-sealed body can be sealed with a resin layer. The resin layer may be in the form of a film (a film resin composition such as a film epoxy resin composition). The cured product according to the present embodiment is a cured product of the resin layer of the sealing sheet according to the present embodiment.

  The sealing sheet which concerns on this embodiment can be used for a semi-additive process method. The semi-additive process method is a method in which an electroless plating layer is formed on an insulating layer and a circuit is formed by electroless plating using this layer as a power feeding layer, and a fine wiring can be formed.

  The sealing sheet which concerns on this embodiment can be used for the sealing by the shaping | molding method (laminate etc.) which does not require a metal mold | die, the sealing by the compression molding which uses a metal mold | die. The sealing sheet which concerns on this embodiment can be used in order to seal an electronic component or an electronic device.

  The arithmetic average roughness (Ra) of the uneven surface of the resin layer is preferably 0.1 μm or more, more preferably 0.2 μm or more, and further preferably 0.3 μm or more from the viewpoint of easily increasing the plating peel strength. The arithmetic average roughness (Ra) of the uneven surface of the resin layer is preferably 2.5 μm or less, more preferably 2.0 μm or less, further preferably 1.5 μm or less, and further preferably 1.0 μm from the viewpoint of easy formation of fine wiring. The following is particularly preferable, and 0.5 μm or less is extremely preferable.

  The thickness of the resin layer may be 25 μm or more, 50 μm or more, or 100 μm or more from the viewpoint of easily preventing cracking of the sealing sheet. The thickness of the resin layer may be 2000 μm or less, 500 μm or less, or 300 μm or less from the viewpoint of sufficiently easily sealing the object to be sealed. The thickness of the cured product according to the present embodiment may be in the range related to the thickness of the resin layer.

  The sealing sheet which concerns on this embodiment may be provided with the metal layer (support body, metal foil etc.) arrange | positioned on the uneven surface of a resin layer. As a metal layer, the metal foil which has an uneven | corrugated pattern (surface uneven | corrugated pattern. The following is the same) mentioned later can be used.

  The sealing sheet which concerns on this embodiment may be provided with the metal layer which has an uneven | corrugated pattern on the opposite side to a metal layer. Moreover, the sealing sheet which concerns on this embodiment may be provided with the film (for example, metal foil and polymer film) which does not have an uneven | corrugated pattern on the opposite side to a metal layer.

  Examples of polymer films (protective films) that do not have an uneven pattern include polyolefin films such as polyethylene films and polypropylene films; polyester films such as polyethylene terephthalate films; polyvinyl chloride films; polycarbonate films; acetylcellulose films; A film etc. are mentioned. The thickness of the polymer film (protective film) that does not have the uneven pattern is not particularly limited, but a viewpoint that a sufficient protective effect can be easily obtained, and the sealing sheet is wound into a roll shape 12-100 micrometers may be sufficient from a viewpoint of reducing the thickness at the time.

  The constituent material of the resin layer is not particularly limited as long as it is a resin usually used for sealing an object to be sealed such as an electronic component. The resin layer is preferably a layer made of a curable resin composition. The curable resin composition may be either thermosetting or photocurable. The resin layer may contain a B-staged curable resin composition (such as an epoxy resin composition).

  As a thermosetting resin composition, the resin composition containing a thermosetting component and an inorganic filler is mentioned, for example. Examples of the thermosetting component include thermosetting resins (such as epoxy resins and melamine resins). The resin layer of the sealing sheet according to the present embodiment includes, for example, an epoxy resin composition. The epoxy resin composition contains, for example, a thermosetting component including (A) an epoxy resin and (B) a curing agent.

((A) Epoxy resin)
(A) The epoxy resin can contain at least one epoxy resin that is liquid at 25 ° C. (hereinafter referred to as “epoxy resin (a1)”) in order to impart flexibility to the film-like epoxy resin composition. . Here, the “epoxy resin that is liquid at 25 ° C.” means that the value obtained by measuring the viscosity of the epoxy resin held at 25 ° C. using an E-type viscometer or a B-type viscometer is 400 Pa · s. The following epoxy resin is shown.

  There is no restriction | limiting in particular as an epoxy resin (a1), For example, the epoxy resin which has a 2 or more glycidyl group in 1 molecule can be used. Examples of the epoxy resin (a1) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, and naphthalene type epoxy resin.

  A commercially available product may be used as the epoxy resin (a1). As commercial products of the epoxy resin (a1), trade name “jER825” (bisphenol A type epoxy resin, epoxy equivalent: 175) manufactured by Mitsubishi Chemical Corporation, trade name “jER806” (bisphenol F type, manufactured by Mitsubishi Chemical Corporation) Epoxy resin, epoxy equivalent: 160), DIC Corporation trade name “HP-4032D” (naphthalene type epoxy resin, epoxy equivalent: 141), DIC Corporation trade name “EXA-4850”, etc. Is mentioned. An epoxy resin (a1) may be used individually by 1 type, and may use 2 or more types together.

  The content of the epoxy resin (a1) is 30% by mass or more based on the total amount of the (A) epoxy resin and the (B) curing agent from the viewpoint of obtaining further excellent handling properties (flexibility, etc.) Or 35% by mass or more, 37% by mass or more, or 40% by mass or more. The content of the epoxy resin (a1) is based on the total amount of the (A) epoxy resin and the (B) curing agent from the viewpoint that the peelability of the protective layer is good when used as a sealing sheet provided with a protective layer. 70 mass% or less may be sufficient as it, and 65 mass% or less may be sufficient. The content of the epoxy resin (a1) is (A) from the viewpoint that the peelability of the protective layer is good when used as a sealing sheet provided with a protective layer while maintaining excellent handling properties (flexibility, etc.). ) Based on the total amount of epoxy resin and (B) curing agent, it may be 30 to 70% by mass or 30 to 65% by mass.

  The content of the epoxy resin (a1) may be 60% by mass or more, and 65% by mass or more based on the total amount of the (A) epoxy resin from the viewpoint of obtaining further excellent handling properties (flexibility, etc.). It may be 70 mass% or more. The content of the epoxy resin (a1) may be 100% by mass or less, and 95% by mass or less, based on the total amount of the (A) epoxy resin, from the viewpoint of obtaining further excellent handling properties (flexibility, etc.). It may be 90 mass% or less.

  (A) The epoxy resin further contains an epoxy resin other than the epoxy resin (a1) that is liquid at 25 ° C. (hereinafter referred to as “epoxy resin (a2)”, for example, an epoxy resin that is not liquid at 25 ° C.). Also good. As the epoxy resin (a2), naphthalene type epoxy resin (tetrafunctional naphthalene type epoxy resin, trifunctional naphthalene type epoxy resin, etc.), anthracene type epoxy resin, trisphenylmethane type epoxy resin, dicyclopentadiene type epoxy resin, biphenyl aralkyl Type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin (o-cresol novolac type epoxy resin, etc.), dihydroxybenzene novolac type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, hydantoin type epoxy resin, Examples include isocyanurate type epoxy resins. The epoxy resin (a2) may be a naphthalene type epoxy resin from the viewpoint of obtaining further excellent heat resistance. An epoxy resin (a2) may be used individually by 1 type, and may use 2 or more types together.

  A commercially available product may be used as the epoxy resin (a2). As a commercial product of epoxy resin (a2), DIC Corporation trade name “HP-4700” (tetrafunctional naphthalene type epoxy resin), trade name “HP-4750” (trifunctional naphthalene type epoxy resin), trade name “HP-4710” (tetrafunctional naphthalene type epoxy resin), trade name “Epicron N-770” (phenol novolac type epoxy resin), trade name “Epicron N-660” (cresol novolac type epoxy resin) and trade name “Epicron” “HP-7200H” (dicyclopentadiene type epoxy resin), trade name “EPPN-502H” (trisphenylmethane type epoxy resin) and trade name “NC-3000” (biphenylaralkyl type epoxy resin) manufactured by Nippon Kayaku Co., Ltd. , Trade name “ESN-355” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. Type epoxy resin), trade name “YX-8800” (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Corporation, trade name “ESCN-190-2” (o-cresol novolac type epoxy resin) manufactured by Sumitomo Chemical Co., Ltd. Etc.

((B) curing agent)
(B) A hardening | curing agent can be especially used without a restriction | limiting especially if it has 2 or more of functional groups which react with a glycidyl group in 1 molecule. (B) As a hardening | curing agent, a phenol resin, an acid anhydride, an imidazole compound, an aliphatic amine, an alicyclic amine, etc. are mentioned. (B) A hardening | curing agent can be used individually by 1 type or in combination of 2 or more types.

  (B) As a phenol resin which is a curing agent, a novolac type phenol resin (a resin obtained by condensation or cocondensation of phenols and aldehydes under an acidic catalyst); trisphenylmethane type phenol resin; polyparavinyl Phenol resins; Phenol / aralkyl resins (such as phenol / aralkyl resins having a xylylene group synthesized from phenols and dimethoxyparaxylene); Phenol resins having a biphenyl skeleton (such as biphenyl aralkyl type phenol resins), and the like. Examples of the phenols include phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, and the like. Examples of the aldehydes include formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde and the like. (B) The curing agent may be a biphenyl aralkyl type phenol resin from the viewpoint of obtaining excellent flame retardancy, or may be a novolac type phenol resin from the viewpoint of obtaining excellent heat resistance. A phenol resin may be used individually by 1 type, and may use 2 or more types together.

  (B) A commercially available product may be used as the curing agent. (B) As a commercial product of the curing agent, trade name “PAPS-PN2” (Novolac type phenol resin) manufactured by Asahi Organic Materials Co., Ltd., trade name “SK Resin HE200C-7” manufactured by Air Water Co., Ltd. ( Biphenyl aralkyl type phenol resin), trade name “HE910-10” (trisphenylmethane type phenol resin), trade names “MEH-7000”, “DL-92”, “H-4” and “M-4” manufactured by Meiwa Kasei Co., Ltd. “HF-1M”, trade name “LVR-8210DL”, “ELP” series and “NC” series manufactured by Gunei Chemical Industry Co., Ltd., trade name “HP-850N” manufactured by Hitachi Chemical Co., Ltd. (novolak type phenol resin) , And trade names “HN-2200”, “HN-2000”, “HN-5500” and “MHAC-P” (all of which are acid anhydride groups) Compound) or the like having the like.

  (A) Ratio of equivalent (epoxy equivalent) of glycidyl group of epoxy resin to equivalent (for example, hydroxyl equivalent) of functional group (for example, phenolic hydroxyl group) that reacts with glycidyl group in (B) curing agent ((A) epoxy The equivalent of the glycidyl group of the resin / (equivalent of the functional group that reacts with the glycidyl group in the (B) curing agent) may be 0.7 or more from the viewpoint of reducing the amount of unreacted (B) curing agent, It may be 0.8 or more, or 0.9 or more. 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 (A) epoxy resin. The ratio may be 0.7 to 2.0 or 0.8 to 1.8 from the viewpoint of reducing the amount of unreacted (A) epoxy resin and (B) curing agent, 0.9-1.7 may be sufficient.

((C) inorganic filler)
(C) As an inorganic filler, a conventionally well-known inorganic filler can be used and it is not specifically limited. (C) As an inorganic filler, barium sulfate; barium titanate; silicas such as amorphous silica, crystalline silica, fused silica, spherical silica; talc; clay; magnesium carbonate; calcium carbonate; aluminum oxide; aluminum hydroxide Silicon nitride; aluminum nitride and the like. (C) The inorganic filler has a viewpoint that an effect of improving dispersibility in the resin and an effect of suppressing sedimentation in the varnish can be easily obtained by surface modification or the like, and a desired value because it has a relatively small coefficient of thermal expansion. Silicas may be used from the viewpoint of easily obtaining cured film characteristics. (C) An inorganic filler may be used individually by 1 type, and may use 2 or more types together.

  (C) The inorganic filler may be surface-modified. The method of surface modification is not particularly limited, but it is simple, has many types of functional groups, and easily imparts desired characteristics, so even surface modification using a silane coupling agent. Good. Silane coupling agents include alkyl silanes, alkoxy silanes, vinyl silanes, epoxy silanes, amino silanes, acrylic silanes, methacryl silanes, mercapto silanes, sulfide silanes, isocyanate silanes, isocinaurate silanes, ureido silanes, sulfur silanes, styryl silanes, alkyls. Examples include chlorosilane and silane having an acid anhydride group. Among these, from the viewpoint of excellent dispersibility in a resin (such as an epoxy resin), at least one selected from the group consisting of phenylaminosilane and silane having an acid anhydride group may be used. A silane coupling agent may be used individually by 1 type, and may use 2 or more types together.

  (C) The average particle diameter of the inorganic filler is such that aggregation of the inorganic filler is easily suppressed and sufficient dispersion is possible, and varnish is used in the production of a film-like resin composition (film-like epoxy resin composition, etc.). From the viewpoint of easily suppressing the sedimentation of particles therein, the following ranges may be used. (C) The average particle diameter of the inorganic filler may be 0.01 μm or more, 0.1 μm or more, or 0.3 μm or more. (C) The average particle diameter of the inorganic filler may exceed 5 μm, may be 5.2 μm or more, and may be 5.5 μm or more. (C) The average particle diameter of the inorganic filler may be 50 μm or less, 25 μm or less, or 10 μm or less. From these viewpoints, the average particle diameter of the (C) inorganic filler may be 0.01 to 50 μm, 0.1 to 25 μm, 0.3 to 10 μm, It may be more than 5 μm and 10 μm or less, may be 5.2 to 10 μm, and may be 5.5 to 10 μm.

  (C) The content of the inorganic filler increases warpage of the electronic component device (semiconductor device, etc.) due to the difference in thermal expansion coefficient between the sealed body (electronic device such as a semiconductor element) and the sealing portion. Can be easily prevented, and cracks are generated in the drying process during the production of the film-like resin composition (film-like epoxy resin composition, etc.), and the film-like resin composition (film-like epoxy resin composition, etc.) From the viewpoint of easily suppressing the problem that the sealed object cannot be sufficiently sealed due to an increase in the melt viscosity, the following range may be used. (C) The content of the inorganic filler may be 50% by mass or more, 60% by mass or more based on the total amount of the resin composition (excluding solvents such as organic solvents), and 70 It may be greater than or equal to mass%. (C) The content of the inorganic filler may be 95% by mass or less or 90% by mass or less based on the total amount of the resin composition (excluding solvents such as organic solvents). From these viewpoints, the content of the inorganic filler (C) may be 50% by mass or more based on the total amount of the resin composition (excluding solvents such as organic solvents), and is 60 to 95% by mass. It may be 70 to 90% by mass.

((D) curing accelerator)
The resin composition according to this embodiment may further contain (D) a curing accelerator. (D) When the curing reaction proceeds without using a curing accelerator, (D) the curing accelerator may not be used.

  (D) Although it does not restrict | limit especially as a hardening accelerator, For example, the group which consists of an amine type hardening accelerator, an imidazole type hardening accelerator, a urea type hardening accelerator, and a phosphorus type hardening accelerator. It may be at least one selected from more. Examples of amine-based curing accelerators include 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonene. Examples of the imidazole curing accelerator include 2-phenyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, and the like. Examples of urea curing accelerators include 3-phenyl-1,1-dimethylurea. Examples of the phosphorus-based curing accelerator include triphenylphosphine and its addition reaction product, (4-hydroxyphenyl) diphenylphosphine, bis (4-hydroxyphenyl) phenylphosphine, tris (4-hydroxyphenyl) phosphine, and the like.

  (D) As a hardening accelerator, the kind of derivative | guide_body is abundant and an imidazole type hardening accelerator may be sufficient from the viewpoint of being easy to obtain desired active temperature. A commercially available product may be used as the imidazole curing accelerator. Examples of commercially available imidazole-based curing accelerators include trade names “CURESOL 2PHZ-PW” and “CURESOL 2P4MZ” manufactured by Shikoku Kasei Kogyo Co., Ltd. (D) A hardening accelerator may be used individually by 1 type, and may use 2 or more types together.

  (D) The content of the curing accelerator is a viewpoint that a sufficient curing accelerating effect can be easily obtained, and a process (coating) for producing a film-like resin composition (film-like epoxy resin composition or the like). And drying), or during the storage of the film-like resin composition (film-like epoxy resin composition, etc.), it is possible to suppress curing, and the film-like resin composition (film-like epoxy resin composition). The following ranges may be used from the viewpoint of easily preventing cracking of the product and the like and molding defects accompanying an increase in melt viscosity. (D) The content of the curing accelerator may be 0.01% by mass or more, based on the total amount of (A) epoxy resin and (B) curing agent, and 0.1% by mass or more. It may be 0.3 mass% or more. (D) The content of the curing accelerator may be 5% by mass or less or 3% by mass or less based on the total amount of (A) epoxy resin and (B) curing agent. It may be 5% by mass or less. From these viewpoints, the content of the (D) curing accelerator may be 0.01 to 5% by mass based on the total amount of the (A) epoxy resin and the (B) curing agent. -3 mass% may be sufficient and 0.3-1.5 mass% may be sufficient.

(Other ingredients)
The resin composition according to the present embodiment may further contain other additives. Examples of such additives include pigments, dyes, mold release agents, antioxidants, stress relaxation agents, coupling agents, surface tension modifiers, ion exchangers, colorants, flame retardants, and the like. 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 as necessary.

<Manufacturing method of sealing sheet>
The manufacturing method of the sealing sheet according to the present embodiment includes a transfer step of bringing a metal member having unevenness into contact with a resin layer and transferring the unevenness to the surface of the resin layer, and the resin layer after the transfer step The arithmetic average roughness (Ra) of the surface is 0.1 μm or more. As a metal member, metal foil is mentioned, for example. In the transfer step, the unevenness may be transferred to the resin layer by forming a resin layer on the metal member, and the unevenness is transferred to the resin layer by pressing the metal member against the resin layer after forming the resin layer. Also good. The manufacturing method of the sealing sheet which concerns on this embodiment may further be equipped with the process (etching process etc.) which removes a metal member from the laminated body obtained by making a metal member contact a resin layer after a transfer process. .

  The arithmetic average roughness (Ra) of the concavo-convex surface of the metal member having concavo-convex is preferably 0.1 μm or more, more preferably 0.2 μm or more from the viewpoint that the concavo-convex is easily transferred to the resin layer and the plating peel strength is easily increased. More preferably, it is 0.3 μm or more. The arithmetic average roughness (Ra) of the uneven surface of the metal member is preferably 2.5 μm or less, more preferably 2.0 μm or less, still more preferably 1.5 μm or less, and further preferably 1.0 μm from the viewpoint of easy formation of fine wiring. The following is particularly preferable, and 0.5 μm or less is extremely preferable.

  The manufacturing method of the sealing sheet which concerns on this embodiment may further be equipped with the resin layer formation process which forms a resin layer before a transfer process. When the resin layer is in the form of a film, for example, the resin layer can be obtained by molding a resin composition (such as an epoxy resin composition) into a film.

  The first aspect of the resin layer forming step is a varnish coating method, for example, a step of forming a coating film on a substrate using a varnish, and heating and drying the coating film to form a resin layer (for example, a film-like layer). (Resin layer). A metal foil having a concavo-convex pattern may be used as the substrate for forming the coating film, and the concavo-convex surface of the concavo-convex surface can be transferred to the resin layer by forming a coating film on the concavo-convex surface of the metal foil. The 2nd aspect of a resin layer formation process is a process of shape | molding a resin composition (for example, solid resin composition) in a sheet form, and obtaining a resin layer (for example, film-form resin layer). From the viewpoint of easily controlling the thickness, a varnish coating method can be used.

  The resin composition used in the resin layer forming step can be produced, for example, by mixing a thermosetting resin, a curing agent, an inorganic filler, and various 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. In the 1st aspect of a resin layer formation process, it can form into a film by the varnish coating method using the varnish obtained by melt | dissolving each compounding component in a solvent etc., for example. In the second aspect of the resin layer forming step, for example, a resin composition (for example, a solid resin composition) prepared by kneading each compounding component with a kneader, two rolls, a continuous kneader or the like is extruded into a sheet shape. A film can be formed.

  A conventionally well-known organic solvent can be used as a solvent. The organic solvent may be a solvent that can dissolve components other than the inorganic filler, and includes aliphatic hydrocarbons, aromatic hydrocarbons, terpenes, halogens, esters, ketones, alcohols, aldehydes. Etc. An organic solvent may be used individually by 1 type, and may use 2 or more types together.

  The organic solvent may be an ester, a ketone or an alcohol from the viewpoint of low environmental burden and from the viewpoint of easily dissolving the thermosetting resin and the curing agent. As the organic solvent, ketones may be used from the viewpoint of particularly easily dissolving the thermosetting resin and the curing agent. The organic solvent may be acetone, methyl ethyl ketone, or 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 may be 2 to 30% by mass or 5 to 25% by mass based on the total amount 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 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.

  In the varnish coating method, a coating sheet obtained by applying varnish to the concavo-convex surface of a metal foil having a concavo-convex pattern can be produced by heating and drying by hot air spraying or the like to produce a sealing sheet having concavo-convex. . Although it does not specifically limit as a coating method used for application | coating, A die coat, a comma coat, etc. are mentioned.

  As heating drying of the said coating film, a coating film can be heated at the temperature of +/- 10 degreeC of the boiling point of an organic solvent in time 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.

  Examples of the metal foil having a concavo-convex pattern include copper foil, nickel foil, and aluminum foil.

  It does not specifically limit as a kind of copper foil, Electrolytic copper foil, rolled copper foil, etc. are mentioned. As a commercial product of copper foil, Mitsui Kinzoku Mining Co., Ltd., trade name: MT18Ex; Furukawa Electric Co., Ltd., trade name: F2-WS12; Fukuda Metal Foil Powder Industry Co., Ltd., trade name: CFT9L-UR-18 , CFT9L-UR-35; manufactured by Nippon Electrolytic Co., Ltd., trade names: YGP-12, YGP-18, and the like.

  The thickness of the metal foil is not particularly limited, but may be 2 to 200 μm from the viewpoint of excellent workability and drying property. With such a thickness, it is possible to prevent a problem that a metal foil (copper foil or the like) as a support is bent during coating. 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.

<Sealing structure and manufacturing method thereof>
The sealing structure according to the present embodiment includes an object to be sealed (first object to be sealed) and a sealing portion that seals the object to be sealed. It is the resin layer of the sealing sheet which concerns on the form, or the sealing sheet obtained by the manufacturing method of the sealing sheet which concerns on this embodiment, or its hardened | cured material. The sealing structure according to the present embodiment is, for example, an electronic component device that includes an electronic component as an object to be sealed. Examples of the electronic component device including the electronic component include a semiconductor device including a semiconductor element.

  The manufacturing method of the sealing structure which concerns on this embodiment is the sealing sheet which concerns on this embodiment, or the resin layer of the sealing sheet obtained by the manufacturing method of the sealing sheet which concerns on this embodiment, or its hardened | cured material The sealing process which seals a to-be-sealed body by the sealing part which is is provided. The manufacturing method of the sealing structure which concerns on this embodiment is a manufacturing method of an electronic component apparatus provided with an electronic component as a to-be-sealed body, for example.

  In the sealing step, for example, the resin layer is brought into contact with the object to be sealed from the side opposite to the uneven surface of the resin layer. In this case, the sealing part can maintain the uneven surface of the resin layer.

  In the sealing process, for example, an embedding process for embedding an electronic component in the resin layer by pressing the resin layer of the sealing sheet against the object to be sealed, and a curing process for curing the resin layer in which the object to be sealed is embedded. And may have.

In the embedding step, for example, the protective film of the sealing sheet is peeled off, and the exposed surface is bonded onto a base material (substrate or the like) on which the object to be sealed is placed, and then a vacuum manufactured by Meiki Seisakusho Co., Ltd. Using a pressure laminator or the like, pressure bonding (lamination) is performed under the following conditions (under reduced pressure of 13 hPa or less).
Depressurization time: 30 seconds Pressure bonding temperature: 90 ° C
Pressure bonding pressure: 0.50 MPa
Pressure bonding time: 45 seconds

  After the pressure bonding, the laminated sealing sheets may be smoothed by, for example, pressing a pressure bonding member from the support side. The press conditions after the smoothing treatment can be the same conditions as the press-bonding conditions for the above-described crimping. The smoothing treatment can be performed with a commercially available laminator. In addition, you may perform lamination | stacking and a smoothing process continuously using said commercially available vacuum laminator.

  In the curing step, for example, the resin layer can be thermally cured. The thermosetting conditions for the resin layer are not particularly limited. For example, although it varies depending on the type of the resin composition, the curing temperature can be in the range of 90 ° C. to 250 ° C., and the curing time can be in the range of 5 minutes to 360 minutes.

  The sealing structure which concerns on this embodiment may be provided with the metal layer arrange | positioned on the sealing part. The said metal layer is arrange | positioned on the uneven surface of the sealing part, for example. The manufacturing method of the sealing structure according to the present embodiment may further include a step of forming a metal layer on the sealing portion.

  The sealing structure according to the present embodiment may further include a sealed body (second sealed body, electronic component, etc.) on the metal layer (on the side opposite to the sealing portion). The manufacturing method of the sealing structure according to the present embodiment further includes a step of arranging an object to be sealed (second object to be sealed, electronic component, etc.) on the metal layer (on the side opposite to the sealing part). You may have.

  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, but the present invention is not limited to these examples.

<Preparation of sealing sheet>
The compounds shown in Table 1 were prepared as components constituting the film-like epoxy resin composition. Details of each component are shown below.

(A) Epoxy resin [component that is liquid at 25 ° C.]
A1: Bisphenol F type epoxy resin (epoxy equivalent: 160, manufactured by Mitsubishi Chemical Corporation, trade name “jER806”)
[Ingredients that are not liquid at 25 ° C]
A2: Trifunctional naphthalene type epoxy resin (epoxy equivalent: 182 manufactured by DIC Corporation, trade name “HP-4750”)

(B) Curing agent B1: Novolac type phenol resin (hydroxyl equivalent: 106, manufactured by Hitachi Chemical Co., Ltd., trade name “HP-850N”)
B2: Compound having an acid anhydride group (methyl-3,6 endomethylene-1,2,3,6-tetrahydrophthalic anhydride, molecular weight: 178, manufactured by Hitachi Chemical Co., Ltd., trade name “MHAC-P”)

(C) Inorganic filler C1: Silica (manufactured by Admatechs, trade name “SX-E2”, phenylaminosilane treatment, average particle size: 5.8 μm)

(D) Curing accelerator D1: 2-phenyl-4-methylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name “CURESOL 2P4MZ”)

(E) Organic solvent E1: Methyl ethyl ketone (Gordo Co., Ltd.)

(F) Copper foil having a concavo-convex pattern (base material)
F1: Furukawa Electric Co., Ltd., trade name “F2-WS12”, Ra: 0.45 μm
F2: manufactured by Nippon Electrolytic Co., Ltd., trade name “YGP-12”, Ra: 1.4 μm

(G) Polymer film (base material)
G1: manufactured by Unitika Ltd., trade name “Unipeel”, Ra: 0.03 μm

(Examples 1 and 2)
Each component of the blending amount (unit: part by mass) shown in Table 1 was charged into a 1 L polyethylene container, and then stirred for 3 hours to disperse and mix to obtain a mixed solution. The mixture was filtered through nylon # 200 mesh (opening diameter: 75 μm), and the filtrate was collected as a varnish-like epoxy resin composition. Next, using a coating machine, (F1) the varnish-like epoxy resin composition is applied on the roughened surface of the copper foil having a concavo-convex pattern, and then dried under the following conditions, whereby the support and the film are formed. A laminate (resin layer thickness: 150 μm) made of an epoxy resin composition (resin layer) was produced. The sealing sheet was obtained by arrange | positioning the protective layer (polyethylene terephthalate film) of 50 micrometers thickness on the opposite side to the support body (F1 copper foil) of a resin layer.
Coating machine: manufactured by Hirano Techseed Co., Ltd. Coating head method: Die Coating and drying speed: 5 m / min Drying conditions (temperature / furnace length): 60 ° C./3.3 m, 90 ° C./3.3 m, 110 ° C./3. 3m

(Examples 3 and 4)
Each component of the blending amount (unit: part by mass) shown in Table 1 was charged into a 1 L polyethylene container, and then stirred for 3 hours to disperse and mix to obtain a mixed solution. The mixture was filtered through nylon # 200 mesh (opening diameter: 75 μm), and the filtrate was collected as a varnish-like epoxy resin composition. Next, by applying this varnish-like epoxy resin composition on the roughened surface of the copper foil having a concavo-convex pattern using a coating machine under the same conditions as in Example 1, A laminate (resin layer thickness: 150 μm) composed of a support and a film-like epoxy resin composition (resin layer) was produced. The sealing sheet was obtained by arrange | positioning the protective layer (polyethylene terephthalate film) of 50 micrometers thickness on the opposite side to the support body (copper foil of F2) of a resin layer.

(Comparative Examples 1 and 2)
Each component of the blending amount (unit: part by mass) shown in Table 1 was charged into a 1 L polyethylene container, and then stirred for 3 hours to disperse and mix to obtain a mixed solution. The mixture was filtered through nylon # 200 mesh (opening diameter: 75 μm), and the filtrate was collected as a varnish-like epoxy resin composition. Next, using a coating machine, (G1) this varnish-like epoxy resin composition was coated on the polymer film under the same conditions as in Example 1 and then dried, whereby the support and the film-like epoxy resin were dried. A laminate (resin layer thickness: 150 μm) made of the composition (resin layer) was prepared. The sealing sheet was obtained by arrange | positioning the protective layer (polyethylene terephthalate film) of 50 micrometers thickness on the opposite side to the support body (G1 polymer film) of a resin layer.

<Production of evaluation substrate>
(1) Lamination of sealing sheet The protective film of the sealing sheet produced by the Example and the comparative example was peeled, and it bonded together so that a resin layer might join with the board | substrate (brand name: E-679) by Hitachi Chemical. It was. Next, using a vacuum pressure laminator manufactured by Meiki Seisakusho Co., Ltd., a laminate was produced by pressure bonding under the following conditions (under reduced pressure of 13 hPa or less).
Depressurization time: 30 seconds Pressure bonding temperature: 90 ° C
Pressure bonding pressure: 0.50 MPa
Pressure bonding time: 45 seconds

(2-1) Curing of resin layer in laminate having copper foil The laminate obtained using the sealing sheet of the example is heated at 100 ° C. for 10 minutes and then at 140 ° C. for 60 minutes. Thus, the resin layer was thermally cured. Then, the resin layer was exposed by etching the copper foil. The arithmetic average roughness (Ra) of the exposed surface of the resin layer (the surface in contact with the copper foil) was 0.1 μm or more.

(2-2) Curing of resin layer in laminate having polymer film The laminate obtained using the sealing sheet of the comparative example is heated at 100 ° C. for 10 minutes and then at 140 ° C. for 60 minutes. Thus, the resin layer was thermally cured. Thereafter, the polymer film was removed to expose the resin layer. The arithmetic average roughness (Ra) of the exposed surface of the resin layer (the surface in contact with the polymer film) was less than 0.1 μm.

(3) Formation of conductor layer Next, a copper plating process was performed on the exposed resin layer. The laminate including the resin layer was treated with an alkali cleaner (cleaner securigant 902) at 60 ° C. for 5 minutes to degrease and clean the surface. After washing, the laminate was treated with a predip solution (Predip Neogant B) at 25 ° C. for 2 minutes. Thereafter, the laminate was treated with an activator solution (activator Neogant 834) at 40 ° C. for 5 minutes to attach a palladium catalyst. Next, it was treated with a reducing solution (reducer Neogant WA) at 30 ° C. for 5 minutes. Next, the laminate was placed in a chemical copper solution (basic print gantt MSK-DK, copper print gantt MSK, stabilizer print gantt MSK), and electroless plating was performed until the plating thickness reached about 0.5 μm. After electroless plating, annealing was performed at a temperature of 120 ° C. for 30 minutes to remove residual hydrogen gas. In all the steps up to the electroless plating step, each step was performed while the processing solution was 1 L on a beaker scale and the laminate was rocked. Next, electrolytic plating was performed on the electroless-plated laminate until the plating thickness reached 20 μm. As electrolytic plating, copper sulfate (reducer Cu) was used, and electrolytic copper plating was performed at a current of 0.6 A / cm ² . After baking at 180 ° C. × 1 hr was performed. Thereafter, the substrate was thoroughly washed with pure water and thoroughly dried with a vacuum dryer to obtain an evaluation substrate.

<Measurement of peel strength>
By etching the copper, a portion having a width of 5 mm and a length of 40 mm was formed on a part of the evaluation substrate, and one end thereof was peeled off at the copper layer / resin interface. Then, using a tensile tester (trade name “Autograph”, manufactured by Shimadzu Corporation), the load when peeled off at room temperature at a tensile speed of 50 mm / min was measured. The measurement results are shown in Table 1.

<Evaluation results>
In Examples 1-4, it turns out that peel strength is improving significantly compared with Comparative Examples 1-2. In Examples 1 to 4, it is considered that the adhesion between the resin layer and the plating interface was improved by the plating biting into the uneven portions of the resin layer. In Comparative Examples 1 and 2, it is considered that the adhesion cannot be obtained because there is no biting of plating.

Claims (10)

  A sealing sheet comprising a resin layer having a surface with an arithmetic average roughness (Ra) of 0.1 μm or more.   The sealing sheet according to claim 1, further comprising a metal layer disposed on the surface of the resin layer. Comprising a transfer step of bringing a metal member having irregularities into contact with the resin layer and transferring the irregularities to the surface of the resin layer;
The manufacturing method of the sealing sheet whose arithmetic mean roughness (Ra) of the said surface of the said resin layer after the said transfer process is 0.1 micrometer or more.   The manufacturing method of the sealing sheet of Claim 3 further equipped with the process of removing the said metal member from the laminated body obtained by making the said metal member contact the said resin layer. A sealed body and a sealing portion for sealing the sealed body,
The said sealing part is the said resin layer of the sealing sheet obtained by the sealing sheet of Claim 1 or 2, or the sealing sheet manufacturing method of Claim 3 or 4, or its hardened | cured material. There is a sealing structure.   The sealing structure according to claim 5, further comprising a metal layer disposed on the sealing portion.   The sealing structure according to claim 5 or 6, wherein the object to be sealed is an electronic component.   The encapsulating sheet according to claim 1 or 2, or the encapsulating part which is the resin layer of the encapsulating sheet obtained by the method for producing an encapsulating sheet according to claim 3 or 4 or a cured product thereof. The manufacturing method of a sealing structure provided with the process of sealing a sealing body.   The manufacturing method of the sealing structure of Claim 8 further equipped with the process of forming a metal layer on the said sealing part.   The manufacturing method of the sealing structure of Claim 8 or 9 whose said to-be-sealed body is an electronic component.