TW201716501A - Epoxy resin composition, film-shaped epoxy resin composition, and electronic device - Google Patents
Epoxy resin composition, film-shaped epoxy resin composition, and electronic device Download PDFInfo
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- TW201716501A TW201716501A TW105124649A TW105124649A TW201716501A TW 201716501 A TW201716501 A TW 201716501A TW 105124649 A TW105124649 A TW 105124649A TW 105124649 A TW105124649 A TW 105124649A TW 201716501 A TW201716501 A TW 201716501A
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
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- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
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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
- H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
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Abstract
Description
本發明是關於一種環氧樹脂組成物、薄膜狀環氧樹脂組成物及電子裝置。本發明是關於一種環氧樹脂組成物及薄膜狀環氧樹脂組成物,其能進行電子零件或電子器件(例如,經配置於印刷線路基板上的電子零件或電子器件)的埋入或密封等;以及,關於使用該等而成的電子裝置。The present invention relates to an epoxy resin composition, a film-like epoxy resin composition, and an electronic device. The present invention relates to an epoxy resin composition and a film-like epoxy resin composition capable of embedding or sealing an electronic component or an electronic device (for example, an electronic component or an electronic component disposed on a printed circuit board). And, regarding the use of such electronic devices.
隨著電子機器的輕薄短小化,半導體裝置的小型化及薄型化亦持續進行。使用與半導體元件幾乎同樣大小之半導體裝置的形態、或在半導體裝置上堆積半導體裝置的構裝形態(Package on Package;堆疊式封裝)正在盛行,可預想今後半導體裝置的小型化及薄型化會更加進行。With the reduction in size and size of electronic devices, the miniaturization and thinning of semiconductor devices have continued. It is expected that the form of a semiconductor device having almost the same size as a semiconductor element or the package form of a semiconductor device stacked on a semiconductor device (Package on Package) is expected to be more compact and thinner in the future. get on.
若半導體元件的精細化持續進展,端子數持續增加,則在半導體元件上要設置全部的外部連接端子(外部連接用的端子)會變得困難。例如,勉強將外部連接端子設置在半導體元件上時,端子間的間距會變得狹窄,同時端子高度會變低,會變得難以確保構裝半導體裝置後的連接可靠度。於是,為了實現半導體裝置的小型化和薄型化,提案了許多新的構裝方法。When the refinement of the semiconductor element continues to progress and the number of terminals continues to increase, it is difficult to provide all of the external connection terminals (terminals for external connection) on the semiconductor element. For example, when the external connection terminal is barely placed on the semiconductor element, the pitch between the terminals becomes narrow, and the height of the terminal becomes low, which makes it difficult to ensure connection reliability after the semiconductor device is mounted. Therefore, in order to achieve miniaturization and thinning of a semiconductor device, many new mounting methods have been proposed.
例如,一種構裝方法及使用該構裝方法來製作的半導體裝置被提出,該構裝方法是將由半導體晶圓進行單片化所製作而成的半導體元件,以具有適當間隔的方式再配置後,使用液狀或固形的樹脂密封材料來將半導體元件密封,並在將半導體元件密封的部分,進一步設置外部連接端子(例如,參照下列專利文獻1~4)。For example, a mounting method and a semiconductor device produced by using the mounting method are proposed. The mounting method is a semiconductor element fabricated by singulating a semiconductor wafer, and then reconfigured at an appropriate interval to be used. A liquid or solid resin sealing material is used to seal the semiconductor element, and an external connection terminal is further provided in a portion where the semiconductor element is sealed (for example, refer to the following Patent Documents 1 to 4).
經再配置的半導體元件的密封,例如利用模塑成形(mold forming)來實行,該模塑成形是將液狀或固形的樹脂密封材料以模具來成形。利用模塑成形來實行密封成形時,有使用轉移模塑成形(transfer molding forming)的情況,該轉移模塑成形是藉由使丸粒狀的樹脂密封材料熔融而獲得的樹脂灌入模具內來進行密封。然而,由於將熔融而獲得的樹脂灌入來成形,故將大面積密封的情況,有產生未填充部的可能性。於是近年開始使用壓縮模塑成形(compression molding forming),其是預先將樹脂密封材料供給到模具或被密封體後進行成形。在壓縮模塑成形,由於是將樹脂密封材料直接供給到模具或被密封體,故有即使是大面積的密封也不易產生未填充部的優點。在壓縮模塑成形,與轉移模塑成形相同,是使用液狀或固形的樹脂密封材料。 [先前技術文獻] (專利文獻)The sealing of the reconfigured semiconductor element is carried out, for example, by mold forming, which is formed by molding a liquid or solid resin sealing material in a mold. When the sealing molding is carried out by molding, there is a case where transfer molding is carried out by pouring a resin obtained by melting a pellet-shaped resin sealing material into a mold. Sealed. However, since the resin obtained by melting is poured and molded, it is possible to seal a large area, and there is a possibility that an unfilled portion is generated. Then, in recent years, compression molding forming has been started, which is performed by supplying a resin sealing material to a mold or a sealed body in advance. In the compression molding, since the resin sealing material is directly supplied to the mold or the sealed body, there is an advantage that the unfilled portion is less likely to be generated even in a large-area seal. In the compression molding, as in the case of the transfer molding, a liquid or solid resin sealing material is used. [Previous Technical Literature] (Patent Literature)
專利文獻1:日本專利第3616615號公報 專利文獻2:日本特開2001-244372號公報 專利文獻3:日本特開2001-127095號公報 專利文獻4:美國專利申請案公開第2007/205513號說明書Patent Document 1: Japanese Patent No. 3616615 Patent Document 2: JP-A-2001-244372 (Patent Document 3: JP-A-2001-127095) Patent Document 4: US Patent Application Publication No. 2007/205513
[發明所欲解決之問題] 不過,近年探討著一種技術,其藉由使用薄膜狀的樹脂密封材料來取代液狀或固形的樹脂密封材料,且藉由不需要模具的成形方法(層合、壓製等)來進行密封。這種情況,從要避免薄膜狀的樹脂密封材料破損而使得實行密封變得困難的觀點而言,對於樹脂密封材料,尋求著優異的處理性(彎曲性等)。[Problems to be Solved by the Invention] However, in recent years, a technique has been explored in which a liquid-like or solid-shaped resin sealing material is replaced by a film-like resin sealing material, and by a method of forming a mold (lamination, Press, etc.) to seal. In this case, from the viewpoint of avoiding breakage of the film-form resin sealing material and making sealing difficult, excellent handleability (bending property, etc.) is sought for the resin sealing material.
將大面積密封時,雖然由於一次能夠密封的面積增加,而操作時間能夠縮短,但會有在密封成形物發生翹曲的情況。密封成形物的翹曲,由於在後續的步驟中會成為誘發缺陷的主因,故尋求著減少密封成形物的翹曲。When the large-area is sealed, the operation time can be shortened due to an increase in the area that can be sealed at one time, but there is a case where the seal molded product is warped. The warpage of the sealed molded article is intended to reduce the warpage of the sealed molded article because it is a main cause of the induced defect in the subsequent step.
本發明是鑑於上述問題而完成,其目的在於提供一種環氧樹脂組成物,其可獲得具有優異的處理性(彎曲性等)的薄膜狀環氧樹脂組成物(薄膜狀的樹脂密封材料),並且能抑制密封後的翹曲。又,本發明的目的在於提供一種薄膜狀環氧樹脂組成物,其具有優異的處理性,並且能抑制密封後的翹曲。並且,本發明的目的在於提供一種電子裝置,其使用了這些環氧樹脂組成物或其硬化物、或者薄膜狀環氧樹脂組成物。 [解決問題之技術手段]The present invention has been made in view of the above problems, and an object of the invention is to provide an epoxy resin composition which can obtain a film-like epoxy resin composition (film-like resin sealing material) having excellent handleability (flexibility, etc.). And it can suppress the warpage after sealing. Further, an object of the present invention is to provide a film-like epoxy resin composition which has excellent handleability and can suppress warpage after sealing. Further, an object of the present invention is to provide an electronic device using these epoxy resin compositions or cured products thereof or film-form epoxy resin compositions. [Technical means to solve the problem]
本發明提供一種環氧樹脂組成物,其含有:(A)環氧樹脂、(B)具有芳香環和羥基之樹脂、(C)聚矽氧粉末(silicone powder)、(D)硬化促進劑、及(E)無機填充劑;其中,前述(A)環氧樹脂,包含在25℃為液狀的環氧樹脂;前述(B)具有芳香環和羥基之樹脂,包含具有萘環和羥基之樹脂;並且,前述在25℃為液狀的環氧樹脂的含量,以前述(A)環氧樹脂與前述(B)具有芳香環和羥基之樹脂的合計量作為基準計,是32質量%以上;前述(C)聚矽氧粉末的含量,以環氧樹脂組成物的總量為基準計,是0.80~7.30質量%,其中,當環氧樹脂組成物含有溶劑時,溶劑不包括在總量中,以下亦同。The present invention provides an epoxy resin composition comprising: (A) an epoxy resin, (B) a resin having an aromatic ring and a hydroxyl group, (C) a silicone powder, (D) a hardening accelerator, And (E) an inorganic filler; wherein the epoxy resin (A) comprises an epoxy resin which is liquid at 25 ° C; and (B) a resin having an aromatic ring and a hydroxyl group, and a resin having a naphthalene ring and a hydroxyl group And the content of the epoxy resin which is liquid at 25 ° C is 32% by mass or more based on the total amount of the epoxy resin (A) and the resin having an aromatic ring and a hydroxyl group (B); The content of the (C) polyfluorene oxide powder is 0.80 to 7.30% by mass based on the total amount of the epoxy resin composition, wherein when the epoxy resin composition contains a solvent, the solvent is not included in the total amount. The same applies to the following.
若藉由本發明之環氧樹脂組成物,將該環氧樹脂組成物成形為薄膜狀的情況中,可獲得具有優異的處理性(彎曲性等)的薄膜狀環氧樹脂組成物。又,若藉由本發明之環氧樹脂組成物,就可抑制密封後的翹曲,尤其,即使在將大面積密封時也能抑制密封後的翹曲。並且,本發明之環氧樹脂組成物,亦能夠獲得優異的耐熱性及阻燃性。When the epoxy resin composition is formed into a film shape by the epoxy resin composition of the present invention, a film-like epoxy resin composition having excellent handleability (flexibility, etc.) can be obtained. Moreover, according to the epoxy resin composition of the present invention, warpage after sealing can be suppressed, and in particular, warpage after sealing can be suppressed even when sealing a large area. Further, the epoxy resin composition of the present invention can also obtain excellent heat resistance and flame retardancy.
前述具有萘環和羥基之樹脂,亦可包含由下述通式(I)表示之化合物。式(I)中,R11 、R12 、R13 、R14 及R15 ,各自獨立地表示氫原子、碳數1~6的烷基或碳數1~2的烷氧基;m1、m2、m3、m4、m5、m6、m7及m8,各自獨立地表示0~2的整數,其中,無m1、m2、m3、m4、m5、m6、m7及m8全部為0的情況;n1表示0~10的整數。The resin having a naphthalene ring and a hydroxyl group may further contain a compound represented by the following formula (I). In the formula (I), R 11 , R 12 , R 13 , R 14 and R 15 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 2 carbon atoms; m1 and m2; And m3, m4, m5, m6, m7, and m8 each independently represent an integer of 0 to 2, wherein no m1, m2, m3, m4, m5, m6, m7, and m8 are all 0; n1 represents 0. An integer of ~10.
前述(C)聚矽氧粉末的含量,以環氧樹脂組成物的總量作為基準計,亦可為2~7質量%。The content of the (C) polyfluorene oxide powder may be 2 to 7% by mass based on the total amount of the epoxy resin composition.
前述(C)聚矽氧粉末,亦可具有一種結構,其是矽氧烷鍵以三維網狀交聯而成。The (C) polyfluorene oxide powder may have a structure in which a siloxane chain is crosslinked in a three-dimensional network.
又,本發明提供一種薄膜狀環氧樹脂組成物,其包含前述環氧樹脂組成物或其硬化物。本發明之薄膜狀環氧樹脂組成物,具有優異的處理性(彎曲性等),並能夠抑制密封後的翹曲,且具有優異的耐熱性及阻燃性。Further, the present invention provides a film-like epoxy resin composition comprising the above epoxy resin composition or a cured product thereof. The film-form epoxy resin composition of the present invention has excellent handleability (bending property, etc.) and can suppress warpage after sealing, and has excellent heat resistance and flame retardancy.
並且,本發明提供一種電子裝置,其具備被密封體與密封部,前述被密封體是選自由電子零件和電子器件所組成之群組中的至少1種,前述密封部將前述被密封體密封;其中,前述密封部,包含前述環氧樹脂組成物或其硬化物、或者包含前述薄膜狀環氧樹脂組成物。 [發明之功效]Furthermore, the present invention provides an electronic device including a sealed body and a sealing portion, wherein the sealed body is at least one selected from the group consisting of an electronic component and an electronic component, and the sealing portion seals the sealed body The sealing portion includes the epoxy resin composition or a cured product thereof or the film-form epoxy resin composition. [Effects of the invention]
若藉由本發明,就能夠提供一種環氧樹脂組成物,其可獲得具有優異的處理性(彎曲性等)的薄膜狀環氧樹脂組成物,並能抑制密封後的翹曲,且具有優異的耐熱性及阻燃性。又,若藉由本發明,就能夠提供一種薄膜狀環氧樹脂組成物,其具有優異的處理性(彎曲性等),並能抑制密封後的翹曲,且具有優異的耐熱性及阻燃性。並且,若藉由本發明,就能夠提供一種電子裝置,其使用了這些環氧樹脂組成物或其硬化物或者薄膜狀環氧樹脂組成物。According to the present invention, it is possible to provide an epoxy resin composition which can obtain a film-like epoxy resin composition having excellent handleability (bending property, etc.) and can suppress warpage after sealing, and has excellent properties. Heat resistance and flame retardancy. Moreover, according to the present invention, it is possible to provide a film-like epoxy resin composition which has excellent handleability (bending property, etc.), suppresses warpage after sealing, and has excellent heat resistance and flame retardancy. . Further, according to the present invention, it is possible to provide an electronic device using the epoxy resin composition or a cured product thereof or a film-like epoxy resin composition.
本發明之薄膜狀環氧樹脂組成物,能夠合適地用於電子零件或電子器件(例如,經配置於印刷線路基板上的電子零件或電子器件)的埋入或密封等。又,本發明之薄膜狀環氧樹脂組成物,不僅能夠合適地用於模塑成形,也能夠合適地用於不需要模具的成形方法(層合、壓製等)。The film-like epoxy resin composition of the present invention can be suitably used for embedding or sealing of an electronic component or an electronic device (for example, an electronic component or an electronic component disposed on a printed circuit board). Further, the film-form epoxy resin composition of the present invention can be suitably used not only for molding but also for a molding method (lamination, pressing, etc.) which does not require a mold.
若藉由本發明,就能夠提供一種薄膜狀環氧樹脂組成物之應用,其是作為密封材料。若藉由本發明,就能夠提供一種薄膜狀環氧樹脂組成物之應用,其是用於電子零件的埋入或密封。若藉由本發明,就能夠提供一種薄膜狀環氧樹脂組成物之應用,其是用於電子器件的埋入或密封。若藉由本發明,就能夠提供一種薄膜狀環氧樹脂組成物之應用,其是用於經配置於印刷線路基板上的電子零件或電子器件的埋入或密封。若藉由本發明,就能夠提供一種薄膜狀環氧樹脂組成物之應用,其是用於模塑成形。若藉由本發明,就能夠提供一種薄膜狀環氧樹脂組成物之應用,其是用於不需要模具的成形方法(層合、壓製等)。According to the present invention, it is possible to provide a film-like epoxy resin composition which is used as a sealing material. According to the present invention, it is possible to provide an application of a film-like epoxy resin composition for embedding or sealing an electronic component. According to the present invention, it is possible to provide an application of a film-like epoxy resin composition for embedding or sealing of an electronic device. According to the present invention, it is possible to provide an application of a film-like epoxy resin composition for embedding or sealing an electronic component or an electronic device disposed on a printed circuit board. According to the present invention, it is possible to provide an application of a film-like epoxy resin composition for molding. According to the present invention, it is possible to provide an application of a film-like epoxy resin composition for a molding method (lamination, pressing, etc.) which does not require a mold.
以下,是針對用以實施本發明之合適的形態來詳細地說明。Hereinafter, the present invention will be described in detail with reference to suitable embodiments for carrying out the invention.
另外,於本說明書中,使用「~」所顯示的數值範圍,是表示將記載於「~」的前後的數值分別作為最小値及最大値所包含的範圍。又,組成物中各成分的量,當組成物中符合各成分的物質是複數種存在時,除非有特別說明,否則就是意味著存在於組成物中該複數種物質的合計量。並且,於本說明書中,所謂以環氧樹脂組成物的總量(合計量)作為基準計,是意味著在環氧樹脂組成物所含有的成分之中,以屏除了有機溶劑等溶劑的成分的總量(固體成分的總量)為基準計。亦即,當環氧樹脂組成物含有溶劑時,屏除了溶劑的成分的總量將成為環氧樹脂組成物的總量(亦即,溶劑不包括在總量中)。In addition, in the present specification, the numerical range displayed by "~" means that the numerical values described before and after "~" are included as the minimum 値 and the maximum 値. Further, the amount of each component in the composition is a total amount of the plurality of substances present in the composition unless otherwise specified. In addition, in the present specification, the total amount (the total amount) of the epoxy resin composition is a component of the solvent contained in the epoxy resin composition, and the solvent is removed by a solvent such as an organic solvent. The total amount (the total amount of solid components) is based on the basis. That is, when the epoxy resin composition contains a solvent, the total amount of the components of the screen except the solvent will become the total amount of the epoxy resin composition (that is, the solvent is not included in the total amount).
<環氧樹脂組成物> 本實施形態之環氧樹脂組成物含有(A)環氧樹脂、(B)具有芳香環和羥基之樹脂、(C)聚矽氧粉末、(D)硬化促進劑、及(E)無機填充劑作為必要成分。於本實施形態之環氧樹脂組成物中,前述(A)環氧樹脂,包含在25℃為液狀的環氧樹脂;前述(B)具有芳香環和羥基之樹脂,包含具有萘環和羥基之樹脂;前述在25℃為液狀的環氧樹脂的含量,以前述(A)環氧樹脂與前述(B)具有芳香環和羥基之樹脂的合計量作為基準計,是32質量%以上;前述(C)聚矽氧粉末的含量,以環氧樹脂組成物的總量作為基準計,是0.80~7.30質量%。但是,當上述環氧樹脂組成物含有溶劑時,環氧樹脂組成物的總量是指屏除了溶劑後的量。<Epoxy Resin Composition> The epoxy resin composition of the present embodiment contains (A) an epoxy resin, (B) a resin having an aromatic ring and a hydroxyl group, (C) a polyfluorene oxide powder, and (D) a curing accelerator. And (E) an inorganic filler as an essential component. In the epoxy resin composition of the present embodiment, the epoxy resin (A) contains an epoxy resin which is liquid at 25 ° C, and the resin (B) which has an aromatic ring and a hydroxyl group, and has a naphthalene ring and a hydroxyl group. The resin; the content of the epoxy resin which is liquid at 25 ° C is 32% by mass or more based on the total amount of the epoxy resin (A) and the resin having an aromatic ring and a hydroxyl group (B); The content of the (C) polyfluorene oxide powder is 0.80 to 7.30% by mass based on the total amount of the epoxy resin composition. However, when the above epoxy resin composition contains a solvent, the total amount of the epoxy resin composition means the amount of the screen after the solvent is removed.
作為本實施形態之環氧樹脂組成物的形狀,可舉出薄膜狀、液狀、固形(顆粒、粉體等)等。本實施形態之環氧樹脂組成物,能夠用於採用模塑成形的密封、採用不需要模具的成形方法(層合、壓製等)的密封等。本實施形態之環氧樹脂組成物,能夠用於電子零件或電子器件的埋入或密封等。作為電子零件,例如可舉出表面聲波濾波器(SAW filter)等的濾波器;感測器等的被動零件。作為電子器件,例如可舉出半導體元件、積體電路、半導體器件等。另外,本實施形態之環氧樹脂組成物,亦能夠用於此等以外的被密封體的埋入或密封。所謂的「埋入」,是意味著將密封材料供給到間隙、高低差等。所謂的「密封」,是意味著以被密封體不會接觸到外部空氣的方式用密封材料被覆著被密封體。The shape of the epoxy resin composition of the present embodiment may be, for example, a film form, a liquid form, or a solid form (particles, powders, etc.). The epoxy resin composition of the present embodiment can be used for sealing by molding, sealing by a molding method (lamination, pressing, etc.) which does not require a mold. The epoxy resin composition of the present embodiment can be used for embedding or sealing an electronic component or an electronic device. Examples of the electronic component include a filter such as a surface acoustic wave filter (SAW filter), and a passive component such as a sensor. Examples of the electronic device include a semiconductor element, an integrated circuit, and a semiconductor device. Further, the epoxy resin composition of the present embodiment can also be used for embedding or sealing the sealed body other than these. The term "buried" means that the sealing material is supplied to the gap, the height difference, and the like. The term "sealing" means that the sealed body is covered with a sealing material so that the sealed body does not come into contact with the outside air.
以下,針對本實施形態之環氧樹脂組成物的各構成成分進行說明。Hereinafter, each constituent component of the epoxy resin composition of the present embodiment will be described.
((A)環氧樹脂) (A)環氧樹脂,為了將柔軟性賦予給薄膜狀環氧樹脂組成物,而包含至少1種在25℃為液狀的環氧樹脂(以下稱為「環氧樹脂(a1)」)。此處,所謂的「在25℃為液狀的環氧樹脂」,是表示使用E型黏度計或B型黏度計來對保持在25℃的該環氧樹脂的黏度進行測定而得的値在400Pa‧s以下的環氧樹脂。(A) Epoxy Resin (A) Epoxy resin contains at least one epoxy resin which is liquid at 25 ° C in order to impart flexibility to the film-form epoxy resin composition (hereinafter referred to as "ring" Oxygen resin (a1)"). Here, the "epoxy resin which is liquid at 25 ° C" means that the viscosity of the epoxy resin held at 25 ° C is measured using an E-type viscometer or a B-type viscometer. Epoxy resin below 400Pa‧s.
作為環氧樹脂(a1),沒有特別限制,例如能夠使用1分子中具有2個以上的縮水甘油基之環氧樹脂。作為環氧樹脂(a1),可舉出雙酚A型環氧樹脂、雙酚F型環氧樹脂、萘型環氧樹脂等。環氧樹脂(a1),從賦予耐熱性的觀點而言,亦可包含易於得到高玻璃轉移溫度(Tg)的萘型環氧樹脂。The epoxy resin (a1) is not particularly limited, and for example, an epoxy resin having two or more glycidyl groups in one molecule can be used. Examples of the epoxy resin (a1) include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a naphthalene type epoxy resin. The epoxy resin (a1) may contain a naphthalene type epoxy resin which is easy to obtain a high glass transition temperature (Tg) from the viewpoint of imparting heat resistance.
作為環氧樹脂(a1),亦可使用市售品。作為環氧樹脂(a1)的市售品,可舉出三菱化學股份有限公司製造的商品名「jER825」(雙酚A型環氧樹脂,環氧當量:175)、三菱化學股份有限公司製造的商品名「jER806」(雙酚F型環氧樹脂,環氧當量:160)、DIC股份有限公司製造的商品名「HP-4032D」(2官能萘型環氧樹脂)等。環氧樹脂(a1),亦可單獨使用1種,亦可併用2種以上。A commercially available product can also be used as the epoxy resin (a1). The commercially available product of the epoxy resin (a1) is a product name "jER825" (bisphenol A type epoxy resin, epoxy equivalent: 175) manufactured by Mitsubishi Chemical Corporation, and manufactured by Mitsubishi Chemical Corporation. The product name is "jER806" (bisphenol F type epoxy resin, epoxy equivalent: 160), and the product name "HP-4032D" (bifunctional naphthalene type epoxy resin) manufactured by DIC Corporation. The epoxy resin (a1) may be used alone or in combination of two or more.
環氧樹脂(a1)的含量,從獲得優異的處理性(彎曲性等)的觀點而言,以(A)環氧樹脂與(B)具有芳香環和羥基之樹脂的合計量作為基準計,是32質量%以上。環氧樹脂(a1)的含量,從獲得更優異的處理性(彎曲性等)的觀點而言,亦可為35質量%以上,亦可為40質量%以上,亦可為45質量%以上,亦可為50質量%以上。環氧樹脂(a1)的含量,從作為設有保護層的密封片來使用的情況下,保護層的剝離性為良好的觀點而言,亦可為70質量%以下,亦可為65質量%以下。環氧樹脂(a1)的含量,從維持優異的處理性(彎曲性等),且作為設有保護層的密封片來使用的情況下,保護層的剝離性為良好的觀點而言,亦可為32~70質量%,亦可為32~65質量%。The content of the epoxy resin (a1) is based on the total amount of the (A) epoxy resin and (B) the resin having an aromatic ring and a hydroxyl group, from the viewpoint of obtaining excellent handleability (bending property, etc.). It is 32% by mass or more. The content of the epoxy resin (a1) may be 35 mass% or more, 40 mass% or more, or 45 mass% or more from the viewpoint of obtaining more excellent handleability (bending property, etc.). It can also be 50% by mass or more. When the content of the epoxy resin (a1) is used as a sealing sheet provided with a protective layer, the peeling property of the protective layer may be 70% by mass or less, or may be 65% by mass. the following. When the content of the epoxy resin (a1) is excellent as handleability (bending property, etc.) and is used as a sealing sheet provided with a protective layer, the peeling property of the protective layer may be good. It is 32 to 70% by mass, and may be 32 to 65% by mass.
環氧樹脂(a1)的含量,從獲得更優異的處理性(彎曲性等)的觀點而言,以(A)環氧樹脂的總量作為基準計,亦可為60質量%以上,亦可為65質量%以上,亦可為70質量%以上。環氧樹脂(a1)的含量,從獲得更優異的處理性(彎曲性等)的觀點而言,以(A)環氧樹脂的總量作為基準計,亦可為100質量%以下,亦可為95質量%以下,亦可為90質量%以下。The content of the epoxy resin (a1) may be 60% by mass or more based on the total amount of the (A) epoxy resin, from the viewpoint of obtaining more excellent handleability (bending property, etc.). It is 65 mass% or more, and may be 70 mass% or more. The content of the epoxy resin (a1) may be 100% by mass or less based on the total amount of the (A) epoxy resin, from the viewpoint of obtaining more excellent handleability (bending property, etc.). It is 95% by mass or less, and may be 90% by mass or less.
(A)環氧樹脂,亦可進而包含在25℃為液狀的環氧樹脂(a1)以外的環氧樹脂(以下稱為「環氧樹脂(a2)」,例如,在25℃並非液狀的環氧樹脂)。作為環氧樹脂(a2),可舉出萘型環氧樹脂(4官能萘型環氧樹脂、3官能萘型環氧樹脂等)、蒽型環氧樹脂、三苯甲烷型環氧樹脂、雙環戊二烯型環氧樹脂、聯苯芳烷基型環氧樹脂、苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂(鄰甲酚酚醛清漆型環氧樹脂等)、二羥苯酚醛清漆型環氧樹脂、縮水甘油酯型環氧樹脂、縮水甘油胺型環氧樹脂、乙內醯脲型環氧樹脂、異氰尿酸酯型環氧樹脂等。作為環氧樹脂(a2),從獲得更優異的耐熱性及阻燃性的觀點而言,亦可為萘型環氧樹脂。環氧樹脂(a2),亦可單獨使用1種,亦可併用2種以上。(A) The epoxy resin may further contain an epoxy resin other than the epoxy resin (a1) which is liquid at 25 ° C (hereinafter referred to as "epoxy resin (a2)", for example, it is not liquid at 25 ° C Epoxy resin). Examples of the epoxy resin (a2) include a naphthalene type epoxy resin (a tetrafunctional naphthalene type epoxy resin, a trifunctional naphthalene type epoxy resin, etc.), a fluorene type epoxy resin, a triphenylmethane type epoxy resin, and a double ring. Pentadiene type epoxy resin, biphenyl aralkyl type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin (o-cresol novolac type epoxy resin, etc.), dihydroxyphenol An aldehyde varnish type epoxy resin, a glycidyl ester type epoxy resin, a glycidylamine type epoxy resin, a behenyl urea type epoxy resin, an isocyanurate type epoxy resin, or the like. The epoxy resin (a2) may be a naphthalene type epoxy resin from the viewpoint of obtaining more excellent heat resistance and flame retardancy. The epoxy resin (a2) may be used alone or in combination of two or more.
作為環氧樹脂(a2),亦可使用市售品。作為環氧樹脂(a2)的市售品,可舉出DIC股份有限公司製造的商品名「HP-4700」(4官能萘型環氧樹脂)、商品名「HP-4750」(3官能萘型環氧樹脂)、商品名「HP-4710」(4官能萘型環氧樹脂)、商品名「EPICLON N-770」(苯酚酚醛清漆型環氧樹脂)、商品名「EPICLON N-660」(甲酚酚醛清漆型環氧樹脂)及商品名「EPICLON HP-7200H」(雙環戊二烯型環氧樹脂);日本化藥股份有限公司製造的商品名「EPPN-502H」(三苯甲烷型環氧樹脂)及商品名「NC-3000」(聯苯芳烷基型環氧樹脂);新日鐵住金化學股份有限公司製造的商品名「ESN-355」(萘型環氧樹脂);三菱化學股份有限公司製造的商品名「YX-8800」(蒽型環氧樹脂);住友化學股份有限公司製造的商品名「ESCN-190-2」(鄰甲酚酚醛清漆型環氧樹脂)等。A commercially available product can also be used as the epoxy resin (a2). As a commercial item of the epoxy resin (a2), the brand name "HP-4700" (4-functional naphthalene type epoxy resin) manufactured by DIC Corporation, and the product name "HP-4750" (3 functional naphthalene type) are mentioned. Epoxy resin), trade name "HP-4710" (4-functional naphthalene epoxy resin), trade name "EPICLON N-770" (phenol novolak epoxy resin), trade name "EPICLON N-660" (A Phenolic novolak type epoxy resin) and trade name "EPICLON HP-7200H" (dicyclopentadiene type epoxy resin); trade name "EPPN-502H" manufactured by Nippon Kayaku Co., Ltd. (triphenylmethane type epoxy) Resin) and trade name "NC-3000" (biphenyl aralkyl type epoxy resin); trade name "ESN-355" (naphthalene type epoxy resin) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.; Mitsubishi Chemical Corporation The product name "YX-8800" (蒽-type epoxy resin) manufactured by the company, and the trade name "ESCN-190-2" (o-cresol novolac type epoxy resin) manufactured by Sumitomo Chemical Co., Ltd.
(A)環氧樹脂,從耐熱性、阻燃性、及B-階段(半硬化)的薄膜狀環氧樹脂組成物的處理性(彎曲性等)會更加提升的觀點而言,在環氧樹脂(a2)之中,亦可包含由下述通式(III)表示之環氧樹脂。於式(III)中,從獲得更優異的耐熱性的觀點而言,n31+n32+n33+n34亦可為 2以上,亦可為3以上。n31+n32+n33+n34,從獲得更優異的處理性(彎曲性等)的觀點而言,亦可為4以下,亦可為3以下。(A) Epoxy resin, in terms of heat resistance, flame retardancy, and handleability (bending property, etc.) of a B-stage (semi-hardened) film-like epoxy resin composition, it is improved in epoxy Among the resins (a2), an epoxy resin represented by the following formula (III) may be contained. In the formula (III), n31+n32+n33+n34 may be 2 or more, or may be 3 or more, from the viewpoint of obtaining more excellent heat resistance. From the viewpoint of obtaining more excellent handleability (bending property, etc.), n31+n32+n33+n34 may be 4 or less, or may be 3 or less.
式(III)中,n31~n34各自獨立地表示0或1;n31+n32+n33+n34表示2以上(n31+n32+n33+n34≧2)。 In the formula (III), n31 to n34 each independently represent 0 or 1; n31+n32+n33+n34 represents 2 or more (n31+n32+n33+n34≧2).
作為以式(III)表示之環氧樹脂,可舉出由下述式(IV)表示之環氧樹脂、由下述式(V)表示之環氧樹脂等。作為由式(III)表示之環氧樹脂,亦可使用市售品。作為以式(IV)表示之環氧樹脂的市售品,例如可舉出DIC股份有限公司製造的商品名「HP-4750」(環氧當量:182)。作為以式(V)表示之環氧樹脂的市售品,例如可舉出DIC股份有限公司製造的商品名「HP-4700」(環氧當量:166)。Examples of the epoxy resin represented by the formula (III) include an epoxy resin represented by the following formula (IV) and an epoxy resin represented by the following formula (V). As the epoxy resin represented by the formula (III), a commercially available product can also be used. The commercially available product of the epoxy resin represented by the formula (IV) is, for example, a product name "HP-4750" (epoxy equivalent: 182) manufactured by DIC Corporation. The commercially available product of the epoxy resin represented by the formula (V) is, for example, a product name "HP-4700" (epoxy equivalent: 166) manufactured by DIC Corporation.
環氧樹脂(a2)的含量,從獲得更優異的耐熱性的觀點而言,以(A)環氧樹脂的總量作為基準計,亦可為10質量%以上,亦可為15質量%以上,亦可為20質量%以上。環氧樹脂(a2)的含量,從獲得更優異的處理性(彎曲性等)的觀點而言,以(A)環氧樹脂的總量作為基準計,亦可為45質量%以下,亦可為42質量%以下,亦可為40質量%以下。The content of the epoxy resin (a2) may be 10% by mass or more, or may be 15% by mass or more based on the total amount of the (A) epoxy resin, from the viewpoint of obtaining more excellent heat resistance. It can also be 20% by mass or more. The content of the epoxy resin (a2) may be 45% by mass or less based on the total amount of the (A) epoxy resin, from the viewpoint of obtaining more excellent handleability (bending property, etc.). It is 42% by mass or less, and may be 40% by mass or less.
((B)具有芳香環和羥基之樹脂) (B)具有芳香環和羥基之樹脂,包含至少1種具有萘環(萘骨架)及羥基的樹脂(以下稱為「樹脂(b1)」)。藉由使用樹脂(b1),由於可以縮小因(A)環氧樹脂與(B)具有芳香環和羥基之樹脂的反應而產生的收縮(反應收縮),故推測能夠抑制密封後的翹曲。又,由於在燃燒時萘骨架會形成碳化層,故能夠賦予阻燃性。作為(B)具有芳香環和羥基之樹脂中的羥基,例如可舉出酚性羥基(直接鍵結在芳香環上的羥基)等。作為酚性羥基,例如可舉出直接鍵結在萘環上的羥基、直接鍵結在苯環上的羥基等。(B) Resin having an aromatic ring and a hydroxyl group (B) A resin having an aromatic ring and a hydroxyl group, and at least one resin having a naphthalene ring (naphthalene skeleton) and a hydroxyl group (hereinafter referred to as "resin (b1)"). By using the resin (b1), shrinkage (reaction shrinkage) due to the reaction of the (A) epoxy resin and (B) the resin having an aromatic ring and a hydroxyl group can be reduced, and therefore it is presumed that warpage after sealing can be suppressed. Further, since the naphthalene skeleton forms a carbonized layer during combustion, flame retardancy can be imparted. The (B) hydroxyl group in the resin having an aromatic ring and a hydroxyl group may, for example, be a phenolic hydroxyl group (a hydroxyl group directly bonded to an aromatic ring). Examples of the phenolic hydroxyl group include a hydroxyl group directly bonded to a naphthalene ring, and a hydroxyl group directly bonded to a benzene ring.
樹脂(b1),從更加抑制密封後的翹曲的觀點而言,亦可包含由下述通式(I)表示之化合物。The resin (b1) may further contain a compound represented by the following formula (I) from the viewpoint of further suppressing warpage after sealing.
式(I)中,R11 、R12 、R13 、R14 及R15 ,各自獨立地表示氫原子、碳數1~6的烷基或碳數1~2的烷氧基;m1、m2、m3、m4、m5、m6、m7及m8,各自獨立地表示0~2的整數,其中,無m1、m2、m3、m4、m5、m6、m7及m8全部為0的情況;n1表示0~10的整數。 In the formula (I), R 11 , R 12 , R 13 , R 14 and R 15 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 2 carbon atoms; m1 and m2; And m3, m4, m5, m6, m7, and m8 each independently represent an integer of 0 to 2, wherein no m1, m2, m3, m4, m5, m6, m7, and m8 are all 0; n1 represents 0. An integer of ~10.
從獲得優異的阻燃性的觀點而言,亦可以R11 、R12 、R13 、R14 及R15 中至少一個是氫原子,亦可以R11 、R12 、R13 、R14 及R15 全部是氫原子。從更加抑制密封後的翹曲的觀點而言,亦可以m1、m2、m3、m4、m5、m6、m7及m8中至少一個是1,亦可以m1、m2、m3、m4、m5、m6、m7及m8全部是1。從耐熱性更加優異的觀點而言,亦可以m1、m2、m3、m4、m5、m6、m7及m8中至少一個是2,亦可以m1、m2、m3、m4、m5、m6、m7及m8全部是2。從成形性、流動性及阻燃性更加優異的觀點而言,n1亦可以是0~10的整數,亦可以是0~6的整數。From the viewpoint of obtaining excellent flame retardancy, at least one of R 11 , R 12 , R 13 , R 14 and R 15 may be a hydrogen atom, or R 11 , R 12 , R 13 , R 14 and R may be used. All 15 are hydrogen atoms. From the viewpoint of further suppressing warpage after sealing, at least one of m1, m2, m3, m4, m5, m6, m7, and m8 may be 1, or m1, m2, m3, m4, m5, m6, M7 and m8 are all 1. From the viewpoint of further excellent heat resistance, at least one of m1, m2, m3, m4, m5, m6, m7, and m8 may be 2, and may be m1, m2, m3, m4, m5, m6, m7, and m8. All are 2. From the viewpoint of further improvement in moldability, fluidity, and flame retardancy, n1 may be an integer of 0 to 10 or an integer of 0 to 6.
以式(I)表示之化合物,從更加抑制密封後的翹曲的觀點、及獲得更優異的耐熱性的觀點而言,亦可具有羥基鍵結在1位及6位的萘環。藉由羥基鍵結在萘環的1位及6位上,而能夠更有效地與(A)環氧樹脂進行反應。以式(I)表示之化合物,從更加抑制密封後的翹曲的觀點、及獲得更優異的耐熱性的觀點而言,亦可包含由下述通式(II)表示之化合物。The compound represented by the formula (I) may have a naphthalene ring having a hydroxyl group bonded to the 1-position and the 6-position from the viewpoint of further suppressing warpage after sealing and obtaining more excellent heat resistance. By reacting a hydroxyl group at the 1st and 6th positions of the naphthalene ring, it is possible to more efficiently react with the (A) epoxy resin. The compound represented by the formula (I) may further contain a compound represented by the following formula (II) from the viewpoint of further suppressing warpage after sealing and obtaining more excellent heat resistance.
式(II)中,R21 、R22 及R23 各自獨立地表示氫原子、碳數1~6的烷基或碳數1~2的烷氧基,彼此亦可相同亦可不同。n2表示0~10的整數。 In the formula (II), R 21 , R 22 and R 23 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 2 carbon atoms, and may be the same or different. N2 represents an integer of 0 to 10.
又,從獲得優異的阻燃性的觀點而言,亦可以R21 、R22 及R23 中至少一個是氫原子,亦可以R21 、R22 及R23 全部是氫原子。從成形性、流動性及阻燃性更加優異的觀點而言,n2亦可以是0~10的整數,亦可以是0~6的整數。Further, to obtain excellent from the viewpoint of flame retardancy, can also be R 21, R 22 and R 23 is a hydrogen atom, at least, can also be R 21, R 22 and R 23 are all hydrogen atoms. From the viewpoint of further improvement in moldability, fluidity, and flame retardancy, n2 may be an integer of 0 to 10 or an integer of 0 to 6.
作為以式(I)表示之化合物,亦可使用市售品。作為以式(I)表示之化合物的市售品,可舉出新日鐵住金化學股份有限公司製造的商品名「SN-180」、「SN-395」、「SN-475N」及「SN-485」等。以式(I)表示之化合物,亦可單獨使用1種,亦可併用2種以上。As the compound represented by the formula (I), a commercially available product can also be used. As a commercial item of the compound represented by the formula (I), the trade names "SN-180", "SN-395", "SN-475N" and "SN-" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. 485" and so on. The compound represented by the formula (I) may be used alone or in combination of two or more.
作為以式(I)表示之化合物,從更加抑制吸水及密封後的翹曲的觀點而言,亦可以是具有由下述通式(VI)表示之結構的化合物(n6表示1以上的整數,例如,新日鐵住金化學股份有限公司製造的商品名「SN-180」)、及具有由下述通式(VII)表示之結構的化合物(n7表示1以上的整數,例如,新日鐵住金化學股份有限公司製造的商品名「SN-475N」)。The compound represented by the formula (I) may be a compound having a structure represented by the following formula (VI) from the viewpoint of further suppressing water absorption and warpage after sealing (n6 represents an integer of 1 or more, For example, the product name "SN-180" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., and a compound having a structure represented by the following general formula (VII) (n7 represents an integer of 1 or more, for example, Nippon Steel & Sumitomo Metal Co., Ltd. The trade name "SN-475N" manufactured by Chemical Co., Ltd.).
(B)具有芳香環和羥基之樹脂,作為樹脂(b1)以外的樹脂,亦可進而包含不具有萘環的樹脂(以下稱為「樹脂(b2)」)。作為樹脂(b2),可舉出一般使用在密封用環氧樹脂組成物中的樹脂等,並沒有特別限制。(B) A resin having an aromatic ring and a hydroxyl group, and a resin other than the resin (b1) may further contain a resin having no naphthalene ring (hereinafter referred to as "resin (b2)"). The resin (b2) is not particularly limited as long as it is a resin which is generally used in the epoxy resin composition for sealing.
作為樹脂(b2),酚醛清漆型酚樹脂(使酚類與醛類在酸性觸媒下進行縮合或共縮合而獲得的樹脂等);三苯甲烷型酚樹脂;聚對乙烯苯酚樹脂;酚-芳烷基樹脂(由酚類及二甲氧基對二甲苯所合成之具有苯二甲基的酚-芳烷基樹脂等);具有聯苯骨架的酚樹脂(聯苯芳烷基型酚樹脂等)等。作為前述酚類,可舉出:苯酚、甲酚、二甲苯酚、間苯二酚、兒茶酚、雙酚A、雙酚F等。作為前述醛類,可舉出:甲醛、乙醛、丙醛、苯甲醛、柳醛等。從獲得優異的阻燃性的觀點而言,樹脂(b2)亦可以是聯苯芳烷基型酚樹脂,從獲得更優異的耐熱性的觀點而言,亦可以是酚醛清漆型酚樹脂。樹脂(b2),亦可單獨使用1種,亦可併用2種以上。As the resin (b2), a novolac type phenol resin (a resin obtained by condensing or co-condensing a phenol with an aldehyde under an acidic catalyst); a triphenylmethane type phenol resin; a poly(p-vinylphenol resin); Aralkyl resin (phenolic aralkyl resin having benzenediyl group synthesized from phenol and dimethoxyp-xylene); phenol resin having biphenyl skeleton (biphenyl aralkyl type phenol resin) and many more. Examples of the phenols include phenol, cresol, xylenol, resorcin, catechol, bisphenol A, and bisphenol F. Examples of the aldehydes include formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, and salicylaldehyde. The resin (b2) may be a biphenyl aralkyl type phenol resin from the viewpoint of obtaining excellent flame retardancy, and may be a novolak type phenol resin from the viewpoint of obtaining more excellent heat resistance. The resin (b2) may be used alone or in combination of two or more.
作為市售的樹脂(b2),可舉出旭有機材工業股份有限公司製造的商品名「PAPS-PN2」(酚醛清漆型酚樹脂);AIR WATER股份有限公司製造的商品名「SK-Resin HE200C-7」(聯苯芳烷基型酚樹脂)及商品名「HE910-10」(三苯甲烷型酚樹脂);明和化成股份有限公司製造的商品名「DL-92」、「H-4」及「HF-1M」;群榮化學工業股份有限公司製造的商品名「LVR-8210DL」、「ELP」系列及「NC」系列;及日立化成股份有限公司製造的商品名「HP-850N」(酚醛清漆型酚樹脂)等。As a commercially available resin (b2), the product name "PAPS-PN2" (phenol novolak type phenol resin) manufactured by Asahi Organic Materials Co., Ltd.; and the trade name "SK-Resin HE200C" manufactured by AIR WATER Co., Ltd. -7" (biphenyl aralkyl phenol resin) and trade name "HE910-10" (triphenylmethane phenol resin); trade names "DL-92" and "H-4" manufactured by Mingwa Chemical Co., Ltd. And "HF-1M"; the product names "LVR-8210DL", "ELP" series and "NC" series manufactured by Qunrong Chemical Industry Co., Ltd.; and the product name "HP-850N" manufactured by Hitachi Chemical Co., Ltd. ( Novolak type phenol resin) and the like.
(A)環氧樹脂的縮水甘油基的當量(環氧當量),其相對於(B)具有芳香環和羥基之樹脂中與前述縮水甘油基進行反應的官能基(例如酚性羥基)的當量(例如羥基當量)的比率((A)環氧樹脂的縮水甘油基的當量/(B)具有芳香環和羥基之樹脂中與前述縮水甘油基進行反應的官能基的當量),從將未反應的(B)具有芳香環和羥基之樹脂抑制在較少的觀點而言,亦可為0.7以上,亦可為0.8以上,亦可為0.9以上。前述比率,從將未反應的(A)環氧樹脂抑制在較少的觀點而言,亦可為2.0以下,亦可為1.8以下,亦可為1.7以下。前述比率,從將未反應的(A)環氧樹脂及未反應的(B)具有芳香環和羥基之樹脂抑制在較少的觀點而言,亦可為0.7~2.0,亦可為0.8~1.8,亦可為0.9~1.7。(A) an equivalent weight (epoxy equivalent) of a glycidyl group of an epoxy resin, which is equivalent to (B) a functional group (for example, a phenolic hydroxyl group) which reacts with the glycidyl group in the resin having an aromatic ring and a hydroxyl group. Ratio of (e.g., hydroxyl equivalent) ((A) equivalent of glycidyl group of epoxy resin / (B) equivalent of functional group reactive with the aforementioned glycidyl group in resin having aromatic ring and hydroxyl group), from unreacted The (B) resin having an aromatic ring and a hydroxyl group may be 0.7 or more, and may be 0.8 or more, or 0.9 or more, from a small viewpoint. The ratio may be 2.0 or less, or 1.8 or less, or 1.7 or less from the viewpoint of suppressing the unreacted (A) epoxy resin to a small extent. The above ratio may be from 0.7 to 2.0 or from 0.8 to 1.8 from the viewpoint of suppressing the unreacted (A) epoxy resin and the unreacted (B) resin having an aromatic ring and a hydroxyl group. It can also be from 0.9 to 1.7.
(A)環氧樹脂的縮水甘油基的當量(環氧當量),其相對於樹脂(b2)中與前述縮水甘油基進行反應的官能基(例如酚性羥基)的當量(例如羥基當量)的比率((A)環氧樹脂的縮水甘油基的當量/樹脂(b2)中與前述縮水甘油基進行反應的官能基的當量),從將未反應的樹脂(b2)抑制在較少的觀點而言,亦可為0.7以上,亦可為0.8以上,亦可為0.9以上。前述比率,從將未反應的(A)環氧樹脂抑制在較少的觀點而言,亦可為2.0以下,亦可為1.8以下,亦可為1.7以下。前述比率,從將未反應的(A)環氧樹脂及未反應的樹脂(b2)抑制在較少的觀點而言,亦可為0.7~2.0,亦可為0.8~1.8,亦可為0.9~1.7。(A) an equivalent (epoxy equivalent) of a glycidyl group of an epoxy resin, which is equivalent to an equivalent (for example, a hydroxyl group equivalent) of a functional group (for example, a phenolic hydroxyl group) which reacts with the glycidyl group in the resin (b2) The ratio ((A) equivalent of the glycidyl group of the epoxy resin / equivalent of the functional group of the resin (b2) which reacts with the glycidyl group) is suppressed from the viewpoint of suppressing the unreacted resin (b2) In other words, it may be 0.7 or more, 0.8 or more, or 0.9 or more. The ratio may be 2.0 or less, or 1.8 or less, or 1.7 or less from the viewpoint of suppressing the unreacted (A) epoxy resin to a small extent. The ratio may be from 0.7 to 2.0, from 0.8 to 1.8, or from 0.9 to from the viewpoint of suppressing the unreacted (A) epoxy resin and the unreacted resin (b2). 1.7.
((C)聚矽氧粉末) 本實施形態之環氧樹脂組成物,藉由含有(C)聚矽氧粉末,而能夠有效地減少密封後的翹曲(例如封裝體的翹曲量)及封裝體破裂,並能夠獲得優異的耐熱性及阻燃性。((C) Polyoxynium Oxide Powder) The epoxy resin composition of the present embodiment can effectively reduce warpage after sealing (for example, the amount of warpage of the package) by containing (C) polyfluorene oxide powder. The package is broken and excellent heat resistance and flame retardancy can be obtained.
(C)聚矽氧粉末的粒子形狀,從流動性優異的觀點而言,亦可以是球狀(圓球狀或略球狀)。作為(C)聚矽氧粉末,例如,能夠使用將粒子形狀為球狀的聚矽氧橡膠粉末的表面以聚矽氧樹脂進行被膜並粉末化而成者等。這樣的(C)聚矽氧粉末,藉由以聚矽氧樹脂進行被膜而不易凝集,具有對樹脂的分散、密封後的翹曲的抑制及耐熱性優異的特徴。(C)聚矽氧粉末,因為具有矽氧烷鍵以三維網狀交聯而成的結構,故能夠獲得耐熱性及阻燃性更加優異的環氧樹脂組成物。(C)聚矽氧粉末,亦可具有二甲基聚矽氧烷所交聯而成的結構。(C) The particle shape of the polyoxynian powder may be spherical (spherical or slightly spherical) from the viewpoint of excellent fluidity. For the (C) polyfluorene oxide powder, for example, a surface of a polyfluorene oxide rubber powder having a spherical shape in a spherical shape can be used as a coating film and powdered. Such a (C) polyfluorene oxide powder is not easily aggregated by a coating of a polyoxyxylene resin, and has a characteristic of suppressing dispersion of a resin, warpage after sealing, and heat resistance. (C) The polyfluorene oxide powder has a structure in which a siloxane chain is crosslinked in a three-dimensional network, so that an epoxy resin composition having more excellent heat resistance and flame retardancy can be obtained. (C) A polyfluorene oxide powder may have a structure in which dimethylpolysiloxane is crosslinked.
作為(C)聚矽氧粉末的市售品,可舉出信越化學工業股份有限公司製造的商品名「KMP597」、「KMP590」、「KMP600」、「KMP601」、「KMP602」、「KMP605」、「KMP701」、「X-52-7042」等。(C)聚矽氧粉末,亦可單獨使用1種,亦可併用2種以上。As a commercial item of the (C) polyoxylized powder, the trade names "KMP597", "KMP590", "KMP600", "KMP601", "KMP602", "KMP605" manufactured by Shin-Etsu Chemical Co., Ltd., "KMP701", "X-52-7042", etc. (C) The polyoxyl powder may be used singly or in combination of two or more.
(C)聚矽氧粉末的平均粒徑的下限値,亦可為0.05μm以上,亦可為0.1μm以上,亦可為2μm以上,亦可為2.5μm以上,亦可為3μm以上。又,(C)聚矽氧粉末的平均粒徑的上限値上午 02:11 2017/5/1,亦可為50μm以下,亦可為45μm以下,亦可為30μm以下,亦可為20以下μm,亦可為10μm以下。亦即,(C)聚矽氧粉末的平均粒徑,亦可為0.05~50μm,亦可為0.1~45μm,亦可為2~30μm,亦可為2.5~20μm,亦可為3~10μm。藉由(C)聚矽氧粉末的平均粒徑在此等範圍,能夠抑制熔融時樹脂組成物的流動性低落。(C)聚矽氧粉末的平均粒徑,可藉由粒度分布測定裝置來測定。The lower limit 平均 of the average particle diameter of the (C) polyoxynium powder may be 0.05 μm or more, 0.1 μm or more, 2 μm or more, 2.5 μm or more, or 3 μm or more. Further, the upper limit of the average particle diameter of the (C) polyfluorene oxide powder may be 50 μm or less, or may be 45 μm or less, or may be 30 μm or less, or may be 20 or less μm, at 02:11 2017/5/1. It can also be 10 μm or less. That is, the average particle diameter of the (C) polyfluorene oxide powder may be 0.05 to 50 μm, 0.1 to 45 μm, 2 to 30 μm, 2.5 to 20 μm, or 3 to 10 μm. When the average particle diameter of the (C) polyoxynized powder is in the above range, the fluidity of the resin composition at the time of melting can be suppressed from being lowered. (C) The average particle diameter of the polyoxynium powder can be measured by a particle size distribution measuring apparatus.
(C)聚矽氧粉末的含量,以環氧樹脂組成物的總量作為基準計是0.80~7.30質量%。藉由(C)聚矽氧粉末的含量在這樣的範圍,薄膜的處理性(彎曲性等)良好,有效地減少密封後的翹曲,且在燃燒時能夠發揮優異的阻燃性。(C)聚矽氧粉末的含量,從薄膜的處理性(彎曲性等)更加良好、更有效地減少密封後的翹曲,且在燃燒時發揮更加優異的阻燃性的觀點而言,亦可為2~7質量%,亦可為3~6質量%。The content of the (C) polyfluorene oxide powder is 0.80 to 7.30% by mass based on the total amount of the epoxy resin composition. When the content of the (C) polyoxynized powder is in such a range, the handleability (bending property, etc.) of the film is good, the warpage after sealing is effectively reduced, and excellent flame retardancy can be exhibited at the time of combustion. (C) The content of the polyfluorene oxide powder is more excellent in handleability (bending property, etc.) of the film, more effectively reducing warpage after sealing, and also exhibiting more excellent flame retardancy at the time of combustion. It may be 2 to 7 mass%, or may be 3 to 6 mass%.
藉由併用樹脂(b1)與(C)聚矽氧粉末,在燃燒時,能夠更有效地發揮優異的阻燃性。這認為是,在燃燒時,藉由碳化層與無機系燃燒殘渣的複合層,因顯示出優異的隔熱效果及氧氣阻隔效果而能發揮出高阻燃效果;其中,該碳化層是藉由樹脂(b1)的縮合芳香環也就是萘環所生成,該無機系燃燒殘渣是由包含(C)聚矽氧粉末的矽氧烷之複合體所得。By using the resin (b1) and the (C) polyfluorene oxide powder in combination, it is possible to more effectively exhibit excellent flame retardancy at the time of combustion. This is considered to be because, at the time of combustion, the composite layer of the carbonized layer and the inorganic combustion residue exhibits a high flame retardant effect by exhibiting an excellent heat insulating effect and an oxygen barrier effect; wherein the carbonized layer is The condensed aromatic ring of the resin (b1), which is a naphthalene ring, is obtained from a composite of siloxane containing (C) polyfluorene oxide powder.
又,近年,從環境保護的觀點而言,由於起源於戴奧辛的問題,針對以十溴為首的鹵素化樹脂有著規範的變動,同樣地銻化合物(含銻化合物)也從毒性面而言有著規範的變動,對於樹脂密封材料出現了無鹵素化(無溴化等)及無銻化的要求。又,已知在塑膠密封IC的高溫暴露特性上,溴化合物(含溴化合物)會帶來不良影響,而期望著溴化合物的減少。本實施形態之環氧樹脂組成物,由於阻燃性優異,故能夠應用在滿足無鹵素化及無銻化的要求之密封材料。因此,本實施形態之環氧樹脂組成物,能夠提供對無鹵素化及無銻化的阻燃性密封材料之應用。In addition, in recent years, from the viewpoint of environmental protection, due to the problem originating from Dioxin, there is a standard change for halogenated resins including decabromo, and similarly, antimony compounds (containing antimony compounds) also have specifications from the toxic surface. The change in the resin sealing material has been required to be halogen-free (no bromination, etc.) and no bismuth. Further, it is known that a bromine compound (a bromine-containing compound) has an adverse effect on a high-temperature exposure property of a plastic sealing IC, and a reduction in a bromine compound is desired. Since the epoxy resin composition of the present embodiment is excellent in flame retardancy, it can be applied to a sealing material that satisfies the requirements of halogen-free and flawless. Therefore, the epoxy resin composition of the present embodiment can provide an application to a halogen-free and non-deuterated flame-retardant sealing material.
((D)硬化促進劑) 作為(D)硬化促進劑,並沒有特別限制,但例如可以是選自由下述硬化促進劑所組成之群組中的至少1種:胺系之硬化促進劑、咪唑系之硬化促進劑、尿素系之硬化促進劑及磷系之硬化促進劑。作為胺系之硬化促進劑,可舉出:1,8-二氮雜雙環5.4.0-7-十一烯、1,5-二氮雜雙環4.3.0-5-壬烯等。作為咪唑系之硬化促進劑,可舉出:2-苯基-4-甲基咪唑、2-乙基-4-甲基咪唑、1-氰乙基-2-乙基-4-甲基咪唑等。作為尿素系之硬化促進劑,可舉出:3-苯基-1,1-二甲脲等。作為磷系之硬化促進劑,可舉出:三苯膦及其加成反應物、(4-羥苯基)二苯膦、雙(4-羥苯基)苯膦、參(4-羥苯基)膦等。(D) Hardening accelerator The (D) curing accelerator is not particularly limited, and may be, for example, at least one selected from the group consisting of the following curing accelerators: an amine-based curing accelerator, An imidazole-based hardening accelerator, a urea-based hardening accelerator, and a phosphorus-based hardening accelerator. Examples of the amine-based hardening accelerator include 1,8-diazabicycloindene 5.4.0-7-undecene and 1,5-diazabicycloindole 4.3.0-5-decene. Wait. Examples of the imidazole-based hardening accelerator include 2-phenyl-4-methylimidazole, 2-ethyl-4-methylimidazole, and 1-cyanoethyl-2-ethyl-4-methylimidazole. Wait. Examples of the urea-based hardening accelerator include 3-phenyl-1,1-dimethylurea. Examples of the phosphorus-based hardening accelerator include triphenylphosphine and an addition reactant thereof, (4-hydroxyphenyl)diphenylphosphine, bis(4-hydroxyphenyl)phenylphosphine, and bis(4-hydroxybenzene). Phosphine and the like.
作為(D)硬化促進劑,從衍生物的種類豐富、且易於獲得期望的活性溫度的觀點而言,亦可以是咪唑系之硬化促進劑。作為咪唑系之硬化促進劑,亦可使用市售品。作為咪唑系之硬化促進劑的市售品,例如可舉出:四國化成工業股份有限公司製造的商品名「CUREZOL 2PHZ-PW」及「CUREZOL 2P4MZ」等。(D)硬化促進劑,亦可單獨使用1種,亦可併用2種以上。The (D) hardening accelerator may be an imidazole-based hardening accelerator from the viewpoint of being rich in a variety of derivatives and easily obtaining a desired activity temperature. A commercially available product can also be used as the imidazole-based hardening accelerator. As a commercial item of the imidazole-based hardening accelerator, the brand name "CUREZOL 2PHZ-PW" and "CUREZOL 2P4MZ" manufactured by Shikoku Chemicals Co., Ltd., etc. are mentioned, for example. (D) The hardening accelerator may be used alone or in combination of two or more.
(D)硬化促進劑的含量,從能夠輕易獲得充分的硬化促進功效的觀點、及在製作薄膜狀環氧樹脂組成物時的步驟(塗佈及乾燥等)中或在薄膜狀環氧樹脂組成物的保管中能夠抑制硬化的進行,並容易防止薄膜狀環氧樹脂組成物的破裂、及隨著熔融黏度上昇的成形不良的觀點而言,亦可在下述的範圍。(D)硬化促進劑的含量,以(A)環氧樹脂與(B)具有芳香環和羥基之樹脂的合計量作為基準計,亦可為0.01質量%以上,亦可為0.1質量%以上,亦可為0.3質量%以上。(D)硬化促進劑的含量,以(A)環氧樹脂與(B)具有芳香環和羥基之樹脂的合計量作為基準計,亦可為5質量%以下,亦可為3質量%以下,亦可為1.5質量%以下。從這些觀點而言,(D)硬化促進劑的含量,以(A)環氧樹脂與(B)具有芳香環和羥基之樹脂的合計量作為基準計,亦可為0.01~5質量%,亦可為0.1~3質量%,亦可為0.3~1.5質量%。(D) The content of the hardening accelerator is from the viewpoint of easily obtaining sufficient curing-promoting effect, the step (coating and drying, etc.) in the production of the film-like epoxy resin composition, or the film-like epoxy resin composition. In the storage of the material, it is possible to suppress the progress of the curing, and it is easy to prevent the film-like epoxy resin composition from being broken and the molding failure due to the increase in the melt viscosity, and may be in the following range. (D) The content of the hardening accelerator may be 0.01% by mass or more, or 0.1% by mass or more based on the total amount of the (A) epoxy resin and (B) the resin having an aromatic ring and a hydroxyl group. It can also be 0.3% by mass or more. (D) The content of the hardening accelerator may be 5% by mass or less, or may be 3% by mass or less based on the total amount of the (A) epoxy resin and (B) the resin having an aromatic ring and a hydroxyl group. It may be 1.5% by mass or less. From these viewpoints, the content of the (D) curing accelerator may be 0.01 to 5% by mass based on the total amount of the (A) epoxy resin and (B) the resin having an aromatic ring and a hydroxyl group. It may be 0.1 to 3% by mass, or may be 0.3 to 1.5% by mass.
((E)無機填充劑) 作為(E)無機填充劑,能夠使用以往習知的無機填充劑,沒有特定地限定。作為(E)無機填充劑,可舉出:硫酸鋇;鈦酸鋇;非晶形二氧化矽、結晶性二氧化矽、熔融二氧化矽、球狀二氧化矽等的二氧化矽類;滑石;黏土;碳酸鎂;碳酸鈣;氧化鋁;氫氧化鋁;氮化矽;氮化鋁等。(E)無機填充劑,從藉由表面改質等而容易獲得對於樹脂中的分散性的提升功效及在清漆中的沈降抑制功效的觀點、及由於具有較小的熱膨脹率而容易獲得期望的硬化膜特性的觀點而言,亦可以是二氧化矽類。(E)無機填充劑,亦可單獨使用1種,亦可併用2種以上。(E) Inorganic Filler As the (E) inorganic filler, a conventionally known inorganic filler can be used, and it is not particularly limited. Examples of the (E) inorganic filler include barium sulfate; barium titanate; cerium oxide such as amorphous cerium oxide, crystalline cerium oxide, molten cerium oxide, and spherical cerium oxide; talc; Clay; magnesium carbonate; calcium carbonate; aluminum oxide; aluminum hydroxide; tantalum nitride; aluminum nitride. (E) Inorganic filler, from the viewpoint of easily improving the dispersibility in the resin and the sedimentation suppressing effect in the varnish by surface modification or the like, and easily obtaining a desired result due to a small thermal expansion rate From the viewpoint of the properties of the cured film, it may be a cerium oxide. (E) The inorganic filler may be used singly or in combination of two or more.
(E)無機填充劑,亦可進行表面改質。作為表面改質的手法,並沒有特別限定,但由於簡便、官能基的種類豐富、易於賦予期望的特性,亦可以是使用了矽烷偶合劑的表面改質。作為矽烷偶合劑,可舉出:烷基矽烷、烷氧矽烷、乙烯基矽烷、環氧矽烷、胺基矽烷、丙烯醯基矽烷、甲基丙烯醯基矽烷、巰基矽烷、硫醚矽烷、異氰酸基矽烷、硫矽烷、苯乙烯基矽烷、烷氯矽烷等。矽烷偶合劑,亦可單獨使用1種,亦可併用2種以上。(E) Inorganic fillers, which can also be surface modified. The method of modifying the surface is not particularly limited, but it may be a surface modification using a decane coupling agent because it is simple and has a wide variety of functional groups and is easy to impart desired properties. Examples of the decane coupling agent include alkyl decane, alkoxy decane, vinyl decane, epoxy decane, amino decane, acryl decyl decane, methacryl decyl decane, decyl decane, thioether decane, and isocyanide. Acid decane, thiodecane, styryl decane, alkyl chlorodecane, and the like. The decane coupling agent may be used alone or in combination of two or more.
(E)無機填充劑的平均粒徑,從無機填充劑的凝集容易受到抑制而能充分分散,並且在薄膜狀環氧樹脂組成物的製作中,在清漆中的粒子的沈降容易受到抑制的觀點而言,亦可在下述的範圍。(E)無機填充劑的平均粒徑,亦可為0.01μm以上,亦可為0.1μm以上,亦可為0.3μm以上。(E)無機填充劑的平均粒徑,亦可為50μm以下,亦可為25μm以下,亦可為10μm以下。從這些觀點而言,(E)無機填充劑的平均粒徑,亦可為0.01~50μm,亦可為0.1~25μm,亦可為0.3~10μm。(E) The average particle size of the inorganic filler is easily suppressed by aggregation of the inorganic filler, and the sedimentation of the particles in the varnish is easily suppressed in the production of the film-form epoxy resin composition. In addition, it can also be in the following range. (E) The average particle diameter of the inorganic filler may be 0.01 μm or more, 0.1 μm or more, or 0.3 μm or more. (E) The average particle diameter of the inorganic filler may be 50 μm or less, 25 μm or less, or 10 μm or less. From these viewpoints, the average particle diameter of the (E) inorganic filler may be 0.01 to 50 μm, 0.1 to 25 μm, or 0.3 to 10 μm.
(E)無機填充劑的含量,從能夠輕易防止由於被密封體(半導體元件等的電子器件等)與密封部的熱膨脹率之差導致電子裝置(半導體裝置等)的翹曲變大,並且能夠輕易抑制在製作薄膜狀環氧樹脂組成物時於乾燥步驟中產生破裂、及由於薄膜狀環氧樹脂組成物的熔融黏度的上昇而被密封體變得無法充分地密封之缺陷的觀點而言,亦可在下述的範圍。(E)無機填充劑的含量,以環氧樹脂組成物的總量作為基準計,亦可為50質量%以上,亦可為60質量%以上,亦可為70質量%以上。(E)無機填充劑的含量,以環氧樹脂組成物的總量作為基準計,亦可為95質量%以下,亦可為90質量%以下。從這些觀點而言,(E)無機填充劑的含量,以環氧樹脂組成物的總量作為基準計,亦可為50質量%以上,亦可為60~95質量%,亦可為70~90質量%。(E) The content of the inorganic filler can easily prevent the warpage of the electronic device (semiconductor device or the like) from being large due to the difference in thermal expansion coefficient between the sealed body (electronic device such as a semiconductor element) and the sealing portion, and can It is easy to suppress the occurrence of cracks in the drying step when the film-form epoxy resin composition is produced, and the defect that the sealed body cannot be sufficiently sealed due to an increase in the melt viscosity of the film-form epoxy resin composition. It can also be in the range below. (E) The content of the inorganic filler may be 50% by mass or more, or 60% by mass or more, or 70% by mass or more based on the total amount of the epoxy resin composition. The content of the inorganic filler (E) may be 95% by mass or less, or may be 90% by mass or less based on the total amount of the epoxy resin composition. From these viewpoints, the content of the (E) inorganic filler may be 50% by mass or more, or may be 60 to 95% by mass, or 70 to 70% based on the total amount of the epoxy resin composition. 90% by mass.
(其他的成分) 本實施形態之環氧樹脂組成物,亦可進而含有其他的添加劑。作為這樣的添加劑,能夠舉出:顏料、染料、脫模劑、抗氧化劑、應力鬆弛劑、偶合劑、表面張力調整劑、離子交換體、著色劑、阻燃劑等。但是,添加劑並不限定在此等之中,本實施形態之環氧樹脂組成物,亦可視需要而含有在該技術領域中周知的各種添加劑。(Other components) The epoxy resin composition of the present embodiment may further contain other additives. Examples of such an additive include a pigment, a dye, a releasing agent, an antioxidant, a stress relaxation agent, a coupling agent, a surface tension adjusting agent, an ion exchanger, a coloring agent, and a flame retardant. However, the additive is not limited thereto, and the epoxy resin composition of the present embodiment may contain various additives known in the art as needed.
<薄膜狀環氧樹脂組成物> 本實施形態之薄膜狀環氧樹脂組成物,包含了本實施形態之環氧樹脂組成物或其硬化物。本實施形態之薄膜狀環氧樹脂組成物,能夠用於採用模塑成形的密封、採用不需要模具的成形方法(層合、壓製等)的密封等。<Film-form epoxy resin composition> The film-form epoxy resin composition of the present embodiment contains the epoxy resin composition of the present embodiment or a cured product thereof. The film-form epoxy resin composition of the present embodiment can be used for sealing by molding, sealing by a molding method (lamination, pressing, etc.) which does not require a mold.
若藉由本實施形態之薄膜狀環氧樹脂組成物,即使在被密封體已大型化的情況下,相較於液狀或固形(顆粒、粉體等)的樹脂密封材料,可均勻地供給密封樹脂到被密封體上,能夠輕易且良好地將被密封體密封。又,相對於當使用了顆粒或粉體的樹脂密封材料時,樹脂密封材料會成為發塵源,而有著裝置或無塵室遭到汚染的情況,若藉由本實施形態之薄膜狀環氧樹脂組成物,就能夠減少發塵的問題且能將密封成形物進行大型化。According to the film-form epoxy resin composition of the present embodiment, even when the sealed body is enlarged, the sealing material can be uniformly supplied in comparison with the resin sealing material of liquid or solid (particles, powders, etc.). The resin is sealed onto the sealed body, and the sealed body can be easily and satisfactorily sealed. Further, when the resin sealing material using particles or powders is used, the resin sealing material may become a dust source, and the device or the clean room may be contaminated, and the film-like epoxy resin of the present embodiment is used. The composition can reduce the problem of dust generation and can enlarge the sealed molded product.
在模塑成形,由於是將密封樹脂成形在模具內,故在將密封成形物進行大型化中,會需要模具的大型化。模具的大型化,因為需要高度模具精度故在技術面的難易度提高,並且模具的製造成本會有大幅增加的情況。相對於此,本實施形態之薄膜狀環氧樹脂組成物,不僅能適用於習知的密封成形方法也就是模塑成形,也能適用於不需要模具的成形方法(層合、壓製等)。In the molding, since the sealing resin is molded into the mold, it is necessary to increase the size of the mold in order to increase the size of the sealed molded article. The enlargement of the mold requires a high degree of mold precision, so that the difficulty of the technical surface is improved, and the manufacturing cost of the mold is greatly increased. On the other hand, the film-form epoxy resin composition of the present embodiment can be applied not only to a conventional sealing molding method, that is, to molding, but also to a molding method (lamination, pressing, etc.) which does not require a mold.
本實施形態之薄膜狀環氧樹脂組成物的厚度,從易於防止薄膜狀環氧樹脂組成物破裂的觀點而言,亦可為25μm以上,亦可為50μm以上。本實施形態之薄膜狀環氧樹脂組成物的厚度,從抑制薄膜狀環氧樹脂組成物的厚度偏差的觀點而言,亦可為500μm以下,亦可為300μm以下。The thickness of the film-form epoxy resin composition of the present embodiment may be 25 μm or more and 50 μm or more from the viewpoint of easily preventing the film-form epoxy resin composition from being broken. The thickness of the film-form epoxy resin composition of the present embodiment may be 500 μm or less or 300 μm or less from the viewpoint of suppressing variation in thickness of the film-form epoxy resin composition.
本實施形態之薄膜狀環氧樹脂組成物,例如,能夠藉由將本實施形態之環氧樹脂組成物或其硬化物成形為薄膜狀來獲得。第1實施形態之薄膜狀環氧樹脂組成物的製造方法,是清漆塗佈法,其具備下述步驟,例如,使用至少含有(A)環氧樹脂、(B)具有芳香環和羥基之樹脂、(C)聚矽氧粉末、(D)硬化促進劑、及(E)無機填充劑的清漆,在支持體上形成塗膜的步驟;和將前述塗膜進行加熱乾燥來獲得薄膜狀環氧樹脂組成物的步驟。第2實施形態之薄膜狀環氧樹脂組成物的製造方法,其具備下述步驟,將至少含有(A)環氧樹脂、(B)具有芳香環和羥基之樹脂、(C)聚矽氧粉末、(D)硬化促進劑、及(E)無機填充劑的固形樹脂組成物成形為薄片狀來獲得薄膜狀環氧樹脂組成物的步驟。從能夠簡便地控制厚度的觀點而言,亦可以是前述清漆塗佈法。The film-form epoxy resin composition of the present embodiment can be obtained, for example, by molding the epoxy resin composition of the present embodiment or a cured product thereof into a film shape. The method for producing a film-form epoxy resin composition according to the first embodiment is a varnish coating method comprising the steps of, for example, using a resin containing at least (A) an epoxy resin and (B) having an aromatic ring and a hydroxyl group. And (C) a polyoxyn powder, (D) a curing accelerator, and (E) a varnish of an inorganic filler, a step of forming a coating film on the support; and heating and drying the coating film to obtain a film-like epoxy The step of the resin composition. The method for producing a film-form epoxy resin composition according to the second embodiment, comprising the steps of: (A) an epoxy resin, (B) a resin having an aromatic ring and a hydroxyl group, and (C) a polyoxyn powder. The step of obtaining a film-like epoxy resin composition by forming a solid resin composition of (D) a curing accelerator and (E) an inorganic filler into a sheet shape. The varnish coating method may be used from the viewpoint of being able to easily control the thickness.
本實施形態之薄膜狀環氧樹脂組成物,例如,能夠藉由混合(A)環氧樹脂、(B)具有芳香環和羥基之樹脂、(C)聚矽氧粉末、(D)硬化促進劑、(E)無機填充劑、及視需要而使用的各種任意成分來製作。作為混合方法,只要各調配成分能夠分散混合則沒有特別限定,但能夠使用研磨機、混合機、攪拌葉片等。視其需要,能夠藉由使用了清漆的清漆塗佈法來製膜,該清漆是將各調配成分溶解於溶劑等而獲得。又,本實施形態之薄膜狀環氧樹脂組成物,亦能夠藉由將固形樹脂組成物擠壓成薄片狀來製膜而獲得,該固形樹脂組成物是使用捏合機、雙輥機、連續捏合裝置等將各調配成分進行捏合所製作而成。The film-form epoxy resin composition of the present embodiment can be, for example, a mixture of (A) epoxy resin, (B) a resin having an aromatic ring and a hydroxyl group, (C) a polyfluorene oxide powder, and (D) a hardening accelerator. (E) an inorganic filler and various optional components used as needed. The mixing method is not particularly limited as long as the respective components can be dispersed and mixed, but a polishing machine, a mixer, a stirring blade, or the like can be used. According to the need, it is possible to form a film by a varnish coating method using a varnish obtained by dissolving each compounding component in a solvent or the like. Further, the film-form epoxy resin composition of the present embodiment can also be obtained by extruding a solid resin composition into a sheet shape, which is a kneader, a twin roll machine, and a continuous kneading. A device or the like is produced by kneading each compounding component.
作為溶劑,能夠使用以往習知的有機溶劑。作為有機溶劑,可舉出:脂肪族烴類、芳香族烴類、萜烯類、鹵素類、酯類、酮類、醇類、醛類等。有機溶劑,亦可單獨使用1種,亦可併用2種以上。As the solvent, a conventionally known organic solvent can be used. Examples of the organic solvent include aliphatic hydrocarbons, aromatic hydrocarbons, terpenes, halogens, esters, ketones, alcohols, and aldehydes. The organic solvent may be used alone or in combination of two or more.
作為有機溶劑,從對環境負荷小的觀點、及易於溶解(A)環氧樹脂及(B)具有芳香環和羥基之樹脂的觀點而言,亦可以是酯類、酮類及醇類。作為有機溶劑,從特別易於溶解(A)環氧樹脂及(B)具有芳香環和羥基之樹脂的觀點而言,亦可以是酮類。作為有機溶劑,從在室溫(25℃)的揮發較少且乾燥時易於去除的觀點而言,亦可以是丙酮、甲基乙基酮及甲基異丁基酮。The organic solvent may be an ester, a ketone or an alcohol from the viewpoint of a small environmental load and a resin which has an aromatic ring and a hydroxyl group which are easily dissolved (A) epoxy resin and (B). The organic solvent may be a ketone from the viewpoint of particularly easily dissolving the (A) epoxy resin and (B) the resin having an aromatic ring and a hydroxyl group. The organic solvent may be acetone, methyl ethyl ketone or methyl isobutyl ketone from the viewpoint of less volatilization at room temperature (25 ° C) and easy removal during drying.
用於製造薄膜狀環氧樹脂組成物的清漆中的有機溶劑的含量,以該清漆的總量作為基準計,亦可為2~30質量%,亦可為5~25質量%。藉由在這樣的範圍,能夠輕易防止薄膜破裂等的缺陷,並且易於獲得充分的最低熔融黏度。又,能夠輕易防止黏著性變得太強而處理性降低的缺陷、及熱硬化時隨著有機溶劑的揮發而發生的發泡等的缺陷。The content of the organic solvent in the varnish for producing the film-like epoxy resin composition may be 2 to 30% by mass or 5 to 25% by mass based on the total amount of the varnish. By such a range, defects such as film breakage can be easily prevented, and a sufficient minimum melt viscosity can be easily obtained. Moreover, it is possible to easily prevent defects such as a problem that the adhesiveness is too strong and the handleability is lowered, and foaming which occurs due to volatilization of the organic solvent during thermal curing.
在清漆塗佈法中,能夠藉由對塗膜吹送熱風等來進行加熱乾燥,藉此製作薄膜狀環氧樹脂組成物,該塗膜是將清漆塗佈在支持體上而獲得。作為使用在塗佈的塗覆方法,並沒有特別限定,但可舉出模具塗佈法、刮刀(comma)式塗佈法等。In the varnish coating method, a film-like epoxy resin composition can be obtained by blowing hot air or the like onto a coating film to obtain a film-like epoxy resin composition, which is obtained by applying a varnish to a support. The coating method to be applied is not particularly limited, and examples thereof include a die coating method, a comma coating method, and the like.
作為支持體,雖然並沒有特別限定,但可舉出高分子薄膜、金屬箔等。作為高分子薄膜,可舉出:聚乙烯薄膜、聚丙烯薄膜等的聚烯烴薄膜;聚對苯二甲酸乙二酯等的聚酯薄膜;聚氯乙烯薄膜;聚碳酸酯薄膜;醋酸纖維素薄膜;聚醯亞胺薄膜;聚醯胺薄膜;四氟乙烯薄膜等。作為金屬箔,可舉出銅箔、鋁箔等。The support is not particularly limited, and examples thereof include a polymer film and a metal foil. Examples of the polymer film include a polyolefin film such as a polyethylene film or a polypropylene film; a polyester film such as polyethylene terephthalate; a polyvinyl chloride film; a polycarbonate film; and a cellulose acetate film. Polyimine film; polyamine film; tetrafluoroethylene film. Examples of the metal foil include copper foil, aluminum foil, and the like.
支持體的厚度,雖然沒有特別限定,但從操作性及乾燥性優異的觀點而言,亦可為2~200μm。若是這樣的厚度,能夠防止支持體在塗佈時斷裂的缺陷、及因為清漆的重量導致支持體在塗佈時撓曲的缺陷。又,當使用從塗佈面及背面之兩面吹送熱風的乾燥機時,亦能夠抑制清漆中的溶劑乾燥受到妨礙之缺陷的發生。The thickness of the support is not particularly limited, but may be 2 to 200 μm from the viewpoint of excellent workability and dryness. With such a thickness, it is possible to prevent the defect that the support is broken at the time of coating, and the defect that the support is deflected at the time of coating due to the weight of the varnish. Further, when a dryer that blows hot air from both the coated surface and the back surface is used, it is possible to suppress the occurrence of defects that hinder the drying of the solvent in the varnish.
作為前述塗膜的加熱乾燥,在全乾燥時間的25%以上的時間中,能夠在有機溶劑的沸點±10℃的溫度將塗膜進行加熱。加熱乾燥,能夠以加熱溫度不相同的2階段以上的步驟來進行。此時,亦可以從低溫度開始進行加熱乾燥,下一個階段的加熱溫度,能夠設定成在前階段的加熱溫度+30℃以內。As the heating and drying of the coating film, the coating film can be heated at a temperature of ±10 ° C of the boiling point of the organic solvent for a period of 25% or more of the total drying time. Heating and drying can be carried out in two or more steps in which the heating temperature is different. At this time, it is also possible to perform heating and drying from a low temperature, and the heating temperature in the next stage can be set to be within the heating temperature of the previous stage + 30 ° C or less.
在本實施形態中,在設置於支持體上的薄膜狀環氧樹脂組成物上,亦可配置以保護為目的的保護層(例如保護膜)。藉由配置了保護層,處理性更加提升,在捲繞的情況下,能夠避免薄膜狀環氧樹脂組成物黏在支持體的背面的缺陷。In the present embodiment, a protective layer (for example, a protective film) for protection may be disposed on the film-form epoxy resin composition provided on the support. By arranging the protective layer, the handleability is further improved, and in the case of winding, defects in which the film-like epoxy resin composition adheres to the back surface of the support can be avoided.
作為保護層,並沒有特別限定,但可舉出高分子薄膜、金屬箔等。作為高分子薄膜,可舉出:聚乙烯薄膜、聚丙烯薄膜等的聚烯烴薄膜;聚對苯二甲酸乙二酯等的聚酯薄膜;聚氯乙烯薄膜;聚碳酸酯薄膜;醋酸纖維素薄膜;四氟乙烯薄膜等。作為金屬箔,可舉出銅箔、鋁箔等。The protective layer is not particularly limited, and examples thereof include a polymer film and a metal foil. Examples of the polymer film include a polyolefin film such as a polyethylene film or a polypropylene film; a polyester film such as polyethylene terephthalate; a polyvinyl chloride film; a polycarbonate film; and a cellulose acetate film. ; tetrafluoroethylene film, etc. Examples of the metal foil include copper foil, aluminum foil, and the like.
保護層的厚度,並沒有特別限定,但從獲得充分的保護功效的觀點、及減少將薄膜狀環氧樹脂組成物捲繞成輥狀時的厚度的觀點而言,亦可為12~100μm。The thickness of the protective layer is not particularly limited, but may be 12 to 100 μm from the viewpoint of obtaining sufficient protective effect and reducing the thickness when the film-form epoxy resin composition is wound into a roll.
若藉由本實施形態,能夠提供一種密封片,其具備支持體、與經配置於該支持體上的薄膜狀環氧樹脂組成物。密封片,亦可在與薄膜狀環氧樹脂組成物之支持體側相反側上進而具備保護層。According to this embodiment, it is possible to provide a sealing sheet comprising a support and a film-like epoxy resin composition disposed on the support. The sealing sheet may further have a protective layer on the side opposite to the support side of the film-like epoxy resin composition.
<電子裝置> 本實施形態之電子裝置,其具備被密封體與密封部,前述被密封體是選自由電子零件及電子器件所組成之群組中的至少1種,前述密封部是將前述被密封體密封;其中,前述密封部,包含本實施形態之環氧樹脂組成物或其硬化物、或者包含本實施形態之薄膜狀環氧樹脂組成物。本實施形態之電子裝置,是使用環氧樹脂組成物或其硬化物、或者使用薄膜狀環氧樹脂組成物將被密封體密封而成。作為具備電子器件的電子裝置,例如可舉出具備半導體元件的半導體裝置。<Electronic device> The electronic device according to the present embodiment includes a sealed body and a sealing portion, and the sealed body is at least one selected from the group consisting of an electronic component and an electronic component, and the sealing portion is configured to The sealing body includes the epoxy resin composition of the present embodiment or a cured product thereof, or the film-form epoxy resin composition of the present embodiment. In the electronic device of the present embodiment, the sealed body is sealed by using an epoxy resin composition or a cured product thereof or a film-like epoxy resin composition. As an electronic device including an electronic device, a semiconductor device including a semiconductor element is mentioned, for example.
本實施形態之電子裝置的製造方法,亦可具備密封步驟與獲得密封部之步驟,前述密封步驟是藉由本實施形態之環氧樹脂組成物(薄膜狀環氧樹脂組成物等),將選自由電子零件及電子器件所組成之群組中的至少1種被密封體密封;前述獲得密封部之步驟是使前述環氧樹脂組成物進行硬化來獲得密封部。密封步驟,例如,是藉由將環氧樹脂組成物(薄膜狀環氧樹脂組成物等)在加熱下進行按壓,來將被密封體(例如設置於基板上的被密封體)密封的步驟。本實施形態之電子裝置的製造方法,例如,亦可具備密封步驟與獲得密封部之步驟,前述密封步驟是藉由在加熱下將薄膜狀環氧樹脂組成物按壓到被密封體上,而藉由薄膜狀環氧樹脂組成物來將被密封體密封;前述獲得密封部之步驟是使已將被密封體密封的薄膜狀環氧樹脂組成物進行硬化來獲得密封部。The method for producing an electronic device according to the present embodiment may include a sealing step and a step of obtaining a sealing portion, wherein the sealing step is selected from the epoxy resin composition (film-like epoxy resin composition or the like) of the present embodiment. At least one of the group consisting of an electronic component and an electronic device is sealed by a sealing body; and the step of obtaining the sealing portion is to cure the epoxy resin composition to obtain a sealing portion. The sealing step is, for example, a step of sealing the sealed body (for example, a sealed body provided on the substrate) by pressing the epoxy resin composition (film-like epoxy resin composition or the like) under heating. The method for manufacturing an electronic device according to the present embodiment may include, for example, a sealing step and a step of obtaining a sealing portion, wherein the sealing step is performed by pressing a film-like epoxy resin composition onto the object to be sealed by heating. The sealed body is sealed by a film-like epoxy resin composition; the step of obtaining the sealing portion is to cure the film-like epoxy resin composition that has been sealed by the sealed body to obtain a sealed portion.
以上,雖然針對本發明之合適的實施形態進行了說明,但本發明並不限定於上述的實施形態中,在不脫離其主旨的範圍內亦可進行適當變更。 [實施例]In the above, the present invention is not limited to the above-described embodiments, and may be appropriately modified without departing from the scope of the invention. [Examples]
以下,藉由實施例來更具體地說明本發明,但本發明的範圍並不限定於這些實施例中。Hereinafter, the present invention will be more specifically illustrated by the examples, but the scope of the invention is not limited to the examples.
<實施例1~5及比較例1~4、6> (薄膜狀環氧樹脂組成物的製作) 作為構成薄膜狀環氧樹脂組成物的成分,準備了表1及表2所示之化合物。各成分的詳細資料如下所示。<Examples 1 to 5 and Comparative Examples 1 to 4, 6> (Production of Film-Form Epoxy Resin Composition) As the components constituting the film-form epoxy resin composition, the compounds shown in Tables 1 and 2 were prepared. The details of each component are shown below.
(A)環氧樹脂 在25℃為液狀的成分 A1:雙酚F型環氧樹脂(環氧當量:160,三菱化學股份有限公司製造,商品名「jER806」) A2:2官能萘型環氧樹脂(環氧當量:141,DIC股份有限公司製造,商品名「HP-4032D」,由下述式表示之化合物)在25℃並非液狀的成分 A3:3官能萘型環氧樹脂(環氧當量:182,DIC股份有限公司製造,商品名「HP-4750」,以式(IV)表示之化合物)(A) Epoxy resin 液 liquid component at 25 ° C A1: bisphenol F type epoxy resin (epoxy equivalent: 160, manufactured by Mitsubishi Chemical Corporation, trade name "jER806") A2: 2-functional naphthalene Epoxy resin (epoxy equivalent: 141, manufactured by DIC Corporation, trade name "HP-4032D", a compound represented by the following formula) is not a liquid component at 25 ° C. A3: 3-functional naphthalene type epoxy resin (epoxy equivalent: 182, manufactured by DIC Corporation, trade name "HP-4750", compound represented by formula (IV))
(B)具有芳香環和羥基之樹脂 具有萘環和羥基之樹脂 B1:由下述式表示之化合物(羥基當量:110,新日鐵住金化學股份有限公司製造,商品名「SN-395」)式中,n表示1以上的整數。 B2:具有以式(VII)表示之結構的化合物(羥基當量:205,新日鐵住金化學股份有限公司製造,商品名「SN-475N」) 不具有萘環的酚樹脂 B3:酚醛清漆型酚樹脂(羥基當量:104,旭有機材工業股份有限公司製造,商品名「PAPS-PN2」)(B) Resin having an aromatic ring and a hydroxyl group Resin having a naphthalene ring and a hydroxyl group B1: a compound represented by the following formula (hydroxy equivalent: 110, manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., trade name "SN-395"") In the formula, n represents an integer of 1 or more. B2: a compound having a structure represented by the formula (VII) (hydroxy equivalent: 205, manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., trade name "SN-475N") 酚 phenol resin having no naphthalene ring B3: novolac Phenolic resin (hydroxy equivalent: 104, manufactured by Asahi Organic Materials Co., Ltd., trade name "PAPS-PN2")
(C)聚矽氧粉末 C1:信越化學工業股份有限公司製造,商品名「KMP605」,平均粒徑:2μm C2:信越化學工業股份有限公司製造,商品名「KMP600」,平均粒徑:5μm C3:信越化學工業股份有限公司製造,商品名「KMP701」,平均粒徑:3.5μm(C) Polyoxynized Powder C1: manufactured by Shin-Etsu Chemical Co., Ltd., trade name "KMP605", average particle size: 2 μm C2: manufactured by Shin-Etsu Chemical Co., Ltd., trade name "KMP600", average particle size: 5 μm C3 :Manufactured by Shin-Etsu Chemical Co., Ltd., trade name "KMP701", average particle size: 3.5μm
(D)硬化促進劑 四國化成工業股份有限公司製造,商品名「CUREZOL 2P4MZ」(D) Hardening accelerator manufactured by Shikoku Chemical Industry Co., Ltd., trade name "CUREZOL 2P4MZ"
(E)無機填充劑 二氧化矽(Admatechs股份有限公司製造,商品名「SX-E2」,苯胺基矽烷處理,平均粒徑:5.8μm)(E) Inorganic filler cerium oxide (manufactured by Admatechs Co., Ltd., trade name "SX-E2", anilino decane treatment, average particle diameter: 5.8 μm)
有機溶劑 甲基乙基酮(GODO股份有限公司製造)Organic solvent methyl ethyl ketone (made by GODO Co., Ltd.)
將顯示於表1及表2的調配量(單位:質量份)的各成分加到1L的聚乙烯容器後,攪拌3小時藉由分散及混合而獲得了混合液。將此混合液以尼龍製造的#200篩(開口徑:75μm)過濾,並採集過濾液作為清漆狀環氧樹脂組成物。藉由使用塗佈機將此清漆狀環氧樹脂組成物塗佈於支持體(38μm厚的聚對苯二甲酸乙二酯,Oji F-Tex股份有限公司製造)上後使之乾燥,製作成支持體及薄膜狀環氧樹脂組成物的積層體(全厚:188μm,樹脂組成物層的厚度:150μm)。另外,塗佈及乾燥的條件如同下述。 ‧塗佈方法:刮刀式塗佈 ‧乾燥速度:1m/分鐘 ‧乾燥條件(溫度/爐長):110℃/3.3m、130℃/3.3m、140℃/3.3mEach component of the blending amount (unit: mass part) shown in Table 1 and Table 2 was added to a 1 L polyethylene container, and the mixture was stirred for 3 hours to obtain a mixed solution. This mixture was filtered through a #200 sieve (opening diameter: 75 μm) made of nylon, and a filtrate was collected as a varnish-like epoxy resin composition. This varnish-like epoxy resin composition was applied onto a support (38 μm thick polyethylene terephthalate, manufactured by Oji F-Tex Co., Ltd.) using a coater, and dried to prepare a varnish-like epoxy resin composition. A laminate of a support and a film-like epoxy resin composition (full thickness: 188 μm, thickness of the resin composition layer: 150 μm). In addition, the conditions of coating and drying are as follows. ‧ Coating method: blade coating ‧ Drying speed: 1 m / min ‧ Drying conditions (temperature / furnace length): 110 ° C / 3.3 m, 130 ° C / 3.3 m, 140 ° C / 3.3 m
<比較例5> 使用顯示於表2的化合物,與實施例1相同地將清漆狀環氧樹脂組成物塗佈於支持體上後並使之乾燥,但樹脂組成物的薄膜化無法進行,而無法獲得薄膜狀環氧樹脂組成物。<Comparative Example 5> Using the compound shown in Table 2, a varnish-like epoxy resin composition was applied onto a support in the same manner as in Example 1 and dried, but the film formation of the resin composition could not be performed. A film-like epoxy resin composition could not be obtained.
<評估> 使用實施例1~5及比較例1~4、6的薄膜狀環氧樹脂組成物進行了以下的評估。另外,針對比較例3,沒有進行翹曲量及耐熱性的評估。針對沒有獲得薄膜狀環氧樹脂組成物的比較例5,將處理性標成表中的「B」。<Evaluation> The following evaluations were carried out using the film-like epoxy resin compositions of Examples 1 to 5 and Comparative Examples 1 to 4 and 6. Further, with respect to Comparative Example 3, the evaluation of the amount of warpage and heat resistance was not performed. For Comparative Example 5 in which the film-like epoxy resin composition was not obtained, the handleability was indicated as "B" in the table.
(處理性(彎曲性)的評估) 薄膜狀環氧樹脂組成物的彎曲性,是使用彎曲試驗機並以下述的順序進行了評估。作為試驗機,準備了YOSHIMITSU精機股份有限公司製造的彎曲試驗機(JIS型type1,圓筒型心軸法)。將支持體及薄膜狀環氧樹脂組成物的積層體切成5cm見方,準備試驗片。使試驗片的支持體側接觸到直徑2mm的圓筒型心軸,將試驗片折彎180°時評估有無薄膜狀環氧樹脂組成物的破裂。將破裂沒發生的情況當作彎曲性良好,表中標成「A」。將破裂有發生的情況當作彎曲性不良,表中標成「B」。將處理性(彎曲性)的評估結果顯示於表1及表2。(Evaluation of Handling Property (Flexibility)) The flexibility of the film-form epoxy resin composition was evaluated in the following order using a bending tester. A bending tester (JIS type 1 and cylindrical mandrel method) manufactured by YOSHIMITSU Seiki Co., Ltd. was prepared as a test machine. The laminate of the support and the film-like epoxy resin composition was cut into 5 cm squares to prepare a test piece. The support side of the test piece was brought into contact with a cylindrical mandrel having a diameter of 2 mm, and the presence or absence of cracking of the film-like epoxy resin composition was evaluated when the test piece was bent by 180°. The case where the crack did not occur was regarded as good bending, and the table was marked "A". The occurrence of cracking is regarded as poor bending, and the table is marked as "B". The evaluation results of the handleability (bending property) are shown in Tables 1 and 2.
(翹曲量的評估) 評估樣品的製作 準備了長度200mm×寬度200mm×厚度1.0mm的NICHIAS股份有限公司製造的NAFLON sheet(商品名:TOMBO 9000-S)。將NAFLON sheet的中心部切成長度120mm×寬度10mm×厚度1.0mm,如第1圖所示,獲得了具有開口10a的試驗片10。在開口10a之中置入長度120mm×寬度10mm×厚度0.725mm的矽(Si)基板,以矽基板不會動的方式,用已切成長度140mm×寬度25mm×厚度0.025mm的NICHIBAN 股份有限公司製造的聚醯亞胺帶,將矽基板的整面及NAFLON sheet從NAFLON sheet的下面開始固定。在沒有用聚醯亞胺帶固定的上面,以覆蓋矽基板上的整面的方式配置了2片厚度150μm的薄膜狀環氧樹脂組成物(使用已切成長度120mm×寬度10mm的薄膜)。將已配置完成的薄膜狀環氧樹脂組成物在真空下(0.1kPa)、溫度110℃、壓力0.1MPa進行了5分鐘的壓製。其次,將壓製的壓力返回常壓,獲得了黏附在矽基板上的薄膜狀環氧樹脂組成物。以矽基板與薄膜狀環氧樹脂組成物的積層體的全厚成為1.00mm的方式研磨了薄膜狀環氧樹脂組成物。藉由將全厚1.00mm的積層體用140℃的烤箱使之硬化2小時後,再使之自然冷卻至25℃,獲得了翹曲評估用樣品。(Evaluation of the amount of warpage) Preparation of the evaluation sample NA A NAFLON sheet (trade name: TOMBO 9000-S) manufactured by NICHIAS Co., Ltd. having a length of 200 mm × a width of 200 mm × a thickness of 1.0 mm was prepared. The center portion of the NAFLON sheet was cut into a length of 120 mm × a width of 10 mm × a thickness of 1.0 mm, and as shown in Fig. 1, a test piece 10 having an opening 10a was obtained. A 矽(Si) substrate having a length of 120 mm, a width of 10 mm, and a thickness of 0.725 mm is placed in the opening 10a, and NICHIBAN Co., Ltd., which has been cut into a length of 140 mm, a width of 25 mm, and a thickness of 0.025 mm, is used in such a manner that the substrate is not moved. The manufactured polyimide film was fixed from the entire surface of the substrate and the NAFLON sheet from the bottom of the NAFLON sheet. Two film-like epoxy resin compositions having a thickness of 150 μm (using a film cut into a length of 120 mm × a width of 10 mm) were placed on the upper surface of the substrate without being covered with a polyimide film. The film-form epoxy resin composition which had been disposed was pressed under vacuum (0.1 kPa) at a temperature of 110 ° C and a pressure of 0.1 MPa for 5 minutes. Next, the pressed pressure was returned to normal pressure, and a film-like epoxy resin composition adhered to the crucible substrate was obtained. The film-form epoxy resin composition was polished so that the total thickness of the laminated body of the ruthenium substrate and the film-form epoxy resin composition was 1.00 mm. The laminate for evaluation of warpage was obtained by hardening a laminate having a full thickness of 1.00 mm in an oven at 140 ° C for 2 hours and then naturally cooling it to 25 ° C.
翹曲量的測定方法 使用三維雷射形狀測定裝置(KEYENCE股份有限公司製造,商品名:LK-030),測定在前述獲得之翹曲評估用樣品在室溫(25℃)中的最大翹曲量。將掃描範圍設定在140mm×20mm,掃描間距設定在1.0mm,掃描速度設定在20mm/s來進行測定。將測定結果顯示於表1及表2。Method for measuring the amount of warpage of The maximum value of the sample for warpage evaluation obtained in the above was measured at room temperature (25 ° C) using a three-dimensional laser shape measuring device (manufactured by KEYENCE Co., Ltd., trade name: LK-030). The amount of warpage. The measurement was performed by setting the scanning range to 140 mm × 20 mm, the scanning pitch to 1.0 mm, and the scanning speed to 20 mm/s. The measurement results are shown in Tables 1 and 2.
(耐熱性的評估) 將支持體及薄膜狀環氧樹脂組成物的積層體切成長度30mm×寬度5mm×厚度0.18mm。其次,使用名機製作所股份有限公司製造的真空加壓層合機MVLP-500,以溫度90℃、抽真空時間30秒、壓力0.5MPa、加壓時間40秒的條件,將薄膜狀環氧樹脂組成物面面向長度100mm×寬度100mm×厚度2mm之NICHIAS股份有限公司製造的NAFLON sheet(商品名:TOMBO 9000-S)面進行層合。之後,將支持著薄膜狀環氧樹脂組成物的支持體剝離後,將NAFLON sheet及薄膜狀環氧樹脂組成物所組成的積層體放入140℃的烤箱2小時使之硬化,獲得了積層於NAFLON sheet的硬化膜。其次,從NAFLON sheet剝離硬化膜,獲得了測定用樣品。使用動態黏彈性測定裝置E-4000(UBM股份有限公司製造),以拉伸模式、夾頭間距離20mm、頻率10Hz、昇溫速度5/min的條件進行測定時的tanδ之峰值作為玻璃轉移溫度(Tg)而得。將耐熱性(玻璃轉移溫度℃)的評估結果顯示於表1及表2。(Evaluation of heat resistance) The laminate of the support and the film-like epoxy resin composition was cut into a length of 30 mm × a width of 5 mm × a thickness of 0.18 mm. Next, a vacuum-pressure laminator MVLP-500 manufactured by Nagoya Seisakusho Co., Ltd. was used to form a film-like epoxy resin under the conditions of a temperature of 90 ° C, a vacuuming time of 30 seconds, a pressure of 0.5 MPa, and a pressurization time of 40 seconds. The surface of the composition was laminated on the surface of a NAFLON sheet (trade name: TOMBO 9000-S) manufactured by NICHIAS Co., Ltd. having a length of 100 mm × a width of 100 mm × a thickness of 2 mm. Thereafter, after the support supporting the film-like epoxy resin composition was peeled off, the laminate of the NAFLON sheet and the film-like epoxy resin composition was placed in an oven at 140 ° C for 2 hours to be hardened, and a laminate was obtained. Hardened film of NAFLON sheet. Next, the cured film was peeled off from the NAFLON sheet, and a sample for measurement was obtained. Using the dynamic viscoelasticity measuring apparatus E-4000 (manufactured by UBM Co., Ltd.), the peak value of tan δ when measured in the tensile mode, the inter-clamp distance of 20 mm, the frequency of 10 Hz, and the temperature increase rate of 5/min was taken as the glass transition temperature ( Tg). The evaluation results of heat resistance (glass transition temperature ° C ) are shown in Tables 1 and 2.
(阻燃性的評估) 從支持體及薄膜狀環氧樹脂組成物的積層體剝離支持體,獲得了薄膜狀環氧樹脂組成物,將此薄膜狀環氧樹脂組成物使用用以成形厚度1/8英吋的試驗片之模具,以轉移式壓製(transfer press)以模具溫度140℃、成形壓力1.0MPa、成形時間10分鐘的條件進行了成形。之後,從模具取出硬化物。然後,以140℃的烤箱進行硬化2小時,獲得了厚度1/8英吋的試驗片。評估方法是依照UL-94試驗法。將評估結果達到「V-1」的情況,表中標成「A」,將評估結果未達到「V-1」的情況,表中標成「B」。將阻燃性的評估結果顯示於表1及表2。(Evaluation of Flame Retardancy) The support was peeled off from the laminate of the support and the film-like epoxy resin composition, and a film-like epoxy resin composition was obtained, and the film-like epoxy resin composition was used to form a thickness of 1 The mold of the test piece of /8 inch was formed by a transfer press at a mold temperature of 140 ° C, a molding pressure of 1.0 MPa, and a molding time of 10 minutes. After that, the cured product is taken out from the mold. Then, it was hardened in an oven at 140 ° C for 2 hours to obtain a test piece having a thickness of 1/8 inch. The evaluation method is in accordance with the UL-94 test method. When the evaluation result is "V-1", the table is marked with "A", and the evaluation result is not up to "V-1", and the table is marked with "B". The evaluation results of the flame retardancy are shown in Tables 1 and 2.
[表1] [Table 1]
[表2] [Table 2]
由前述的結果,實施例之環氧樹脂組成物,不論是處理性、翹曲量、耐熱性及阻燃性全都良好。相對於此,在比較例1、2及6,雖然處理性優異,但樹脂密封後的基板翹曲大,翹曲量差,並且阻燃性也差。在比較例3,雖然阻燃性優異,但柔軟性低且處理性差。在比較例4,雖然處理性及阻燃性優異,但樹脂密封後的基板翹曲大,翹曲量差。在比較例5,無法薄膜化,處理性差。From the above results, the epoxy resin composition of the examples was excellent in handleability, warpage amount, heat resistance and flame retardancy. On the other hand, in Comparative Examples 1, 2, and 6, although the handleability was excellent, the substrate after resin sealing was warped, the amount of warpage was inferior, and the flame retardancy was also inferior. In Comparative Example 3, although the flame retardancy was excellent, the flexibility was low and the handleability was poor. In Comparative Example 4, although the handleability and the flame retardancy were excellent, the substrate after the resin sealing was warped and the amount of warpage was poor. In Comparative Example 5, the film formation was impossible, and the handleability was poor.
10‧‧‧試驗片
10a‧‧‧開口10‧‧‧Test strips
10a‧‧‧ openings
第1圖是表示用以評估翹曲量的試驗片的平面圖。Fig. 1 is a plan view showing a test piece for evaluating the amount of warpage.
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CN103827162B (en) * | 2011-09-29 | 2016-06-15 | 日立化成株式会社 | Composition epoxy resin and electronic part apparatus |
JP6135991B2 (en) * | 2012-10-11 | 2017-05-31 | パナソニックIpマネジメント株式会社 | Epoxy resin inorganic composite sheet for sealing |
JP2014132058A (en) * | 2013-01-07 | 2014-07-17 | Mitsubishi Gas Chemical Co Inc | Curable resin composition and cured product |
JP2014185296A (en) * | 2013-03-25 | 2014-10-02 | Asahi Kasei E-Materials Corp | Liquid resin composition and processed product |
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2016
- 2016-08-01 CN CN201680058152.4A patent/CN108137793B/en active Active
- 2016-08-01 JP JP2017533061A patent/JP6801659B2/en active Active
- 2016-08-01 WO PCT/JP2016/072537 patent/WO2017022721A1/en active Application Filing
- 2016-08-01 KR KR1020187006050A patent/KR102477938B1/en active IP Right Grant
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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TWI787295B (en) * | 2017-06-29 | 2022-12-21 | 日商昭和電工材料股份有限公司 | Resin composition for encapsulation, semiconductor package and method of producing semiconductor package |
TWI839971B (en) * | 2017-06-29 | 2024-04-21 | 日商力森諾科股份有限公司 | Resin composition for encapsulation, semiconductor package and method of producing semiconductor package |
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Publication number | Publication date |
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CN108137793A (en) | 2018-06-08 |
TWI728992B (en) | 2021-06-01 |
KR20180037017A (en) | 2018-04-10 |
JPWO2017022721A1 (en) | 2018-05-24 |
CN108137793B (en) | 2021-12-24 |
WO2017022721A1 (en) | 2017-02-09 |
JP6801659B2 (en) | 2020-12-16 |
KR102477938B1 (en) | 2022-12-14 |
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