TW201514011A - Method of manufacturing film for parts packaging - Google Patents
Method of manufacturing film for parts packaging Download PDFInfo
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- TW201514011A TW201514011A TW103122061A TW103122061A TW201514011A TW 201514011 A TW201514011 A TW 201514011A TW 103122061 A TW103122061 A TW 103122061A TW 103122061 A TW103122061 A TW 103122061A TW 201514011 A TW201514011 A TW 201514011A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/015—Biocides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
- H01L23/295—Organic, e.g. plastic containing a filler
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08J2367/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the hydroxy and the carboxyl groups directly linked to aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
- C08L2203/162—Applications used for films sealable films
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Laminated Bodies (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
Abstract
Description
本發明關於用於封裝電子零件等之零件的零件封裝用薄膜之製造方法。 The present invention relates to a method of manufacturing a film for component packaging for packaging components such as electronic parts.
近年來，智慧型手機、平板終端(平板PC)等小型的高機能攜帶終端之需要係增大。對於使如此的高機能攜帶終端發揮機能用的半導體裝置等，要求更小型化及高機能化。作為如此的半導體裝置之構造，例如以將半導體晶片等零件2個以上包含在內之方式所封裝的多晶片封裝，更且將複數個的多晶片封裝彼此互相接合，再藉由一體地封裝而構成之稱為層疊封裝(PoP)的構造係受到注目。 In recent years, the demand for small high-capacity portable terminals such as smart phones and tablet terminals (table PCs) has increased. In order to make such a high-performance portable terminal function as a semiconductor device, it is required to be more compact and highly functional. As a structure of such a semiconductor device, for example, a multi-chip package in which two or more components such as a semiconductor wafer are included, and a plurality of multi-chip packages are bonded to each other, and then integrally packaged A structure called a package-on-package (PoP) is attracting attention.
又，有提案零件內藏電路板，其係藉由將半導體晶片、電容器等零件藏於內層電路基板之內，而成為可一邊增大零件的搭載量，一邊謀求小型化之印刷配線板。 In addition, a printed circuit board in which a semiconductor wafer, a capacitor, and the like are housed in the inner layer circuit board, and the number of components to be mounted is increased, and the printed wiring board is reduced in size.
為了將如上述的多晶片封裝、層疊封裝(Package on Package)、零件內藏電路板中所含有的零件予以封裝，有使用在支持體上設有封裝材料之樹脂組成物層的薄片材料之情況。 In order to package the components included in the multi-chip package, the package on package, and the built-in circuit board as described above, there is a case where a sheet material in which a resin composition layer of a sealing material is provided on a support is used. .
於如此習知的薄片材料中，由於有樹脂組成物層之厚度不足而無法將零件充分地封裝之情況，故有提案為了更增厚樹脂組成物層之厚度，將設有樹脂組成物層的薄片材料之樹脂組成物層彼此予以貼合之方法(參照專利文獻1)。 In such a conventional sheet material, since the thickness of the resin composition layer is insufficient and the component cannot be sufficiently encapsulated, it is proposed to provide a resin composition layer in order to further thicken the thickness of the resin composition layer. A method in which the resin composition layers of the sheet material are bonded to each other (see Patent Document 1).
〔專利文獻1〕特開2012-25907號公報 [Patent Document 1] JP-A-2012-25907
然而，於為了更增厚樹脂組成物層之厚度，將預先形成的2片之薄片材料彼此貼的上述背景技術之方法中，有起因於貼合步驟，在經貼合步驟所更厚形成的樹脂組成物層內發生空隙，或發生剝離而部分地品質變不均，或尤其在將貼合步驟後的薄片狀材料捲取成捲筒狀時，起因於樹脂組成物層之兩主面上所貼合的載體材(支持體、保護薄膜等)之厚度厚，發生捲繞偏移或皺紋等之問題點。 However, in the above-described method of the prior art in which the two sheets of the sheet material which are formed in advance are thickened in order to further thicken the thickness of the resin composition layer, there is a thickening process which is formed by the bonding step due to the bonding step. A void occurs in the resin composition layer, or peeling occurs, and part of the quality becomes uneven, or particularly when the sheet-like material after the bonding step is wound into a roll shape, the two main faces of the resin composition layer are caused. The thickness of the carrier material (support, protective film, etc.) to be bonded is thick, and problems such as winding deviation or wrinkles occur.
本發明者們鑒於因近年的技術之進步，而可能邊實施成膜步驟邊測定所形成的層之厚度而管理之狀況，發現藉由直接的塗佈，邊將樹脂組成物層之厚度控制在指定的厚度邊進一步增厚之以往被視為困難的手段，亦可解決上述 的問題點，終於完成本發明。即，本發明提供下述〔1〕~〔12〕。 The inventors of the present invention have found that the thickness of the resin composition layer can be controlled by direct coating in view of the progress of the technique in recent years, while measuring the thickness of the formed layer while performing the film formation step. The thickening of the specified thickness side has been regarded as a difficult means in the past and can also be solved as described above. The problem is finally completed by the present invention. That is, the present invention provides the following [1] to [12].
〔1〕一種零件封裝用薄膜之製造方法，其包含：(A)準備具有支持體與設置在該支持體上的暫時樹脂組成物層之附支持體的暫時樹脂組成物層之步驟；與，(B)於前述附支持體的暫時樹脂組成物層之暫時樹脂組成物層上，塗佈樹脂組成物而形成塗佈膜，將該塗佈膜予以乾燥處理而使與前述暫時樹脂組成物層一體化之步驟；僅進行1次或重複2次以上的前述步驟(B)，將厚度為200μm~700μm的樹脂組成物層形成在前述支持體上。 [1] A method for producing a film for component encapsulation, comprising: (A) a step of preparing a temporary resin composition layer having a support of a support and a temporary resin composition layer provided on the support; (B) coating a resin composition on the temporary resin composition layer of the temporary resin composition layer of the support, forming a coating film, and drying the coating film to form the temporary resin composition layer Step of integration; the above step (B) is carried out only once or twice or more, and a resin composition layer having a thickness of 200 μm to 700 μm is formed on the support.
〔2〕如〔1〕記載的零件封裝用薄膜之製造方法，其中使形成前述暫時樹脂組成物層用之樹脂組成物之組成與形成前述塗佈膜用之樹脂組成物之組成成為相同組成，形成前述樹脂組成物層。 [2] The method for producing a film for component encapsulation according to the above aspect, wherein the composition of the resin composition for forming the temporary resin composition layer and the composition of the resin composition for forming the coating film have the same composition. The aforementioned resin composition layer is formed.
〔3〕如〔1〕或〔2〕記載的零件封裝用薄膜之製造方法，其中前述步驟(A)係藉由在前述支持體上塗佈樹脂組成物，乾燥處理以形成暫時樹脂組成物層，而準備附支持體的暫時樹脂組成物層之步驟。 [3] The method for producing a film for component encapsulation according to [1], wherein the step (A) is performed by applying a resin composition on the support and drying to form a temporary resin composition layer. And preparing a step of attaching a temporary resin composition layer of the support.
〔4〕如〔1〕~〔3〕中任一項記載的零件封裝用薄膜之製造方法，其中為了使前述塗佈膜乾燥之乾燥條件係溫度為70℃~150℃，時間為3分鐘~15分鐘。 [4] The method for producing a film for component encapsulation according to any one of [1] to [3] wherein the drying condition for drying the coating film is 70 ° C to 150 ° C for 3 minutes. 15 minutes.
〔5〕如〔4〕記載的零件封裝用薄膜之製造方法，其 中使為了形成前述暫時樹脂組成物層之第1乾燥條件與為了形成前述樹脂組成物層之第2乾燥條件不同，進行前述乾燥處理。 [5] The method for producing a film for component packaging according to [4], wherein The drying treatment is performed in order to form the first drying condition of the temporary resin composition layer and the second drying condition for forming the resin composition layer.
〔6〕如〔5〕記載的零件封裝用薄膜之製造方法，其中使前述第1乾燥條件的時間比前述第2乾燥條件的時間還短。 [6] The method for producing a film for component encapsulation according to [5], wherein the time of the first drying condition is shorter than the time of the second drying condition.
〔7〕如〔1〕~〔6〕中任一項記載的零件封裝用薄膜之製造方法，其中前述暫時樹脂組成物層之厚度為100μm以上。 The method for producing a film for component encapsulation according to any one of the above aspects, wherein the temporary resin composition layer has a thickness of 100 μm or more.
〔8〕如〔1〕~〔7〕中任一項記載的零件封裝用薄膜之製造方法，其中前述支持體係經脫模處理的聚對苯二甲酸乙二酯薄膜。 [8] The method for producing a film for component encapsulation according to any one of [1] to [7] wherein the support system is subjected to a release treatment of a polyethylene terephthalate film.
〔9〕如〔1〕~〔8〕中任一項記載的零件封裝用薄膜之製造方法，其中前述樹脂組成物包含環氧樹脂、硬化劑及無機填充材。 The method for producing a film for component encapsulation according to any one of the above aspects, wherein the resin composition comprises an epoxy resin, a curing agent, and an inorganic filler.
〔10〕如〔1〕~〔9〕中任一項記載的零件封裝用薄膜之製造方法，其中使用長條的支持體作為前述支持體，以輥對輥方式進行前述步驟(A)及前述步驟(B)中之任一者或兩者。 The method for producing a film for component encapsulation according to any one of the aspects of the present invention, wherein the step (A) and the aforementioned step are performed by a roll-to-roll method using a long support as the support. Either or both of step (B).
〔11〕如〔1〕~〔10〕中任一項記載的零件封裝用薄膜之製造方法，其中前述零件封裝用薄膜係捲筒狀的零件封裝用薄膜，其更具有接合於樹脂組成物層且彼厚度比前述支持體之厚度還薄的保護薄膜。 The method for producing a film for component encapsulation according to any one of the aspects of the present invention, wherein the film for component encapsulation is a roll-formed film for component encapsulation, further comprising a resin composition layer And a protective film which is thinner than the thickness of the aforementioned support.
〔12〕如〔1〕~〔11〕中任一項記載的零件封裝用 薄膜之製造方法，其中前述樹脂組成物層之最低熔融黏度為50泊~10000泊之範圍。 [12] The component package according to any one of [1] to [11] In the method for producing a film, the lowest melt viscosity of the resin composition layer is in the range of 50 poise to 10,000 poise.
〔13〕如〔1〕~〔12〕中任一項記載的零件封裝用薄膜之製造方法，其中前述樹脂組成物層之殘留溶劑率為5質量%以下。 The method for producing a film for component encapsulation according to any one of the above aspects, wherein the resin composition layer has a residual solvent ratio of 5% by mass or less.
藉由本發明的零件封裝用薄膜之製造方法，可抑制零件封裝用薄膜之製造時空隙之發生，良率佳，可製造厚度為200μm左右以上的比較厚之高品質的零件封裝用薄膜。再者，由本發明的零件封裝用薄膜之製造方法所得的零件封裝用薄膜，係最低熔融黏度低而埋入性優異，由於是在硬化時於樹脂組成物層(硬化體)內不易發生空隙之優異薄膜，可適用於多晶片封裝、層疊封裝、零件內藏電路板等上所搭載或內藏的零件之封裝步驟。 According to the method for producing a film for a component package of the present invention, it is possible to suppress the occurrence of voids in the production of the film for component packaging, and it is excellent in yield, and a relatively high-quality film for component packaging having a thickness of about 200 μm or more can be produced. In addition, the film for component encapsulation obtained by the method for producing a film for component encapsulation of the present invention has a low minimum melt viscosity and is excellent in embedding property, and is less likely to cause voids in the resin composition layer (hardened body) during curing. The excellent film can be applied to the packaging steps of components mounted or built in multi-chip packages, stacked packages, built-in circuit boards, and the like.
以下，詳細說明本發明的零件封裝用薄膜(以下，亦稱為接著薄膜)之製造方法。 Hereinafter, a method of producing a film for component encapsulation of the present invention (hereinafter also referred to as a film) will be described in detail.
本發明的零件封裝用薄膜之製造方法的特徵為包含：(A)準備具有支持體與設置在該支持體上的暫時樹脂組成物層之附支持體的暫時樹脂組成物層之步驟(稱為步驟(A))；與，(B)於前述附支持體的暫時樹脂組成物層之暫時樹脂組成物層上，塗佈樹脂組成物，將塗佈膜予 以乾燥處理而使與前述暫時樹脂組成物層一體化之步驟(稱為步驟(B))；僅進行1次或重複2次以上的前述步驟(B)，將厚度為200μm~700μm的樹脂組成物層形成在前述支持體上。 The method for producing a film for component encapsulation of the present invention is characterized by comprising: (A) a step of preparing a temporary resin composition layer having a support of a support and a temporary resin composition layer provided on the support (refer to Step (A)); and (B) coating a resin composition on the temporary resin composition layer of the temporary resin composition layer of the above-mentioned support, and coating the coating film a step of integrating with the temporary resin composition layer by drying treatment (referred to as step (B)); performing the above step (B) only once or twice or more, and forming a resin having a thickness of 200 μm to 700 μm The layer is formed on the aforementioned support.
此處，所謂的「樹脂組成物」，就是意指包含暫時樹脂組成物層、形成樹脂組成物層用的材料(成分)之組成物。又，指樹使脂組成物更溶解於有機溶劑等的媒質(溶劑)或分散之液狀體的樹脂清漆。即，樹脂清漆係「樹脂組成物」之一態樣。因此，本說明書中稱為「樹脂組成物」時，為包含「樹脂清漆」之情況。 Here, the "resin composition" means a composition containing a temporary resin composition layer and a material (component) for forming a resin composition layer. Further, the resin is a resin varnish in which a resin is more dissolved in a medium (solvent) such as an organic solvent or a dispersed liquid. That is, the resin varnish is one of the "resin compositions". Therefore, in the case of the term "resin composition", the term "resin varnish" is included.
再者，所謂的「暫時樹脂組成物層」及「樹脂組成物層」，就是指將由樹脂組成物所成的塗佈膜予以乾燥處理，使揮發成分之含量(溶劑殘留量)成為指定量以下之層構造體。 In addition, the "temporary resin composition layer" and the "resin composition layer" mean that the coating film formed of the resin composition is dried, and the content of the volatile component (residual solvent amount) is less than or equal to the specified amount. Layer structure.
藉由使用口模塗佈機等之習知任意的合適塗佈手段，將樹脂組成物塗佈於支持體上而形成塗佈膜，將此塗佈膜予以乾燥處理，可形成暫時樹脂組成物層及樹脂組成物層。 The resin composition is applied onto a support by a suitable coating means such as a die coater to form a coating film, and the coating film is dried to form a temporary resin composition. Layer and resin composition layer.
首先，進行準備具有支持體與設置在該支持體上的暫時樹脂組成物層之附支持體的暫時樹脂組成物層之步驟(A)。 First, a step (A) of preparing a temporary resin composition layer having a support and a support of a temporary resin composition layer provided on the support is performed.
作為步驟(A)之附支持體的暫時樹脂組成物層，例 如可使用預先製造之在指定的儲存條件下儲存之附支持體的暫時樹脂組成物層，且亦可使用市售之附支持體的暫時樹脂組成物層(於支持體上設有相當於「暫時樹脂組成物層」的樹脂組成物層之構造體)。 As a temporary resin composition layer attached to the support of the step (A), an example For example, a temporary resin composition layer of a support which is pre-manufactured and stored under specified storage conditions may be used, and a commercially available temporary resin composition layer (with a corresponding equivalent on the support) may be used. The structure of the resin composition layer of the temporary resin composition layer).
支持體係由具有對向的2個主面之板狀體或薄膜所構成之構造體。作為支持體，例如可舉出由塑膠材料所成之薄膜、金屬箔、脫模紙，較佳為由塑膠材料所成之薄膜、金屬箔。作為支持體，亦可使用長條的薄膜。 The support system is a structure composed of a plate-like body or a film having two main faces facing each other. Examples of the support include a film made of a plastic material, a metal foil, and a release paper, and a film made of a plastic material or a metal foil is preferable. As the support, a long film can also be used.
使用由塑膠材料所成之薄膜作為支持體時，於塑膠材料中，例如可舉出聚對苯二甲酸乙二酯(PET)、聚萘二甲酸乙二酯(PEN)等之聚酯、聚碳酸酯(PC)、聚甲基丙烯酸甲酯(PMMA)等之壓克力、環狀聚烯烴、三乙醯纖維素(TAC)、聚醚硫化物(PES)、聚醚酮、聚醯亞胺等。其中，較佳為聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯，特佳為便宜的聚對苯二甲酸乙二酯。 When a film made of a plastic material is used as the support, examples of the plastic material include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN). Acrylic (PC), polymethyl methacrylate (PMMA), etc. Acrylic, cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, poly phthalate Amines, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and polyethylene terephthalate is particularly preferred.
使用金屬箔作為支持體時，於金屬箔中，例如可舉出銅箔、鋁箔等，較佳為銅箔。作為銅箔，可使用由銅的單金屬所成之箔，也可使用由銅與其它金屬(例如，錫、鉻、銀、鎂、鎳、鋯、矽、鈦等)之合金所成之箔。 When a metal foil is used as the support, the metal foil may, for example, be a copper foil or an aluminum foil, and is preferably a copper foil. As the copper foil, a foil made of a single metal of copper may be used, or a foil made of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, hafnium, titanium, etc.) may be used. .
於支持體上，在與後述的暫時樹脂組成物層或樹脂組成物層接合之面、塗佈樹脂組成物之面，亦可施予消光處理、電暈處理。 On the support, a matte treatment or a corona treatment may be applied to the surface to which the temporary resin composition layer or the resin composition layer to be described later is bonded, and the surface on which the resin composition is applied.
又，作為支持體，亦可使用在與暫時樹脂組成物層或樹脂組成物層接合之側、塗佈樹脂組成物之側，具有脫模層之附脫模層的支持體。作為用於附脫模層的支持體之脫模層的形成之脫模劑，例如可舉出由醇酸樹脂、聚烯烴樹脂、胺基甲酸酯樹脂及矽氧樹脂所成之群組中選出的1種以上之脫模劑。附脫模層的支持體係可使用市售品，例如可舉出具有以醇酸樹脂系脫模劑作為主成分之脫模層的PET薄膜之LINTEC(股)製的「SK-1」、「AL-5」、「AL-7」等。 Further, as the support, a support having a release layer attached to the temporary resin composition layer or the resin composition layer and the side of the resin composition coated with the release layer may be used. The release agent for forming the release layer of the support for the release layer may, for example, be a group of an alkyd resin, a polyolefin resin, a urethane resin, and a silicone resin. One or more selected release agents. For the support system with a release layer, a commercially available product can be used. For example, "SK-1" manufactured by LINTEC Co., Ltd., which has a release film of a release layer containing an alkyd-based release agent as a main component, can be used. AL-5", "AL-7", etc.
支持體之厚度係沒有特別的限定，但較佳為5μm~75μm之範圍，更佳為10μm~60μm之範圍。再者，使用附脫模層的支持體時，附脫模層的支持體全體之厚度較佳為上述範圍內。 The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. Further, when the support having the release layer is used, the thickness of the entire support having the release layer is preferably within the above range.
形成暫時樹脂組成物層用的樹脂組成物之材料(成分)係如後述。 The material (component) of the resin composition for forming the temporary resin composition layer will be described later.
形成暫時樹脂組成物層用的塗佈膜之乾燥處理，係可藉由加熱、熱風噴吹等眾所周知的任意合適之乾燥方法實施。藉由此乾燥處理，塗佈膜係成為暫時樹脂組成物層。此處，將暫時樹脂組成物層之形成用的乾燥條件稱為「第1乾燥條件」。第1乾燥條件係可考慮含有樹脂組成物或樹脂清漆的有機溶劑之沸點等而決定。第1乾燥條件，例如於使用含有30質量%~60質量%的有機溶劑之樹脂清 漆時，溫度可為70℃~150℃，時間可為3分鐘~15分鐘。再者，從使良率提高之觀點來看，暫時樹脂組成物層之厚度較佳為100μm以上，更佳為150μm以上。 The drying treatment of the coating film for forming the temporary resin composition layer can be carried out by any suitable drying method known as heating or hot air blowing. By this drying treatment, the coating film becomes a temporary resin composition layer. Here, the drying condition for forming the temporary resin composition layer is referred to as "first drying condition". The first drying condition can be determined in consideration of the boiling point of the organic solvent containing the resin composition or the resin varnish. The first drying condition is, for example, using a resin containing 30% by mass to 60% by mass of an organic solvent. When lacquering, the temperature can be 70 ° C ~ 150 ° C, the time can be 3 minutes ~ 15 minutes. Further, from the viewpoint of improving the yield, the thickness of the temporary resin composition layer is preferably 100 μm or more, and more preferably 150 μm or more.
如以上地準備「附支持體的暫時樹脂組成物層」(以下亦稱為暫時接著薄膜)。 As described above, "the temporary resin composition layer with a support" (hereinafter also referred to as a temporary adhesive film) is prepared.
一旦儲存於附支持體的暫時樹脂組成物層或暫時樹脂組成物層上進行1次以上的樹脂組成物之塗佈及乾燥處理的製造途中之構造體時，即一旦中斷樹脂組成物層的製造步驟，間隔時間再度開始時，較佳為更設置保護薄膜，該保護薄膜係接合於暫時樹脂組成物層之與支持體不接合之側的面(即，與支持體相反側的面)。此保護薄膜係有助於防止灰塵等對於暫時樹脂組成物層之附著或損傷。作為保護薄膜，例如可使用聚丙烯薄膜、聚乙烯薄膜等。又，可使用由與支持體之材料相同的材料所成之薄膜。保護薄膜之厚度係沒有特別的限定，例如為1μm~40μm。保護薄膜之厚度較佳為比支持體之厚度還薄。 When the structure is applied to the temporary resin composition layer or the temporary resin composition layer of the support, and the structure of the resin composition is applied and dried, the resin composition layer is interrupted. In the step, when the interval is started again, it is preferable to further provide a protective film which is bonded to a surface of the temporary resin composition layer which is not joined to the support (that is, a surface opposite to the support). This protective film helps to prevent adhesion or damage to the temporary resin composition layer by dust or the like. As the protective film, for example, a polypropylene film, a polyethylene film, or the like can be used. Further, a film made of the same material as that of the support can be used. The thickness of the protective film is not particularly limited and is, for example, 1 μm to 40 μm. The thickness of the protective film is preferably thinner than the thickness of the support.
保護薄膜對附支持體的暫時樹脂組成物層之貼合，係可使用習知的層合裝置進行。 The bonding of the protective film to the temporary resin composition layer of the support can be carried out using a conventional laminating apparatus.
其次，進行於步驟(A)所準備之附支持體的暫時樹脂組成物層之暫時樹脂組成物層上，塗佈樹脂組成物而形成塗佈膜，使此塗佈膜乾燥而與暫時樹脂組成物層一體化之步驟(B)。 Next, the resin composition is applied onto the temporary resin composition layer of the temporary resin composition layer of the support prepared in the step (A) to form a coating film, and the coating film is dried to form a temporary resin composition. Step (B) of integration of the layers.
步驟(B)係僅進行1次或重複2次以上，以厚度(之總計)成為200μm~700μm的指定厚度之方式，將樹脂組成物層形成於支持體上。如此地，藉由使樹脂組成物層成為200μm以上之厚度，可適宜地進行零件之封裝，藉由成為700μm以下之厚度，可使良率提高。樹脂組成物層之厚度較佳為250μm~600μm。 The step (B) is carried out only once or twice or more, and the resin composition layer is formed on the support so that the thickness (the total) becomes a specified thickness of 200 μm to 700 μm. By setting the resin composition layer to a thickness of 200 μm or more, the package can be suitably packaged, and the thickness can be improved by a thickness of 700 μm or less. The thickness of the resin composition layer is preferably from 250 μm to 600 μm.
於此情況中，藉由在暫時樹脂組成物層上，塗佈樹脂組成物而形成塗佈膜，將此塗佈膜予以乾燥處理而使與暫時樹脂組成物層一體化，形成指定厚度的樹脂組成物層。 In this case, a coating film is formed by coating a resin composition on the temporary resin composition layer, and the coating film is dried to be integrated with the temporary resin composition layer to form a resin having a predetermined thickness. Composition layer.
此時，步驟(A)的形成暫時樹脂組成物層用之樹脂組成物之組成與步驟(B)的形成塗佈膜用之樹脂組成物之組成，係可相同或相異。 In this case, the composition of the resin composition for forming the temporary resin composition layer in the step (A) and the composition of the resin composition for forming the coating film in the step (B) may be the same or different.
又，步驟(A)的暫時樹脂組成物層之厚度與樹脂組成物層中之經由步驟(B)所附加的部分之厚度，係可相同或相異。換言之，(i)可以與暫時樹脂組成物層之厚度相同的厚度來形成經由步驟(B)所附加的部分之厚度，(ii)亦可以與暫時樹脂組成物層之厚度相異的厚度來形成經由步驟(B)所附加的部分之厚度。 Further, the thickness of the temporary resin composition layer of the step (A) may be the same as or different from the thickness of the portion of the resin composition layer which is added via the step (B). In other words, (i) the thickness of the portion added via the step (B) may be formed to have the same thickness as the thickness of the temporary resin composition layer, and (ii) may be formed to a thickness different from the thickness of the temporary resin composition layer. The thickness of the portion added via step (B).
於前述(ii)之情況中，可以比經由步驟(B)所附加的部分之厚度還厚之方式來形成暫時樹脂組成物層之厚度，亦可以比經由步驟(B)所附加的部分之厚度還薄之方式來形成暫時樹脂組成物層之厚度。 In the case of the above (ii), the thickness of the temporary resin composition layer may be formed thicker than the thickness of the portion added via the step (B), or may be greater than the thickness of the portion added via the step (B). The thickness of the temporary resin composition layer is also formed in a thin manner.
於此情況中，藉由重複2次以上的在步驟(A)的暫時樹脂組成物層上，塗佈樹脂組成物而形成塗佈膜，使此塗佈膜乾燥之步驟，使各步驟所形成之層與暫時樹脂組成物層一體化，而形成指定厚度的樹脂組成物層。 In this case, a step of forming a coating film by applying a resin composition on the temporary resin composition layer of the step (A) is repeated two or more times, and the coating film is dried to form each step. The layer is integrated with the temporary resin composition layer to form a resin composition layer having a specified thickness.
再者，重複2次以上的步驟(B)時，對於僅進行1次以上的步驟(B)但未到達最終的指定厚度之製造途中的層構造，亦稱為「暫時樹脂組成物層」。 In addition, when the step (B) is repeated two or more times, the layer structure in the middle of the manufacturing process in which the step (B) is performed only once or more, but the final specified thickness is not obtained, is also referred to as a "temporary resin composition layer".
此時，步驟(A)的形成暫時樹脂組成物層用之樹脂組成物之組成，及重複2次以上的步驟(B)各自之形成塗佈膜用的樹脂組成物之組成，係可相同或相異。換言之，於步驟(A)的樹脂組成物與2次以上的步驟(B)各自中，樹脂組成物之組成係可皆相同，也可皆相異，亦可為此等之中的複數互相相異，且其餘為相同。 In this case, the composition of the resin composition for forming the temporary resin composition layer in the step (A), and the composition of the resin composition for forming the coating film in the step (B) of the step (B) may be the same or Different. In other words, in the resin composition of the step (A) and the step (B) of the second or more steps, the composition of the resin composition may be the same or different, and the plural phases may be mutually Different, and the rest are the same.
又，步驟(A)的暫時樹脂組成物層之厚度與藉由樹脂組成物層中的重複進行2次以上的步驟(B)各自而附加的部分之厚度，係可相同或相異。換言之，步驟(A)的暫時樹脂組成物層之厚度及藉由2次以上的步驟(B)而附加的部分之厚度，各自可皆相同，也可皆相異，亦可為此等之中的複數互相相異，且其餘為相同。步驟(A)的暫時樹脂組成物層之厚度及藉由2次以上的步驟(B)而附加的部分之厚度，各自可考慮塗佈裝置、薄膜的搬送裝置之搬送速度等，如上述任意適宜地設定。步驟(A) 的暫時樹脂組成物層之厚度及藉由2次以上的步驟(B)而附加的部分之厚度，各自從暫時樹脂組成物層、樹脂組成物層的乾燥程度、處理等之觀點來看，較佳為200μm以下。再者，從使良率提高之觀點來看，暫時樹脂組成物層之厚度較佳為100μm以上，更佳為150μm以上。 Further, the thickness of the portion of the temporary resin composition layer in the step (A) and the portion of the step (B) which is repeated twice or more in the resin composition layer may be the same or different. In other words, the thickness of the temporary resin composition layer of the step (A) and the thickness of the portion added by the step (B) of the second or more steps may be the same or different, and may be used for this purpose. The plurals are different from each other, and the rest are the same. The thickness of the temporary resin composition layer in the step (A) and the thickness of the portion to be added by the step (B) or more may be considered as appropriate in any of the above-described coating apparatus and the conveying speed of the film conveying apparatus. Ground setting. Step (A) The thickness of the temporary resin composition layer and the thickness of the portion to be added by the second or more steps (B) are each from the viewpoints of the degree of drying of the temporary resin composition layer and the resin composition layer, treatment, and the like. Good is below 200μm. Further, from the viewpoint of improving the yield, the thickness of the temporary resin composition layer is preferably 100 μm or more, and more preferably 150 μm or more.
步驟(A)的暫時樹脂組成物層之厚度及藉由2次以上的步驟(B)而附加的部分之厚度，當各自皆相異時，或此等之中的複數互相相異且其餘為相同時的厚度之大小關係沒有特別的限定。 The thickness of the temporary resin composition layer of the step (A) and the thickness of the portion added by the step (B) two or more times are different when each of them is different, or the plurals among the plurality are different from each other and the rest are The magnitude relationship of the thickness at the same time is not particularly limited.
形成樹脂組成物層用的塗佈膜之乾燥處理，係與暫時樹脂組成物層之形成步驟中的乾燥處理同樣地，可藉由加熱、熱風噴吹等之眾所周知的任意合適之乾燥方法實施。藉由此乾燥處理，塗佈膜成為與暫時樹脂組成物層一體構成之樹脂組成物層。此處，將可進行1次以上的步驟(B)之乾燥條件稱為「第2乾燥條件」。第2乾燥條件可考慮樹脂組成物所含有的有機溶劑之沸點等而決定。第2乾燥條件係溫度可為70℃~150℃，時間可為3分鐘~15分鐘。 The drying treatment of the coating film for forming the resin composition layer can be carried out by any suitable drying method known as heating or hot air blowing, similarly to the drying treatment in the step of forming the temporary resin composition layer. By this drying treatment, the coating film becomes a resin composition layer which is integrally formed with the temporary resin composition layer. Here, the drying condition in which the step (B) can be performed once or more is referred to as "second drying condition". The second drying condition can be determined in consideration of the boiling point of the organic solvent contained in the resin composition and the like. The second drying condition may be from 70 ° C to 150 ° C and the time may be from 3 minutes to 15 minutes.
於上述之乾燥處理中，亦可使步驟(A)的形成暫時樹脂組成物層用之第1乾燥條件與步驟(B)的第2乾燥條件不同，而進行乾燥處理。此時，從提高樹脂組成物層之厚度的精度之觀點來看，較佳為使第1乾燥條件的時間 比第2乾燥條件的時間還短，及/或使第1乾燥條件的溫度(平均溫度)比第2乾燥條件的溫度(平均溫度)還低。 In the above drying treatment, the first drying condition for forming the temporary resin composition layer in the step (A) may be different from the second drying condition of the step (B), and drying treatment may be performed. At this time, from the viewpoint of improving the accuracy of the thickness of the resin composition layer, it is preferable to set the time of the first drying condition. It is shorter than the time of the second drying condition, and/or the temperature (average temperature) of the first drying condition is lower than the temperature (average temperature) of the second drying condition.
又，步驟(A)的第1乾燥條件及重複2次以上之步驟(B)的第2乾燥條件，各自可互相相同或相異。換言之，第1乾燥條件及進行2次以上之第2乾燥條件，各自可為皆相同之條件，也可皆相異，亦可為此等之中的複數互相相異，且其餘為相同。 Further, the first drying condition of the step (A) and the second drying condition of the step (B) of repeating two or more times may be the same or different from each other. In other words, the first drying condition and the second drying condition of two or more times may be the same or different, and the plural numbers may be different from each other, and the rest are the same.
再者，當第1乾燥條件及第2乾燥條件的乾燥處理係邊搬送捲筒狀的長條支持體邊進行時，乾燥處理係對邊移動邊露出之區域連續地行。結果長條的暫時樹脂組成物層、樹脂組成物層係被均勻地乾燥處理。 In addition, when the drying process of the first drying condition and the second drying condition is performed while conveying the roll-shaped elongated support, the drying process is continuously performed in the region where the side is moved while being exposed. As a result, the long temporary resin composition layer and the resin composition layer were uniformly dried.
又，所形成的樹脂組成物層中之殘留溶劑率，從防止硬化時在樹脂組成物層(硬化體)內發生空隙之觀點來看，較佳為5質量%以下。又，從提高樹脂組成物層的操作性之觀點來看，殘留溶劑率較佳為1.5質量%以上。 In addition, the residual solvent ratio in the resin composition layer to be formed is preferably 5% by mass or less from the viewpoint of preventing voids in the resin composition layer (hardened body) during curing. Moreover, from the viewpoint of improving the workability of the resin composition layer, the residual solvent ratio is preferably 1.5% by mass or more.
於附支持體的暫時樹脂組成物層上，設有接於暫時樹脂組成物層的保護薄膜之情況，係在剝離保護薄膜後所露出的暫時樹脂組成物層上，塗佈樹脂組成物。 When a protective film attached to the temporary resin composition layer is provided on the temporary resin composition layer of the support, the resin composition is applied onto the temporary resin composition layer exposed after the protective film is peeled off.
上述的暫時樹脂組成物層之形成步驟及/或樹脂組成物層之形成步驟，較佳為逐次計測所形成的暫時樹脂組成物層及/或樹脂組成物層之厚度是否成為指定的厚度，邊管理厚度邊實施。如此地，可進一步提高樹脂組成物層之厚度的均勻性，可進一步提高零件封裝用薄膜之品質。 In the step of forming the temporary resin composition layer and/or the step of forming the resin composition layer, it is preferable to sequentially measure whether or not the thickness of the temporary resin composition layer and/or the resin composition layer formed is a predetermined thickness. Manage thickness implementation. In this way, the uniformity of the thickness of the resin composition layer can be further improved, and the quality of the film for component packaging can be further improved.
步驟(A)及步驟(B)中的任一者或兩者，較佳為使用長條的支持體作為支持體，以輥對輥方式進行。步驟(A)及步驟(B)中的任一者或兩者係可以分批方式進行，而且步驟(A)及進行1次以上的步驟(B)各自亦可組合輥對輥方式與分批方式進行。 Either or both of the step (A) and the step (B) are preferably carried out by a roll-to-roll method using a long support as a support. Any one or both of the steps (A) and (B) may be carried out in batch mode, and the step (A) and the step (B) performed one or more times may each be combined with a roll-to-roll method and a batch Way to proceed.
輥對輥方式的暫時樹脂組成物層及/或樹脂組成物層之形成步驟，係藉由一邊將在捲出輥及包含捲取輥的至少2個輥間伸張的長條支持體(基板、薄膜)連續地搬送，一邊於捲出輥及捲取輥間所露出的支持體的一側主面上塗佈樹脂組成物而形成塗佈膜，連續地將塗佈膜予以乾燥處理而形成暫時樹脂組成物層或樹脂組成物層，再測定所連續形成的層之厚度而進行。 The step of forming the temporary resin composition layer and/or the resin composition layer by the roll-to-roll method is by using a long support (substrate, between the take-up roll and at least two rolls including the take-up roll) The film is continuously conveyed, and a resin film is applied to one main surface of the support exposed between the take-up roll and the take-up roll to form a coating film, and the coating film is continuously dried to form a temporary film. The resin composition layer or the resin composition layer is measured by measuring the thickness of the continuously formed layer.
步驟(A)與進行1次或重複2次以上的步驟(B)，亦可以輥對輥方式作為一連串的步驟實施。此等之步驟若藉由輥對輥方式實施，則可進一步提高良率。 The step (A) and the step (B) of performing one time or repeating two times or more may also be carried out as a series of steps in a roll-to-roll method. If these steps are carried out by a roll-to-roll method, the yield can be further improved.
本發明之零件封裝用薄膜亦可更具備覆蓋於樹脂組成物層之不與支持體接合之側的面(即與支持體相反側之面)上之保護薄膜。保護薄膜係有助於防止灰塵等對於樹脂組成物層之附著或損傷。作為保護薄膜之材料，可使用與對於暫時樹脂組成物層、支持體所說明之材料相同的材料。保護薄膜之厚度係沒有特別的限定，但例如為1μm~40μm。特別地，於製作捲筒狀的零件封裝用薄膜時，從可防止捲繞偏移或皺紋來看，保護薄膜之厚度較佳為比支持體之厚度還薄。零件封裝用薄膜係於實施封裝步驟之 際，藉由剝離保護薄膜，使樹脂組成物層露出而可使用。 The film for component encapsulation of the present invention may further include a protective film covering the surface of the resin composition layer which is not joined to the support (i.e., the surface opposite to the support). The protective film helps prevent adhesion or damage to the resin composition layer by dust or the like. As the material of the protective film, the same material as that described for the temporary resin composition layer and the support can be used. The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. In particular, in the case of producing a roll-shaped film for component encapsulation, the thickness of the protective film is preferably thinner than the thickness of the support from the viewpoint of preventing winding deviation or wrinkles. The film for component packaging is used in the packaging step Further, by peeling off the protective film, the resin composition layer is exposed and used.
此處，說明用於暫時樹脂組成物層、樹脂組成物層之形成的樹脂組成物之成分。再者，於本說明書中之說明中，各成分之含量係以樹脂組成物中的不揮發成分之合計為100質量%時之量。 Here, the components of the resin composition for forming the temporary resin composition layer and the resin composition layer will be described. In the description of the present specification, the content of each component is an amount when the total amount of nonvolatile components in the resin composition is 100% by mass.
零件封裝用薄膜係如已經說明，包含支持體與以接合於該支持體之方式所設置的樹脂組成物層。而且，樹脂組成物層之厚度為200μ~700μm。作為樹脂組成物層之材料所用的樹脂組成物，可使用熱硬化性樹脂，較佳為包含環氧樹脂、硬化劑及無機填充材之樹脂組成物。樹脂組成物亦可更包含熱塑性樹脂、硬化促進劑、難燃劑及橡膠粒子等之添加劑。以下，分別說明此等。 The film for component encapsulation, as already described, includes a support and a resin composition layer provided to be bonded to the support. Further, the thickness of the resin composition layer is 200 μ to 700 μm. As the resin composition used for the material of the resin composition layer, a thermosetting resin can be used, and a resin composition containing an epoxy resin, a curing agent, and an inorganic filler is preferable. The resin composition may further contain additives such as a thermoplastic resin, a hardening accelerator, a flame retardant, and rubber particles. Hereinafter, these are explained separately.
作為環氧樹脂，例如可舉出雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、雙酚AF型環氧樹脂、二環戊二烯型環氧樹脂、三苯酚環氧樹脂、萘酚酚醛清漆環氧樹脂、苯酚酚醛清漆型環氧樹脂、第三丁基兒茶酚型環氧樹脂、萘型環氧樹脂、萘酚型環氧樹脂、蒽型環氧樹脂、環氧丙基胺型環氧樹脂、環氧丙基酯型環氧樹脂、甲酚酚醛清漆型環氧樹脂、聯苯型環氧樹脂、線狀脂肪族環氧樹脂、具有丁二烯構造的環氧樹脂、脂環式環氧 樹脂、雜環式環氧樹脂、含螺環的環氧樹脂、環己烷二甲醇型環氧樹脂、伸萘基醚型環氧樹脂及三羥甲基型環氧樹脂等。環氧樹脂係可單獨1種使用，或可併用2種以上。 Examples of the epoxy resin include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AF epoxy resin, and dicyclopentadiene epoxy resin. , trisphenol epoxy resin, naphthol novolac epoxy resin, phenol novolak epoxy resin, t-butyl catechol epoxy resin, naphthalene epoxy resin, naphthol epoxy resin, 蒽 type Epoxy resin, epoxy propyl amine epoxy resin, epoxy propyl ester epoxy resin, cresol novolak epoxy resin, biphenyl epoxy resin, linear aliphatic epoxy resin, with D Diene-structured epoxy resin, alicyclic epoxy Resin, heterocyclic epoxy resin, epoxy resin containing a spiro ring, cyclohexane dimethanol type epoxy resin, a naphthyl ether type epoxy resin, and a trimethylol type epoxy resin. The epoxy resin may be used alone or in combination of two or more.
環氧樹脂較佳為包含在1分子中具有2個以上的環氧基之環氧樹脂。環氧樹脂的不揮發成分為100質量%時，至少50質量%以上較佳為在1分子中具有2個以上的環氧基之環氧樹脂。其中，較佳為包含在1分子中具有2個以上的環氧基，於溫度20℃為液狀的環氧樹脂(以下稱為「液狀環氧樹脂」)，與在1分子中具有3個以上的環氧基，於溫度20℃為固體狀的環氧樹脂(以下稱為「固體狀環氧樹脂」)。作為環氧樹脂，藉由併用液狀環氧樹脂與固體狀環氧樹脂，而得到具有優異的可撓性之樹脂組成物。又，將樹脂組成物硬化而形成的封裝層(硬化體)之斷裂強度亦升高。 The epoxy resin is preferably an epoxy resin containing two or more epoxy groups in one molecule. When the nonvolatile content of the epoxy resin is 100% by mass, at least 50% by mass or more is preferably an epoxy resin having two or more epoxy groups in one molecule. In particular, it is preferable to include an epoxy resin having two or more epoxy groups in one molecule and a liquid at a temperature of 20 ° C (hereinafter referred to as "liquid epoxy resin"), and having 3 molecules in one molecule. One or more epoxy groups are solid epoxy resins (hereinafter referred to as "solid epoxy resins") at a temperature of 20 ° C. As the epoxy resin, a liquid epoxy resin and a solid epoxy resin are used in combination to obtain a resin composition having excellent flexibility. Further, the breaking strength of the encapsulating layer (hardened body) formed by curing the resin composition is also increased.
作為液狀環氧樹脂，例如較佳為雙酚A型環氧樹脂、雙酚F型環氧樹脂、苯酚酚醛清漆型環氧樹脂、2官能脂肪族環氧樹脂或萘型環氧樹脂，可舉出雙酚A型環氧樹脂、雙酚F型環氧樹脂或萘型環氧樹脂。作為液狀環氧樹脂之具體例，可舉出DIC(股)製的「HP4032」、「HP4032D」、「HP4032SS」(萘型環氧樹脂)、三菱化學(股)製的「jER828EL」、「jER1007」(雙酚A型環氧樹脂)、「jER807」(雙酚F型環氧樹脂)、「jER152」(苯酚酚醛清漆型環氧樹脂)、新日鐵化學(股)製的「ZX1059」(雙酚A型環氧樹脂與雙酚F型 環氧樹脂之混合品)、「YL7410」(2官能脂肪族環氧樹脂)等。此等係可單獨1種使用，或可併用2種以上。 As the liquid epoxy resin, for example, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolak type epoxy resin, a bifunctional aliphatic epoxy resin or a naphthalene type epoxy resin is preferable. A bisphenol A type epoxy resin, a bisphenol F type epoxy resin or a naphthalene type epoxy resin is mentioned. Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC Co., Ltd., and "jER828EL" manufactured by Mitsubishi Chemical Corporation. jER1007" (bisphenol A type epoxy resin), "jER807" (bisphenol F type epoxy resin), "jER152" (phenol novolak type epoxy resin), "ZX1059" manufactured by Nippon Steel Chemical Co., Ltd. (bisphenol A type epoxy resin and bisphenol F type "Epoxy resin mixture", "YL7410" (2-functional aliphatic epoxy resin). These may be used alone or in combination of two or more.
作為固體狀環氧樹脂，例如可舉出結晶性2官能環氧樹脂、4官能萘型環氧樹脂、甲酚酚醛清漆型環氧樹脂、二環戊二烯型環氧樹脂、三苯酚環氧樹脂、萘酚酚醛清漆環氧樹脂、聯苯型環氧樹脂、伸萘基醚型環氧樹脂。作為固體狀環氧樹脂之具體例，可舉出DIC(股)製的「HP-4700」、「HP-4710」(4官能萘型環氧樹脂)、「N-690」(甲酚酚醛清漆型環氧樹脂)、「N-695」(甲酚酚醛清漆型環氧樹脂)、「HP-7200」(二環戊二烯型環氧樹脂)、「EXA7311」、「EXA7311-G3」、「HP6000」(伸萘基醚型環氧樹脂)、日本化藥(股)製的「EPPN-502H」(三苯酚環氧樹脂)、「NC7000L」(萘酚酚醛清漆環氧樹脂)、「NC3000H」、「NC3000」、「NC3000H」、「NC3000L」、「NC3100」(聯苯型環氧樹脂)、新日鐵化學(股)製的「ESN475」(萘酚酚醛清漆型環氧樹脂)、「ESN485」(萘酚酚醛清漆型環氧樹脂)、三菱化學(股)製的「YX4000H」、「YL6121」(聯苯型環氧樹脂)、結晶性2官能環氧樹脂的「YX4000HK」(聯二甲酚型環氧樹脂)等。 Examples of the solid epoxy resin include a crystalline bifunctional epoxy resin, a tetrafunctional naphthalene epoxy resin, a cresol novolac epoxy resin, a dicyclopentadiene epoxy resin, and a trisphenol epoxy resin. Resin, naphthol novolac epoxy resin, biphenyl type epoxy resin, and naphthyl ether type epoxy resin. Specific examples of the solid epoxy resin include "HP-4700" manufactured by DIC Co., Ltd., "HP-4710" (4-functional naphthalene epoxy resin), and "N-690" (cresol novolac varnish). Type epoxy resin), "N-695" (cresol novolac type epoxy resin), "HP-7200" (dicyclopentadiene type epoxy resin), "EXA7311", "EXA7311-G3", " "HPPN-502H" (trisphenol epoxy resin), "NC7000L" (naphthol novolac epoxy resin), "NC3000H" manufactured by Nippon Kayaku Co., Ltd. "ESN475" (naphthol novolak type epoxy resin) manufactured by Nippon Steel Chemical Co., Ltd., "NC3000", "NC3000H", "NC3000L", "NC3100" (biphenyl type epoxy resin), "ESN485" "Ya4000", a "naphthol novolak type epoxy resin", "YX4000H", "YL6121" (biphenyl type epoxy resin) made of Mitsubishi Chemical Corporation, and "YX4000HK" (bimethicone) of a crystalline bifunctional epoxy resin Phenolic epoxy resin).
作為環氧樹脂，併用液狀環氧樹脂與固體狀環氧樹脂時，彼等之量比(液狀環氧樹脂：固體狀環氧樹脂)以質量比計較佳為1：0.1~1：4之範圍。藉由使液狀環氧樹脂與固體狀環氧樹脂之量比成為該範圍，得到(i)以接 著薄膜之形態使用時，帶來適度的黏著性，(ii)以接著薄膜之形態使用時，得到充分的可撓性，操作性升高，以及(iii)可得到具有充分的斷裂強度之硬化體等之效果。 從上述(i)~(iii)的效果之觀點來看，液狀環氧樹脂與固體狀環氧樹脂之量比(液狀環氧樹脂：固體狀環氧樹脂)以質量比計較佳為1：0.3~1：3.5之範圍，更佳為1：0.6~1：3之範圍，特佳為1：0.8~1：2.5之範圍。 When the epoxy resin and the solid epoxy resin are used together, the ratio (liquid epoxy resin: solid epoxy resin) is preferably 1:0.1 to 1:4 by mass ratio. The scope. By setting the ratio of the liquid epoxy resin to the solid epoxy resin to be in this range, (i) is obtained. When used in the form of a film, it imparts moderate adhesion, (ii) when used in the form of a film, sufficient flexibility is obtained, workability is improved, and (iii) hardening with sufficient breaking strength is obtained. The effect of body. From the viewpoints of the effects (i) to (iii) above, the ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is preferably 1 by mass ratio. The range of 0.3~1:3.5, more preferably the range of 1:0.6~1:3, especially the range of 1:0.8~1:2.5.
樹脂組成物中的環氧樹脂之含量較佳為3質量%~50質量%，更佳為5質量%~45質量%，尤佳為5質量%~40質量%，特佳為7質量%~35質量%。 The content of the epoxy resin in the resin composition is preferably from 3% by mass to 50% by mass, more preferably from 5% by mass to 45% by mass, even more preferably from 5% by mass to 40% by mass, particularly preferably from 7% by mass to 5% by mass. 35 mass%.
環氧樹脂之環氧當量較佳為50~3000之範圍，更佳為80~2000之範圍，尤佳為110~1000之範圍。藉由成為如此的範圍，可得到交聯密度充分之硬化體。再者，環氧當量係可依照JIS K7236規格化之方法測定，此處，所謂的環氧當量，就是含有1當量的環氧基之樹脂的質量。 The epoxy equivalent of the epoxy resin is preferably in the range of 50 to 3,000, more preferably in the range of 80 to 2,000, and particularly preferably in the range of 110 to 1,000. By such a range, a hardened body having a sufficient crosslinking density can be obtained. Further, the epoxy equivalent can be measured according to the method standardized by JIS K7236. Here, the epoxy equivalent is the mass of the resin containing 1 equivalent of an epoxy group.
作為硬化劑，只要具有將上述環氧樹脂硬化之機能，則沒有特別的限定，例如可舉出苯酚系硬化劑、萘酚系硬化劑、活性酯系硬化劑、苯并系硬化劑及氰酸酯系硬化劑。硬化劑係可單獨1種使用，或可併用2種以上。 The curing agent is not particularly limited as long as it has a function of curing the above-mentioned epoxy resin, and examples thereof include a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, and benzo. It is a hardener and a cyanate-based hardener. The curing agent may be used alone or in combination of two or more.
作為苯酚系硬化劑及萘酚系硬化劑，例如可舉出具有酚醛清漆構造的苯酚系硬化劑、具有酚醛清漆構造的萘酚系硬化劑、含氮苯酚系硬化劑、含有三骨架的甲酚系硬 化劑、含有三骨架的苯酚系硬化劑。 Examples of the phenol-based curing agent and the naphthol-based curing agent include a phenol-based curing agent having a novolac structure, a naphthol-based curing agent having a novolak structure, and a nitrogen-containing phenol-based curing agent. Skeletal cresol-based hardener, containing three a phenolic hardener of the skeleton.
作為苯酚系硬化劑及萘酚系硬化劑之具體例，例如可舉出明和化成(股)製的「MEH-7700」、「MEH-7810」、「MEH-7851」、日本化藥(股)製的「NHN」、「CBN」、「GPH」、東都化成(股)製的「SN170」、「SN180」、「SN190」、「SN475」、「SN485」、「SN495」、「SN375」、「SN395」、DIC(股)製的「LA7052」、「LA7054」、「LA3018」等。 Specific examples of the phenolic curing agent and the naphthol-based curing agent include "MEH-7700", "MEH-7810", "MEH-7851", and Nippon Chemical Co., Ltd., manufactured by Megumi Kasei Co., Ltd. "SNN", "SNH", "SN180", "SN190", "SN475", "SN485", "SN495", "SN375", "NSN", "CBN", "GPH", and Dongdu Chemicals Co., Ltd. SN395", DIC (shares) system "LA7052", "LA7054", "LA3018", etc.
作為活性酯系硬化劑，並沒有特別的限制，但一般較宜使用苯酚酯類、噻吩酯類、N-羥基胺酯類、雜環羥基化合物之酯類等之在1分子中具有2個以上的反應活性高之酯基的化合物。該活性酯系硬化劑較佳為藉由羧酸化合物及/或硫羧酸化合物與羥基化合物及/或硫醇化合物之縮合反應而得之活性酯系硬化劑。特別地從耐熱性提高之觀點來看，較佳為由羧酸化合物與羥基化合物所得之活性酯系硬化劑，更佳為由羧酸化合物與苯酚化合物及/或萘酚化合物所得之活性酯系硬化劑。作為羧酸化合物，例如可舉出苯甲酸、醋酸、琥珀酸、馬來酸、伊康酸、苯二甲酸、間苯二甲酸、對苯二甲酸、苯均四酸等。作為苯酚化合物或萘酚化合物，例如可舉出氫醌、間苯二酚、雙酚A、雙酚F、雙酚S、還原酚酞、甲基化雙酚A、甲基化雙酚F、甲基化雙酚S、苯酚、鄰甲酚、間甲酚、對甲酚、兒茶酚、α-萘酚、β-萘酚、1,5-二羥基萘、1,6-二羥基萘、2,6-二羥基萘、二羥基二苯基酮、三羥基二苯基酮、四羥 基二苯基酮、根皮三酚(phloroglucin)、苯三酚、二環戊二烯型之二酚化合物、苯酚酚醛清漆等。 The active ester-based curing agent is not particularly limited, and it is generally preferred to use two or more molecules in one molecule, such as phenol esters, thiophene esters, N-hydroxylamine esters, and esters of heterocyclic hydroxy compounds. A highly reactive ester-based compound. The active ester-based curing agent is preferably an active ester-based curing agent obtained by a condensation reaction of a carboxylic acid compound and/or a sulfuric acid compound with a hydroxy compound and/or a thiol compound. Particularly, from the viewpoint of improvement in heat resistance, an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester system derived from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferred. hardener. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or the naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, reduced phenolphthalein, methylated bisphenol A, methylated bisphenol F, and A. Bisphenol bisphenol, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxydiphenyl ketone, trihydroxydiphenyl ketone, tetrahydroxyl Diphenyl ketone, phloroglucin, benzenetriol, dicyclopentadiene diphenol compound, phenol novolac, and the like.
作為活性酯系硬化劑，具體地可舉出含有二環戊二烯型二酚縮合構造的活性酯化合物、含有萘構造的活性酯化合物、含有苯酚酚醛清漆的乙醯化物之活性酯化合物、含有苯酚酚醛清漆的苯甲醯化物的活性酯化合物。 Specific examples of the active ester-based curing agent include an active ester compound containing a dicyclopentadiene-type diphenol condensation structure, an active ester compound containing a naphthalene structure, and an active ester compound containing an acetylated phenol novolak. An active ester compound of a benzamidine compound of a phenol novolac.
作為活性酯系硬化劑的市售品，於含有二環戊二烯型二酚縮合構造的活性酯化合物中，可舉出「EXB9451」、「EXB9460」、「EXB9460S」、「HPC-8000-65T」(DIC(股)製)，於含有萘構造的活性酯化合物中，可舉出「EXB9416-70BK」(DIC(股)製)，於含有苯酚酚醛清漆的乙醯化物之活性酯化合物中，可舉出「DC808」(三菱化學(股)製)，於含有苯酚酚醛清漆的苯甲醯化物之活性酯化合物中，可舉出「YLH1026」(三菱化學(股)製)等。 As a commercial product of the active ester-based curing agent, "EXB9451", "EXB9460", "EXB9460S", and "HPC-8000-65T" are included in the active ester compound containing a dicyclopentadiene-type diphenol condensation structure. In the active ester compound containing a naphthalene structure, "EXB9416-70BK" (manufactured by DIC Co., Ltd.), in an active ester compound of an acetonide containing a phenol novolak, "DC808" (manufactured by Mitsubishi Chemical Corporation), and "YLH1026" (manufactured by Mitsubishi Chemical Corporation), etc., may be mentioned as an active ester compound of a benzamidine compound containing a phenol novolak.
作為苯并系硬化劑之具體例，可舉出昭和高分子(股)製的「HFB2006M」、四國化成工業(股)製的「P-d」、「F-a」。 Benzo Specific examples of the curing agent include "HFB2006M" manufactured by Showa Polymer Co., Ltd., and "Pd" and "Fa" manufactured by Shikoku Chemical Industries Co., Ltd.
作為氰酸酯系硬化劑，例如可舉出雙酚A二氰酸酯、聚苯酚氰酸酯(寡聚(3-亞甲基-1,5-伸苯基氰酸酯)、4,4’-亞甲基雙(2,6-二甲基苯基氰酸酯)、4,4’-亞乙基二苯基二氰酸酯、六氟雙酚A二氰酸酯、2,2-雙(4-氰酸根)苯基丙烷、1,1-雙(4-氰酸根苯基甲烷)、雙(4-氰酸根-3,5-二甲基苯基)甲烷、1,3-雙(4-氰酸根苯基-1- (甲基亞乙基))苯、雙(4-氰酸根苯基)硫醚及雙(4-氰酸根苯基)醚等之2官能氰酸酯樹脂、由苯酚酚醛清漆及甲酚酚醛清漆等所衍生之多官能氰酸酯樹脂、此等氰酸酯樹脂一部分經三化之預聚物等。作為氰酸酯系硬化劑之具體例，可舉出LONZA日本(股)製的「PT30」及「PT60」(皆苯酚酚醛清漆型多官能氰酸酯樹脂)、「BA230」(雙酚A二氰酸酯的一部分或全部經三化之三聚物的預聚物)等。 Examples of the cyanate-based curing agent include bisphenol A dicyanate and polyphenol cyanate (oligo(3-methylene-1,5-phenylene), 4,4). '-Methylene bis(2,6-dimethylphenyl cyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2 - bis(4-cyanate) phenylpropane, 1,1-bis(4-cyanylphenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3- 2-functional cyanate esters such as bis(4-cyanylphenyl-1-(methylethylidene))benzene, bis(4-cyanylphenyl) sulfide, and bis(4-cyanylphenyl) ether a resin, a polyfunctional cyanate resin derived from a phenol novolac, a cresol novolak, or the like, and a portion of the cyanate resin Prepolymers and the like. Specific examples of the cyanate-based curing agent include "PT30" and "PT60" (all phenol novolac type polyfunctional cyanate resins) manufactured by LONZA Japan Co., Ltd., and "BA230" (bisphenol A II) Part or all of the cyanate ester Prepolymer of a terpolymer) and the like.
環氧樹脂與硬化劑之量比，以〔環氧樹脂的環氧基之合計數〕：〔硬化劑的反應基之合計數〕之比率計，較佳為1：0.2~1：2之範圍，更佳為1：0.3~1：1.5之範圍，尤佳為1：0.4~1：1之範圍。此處，所謂硬化劑的反應基，就是活性經基、活性酯基等，隨著硬化劑之種類而不同。又，所謂環氧樹脂的環氧基之合計數，就是將各環氧樹脂的不揮發成分之質量除以環氧當量而得之值，對於全部的環氧樹脂進行合計之值。所謂硬化劑的反應基之合計數，就是將各硬化劑的不揮發成分之質量除以反應基當量而得之值，對於全部的硬化劑進行合計之值。藉由使環氧樹脂與硬化劑之量比成為該範圍內，作為硬化物時的耐熱性係進一步升高。 The ratio of the epoxy resin to the hardener is preferably in the range of 1:0.2 to 1:2, based on the ratio of [the total number of epoxy groups of the epoxy resin]: [the total number of reactive groups of the hardener]. More preferably, it is in the range of 1:0.3 to 1:1.5, and particularly preferably in the range of 1:0.4 to 1:1. Here, the reactive group of the curing agent is an active trans group, an active ester group or the like, which varies depending on the type of the curing agent. Further, the total number of epoxy groups of the epoxy resin is a value obtained by dividing the mass of the nonvolatile component of each epoxy resin by the epoxy equivalent, and the total value of all the epoxy resins is obtained. The total number of the reactive groups of the curing agent is a value obtained by dividing the mass of the non-volatile component of each curing agent by the equivalent of the reactive group, and the total value of all the curing agents is calculated. When the ratio of the amount of the epoxy resin to the curing agent is within this range, the heat resistance as a cured product is further increased.
用於暫時樹脂組成物層、樹脂組成物層之形成的樹脂組成物，從防止成為硬化體時膨脹率降低而與和硬化體封 裝的零件等之熱膨脹之差所造成的裂紋、電路畸變等的不良狀況之發生，防止熔融黏度的過度降低，抑制零件的位置偏移，高精度地封裝之觀點來看，較佳為包含無機填充材。 A resin composition for forming a temporary resin composition layer or a resin composition layer, which has a reduced expansion ratio and a hardened body when it is prevented from being a hardened body The occurrence of defects such as cracks and circuit distortion caused by the difference in thermal expansion of the mounted components, etc., prevents excessive decrease in melt viscosity, suppresses positional displacement of components, and preferably contains inorganic particles from the viewpoint of high-precision packaging. Filling material.
樹脂組成物中的無機填充材之含量，從使硬化體的熱膨脹率降低，防止熔融黏度的過度降低而抑制零件的位置偏移，可高精度地封裝之觀點之點，較佳為30質量%以上，更佳為40質量%以上，尤佳為50質量%以上，尤更佳為60質量%以上，特佳為62質量%以上、64質量%以上、或66質量%以上。特別地從抑制零件的位置偏移之觀點來看，樹脂組成物中的無機填充材之含量較佳為50質量%以上。樹脂組成物中的無機填充材之含量的上限，從硬化體的機械強度之觀點來看，較佳為90質量%以下，更佳為85質量%以下。 The content of the inorganic filler in the resin composition is preferably 30% by mass from the viewpoint of reducing the thermal expansion coefficient of the cured body, preventing the excessive decrease in the melt viscosity, and suppressing the positional displacement of the component, and providing high-precision packaging. The above is more preferably 40% by mass or more, particularly preferably 50% by mass or more, more preferably 60% by mass or more, particularly preferably 62% by mass or more, 64% by mass or more, or 66% by mass or more. In particular, the content of the inorganic filler in the resin composition is preferably 50% by mass or more from the viewpoint of suppressing the positional displacement of the component. The upper limit of the content of the inorganic filler in the resin composition is preferably 90% by mass or less, and more preferably 85% by mass or less from the viewpoint of mechanical strength of the cured product.
作為無機填充材，例如可舉出矽石、氧化鋁、硫酸鋇、滑石、黏土、雲母粉、氫氧化鋁、氫氧化鎂、碳酸鈣、碳酸鎂、氧化鎂、氮化硼、硼酸鋁、鈦酸鋇、鈦酸鍶、鈦酸鈣、鈦酸鎂、鈦酸鉍、氧化鈦、鋯酸鋇及鋯酸鈣等。於此等之中，特別合適為無定形矽石、熔融矽石、結晶矽石、合成矽石、中空矽石等之矽石。又，作為矽石，較佳為球狀矽石。無機填充材係可單獨1種使用，也可組合2種以上使用。作為市售的球狀(熔融)矽石，可舉出(股)ADMATECHS製「SOC2」、「SOC1」、「SOC4」、「SOC5」、「SOC6」。 Examples of the inorganic filler include vermiculite, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, and titanium. Barium strontium, barium titanate, calcium titanate, magnesium titanate, barium titanate, titanium oxide, barium zirconate and calcium zirconate. Among these, it is particularly suitable as a vermiculite such as amorphous vermiculite, molten vermiculite, crystalline vermiculite, synthetic vermiculite, hollow vermiculite or the like. Further, as the vermiculite, a spherical vermiculite is preferred. The inorganic fillers may be used alone or in combination of two or more. As a commercially available spherical (melted) vermiculite, "SOC2", "SOC1", "SOC4", "SOC5", and "SOC6" manufactured by ADMATECHS can be cited.
無機填充材之平均粒徑，從提高樹脂組成物的流動性而實現充分的埋入性之觀點來看，較佳為0.01μm~4μm之範圍，更佳為0.05μm~2.5μm之範圍，尤佳為0.1μm~1.5μm之範圍，尤更佳為0.3μm~1.0μm之範圍。無機填充材之平均粒徑係可藉由以米氏(Mie)散射理論為基礎的雷射繞射．散射法進行測定。具體地，可藉由雷射繞射散射式粒度分布測定裝置，以體積基準作成無機填充材之粒度分布，將其中位徑當作平均粒徑而測定。於無機填充材之平均粒徑的測定中，較佳可使用無機填充劑經由超音波分散在水中之測定樣品。作為雷射繞射散射式粒度分布測定裝置，可使用(股)堀場製作所製LA-500等。 The average particle diameter of the inorganic filler is preferably in the range of 0.01 μm to 4 μm, more preferably in the range of 0.05 μm to 2.5 μm, from the viewpoint of improving the fluidity of the resin composition and achieving sufficient embedding property. It is preferably in the range of 0.1 μm to 1.5 μm, and more preferably in the range of 0.3 μm to 1.0 μm. The average particle size of the inorganic filler can be obtained by laser diffraction based on the Mie scattering theory. The scattering method was used for the measurement. Specifically, the particle size distribution of the inorganic filler can be determined on a volume basis by a laser diffraction scattering type particle size distribution measuring apparatus, and the median diameter can be measured as an average particle diameter. In the measurement of the average particle diameter of the inorganic filler, it is preferred to use a measurement sample in which an inorganic filler is dispersed in water via ultrasonic waves. As the laser diffraction scattering type particle size distribution measuring apparatus, LA-500 or the like manufactured by Horiba, Ltd. can be used.
從提高耐濕性及分散性之觀點來看，無機填充材較佳為經胺基矽烷系偶合劑、環氧基矽烷系偶合劑、巰基矽烷系偶合劑、矽烷系偶合劑、有機矽氮烷化合物、鈦酸酯系偶合劑等之1種以上的表面處理劑所處理者。作為表面處理劑之市售品，例如可舉出信越化學工業(股)製「KBM403」(3-環氧丙氧基丙基三甲氧基矽烷)、信越化學工業(股)製「KBM803」(3-巰基丙基三甲氧基矽烷)、信越化學工業(股)製「KBE903」(3-胺基丙基三乙氧基矽烷)、信越化學工業(股)製「KBM573」(N-苯基-3-胺基丙基三甲氧基矽烷)、信越化學工業(股)製「SZ-31」(六甲基二矽氮烷)等。 The inorganic filler is preferably an amino decane coupling agent, an epoxy decane coupling agent, a mercapto decane coupling agent, a decane coupling agent, or an organic decazane from the viewpoint of improving moisture resistance and dispersibility. A treatment of one or more kinds of surface treatment agents such as a compound or a titanate coupling agent. As a commercial product of the surface treatment agent, "KBM403" (3-glycidoxypropyltrimethoxydecane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM803" manufactured by Shin-Etsu Chemical Co., Ltd. "M-Mercaptopropyltrimethoxydecane", "KBE903" (3-Aminopropyltriethoxydecane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl) manufactured by Shin-Etsu Chemical Co., Ltd. 3-Aminopropyltrimethoxydecane), "SZ-31" (hexamethyldioxane) manufactured by Shin-Etsu Chemical Co., Ltd., etc.
經表面處理劑所表面處理之無機填充材，係可在經由溶劑(例如甲基乙基酮(MEK))洗淨處理後，測定無機 填充材的每單位表面積之碳量。具體地，將作為溶劑的充分量之MEK加到經表面處理劑所表面處理之無機填充材中，在25℃超音波洗淨5分鐘。去除上清液，使固體成分乾燥後，使用碳分析計測定無機填充材之每單位表面積的碳量。作為碳分析計，可使用(股)堀場製作所製「EMIA-320V」等。 The inorganic filler surface-treated by the surface treatment agent can be determined after being washed by a solvent such as methyl ethyl ketone (MEK). The amount of carbon per unit surface area of the filler. Specifically, a sufficient amount of MEK as a solvent was added to the inorganic filler surface-treated with the surface treatment agent, and ultrasonically washed at 25 ° C for 5 minutes. After removing the supernatant and drying the solid component, the amount of carbon per unit surface area of the inorganic filler was measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by Horiba Ltd. can be used.
無機填充材之每單位表面積的碳量，從無機填充材之分散性提高之觀點來看，較佳為0.02mg/m2以上，更佳為0.1mg/m2以上，尤佳為0.2mg/m2以上。另一方面，從抑制樹脂組成物層之熔融黏度的上升之觀點來看，無機填充材之每單位表面積的碳量較佳為1mg/m2以下，更佳為0.8mg/m2以下，尤佳為0.5mg/m2以下。 The amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m 2 or more, more preferably 0.1 mg/m 2 or more, and particularly preferably 0.2 mg/% from the viewpoint of improving the dispersibility of the inorganic filler. m 2 or more. On the other hand, the amount of carbon per unit surface area of the inorganic filler is preferably 1 mg/m 2 or less, more preferably 0.8 mg/m 2 or less, from the viewpoint of suppressing an increase in the melt viscosity of the resin composition layer. Preferably it is 0.5 mg/m 2 or less.
樹脂組成物較佳為分別包含由作為無機填充材的矽石、作為環氧樹脂的液狀環氧樹脂與固體狀環氧樹脂之混合物(液狀環氧樹脂：固體狀環氧樹脂之質量比較佳為1：0.1~1：4之範圍，更佳為1：0.3~1：3.5之範圍，尤佳為1：0.6~1：3之範圍，特佳為1：0.8~1：2.5之範圍)、作為硬化劑的苯酚系硬化劑、萘酚系硬化劑、活性酯系硬化劑及氰酸酯系硬化劑所成之群組中選出的的1種以上(較佳為由苯酚系硬化劑、萘酚系硬化劑所成之群組中選出的1種以上，更佳為由含有三骨架的苯酚酚醛清漆樹脂、萘酚系硬化劑所成之群組中選出的1種以上，尤佳為含有三骨架的苯酚酚醛清漆樹脂之硬化劑)。關於組合含有特定成分的樹脂組成物，無機填充材、環氧樹脂 及硬化劑之合適含量亦如上述，但其中較佳為無機填充材之含量係30質量%~90質量%之範圍，環氧樹脂之含量係3質量%~50質量%之範圍，更佳為無機填充材之含量係50質量%~90質量%之範圍，環氧樹脂之含量係5質量%~45質量%之範圍。關於硬化劑之含量，係以環氧樹脂的環氧基合計數與硬化劑的反應基之合計數比較佳成為1：0.2~1：2之範圍，更佳成為1：0.3~1：1.5之範圍，尤佳成為1：0.4~1：1之範圍而含有。 The resin composition preferably comprises a mixture of a vermiculite as an inorganic filler, a liquid epoxy resin as an epoxy resin, and a solid epoxy resin (liquid epoxy resin: solid epoxy resin quality comparison) The range of 1:0.1~1:4, preferably the range of 1:0.3~1:3.5, especially the range of 1:0.6~1:3, especially the range of 1:0.8~1:2.5 One or more selected from the group consisting of a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, and a cyanate-based curing agent as a curing agent (preferably, a phenol-based curing agent) One or more selected from the group consisting of naphthol-based curing agents, more preferably three-containing One or more selected from the group consisting of a phenol novolac resin and a naphthol-based curing agent, and particularly preferably three Skeleton phenol novolac resin hardener). With respect to the combination of the resin composition containing the specific component, the suitable content of the inorganic filler, the epoxy resin, and the hardener is also as described above, but preferably, the content of the inorganic filler is in the range of 30% by mass to 90% by mass, and the epoxy The content of the resin is in the range of 3% by mass to 50% by mass, more preferably the content of the inorganic filler is in the range of 50% by mass to 90% by mass, and the content of the epoxy resin is in the range of 5% by mass to 45% by mass. The content of the hardener is preferably in the range of 1:0.2 to 1:2, more preferably 1:0.3 to 1:1.5, based on the total number of epoxy groups of the epoxy resin and the reactive group of the curing agent. The range is particularly preferable to be in the range of 1:0.4 to 1:1.
作為熱塑性樹脂，例如可舉出苯氧樹脂、丙烯酸樹脂、聚乙烯縮醛樹脂、聚醯亞胺樹脂、聚醯胺醯亞胺樹脂、聚醚碸樹脂及聚碸樹脂等。熱塑性樹脂係可單獨1種使用，或可併用2種以上。 Examples of the thermoplastic resin include a phenoxy resin, an acrylic resin, a polyvinyl acetal resin, a polyimide resin, a polyamidoximine resin, a polyether oxime resin, and a polyfluorene resin. The thermoplastic resin may be used alone or in combination of two or more.
熱塑性樹脂的聚苯乙烯換算之重量平均分子量較佳為8,000~70,000之範圍，更佳為10,000~60,000之範圍，尤佳為20,000~60,000之範圍。熱塑性樹脂的聚苯乙烯換算之重量平均分子量係以凝膠滲透層析(GPC)法測定。具體地，熱塑性樹脂的聚苯乙烯換算之重量平均分子量，係可使用(股)島津製作所製LC-9A/RID-6A作為測定裝置，使用昭和電工(股)製Shodex K-800P/K-804L/K-804L作為管柱，使用氯仿等作為移動相，於40℃的管柱溫度進行測定，使用標準聚苯乙烯的校正曲線來算出。 The polystyrene-equivalent weight average molecular weight of the thermoplastic resin is preferably in the range of 8,000 to 70,000, more preferably in the range of 10,000 to 60,000, and particularly preferably in the range of 20,000 to 60,000. The polystyrene-equivalent weight average molecular weight of the thermoplastic resin is measured by a gel permeation chromatography (GPC) method. Specifically, the weight average molecular weight of the thermoplastic resin in terms of polystyrene can be used as a measuring device using LC-9A/RID-6A manufactured by Shimadzu Corporation, and Shodex K-800P/K-804L manufactured by Showa Denko Co., Ltd. /K-804L was used as a column, and chloroform or the like was used as a mobile phase, and it was measured at a column temperature of 40 ° C, and was calculated using a calibration curve of standard polystyrene.
作為苯氧樹脂，例如可舉出具有由雙酚A骨架、雙酚 F骨架、雙酚S骨架、雙酚蒽醌骨架、酚醛清漆骨架、聯苯骨架、茀骨架、二環戊二烯骨架、降冰片烯骨架、萘骨架、蒽骨架、金剛烷骨架、萜烯骨架及三甲基環己烷骨架所成之群組中選出的1種以上之骨架的苯氧樹脂。苯氧樹脂之末端亦可為酚性羥基、環氧基等之任一官能基。苯氧樹脂係可單獨1種使用，或可併用2種以上。作為苯氧樹脂之具體例，可舉出三菱化學(股)製之「1256」及「4250」(皆含有雙酚A骨架的苯氧樹脂)、「YX8100」(含有雙酚S骨架的苯氧樹脂)及「YX6954」(含有雙酚蒽醌骨架的苯氧樹脂)，另外還可舉出東都化成(股)製之「FX280」及「FX293」、三菱化學(股)製之「YL7553」、「YL6794」、「YL7213」、「YL7290」及「YL7482」等。 Examples of the phenoxy resin include a bisphenol A skeleton and bisphenol. F skeleton, bisphenol S skeleton, bisphenol fluorene skeleton, novolak skeleton, biphenyl skeleton, anthracene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton And a phenoxy resin having one or more kinds of skeletons selected from the group consisting of trimethylcyclohexane skeletons. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. The phenoxy resin may be used alone or in combination of two or more. Specific examples of the phenoxy resin include "1256" and "4250" (a phenoxy resin containing a bisphenol A skeleton) and "YX8100" (a phenoxy group containing a bisphenol S skeleton) manufactured by Mitsubishi Chemical Corporation. "Resin" and "YX6954" (phenoxy resin containing a bisphenol fluorene skeleton), "FX280" and "FX293" manufactured by Toho Chemical Co., Ltd., and "YL7553" manufactured by Mitsubishi Chemical Corporation. "YL6794", "YL7213", "YL7290" and "YL7482".
作為丙烯酸樹脂，從使封裝層的熱膨脹率及彈性率進一步降低之觀點來看，較佳為含官能基的丙烯酸樹脂，更佳為Tg(玻璃轉移點)為25℃以下之含環氧基的丙烯酸樹脂。 The acrylic resin is preferably a functional group-containing acrylic resin from the viewpoint of further lowering the thermal expansion coefficient and the elastic modulus of the encapsulating layer, and more preferably an epoxy group having a Tg (glass transition point) of 25 ° C or less. Acrylic.
含官能基的丙烯酸樹脂之數量平均分子量(Mn)，較佳為10000~1000000，更佳為30000~900000。 The number average molecular weight (Mn) of the functional group-containing acrylic resin is preferably from 10,000 to 1,000,000, more preferably from 30,000 to 900,000.
含官能基的丙烯酸樹脂之官能基當量，較佳為1000~50000，更佳為2500~30000。 The functional group equivalent of the functional group-containing acrylic resin is preferably from 1,000 to 50,000, more preferably from 2,500 to 30,000.
作為Tg為25℃以下之含環氧基的丙烯酸樹脂，較佳係Tg為25℃以下之含環氧基的丙烯酸酯共聚物樹脂，作為其具體例，可舉出Nagase Chemtex(股)製之「SG- 80H」(含環氧基的丙烯酸酯共聚物樹脂(數量平均分子量Mn：350000g/mol，環氧值0.07eq/kg，Tg11℃))、Nagase Chemtex(股)製之「SG-P3」(含環氧基的丙烯酸酯共聚物樹脂(數量平均分子量Mn：850000g/mol，環氧值0.21eq/kg，Tg12℃))。 The epoxy group-containing acrylic resin having a Tg of 25 ° C or less is preferably an epoxy group-containing acrylate copolymer resin having a Tg of 25 ° C or less, and specific examples thereof include Nagase Chemtex. "SG- 80H" (epoxy group-containing acrylate copolymer resin (number average molecular weight Mn: 350,000 g/mol, epoxy value 0.07 eq/kg, Tg 11 ° C)), Nagase Chemtex ("SG-P3") (including Epoxy group acrylate copolymer resin (number average molecular weight Mn: 850,000 g/mol, epoxy value 0.21 eq/kg, Tg 12 ° C)).
作為聚乙烯縮醛樹脂之具體例，可舉出電氣化學工業(股)製之電化Butyral 4000-2、5000-A、6000-C、6000-EP、積水化學工業(股)製之S-LEC BH系列、BX系列、KS系列、BL系列、BM系列等。 Specific examples of the polyvinyl acetal resin include an electrochemically charged Butyral 4000-2, 5000-A, 6000-C, 6000-EP, and S-LEC manufactured by Sekisui Chemical Industry Co., Ltd. BH series, BX series, KS series, BL series, BM series, etc.
作為聚醯亞胺樹脂之具體例，可舉出新日本理化(股)製之「Rikacoat SN20」及「Rikacoat PN20」。作為聚醯亞胺樹脂之具體例，還可舉出使2官能性羥基末端聚丁二烯、二異氰酸酯化合物及四元酸酐反應而得之線狀聚醯亞胺(特開2006-37083號公報中記載之聚醯亞胺樹脂)、含聚矽氧烷骨架的聚醯亞胺(特開2002-12667號公報及日本特開2000-319386號公報等中記載之聚醯亞胺樹脂)等之改性聚醯亞胺。 Specific examples of the polyimine resin include "Rikacoat SN20" and "Rikacoat PN20" manufactured by Nippon Chemical and Chemical Co., Ltd. Specific examples of the polyimine resin include a linear polyimine obtained by reacting a bifunctional hydroxyl-terminated polybutadiene, a diisocyanate compound, and a tetrabasic acid anhydride (JP-A-2006-37083) (Polyimide resin described in the above), a polyfluorene-containing polyalkylene group (polyimide resin described in JP-A-2002-210667, JP-A-2000-319386, etc.) Modified polyimine.
作為聚醯胺醯亞胺樹脂之具體例，可舉出東洋紡績(股)製之「Vylomax HR11NN」及「Vylomax HR16NN」。作為聚醯胺醯亞胺樹脂之具體例，還可舉出日立化成工業(股)製之含聚矽氧烷骨架的聚醯胺醯亞胺「KS9100」、「KS9300」等之改性聚醯胺醯亞胺。 Specific examples of the polyamidoximine resin include "Vylomax HR11NN" and "Vylomax HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of the polyamidoximine resin include modified polyfluorenes such as polyacrylamide skeleton-containing polyamine amidoxime "KS9100" and "KS9300" manufactured by Hitachi Chemical Co., Ltd. Amine quinone.
作為聚醚碸樹脂之具體例，可舉出住友化學(股)製之「PES5003P」等。 Specific examples of the polyether oxime resin include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd., and the like.
作為聚碸樹脂之具體例，可舉出Solvay Advanced Polymers(股)製之聚碸「P1700」、「P3500」等。 Specific examples of the polyfluorene resin include polydips "P1700" and "P3500" manufactured by Solvay Advanced Polymers Co., Ltd.
樹脂組成物中的熱塑性樹脂之含量較佳為0.1質量%~20質量%。藉由使熱塑性樹脂之含量成為該範圍內，樹脂組成物之黏度係成為適度，可形成厚度或整體性狀均勻的樹脂組成物層。樹脂組成物中的熱塑性樹脂之含量更佳為0.5質量%~10質量%。 The content of the thermoplastic resin in the resin composition is preferably from 0.1% by mass to 20% by mass. When the content of the thermoplastic resin is within this range, the viscosity of the resin composition is moderate, and a resin composition layer having a uniform thickness or overall properties can be formed. The content of the thermoplastic resin in the resin composition is more preferably from 0.5% by mass to 10% by mass.
作為硬化促進劑，例如可舉出磷系硬化促進劑、胺系硬化促進劑、咪唑系硬化促進劑、胍系硬化促進劑等。 Examples of the curing accelerator include a phosphorus-based curing accelerator, an amine-based curing accelerator, an imidazole-based curing accelerator, and an oxime-based curing accelerator.
作為磷系硬化促進劑，例如可舉出三苯基膦、硼酸鏻化合物、四苯基鏻四苯基硼酸鹽、正丁基鏻四苯基硼酸鹽、四丁基鏻癸酸鹽、(4-甲基苯基)三苯基鏻硫氰酸鹽、四苯基鏻硫氰酸鹽、丁基三苯基鏻硫氰酸鹽等。 Examples of the phosphorus-based hardening accelerator include triphenylphosphine, a barium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, and tetrabutylphosphonate. -Methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, and the like.
作為胺系硬化促進劑，例如可舉出三乙胺、三丁胺等之三烷基胺、4-二甲基胺基吡啶、苄基二甲基胺、2,4,6,-三(二甲基胺基甲基)苯酚、1,8-二氮雜雙環(5,4,0)-十一烯等。 Examples of the amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, and 2,4,6,-tri ( Dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, and the like.
作為咪唑系硬化促進劑，例如可舉出2-甲基咪唑、2-十一基咪唑、2-十七基咪唑、1,2-二甲基咪唑、2-乙基-4-甲基咪唑、1,2-二甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、1-苄基-2-甲基咪唑、1-苄基-2-苯基咪唑、1-氰基乙基-2-甲基咪唑、1-氰基乙基-2-十一 基咪唑、1-氰基乙基-2-乙基-4-甲基咪唑、1-氰基乙基-2-苯基咪唑、1-氰基乙基-2-十一基咪唑鎓偏苯三酸鹽、1-氰基乙基-2-苯基咪唑鎓偏苯三酸鹽、2,4-二胺基-6-〔2’-甲基咪唑基-(1’)〕-乙基-s-三、2,4-二胺基-6-〔2’-十一基咪唑基-(1’)〕-乙基-s-三、2,4-二胺基-6-〔2’-乙基-4’-甲基咪唑基-(1’)〕-乙基-s-三、2,4-二胺基-6-〔2’-甲基咪唑基-(1’)〕-乙基-s-三異三聚氰酸加成物、2-苯基咪唑異三聚氰酸加成物、2-苯基-4,5-二羥基甲基咪唑、2-苯基-4-甲基-5羥基甲基咪唑、2,3-二氫-1H-吡咯并〔1,2-a〕苯并咪唑、1-十二基-2-甲基-3-苄基咪唑鎓氯化物、2-甲基咪唑啉、2-苯基咪唑啉等之咪唑化合物及咪唑化合物與環氧樹脂之加成物。 Examples of the imidazole-based hardening accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methylimidazole. 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1 -benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4 -methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazole Triammonium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-three 2,4-Diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-three 2,4-Diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-three 2,4-Diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-three Iso-cyanuric acid adduct, 2-phenylimidazolium isocyanurate adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxyl Methylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methyl An imidazole compound such as imidazoline or 2-phenylimidazoline and an adduct of an imidazole compound and an epoxy resin.
作為胍系硬化促進劑，例如可舉出氰基胍、1-甲基胍、1-乙基胍、1-環己基胍、1-苯基胍、1-(鄰甲苯基)胍、二甲基胍、二苯基胍、三甲基胍、四甲基胍、五甲基胍、1,5,7-三氮雜雙環〔4.4.0〕癸-5-烯、7-甲基-1,5,7-三氮雜雙環〔4.4.0〕癸-5-烯、1-甲基雙胍、1-乙基雙胍、1-正丁基雙胍、1-正十八基雙胍、1,1-二甲基雙胍、1,1-二乙基雙胍、1-環己基雙胍、1-烯丙基雙胍、1-苯基雙胍、1-(鄰甲苯基)雙胍等。 Examples of the oxime-based hardening accelerator include cyanoguanidine, 1-methyl fluorene, 1-ethyl hydrazine, 1-cyclohexyl fluorene, 1-phenyl fluorene, 1-(o-tolyl) fluorene, and dimethyl. Base, diphenyl hydrazine, trimethyl hydrazine, tetramethyl hydrazine, pentamethyl hydrazine, 1,5,7-triazabicyclo[4.4.0] 癸-5-ene, 7-methyl-1 ,5,7-triazabicyclo[4.4.0]non-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1 - dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide, and the like.
硬化促進劑係可單獨1種使用，或可組合2種以上使用。樹脂組成物中的硬化促進劑之含量，以環氧樹脂與硬化劑之不揮發成分的合計量作為100質量%時，較佳為以0.05質量%~3質量%之範圍內使用。 -難燃劑- The curing accelerators may be used alone or in combination of two or more. When the total amount of the non-volatile components of the epoxy resin and the curing agent is 100% by mass, the content of the curing accelerator in the resin composition is preferably from 0.05% by mass to 3% by mass. - Flame retardant -
作為難燃劑，例如可舉出有機磷系難燃劑、有機系含氮的磷化合物、氮化合物、矽氧系難燃劑、金屬氫氧化物等。作為可用的難燃劑之例，可舉出三光(股)製「HCA-HQ」。難燃劑係可單獨1種使用，或可併用2種以上。樹脂組成物層中的難燃劑之含量係沒有特別的限定，但較佳為0.5質量%~10質量%，更佳為1質量%~9質量%，尤佳為1.5質量%~8質量%。 Examples of the flame retardant include an organic phosphorus-based flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a xenon-based flame retardant, and a metal hydroxide. As an example of the usable flame retardant, "HCA-HQ" manufactured by Sanko Co., Ltd. is mentioned. The flame retardant may be used alone or in combination of two or more. The content of the flame retardant in the resin composition layer is not particularly limited, but is preferably 0.5% by mass to 10% by mass, more preferably 1% by mass to 9% by mass, and particularly preferably 1.5% by mass to 8% by mass. .
作為橡膠粒子，例如可使用不溶解於後述的有機溶劑中，與上述的環氧樹脂、硬化劑及熱塑性樹脂等亦不相溶之橡膠粒子。如此的橡膠粒子一般係將橡膠成分的分子量增大到不溶解在有機溶劑或樹脂中之程度為止，成為粒狀而調製。 As the rubber particles, for example, rubber particles which are not dissolved in an organic solvent to be described later and are incompatible with the above-mentioned epoxy resin, curing agent, thermoplastic resin or the like can be used. Such rubber particles are generally prepared by increasing the molecular weight of the rubber component to such an extent that it is not dissolved in the organic solvent or the resin.
作為橡膠粒子，例如可舉出芯殼型橡膠粒子、交聯丙烯腈丁二烯橡膠粒子、交聯苯乙烯丁二烯橡膠粒子、丙烯酸橡膠粒子等。芯殼型橡膠粒子係具有芯層與殼層之橡膠粒子，例如可舉出外層的殼層由玻璃狀聚合物構成且內層的芯層由橡膠狀聚合物構成之2層構造，或外層的殼層由玻璃狀聚合物構成，中間層由橡膠狀聚合物構成且芯層由玻璃狀聚合物構成之3層構造的橡膠粒子等。玻璃狀聚合物層例如係由甲基丙烯酸甲酯聚合物等所構成，橡膠狀聚 合物層例如係由丙烯酸丁酯聚合物(丁基橡膠)等所構成。作為可用的橡膠粒子之例，可舉出GANZ(股)製「Stafilrod AC3816N」。橡膠粒子係可單獨1種使用，或可併用2種以上。 Examples of the rubber particles include core-shell type rubber particles, crosslinked acrylonitrile butadiene rubber particles, crosslinked styrene butadiene rubber particles, and acrylic rubber particles. The core-shell type rubber particles are rubber particles having a core layer and a shell layer, and examples thereof include a two-layer structure in which a shell layer of an outer layer is composed of a glassy polymer and a core layer of an inner layer is composed of a rubber-like polymer, or an outer layer. The rubber layer having a three-layer structure in which the shell layer is composed of a glassy polymer and the intermediate layer is composed of a rubber-like polymer and the core layer is made of a glassy polymer. The glassy polymer layer is composed, for example, of a methyl methacrylate polymer or the like, and is rubberized. The composition layer is composed of, for example, a butyl acrylate polymer (butyl rubber) or the like. An example of the rubber particles that can be used is "Stafilrod AC3816N" manufactured by GANZ Co., Ltd. The rubber particles may be used alone or in combination of two or more.
橡膠粒子的平均粒徑較佳為0.005μm~1μm之範圍，更佳為0.2μm~0.6μm之範圍。橡膠粒子的平均粒徑係可使用動態光散射法來測定。例如，可藉由超音波等使橡膠粒子均勻分散在適當的有機溶劑中，使用濃厚系粒徑分析器(FPAR-1000；大塚電子(股)製)，以質量基準作成橡膠粒子的粒度分布，將其中位徑當作平均粒徑而測定。樹脂組成物中的橡膠粒子之含量較佳為1質量%~10質量%，更佳為2質量%~5質量%。 The average particle diameter of the rubber particles is preferably in the range of 0.005 μm to 1 μm, more preferably in the range of 0.2 μm to 0.6 μm. The average particle diameter of the rubber particles can be measured by a dynamic light scattering method. For example, the rubber particles can be uniformly dispersed in a suitable organic solvent by ultrasonic waves or the like, and a particle size distribution of rubber particles can be prepared on a mass basis using a thick particle size analyzer (FPAR-1000; manufactured by Otsuka Electronics Co., Ltd.). The median diameter was measured as an average particle diameter. The content of the rubber particles in the resin composition is preferably from 1% by mass to 10% by mass, more preferably from 2% by mass to 5% by mass.
用於樹脂組成物層之形成的樹脂組成物，視需要亦可含有例如以調整樹脂組成物層或硬化體的特性為目的之其它添加劑。作為該其它的添加劑，例如可舉出有機銅化合物、有機鋅化合物及有機鈷化合物等之有機金屬化合物，以及有機填料、增黏劑、消泡劑、均平劑、密接性賦予劑及著色劑等之樹脂添加劑等。 The resin composition used for the formation of the resin composition layer may contain, for example, other additives for the purpose of adjusting the properties of the resin composition layer or the cured body. Examples of the other additives include organometallic compounds such as an organic copper compound, an organic zinc compound, and an organic cobalt compound, and an organic filler, a tackifier, an antifoaming agent, a leveling agent, an adhesion imparting agent, and a coloring agent. Such as resin additives and the like.
作為作成樹脂清漆時所使用的有機溶劑，例如可舉出丙酮、甲基乙基酮及環己酮等之酮類、醋酸乙酯、醋酸丁酯、纖維素醋酸酯、丙二醇單甲基醚醋酸酯、卡必醇醋酸酯等之醋酸酯類、溶纖劑及丁基卡必醇等之卡必醇類、甲 苯及二甲苯等之芳香族烴類、二甲基甲醯胺、二甲基乙醯胺及N-甲基吡咯烷酮等之醯胺系溶劑等。有機溶劑係可單獨1種使用，或可併用2種以上。步驟(A)之形成暫時樹脂組成物層用的樹脂清漆中所含有的有機溶劑及後述步驟(B)各自之樹脂清漆中所含有的有機溶劑，係可相同或相異。 Examples of the organic solvent used in the production of the resin varnish include ketones such as acetone, methyl ethyl ketone and cyclohexanone, ethyl acetate, butyl acetate, cellulose acetate, and propylene glycol monomethyl ether acetate. Acetate such as ester, carbitol acetate, cellosolve, carbitol, etc. An aromatic hydrocarbon such as benzene or xylene, a guanamine solvent such as dimethylformamide, dimethylacetamide or N-methylpyrrolidone. The organic solvent may be used alone or in combination of two or more. The organic solvent contained in the resin varnish for forming the temporary resin composition layer of the step (A) and the organic solvent contained in the resin varnish of each of the steps (B) described later may be the same or different.
於本發明之零件封裝用薄膜中，樹脂組成物層之最低熔融黏度，係以埋入性、可防止熱硬化步驟時的樹脂垂滴作為條件，而沒有特別的限定，但較佳為50泊以上，更佳為200泊以上，尤佳為500泊以上。樹脂組成物層之最低熔融黏度的上限係沒有特別的限制，但較佳為10000泊以下，更佳為8000泊以下，尤佳為6000泊以下，尤更佳為4000泊以下，特佳為1500泊以下。 In the film for component encapsulation of the present invention, the lowest melt viscosity of the resin composition layer is not particularly limited as long as it is embedding and prevents the resin dripping in the thermal curing step, but is preferably 50 poise. More preferably, it is 200 poise or more, and more preferably 500 poise or more. The upper limit of the lowest melt viscosity of the resin composition layer is not particularly limited, but is preferably 10,000 poise or less, more preferably 8,000 poise or less, and particularly preferably 6,000 poise or less, more preferably 4,000 poise or less, and particularly preferably 1500 poise. Parked below.
此處，所謂樹脂組成物層的「最低熔融黏度」，就是指樹脂組成物層之樹脂因加熱處理而熔融之際，樹脂組成物層呈現的最低黏度。詳細地，若以固定的升溫速度來加熱處理樹脂組成物層而使樹脂熔融，則初期階段係熔融黏度隨溫度上升而降低，然後若超過某一溫度則隨著溫度上升而熔融黏度亦上升。所謂「最低熔融黏度」，就是指該極小點之熔融黏度。 Here, the "lowest melt viscosity" of the resin composition layer means the lowest viscosity of the resin composition layer when the resin of the resin composition layer is melted by heat treatment. In detail, when the resin composition layer is heated and treated at a fixed temperature increase rate to melt the resin, the melt viscosity in the initial stage decreases as the temperature rises, and if it exceeds a certain temperature, the melt viscosity increases as the temperature rises. The so-called "minimum melt viscosity" refers to the melt viscosity of the minimum point.
樹脂組成物層之最低熔融黏度係可藉由動態黏彈性法進行測定。具體地，熱硬化性樹脂組成物層之最低熔融黏度，係可藉由在測定開始溫度60℃、升溫速度5℃/分鐘、振動數1Hz、應變1deg之條件下進行動態黏彈性測 定而得。作為動態黏彈性測定裝置，例如可舉出(股)UBM公司製的「Rheosol-G3000」。 The lowest melt viscosity of the resin composition layer can be measured by a dynamic viscoelastic method. Specifically, the lowest melt viscosity of the thermosetting resin composition layer can be measured by dynamic viscoelasticity at a measurement start temperature of 60 ° C, a temperature increase rate of 5 ° C / min, a vibration number of 1 Hz, and a strain of 1 deg. Set it for you. As the dynamic viscoelasticity measuring device, for example, "Rheosol-G3000" manufactured by UBM Corporation can be cited.
可被由本發明之製造方法所得之零件封裝用薄膜所封裝的零件，係沒有特別的限定，可舉出符合所欲之機能的任意適宜之零件。作為可被零件封裝用薄膜所封裝之零件，例如除了電容器、電感器、電阻等之被動零件，還有半導體晶片、半導體晶片封裝等之主動零件。本發明之零件封裝用薄膜係可適用於例如零件內藏電路板之零件的封裝步驟。本發明之零件封裝用薄膜係特別適用於覆晶晶片組裝的半導體晶片、半導體晶片封裝(多晶片封裝)等之封裝步驟(底部填充模塑)。 The component that can be encapsulated by the film for component encapsulation obtained by the production method of the present invention is not particularly limited, and any suitable component that satisfies the desired function can be mentioned. As a component that can be encapsulated by a film for component packaging, for example, a passive component such as a capacitor, an inductor, or a resistor, and an active component such as a semiconductor wafer or a semiconductor chip package. The film for component encapsulation of the present invention can be applied to, for example, a packaging step of a component in a component-embedded circuit board. The film for component encapsulation of the present invention is particularly suitable for a packaging step (underfill molding) of a wafer wafer-assembled semiconductor wafer, a semiconductor wafer package (multi-chip package), or the like.
若使用本發明之製造方法所得之零件封裝用薄膜來實施封裝步驟，則搭載厚度較厚的零件時，即使形成封裝層的封裝面之凹凸的高度差大時，也可有效果地埋入，高精度地形成封裝層(封裝部)。藉由此封裝步驟，可良率佳地有效率製造更高品質的零件內藏電路板、半導體裝置。 When the packaging step is performed using the film for component encapsulation obtained by the production method of the present invention, when a thick component is mounted, even if the height difference of the unevenness of the package surface of the encapsulation layer is large, it can be effectively embedded. The encapsulation layer (encapsulation portion) is formed with high precision. By this packaging step, it is possible to efficiently manufacture higher quality built-in circuit boards and semiconductor devices with good yield.
作為使用本發明之製造方法所得之零件封裝用薄膜的零件內藏電路板、半導體裝置之用途，例如可舉出電氣製品(例如電腦、行動電話、數位相機及電視等)及交通工具(例如機車、汽車、電車、船舶及航空機等)等之動作的控制等用之各種形態的零件內藏電路板、半導體裝置。 Examples of the use of the component-embedded circuit board and the semiconductor device of the film for component packaging obtained by the production method of the present invention include electrical products (for example, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (for example, locomotives). In various types of parts, such as control of the operation of automobiles, electric cars, ships, aircrafts, etc., built-in circuit boards and semiconductor devices.
說明使用由本發明之製造方法所得之零件封裝用薄膜 的封裝步驟之例。 A film for a component package obtained by the production method of the present invention is used An example of a packaging step.
首先，準備搭載有封裝對象的零件之零件內藏電路板、半導體裝置。以零件封裝用薄膜的樹脂組成物層接觸封裝對象的零件之表面的方式載置。其次，例如藉由實施加壓成形步驟或真空層合步驟，而將零件埋入樹脂組成物層中及被覆。 First, a circuit board or a semiconductor device in which a component to be packaged is mounted is prepared. The resin composition layer of the film for component packaging is placed in contact with the surface of the component to be packaged. Next, the part is buried in the resin composition layer and covered, for example, by performing a press forming step or a vacuum lamination step.
該加壓成形步驟或真空層合步驟，係可以不損害所封裝的零件之機能者作為條件，在任意適宜的條件下進行。此時的溫度條件、加壓條件係可考慮樹脂組成物層之最低熔融黏度而決定。如此的加壓成形步驟或真空層合步驟係可使用市售的真空加壓裝置、真空層合裝置實施。由於半導體晶片一般有因應力、加熱處理而劣化之虞，故較佳為藉由使用真空層合裝置的真空層合步驟進行埋入。如此的真空層合條件，例如可在壓力1~11kgf/cm2、溫度70~140℃、時間5~180秒之條件下進行。 The press forming step or the vacuum laminating step can be carried out under any suitable conditions without impairing the function of the packaged parts. The temperature conditions and pressurization conditions at this time are determined in consideration of the lowest melt viscosity of the resin composition layer. Such a press forming step or a vacuum laminating step can be carried out using a commercially available vacuum pressurizing device or a vacuum laminating device. Since a semiconductor wafer generally has a defect due to stress and heat treatment, it is preferably buried by a vacuum lamination step using a vacuum lamination apparatus. Such vacuum lamination conditions can be carried out, for example, at a pressure of 1 to 11 kgf/cm 2 , a temperature of 70 to 140 ° C, and a time of 5 to 180 seconds.
支持體係可在加壓成形步驟或真空層合步驟之後，自樹脂組成物層剝離，也可在熱硬化步驟之後剝離。支持體較佳為在熱硬化步驟之後剝離。再者，例如藉由支持體附加散熱機能、保護機能等時，可不自樹脂組成物層或硬化體來剝離支持體，而且直接利用。 The support system may be peeled off from the resin composition layer after the pressure forming step or the vacuum lamination step, or may be peeled off after the heat hardening step. The support is preferably peeled off after the heat hardening step. Further, for example, when the support is provided with a heat dissipation function, a protective function, or the like, the support can be peeled off from the resin composition layer or the cured body, and can be used as it is.
其次，實施將埋入有零件的樹脂組成物層予以加熱處理而熱硬化之熱硬化步驟。藉由此熱硬化步驟，樹脂組成物層係硬化而成為封裝層。 Next, a thermal curing step of thermally curing the resin composition layer in which the parts are embedded is heat-treated. By this thermal hardening step, the resin composition layer is hardened and becomes an encapsulation layer.
該熱硬化步驟的加熱處理之條件係沒有特別的限定， 可以不損害所封裝的零件之機能者作為條件，考慮樹脂組成物層之最低熔融黏度等而決定。又，該熱硬化步驟較佳為在大氣壓下(常壓下)進行。 The conditions of the heat treatment in the heat hardening step are not particularly limited. The condition of the packaged component can be determined without considering the function of the packaged component, and the lowest melt viscosity of the resin composition layer can be determined. Further, the heat hardening step is preferably carried out under atmospheric pressure (at normal pressure).
藉由以上的封裝步驟，樹脂組成物層成為封裝零件的硬化體，即封裝層。 By the above encapsulation step, the resin composition layer becomes a hardened body of the package part, that is, an encapsulation layer.
依所欲亦可實施將具備封裝層的構造體切斷成2個以上的單片之單片化步驟。此單片化步驟例如可藉由具有旋轉刀的習知切割裝置，研削邊際(margin)區域來切斷而進行。藉由此單片化步驟，形成有封裝層的構造體係各自將零件包含在內，單片化成且具備封裝的封裝部之複數個的機能元件。 The singulation step of cutting the structure having the encapsulating layer into two or more single pieces may be carried out as desired. This singulation step can be performed, for example, by cutting a margin region by a conventional cutting device having a rotary blade. By the singulation step, each of the structural systems in which the encapsulation layer is formed includes a plurality of functional elements that are singulated and have a packaged portion of the package.
以下藉由實施例來具體地說明本發明，惟本發明不受此等的實施例所限定。再者，於以下之記載中，「份」及「%」只要沒有另行明示，則分別意指「質量份」及「質量%」。 The invention is specifically described by the following examples, but the invention is not limited by the examples. In addition, in the following descriptions, "parts" and "%" mean "parts by mass" and "% by mass" unless otherwise stated.
首先，說明後述的實施例及比較例中所使用的零件封裝用薄膜之製造方法中的各種測定方法及評價方法。 First, various measurement methods and evaluation methods in the method for producing a film for component encapsulation used in the examples and comparative examples described later will be described.
後述的實施例及比較例所製造之捲取成捲筒狀的長條 接著薄膜中的樹脂組成物層之最低熔融黏度溫度，係使用動態黏彈性測定裝置((股)UBM公司製「Rheosol-G3000」)進行測定。將作為試料的構成樹脂組成物層之樹脂組成物1g載置於直徑18mm的平行板上，在開始溫度為60℃，自60℃至200℃為止，以5℃/分鐘的升溫速度升溫，測定溫度的間隔為2.5℃，振動數為1Hz，應變為1deg之測定條件下，測定對應於最低熔融黏度之溫度。 Strips rolled into rolls in the examples and comparative examples described later The lowest melt viscosity temperature of the resin composition layer in the film was measured using a dynamic viscoelasticity measuring apparatus ("Rheosol-G3000" manufactured by UBM). 1 g of the resin composition constituting the resin composition layer as a sample was placed on a parallel plate having a diameter of 18 mm, and the temperature was raised at a temperature rise rate of 5 ° C/min from 60 ° C to 200 ° C at a starting temperature of 60 ° C. The temperature corresponding to the lowest melt viscosity was measured under the measurement conditions of a temperature interval of 2.5 ° C, a vibration number of 1 Hz, and a strain of 1 deg.
自後述的實施例及比較例所製作的接著薄膜切出10cm見方，首先測定乾燥處理前之質量。然後，藉由在130℃乾燥處理15分鐘，而使接著薄膜中之溶劑揮發，測定乾燥處理後之質量。然後，由下述之計算式，求得層中所殘留的溶劑之比例的殘留溶劑率(質量%)。 The adhesive film produced in the examples and the comparative examples described later was cut out to 10 cm square, and the mass before the drying treatment was first measured. Then, the solvent in the film was volatilized by drying at 130 ° C for 15 minutes, and the mass after the drying treatment was measured. Then, the residual solvent ratio (% by mass) of the ratio of the solvent remaining in the layer was determined by the following calculation formula.
計算式：殘留溶劑率(質量%)={(乾燥處理前的質量-乾燥處理後的質量)/(乾燥處理前的質量-PET薄膜的質量)}×100 Calculation formula: residual solvent ratio (% by mass) = {(mass before drying treatment - mass after drying treatment) / (mass before drying treatment - mass of PET film)} × 100
接著薄膜之樹脂組成物層中的空隙等缺陷之確認，係切出所得之捲筒狀的接著薄膜中在長度方向的最初及最後之各1m，首先目視確認全體，再自所切出的1m長度之接著薄膜中更切出的5cm見方之小片接著薄膜(自1m長度 的接著薄膜之四角落附近及中央附近的5個地方所出的小片)之5個樣品，用光學顯微鏡(KEYENCY公司製「VH-5500」)確認。 Then, the defects such as the voids in the resin composition layer of the film were confirmed, and the first and the last 1 m in the longitudinal direction of the obtained roll-shaped film were cut out, and the whole was visually confirmed first, and then 1 m was cut out. A 5 cm square piece of film that is more cut out in the film of the length followed by a film (from a length of 1 m) Five samples of the small pieces which were produced in the vicinity of the four corners of the film and in the vicinity of the center were confirmed by an optical microscope ("VH-5500" manufactured by KEYENCY Co., Ltd.).
評價基準： Evaluation criteria:
○：沒有空隙等(Φ100μm以上)之缺陷。 ○: There is no defect such as a void or the like (Φ100 μm or more).
×：空隙等(Φ100μm以上)之缺陷為1個以上。 x: One or more defects of voids or the like (Φ100 μm or more).
將雙酚型環氧樹脂(新日鐵化學(股)製「ZX1059」，雙酚A型的環氧樹脂與雙酚F型的環氧樹脂之1：1(質量比)混合品)10份、結晶性2官能環氧樹脂(三菱化學(股)製「YX4000HK」，環氧當量約185)10份、聯苯型環氧樹脂(日本化藥(股)製「NC3000H」)10份、苯氧樹脂(三菱化學(股)製「YL7553BH30」、固體成分30質量%的MEK溶液)5份，邊在溶劑油40份中攪拌邊使加熱溶解。冷卻至室溫為止後，於其中混入活性酯化合物(DIC(股)製「HPC8000-65T」，活性基當量約223之不揮發分65質量%的甲苯溶液)15份、含三的甲酚系硬化劑(羥基當量151，DIC(股)製「LA-3018-50P」)之固體成分50%的甲氧基丙醇溶液15份、含環氧基的丙烯酸酯共聚物(數量平均分子量Mn：850000g/mol，環氧值0.21eq/kg，Tg12℃，Nagase Chemtex(股)製「SG-P3」)之固體成分15%的MEK溶 液50份、硬化促進劑(4-二甲基胺基吡啶，固體成分2質量%之MEK溶液)5份、難燃劑(三光(股)製「HCA-HQ」，10-(2,5-二羥基苯基)-10-氫-9-氧雜-10-磷雜菲-10-氧化物，平均粒徑2μm)2份、經胺基矽烷系偶合劑(信越化學工業(股)製「KBM573」)所表面處理之球形矽石(平均粒徑2.2μm，(股)ADMATECHS製「SOC6」，每單位面積的碳量0.4mg/m2)200份，用高速旋轉混合機均勻地分散，調製樹脂清漆1。下述表1中顯示組成(不揮發成分換算)。 10 parts of bisphenol type epoxy resin (ZX1059 made by Nippon Steel Chemical Co., Ltd.), 1:1 (mass ratio) of bisphenol A type epoxy resin and bisphenol F type epoxy resin) , a crystalline bifunctional epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent: 185), 10 parts, and a biphenyl type epoxy resin ("NC3000H" manufactured by Nippon Kayaku Co., Ltd.), 10 parts, benzene 5 parts of an oxygen resin ("GL7553BH30" manufactured by Mitsubishi Chemical Co., Ltd., and a MEK solution of 30% by mass of a solid component) was dissolved while stirring in 40 parts of a solvent oil. After cooling to room temperature, an active ester compound ("HPC8000-65T" manufactured by DIC Co., Ltd., a toluene solution having a nonvolatile content of 65% by mass of about 223) was mixed therein with 15 parts, including three a cresol-based curing agent (hydroxyl equivalent 151, DIC ("LA-3018-50P"), a solid component 50% methoxypropanol solution, 15 parts, epoxy group-containing acrylate copolymer (quantity The average molecular weight Mn: 850,000 g/mol, epoxy value 0.21 eq/kg, Tg 12 ° C, Nagase Chemtex ("SG-P3"), solid component 15% MEK solution 50 parts, hardening accelerator (4-dimethyl Amino-aminopyridine, MEK solution of 2% by mass of solid component) 5 parts, flame retardant (HCA-HQ, manufactured by Sanguang Co., Ltd., 10-(2,5-dihydroxyphenyl)-10-hydrogen-9 -Oxo-10-phosphaphenanthrene-10-oxide, 2 μm of an average particle diameter of 2 μm, spherical vermiculite surface-treated with an amine decane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) The average particle diameter was 2.2 μm, and the "SOC6" manufactured by ADMATECHS, having a carbon content of 0.4 mg/m 2 per unit area, was 200 parts, and uniformly dispersed by a high-speed rotary mixer to prepare a resin varnish 1. The composition is shown in Table 1 below (in terms of nonvolatile content).
準備附醇酸樹脂系脫模層的PET薄膜(厚度38μm，LINTEC(股)製「AL5」)作為支持體。藉由用口模塗佈機，將上述實施例1所得之樹脂清漆1均勻地塗佈在醇酸樹脂系脫模層側之該支持體的表面上，於80℃~120℃(平均100℃)乾燥處理5分鐘，而形成乾燥處理後的厚度為150μm之暫時樹脂組成物層，於所形成的暫時樹脂組成物層之表面上，一邊在60℃連續地貼合厚度15μm的聚丙烯薄膜(王子特殊紙(股)製「Alfan MA-411」之平滑面側)作為保護薄膜，一邊捲取成捲筒狀，而得到捲筒狀之附保護薄膜的暫時接著薄膜。 A PET film (thickness: 38 μm, "AL5" manufactured by LINTEC Co., Ltd.) having an alkyd-based release layer was prepared as a support. The resin varnish 1 obtained in the above Example 1 was uniformly applied onto the surface of the support on the side of the alkyd resin release layer by a die coater at 80 ° C to 120 ° C (average 100 ° C). After drying for 5 minutes, a temporary resin composition layer having a thickness of 150 μm after drying treatment was formed, and a polypropylene film having a thickness of 15 μm was continuously bonded to the surface of the formed temporary resin composition layer at 60 ° C ( The smooth surface side of the "Alfan MA-411" manufactured by Prince's Special Paper Co., Ltd.) is wound into a roll shape as a protective film to obtain a temporary adhesive film having a roll-shaped protective film.
其次，藉由一邊將捲筒狀之附保護薄膜的暫時接著薄膜予以捲出，一邊剝離聚丙烯薄膜及捲取，同時在所露出的樹脂組成物層之表面上，再度用口模塗佈機均勻地塗佈 實施例1所得之樹脂清漆1，於80℃~130℃(平均105℃)乾燥處理5分鐘，而形成乾燥處理後的總厚為300μm之樹脂組成物層，同樣地於樹脂組成物層之表面上，一邊在60℃連續地貼合厚度15μm的聚丙烯薄膜(王子特殊紙(股)製「Alfan MA-411」之平滑面側)作為保護薄膜，一邊捲取成捲筒狀，而得到捲筒狀之附保護薄膜的接著薄膜。 Next, by peeling off the temporary film of the roll-shaped protective film, the polypropylene film is peeled off and wound up, and on the surface of the exposed resin composition layer, the die coater is again used. Uniform coating The resin varnish 1 obtained in Example 1 was dried at 80 ° C to 130 ° C (average 105 ° C) for 5 minutes to form a resin composition layer having a total thickness of 300 μm after drying, similarly on the surface of the resin composition layer. On the other hand, a polypropylene film (a smooth surface side of "Alfan MA-411" manufactured by Oji Paper Co., Ltd.) having a thickness of 15 μm was continuously bonded at 60 ° C as a protective film, and wound up in a roll shape to obtain a roll. A tubular film attached to the protective film.
藉由已經說明的上述測定方法及評價方法，測定殘留溶劑率及最低熔融黏度，評價空隙有無發生。表2中顯示結果。 The residual solvent ratio and the lowest melt viscosity were measured by the above-described measurement method and evaluation method, and the presence or absence of voids was evaluated. The results are shown in Table 2.
殘留溶劑率為2.8質量%，最低熔融黏度為920泊，其溫度為155℃。沒有看到空隙等缺陷之發生。 The residual solvent ratio was 2.8% by mass, the lowest melt viscosity was 920 poise, and the temperature was 155 °C. No defects such as voids were observed.
將雙酚型環氧樹脂(新日鐵化學(股)製「ZX1059」，雙酚A型與雙酚F型的1：1(質量比)混合品)5份、2官能脂肪族環氧樹脂(三菱化學(股)製「YL7410」)5份、結晶性2官能環氧樹脂(三菱化學(股)製「YX4000HK」、環氧當量約185)10份、聯苯型環氧樹脂(日本化藥(股)製「NC3000H」)10份、雙酚A型環氧樹脂(三菱化學(股)製「jER1007」，環氧當量約2000)3份、橡膠粒子(GANZ化成(股)製Stafilrod AC3816N)2份，邊在溶劑油48份中攪拌邊使 加熱溶解。冷卻至室溫為止後，於其中混入含三的苯酚系硬化劑(羥基當量125，DIC(股)製「LA-7054」)之固體成分60%的MEK溶液12份、萘酚系硬化劑(羥基當量215，新日鐵化學(股)製「SN-485」)之固體成分60%的MEK溶液12份、硬化促進劑(4-二甲基胺基吡啶，固體成分2質量%的MEK溶液)3份、難燃劑(三光(股)製「HCA-HQ」，10-(2,5-二羥基苯基)-10-氫-9-氧雜-10-磷雜菲-10-氧化物，平均粒徑2μm)2份、經胺基矽烷系偶合劑(信越化學工業(股)製，「KBM573」)所表面處理之球形矽石(平均粒徑1.2μm，(股)ADMATECHS製「SOC4」，每單位面積的碳量0.5mg/m2)250份，用高速旋轉混合機均勻地分散，調製樹脂清漆2。下述表1中顯示其組成。 Bisphenol type epoxy resin (ZX1059 made by Nippon Steel Chemical Co., Ltd., 1:1 (mass ratio) mixture of bisphenol A type and bisphenol F type), 2 parts of aliphatic epoxy resin (Mitsubishi Chemical Co., Ltd. "YL7410") 5 parts, crystalline bifunctional epoxy resin ("XX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 185) 10 parts, biphenyl type epoxy resin (Japan) 10 parts of "Non-Pharmaceutical""NC3000H"), bisphenol A type epoxy resin ("JER1007" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent: 2000), 3 parts, rubber particles (Stafilrod AC3816N manufactured by GANZ Chemical Co., Ltd.) 2 parts were dissolved by heating while stirring in 48 parts of solvent oil. After cooling to room temperature, mix it with three 12 parts of MEK solution of 60% solid content of phenol-based curing agent (hydroxy equivalent: 125, DIC ("LA-7054"), naphthol-based curing agent (hydroxy equivalent 215, manufactured by Nippon Steel Chemical Co., Ltd.) "SN-485") 12 parts solid solution 60% MEK solution, hardening accelerator (4-dimethylaminopyridine, solid content 2% by mass MEK solution) 3 parts, flame retardant (three light (share) "HCA-HQ", 10-(2,5-dihydroxyphenyl)-10-hydrogen-9-oxa-10-phosphaphenanthrene-10-oxide, average particle size 2 μm) 2 parts, amine A sulfonium-based coupling agent ("KBM573") manufactured by Shin-Etsu Chemical Co., Ltd. ("KBM573") has an average particle diameter of 1.2 μm and a "SOC4" manufactured by ADMATECHS. The amount of carbon per unit area is 0.5 mg/ m 2 ) 250 parts, uniformly dispersed by a high-speed rotary mixer to prepare a resin varnish 2. The composition is shown in Table 1 below.
準備附醇酸樹脂系脫模層的PET薄膜(厚度38μm，LINTEC(股)製「AL5」)作為支持體。藉由用口模塗佈機，將上述實施例2所得之樹脂清漆2均勻地塗佈在醇酸樹脂系脫模層側之支持體的表面上，於80℃~120℃(平均100℃)乾燥處理8分鐘，而形成乾燥處理後的厚度為200μm之暫時樹脂組成物層，於暫時樹脂組成物層之表面上，一邊在60℃連續地貼合厚度15μm的聚丙烯薄膜(王子特殊紙(股)製「Alfan MA-411」之平滑面側)作為保護薄膜，一邊捲取成捲筒狀，而得到捲筒狀之附保護薄膜 的暫時接著薄膜。 A PET film (thickness: 38 μm, "AL5" manufactured by LINTEC Co., Ltd.) having an alkyd-based release layer was prepared as a support. The resin varnish 2 obtained in the above Example 2 was uniformly applied onto the surface of the support of the alkyd resin-based release layer by a die coater at 80 ° C to 120 ° C (average 100 ° C). After drying for 8 minutes, a temporary resin composition layer having a thickness of 200 μm after drying treatment was formed, and a polypropylene film having a thickness of 15 μm was continuously attached to the surface of the temporary resin composition layer at 60 ° C (Prince Special Paper ( The smooth side of the "Alfan MA-411" system is rolled up into a roll shape as a protective film to obtain a roll-shaped protective film. Temporarily follow the film.
其次，藉由一邊將捲筒狀之附保護薄膜的暫時接著薄膜予以捲出，一邊剝離聚丙烯薄膜及捲取，同時在所露出的樹脂組成物層之表面上，再度用口模塗佈機均勻地塗佈實施例2所得之樹脂清漆2，於80℃~120℃(平均100℃)乾燥處理10分鐘，而形成乾燥處理後的總厚為400μm之樹脂組成物層，同樣地於樹脂組成物層之表面上，一邊在60℃連續地貼合厚度15μm的聚丙烯薄膜(王子特殊紙(股)製「Alfan MA-411」之平滑面側)作為保護薄膜，一邊捲取成捲筒狀，而得到捲筒狀之附保護薄膜的接著薄膜。 Next, by peeling off the temporary film of the roll-shaped protective film, the polypropylene film is peeled off and wound up, and on the surface of the exposed resin composition layer, the die coater is again used. The resin varnish 2 obtained in Example 2 was uniformly applied, and dried at 80 ° C to 120 ° C (average 100 ° C) for 10 minutes to form a resin composition layer having a total thickness of 400 μm after the drying treatment, similarly to the resin composition. On the surface of the layer, a polypropylene film (a smooth surface side of "Alfan MA-411" manufactured by Oji Paper Co., Ltd.) having a thickness of 15 μm was continuously bonded to the surface of the layer as a protective film, and rolled up into a roll shape. The film of the roll-up of the protective film was obtained.
藉由已經說明的上述之測定方法及評價方法，測定殘留溶劑率及最低熔融黏度，評價空隙有無發生。表2中顯示結果。 The residual solvent ratio and the lowest melt viscosity were measured by the above-described measurement method and evaluation method, and the presence or absence of voids was evaluated. The results are shown in Table 2.
殘留溶劑率為3.7質量%，最低熔融黏度為3200泊，且其溫度為110℃。沒有看到空隙等缺陷之發生。 The residual solvent ratio was 3.7% by mass, the lowest melt viscosity was 3,200 poise, and the temperature was 110 °C. No defects such as voids were observed.
準備附醇酸樹脂系脫模層的PET薄膜(厚度38μm，LINTEC(股)製「AL5」)作為支持體。藉由用口模塗佈機，將上述實施例1所得之樹脂清漆1均勻地塗佈在醇酸樹脂系脫模層側之支持體的表面上，於80℃~130℃(平均105℃)乾燥處理10分鐘，而形成乾燥處理後的厚度 為300μm之樹脂組成物層，於樹脂組成物層之表面上，一邊在60℃連續地貼合厚度15μm的聚丙烯薄膜(王子特殊紙(股)製「Alfan MA-411」之平滑面側)作為保護薄膜，一邊捲取成捲筒狀，而得到捲筒狀之附保護薄膜的接著薄膜。 A PET film (thickness: 38 μm, "AL5" manufactured by LINTEC Co., Ltd.) having an alkyd-based release layer was prepared as a support. The resin varnish 1 obtained in the above Example 1 was uniformly applied onto the surface of the support of the alkyd resin-based release layer by a die coater at 80 ° C to 130 ° C (average 105 ° C). Drying for 10 minutes to form a thickness after drying In the resin composition layer of 300 μm, a polypropylene film having a thickness of 15 μm was continuously bonded to the surface of the resin composition layer at 60° C. (the smooth side of "Alfan MA-411" manufactured by Oji Paper Co., Ltd.) As a protective film, it is wound up in a roll shape, and the roll-form adhesive film of the protective film is obtained.
藉由已經說明的上述之測定方法及評價方法，測定殘留溶劑率及最低熔融黏度。表2中顯示結果。 The residual solvent ratio and the lowest melt viscosity were measured by the above-described measurement method and evaluation method. The results are shown in Table 2.
殘留溶劑率為5.8質量%，最低熔融黏度為100泊以下，由於熔融黏度的測定中發生樣品的樹脂垂滴，無法測定正確的最低熔融黏度。 The residual solvent ratio was 5.8% by mass, and the lowest melt viscosity was 100 poise or less. Since the resin dripping of the sample occurred during the measurement of the melt viscosity, the correct minimum melt viscosity could not be measured.
如此地熔融黏度過低的接著薄膜，預料在實際使用的熱硬化步驟中，亦發生樹脂垂滴，而不耐實用。 In such a film in which the viscosity is too low, it is expected that a resin drip occurs in the heat hardening step actually used, and is not practical.
準備附醇酸樹脂系脫模層的PET薄膜(厚度38μm，LINTEC(股)製「AL5」)作為支持體。藉由用口模塗佈機，將上述實施例2所得之樹脂清漆2均勻地塗佈在支持體的醇酸樹脂系脫模層側之表面上，於80℃~130℃(平均105℃)乾燥處理10分鐘，而形成乾燥處理後的厚度為400μm之樹脂組成物層，於樹脂組成物層之表面上，一邊在60℃連續地貼合厚度15μm的聚丙烯薄膜(王子特殊紙(股)製「Alfan MA-411」之平滑面側)，一邊捲取成捲筒狀，而得到捲筒狀之附保護薄膜的接著薄膜。 A PET film (thickness: 38 μm, "AL5" manufactured by LINTEC Co., Ltd.) having an alkyd-based release layer was prepared as a support. The resin varnish 2 obtained in the above Example 2 was uniformly applied onto the surface of the alkyd-based release layer side of the support by a die coater at 80 ° C to 130 ° C (average 105 ° C). After drying for 10 minutes, a resin composition layer having a thickness of 400 μm after drying treatment was formed, and a polypropylene film having a thickness of 15 μm was continuously bonded to the surface of the resin composition layer at 60° C. (Prince Special Paper) The smooth side of "Alfan MA-411" was rolled up into a roll shape to obtain a roll-up adhesive film with a protective film.
比較例2之附保護薄膜的接著薄膜，係於上述的乾燥處理中無法充分乾燥，保護薄膜係與樹脂組成物層強地黏著，由於在保護薄膜的剝離時樹脂組成物層斷裂等，不耐實質地處理，故無法進行熔融黏度之測定、空隙有無發生之評價。 The adhesive film of the protective film of Comparative Example 2 was not sufficiently dried in the above drying treatment, and the protective film was strongly adhered to the resin composition layer, and the resin composition layer was broken during peeling of the protective film, and the like. Substantially, it is impossible to measure the melt viscosity and the presence or absence of voids.
準備附醇酸樹脂系脫模層的PET薄膜(厚度38μm，LINTEC(股)製「AL5」)作為支持體。藉由用口模塗佈機，將上述實施例1所得之樹脂清漆1均勻地塗佈在醇酸樹脂系脫模層側之支持體的表面上，於80℃~120℃(平均100℃)乾燥處理5分鐘，而形成乾燥處理後的厚度為150μm之暫時樹脂組成物層，於暫時樹脂組成物層之表面上，一邊在60℃連續地貼合厚度15μm的聚丙烯薄膜(王子特殊紙(股)製「Alfan MA-411」之平滑面側)作為保護薄膜，一邊捲取成捲筒狀，而得到捲筒狀之附保護薄膜的暫時接著薄膜。 A PET film (thickness: 38 μm, "AL5" manufactured by LINTEC Co., Ltd.) having an alkyd-based release layer was prepared as a support. The resin varnish 1 obtained in the above Example 1 was uniformly applied onto the surface of the support of the alkyd resin-based release layer by a die coater at 80 ° C to 120 ° C (average 100 ° C). After drying for 5 minutes, a temporary resin composition layer having a thickness of 150 μm after drying treatment was formed, and a polypropylene film having a thickness of 15 μm was continuously attached to the surface of the temporary resin composition layer at 60 ° C (Prince Special Paper ( As a protective film, the "smooth side of the "Alfan MA-411") was wound into a roll shape to obtain a temporary adhesive film having a roll-shaped protective film.
其次，邊剝離聚丙烯薄膜邊捲取，同時一邊用熱輥在60℃連續地貼合2片的接著薄膜各自露出的2層之暫時樹脂組成物層的表面彼此，一邊捲取成捲筒狀，而得到樹脂組成物層之厚度總計為150×2=300μm之捲筒狀的貼合型接著薄膜。 Then, while the polypropylene film was peeled off, the surface of the temporary resin composition layers of the two layers of the two exposed films which were respectively adhered to each other by a hot roll at 60 ° C was continuously wound, and rolled up into a roll shape. Further, a roll-shaped bonded back film having a total thickness of the resin composition layer of 150 × 2 = 300 μm was obtained.
藉由已經說明的上述測定方法及評價方法，測定殘留 溶劑率及最低熔融黏度，評價空隙有無發生。表2中顯示結果。 Determination of the residue by the above-described measurement method and evaluation method Solvent rate and minimum melt viscosity were evaluated for the presence or absence of voids. The results are shown in Table 2.
殘留溶劑率為2.2質量%，最低熔融黏度為1600泊，其溫度為150℃。 The residual solvent ratio was 2.2% by mass, the lowest melt viscosity was 1600 poise, and the temperature was 150 °C.
比較例3之接著薄膜係Φ100μm至500μm的空隙為樹脂組成物層之長度1m之範圍，於最初的1m之範圍中觀察到11個，於最後的1m之範圍中觀察到5個，品質上有問題。 In the film of Comparative Example 3, the voids of Φ 100 μm to 500 μm were in the range of 1 m in length of the resin composition layer, 11 were observed in the first 1 m range, and 5 in the last 1 m range, and the quality was observed. problem.
推測因上述品質上的問題點係在貼合步驟的樹脂組成物層彼此之間發生，更且由於使用具有接著薄膜為相同厚度的2片之附脫模層的PET薄膜，成為此等貼附於樹脂組成物層的兩表面上之捲筒狀的構造時，由於無可避免地對樹脂組成物層施加應力，而容易發生缺陷。 It is presumed that the above-mentioned quality problems are caused by the resin composition layers in the bonding step, and the PET film having the release layer having two sheets of the same thickness as the film is used as the attachment. In the roll-like configuration on both surfaces of the resin composition layer, since stress is inevitably applied to the resin composition layer, defects are likely to occur.
於暫時樹脂組成物層上更塗布樹脂清漆的實施例1及2中，可得到最低熔融黏度、殘留溶劑率成為合適範圍，且空隙、偏移等的不良狀況之發生經抑制的優異樹脂組成物層。 In the first and second embodiments in which the resin varnish is further applied to the temporary resin composition layer, the resin composition having the lowest melt viscosity and the residual solvent ratio is in an appropriate range, and the occurrence of defects such as voids and offset is suppressed. Floor.
另一方面，於比較例1中，由無法使最低熔融黏度成為合適範圍，在熔融黏度之測定中發生樹脂垂滴，耐不住實用。又，於比較例2中，雖然使用與實施例2相同的樹脂清漆2，但無法得到充分的特性，耐不住實用。再者，於比較例3中，與習知技術同樣地進行貼合，結果發生多數的空隙，確認在品質上有問題。 On the other hand, in Comparative Example 1, since the lowest melt viscosity could not be made into an appropriate range, resin dripping occurred in the measurement of the melt viscosity, and it was not practical. Further, in Comparative Example 2, the same resin varnish 2 as in Example 2 was used, but sufficient characteristics could not be obtained and it was not practical. Further, in Comparative Example 3, the bonding was carried out in the same manner as in the prior art, and as a result, a large number of voids occurred, and it was confirmed that there was a problem in quality.
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| JP6610612B2 (en) * | 2017-04-28 | 2019-11-27 | 味の素株式会社 | Resin sheet with support |
| JP7210031B2 (en) * | 2017-11-27 | 2023-01-23 | ナミックス株式会社 | Film semiconductor sealing material |
| WO2019106953A1 (en) * | 2017-11-30 | 2019-06-06 | 京セラ株式会社 | Resin sheet, semiconductor device and method for producing semiconductor device |
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