TW201821547A - Thermosetting resin composition, resin film with carrier, printed wiring board and semiconductor device - Google Patents
Thermosetting resin composition, resin film with carrier, printed wiring board and semiconductor device Download PDFInfo
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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
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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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
- C08L101/00—Compositions of unspecified macromolecular compounds
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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
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
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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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
Abstract
Description
本發明係有關一種熱硬化性樹脂組成物、附載體樹脂膜、印刷配線基板及半導體裝置。 The present invention relates to a thermosetting resin composition, a carrier-attached resin film, a printed wiring board, and a semiconductor device.
在目前為止的環氧樹脂組成物中，從減小尺寸變化之觀點考慮，進行了各種各樣的開發。作為該種技術，例如可以舉出專利文獻1中記載之環氧樹脂組成物。作為該環氧樹脂組成物的環氧樹脂，使用雙酚F型環氧樹脂(專利文獻1的0124段、實施例2)。 In the epoxy resin composition of the prior art, various developments have been made from the viewpoint of reducing the dimensional change. As such a technique, for example, an epoxy resin composition described in Patent Document 1 can be mentioned. As the epoxy resin of the epoxy resin composition, a bisphenol F-type epoxy resin (No. 0124 of Patent Document 1, and Example 2) was used.
【先前技術文獻】 [Previous Technical Literature]
【專利文獻】 [Patent Literature]
【專利文獻1】：日本特開2013-23667號公報 [Patent Document 1]: JP-A-2013-23667
然而，在近年的半導體封裝中，越來越趨向薄層化。基於這樣的開發環境，本發明人進行研究之結果，判明了在上述文獻中記載之環氧樹脂組成物的硬化物中，在強韌性方面具有改善的餘地。 However, in recent years, semiconductor packages have become more and more thin. Based on the results of the research conducted by the present inventors, it has been found that the cured product of the epoxy resin composition described in the above document has room for improvement in toughness.
本發明人進一步對用於形成印刷配線基板中之絕緣層的熱硬化性樹脂組成物進行研究，並且作為與強韌性相關之特性，著眼於彈性模數和伸長率。進一步深入研究之結果，判明了藉由兼顧低彈性和高伸長 度，可實現優異之強韌性。並且，發現藉由採用在30℃之儲存彈性模數E'30作為彈性模數的指標，並採用藉由拉伸試驗測得之拉伸伸長率作為伸長率的指標，能夠最佳地評價低彈性和高伸長度。 The present inventors further studied the thermosetting resin composition for forming an insulating layer in a printed wiring board, and focused on the modulus of elasticity and the elongation as characteristics relating to toughness. Further in-depth research has shown that excellent toughness can be achieved by taking into account both low elasticity and high elongation. Further, it was found that by using the storage elastic modulus E' 30 at 30 ° C as an index of the elastic modulus and using the tensile elongation measured by the tensile test as an index of elongation, the lowest evaluation can be optimally performed. Elasticity and high elongation.
基於該種見解進行深入研究之結果，發現藉由將熱硬化性樹脂組成物的硬化物的儲存彈性模數E'30設為特定值以下且將拉伸伸長率設為特定值以上，能夠提高熱硬化性樹脂組成物的硬化物的強韌性，並完成了本發明。 As a result of intensive investigation based on such a finding, it has been found that the storage elastic modulus E' 30 of the cured product of the thermosetting resin composition can be increased by a specific value or less and the tensile elongation is set to a specific value or more. The toughness of the cured product of the thermosetting resin composition, and completed the present invention.
依本發明，提供一種熱硬化性樹脂組成物，用於形成印刷配線基板中之絕緣層，前述熱硬化性樹脂組成物含有：熱硬化性樹脂；硬化劑；及無機填充材料，當對該熱硬化性樹脂組成物的硬化物進行了動態黏彈性測量時，前述硬化物在30℃之儲存彈性模數E'30為1GPa以上且10GPa以下，當對前述硬化物進行了拉伸試驗時，前述硬化物的拉伸伸長率為2%以上。 According to the present invention, there is provided a thermosetting resin composition for forming an insulating layer in a printed wiring board, wherein the thermosetting resin composition contains: a thermosetting resin; a hardener; and an inorganic filler when the heat is applied When the cured product of the curable resin composition is subjected to dynamic viscoelasticity measurement, the storage elastic modulus E' 30 of the cured product at 30 ° C is 1 GPa or more and 10 GPa or less. When the cured product is subjected to a tensile test, the aforementioned The cured product has a tensile elongation of 2% or more.
並且，依本發明，提供一種附載體樹脂膜，其具備：載體基材；及設置於前述載體基材上且由上述熱硬化性樹脂組成物形成的樹脂膜。 Further, according to the invention, there is provided a carrier-attached resin film comprising: a carrier substrate; and a resin film provided on the carrier substrate and formed of the thermosetting resin composition.
並且，依本發明，提供一種印刷配線基板，其具備絕緣層，前述絕緣層由上述熱硬化性樹脂組成物的樹脂膜的硬化物構成。 Further, according to the invention, there is provided a printed wiring board comprising an insulating layer, wherein the insulating layer is made of a cured product of a resin film of the thermosetting resin composition.
並且，依本發明，提供一種半導體裝置，其具備：上述印刷配線基板；及搭載於前述印刷配線基板的電路層上或者內置於前述印刷配線基板之半導體元件。 Further, according to the invention, there is provided a semiconductor device comprising: the printed wiring board; and a semiconductor element mounted on the circuit layer of the printed wiring board or built in the printed wiring board.
依本發明，提供一種可得到強韌性優異之絕緣層之熱硬化性樹脂、使用了該熱硬化性樹脂之附載體樹脂膜、印刷配線基板及半導體裝置。 According to the invention, there is provided a thermosetting resin capable of obtaining an insulating layer excellent in toughness, a carrier resin film using the thermosetting resin, a printed wiring board, and a semiconductor device.
10‧‧‧樹脂膜 10‧‧‧ resin film
12‧‧‧載體基材 12‧‧‧ Carrier substrate
100‧‧‧附載體樹脂膜 100‧‧‧with carrier resin film
105‧‧‧金屬箔 105‧‧‧metal foil
300、500、600、700‧‧‧印刷配線基板 300, 500, 600, 700‧‧‧ Printed wiring substrates
301、305、401、540、550、560、612、630、632、712、730、732‧‧‧絕緣層 301, 305, 401, 540, 550, 560, 612, 630, 632, 712, 730, 732 ‧ ‧ insulation
303、542、552、562、614、618、640、650、714、718、740‧‧‧金屬層 303, 542, 552, 562, 614, 618, 640, 650, 714, 718, 740‧‧‧ metal layers
307‧‧‧通孔 307‧‧‧through hole
308‧‧‧無電解金屬鍍膜 308‧‧‧Electroless metal coating
309‧‧‧電解金屬鍍層 309‧‧‧Electrolytic metal plating
400‧‧‧半導體裝置 400‧‧‧Semiconductor device
407、620、720‧‧‧半導體元件 407, 620, 720‧‧‧ semiconductor components
410‧‧‧焊錫凸塊 410‧‧‧ solder bumps
413‧‧‧封裝材料層 413‧‧‧Package material layer
510‧‧‧支撐基板 510‧‧‧Support substrate
520‧‧‧載體箔 520‧‧‧Carrier foil
530‧‧‧金屬箔 530‧‧‧metal foil
610、710‧‧‧無芯樹脂基板 610, 710‧‧‧ Coreless resin substrate
616、716‧‧‧通路配線 616, 716‧‧‧ path wiring
652‧‧‧第1金屬層 652‧‧‧1st metal layer
654‧‧‧第2金屬層 654‧‧‧2nd metal layer
圖1係表示本實施形態中之附載體樹脂膜的構成的一例之剖面圖。 Fig. 1 is a cross-sectional view showing an example of a structure of a resin film with a carrier in the embodiment.
圖2中，圖2(a)及圖2(b)係表示本實施形態中之印刷配線基板的構成的一例之剖面圖。 2(a) and 2(b) are cross-sectional views showing an example of a configuration of a printed wiring board in the embodiment.
圖3中，圖3(a)及圖3(b)係表示本實施形態中之半導體裝置的構成的一例之剖面圖。 In Fig. 3, Fig. 3 (a) and Fig. 3 (b) are cross-sectional views showing an example of a configuration of a semiconductor device in the present embodiment.
圖4中，圖4(a)~圖4(c)係表示本實施形態中之印刷配線基板的製造步驟的一例之製程剖面圖。 4(a) to 4(c) are process cross-sectional views showing an example of a manufacturing procedure of the printed wiring board in the embodiment.
圖5係表示本實施形態中之印刷配線基板的構成的一例之剖面圖。 Fig. 5 is a cross-sectional view showing an example of a configuration of a printed wiring board in the embodiment.
圖6係表示本實施形態中之印刷配線基板的構成的一例之剖面圖。 Fig. 6 is a cross-sectional view showing an example of a configuration of a printed wiring board in the embodiment.
以下，利用圖式對本發明的實施形態進行說明。另外，在所有圖式中，對同樣的構成要素標註同樣的符號，並適當省略說明。 Hereinafter, embodiments of the present invention will be described using the drawings. In the drawings, the same components are denoted by the same reference numerals, and the description is omitted as appropriate.
本實施形態的熱硬化性樹脂組成物含有熱硬化性樹脂、硬化劑及無機填充材料。並且，本實施形態的熱硬化性樹脂組成物，當對該熱硬化性樹脂組成物的硬化物進行了動態黏彈性測量時，前述硬化物在30℃之儲存彈性模數E'30為1GPa以上且10GPa以下，且當對前述硬化物進行了拉伸試驗時，前述硬化物的拉伸伸長率為2%以上。該種熱硬化性樹脂組成物用於形成印刷配線基板中之絕緣層。 The thermosetting resin composition of the present embodiment contains a thermosetting resin, a curing agent, and an inorganic filler. Further, in the thermosetting resin composition of the present embodiment, when the cured product of the thermosetting resin composition is subjected to dynamic viscoelasticity measurement, the storage elastic modulus E' 30 of the cured product at 30 ° C is 1 GPa or more. Further, when the cured product is subjected to a tensile test at 10 GPa or less, the tensile elongation of the cured product is 2% or more. This thermosetting resin composition is used to form an insulating layer in a printed wiring board.
本發明人進一步對用於形成印刷配線基板中之絕緣層的熱硬化性樹脂組成物進行研究，作為與強韌性相關之特性，著眼於儲存彈性模數和拉伸伸長率。進一步深入研究之結果，判明了在含有熱硬化性樹脂、硬化劑及無機填充材料之熱硬化性樹脂組成物的硬化物中，藉由兼顧低彈性和高伸長度，能夠發揮優異之強韌性。 The present inventors further studied the thermosetting resin composition for forming an insulating layer in a printed wiring board, and focused on the storage elastic modulus and tensile elongation as characteristics relating to toughness. As a result of further intensive studies, it has been found that a cured product of a thermosetting resin composition containing a thermosetting resin, a curing agent, and an inorganic filler can exhibit excellent toughness by achieving both low elasticity and high elongation.
對評價這樣的熱硬化性樹脂組成物的硬化物的物性之方法進行詳細研究之結果，發現藉由採用在30℃之儲存彈性模數E'30作為彈性模數的指標，並採用藉由拉伸試驗測量出之拉伸伸長率作為伸長率的指標，能夠最佳地評價低彈性和高伸長度。 As a result of detailed examination of the method for evaluating the physical properties of the cured product of the thermosetting resin composition, it was found that by using the storage elastic modulus E' 30 at 30 ° C as an index of the elastic modulus, and by pulling The tensile elongation measured by the tensile test is used as an index of elongation, and the low elasticity and high elongation can be optimally evaluated.
詳細的機理雖然不明確，但認為在基於熱硬化性樹脂之三維網絡結構中，藉由高度控制交聯點間距離或交聯點數，能夠實現交聯密度的最佳化，能夠實現兼顧低彈性和高伸長度。例如，作為用於控制交聯密度並將上述儲存彈性模數及上述拉伸伸長率設在所希望的數值範圍之要素，可以舉出使用每個官能基的分子量大且具備柔軟的骨架之熱硬化性樹脂等。 Although the detailed mechanism is not clear, it is considered that in the three-dimensional network structure based on the thermosetting resin, by controlling the distance between the crosslinking points or the number of crosslinking points, the crosslinking density can be optimized, and the low balance can be achieved. Elasticity and high elongation. For example, as an element for controlling the crosslinking density and setting the storage elastic modulus and the tensile elongation to a desired numerical range, a heat having a large molecular weight per one functional group and having a soft skeleton can be cited. Curable resin, etc.
基於該種見解進行深入研究之結果，發現藉由將熱硬化性樹 脂組成物的硬化物的儲存彈性模數E'30設為1GPa以上且10GPa以下，且將拉伸伸長率設為2%以上，能夠兼顧熱硬化性樹脂組成物的硬化物的低彈性和高伸長度，並發揮優異之強韌性，從而完成了本發明。 As a result of intensive investigation based on the above-mentioned findings, it has been found that the storage elastic modulus E' 30 of the cured product of the thermosetting resin composition is 1 GPa or more and 10 GPa or less, and the tensile elongation is 2% or more. The present invention has been accomplished by taking into consideration the low elasticity and high elongation of the cured product of the thermosetting resin composition and exhibiting excellent toughness.
本實施形態中，印刷配線基板中之絕緣層能夠用於芯層、增建層(build-up layer)(層間絕緣層)、阻焊層(solder resist layer)等構成印刷配線基板之絕緣性構件中。作為上述印刷配線基板，可以舉出具有芯層、增建層(層間絕緣層)、阻焊層之印刷配線基板、不具有芯層之印刷配線基板、用於面板封裝製程(PLP)之無芯基板、MIS(Molded Interconnect Substrate：模封互連基板)基板等。 In the present embodiment, the insulating layer in the printed wiring board can be used for an insulating member constituting a printed wiring board such as a core layer, a build-up layer (interlayer insulating layer), a solder resist layer, or the like. in. Examples of the printed wiring board include a printed wiring board having a core layer, an build-up layer (interlayer insulating layer), and a solder resist layer, a printed wiring board having no core layer, and a coreless package manufacturing process (PLP). Substrate, MIS (Molded Interconnect Substrate) substrate, and the like.
由本實施形態的熱硬化性樹脂組成物形成之樹脂膜的硬化物用於上述絕緣層，例如亦能夠用於不具有芯層之印刷配線基板中之增建層或阻焊層、用於PLP中之無芯基板的層間絕緣層或阻焊層、MIS基板的層間絕緣層或阻焊層等。如此，在用於一次製作複數個半導體封裝體之大面積的印刷配線基板中，本實施形態的樹脂膜的硬化物亦可適用於構成該印刷配線基板之層間絕緣層或阻焊層。 The cured product of the resin film formed of the thermosetting resin composition of the present embodiment is used for the insulating layer, and can be used, for example, in an additive layer or a solder resist layer in a printed wiring board having no core layer, and is used in a PLP. An interlayer insulating layer or a solder resist layer of the coreless substrate, an interlayer insulating layer of the MIS substrate, or a solder resist layer. As described above, in the printed wiring board having a large area for producing a plurality of semiconductor packages at one time, the cured product of the resin film of the present embodiment can be applied to the interlayer insulating layer or the solder resist layer constituting the printed wiring board.
藉由將本實施形態的樹脂膜的硬化物利用於絕緣層，強韌性優異，因此在製造大面積的面板尺寸封裝體之面板級製程中，能夠抑制面板(無芯基板)的翹曲、或搬送時或安裝時之基板龜裂。 Since the cured product of the resin film of the present embodiment is used for the insulating layer, the toughness is excellent. Therefore, in the panel-level process for manufacturing a large-area panel-sized package, warpage of the panel (coreless substrate) can be suppressed, or The substrate is cracked during transport or installation.
並且，本實施形態的樹脂膜的硬化物中，能夠在具有柔軟骨架之基體樹脂中高填充無機填充材料。藉此，能夠降低上述樹脂膜的硬化物的線膨脹係數，因此能夠充分抑制獲得之半導體封裝體的翹曲。 Further, in the cured product of the resin film of the present embodiment, the inorganic filler can be highly filled in the matrix resin having a soft skeleton. Thereby, the linear expansion coefficient of the cured product of the resin film can be reduced, so that the warpage of the obtained semiconductor package can be sufficiently suppressed.
對本實施形態的熱硬化性樹脂組成物的各成分進行說明。 Each component of the thermosetting resin composition of the present embodiment will be described.
如上所述，本實施形態的熱硬化性樹脂組成物例如含有熱硬化性樹脂、硬化劑及無機填充材料。 As described above, the thermosetting resin composition of the present embodiment contains, for example, a thermosetting resin, a curing agent, and an inorganic filler.
(熱硬化性樹脂) (thermosetting resin)
作為熱硬化性樹脂，例如可以舉出環氧樹脂、順丁烯二醯亞胺化合物等。可以將該等單獨使用，亦可以將2種以上組合使用。本實施形態中，較佳為熱硬化性樹脂至少含有環氧樹脂或順丁烯二醯亞胺化合物，尤其較佳為含有環氧樹脂。 Examples of the thermosetting resin include an epoxy resin and a maleimide compound. These may be used alone or in combination of two or more. In the present embodiment, it is preferred that the thermosetting resin contains at least an epoxy resin or a maleimide compound, and particularly preferably an epoxy resin.
並且，本實施形態的熱硬化性樹脂在25℃室溫較佳為液態。藉此，能夠提高各成分在熱硬化性樹脂組成物中之分散性。並且，能夠提高無機填充材料的填充量。 Further, the thermosetting resin of the present embodiment is preferably liquid at room temperature at 25 ° C. Thereby, the dispersibility of each component in the thermosetting resin composition can be improved. Further, the filling amount of the inorganic filler can be increased.
本實施形態的熱硬化性樹脂在25℃之黏度的下限值例如為0.1Pa．s以上，較佳為0.5Pa．s以上，更佳為1Pa．s以上。藉此，能夠提高熱硬化性樹脂組成物的成膜性。另一方面，在25℃之黏度的上限值例如為200Pa．s以下，較佳為100Pa．s以下，更佳為50Pa．s以下。藉此，能夠提高熱硬化性樹脂組成物的分散性。 The lower limit of the viscosity of the thermosetting resin of the present embodiment at 25 ° C is, for example, 0.1 Pa. Above s, preferably 0.5 Pa. Above s, more preferably 1Pa. s above. Thereby, the film formability of the thermosetting resin composition can be improved. On the other hand, the upper limit of the viscosity at 25 ° C is, for example, 200 Pa. Below s, preferably 100 Pa. Below s, more preferably 50Pa. s below. Thereby, the dispersibility of the thermosetting resin composition can be improved.
本實施形態的環氧樹脂的環氧當量的下限值例如為300g/eq以上，較佳為330g/eq以上，更佳為350g/eq以上。藉此，能夠適當控制交聯點分子量，因此能夠實現最佳交聯密度的熱硬化性樹脂組成物的硬化物。並且，能夠提高熱硬化性樹脂組成物的硬化物的斷裂伸長率。另一方面，上述環氧當量的上限值並沒有特別限定，例如為700g/eq以下，較佳為600g/eq以下，更佳為500g/eq以下。藉此，能夠提高熱硬化性樹脂組成物的硬化物的強度。 The lower limit of the epoxy equivalent of the epoxy resin of the present embodiment is, for example, 300 g/eq or more, preferably 330 g/eq or more, and more preferably 350 g/eq or more. Thereby, the molecular weight of the crosslinking point can be appropriately controlled, and therefore, a cured product of the thermosetting resin composition having the optimum crosslinking density can be realized. Further, the elongation at break of the cured product of the thermosetting resin composition can be improved. On the other hand, the upper limit of the epoxy equivalent is not particularly limited, and is, for example, 700 g/eq or less, preferably 600 g/eq or less, and more preferably 500 g/eq or less. Thereby, the strength of the cured product of the thermosetting resin composition can be improved.
並且，本實施形態的環氧樹脂的重量平均分子量(Mw)的下限值並沒有特別限定，但較佳為Mw300以上，更佳為Mw800以上。若Mw為上述下限值以上，則能夠抑制樹脂膜的硬化物中產生黏性。Mw的上限值並沒有特別限定，但較佳為Mw20,000以下，更佳為Mw15,000以下。若Mw為上述上限值以下，則處理性得到提高，容易形成樹脂膜。環氧樹脂的Mw例如能夠利用GPC進行測量。 Further, the lower limit of the weight average molecular weight (Mw) of the epoxy resin of the present embodiment is not particularly limited, but is preferably Mw of 300 or more, and more preferably Mw of 800 or more. When Mw is at least the above lower limit value, it is possible to suppress the occurrence of stickiness in the cured product of the resin film. The upper limit of Mw is not particularly limited, but is preferably 20,000 or less, more preferably Mw15,000 or less. When Mw is at most the above upper limit value, handleability is improved, and a resin film is easily formed. The Mw of the epoxy resin can be measured, for example, by GPC.
本實施形態的環氧樹脂較佳為含有至少一種以上在25℃室溫為液態且其環氧當量在上述範圍內之第1環氧樹脂。 The epoxy resin of the present embodiment preferably contains at least one or more first epoxy resins which are liquid at room temperature at 25 ° C and have an epoxy equivalent in the above range.
作為第1環氧樹脂的種類，並沒有特別限定，例如可以舉出雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚E型環氧樹脂、雙酚S型環氧樹脂、雙酚M型環氧樹脂、雙酚P型環氧樹脂、雙酚Z型環氧樹脂等雙酚型環氧樹脂；苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、四酚基乙烷型酚醛清漆型環氧樹脂、具有縮合環芳香族烴結構之酚醛清漆型環氧樹脂等酚醛清漆型環氧樹脂；聯苯型環氧樹脂；伸二甲苯型環氧樹脂、聯苯基芳烷基型環氧樹脂等芳烷基型環氧樹脂；伸萘基醚型環氧樹脂、萘酚型環氧樹脂、萘二酚型環氧樹脂、2官能至4官能萘型環氧樹脂、聯萘型環氧樹脂、萘芳烷基型環氧樹脂等萘型環氧樹脂；蒽型環氧樹脂；苯氧基型環氧樹脂；二環戊二烯型環氧樹脂；降莰烯型環氧樹脂；金剛烷型環氧樹脂；茀型環氧樹脂；聚醚型環氧樹脂等。作為第1環氧樹脂，可以將該等單獨使用，亦可以將2種以上組合使用。在第1環氧樹脂中，從黏度的觀點考慮，能夠使用選自雙酚A型環氧樹脂、茀型環氧樹脂、2官能萘型環氧樹脂及聚醚型環氧樹脂中之至少一種以上。 The type of the first epoxy resin is not particularly limited, and examples thereof include a bisphenol A epoxy resin, a bisphenol F epoxy resin, a bisphenol E epoxy resin, and a bisphenol S epoxy resin. Bisphenol M type epoxy resin, bisphenol P type epoxy resin, bisphenol Z type epoxy resin and other bisphenol type epoxy resin; phenol novolak type epoxy resin, cresol novolak type epoxy resin, tetraphenol A novolak type epoxy resin such as a styrene-type epoxy resin, a novolak type epoxy resin having a condensed cyclic aromatic hydrocarbon structure, a biphenyl type epoxy resin, a xylene type epoxy resin, a biphenyl group Aralkyl type epoxy resin such as aralkyl type epoxy resin; stretch naphthyl ether type epoxy resin, naphthol type epoxy resin, naphthalene diphenol type epoxy resin, 2-functional to 4-functional naphthalene type epoxy resin , naphthalene type epoxy resin such as naphthalene type epoxy resin, naphthalene aralkyl type epoxy resin; bismuth type epoxy resin; phenoxy type epoxy resin; dicyclopentadiene type epoxy resin; Epoxy resin; adamantane type epoxy resin; bismuth type epoxy resin; polyether type epoxy resin. These first epoxy resins may be used alone or in combination of two or more. In the first epoxy resin, at least one selected from the group consisting of a bisphenol A epoxy resin, a fluorene epoxy resin, a bifunctional naphthalene epoxy resin, and a polyether epoxy resin can be used from the viewpoint of viscosity. the above.
並且，作為本實施形態的環氧樹脂，除了上述第1環氧樹脂以外，還可以併用其他的第2環氧樹脂。作為該第2環氧樹脂，能夠從作為第1環氧樹脂而舉出之環氧樹脂的種類中選擇。 Further, as the epoxy resin of the present embodiment, in addition to the above first epoxy resin, another second epoxy resin may be used in combination. The second epoxy resin can be selected from the types of epoxy resins which are mentioned as the first epoxy resin.
在環氧樹脂中，從能夠更進一步提高獲得之印刷配線基板的耐熱性及絕緣可靠性之觀點考慮，較佳為使用選自雙酚型環氧樹脂、酚醛清漆型環氧樹脂、聯苯型環氧樹脂、芳烷基型環氧樹脂、萘型環氧樹脂、蒽型環氧樹脂及二環戊二烯型環氧樹脂中之一種或兩種以上。並且，更佳為使用選自芳烷基型環氧樹脂、具有縮合環芳香族烴結構之酚醛清漆型環氧樹脂及萘型環氧樹脂中之一種或兩種以上。 In the epoxy resin, from the viewpoint of further improving the heat resistance and insulation reliability of the obtained printed wiring board, it is preferred to use a bisphenol type epoxy resin, a novolak type epoxy resin, or a biphenyl type. One or more of an epoxy resin, an aralkyl type epoxy resin, a naphthalene type epoxy resin, a fluorene type epoxy resin, and a dicyclopentadiene type epoxy resin. Further, it is more preferred to use one or more selected from the group consisting of an aralkyl type epoxy resin, a novolac type epoxy resin having a condensed cyclic aromatic hydrocarbon structure, and a naphthalene type epoxy resin.
環氧樹脂的含量的下限值相對於熱硬化性樹脂組成物整體(除溶劑以外的總固體成分)100重量%，較佳為3重量%以上，更佳為4重量%以上，進而較佳為5重量%以上為。若環氧樹脂的含量為上述下限值以上，則處理性得到提高，容易形成樹脂膜。另一方面，環氧樹脂的含量的上限值相對於熱硬化性樹脂組成物整體並沒有特別限定，例如較佳為60重量%以下，更佳為45重量%以下，進而較佳為30重量%以下為。若環氧樹脂的含量為上述上限值以下，則有時獲得之印刷配線基板的強度或阻燃性得到提高，或者印刷配線基板的線膨脹係數降低，翹曲的減少效果得到提高等。 The lower limit of the content of the epoxy resin is preferably 100% by weight or more, more preferably 3% by weight or more, more preferably 4% by weight or more, based on the total amount of the thermosetting resin composition (total solid content other than the solvent). It is 5% by weight or more. When the content of the epoxy resin is at least the above lower limit value, handleability is improved, and a resin film is easily formed. On the other hand, the upper limit of the content of the epoxy resin is not particularly limited, and is preferably, for example, 60% by weight or less, more preferably 45% by weight or less, and still more preferably 30% by weight. % below. When the content of the epoxy resin is at most the above upper limit value, the strength and flame retardancy of the printed wiring board obtained may be improved, or the linear expansion coefficient of the printed wiring board may be lowered, and the effect of reducing warpage may be improved.
另外，熱硬化性樹脂組成物的總固體成分係指熱硬化性樹脂組成物中所含之除溶劑以外的成分整體。以下，本說明書中相同。 In addition, the total solid content of the thermosetting resin composition means the whole component except the solvent contained in the thermosetting resin composition. Hereinafter, the same is true in the present specification.
(順丁烯二醯亞胺化合物) (m-butylene imine compound)
本實施形態的熱硬化性樹脂組成物能夠含有順丁烯二醯亞胺化合物。 The thermosetting resin composition of the present embodiment can contain a maleimide compound.
本實施形態中，順丁烯二醯亞胺化合物的順丁烯二醯亞胺基具有5員環的平面結構。並且，順丁烯二醯亞胺基的雙鍵在分子間容易相互作用，極性較高。因此，與具有順丁烯二醯亞胺基、苯環、其他平面結構之化合物等顯示較強的分子間相互作用，能夠抑制分子運動。因此，熱硬化性樹脂組成物藉由含有順丁烯二醯亞胺化合物，能夠減小獲得之絕緣層的線膨脹係數，並提高玻璃轉移溫度，進而能夠提高耐熱性。 In the present embodiment, the maleimide group of the maleimide compound has a planar structure of a 5-membered ring. Further, the double bond of the maleimide group is easily interacted between molecules and has a high polarity. Therefore, it exhibits strong intermolecular interaction with a compound having a maleimide group, a benzene ring, or other planar structure, and can suppress molecular motion. Therefore, by including the maleimide compound, the thermosetting resin composition can reduce the linear expansion coefficient of the obtained insulating layer, increase the glass transition temperature, and further improve heat resistance.
作為上述順丁烯二醯亞胺化合物，較佳為在分子內具有至少2個順丁烯二醯亞胺基之順丁烯二醯亞胺化合物。 The maleimide compound is preferably a maleimide compound having at least two maleimide groups in the molecule.
作為醯亞胺擴張型雙順丁烯二醯亞胺，例如可以舉出由以下的式(a1)表示之順丁烯二醯亞胺化合物、由以下的式(a2)表示之順丁烯二醯亞胺化合物、由以下的式(a3)表示之順丁烯二醯亞胺化合物等。作為由式(a1)表示之順丁烯二醯亞胺化合物的具體例，可以舉出BMI-1500(規劃者微粒公司製，分子量1500)等。作為由式(a2)表示之順丁烯二醯亞胺化合物的具體例，可以舉出BMI-1700(規劃者微粒公司製，分子量1700)、BMI-1400(規劃者微粒公司製，分子量1400)等。作為由式(a3)表示之順丁烯二醯亞胺化合物的具體例，可以舉出BMI-3000(規劃者微粒公司製，分子量3000)等。 For example, the maleimide compound represented by the following formula (a1) and the maleic acid represented by the following formula (a2) are exemplified as the bis-iminyl dipyrene diimide. The quinone imine compound, a maleimide compound represented by the following formula (a3), and the like. Specific examples of the maleimide compound represented by the formula (a1) include BMI-1500 (manufactured by Planner Fine Industries, Ltd., molecular weight: 1,500). Specific examples of the maleimide compound represented by the formula (a2) include BMI-1700 (manufactured by Planner Fine Particles Co., Ltd., molecular weight: 1700) and BMI-1400 (manufactured by Planner Microparticle Co., Ltd., molecular weight: 1400). Wait. Specific examples of the maleimide compound represented by the formula (a3) include BMI-3000 (manufactured by Planner Fine Particles Co., Ltd., molecular weight 3000).
上述式(a1)中，n表示1以上且10以下的整數。 In the above formula (a1), n represents an integer of 1 or more and 10 or less.
上述式(a2)中，n表示1以上且10以下的整數。 In the above formula (a2), n represents an integer of 1 or more and 10 or less.
上述式(a3)中，n表示1以上且10以下的整數。 In the above formula (a3), n represents an integer of 1 or more and 10 or less.
上述順丁烯二醯亞胺化合物的重量平均分子量(Mw)的下限值並沒有特別限定，但較佳為Mw400以上，特佳為Mw800以上。若Mw為上述下限值以上，則能夠抑制絕緣層中產生黏性。Mw的上限值並沒有特別限定，但較佳為Mw4000以下，更佳為Mw2500以下。若Mw為上述上限值以下，則製作絕緣層時，處理性得到提高，容易形成絕緣層。順丁烯二醯亞胺化合物的Mw例如能夠利用GPC(凝膠滲透層析術，標準物質：聚苯乙烯換算)進行測量。 The lower limit of the weight average molecular weight (Mw) of the above-mentioned maleimide compound is not particularly limited, but is preferably Mw of 400 or more, and particularly preferably Mw of 800 or more. When Mw is at least the above lower limit value, it is possible to suppress the occurrence of stickiness in the insulating layer. The upper limit of Mw is not particularly limited, but is preferably Mw 4000 or less, more preferably Mw 2500 or less. When Mw is at most the above upper limit value, when an insulating layer is formed, handleability is improved, and an insulating layer is easily formed. The Mw of the maleimide compound can be measured, for example, by GPC (gel permeation chromatography, standard material: polystyrene conversion).
並且，在兩末端具有順丁烯二醯亞胺基之上述醯亞胺擴張型雙順丁烯二醯亞胺的Mw能夠視為交聯點間分子量。 Further, the Mw of the above-described quinone imidazole-type dim-butylene iminoimide having a maleimide group at both ends can be regarded as a molecular weight between cross-linking points.
本實施形態中，熱硬化性樹脂組成物中所含之順丁烯二醯亞胺化合物的含量並沒有特別限定，當將熱硬化性樹脂組成物的總固體成分(亦即，除溶劑以外之成分)設為100重量%時，較佳為1.0重量%以上且25.0重量%以下，更佳為3.0重量%以上且20.0重量%以下。若順丁烯二醯亞胺化合物的含量在上述範圍內，則能夠更進一步提高獲得之絕緣層的低熱收縮性及耐藥品性的平衡。 In the present embodiment, the content of the maleimide compound contained in the thermosetting resin composition is not particularly limited, and the total solid content of the thermosetting resin composition (that is, the solvent other than the solvent) is not particularly limited. When the component is 100% by weight, it is preferably 1.0% by weight or more and 25.0% by weight or less, more preferably 3.0% by weight or more and 20.0% by weight or less. When the content of the maleimide compound is within the above range, the balance between the low heat shrinkability and the chemical resistance of the obtained insulating layer can be further improved.
(苯并(benzoxazine)化合物) (Benzene (benzoxazine) compound)
本實施形態的熱硬化性樹脂組成物可以含有苯并化合物。 The thermosetting resin composition of the present embodiment may contain benzo Compound.
苯并化合物為具有苯并環之化合物。作為苯并化合物，例如能夠使用選自由下述式(2)表示之化合物、由下述式(3)表示之化合物中之一種或兩種以上。 Benzo Compound with benzo a compound of the ring. Benzo For the compound, for example, one or two or more selected from the group consisting of a compound represented by the following formula (2) and a compound represented by the following formula (3) can be used.
(上述式(2)中，X2分別獨立地為碳數1以上且10以下的伸烷基、下述式(1a)表示之基、“-SO2-”表示之基、“-CO-”表示之基、氧原子或單鍵，R2分別獨立地為碳數1以上且6以下的烴基，c分別獨立地為0以上且4以下的整數。) (In the above formula (2), X 2 is independently an alkylene group having 1 or more and 10 or less carbon atoms, a group represented by the following formula (1a), a group represented by "-SO 2 -", and "-CO-". "denotes the group, an oxygen atom or a single bond, R 2 are each independently a carbon number of 1 or more and 6 or less hydrocarbon groups, C are each independently an integer of 0 or more and 4 or less.)
(上述式(3)中，X3分別獨立地為碳數1以上且10以下的伸烷基、下述式(1a)表示之基、“-SO2-”表示之基、“-CO-”表示之基、氧原子或單鍵，R3分別獨立地為碳數1以上且6以下的烴基，d分別獨立地為0以上且4以下的整數。) (In the above formula (3), X 3 is each independently an alkylene group having 1 or more and 10 or less carbon atoms, a group represented by the following formula (1a), a group represented by "-SO 2 -", and "-CO-". " represents a group, an oxygen atom or a single bond, and each of R 3 is independently a hydrocarbon group having 1 or more and 6 or less carbon atoms, and d is independently an integer of 0 or more and 4 or less.)
(上述式(1a)中，Y為具有芳香族環之碳數6以上且30以下的烴基，n2為0以上的整數。) (In the above formula (1a), Y is a hydrocarbon group having an aromatic ring having 6 or more and 30 or less carbon atoms, and n 2 is an integer of 0 or more.)
上述式(1a)中，具有芳香族環之碳數6以上且30以下的烴基可以僅由芳香族環構成，亦可以具有除芳香族環以外的烴基。Y所具有之芳香族環可以是1個，亦可以是2個以上。當Y具有2個以上的芳香族環時，該等芳香族環可以相同亦可以不同。並且，上述芳香族環可以是單環結構及多環結構中的任一種。 In the above formula (1a), the hydrocarbon group having 6 or more and 30 or less carbon atoms of the aromatic ring may be composed only of an aromatic ring, or may have a hydrocarbon group other than the aromatic ring. Y may have one or more aromatic rings. When Y has two or more aromatic rings, the aromatic rings may be the same or different. Further, the aromatic ring may be any of a monocyclic structure and a polycyclic structure.
作為具有芳香族環之碳數6以上且30以下的烴基，例如可以舉出從苯、聯苯、萘、蒽、茀、菲、二環戊二烯并苯(indacene)、聯三苯(terphenyl)、苊(acenaphthylene)、萉(phenalene)等具有芳香族性之化合物的核中除去 2個氫原子而成之2價的基。 Examples of the hydrocarbon group having an aromatic ring having 6 or more and 30 or less carbon atoms include benzene, biphenyl, naphthalene, anthracene, anthracene, phenanthrene, indacene, and terphenyl. A divalent group in which two hydrogen atoms are removed from the core of an aromatic compound such as acenaphthylene or phenalene.
並且，該等芳香族烴基可以具有取代基。在此，芳香族烴基具有取代基係指構成芳香族烴基之氫原子的一部分或全部被取代基取代。作為取代基，例如可以舉出烷基。 Further, the aromatic hydrocarbon groups may have a substituent. Here, the substituent of the aromatic hydrocarbon group means that a part or the whole of the hydrogen atom constituting the aromatic hydrocarbon group is substituted with a substituent. As a substituent, an alkyl group is mentioned, for example.
作為該取代基之烷基較佳為鏈狀的烷基。並且，其碳數較佳為1以上且10以下，更佳為1以上且6以下，特佳為1以上且4以下。具體而言，可以舉出甲基、乙基、丙基、異丙基、丁基、三級丁基、二級丁基等。 The alkyl group as the substituent is preferably a chain alkyl group. Further, the carbon number is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less, and particularly preferably 1 or more and 4 or less. Specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tertiary butyl group, and a secondary butyl group.
該種基Y較佳具有從苯或萘中除去2個氫原子而成之基，作為上述式(1a)表示之基，更佳為下述式(1a-1)、(1a-2)中的任一個表示之基。藉此，由熱硬化性樹脂組成物獲得之絕緣層發揮優異之耐熱性。 The group Y preferably has a group in which two hydrogen atoms are removed from benzene or naphthalene, and is represented by the above formula (1a), and more preferably in the following formulas (1a-1) and (1a-2). Any of the bases of the representation. Thereby, the insulating layer obtained from the thermosetting resin composition exhibits excellent heat resistance.
上述式(1a-1)、(1a-2)中，R4分別獨立地為碳數1以上且6以下的烴基。e分別獨立地為0以上且4以下的整數，更佳為0。 In the above formulae (1a-1) and (1a-2), R 4 is each independently a hydrocarbon group having 1 or more and 6 or less carbon atoms. e is independently an integer of 0 or more and 4 or less, and more preferably 0.
另外，在上述式(1a)表示之基中，n2為0以上的整數即可，較佳為0以上且5以下的整數，更佳為1以上且3以下的整數，特佳為1或2。 Further, in the group represented by the above formula (1a), n 2 may be an integer of 0 or more, preferably an integer of 0 or more and 5 or less, more preferably an integer of 1 or more and 3 or less, particularly preferably 1 or more. 2.
上述式(2)及上述式(3)中之X2及X3例如較佳分別獨立地為碳數1以上且10以下的直鏈狀或支鏈狀的伸烷基。作為該直鏈狀的伸烷基，具體而言，可以舉出亞甲基、伸乙基、伸丙基、伸丁基、伸戊基、伸己基、伸庚基、伸辛基、伸壬基、伸癸基、三亞甲基、四亞甲基、五亞甲基、六亞甲基等。並且，作為支鏈狀的伸烷基，具體而言，可以舉出-C(CH3)2-(伸異丙基)、-CH(CH3)-、-CH(CH2CH3)-、-C(CH3)(CH2CH3)-、-C(CH3)(CH2CH2CH3)-、-C(CH2CH3)2-等烷基亞甲基；-CH(CH3)CH2-、-CH(CH3)CH(CH3)-、-C(CH3)2CH2-、-CH(CH2CH3)CH2-、-C(CH2CH3)2-CH2-等烷基伸乙基等。 X 2 and X 3 in the above formula (2) and the above formula (3) are preferably each independently a linear or branched alkylene group having 1 or more and 10 or less carbon atoms. Specific examples of the linear alkylene group include a methylene group, an exoethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an exopeptide group, and a hydrazine group. Base, thiol, trimethylene, tetramethylene, pentamethylene, hexamethylene and the like. Further, examples of the branched alkylene group include -C(CH 3 ) 2 -(extended isopropyl), -CH(CH 3 )-, -CH(CH 2 CH 3 )-. , -C(CH 3 )(CH 2 CH 3 )-, -C(CH 3 )(CH 2 CH 2 CH 3 )-, -C(CH 2 CH 3 ) 2 -, etc. alkylmethylene; -CH (CH 3 )CH 2 -, -CH(CH 3 )CH(CH 3 )-, -C(CH 3 ) 2 CH 2 -, -CH(CH 2 CH 3 )CH 2 -, -C(CH 2 CH 3 ) 2 -CH 2 -etc.
並且，X2及X3中之伸烷基的碳數係1以上且10以下即可，但更佳為1以上且7以下，進而較佳為1以上且3以下。具體而言，作為具有該種碳數之伸烷基，例如可以舉出亞甲基、伸乙基、伸丙基、伸異丙基。 Further, the carbon number of the alkylene group in X 2 and X 3 may be 1 or more and 10 or less, and more preferably 1 or more and 7 or less, and still more preferably 1 or more and 3 or less. Specifically, examples of the alkylene group having such a carbon number include a methylene group, an exoethyl group, a stretched propyl group, and an extended isopropyl group.
並且，上述式(2)及上述式(3)中之R2及R3例如分別獨立地為碳數1以上且6以下的烴基，較佳為碳數1或2的烴基，具體而言，為甲基或乙基。 Further, in the above formula (2) and the above formula (3), R 2 and R 3 are each independently a hydrocarbon group having 1 or more and 6 or less carbon atoms, preferably a hydrocarbon group having 1 or 2 carbon atoms. Specifically, It is a methyl or ethyl group.
並且，上述式(2)及上述式(3)中之c及d例如分別獨立地為0以上且4以下的整數，較佳為0以上且2以下的整數，更佳為0。 Further, c and d in the above formula (2) and the above formula (3) are each independently an integer of 0 or more and 4 or less, preferably an integer of 0 or more and 2 or less, and more preferably 0.
在上述式(2)表示之化合物及上述式(3)表示之化合物中，該種苯并化合物較佳為上述式(2)表示之化合物。藉此，由熱硬化 性樹脂組成物獲得之絕緣層能夠發揮更優異之低熱收縮性及耐藥品性。 In the compound represented by the above formula (2) and the compound represented by the above formula (3), the benzoic acid The compound is preferably a compound represented by the above formula (2). Thereby, the insulating layer obtained from the thermosetting resin composition can exhibit more excellent low heat shrinkability and chemical resistance.
並且，該上述式(2)表示之化合物中，較佳上述X2為碳數1以上且3以下的直鏈狀或支鏈狀的伸烷基，R2為1或2的烴基，c為0以上且2以下的整數。或者，上述X2為上述式(1a-1)、(1a-2)中的任一個所表示之基，c較佳為0。藉此，由熱硬化性樹脂組成物獲得之絕緣層能夠發揮更優異之低熱收縮性及耐藥品性。 Further, in the compound represented by the above formula (2), it is preferred that the X 2 is a linear or branched alkylene group having 1 or more and 3 or less carbon atoms, and R 2 is a hydrocarbon group of 1 or 2, and c is An integer of 0 or more and 2 or less. Alternatively, X 2 is a group represented by any one of the above formulas (1a-1) and (1a-2), and c is preferably 0. Thereby, the insulating layer obtained from the thermosetting resin composition can exhibit more excellent low heat shrinkability and chemical resistance.
作為苯并化合物的較佳的具體例，例如可以舉出選自由下述式(2-1)表示之化合物、由下述式(2-2)表示之化合物、由下述式(2-3)表示之化合物、由下述式(3-1)表示之化合物、由下述式(3-2)表示之化合物及由下述式(3-3)表示之化合物中之一種或兩種以上。 Benzo Preferable specific examples of the compound include a compound represented by the following formula (2-1), a compound represented by the following formula (2-2), and a formula (2-3). The compound, a compound represented by the following formula (3-1), a compound represented by the following formula (3-2), and one or more compounds represented by the following formula (3-3).
(上述式(2-3)中，R分別獨立地為碳數1~4的烴基。) (In the above formula (2-3), R is independently a hydrocarbon group having 1 to 4 carbon atoms.)
熱硬化性樹脂組成物中所含之苯并化合物的含量並沒有特別限定，當將熱硬化性樹脂組成物的總固體成分(亦即，除溶劑以外的成分)設為100重量%時，較佳為1.0重量%以上且25.0重量%以下，更佳為3.0重量%以上且20.0重量%以下。若苯并化合物的含量在上述範 圍內，則能夠更進一步提高獲得之絕緣層的低熱收縮性及耐藥品性。 Benzoin contained in the thermosetting resin composition The content of the compound is not particularly limited, and when the total solid content (that is, the component other than the solvent) of the thermosetting resin composition is 100% by weight, it is preferably 1.0% by weight or more and 25.0% by weight or less. More preferably, it is 3.0% by weight or more and 20.0% by weight or less. Benzo When the content of the compound is within the above range, the low heat shrinkability and chemical resistance of the obtained insulating layer can be further improved.
(無機填充材料) (inorganic filler)
本實施形態的熱硬化性樹脂組成物能夠含有無機填充材料。 The thermosetting resin composition of the present embodiment can contain an inorganic filler.
作為無機填充材料，例如能夠舉出滑石、燒成黏土、未燒成黏土、雲母、玻璃等矽酸鹽；氧化鈦、氧化鋁、水鋁石、二氧化矽、熔融二氧化矽等氧化物；碳酸鈣、碳酸鎂、水滑石等碳酸鹽；氫氧化鋁、氫氧化鎂、氫氧化鈣等氫氧化物；硫酸鋇、硫酸鈣、亞硫酸鈣等硫酸鹽或亞硫酸鹽；硼酸鋅、偏硼酸鋇、硼酸鋁、硼酸鈣、硼酸鈉等硼酸鹽；氮化鋁、氮化硼、氮化矽、氮化碳等氮化物；鈦酸鍶、鈦酸鋇等鈦酸鹽等。 Examples of the inorganic filler include talc such as talc, fired clay, unfired clay, mica, and glass; oxides such as titanium oxide, aluminum oxide, diaspore, cerium oxide, and molten cerium oxide; Carbonate such as calcium carbonate, magnesium carbonate or hydrotalcite; hydroxide such as aluminum hydroxide, magnesium hydroxide or calcium hydroxide; sulfate or sulfite such as barium sulfate, calcium sulfate or calcium sulfite; zinc borate and metaboric acid Boric acid such as barium, aluminum borate, calcium borate or sodium borate; nitride such as aluminum nitride, boron nitride, tantalum nitride or carbon nitride; titanate such as barium titanate or barium titanate.
在該等之中，較佳為滑石、氧化鋁、玻璃、二氧化矽、雲母、氫氧化鋁、氫氧化鎂，特佳為二氧化矽。作為無機填充材料，可以單獨使用該等之中的1種，亦可以併用2種以上。 Among these, talc, alumina, glass, cerium oxide, mica, aluminum hydroxide, magnesium hydroxide, and particularly preferably cerium oxide are preferable. As the inorganic filler, one type of these may be used alone or two or more types may be used in combination.
上述無機填充材料的平均粒徑的下限值並沒有特別限定，例如較佳為0.01μm以上，更佳為0.05μm以上，進而較佳為0.5μm以上。藉此，能夠抑制上述熱硬化性樹脂的清漆的黏度變高，能夠提高製作絕緣層時的作業性。並且，無機填充材料的平均粒徑的上限值並沒有特別限定，例如較佳為5.0μm以下，更佳為2.0μm以下，進而較佳為1.0μm以下。藉此，能夠抑制在上述熱硬化性樹脂的清漆中無機填充材料的沉降等現象，能夠獲得更均勻的樹脂膜。並且，在印刷配線基板的電路尺寸L/S小於20μm/20μm時，能夠抑制對配線之間的絕緣性帶來影響。 The lower limit of the average particle diameter of the inorganic filler is not particularly limited, and is, for example, preferably 0.01 μm or more, more preferably 0.05 μm or more, and still more preferably 0.5 μm or more. Thereby, it is possible to suppress the viscosity of the varnish of the thermosetting resin to be high, and it is possible to improve the workability in producing the insulating layer. Further, the upper limit of the average particle diameter of the inorganic filler is not particularly limited, and is, for example, preferably 5.0 μm or less, more preferably 2.0 μm or less, still more preferably 1.0 μm or less. Thereby, it is possible to suppress a phenomenon such as sedimentation of the inorganic filler in the varnish of the thermosetting resin, and it is possible to obtain a more uniform resin film. Further, when the circuit size L/S of the printed wiring board is less than 20 μm/20 μm, it is possible to suppress the influence on the insulation between the wirings.
本實施形態中，無機填充材料的平均粒徑例如能夠藉由雷射繞射式粒度分佈測量裝置(堀場製作所股份有限公司製，LA-500)，以體積基準測量粒 子的粒度分佈，將其中值直徑(D50)作為平均粒徑。 In the present embodiment, the average particle diameter of the inorganic filler can be measured by a laser diffraction type particle size distribution measuring apparatus (LA-500, manufactured by Horiba, Ltd., LA), and the particle size distribution of the particles can be measured on a volume basis. The diameter (D50) is taken as the average particle diameter.
並且，本實施形態中，當無機填充材料的含量為65重量%以上時，該無機填充材料的平均粒徑的下限值例如較佳為0.5μm以上，更佳為0.6μm以上，進而較佳為0.8μm以上。另一方面，該無機填充材料的平均粒徑的下限值例如較佳為2μm以下，更佳為1.9μm以下，進而較佳為1.8μm以下。藉由將無機填充材料的含量設在上述範圍內，能夠減少樹脂膜的硬化物的翹曲，並且進一步提高強度。 In the present embodiment, when the content of the inorganic filler is 65% by weight or more, the lower limit of the average particle diameter of the inorganic filler is preferably 0.5 μm or more, more preferably 0.6 μm or more, and further preferably It is 0.8 μm or more. On the other hand, the lower limit of the average particle diameter of the inorganic filler is, for example, preferably 2 μm or less, more preferably 1.9 μm or less, still more preferably 1.8 μm or less. By setting the content of the inorganic filler in the above range, it is possible to reduce the warpage of the cured product of the resin film and further improve the strength.
並且，無機填充材料並沒有特別限定，既可以使用平均粒徑為單分散的無機填充材料，亦可以使用平均粒徑為多分散的無機填充材料。另外，亦可以併用1種或2種以上平均粒徑為單分散和/或多分散的無機填充材料。 Further, the inorganic filler is not particularly limited, and an inorganic filler having an average particle diameter of monodisperse may be used, or an inorganic filler having an average particle diameter of polydisperse may be used. Further, one type or two or more types of inorganic fillers having an average particle diameter of monodisperse and/or polydisperse may be used in combination.
上述無機填充材料較佳含有二氧化矽粒子。上述二氧化矽粒子的平均粒徑並沒有特別限定，例如較佳為5.0μm以下，更佳為0.1μm以上且4.0μm以下，進而較佳為0.2μm以上且2.0μm以下。若使用之二氧化矽粒子的平均粒徑在上述範圍內，則能夠進一步提高無機填充材料對樹脂膜之填充性。 The inorganic filler preferably contains cerium oxide particles. The average particle diameter of the cerium oxide particles is not particularly limited, and is, for example, preferably 5.0 μm or less, more preferably 0.1 μm or more and 4.0 μm or less, and still more preferably 0.2 μm or more and 2.0 μm or less. When the average particle diameter of the cerium oxide particles used is within the above range, the filling property of the inorganic filler with respect to the resin film can be further improved.
無機填充材料的含量的下限值相對於熱硬化性樹脂組成物的總固體成分100重量%並沒有特別限定，例如較佳為65重量%以上，更佳為70重量%以上，進而較佳為75重量%以上。藉此，尤其能夠降低樹脂膜的硬化物熱膨脹率，並且尤其能夠降低其吸水率。藉此，能夠抑制半導體封裝體的翹曲。並且，本實施形態的樹脂膜的硬化物能夠以維持高伸長率之狀態提高無機填充材料的含量，因此能夠提高應力緩和性。另一方面， 無機填充材料的含量的上限值相對於熱硬化性樹脂組成物的總固體成分100重量%並沒有特別限定，例如較佳為98重量%以下，更佳為95重量%以下，進而較佳為90重量%以下。藉由無機填充材料的含量在上述範圍內，能夠提高樹脂膜的硬化物的加工性。 The lower limit of the content of the inorganic filler is not particularly limited as long as it is 100% by weight based on the total solid content of the thermosetting resin composition, and is preferably, for example, 65% by weight or more, more preferably 70% by weight or more, and still more preferably 75 wt% or more. Thereby, in particular, the thermal expansion rate of the cured product of the resin film can be lowered, and in particular, the water absorption rate thereof can be lowered. Thereby, warping of the semiconductor package can be suppressed. Further, in the cured product of the resin film of the present embodiment, the content of the inorganic filler can be increased while maintaining a high elongation, and thus the stress relaxation property can be improved. On the other hand, the upper limit of the content of the inorganic filler is not particularly limited, and is preferably 98% by weight or less, and more preferably 95% by weight or less, based on 100% by weight of the total solid content of the thermosetting resin composition. Further, it is preferably 90% by weight or less. When the content of the inorganic filler is within the above range, the workability of the cured product of the resin film can be improved.
(硬化劑) (hardener)
本實施形態的熱硬化性樹脂組成物能夠含有硬化劑。 The thermosetting resin composition of the present embodiment can contain a curing agent.
作為上述硬化劑並沒有特別限定，例如可以舉出苄基二甲胺(BDMA)、2,4,6-三-二甲基胺基甲基苯酚(DMP-30)等3級胺化合物；2-甲基咪唑、2-乙基-4-甲基咪唑(EMI24)、2-苯基-4-甲基咪唑(2P4MZ)、2-苯基咪唑(2PZ)、2-苯基-4-甲基-5-羥基咪唑(2P4MHZ)、1-苄基-2-苯基咪唑(1B2PZ)等咪唑化合物；BF3錯合物等路易斯酸等催化劑型的硬化劑。 The curing agent is not particularly limited, and examples thereof include a tertiary amine compound such as benzyldimethylamine (BDMA) or 2,4,6-tris-dimethylaminomethylphenol (DMP-30); -methylimidazole, 2-ethyl-4-methylimidazole (EMI24), 2-phenyl-4-methylimidazole (2P4MZ), 2-phenylimidazole (2PZ), 2-phenyl-4-methyl An imidazole compound such as a 5-hydroxyimidazole (2P4MHZ) or 1-benzyl-2-phenylimidazole (1B2PZ); or a catalyst type curing agent such as a Lewis acid such as a BF 3 complex.
並且，例如亦能夠使用除了二伸乙基三胺(DETA)、三伸乙基四胺(TETA)、間二甲苯二胺(MXDA)等脂肪族多胺、間伸苯二胺、對伸苯二胺、鄰二甲苯二胺、4,4'-二胺基二苯基甲烷、4,4'-二胺基二苯基丙烷、4,4'-二胺基二苯基醚、4,4'-二胺基二苯基碸、3,3'-二胺基二苯基碸、1,5-二胺基萘、4,4'-(對伸苯基二亞異丙基)二苯胺、2,2-[4-(4-胺基苯氧基)苯基]丙烷、4,4'-二胺基-3,3'-二甲基二苯基甲烷、4,4'-二胺基-3,3'-二乙基-5,5'-二甲基二苯基甲烷、3,3'-二乙基-4,4'-二胺基二苯基甲烷等芳香族多胺以外，包括二氰二胺(DICY)、有機酸二醯肼等之多胺化合物；包括六氫酞酸酐(HHPA)、甲基四氫酞酸酐(MTHPA)等脂環族酸酐、偏苯三甲酸酐(TMA)、均苯四甲酸酐(PMDA)、二苯甲酮四羧酸二酐(BTDA)等芳香族酸酐等之酸酐；多硫化物、硫酯、硫醚等多硫醇化合物；異氰酸酯預聚物、封端異氰酸酯等 異氰酸酯化合物；含羧酸之聚酯樹脂等有機酸類等聚加成型的硬化劑；2,2'-亞甲基雙(4-乙基-6-三級丁基苯酚)、2,2'-亞甲基雙(4-甲基-6-三級丁基苯酚)、4,4'-伸丁基雙(3-甲基-6-三級丁基苯酚)、4,4'-硫代雙(3-甲基-6-三級丁基苯酚)、2,6-二-三級丁基-4-甲基苯酚、2,5-二-三級丁基對苯二酚、1,3,5-三(3,5-二-三級丁基-4-羥基苄基)-1,3,5-三-2,4,6(1H,3H,5H)三酮等酚系化合物。 Further, for example, an aliphatic polyamine such as diethyltriamine (DETA), triethylethylenetetramine (TETA) or m-xylenediamine (MXDA), an exophenyleneamine, or a parabens can also be used. Diamine, o-xylene diamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, 4, 4'-Diaminodiphenylanthracene, 3,3'-diaminodiphenylanthracene, 1,5-diaminonaphthalene, 4,4'-(p-phenylenediphenylene) Aniline, 2,2-[4-(4-aminophenoxy)phenyl]propane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'- Aromatic amines such as diamino-3,3'-diethyl-5,5'-dimethyldiphenylmethane and 3,3'-diethyl-4,4'-diaminodiphenylmethane In addition to polyamines, polyamine compounds including dicyandiamide (DICY) and organic acid bismuth; alicyclic anhydrides such as hexahydrophthalic anhydride (HHPA), methyltetrahydrophthalic anhydride (MTHPA), and benzene An acid anhydride such as an aromatic acid anhydride such as tricarboxylic anhydride (TMA), pyromellitic anhydride (PMDA) or benzophenone tetracarboxylic dianhydride (BTDA); or a polythiol compound such as polysulfide, thioester or thioether; Isocyanate prepolymer, blocked isocyanate, etc. a polyaddition hardening agent such as an acid ester compound; an organic acid such as a carboxylic acid-containing polyester resin; 2,2'-methylenebis(4-ethyl-6-tertiarybutylphenol), 2,2' -methylene bis(4-methyl-6-tertiary butyl phenol), 4,4'-tert-butyl bis(3-methyl-6-tertiary butyl phenol), 4,4'-sulfur Bis(3-methyl-6-tertiary butylphenol), 2,6-di-tertiary butyl-4-methylphenol, 2,5-di-tertiary butyl hydroquinone, 1 ,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-three a phenolic compound such as a 2,4,6 (1H, 3H, 5H) triketone.
另外，作為第2硬化劑，例如亦可以使用酚醛清漆型酚樹脂、甲階酚醛型酚樹脂等酚樹脂系硬化劑；如含羥甲基之尿素樹脂之類的尿素樹脂；如含羥甲基之三聚氰胺樹脂之類的三聚氰胺樹脂等縮合型的硬化劑。該等可以單獨使用，亦可以將2種以上組合使用。 Further, as the second curing agent, for example, a phenol resin-based curing agent such as a novolac type phenol resin or a resol type phenol resin; a urea resin such as a methylol-containing urea resin; and a methylol group-containing resin may be used. A condensing type curing agent such as a melamine resin such as a melamine resin. These may be used alone or in combination of two or more.
上述酚樹脂系硬化劑為在一個分子內具有2個以上酚性羥基之單體、寡聚物、聚合物整體，其分子量、分子結構並沒有特別限定，例如可以舉出苯酚酚醛清漆樹脂、甲酚酚醛清漆樹脂、萘酚酚醛清漆樹脂等酚醛清漆型酚樹脂；三酚甲烷型酚樹脂等多官能型酚樹脂；萜改質酚樹脂、二環戊二烯改質酚樹脂等改質酚樹脂；具有伸苯基骨架和/或伸聯苯基骨架之酚芳烷基樹脂、具有伸苯基和/或伸聯苯基骨架之萘酚芳烷基樹脂等芳烷基型樹脂；雙酚A、雙酚F等雙酚化合物等。該等可以單獨使用1種，亦可以併用2種以上。在該等之中，從硬化性的觀點考慮，可以使用羥基當量為90g/eq以上且250g/eq以下的酚樹脂系硬化劑。 The phenol resin-based curing agent is a monomer, an oligomer, or a polymer having two or more phenolic hydroxyl groups in one molecule, and the molecular weight and molecular structure thereof are not particularly limited, and examples thereof include a phenol novolak resin and a Non-phenolic phenol resin such as phenol novolac resin, naphthol novolac resin; polyfunctional phenol resin such as trisphenol methane phenol resin; modified phenol resin such as phenol modified resin or dicyclopentadiene modified phenol resin An aralkyl type resin such as a phenol aralkyl resin having a pendant phenyl skeleton and/or a biphenyl skeleton, a naphthol aralkyl resin having a pendant phenyl group and/or a phenyl group extending; a bisphenol A , bisphenol compounds such as bisphenol F, and the like. These may be used alone or in combination of two or more. Among these, a phenol resin-based curing agent having a hydroxyl group equivalent of 90 g/eq or more and 250 g/eq or less can be used from the viewpoint of curability.
酚樹脂的重量平均分子量並沒有特別限定，但重量平均分子量較佳為4×102以上且1.8×103以下，更佳為5×102以上且1.5×103以下。藉由將重量平均分子量設為上述下限值以上，難以發生預浸體中產生黏性等問題，藉由 設為上述上限值以下，在製作預浸體時，在纖維基材中之含浸性得到提高，能夠獲得更均勻的產品。 The weight average molecular weight of the phenol resin is not particularly limited, but the weight average molecular weight is preferably 4 × 10 2 or more and 1.8 × 10 3 or less, more preferably 5 × 10 2 or more and 1.5 × 10 3 or less. When the weight average molecular weight is at least the above lower limit value, problems such as generation of stickiness in the prepreg are less likely to occur, and when the prepreg is produced at a temperature equal to or lower than the above upper limit, impregnation in the fiber base material is performed. Sexuality is improved and a more uniform product can be obtained.
硬化劑的含量的下限值相對於熱硬化性樹脂組成物的總固體成分100重量%並沒有特別限定，例如較佳為0.01重量%以上，更佳為0.05重量%以上，進而較佳為0.2重量%以上。藉由將硬化劑的含量設為上述下限值以上，能夠充分發揮促進硬化之效果。另一方面，硬化劑的含量的上限值相對於熱硬化性樹脂組成物的總固體成分100重量%並沒有特別限定，例如較佳為15重量%以下，更佳為10重量%以下，進而較佳為8重量%以下。若硬化劑的含量為上述上限值以下，則能夠進一步提高預浸體的保存性。 The lower limit of the content of the curing agent is not particularly limited, and is preferably 0.01% by weight or more, more preferably 0.05% by weight or more, and still more preferably 0.2% by weight based on 100% by weight of the total solid content of the thermosetting resin composition. More than weight%. When the content of the curing agent is at least the above lower limit value, the effect of promoting hardening can be sufficiently exhibited. On the other hand, the upper limit of the content of the curing agent is not particularly limited, and is preferably 15% by weight or less, more preferably 10% by weight or less, based on 100% by weight of the total solid content of the thermosetting resin composition. It is preferably 8% by weight or less. When the content of the curing agent is at most the above upper limit value, the preservability of the prepreg can be further improved.
(氰酸酯樹脂) (cyanate resin)
本實施形態的熱硬化性樹脂組成物能夠進一步含有氰酸酯樹脂。 The thermosetting resin composition of the present embodiment can further contain a cyanate resin.
氰酸酯樹脂在分子內具有氰酸酯基(-O-CN)，能夠使用在分子內具有2個以上氰酸酯基之樹脂。作為該種氰酸酯樹脂並沒有特別限定，例如能夠藉由使鹵化氰化合物與酚類或萘酚類進行反應並且依據需要利用加熱等方法進行預聚物化而獲得。並且，亦能夠使用如此製備出之市售品。 The cyanate resin has a cyanate group (-O-CN) in the molecule, and a resin having two or more cyanate groups in the molecule can be used. The cyanate resin is not particularly limited, and can be obtained, for example, by reacting a halogenated cyanide compound with a phenol or a naphthol, and prepolymerizing it by a method such as heating as needed. Further, a commercially available product thus prepared can also be used.
藉由使用氰酸酯樹脂，能夠減小樹脂膜的硬化物的線膨脹係數。另外，能夠提高樹脂膜的硬化物的電氣特性(低介電常數、低介電損耗角正切)、機械強度等。 By using a cyanate resin, the linear expansion coefficient of the cured product of the resin film can be reduced. Further, electrical properties (low dielectric constant, low dielectric loss tangent), mechanical strength, and the like of the cured product of the resin film can be improved.
氰酸酯樹脂例如能夠舉出酚醛清漆型氰酸酯樹脂；雙酚A型氰酸酯樹脂、雙酚E型氰酸酯樹脂、四甲基雙酚F型氰酸酯樹脂等雙酚型氰酸酯樹脂；藉由萘酚芳烷基型酚樹脂與鹵化氰的反應而獲得之萘酚芳 烷基型氰酸酯樹脂；二環戊二烯型氰酸酯樹脂；聯苯烷基型氰酸酯樹脂等。在該等之中，較佳為酚醛清漆型氰酸酯樹脂、萘酚芳烷基型氰酸酯樹脂，更佳為酚醛清漆型氰酸酯樹脂。藉由使用酚醛清漆型氰酸酯樹脂，樹脂膜的硬化物的交聯密度增加，耐熱性得到提高。 Examples of the cyanate resin include a novolac type cyanate resin; a bisphenol type cyanate resin, a bisphenol E type cyanate resin, and a tetramethyl bisphenol F type cyanate resin; Acid ester resin; naphthol aralkyl type cyanate resin obtained by reaction of naphthol aralkyl type phenol resin with cyanogen halide; dicyclopentadiene type cyanate resin; biphenyl alkyl type cyanide An acid ester resin or the like. Among these, a novolak type cyanate resin or a naphthol aralkyl type cyanate resin is preferable, and a novolak type cyanate resin is more preferable. By using a novolac type cyanate resin, the crosslinking density of the cured product of the resin film is increased, and heat resistance is improved.
作為其理由，可以舉出酚醛清漆型氰酸酯樹脂在硬化反應後形成三環。另外，認為是由於酚醛清漆型氰酸酯樹脂在其結構上苯環的比例較高，容易碳化。並且，含有酚醛清漆型氰酸酯樹脂之樹脂膜的硬化物具有優異之剛性。藉此，能夠更進一步提高樹脂膜的硬化物的耐熱性。 For this reason, it can be mentioned that the novolac type cyanate resin forms three after the hardening reaction. ring. Further, it is considered that the novolac type cyanate resin has a high proportion of a benzene ring in its structure and is easily carbonized. Further, the cured product of the resin film containing the novolac type cyanate resin has excellent rigidity. Thereby, the heat resistance of the cured product of the resin film can be further improved.
作為酚醛清漆型氰酸酯樹脂，例如能夠使用下述通式(I)表示之樹脂。 As the novolac type cyanate resin, for example, a resin represented by the following formula (I) can be used.
通式(I)表示之酚醛清漆型氰酸酯樹脂的平均重複單元n為任意的整數。平均重複單元n並沒有特別限定，但較佳為1以上，更佳為2以上。若平均重複單元n為上述下限值以上，則酚醛清漆型氰酸酯樹脂的耐熱性得到提高，能夠抑制加熱時寡聚物脫離、揮發。並且，平均重複單元n並沒有特別限定，但較佳為10以下，更佳為7以下。若n為上述上限值以下，則能夠抑制熔融黏度變高，能夠提高樹脂膜的成形性。 The average repeating unit n of the novolac type cyanate resin represented by the formula (I) is an arbitrary integer. The average repeating unit n is not particularly limited, but is preferably 1 or more, and more preferably 2 or more. When the average repeating unit n is at least the above lower limit value, the heat resistance of the novolac type cyanate resin is improved, and detachment and volatilization of the oligomer at the time of heating can be suppressed. Further, the average repeating unit n is not particularly limited, but is preferably 10 or less, more preferably 7 or less. When n is at most the above upper limit value, the melt viscosity can be suppressed from being increased, and the moldability of the resin film can be improved.
並且，作為氰酸酯樹脂，亦可以較佳地使用下述通式(II)表示之萘酚芳烷基型氰酸酯樹脂。下述通式(II)表示之萘酚芳烷基型氰酸 酯樹脂例如為使藉由α-萘酚或β-萘酚等萘酚類與對苯二甲醇(p-xylylene glycol)、α,α'-二甲氧基-對二甲苯、1,4-二(2-羥基-2-丙基)苯等的反應而獲得之萘酚芳烷基型酚樹脂與鹵化氰縮合而獲得之樹脂。通式(II)的重複單元n較佳為10以下的整數。若重複單元n為10以下，則能夠獲得更均勻的樹脂膜。並且，具有合成時難以發生分子內聚合、水洗時的分液性得到提高、能夠防止收量下降之傾向。 Further, as the cyanate resin, a naphthol aralkyl type cyanate resin represented by the following formula (II) can also be preferably used. The naphthol aralkyl type cyanate resin represented by the following formula (II) is, for example, a naphthol such as α-naphthol or β-naphthol and p-xylylene glycol or α. And a naphthol aralkyl type phenol resin obtained by reacting α'-dimethoxy-p-xylylene, 1,4-bis(2-hydroxy-2-propyl)benzene or the like with a halogenated cyanide Resin. The repeating unit n of the formula (II) is preferably an integer of 10 or less. When the repeating unit n is 10 or less, a more uniform resin film can be obtained. In addition, it is difficult to cause intramolecular polymerization during synthesis, and the liquid separation property at the time of water washing is improved, and the tendency to reduce the yield can be prevented.
(式中，R分別獨立地表示氫原子或甲基，n表示1以上且10以下的整數。) (In the formula, R each independently represents a hydrogen atom or a methyl group, and n represents an integer of 1 or more and 10 or less.)
並且，氰酸酯樹脂可以單獨使用1種，亦可以併用2種以上，亦可以將1種或2種以上與該等的預聚物併用。 Further, the cyanate resin may be used singly or in combination of two or more kinds, and one or two or more kinds may be used in combination with the prepolymers.
氰酸酯樹脂的含量的下限值相對於熱硬化性樹脂組成物的總固體成分100重量%，例如較佳為1重量%以上，更佳為2重量%以上，進而較佳為3重量%以上。能夠實現樹脂膜的硬化物的低線膨脹化、高彈性模數化。另一方面，氰酸酯樹脂的含量的上限值相對於熱硬化性樹脂組成物的總固體成分100重量%並沒有特別限定，例如較佳為30重量%以下，更佳為25重量%以下，進而較佳為20重量%以下。能夠提高耐熱性或耐濕性。並且，若氰酸酯樹脂的含量在上述範圍內，則能夠更進一步提高樹脂 膜的硬化物的儲存彈性模數E'。 The lower limit of the content of the cyanate resin is preferably 1% by weight or more, more preferably 2% by weight or more, and still more preferably 3% by weight based on 100% by weight of the total solid content of the thermosetting resin composition. the above. It is possible to achieve low linear expansion and high elastic modulus of the cured product of the resin film. On the other hand, the upper limit of the content of the cyanate resin is not particularly limited, and is preferably 30% by weight or less, and more preferably 25% by weight or less based on 100% by weight of the total solid content of the thermosetting resin composition. Further, it is preferably 20% by weight or less. It can improve heat resistance or moisture resistance. Further, when the content of the cyanate resin is within the above range, the storage elastic modulus E' of the cured product of the resin film can be further increased.
(苯氧樹脂(phenoxy resin)) (phenoxy resin)
本實施形態的熱硬化性樹脂組成物例如可以含有苯氧樹脂。 The thermosetting resin composition of the present embodiment may contain, for example, a phenoxy resin.
作為上述苯氧樹脂，例如可以舉出具有雙酚骨架之苯氧樹脂、具有萘骨架之苯氧樹脂、具有蒽骨架之苯氧樹脂、具有聯苯骨架之苯氧樹脂等。並且，亦能夠使用具有複數種該等骨架之結構的苯氧樹脂。 Examples of the phenoxy resin include a phenoxy resin having a bisphenol skeleton, a phenoxy resin having a naphthalene skeleton, a phenoxy resin having an anthracene skeleton, and a phenoxy resin having a biphenyl skeleton. Further, a phenoxy resin having a structure of a plurality of such skeletons can also be used.
在該等之中，苯氧樹脂中較佳使用具有聯苯骨架及雙酚S骨架之苯氧樹脂。藉由聯苯骨架具有之剛直性，能夠提高苯氧樹脂的玻璃轉移溫度，並且藉由雙酚S骨架的存在，能夠提高苯氧樹脂與金屬的密接性。其結果，能夠實現絕緣層的耐熱性的提高，並且能夠提高配線層對絕緣層之密接性。並且，苯氧樹脂中亦較佳使用具有雙酚A骨架及雙酚F骨架之苯氧樹脂。藉此，能夠進一步提高配線層與絕緣層的密接性。 Among these, a phenoxy resin having a biphenyl skeleton and a bisphenol S skeleton is preferably used in the phenoxy resin. By the rigidity of the biphenyl skeleton, the glass transition temperature of the phenoxy resin can be increased, and the adhesion of the phenoxy resin to the metal can be improved by the presence of the bisphenol S skeleton. As a result, the heat resistance of the insulating layer can be improved, and the adhesion of the wiring layer to the insulating layer can be improved. Further, a phenoxy resin having a bisphenol A skeleton and a bisphenol F skeleton is preferably used in the phenoxy resin. Thereby, the adhesion between the wiring layer and the insulating layer can be further improved.
並且，亦較佳使用具有下述通式(X)表示之雙酚苯乙酮結構之苯氧樹脂。 Further, a phenoxy resin having a bisphenol acetophenone structure represented by the following formula (X) is also preferably used.
(上述式(X)中，R1彼此可以相同亦可以不同，係氫原子、碳數1以上且10以下的烴基或選自鹵素元素中之基，R2為氫原子、碳數1 以上且10以下的烴基或選自鹵素元素中之基，R3為氫原子或碳數1以上且10以下的烴基，m為0以上且5以下的整數。) (In the above formula (X), R 1 may be the same or different, and is a hydrogen atom, a hydrocarbon group having 1 or more and 10 or less carbon atoms, or a group selected from a halogen element, and R 2 is a hydrogen atom and has a carbon number of 1 or more. a hydrocarbon group of 10 or less or a group selected from a halogen element, and R 3 is a hydrogen atom or a hydrocarbon group having 1 or more and 10 or less carbon atoms, and m is an integer of 0 or more and 5 or less.
含有雙酚苯乙酮結構之苯氧樹脂由於具有高體積結構，因此溶劑溶解性及與摻合之熱硬化性樹脂成分之相容性優異。並且，由於能夠形成低粗糙度且均勻的粗糙面，因此能夠提高絕緣層的SAP特性。 Since the phenoxy resin having a bisphenol acetophenone structure has a high volume structure, it is excellent in solvent solubility and compatibility with a blended thermosetting resin component. Further, since a rough surface having a low roughness and a uniform roughness can be formed, the SAP characteristics of the insulating layer can be improved.
具有雙酚苯乙酮結構之苯氧樹脂能夠藉由利用催化劑使環氧樹脂和酚樹脂高分子量化之方法等公知的方法進行合成。 The phenoxy resin having a bisphenol acetophenone structure can be synthesized by a known method such as a method of polymerizing an epoxy resin and a phenol resin by a catalyst.
具有雙酚苯乙酮結構之苯氧樹脂可以含有除通式(X)的雙酚苯乙酮結構以外的結構，該結構並沒有特別限定，可以舉出雙酚A型、雙酚F型、雙酚S型、聯苯型、苯酚酚醛清漆型、甲酚酚醛清漆型結構等。其中，作為除雙酚苯乙酮結構以外的結構，含有聯苯型結構之苯氧樹脂的玻璃轉移溫度高，因此較佳。 The phenoxy resin having a bisphenol acetophenone structure may have a structure other than the bisphenol acetophenone structure of the formula (X), and the structure is not particularly limited, and examples thereof include a bisphenol A type and a bisphenol F type. Bisphenol S type, biphenyl type, phenol novolac type, cresol novolak type structure, and the like. Among them, as a structure other than the bisphenol acetophenone structure, the phenoxy resin containing a biphenyl type structure is preferred because it has a high glass transition temperature.
含有雙酚苯乙酮結構之苯氧樹脂中的通式(X)的雙酚苯乙酮結構的含量並沒有特別限定，較佳為5莫耳%以上且95莫耳%以下，更佳為10莫耳%以上且85莫耳%以下，進而較佳為15莫耳%以上且75莫耳%以下。若含量為上述下限值以上，則能夠充分發揮提高耐熱性、耐濕可靠性之效果。並且，若含量為上述上限值以下，則能夠提高溶劑溶解性。 The content of the bisphenol acetophenone structure of the formula (X) in the phenoxy resin having a bisphenol acetophenone structure is not particularly limited, but is preferably 5 mol% or more and 95 mol% or less, more preferably 10 mol% or more and 85 mol% or less, further preferably 15 mol% or more and 75 mol% or less. When the content is at least the above lower limit value, the effect of improving heat resistance and moisture resistance reliability can be sufficiently exhibited. Further, when the content is at most the above upper limit value, solvent solubility can be improved.
苯氧樹脂的重量平均分子量(Mw)的下限值例如較佳為10,000以上，更佳為15,000以上，進而較佳為20,000以上。藉此，能夠提高與其他樹脂之相容性及在溶劑中之溶解性。另一方面，苯氧樹脂的重量平均分子量(Mw)的上限值例如較佳為60,000以下，更佳為55，000以下，進而較佳為50，000以下。藉此，絕緣層的成膜性提高，能夠抑制在用於製 造印刷配線基板時發生不良情況。 The lower limit of the weight average molecular weight (Mw) of the phenoxy resin is, for example, preferably 10,000 or more, more preferably 15,000 or more, still more preferably 20,000 or more. Thereby, compatibility with other resins and solubility in a solvent can be improved. On the other hand, the upper limit of the weight average molecular weight (Mw) of the phenoxy resin is, for example, preferably 60,000 or less, more preferably 55,000 or less, still more preferably 50,000 or less. Thereby, the film formability of the insulating layer is improved, and it is possible to suppress occurrence of defects in the production of the printed wiring board.
苯氧樹脂的含量並沒有特別限定，相對於除無機填充材料以外的熱硬化性樹脂組成物整體，較佳為0.5重量%以上且40重量%以下，更佳為1重量%以上且20重量%以下。若含量為上述下限值以上，則能夠抑制絕緣層的機械強度下降及絕緣層與導體電路的電鍍密接性下降。若為上述上限值以下，則能夠抑制絕緣層的熱膨脹率增加，能夠抑制耐熱性下降。 The content of the phenoxy resin is not particularly limited, and is preferably 0.5% by weight or more and 40% by weight or less, and more preferably 1% by weight or more and 20% by weight or less based on the total amount of the thermosetting resin composition other than the inorganic filler. the following. When the content is at least the above lower limit value, it is possible to suppress a decrease in mechanical strength of the insulating layer and a decrease in plating adhesion between the insulating layer and the conductor circuit. When it is at most the above upper limit value, it is possible to suppress an increase in the thermal expansion coefficient of the insulating layer, and it is possible to suppress a decrease in heat resistance.
(硬化促進劑) (hardening accelerator)
本實施形態的熱硬化性樹脂組成物例如可以含有硬化促進劑。藉此，能夠提高熱硬化性樹脂組成物的硬化性。作為硬化促進劑，能夠使用促進熱硬化性樹脂的硬化反應之化合物，其種類並沒有特別限定。本實施形態中，作為硬化促進劑，例如能夠含有選自以下中之一種或兩種以上：環烷酸鋅、環烷酸鈷、辛酸錫、辛酸鈷、辛酸鋅、雙乙醯丙酮鈷(II)、三乙醯丙酮鈷(III)等有機金屬鹽、三乙胺、三丁胺、二氮雜雙環[2,2,2]辛烷等3級胺類、2-苯基咪唑、2-苯基-4-甲基咪唑、2-乙基-4-乙基咪唑、2-苯基-4-乙基咪唑、2-苯基-4-甲基-5-羥基咪唑、2-苯基-4-甲基-5-羥基甲基咪唑、2-苯基-4,5-二羥基咪唑等咪唑類、苯酚、雙酚A、壬基苯酚等酚化合物、乙酸、安息香酸、水楊酸、對甲苯磺酸等有機酸及鎓鹽化合物。在該等之中，從更有效地提高硬化性之觀點考慮，更佳為含有鎓鹽化合物。 The thermosetting resin composition of the present embodiment may contain, for example, a curing accelerator. Thereby, the hardenability of the thermosetting resin composition can be improved. As the curing accelerator, a compound which accelerates the curing reaction of the thermosetting resin can be used, and the kind thereof is not particularly limited. In the present embodiment, the curing accelerator may contain, for example, one or more selected from the group consisting of zinc naphthenate, cobalt naphthenate, tin octoate, cobalt octoate, zinc octoate, and cobalt acetonate (II). ), an organic metal salt such as triethyl hydrazine acetone (III), a tertiary amine such as triethylamine, tributylamine or diazabicyclo[2,2,2]octane, 2-phenylimidazole, 2- Phenyl-4-methylimidazole, 2-ethyl-4-ethylimidazole, 2-phenyl-4-ethylimidazole, 2-phenyl-4-methyl-5-hydroxyimidazole, 2-phenyl Imidazoles such as -4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dihydroxyimidazole, phenolic compounds such as phenol, bisphenol A, nonylphenol, acetic acid, benzoic acid, salicylic acid An organic acid such as p-toluenesulfonic acid or a phosphonium salt compound. Among these, it is more preferable to contain an onium salt compound from the viewpoint of more effectively improving the hardenability.
用作硬化促進劑之鎓鹽化合物並沒有特別限定，例如能夠使用下述通式(2)表示之化合物。 The onium salt compound to be used as the curing accelerator is not particularly limited, and for example, a compound represented by the following formula (2) can be used.
(式(2)中，P表示磷原子，R3、R4、R5及R6分別表示經取代或未經取代之具有芳香環或雜環之有機基、或經取代或未經取代之脂肪族基，彼此可以相同亦可以不同。A表示在分子內具有至少1個以上能夠釋放到分子外之質子之n(n1)價的質子供體的陰離子、或其錯陰離子) (In the formula (2), P represents a phosphorus atom, and R 3 , R 4 , R 5 and R 6 each represent a substituted or unsubstituted organic group having an aromatic ring or a heterocyclic ring, or substituted or unsubstituted The aliphatic groups may be the same or different from each other. A represents at least one or more n(n) capable of releasing protons outside the molecule in the molecule. 1) the anion of the valence proton donor, or its aberrant anion)
硬化促進劑的含量的下限值例如相對於熱硬化性樹脂組成物的總固體成分100重量%，例如較佳為0.01重量%以上，更佳為0.05重量%以上。藉由將硬化促進劑的含量設為上述下限值以上，能夠更有效地提高熱硬化性樹脂組成物的硬化性。另一方面，硬化促進劑的含量的上限值例如相對於熱硬化性樹脂組成物的總固體成分100重量%，較佳為2.5重量%以下，更佳為1重量%以下。藉由將硬化促進劑的含量設為上述上限值以下，能夠提高熱硬化性樹脂組成物的保存性。 The lower limit of the content of the curing accelerator is, for example, preferably 0.01% by weight or more, and more preferably 0.05% by weight or more based on 100% by weight of the total solid content of the thermosetting resin composition. When the content of the curing accelerator is at least the above lower limit value, the curability of the thermosetting resin composition can be more effectively improved. On the other hand, the upper limit of the content of the curing accelerator is, for example, preferably 2.5% by weight or less, and more preferably 1% by weight or less based on 100% by weight of the total solid content of the thermosetting resin composition. By setting the content of the curing accelerator to be equal to or less than the above upper limit, the storage stability of the thermosetting resin composition can be improved.
(偶合劑) (coupling agent)
本實施形態的熱硬化性樹脂組成物可以含有偶合劑。偶合劑可以在製備熱硬化性樹脂組成物時直接添加，亦可以預先添加於無機填充材料中。藉由使用偶合劑，能夠提高無機填充材料與各樹脂的界面的潤濕性。因此，較佳為使用偶合劑，能夠改良樹脂膜的硬化物的耐熱性。並且，藉由使用偶合劑，能夠提高與銅箔之密接性。另外，由於能夠提高耐吸濕性，因此即使置於濕度環境下，亦能夠維持與銅箔之密接性。 The thermosetting resin composition of the present embodiment may contain a coupling agent. The coupling agent may be added directly in the preparation of the thermosetting resin composition, or may be added to the inorganic filler in advance. By using a coupling agent, the wettability of the interface between the inorganic filler and each resin can be improved. Therefore, it is preferred to use a coupling agent to improve the heat resistance of the cured product of the resin film. Further, by using a coupling agent, the adhesion to the copper foil can be improved. Further, since the moisture absorption resistance can be improved, the adhesion to the copper foil can be maintained even when placed in a humidity environment.
作為偶合劑，例如可以舉出環氧基矽烷偶合劑、陽離子型矽烷偶合劑、胺基矽烷偶合劑等矽烷偶合劑、鈦酸酯系偶合劑及矽油型偶合劑等。偶合劑可以單獨使用一種，亦可以併用兩種以上。本實施形態中，偶合劑可以含有矽烷偶合劑。 Examples of the coupling agent include a decane coupling agent such as an epoxy decane coupling agent, a cationic decane coupling agent, and an amino decane coupling agent, a titanate coupling agent, and an oil-type coupling agent. The coupling agent may be used alone or in combination of two or more. In the present embodiment, the coupling agent may contain a decane coupling agent.
藉此，能夠提高無機填充材料與各樹脂的界面的潤濕性，能夠進一步提高樹脂膜的硬化物的耐熱性。 Thereby, the wettability of the interface between the inorganic filler and each resin can be improved, and the heat resistance of the cured product of the resin film can be further improved.
作為矽烷偶合劑並沒有特別限定，例如可以舉出環氧基矽烷、胺基矽烷、烷基矽烷、脲矽烷、巰基矽烷、乙烯基矽烷等。 The decane coupling agent is not particularly limited, and examples thereof include epoxy decane, amino decane, alkyl decane, urea decane, decyl decane, and vinyl decane.
作為具體的化合物，例如可以舉出γ-胺基丙基三乙氧基矽烷、γ-胺基丙基三甲氧基矽烷、N-β(胺基乙基)γ-胺基丙基三甲氧基矽烷、N-β(胺基乙基)γ-胺基丙基甲基二甲氧基矽烷、N-苯基γ-胺基丙基三乙氧基矽烷、N-苯基γ-胺基丙基三甲氧基矽烷、N-β(胺基乙基)γ-胺基丙基三乙氧基矽烷、N-6-(胺基己基)3-胺基丙基三甲氧基矽烷、N-(3-(三甲氧基矽基丙基)-1,3-苯二甲烷、γ-環氧丙氧基丙基三乙氧基矽烷、γ-環氧丙氧基丙基三甲氧基矽烷、γ-環氧丙氧基丙基甲基二甲氧基矽烷、β-(3,4-環氧基環己基)乙基三甲氧基矽烷、γ-巰基丙基三甲氧基矽烷、甲基三甲氧基矽烷、γ-脲丙基三乙氧基矽烷、乙烯基三乙氧基矽烷等，能夠使用該等之中的一種或者將兩種以上組合使用。在該等之中，較佳為環氧基矽烷、巰基矽烷、胺基矽烷，作為胺基矽烷，更佳為1級胺基矽烷或苯胺基矽烷。 Specific examples of the compound include γ-aminopropyltriethoxydecane, γ-aminopropyltrimethoxydecane, and N-β(aminoethyl)γ-aminopropyltrimethoxy.矽, N-β(aminoethyl)γ-aminopropylmethyldimethoxydecane, N-phenylγ-aminopropyltriethoxydecane, N-phenylγ-aminopropyl Trimethoxy decane, N-β (aminoethyl) γ-aminopropyl triethoxy decane, N-6-(aminohexyl) 3-aminopropyltrimethoxy decane, N-( 3-(trimethoxymercaptopropyl)-1,3-benzenedimethane, γ-glycidoxypropyltriethoxydecane, γ-glycidoxypropyltrimethoxydecane, γ - glycidoxypropylmethyldimethoxydecane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, γ-mercaptopropyltrimethoxydecane, methyltrimethoxy One of these may be used, or two or more types may be used in combination, such as decane, γ-ureidopropyltriethoxy decane, vinyl triethoxy decane, etc. Among these, epoxy is preferred. Base decane, mercapto decane, amino decane, as the amino decane, more preferably a grade 1 amino decane or aniline Base decane.
偶合劑的添加量相對於無機填充材料的比表面積能夠適當進行調整。該種偶合劑的添加量的下限值例如相對於熱硬化性樹脂組成物 的總固體成分100重量%，較佳為0.01重量%以上，更佳為0.05重量%以上。若偶合劑的含量為上述下限值以上，則能夠充分包覆無機填充材料，能夠提高樹脂膜的硬化物的耐熱性。另一方面，偶合劑的添加量的上限值例如相對於熱硬化性樹脂組成物的總固體成分100重量%，較佳為3重量%以下，更佳為1.5重量%以下。若偶合劑的含量為上述上限值以下，則能夠抑制對反應帶來影響，能夠抑制樹脂膜的硬化物的彎曲強度等下降。 The amount of the coupling agent added can be appropriately adjusted with respect to the specific surface area of the inorganic filler. The lower limit of the amount of the coupling agent to be added is, for example, 100% by weight or more based on the total solid content of the thermosetting resin composition, preferably 0.01% by weight or more, more preferably 0.05% by weight or more. When the content of the coupling agent is at least the above lower limit value, the inorganic filler can be sufficiently coated, and the heat resistance of the cured product of the resin film can be improved. On the other hand, the upper limit of the amount of the coupling agent to be added is, for example, preferably 100% by weight or less, and more preferably 1.5% by weight or less based on 100% by weight of the total solid content of the thermosetting resin composition. When the content of the coupling agent is at most the above upper limit value, it is possible to suppress the influence on the reaction, and it is possible to suppress a decrease in the bending strength or the like of the cured product of the resin film.
(添加劑) (additive)
另外，在不損害本發明的目的之範圍內，本實施形態的熱硬化性樹脂組成物中可以含有除上述成分(熱硬化性樹脂、硬化劑、無機填充材料、硬化促進劑、偶合劑)以外的添加劑：含有綠、紅、藍、黄及黑等染料、黑色顏料等顏料、色素中的至少一種以上之著色劑、低應力劑、消泡劑、調平劑、紫外線吸收劑、發泡劑、抗氧化劑、阻燃劑、離子捕捉劑等。該等可以單獨使用，亦可以將2種以上組合使用。 In addition, the thermosetting resin composition of the present embodiment may contain, in addition to the above components (thermosetting resin, curing agent, inorganic filler, curing accelerator, and coupling agent), in addition to the object of the present invention. Additives: pigments such as green, red, blue, yellow and black dyes, black pigments, pigments, pigments, low-stress agents, defoamers, leveling agents, UV absorbers, foaming agents , antioxidants, flame retardants, ion trapping agents, etc. These may be used alone or in combination of two or more.
本實施形態的熱硬化性樹脂組成物亦可以不含低應力劑或橡膠成分。在該情況下，本實施形態的熱硬化性樹脂組成物的硬化物亦能夠提高無機填充材料的填充率，並且設為低彈性模數，因此能夠抑制基板製程中之翹曲或由搬送中衝擊引起之龜裂。 The thermosetting resin composition of the present embodiment may not contain a low stress agent or a rubber component. In this case, the cured product of the thermosetting resin composition of the present embodiment can also increase the filling rate of the inorganic filler and have a low modulus of elasticity. Therefore, it is possible to suppress warpage during the substrate process or impact during transportation. Caused by cracks.
作為顏料，可以舉出高嶺土、合成氧化鐵紅、鎘黃、鎳鈦黄、鍶黄、含水氧化鉻、氧化鉻、鋁酸鈷、合成群青等無機顏料、酞菁等多環顏料、偶氮顏料等。 Examples of the pigment include inorganic pigments such as kaolin, synthetic iron oxide red, cadmium yellow, nickel titanium yellow, yttrium yellow, hydrous chromium oxide, chromium oxide, cobalt aluminate, synthetic ultramarine, polycyclic pigments such as phthalocyanine, and azo pigments. Wait.
作為染料，可以舉出異吲哚啉酮、異吲哚啉、喹啉黃(quinophthalone)、(xanthene)、二酮基吡咯并吡咯、苝(perylene)、 紫環酮(perinone)、蒽醌、靛、、喹吖酮(quinacridone)、苯并咪唑酮、紫蒽酮、酞菁、次甲基偶氮等。 Examples of the dye include isoindolinone, isoporphyrin, quinophthalone, and (xanthene), diketopyrrolopyrrole, perylene, perinone, hydrazine, hydrazine, , quinacridone, benzimidazolone, purpurinone, phthalocyanine, methine azo, and the like.
本實施形態中，清漆狀的熱硬化性樹脂組成物能夠含有溶劑。 In the present embodiment, the varnish-like thermosetting resin composition can contain a solvent.
作為上述溶劑，例如可以舉出丙酮、甲基乙基酮、甲基異丁基酮、甲苯、乙酸乙酯、庚烷、環己烷、環己酮、四氫呋喃、二甲基甲醯胺、二甲基乙醯胺、二甲基亞碸、乙二醇、賽路蘇系、卡必醇系、苯甲醚及N-甲基吡咯啶酮等有機溶劑。該等可以單獨使用，亦可以將2種以上組合使用。 Examples of the solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, ethyl acetate, heptane, cyclohexane, cyclohexanone, tetrahydrofuran, dimethylformamide, and the like. An organic solvent such as methyl acetamide, dimethyl hydrazine, ethylene glycol, serotonin, carbitol, anisole or N-methylpyrrolidone. These may be used alone or in combination of two or more.
在熱硬化性樹脂組成物為清漆狀的情況下，熱硬化性樹脂組成物的固體成分含量例如較佳為30重量%以上且80重量%以下，更佳為40重量%以上且70重量%以下。藉此，能夠獲得作業性或成膜性非常優異之熱硬化性樹脂組成物。 When the thermosetting resin composition is in the form of a varnish, the solid content of the thermosetting resin composition is, for example, preferably 30% by weight or more and 80% by weight or less, more preferably 40% by weight or more and 70% by weight or less. . Thereby, a thermosetting resin composition which is excellent in workability or film formability can be obtained.
清漆狀的熱硬化性樹脂組成物能夠藉由使用例如超音波分散方式、高壓衝突式分散方式、高速旋轉分散方式、珠磨方式、高速剪切分散方式及自轉公轉式分散方式等各種混合機，將上述各成分於溶劑中進行溶解、混合、攪拌而製備。 The varnish-like thermosetting resin composition can be used in various mixers such as an ultrasonic dispersion method, a high pressure conflict type dispersion method, a high-speed rotary dispersion method, a bead milling method, a high-speed shear dispersion method, and a self-rotating revolution dispersion method. The above components are prepared by dissolving, mixing, and stirring in a solvent.
接著，對本實施形態的樹脂膜進行說明。 Next, the resin film of the present embodiment will be described.
本實施形態的樹脂膜能夠藉由將清漆狀之上述熱硬化性樹脂組成物進行薄膜化而獲得。例如，本實施形態的樹脂膜能夠藉由對塗佈清漆狀的熱硬化性樹脂組成物而獲得之塗佈膜除去溶劑而獲得。在該種樹脂膜中，溶劑含有率相對於樹脂膜整體能夠設為5重量%以下。本實施形態中，例如可以在100℃~150℃、1分鐘~5分鐘的條件下實施除去溶劑之製 程。藉此，能夠抑制含有熱硬化性樹脂之樹脂膜的硬化的進行，並且充分除去溶劑。 The resin film of the present embodiment can be obtained by thinning the above-mentioned thermosetting resin composition in the form of a varnish. For example, the resin film of the present embodiment can be obtained by removing a solvent from a coating film obtained by applying a varnish-like thermosetting resin composition. In the resin film, the solvent content can be 5% by weight or less based on the entire resin film. In the present embodiment, for example, the solvent removal process can be carried out at 100 ° C to 150 ° C for 1 minute to 5 minutes. Thereby, the progress of hardening of the resin film containing a thermosetting resin can be suppressed, and a solvent can fully remove.
(附載體樹脂膜) (with carrier resin film)
接著，對本實施形態的附載體樹脂膜進行說明。 Next, the carrier-attached resin film of the present embodiment will be described.
圖1係表示本實施形態中之附載體樹脂膜100的構成的一例之剖面圖。 Fig. 1 is a cross-sectional view showing an example of a configuration of a carrier resin film 100 in the present embodiment.
如圖1所示，本實施形態的附載體樹脂膜100能夠具備載體基材12、及設置於載體基材12上之由上述熱硬化性樹脂組成物形成之樹脂膜10。藉此，能夠提高樹脂膜10的處理性。 As shown in FIG. 1, the carrier-attached resin film 100 of the present embodiment can include a carrier substrate 12 and a resin film 10 formed of the above-described thermosetting resin composition provided on the carrier substrate 12. Thereby, the handleability of the resin film 10 can be improved.
附載體樹脂膜100可以是能夠捲取之卷形狀，亦可以是矩形形狀等單片形狀。 The carrier-attached resin film 100 may have a roll shape that can be wound up, or may have a single-piece shape such as a rectangular shape.
本實施形態中，作為載體基材12，例如能夠使用高分子薄膜或金屬箔等。作為該高分子薄膜並沒有特別限定，例如可以舉出聚乙烯、聚丙烯等聚烯烴、聚對酞酸乙二酯(polyethylene terephthalate)、聚對酞酸丁二酯(polybutylene terephthalate)等聚酯、聚碳酸酯、聚矽氧(silicone)片等脫模紙、氟系樹脂、聚醯亞胺樹脂等具有耐熱性之熱塑性樹脂片等。作為該金屬箔並沒有特別限定，例如可以舉出銅或銅系合金、鋁或鋁系合金、鐵或鐵系合金、銀或銀系合金、金或金系合金、鋅或鋅系合金、鎳或鎳系合金、錫或錫系合金等。在該等之中，由聚對酞酸乙二酯構成之片價格低廉及容易調節剝離強度，因此為最佳。藉由將由該材料構成之片用作載體基材12，容易將樹脂膜10以適度的強度從載體基材12上剝離。 In the present embodiment, as the carrier substrate 12, for example, a polymer film, a metal foil, or the like can be used. The polymer film is not particularly limited, and examples thereof include polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate, and polybutylene terephthalate. A heat-resistant thermoplastic resin sheet such as a release paper such as polycarbonate or a silicone sheet, a fluorine resin or a polyimide resin. The metal foil is not particularly limited, and examples thereof include copper or a copper alloy, aluminum or aluminum alloy, iron or iron alloy, silver or silver alloy, gold or gold alloy, zinc or zinc alloy, and nickel. Or nickel-based alloys, tin or tin-based alloys. Among these, the sheet composed of polyethylene terephthalate is inexpensive and easy to adjust the peel strength, and therefore is preferable. By using a sheet composed of the material as the carrier substrate 12, the resin film 10 is easily peeled off from the carrier substrate 12 with an appropriate strength.
樹脂膜10的厚度的下限值並沒有特別限定，例如較佳為1μm以上，更佳為3μm以上，進而較佳為5μm以上。藉此，能夠提高樹 脂膜10的機械強度。另一方面，樹脂膜10的厚度的上限值並沒有特別限定，例如較佳為500μm以下，更佳為300μm以下，進而較佳為100μm以下。藉此，能夠實現半導體裝置的薄層化。 The lower limit of the thickness of the resin film 10 is not particularly limited, and is, for example, preferably 1 μm or more, more preferably 3 μm or more, and still more preferably 5 μm or more. Thereby, the mechanical strength of the resin film 10 can be improved. On the other hand, the upper limit of the thickness of the resin film 10 is not particularly limited, and is, for example, preferably 500 μm or less, more preferably 300 μm or less, and still more preferably 100 μm or less. Thereby, thinning of the semiconductor device can be achieved.
載體基材的厚度並沒有特別限定，例如較佳為10~100μm，更佳為10~70μm。藉此，製造附載體樹脂膜100時之處理性變得更良好。 The thickness of the carrier substrate is not particularly limited, and is, for example, preferably 10 to 100 μm, more preferably 10 to 70 μm. Thereby, the rationality at the time of manufacturing the carrier resin film 100 becomes more favorable.
本實施形態的附載體樹脂膜100可以是單層，亦可以是多層，能夠含有1種或2種以上的樹脂膜10。當該樹脂片為多層時，各樹脂片可以由相同種類構成，亦可以由不同種類構成。並且，附載體樹脂膜100可以在樹脂膜10上的最外層側具有保護膜。 The carrier-attached resin film 100 of the present embodiment may be a single layer or a plurality of layers, and may contain one or two or more kinds of the resin films 10. When the resin sheet is a plurality of layers, each of the resin sheets may be composed of the same kind or may be composed of different types. Further, the carrier-attached resin film 100 may have a protective film on the outermost layer side of the resin film 10.
本實施形態中，作為形成附載體樹脂膜100之方法並沒有特別限定。作為該方法，例如能夠使用如下方法：藉由使用各種塗佈裝置，將清漆狀的熱硬化性樹脂組成物塗佈於載體基材12上而形成塗佈膜之後，藉由適當乾燥該塗佈膜而除去溶劑。 In the present embodiment, the method of forming the carrier-attached resin film 100 is not particularly limited. As such a method, for example, a coating film can be formed by applying a varnish-like thermosetting resin composition onto a carrier substrate 12 by using various coating apparatuses, and then drying the coating by appropriate drying. The membrane was removed to remove the solvent.
對本實施形態的樹脂膜的特性進行說明。 The characteristics of the resin film of the present embodiment will be described.
如上所述，本實施形態的樹脂膜為由上述熱硬化性樹脂組成物形成之樹脂膜。 As described above, the resin film of the present embodiment is a resin film formed of the above thermosetting resin composition.
本實施形態的上述樹脂膜的硬化物中，能夠兼顧低彈性特性和高伸長度特性，因此能夠實現優異之強韌性。 In the cured product of the resin film of the present embodiment, both the low elastic properties and the high elongation properties can be achieved, so that excellent toughness can be achieved.
當對本實施形態中之熱硬化性樹脂組成物的硬化物進行了動態黏彈性測量時，該硬化物在30℃之儲存彈性模數E'30的上限值為10GPa以下，但較佳為9GPa以下，更佳為8GPa以下。藉此，能夠實現低彈性優 異之樹脂膜的硬化物。另一方面，上述在30℃之儲存彈性模數E'30的下限值為1GPa以上。藉此，可獲得特定的彈性模數，因此可獲得強度優異之樹脂膜的硬化物。 When the cured product of the thermosetting resin composition of the present embodiment is subjected to dynamic viscoelasticity measurement, the upper limit of the storage elastic modulus E' 30 of the cured product at 30 ° C is 10 GPa or less, but preferably 9 GPa. Hereinafter, it is more preferably 8 GPa or less. Thereby, a cured product of a resin film excellent in low elasticity can be achieved. On the other hand, the lower limit of the storage elastic modulus E' 30 at 30 ° C is 1 GPa or more. Thereby, a specific elastic modulus can be obtained, and thus a cured product of a resin film excellent in strength can be obtained.
當對本實施形態中之熱硬化性樹脂組成物的硬化物進行了拉伸試驗時，硬化物的拉伸伸長率的下限值為2%以上，但較佳為3%以上，更佳為4%以上。藉此，可獲得柔軟性及伸長性優異之樹脂膜的硬化物。並且，可獲得高填充無機填充材料的同時具有高伸長性之樹脂膜的硬化物。另一方面，上述拉伸伸長率的上限值並沒有特別限定，例如可以設為40%以下。 When the cured product of the thermosetting resin composition of the present embodiment is subjected to a tensile test, the lower limit of the tensile elongation of the cured product is 2% or more, preferably 3% or more, more preferably 4 %the above. Thereby, a cured product of a resin film excellent in flexibility and elongation can be obtained. Further, a cured product of a resin film having high elongation while highly filling the inorganic filler can be obtained. On the other hand, the upper limit of the tensile elongation is not particularly limited, and may be, for example, 40% or less.
本實施形態中，由於能夠減小上述儲存彈性模數，並且提高上述拉伸伸長率，因此可獲得強韌性優異之樹脂膜的硬化物。 In the present embodiment, since the storage elastic modulus can be made small and the tensile elongation is increased, a cured product of a resin film having excellent toughness can be obtained.
本實施形態中，熱硬化性樹脂組成物的硬化物的玻璃轉移溫度的下限值並沒有特別限定，例如較佳為10℃以上，更佳為15℃以上，進而較佳為20℃以上。藉由將硬化物的玻璃轉移溫度設在室溫25℃±約10℃的範圍內，在實際溫度下之上述硬化物的彈性特性和伸長特性更優異。藉此，能夠充分抑制搬送時之基板的翹曲及龜裂。並且，上述玻璃轉移溫度的上限值並沒有特別限定，例如可以設為220℃以下，較佳為110℃以下，更佳為80℃以下，進而較佳為35℃以下。 In the present embodiment, the lower limit of the glass transition temperature of the cured product of the thermosetting resin composition is not particularly limited, and is, for example, preferably 10° C. or higher, more preferably 15° C. or higher, and still more preferably 20° C. or higher. By setting the glass transition temperature of the cured product to a temperature of 25 ° C ± 10 ° C at room temperature, the cured product at the actual temperature is more excellent in elastic properties and elongation properties. Thereby, warping and cracking of the substrate at the time of conveyance can be sufficiently suppressed. Further, the upper limit of the glass transition temperature is not particularly limited, and may be, for example, 220 ° C or lower, preferably 110 ° C or lower, more preferably 80 ° C or lower, and still more preferably 35 ° C or lower.
本實施形態中，熱硬化性樹脂組成物的硬化物的損耗正切tan δ的峰值的下限值例如較佳為0.25以上，更佳為0.3以上，進而較佳為0.45以上。藉此，上述硬化物能夠吸收能量，因此能夠減小由起因於構件間的膨脹係數差之應力等引起之影響而抑制基板龜裂。藉由將損耗正切 tan δ的峰值的下限值設為0.5以上，能夠實現非常優異之伸長性。另一方面，上述損耗正切tan δ的峰值的上限值並沒有特別限定，例如較佳為1以下，更佳為0.95以下，進而較佳為0.9以下。 In the present embodiment, the lower limit of the peak value of the loss tangent tan δ of the cured product of the thermosetting resin composition is, for example, preferably 0.25 or more, more preferably 0.3 or more, still more preferably 0.45 or more. Thereby, since the hardened material can absorb energy, it is possible to reduce the influence of the stress caused by the difference in the expansion coefficient between the members and the like, thereby suppressing the crack of the substrate. By setting the lower limit of the peak value of the loss tangent tan δ to 0.5 or more, extremely excellent elongation can be achieved. On the other hand, the upper limit of the peak value of the loss tangent tan δ is not particularly limited, and is preferably 1 or less, more preferably 0.95 or less, still more preferably 0.9 or less.
並且，熱硬化性樹脂組成物的硬化物的上述損耗正切tan δ的峰值的半值寬的下限值例如較佳為20以上，更佳為30以上，進而較佳為35以上。藉此，能夠提高上述硬化物相對於溫度變化之能量吸收性。另一方面，上述損耗正切tan δ的峰的半值寬的上限值並沒有特別限定，例如較佳為100以下，更佳為90以下，進而較佳為80以下。藉此，能夠抑制上述硬化物的彈性模數相對於溫度變化之變化，因此能夠提高連接可靠性。 In addition, the lower limit of the half value width of the peak of the loss tangent tan δ of the cured product of the thermosetting resin composition is, for example, preferably 20 or more, more preferably 30 or more, still more preferably 35 or more. Thereby, the energy absorbability of the cured product with respect to temperature change can be improved. On the other hand, the upper limit of the half value width of the peak of the loss tangent tan δ is not particularly limited, and is preferably, for example, 100 or less, more preferably 90 or less, still more preferably 80 or less. Thereby, the change in the elastic modulus of the cured product with respect to the temperature change can be suppressed, so that the connection reliability can be improved.
上述玻璃轉移溫度、損耗正切tan δ及儲存彈性模數能夠使用動態黏彈性分析裝置(DMA)進行測量。並且，上述玻璃轉移溫度係在藉由升溫速度5℃/min、頻率1Hz的條件下之動態黏彈性測量而獲得之曲線上損耗正切tan δ呈現最大值之溫度。並且，上述損耗正切tan δ及上述儲存彈性模數能夠藉由在升溫速度5℃/min、頻率1Hz的條件下之動態黏彈性測量而計算出損耗正切tan δ、在30℃之儲存彈性模數E'30。 The above glass transition temperature, loss tangent tan δ, and storage elastic modulus can be measured using a dynamic viscoelasticity analyzer (DMA). Further, the glass transition temperature is a temperature at which the loss tangent tan δ exhibits a maximum value on the curve obtained by dynamic viscoelasticity measurement under the conditions of a temperature increase rate of 5 ° C/min and a frequency of 1 Hz. Further, the loss tangent tan δ and the storage elastic modulus can be calculated by dynamic viscoelasticity measurement at a temperature increase rate of 5 ° C/min and a frequency of 1 Hz to calculate a loss tangent tan δ and a storage elastic modulus at 30 ° C. E' 30 .
本實施形態中，玻璃轉移溫度、損耗正切tan δ及儲存彈性模數能夠依據測量結果進行計算，該測量結果係藉由對在200℃熱處理2小時而獲得之樹脂膜的硬化物，例如使用動態黏彈性測量裝置在頻率1Hz、升溫速度5℃/分鐘的條件下進行動態黏彈性試驗而獲得。作為動態黏彈性測量裝置並沒有特別限定，例如能夠使用DMA裝置(TA Instruments公司製，Q800)。 In the present embodiment, the glass transition temperature, the loss tangent tan δ, and the storage elastic modulus can be calculated based on the measurement results obtained by heat-treating the resin film obtained by heat-treating at 200 ° C for 2 hours, for example, using dynamics. The viscoelasticity measuring device was obtained by performing a dynamic viscoelasticity test under the conditions of a frequency of 1 Hz and a temperature increase rate of 5 ° C/min. The dynamic viscoelasticity measuring device is not particularly limited, and for example, a DMA device (manufactured by TA Instruments, Q800) can be used.
本實施形態中，上述拉伸伸長率能夠如下測量。首先，將在 200℃熱處理2小時而獲得之樹脂膜的硬化物切成縱100mm×橫6mm的試驗片。拉伸試驗中，將該試驗片夾在以一定的距離配置之卡盤上，進行直至試驗片斷裂為止以一定的速度拉伸之評價。此時，使用精密萬能試驗機(島津製作所股份有限公司製，AUTOGRAPH AG-IS)，並使用初期卡盤間距離L：20mm、試驗片的厚度：0.1mm、測量溫度：25℃、試驗速度：1mm/分鐘的條件。在上述拉伸試驗中，拉伸伸長率(%)依據在上述條件下斷裂時的位移量和初期卡盤間距離進行計算。 In the present embodiment, the tensile elongation can be measured as follows. First, the cured product of the resin film obtained by heat treatment at 200 ° C for 2 hours was cut into test pieces of 100 mm in length × 6 mm in width. In the tensile test, the test piece was placed on a chuck placed at a constant distance, and the evaluation was performed at a constant speed until the test piece was broken. In this case, a precision universal testing machine (AUTOGRAPH AG-IS, manufactured by Shimadzu Corporation) was used, and the distance between the initial chucks was L: 20 mm, the thickness of the test piece was 0.1 mm, the measurement temperature was 25 ° C, and the test speed was: 1 mm/min condition. In the above tensile test, the tensile elongation (%) was calculated in accordance with the amount of displacement at the time of breaking under the above conditions and the initial inter-clip distance.
本實施形態中，樹脂膜的硬化物在50℃至250℃的範圍內計算出之平均線膨脹係數的上限值例如較佳為120ppm/℃以下，更佳為110ppm/℃以下，進而較佳為90ppm/℃以下。藉此，能夠減少製造製程中之印刷配線基板的翹曲。並且，能夠減少獲得之半導體封裝體的翹曲。另一方面，上述平均線膨脹係數的下限值並沒有特別限定，例如較佳為1ppm/℃以上，更佳為10ppm/℃以上。 In the present embodiment, the upper limit of the average linear expansion coefficient calculated from the cured product of the resin film in the range of 50 ° C to 250 ° C is preferably 120 ppm / ° C or less, more preferably 110 ppm / ° C or less, and further preferably. It is 90 ppm/°C or less. Thereby, the warpage of the printed wiring board in the manufacturing process can be reduced. Moreover, the warpage of the obtained semiconductor package can be reduced. On the other hand, the lower limit of the average linear expansion coefficient is not particularly limited, and is, for example, preferably 1 ppm/° C. or higher, and more preferably 10 ppm/° C. or higher.
上述線膨脹係數例如能夠使用熱機械分析裝置TMA進行測量。具體而言，上述線膨脹係數，例如使用熱機械分析裝置TMA(TA Instruments公司製，Q400)，在溫度範圍50至250℃、升溫速度10℃/min、荷重10g、拉伸模式的條件下進行2次熱機械分析(TMA)測量。計算出在50℃至250℃的範圍內之平面方向(XY方向)的線膨脹係數的平均值。另外，線膨脹係數採用第2次的值。 The linear expansion coefficient described above can be measured, for example, using a thermomechanical analysis device TMA. Specifically, the linear expansion coefficient is carried out, for example, using a thermomechanical analyzer TMA (manufactured by TA Instruments, Q400) under the conditions of a temperature range of 50 to 250 ° C, a temperature increase rate of 10 ° C/min, a load of 10 g, and a tensile mode. 2 thermomechanical analysis (TMA) measurements. The average value of the linear expansion coefficients in the plane direction (XY direction) in the range of 50 ° C to 250 ° C was calculated. In addition, the coefficient of linear expansion is the second value.
本實施形態中，例如藉由分別適當選擇構成熱硬化性樹脂組成物之成分的種類或摻合比例等，能夠將熱硬化性樹脂組成物的硬化物的上述儲存彈性模數或上述拉伸伸長率設在希望的範圍內。在該等之中，作 為用於將上述儲存彈性模數或上述拉伸伸長率設在希望的數值範圍之要素，例如可以舉出藉由使用每個官能基的分子量大且具備柔軟的骨架之熱硬化性樹脂來控制上述硬化物的交聯密度等。 In the present embodiment, the storage elastic modulus or the tensile elongation of the cured product of the thermosetting resin composition can be appropriately selected, for example, by appropriately selecting the type or blending ratio of the components constituting the thermosetting resin composition. The rate is set within the desired range. Among these, as an element for setting the storage elastic modulus or the tensile elongation in a desired numerical range, for example, a molecular weight of each functional group is large and a soft skeleton is provided. The thermosetting resin controls the crosslinking density and the like of the cured product.
(印刷配線基板) (printed wiring board)
本實施形態的印刷配線基板具備由上述樹脂膜的硬化物(熱硬化性樹脂組成物的硬化物)構成之絕緣層。 The printed wiring board of the present embodiment includes an insulating layer made of a cured product of the resin film (a cured product of a thermosetting resin composition).
本實施形態中，樹脂膜的硬化物例如能夠用於通常的印刷配線基板的芯層或增建層或阻焊層、不具有芯層之印刷配線基板上之增建層或阻焊層、用於PLP之無芯基板的層間絕緣層或阻焊層、MIS基板的層間絕緣層或阻焊層等。在用於一次製作複數個半導體封裝體之大面積的印刷配線基板中，該種絕緣層亦能夠較佳地用於構成該印刷配線基板之層間絕緣層或阻焊層。 In the present embodiment, the cured product of the resin film can be used, for example, in a core layer or an additional layer or a solder resist layer of a normal printed wiring board, or an build-up layer or a solder resist layer on a printed wiring board having no core layer. An interlayer insulating layer or a solder resist layer of a coreless substrate of PLP, an interlayer insulating layer of a MIS substrate, or a solder resist layer. In a large-sized printed wiring board for producing a plurality of semiconductor packages at a time, such an insulating layer can also be preferably used to constitute an interlayer insulating layer or a solder resist layer of the printed wiring substrate.
接著，使用圖2(a)及圖2(b)，對本實施形態的印刷配線基板300的一例進行說明。 Next, an example of the printed wiring board 300 of the present embodiment will be described with reference to FIGS. 2(a) and 2(b).
本實施形態的印刷配線基板300具備由上述樹脂膜10的硬化物構成之絕緣層。如圖2(a)所示，上述印刷配線基板300可以具有具備絕緣層301(芯層)和絕緣層401(阻焊層)之結構。並且，如圖2(b)所示，上述印刷配線基板300亦可以具有具備絕緣層301(芯層)、絕緣層305(增建層)及絕緣層401(阻焊層)之結構。該等芯層、增建層、阻焊層各自例如能夠由本實施形態的樹脂膜的硬化物構成。該芯層亦可以由使本實施形態的熱硬化性樹脂組成物含浸於纖維基材中而成之預浸體硬化而獲得之硬化體構成。 The printed wiring board 300 of the present embodiment includes an insulating layer made of a cured product of the resin film 10. As shown in FIG. 2(a), the printed wiring board 300 may have a structure including an insulating layer 301 (core layer) and an insulating layer 401 (solder resist layer). Further, as shown in FIG. 2(b), the printed wiring board 300 may have a structure including an insulating layer 301 (core layer), an insulating layer 305 (additive layer), and an insulating layer 401 (solder resist layer). Each of the core layer, the buildup layer, and the solder resist layer can be made of, for example, a cured product of the resin film of the present embodiment. The core layer may be formed of a hardened body obtained by curing a prepreg obtained by impregnating a thermosetting resin composition of the present embodiment with a prepreg.
由本實施形態的樹脂膜形成之硬化物可以不含玻璃布或紙基材等纖維基材。藉此，能夠設為特別適合於形成增建層(層間絕緣層)或阻焊層之構成。 The cured product formed of the resin film of the present embodiment may not contain a fiber base material such as a glass cloth or a paper base material. Thereby, it is possible to provide a configuration which is particularly suitable for forming an build-up layer (interlayer insulating layer) or a solder resist layer.
並且，本實施形態之印刷配線基板300可以是單面印刷配線基板，亦可以是雙面印刷配線基板或多層印刷配線基板。雙面印刷配線基板係指在絕緣層301的雙面積層金屬層303而成之印刷配線基板。並且，多層印刷配線基板係指藉由電鍍通孔法或增建法等在作為芯層之絕緣層301上積層2層以上增建層(例如，絕緣層305)而成之印刷配線基板。 Further, the printed wiring board 300 of the present embodiment may be a single-sided printed wiring board, or may be a double-sided printed wiring board or a multilayer printed wiring board. The double-sided printed wiring board refers to a printed wiring board in which the double-layer metal layer 303 of the insulating layer 301 is formed. In addition, the multilayer printed wiring board is a printed wiring board in which two or more layers (for example, an insulating layer 305) are laminated on the insulating layer 301 as a core layer by a plating via method or an extension method.
另外，本實施形態中，通孔307只要是用於將層之間電連接之孔即可，可以是貫穿孔及非貫穿孔中的任一種。通孔307可以將金屬埋設而形成。該埋設之金屬可以具有被無電解金屬鍍膜308覆蓋之結構。 Further, in the present embodiment, the through hole 307 may be any hole for electrically connecting the layers, and may be any of a through hole and a non-through hole. The through hole 307 can be formed by embedding a metal. The buried metal may have a structure covered by the electroless metal plating film 308.
並且，本實施形態中，上述金屬層303例如可以是電路圖案，亦可以是電極焊盤。該金屬層303例如可以具有金屬箔105及電解金屬鍍層309的金屬積層結構。 Further, in the present embodiment, the metal layer 303 may be, for example, a circuit pattern or an electrode pad. The metal layer 303 may have, for example, a metal laminated structure of the metal foil 105 and the electrolytic metal plating layer 309.
金屬層303例如藉由SAP(半加成製程)法形成於經藥液處理或電漿處理之金屬箔105或由本實施形態的樹脂膜的硬化物形成之絕緣層(例如，絕緣層301或絕緣層305)的表面上。例如，在金屬箔105或絕緣層301、305上實施無電解金屬鍍膜308之後，藉由抗鍍劑保護非電路形成部，藉由電解電鍍進行電解金屬鍍層309的形成，除去抗鍍劑並藉由快速蝕刻將電解金屬鍍膜309圖案化，藉此形成金屬層303。 The metal layer 303 is formed, for example, by a SAP (semi-additive process) method on the metal foil 105 treated by the chemical liquid treatment or the plasma treatment or the insulating layer formed of the cured product of the resin film of the present embodiment (for example, the insulating layer 301 or the insulation) On the surface of layer 305). For example, after the electroless metal plating film 308 is applied on the metal foil 105 or the insulating layers 301 and 305, the non-circuit forming portion is protected by a plating resist, and the electrolytic metal plating layer 309 is formed by electrolytic plating to remove the plating resist and borrow The electrolytic metal plating film 309 is patterned by rapid etching, thereby forming the metal layer 303.
並且，本實施形態的印刷配線基板300能夠設為不含玻璃纖維之樹脂基板。例如，作為芯層之絕緣層301可以是不含玻璃纖維之構成。 使用了該種樹脂基板之半導體封裝體中，亦能夠降低樹脂膜的硬化物的線膨脹係數，因此能夠充分抑制封裝體翹曲。 Further, the printed wiring board 300 of the present embodiment can be a resin substrate containing no glass fibers. For example, the insulating layer 301 as a core layer may be constructed without glass fibers. In the semiconductor package using such a resin substrate, the linear expansion coefficient of the cured product of the resin film can also be reduced, so that the package warpage can be sufficiently suppressed.
(半導體封裝體) (semiconductor package)
接著，對本實施形態的半導體裝置400進行說明。圖3(a)及圖3(b)係表示半導體裝置400的構成的一例之剖面圖。 Next, the semiconductor device 400 of the present embodiment will be described. 3(a) and 3(b) are cross-sectional views showing an example of the configuration of the semiconductor device 400.
本實施形態的半導體裝置400能夠具備印刷配線基板300及半導體元件，該半導體元件搭載於印刷配線基板300的電路層上，或者內置於印刷配線基板300。 The semiconductor device 400 of the present embodiment can include a printed wiring board 300 and a semiconductor element mounted on the circuit layer of the printed wiring board 300 or built in the printed wiring board 300.
例如，圖3(a)所示之半導體裝置400具有在圖3(a)所示之印刷配線基板300的電路層(金屬層303)上搭載有半導體元件407之結構。另一方面，圖3(b)所示之半導體裝置400具有在圖3(b)所示之印刷配線基板300的電路層(金屬層303)上搭載有半導體元件407之結構。半導體元件407被封裝材料層413覆蓋。該種半導體封裝體可以是半導體元件407經由焊錫凸塊410及金屬層303與印刷配線基板300電連接之倒裝晶片(flip chip)結構。 For example, the semiconductor device 400 shown in FIG. 3(a) has a structure in which a semiconductor element 407 is mounted on a circuit layer (metal layer 303) of the printed wiring board 300 shown in FIG. 3(a). On the other hand, the semiconductor device 400 shown in FIG. 3(b) has a structure in which the semiconductor element 407 is mounted on the circuit layer (metal layer 303) of the printed wiring board 300 shown in FIG. 3(b). The semiconductor element 407 is covered by the encapsulation material layer 413. Such a semiconductor package may be a flip chip structure in which the semiconductor element 407 is electrically connected to the printed wiring substrate 300 via the solder bump 410 and the metal layer 303.
本實施形態中，作為半導體封裝體的結構，並不限定於上述倒裝晶片連接結構，可以具有各種結構，例如能夠使用扇出(Fan Out)結構。由本實施形態的樹脂膜的硬化物形成之絕緣層在具有扇出結構之半導體封裝體的製造製程中能夠抑制基板翹曲或基板龜裂。 In the present embodiment, the structure of the semiconductor package is not limited to the above-described flip chip connection structure, and may have various structures. For example, a fan-out structure can be used. The insulating layer formed of the cured product of the resin film of the present embodiment can suppress substrate warpage or substrate cracking in the manufacturing process of the semiconductor package having the fan-out structure.
接著，對本實施形態的印刷配線基板的變形例進行說明。圖4(a)~圖4(c)係印刷配線基板500的製造製程的一例的製程剖面圖。如圖4(c)所示，本變形例的印刷配線基板500為不具有芯層之印刷配線 基板。 Next, a modification of the printed wiring board of the embodiment will be described. 4( a ) to 4 ( c ) are process cross-sectional views showing an example of a manufacturing process of the printed wiring board 500 . As shown in Fig. 4 (c), the printed wiring board 500 of the present modification is a printed wiring board having no core layer.
本實施形態的印刷配線基板500能夠設為不具備具有纖維基材之芯層之例如由增建層和阻焊層構成之無芯樹脂基板。該等增建層和阻焊層較佳由本實施形態的樹脂膜的硬化物形成之絕緣層構成。例如，圖4(c)所示之印刷配線基板500具備2層增建層(絕緣層540、550)和阻焊層(絕緣層560)。另外，印刷配線基板500的增建層可以是單層，亦可以具有2個以上的複數層。 The printed wiring board 500 of the present embodiment can be a coreless resin substrate which is not provided with a core layer having a fiber base material, for example, an extension layer and a solder resist layer. The build-up layer and the solder resist layer are preferably made of an insulating layer formed of a cured product of the resin film of the present embodiment. For example, the printed wiring board 500 shown in FIG. 4(c) includes two layers of buildup layers (insulating layers 540 and 550) and a solder resist layer (insulating layer 560). Further, the buildup layer of the printed wiring board 500 may be a single layer or may have two or more plural layers.
由本實施形態的樹脂膜的硬化物形成之絕緣層由於其強韌性優異，因此能夠抑制印刷配線基板500的翹曲或搬送時之龜裂。 Since the insulating layer formed of the cured product of the resin film of the present embodiment is excellent in toughness, it is possible to suppress warpage of the printed wiring board 500 or cracking during transportation.
圖4(c)所示之金屬層542、552、562可以是電路圖案，亦可以是電極焊盤，或者如上所述可以利用SAP法形成。該等金屬層542、552、562可以是單層，亦可以是複數個金屬層。 The metal layers 542, 552, 562 shown in FIG. 4(c) may be circuit patterns, may be electrode pads, or may be formed by the SAP method as described above. The metal layers 542, 552, and 562 may be a single layer or a plurality of metal layers.
印刷配線基板500可以具有能夠在平面上搭載複數個半導體元件之大面積。藉此，在一次將搭載於印刷配線基板500之複數個半導體元件封裝之後，將該等進行單個化，藉此能夠獲得複數個半導體封裝體。另外，印刷配線基板500能夠製成大致圓形形狀或矩形形狀等面板基板。 The printed wiring board 500 can have a large area in which a plurality of semiconductor elements can be mounted on a plane. Thereby, the plurality of semiconductor elements mounted on the printed wiring board 500 are packaged at a time, and then singulated, thereby obtaining a plurality of semiconductor packages. Further, the printed wiring board 500 can be formed into a panel substrate such as a substantially circular shape or a rectangular shape.
上述印刷配線基板500的製造方法並沒有特別限定，例如能夠藉由在支撐基板510上形成增建層、阻焊層之後剝離該支撐基板510而獲得。具體而言，如圖4(a)所示，在大面積的支撐基板510(例如，由SUS構成之板構件)上配置載體箔520、金屬箔530(例如，銅箔)。此時，能夠在支撐基板510與載體箔520之間設置未圖示之接著樹脂。接著，在金屬箔530上形成金屬層542。將該金屬層542例如藉由SAP方法等通常的方法進 行圖案化。接著，藉由加熱加壓成形法等積層上述附載體樹脂膜之後，從附載體樹脂膜上剝離載體基材。並且，將樹脂膜硬化。重複進行3次該等過程，形成2層增建層和1層阻焊層。 The method of manufacturing the printed wiring board 500 is not particularly limited. For example, it can be obtained by forming the build-up layer and the solder resist layer on the support substrate 510 and then peeling off the support substrate 510. Specifically, as shown in FIG. 4( a ), a carrier foil 520 and a metal foil 530 (for example, a copper foil) are disposed on a large-area support substrate 510 (for example, a plate member made of SUS). At this time, a bonding resin (not shown) can be provided between the support substrate 510 and the carrier foil 520. Next, a metal layer 542 is formed on the metal foil 530. The metal layer 542 is patterned by, for example, a usual method such as the SAP method. Then, the carrier-attached resin film is laminated by a heat press molding method or the like, and then the carrier substrate is peeled off from the carrier-attached resin film. Further, the resin film is cured. These processes were repeated three times to form a two-layer build-up layer and a one-layer solder resist layer.
然後，如圖4(b)所示，剝離支撐基板510。並且，藉由蝕刻等除去金屬箔530。 Then, as shown in FIG. 4(b), the support substrate 510 is peeled off. Further, the metal foil 530 is removed by etching or the like.
藉由以上，獲得圖4(c)所示之印刷配線基板500。 Thus, the printed wiring board 500 shown in FIG. 4(c) is obtained.
接著，對本實施形態的印刷配線基板的變形例進行說明。圖5係表示印刷配線基板600的構成的一例之剖面圖。 Next, a modification of the printed wiring board of the embodiment will be described. FIG. 5 is a cross-sectional view showing an example of the configuration of the printed wiring board 600.
圖5所示之印刷配線基板600可以由用於PLP(面板級封裝)製程之無芯樹脂基板610構成。PLP製程中，例如能夠利用配線板製程獲得具有晶圓以上的大面積之面板尺寸封裝體。藉由使用PLP製程，與晶圓級製程相比，能夠更高效地提高半導體封裝體的生產性。 The printed wiring board 600 shown in FIG. 5 can be constituted by a coreless resin substrate 610 for a PLP (Panel Level Package) process. In the PLP process, for example, a panel size package having a large area of a wafer or more can be obtained by a wiring board process. By using the PLP process, the productivity of the semiconductor package can be improved more efficiently than the wafer level process.
本實施形態中，無芯樹脂基板610的絕緣層612(層間絕緣層)或絕緣層630、632(阻焊層)可以藉由絕緣層構成，該絕緣層由本實施形態的樹脂膜的硬化物形成。本實施形態的樹脂膜的硬化物由於其強韌性優異，因此在PLP製程中，能夠有效地抑制印刷配線基板600的翹曲、或特別在搬送時或安裝時之無芯樹脂基板610的龜裂。 In the present embodiment, the insulating layer 612 (interlayer insulating layer) or the insulating layers 630 and 632 (solder resist layer) of the coreless resin substrate 610 can be formed of an insulating layer formed of a cured product of the resin film of the present embodiment. . Since the cured product of the resin film of the present embodiment is excellent in toughness, it is possible to effectively suppress warpage of the printed wiring board 600 or particularly cracking of the coreless resin substrate 610 during transportation or mounting in the PLP process. .
並且，本實施形態的印刷配線基板600具有如能夠在其平面內搭載複數個半導體元件(未圖示)之大面積。並且，在一次將沿印刷配線基板600的面內方向搭載之複數個半導體元件封裝之後，將該等進行單個化，藉此能夠獲得複數個半導體封裝體。本實施形態中，由於能夠降低樹脂膜的硬化物的線膨脹係數，因此能夠在PLP製程中獲得之半導體封裝 體中抑制封裝體翹曲。 Further, the printed wiring board 600 of the present embodiment has a large area in which a plurality of semiconductor elements (not shown) can be mounted in a plane. Then, a plurality of semiconductor elements mounted in the in-plane direction of the printed wiring board 600 are packaged at a time, and then singulated, thereby obtaining a plurality of semiconductor packages. In the present embodiment, since the linear expansion coefficient of the cured product of the resin film can be reduced, the package warp can be suppressed in the semiconductor package obtained in the PLP process.
印刷配線基板600能夠具備無芯樹脂基板610及形成於其表面之阻焊層(絕緣層630、632)。無芯樹脂基板610可以具有內置之半導體元件620。半導體元件620能夠經由通路(via)配線616電連接。並且，無芯樹脂基板610能夠至少具有絕緣層612(層間絕緣層)及通路配線616。經由通路配線616，能夠將下表面的金屬層640(電極焊盤)和上表面的金屬層618(柱)電連接。並且，通路配線616例如能夠經由金屬層614(柱)與金屬層640連接。在無芯樹脂基板610中，通路配線616及金屬層614被埋設。作為柱之金屬層614的表面可以與無芯樹脂基板610的表面構成同一平面。在本實施形態的印刷配線基板600中，無芯樹脂基板610由單層的層間絕緣層構成，但並不限定於該構成，亦可以具有積層有複數個層間絕緣層之結構。在該種層間絕緣層中可以至少形成有通路配線616作為層間連接配線。並且，本實施形態中，通路配線616、金屬層614或金屬層618例如可以由銅等金屬構成。 The printed wiring board 600 can include a coreless resin substrate 610 and a solder resist layer (insulating layers 630 and 632) formed on the surface thereof. The coreless resin substrate 610 may have a built-in semiconductor component 620. The semiconductor element 620 can be electrically connected via via wiring 616. Further, the coreless resin substrate 610 can have at least an insulating layer 612 (interlayer insulating layer) and a via wiring 616. The metal layer 640 (electrode pad) on the lower surface and the metal layer 618 (column) on the upper surface can be electrically connected via the via wiring 616. Further, the via wiring 616 can be connected to the metal layer 640 via the metal layer 614 (column), for example. In the coreless resin substrate 610, the via wiring 616 and the metal layer 614 are buried. The surface of the metal layer 614 as a pillar may be flush with the surface of the coreless resin substrate 610. In the printed wiring board 600 of the present embodiment, the coreless resin substrate 610 is composed of a single-layer interlayer insulating layer. However, the present invention is not limited to this configuration, and may have a structure in which a plurality of interlayer insulating layers are laminated. At least the via wiring 616 may be formed as the interlayer connection wiring in the interlayer insulating layer. Further, in the present embodiment, the via wiring 616, the metal layer 614, or the metal layer 618 may be made of, for example, a metal such as copper.
並且，無芯樹脂基板610的上表面和下表面可以被阻焊層(絕緣層630、632)覆蓋。例如，絕緣層630能夠覆蓋形成於絕緣層612的表面上之金屬層650。金屬層650由第1金屬層652(鍍層)和第2金屬層654(無電解鍍層)構成，例如可以是利用SAP法形成之金屬層。金屬層650例如可以是電路圖案或電極焊盤。 Also, the upper surface and the lower surface of the coreless resin substrate 610 may be covered by the solder resist layer (insulating layers 630, 632). For example, the insulating layer 630 can cover the metal layer 650 formed on the surface of the insulating layer 612. The metal layer 650 is composed of a first metal layer 652 (plating layer) and a second metal layer 654 (electroless plating layer), and may be, for example, a metal layer formed by an SAP method. Metal layer 650 can be, for example, a circuit pattern or an electrode pad.
並且，本實施形態的印刷配線基板600的製造方法並沒有特別限定，例如能夠使用如下方法。例如，在支撐基板上形成絕緣層612。接著，在絕緣層612形成通路，藉由電鍍方法在通路內形成埋設有金屬膜的 通路配線616。接著，藉由SAP方法在絕緣層612的表面上形成再配線(金屬層650)。然後，可以積層具有該種層間連接配線之複數個層間絕緣層。然後，形成阻焊層(絕緣層630、632)。 Further, the method of manufacturing the printed wiring board 600 of the present embodiment is not particularly limited, and for example, the following method can be used. For example, an insulating layer 612 is formed on the support substrate. Next, a via is formed in the insulating layer 612, and a via wiring 616 in which a metal film is buried is formed in the via by a plating method. Next, rewiring (metal layer 650) is formed on the surface of the insulating layer 612 by the SAP method. Then, a plurality of interlayer insulating layers having such interlayer connection wirings may be laminated. Then, a solder resist layer (insulating layers 630, 632) is formed.
藉由以上，能夠獲得印刷配線基板600。 According to the above, the printed wiring board 600 can be obtained.
接著，對本實施形態的印刷配線基板的變形例進行說明。圖6係表示印刷配線基板700的構成的一例之剖面圖。 Next, a modification of the printed wiring board of the embodiment will be described. FIG. 6 is a cross-sectional view showing an example of the configuration of the printed wiring board 700.
圖6所示之印刷配線基板700能夠由帶柱之基板(MIS基板)構成。例如，帶柱之基板能夠由無芯樹脂基板710構成，該無芯樹脂基板具有在絕緣層712(層間絕緣層)內埋設有通路配線716和金屬層718(柱)之結構。帶柱之基板可以是被單個化之後的基板，亦可以是單個化前的具有大面積之基板(例如，如晶圓之類的支撐體)。 The printed wiring board 700 shown in FIG. 6 can be constituted by a column-attached substrate (MIS substrate). For example, the substrate with a pillar can be composed of a coreless resin substrate 710 having a structure in which a via wiring 716 and a metal layer 718 (column) are buried in an insulating layer 712 (interlayer insulating layer). The substrate with the pillars may be a substrate after being singulated, or may be a substrate having a large area before singulation (for example, a support such as a wafer).
藉由使用本實施形態的印刷配線基板700，能夠將半導體封裝體的生產性高效地提高至與晶圓級製程相同程度以上。 By using the printed wiring board 700 of the present embodiment, the productivity of the semiconductor package can be efficiently improved to the same level as or higher than the wafer level process.
本實施形態中，無芯樹脂基板710的絕緣層712(層間絕緣層)或絕緣層730、732(阻焊層)可以以由本實施形態的樹脂膜的硬化物形成之絕緣層構成。本實施形態的樹脂膜的硬化物由於其強韌性優異，因此能夠有效地抑制印刷配線基板700的翹曲、或特別是搬送時或安裝時之無芯樹脂基板710的龜裂。 In the present embodiment, the insulating layer 712 (interlayer insulating layer) or the insulating layers 730 and 732 (solder resist layer) of the coreless resin substrate 710 can be formed of an insulating layer formed of a cured product of the resin film of the present embodiment. Since the cured product of the resin film of the present embodiment is excellent in toughness, it is possible to effectively suppress warpage of the printed wiring board 700, or particularly cracking of the coreless resin substrate 710 at the time of conveyance or mounting.
並且，本實施形態的印刷配線基板700具有如能夠在其平面內搭載複數個半導體元件(未圖示)之大面積。並且，在一次將沿印刷配線基板700的面內方向搭載之複數個半導體元件封裝之後，將該等進行單個化，藉此能夠獲得複數個半導體封裝體。由於能夠降低本實施形態的樹 脂膜的硬化物的線膨脹係數，因此能夠在獲得之半導體封裝體中抑制封裝體翹曲。 Further, the printed wiring board 700 of the present embodiment has a large area in which a plurality of semiconductor elements (not shown) can be mounted in a plane. Then, a plurality of semiconductor elements mounted in the in-plane direction of the printed wiring board 700 are packaged at a time, and then singulated, thereby obtaining a plurality of semiconductor packages. Since the linear expansion coefficient of the cured product of the resin film of the present embodiment can be reduced, the package warp can be suppressed in the obtained semiconductor package.
印刷配線基板700能夠具備無芯樹脂基板710及形成於其表面之阻焊層(絕緣層730、732)。無芯樹脂基板710可以具有內置之半導體元件720。半導體元件720能夠經由通路配線716電連接。並且，無芯樹脂基板710能夠至少具有絕緣層712(層間絕緣層)及通路配線716及金屬層718(柱)。經由通路配線716，能夠將下表面的金屬層714(柱)和上表面的金屬層718(柱)電連接。並且，埋設於絕緣層712內之金屬層714能夠與形成於絕緣層712的表面之金屬層740(電極焊盤)連接。並且，絕緣層712的表面可以具有研磨面。金屬層718的一面可以與絕緣層712的研磨面構成同一平面。 The printed wiring board 700 can include a coreless resin substrate 710 and a solder resist layer (insulating layers 730 and 732) formed on the surface thereof. The coreless resin substrate 710 may have a built-in semiconductor element 720. The semiconductor element 720 can be electrically connected via the via wiring 716. Further, the coreless resin substrate 710 can have at least an insulating layer 712 (interlayer insulating layer), a via wiring 716, and a metal layer 718 (column). The metal layer 714 (column) on the lower surface and the metal layer 718 (column) on the upper surface can be electrically connected via the via wiring 716. Further, the metal layer 714 embedded in the insulating layer 712 can be connected to the metal layer 740 (electrode pad) formed on the surface of the insulating layer 712. Also, the surface of the insulating layer 712 may have a polished surface. One side of the metal layer 718 may be flush with the polished surface of the insulating layer 712.
在本實施形態的印刷配線基板700中，無芯樹脂基板710由單層的層間絕緣層構成，但並不限定於該構成，亦可以具有積層有複數個層間絕緣層之結構。在該種層間絕緣層中可以形成有通路配線716及金屬層718(柱)作為層間連接配線。並且，本實施形態中，通路配線716、金屬層714或金屬層718例如可以由銅等金屬構成。並且，無芯樹脂基板710的上表面和下表面可以被阻焊層(絕緣層730、732)覆蓋。 In the printed wiring board 700 of the present embodiment, the coreless resin substrate 710 is composed of a single layer of an interlayer insulating layer. However, the present invention is not limited to this configuration, and may have a structure in which a plurality of interlayer insulating layers are laminated. A via wiring 716 and a metal layer 718 (column) may be formed as interlayer connection wiring in such an interlayer insulating layer. Further, in the present embodiment, the via wiring 716, the metal layer 714, or the metal layer 718 may be made of, for example, a metal such as copper. Also, the upper surface and the lower surface of the coreless resin substrate 710 may be covered by the solder resist layer (insulating layers 730, 732).
並且，本實施形態的印刷配線基板700的製造方法並沒有特別限定，例如能夠使用如下方法。例如，在支撐基板上，於絕緣層上形成銅柱(例如，金屬層718)。進一步用絕緣層將銅柱埋入。接著，藉由研磨或化學蝕刻等方法，使該銅柱的表面露出(亦即，進行銅柱的出頭)。接著，藉由SAP方法形成再配線。藉由該種製程，能夠形成具有層間絕緣層之無 芯樹脂基板710。然後，可以藉由將形成層間絕緣層之製程重複複數次而將具有層間連接配線之層間絕緣層積層複數層。然後，形成阻焊層(絕緣層730、732)。 Further, the method of manufacturing the printed wiring board 700 of the present embodiment is not particularly limited, and for example, the following method can be used. For example, on the support substrate, a copper pillar (for example, a metal layer 718) is formed on the insulating layer. The copper pillar is further buried with an insulating layer. Next, the surface of the copper pillar is exposed by grinding or chemical etching (that is, the exit of the copper pillar). Next, rewiring is formed by the SAP method. By this process, the coreless resin substrate 710 having the interlayer insulating layer can be formed. Then, a plurality of layers of the interlayer insulating layer having the interlayer connection wiring can be laminated by repeating the process of forming the interlayer insulating layer a plurality of times. Then, a solder resist layer (insulating layers 730, 732) is formed.
藉由以上，能夠獲得印刷配線基板700。 According to the above, the printed wiring board 700 can be obtained.
以上，參閱圖式對本發明的實施形態進行了敘述，但該等為本發明的例示，亦能夠採用除上述以外的各種各樣的構成。 Although the embodiments of the present invention have been described above with reference to the drawings, these are examples of the present invention, and various configurations other than the above may be employed.
【實施例】 [Examples]
以下，參閱實施例對本發明進行詳細說明，但本發明不受該等實施例記載的任何限定。 Hereinafter, the present invention will be described in detail with reference to the examples, but the present invention is not limited by the examples.
(熱硬化性樹脂組成物的製備) (Preparation of thermosetting resin composition)
對於實施例及比較例，製備出清漆狀的熱硬化性樹脂組成物。 In the examples and comparative examples, a varnish-like thermosetting resin composition was prepared.
首先，以表1所示之固體成分比例使各成分溶解或分散，以在甲基乙基酮中不揮發成分成為70重量%之方式，使用高速攪拌裝置進行攪拌，製備出樹脂清漆。 First, the components were dissolved or dispersed in a ratio of the solid content shown in Table 1, and the resin varnish was prepared by stirring with a high-speed stirring device so that the nonvolatile content of the methyl ethyl ketone was 70% by weight.
另外，表1中之表示各成分的摻合比例之數值表示各成分相對於熱硬化性樹脂組成物的固體成分整體之摻合比例(重量%)。 In addition, the numerical value of the blending ratio of each component in Table 1 shows the blending ratio (% by weight) of each component with respect to the solid content of the thermosetting resin composition as a whole.
表1中之各成分的詳細內容如下。 The details of each component in Table 1 are as follows.
實施例及比較例中使用了以下原料。 The following materials were used in the examples and comparative examples.
(熱硬化性樹脂) (thermosetting resin)
熱硬化性樹脂1：茀型環氧樹脂(EG-280，大阪瓦斯化學股份有限公司製，在25℃為液體，黏度6Pa．s，環氧當量460g/eq) Thermosetting resin 1: 茀-type epoxy resin (EG-280, manufactured by Osaka Gas Chemical Co., Ltd., liquid at 25 ° C, viscosity 6 Pa.s, epoxy equivalent 460 g / eq)
熱硬化性樹脂2：雙酚A型環氧樹脂(EXA-4850-150，迪愛生股份有限 公司製，在25℃下為液體，黏度15Pa．s，環氧當量450g/eq) Thermosetting Resin 2: Bisphenol A type epoxy resin (EXA-4850-150, manufactured by Di Ai Sheng Co., Ltd., liquid at 25 ° C, viscosity 15 Pa.s, epoxy equivalent 450 g / eq)
熱硬化性樹脂3：聚醚型環氧樹脂(AER-9000，旭化成股份有限公司製，在25℃為液體，黏度1Pa．s，環氧當量380g/eq) Thermosetting resin 3: Polyether epoxy resin (AER-9000, manufactured by Asahi Kasei Co., Ltd., liquid at 25 ° C, viscosity 1 Pa.s, epoxy equivalent 380 g / eq)
熱硬化性樹脂4：雙酚F型環氧樹脂(EPICLON、830S，迪愛生股份有限公司製，黏度3.8Pa．s，環氧當量171g/eq) Thermosetting Resin 4: Bisphenol F-type epoxy resin (EPICLON, 830S, manufactured by Di Ai Sheng Co., Ltd., viscosity 3.8 Pa.s, epoxy equivalent 171 g/eq)
熱硬化性樹脂5：雙順丁烯二醯亞胺(BMI-1500、規劃者微粒公司製，黏度40Pa．s，重量平均分子量(Mw)1500) Thermosetting resin 5: bis-m-butylene diimide (BMI-1500, manufactured by Planner Microparticles, viscosity 40 Pa.s, weight average molecular weight (Mw) 1500)
熱硬化性樹脂6：伸萘基醚型環氧樹脂(HP-6000，迪愛生股份有限公司製，環氧當量250g/eq) Thermosetting resin 6: a naphthyl ether type epoxy resin (HP-6000, manufactured by Di Aisheng Co., Ltd., epoxy equivalent 250 g/eq)
熱硬化性樹脂的黏度在室溫25℃使用E型黏度計進行了測量。 The viscosity of the thermosetting resin was measured at room temperature of 25 ° C using an E-type viscometer.
(苯并化合物) (Benzene Compound)
苯并化合物1：下述式表示之苯并化合物(四國化成工業股份有限公司製，P-d型苯并) Benzo Compound 1: Benzene represented by the following formula Compound (made by Shikoku Chemical Industry Co., Ltd., Pd type benzophenone) )
(苯氧樹脂) (phenoxy resin)
苯氧樹脂1：苯氧樹脂(YX6954，三菱化學股份有限公司製，Mw：40,000) Phenoxy resin 1: phenoxy resin (YX6954, manufactured by Mitsubishi Chemical Corporation, Mw: 40,000)
苯氧樹脂2：苯氧樹脂(YX6900，三菱化學股份有限公司製，Mw：15,000) Phenoxy resin 2: phenoxy resin (YX6900, manufactured by Mitsubishi Chemical Corporation, Mw: 15,000)
(其他) (other)
(甲基)丙烯酸酯聚合物1：PMS-13-7，長瀨化成股份有限公司製，Mw：10×104，環氧改質丙烯酸樹脂，Tg=17℃，環氧值=0.20eq/kg (Meth)acrylate polymer 1: PMS-13-7, manufactured by Nagase Chemical Co., Ltd., Mw: 10 × 10 4 , epoxy modified acrylic resin, Tg = 17 ° C, epoxy value = 0.20 eq / Kg
(硬化劑) (hardener)
硬化劑1：酚系硬化劑(苯酚酚醛清漆樹脂，住友電木股份有限公司製，HF-3) Hardener 1: phenolic hardener (phenol novolac resin, manufactured by Sumitomo Bakelite Co., Ltd., HF-3)
硬化劑2：酚系硬化劑(日本化藥公司製，GPH-103) Hardener 2: phenolic hardener (GPH-103, manufactured by Nippon Kayaku Co., Ltd.)
硬化劑3：胺系硬化劑(二乙基甲苯二胺，MITSUI FINE CHEMICALS,INC.製，DETDA) Hardener 3: Amine-based hardener (diethyltoluenediamine, manufactured by MITSUI FINE CHEMICALS, INC., DETDA)
硬化劑4：催化劑型硬化劑/咪唑化合物(四國化成工業股份有限公司製，Curezol 1B2PZ) Hardener 4: Catalyst-type hardener/imidazole compound (Curezol 1B2PZ, manufactured by Shikoku Chemical Industry Co., Ltd.)
(無機填充材料) (inorganic filler)
無機填充材料1：球狀二氧化矽(Admatechs Co.,Ltd.製SO-C4，平均粒徑1.0μm，苯基胺基矽烷處理) Inorganic filler material 1: spherical cerium oxide (SO-C4 manufactured by Admatechs Co., Ltd., average particle diameter: 1.0 μm, treated with phenylamino decane)
(偶合劑) (coupling agent)
偶合劑1：矽烷偶合劑(N-苯基γ-胺基丙基三甲氧基矽烷，信越化學工業股份有限公司製，KBM-573) Coupling agent 1: decane coupling agent (N-phenyl γ-aminopropyltrimethoxy decane, manufactured by Shin-Etsu Chemical Co., Ltd., KBM-573)
(附載體樹脂膜) (with carrier resin film)
實施例及比較例中，將獲得之樹脂清漆塗佈於作為載體基材之PET薄膜上之後，在120℃、5分鐘的條件下除去溶劑而形成了厚度25μm的樹脂膜。藉此，獲得了附載體樹脂膜。 In the examples and the comparative examples, the obtained resin varnish was applied onto a PET film as a carrier substrate, and then the solvent was removed under conditions of 120 ° C for 5 minutes to form a resin film having a thickness of 25 μm. Thereby, a carrier resin film was obtained.
(半導體封裝體的製造) (Manufacture of semiconductor package)
1．印刷配線基板的製造 1. Manufacturing of printed wiring boards
首先，準備了使用極薄銅箔(三井金屬鑛業股份有限公司製，Micro Thin Ex，2.0μm)之雙面覆銅積層板(住友電木股份有限公司製，LAZ-4785TH-G，絕緣層厚度0.2mm)。接著，在雙面覆銅積層板表面的極薄銅箔層上實施約1μm的粗糙化處理之後，利用二氧化碳雷射形成了層間連接用的φ80μm的通孔。接著，將形成有通孔之雙面覆銅積層板在60℃的膨潤液(Atotech Japan K.K.製，Swelling Dip Securiganth P)中浸漬5分鐘，進而在80℃的過錳酸鉀水溶液(Atotech Japan K.K.製，Concentrate Compact CP)中浸漬2分鐘之後中和而進行了通孔內的除膠渣處理。接著，對除膠渣處理後的雙面覆銅積層板以厚度0.5μm進行無電解鍍銅而以厚度18μm形成電解鍍銅用抗蝕劑層，並進行圖案鍍銅，然後在150℃加熱30分鐘而進行了後硬化(post cure)。接著，剝離抗鍍劑，並對整個剝離之面進行快速蝕刻而在L/S=15/15μm的雙面形成了電路圖案。 First, a double-sided copper-clad laminate using ultra-thin copper foil (Micro Thin Ex, 2.0 μm, manufactured by Mitsui Mining Co., Ltd.) (manufactured by Sumitomo Bakelite Co., Ltd., LAZ-4785TH-G, thickness of insulating layer) was prepared. 0.2mm). Next, a roughening treatment of about 1 μm was performed on the ultra-thin copper foil layer on the surface of the double-sided copper clad laminate, and then a through hole of φ80 μm for interlayer connection was formed by carbon dioxide laser. Next, the double-sided copper-clad laminate in which the through holes were formed was immersed in a swelling solution (Stoing Japan, Swelling Dip Securiganth P, manufactured by Atotech Japan KK) at 60 ° C for 5 minutes, and further, an aqueous potassium permanganate solution at 80 ° C (Atotech Japan KK) The solution was neutralized after immersion for 2 minutes in Concentrate Compact CP), and the desmear treatment in the through holes was performed. Next, the double-sided copper-clad laminate after the desmear treatment was subjected to electroless copper plating at a thickness of 0.5 μm to form a resist layer for electrolytic copper plating with a thickness of 18 μm, and patterned copper plating, followed by heating at 150 ° C. Post cure was performed in minutes. Next, the plating resist was peeled off, and the entire peeled surface was quickly etched to form a circuit pattern on both sides of L/S = 15/15 μm.
對形成電路圖案之後的電路基板，以樹脂膜與電路圖案對向之方式將上述中獲得之附載體樹脂膜(作為層間絕緣膜)積層於雙面之後，使用2階段真空加壓式層壓裝置(名機製作所股份有限公司製，MVLP-500)減壓30秒鐘，並在10hPa以下，作為第1階段條件於溫度120℃、壓力0.8MPa、 30秒、以及作為第2階段條件於溫度120℃、壓力1.0MPa、60秒，利用SUS鏡面板進行了真空加熱加壓成形。接著，從附載體樹脂膜剝離載體基材之後，在200℃、2小時的條件下，將電路圖案上的樹脂膜進行了硬化。接著，利用半加成法進行電路加工，將在上述中獲得之附載體樹脂膜(作為阻焊層)同樣積層於雙面，並進行雷射開口而獲得了印刷配線基板。 After the circuit substrate on which the circuit pattern is formed, the carrier-attached resin film (as an interlayer insulating film) obtained above is laminated on both sides with the resin film and the circuit pattern facing each other, and a two-stage vacuum pressure type laminating apparatus is used. (Mega, Ltd., MVLP-500) was depressurized for 30 seconds and at 10 hPa or less, as the first stage conditions at a temperature of 120 ° C, a pressure of 0.8 MPa, 30 seconds, and a second stage condition at a temperature of 120. At a temperature of ° C and a pressure of 1.0 MPa for 60 seconds, vacuum heat and pressure molding was carried out using a SUS mirror panel. Next, after peeling off the carrier substrate from the carrier-attached resin film, the resin film on the circuit pattern was cured under the conditions of 200 ° C for 2 hours. Then, the circuit was processed by the semi-additive method, and the carrier-attached resin film (as a solder resist layer) obtained as described above was laminated on both sides, and a laser opening was formed to obtain a printed wiring board.
2．半導體裝置的製造 2. Semiconductor device manufacturing
在獲得之印刷配線基板之上安裝10mm×10mm×100μm厚度的帶焊錫凸塊之半導體元件，並以底部填充劑(住友電木股份有限公司製、CRP-4160G)密封，在150℃使其硬化了2小時。最後，以15mm×15mm切片而獲得了半導體裝置。 A semiconductor component with solder bumps having a thickness of 10 mm × 10 mm × 100 μm was mounted on the obtained printed wiring board, and sealed with an underfill (manufactured by Sumitomo Bakelite Co., Ltd., CRP-4160G), and hardened at 150 ° C. It took 2 hours. Finally, a semiconductor device was obtained by slicing at 15 mm × 15 mm.
實施例及比較例中，進行了如下評價。將評價結果示於表2。 In the examples and comparative examples, the following evaluations were made. The evaluation results are shown in Table 2.
(硬化物) (hardened)
積層4片從獲得之附載體樹脂膜剝離作為載體基材之PET薄膜而成之樹脂膜而製作出厚度100μm的樹脂片。接著，將該樹脂片在200℃熱處理2小時而獲得了熱硬化性樹脂組成物的硬化物。 Four sheets of a resin film obtained by peeling a PET film as a carrier substrate from the obtained carrier-attached resin film were laminated to prepare a resin sheet having a thickness of 100 μm. Next, the resin sheet was heat-treated at 200 ° C for 2 hours to obtain a cured product of a thermosetting resin composition.
(儲存彈性模數) (storage elastic modulus)
(2)儲存彈性模數E' (2) Storage elastic modulus E'
使用動態黏彈性測量裝置(DMA裝置，TA Instruments公司製，Q800)進行了儲存彈性模數E'的測量。 The measurement of the storage elastic modulus E' was performed using a dynamic viscoelasticity measuring device (DMA device, manufactured by TA Instruments, Q800).
從獲得之硬化物切出了8mm×40mm的試片。對切出之試片，在升溫速度5℃/min、頻率1Hz進行在30℃之儲存彈性模數測量，計算出在30℃之儲存彈性模數E'30。 A test piece of 8 mm × 40 mm was cut out from the obtained cured product. For the cut test piece, the storage elastic modulus measurement at 30 ° C was performed at a temperature increase rate of 5 ° C / min and a frequency of 1 Hz, and a storage elastic modulus E' 30 at 30 ° C was calculated.
(拉伸伸長率) (tensile elongation)
將獲得之硬化物切成縱100mm×橫6mm的試驗片。拉伸試驗中，將該試驗片夾在以一定距離配置之卡盤上，進行了直至試驗片斷裂為止以一定的速度拉伸之評價。此時，使用精密萬能試驗機(島津製作所股份有限公司製，AUTOGRAPH AG-IS)，並使用了初期卡盤間距離L：20mm、試驗片的厚度：0.1mm、測量溫度：25℃、試驗速度：1mm/分鐘的條件。在上述拉伸試驗中，拉伸伸長率(%)依據在上述條件下斷裂時的位移量和初期卡盤間距離進行了計算。 The obtained cured product was cut into test pieces of 100 mm in length × 6 mm in width. In the tensile test, the test piece was placed on a chuck placed at a predetermined distance, and evaluation was performed at a constant speed until the test piece was broken. In this case, a precision universal testing machine (AUTOGRAPH AG-IS, manufactured by Shimadzu Corporation) was used, and the initial inter-cartridge distance L: 20 mm, the thickness of the test piece: 0.1 mm, the measurement temperature: 25 ° C, and the test speed were used. : Condition of 1 mm/min. In the above tensile test, the tensile elongation (%) was calculated in accordance with the amount of displacement at the time of breaking under the above conditions and the initial inter-clip distance.
(平均線膨脹係數(50℃至250℃)) (Average linear expansion coefficient (50 ° C to 250 ° C))
從獲得之硬化物切出了4mm×40mm的試片。對切出之試片，使用熱機械分析裝置TMA(TA Instruments公司製，Q400)，在溫度範圍50~250℃、 升溫速度10℃/min、荷重10g、拉伸模式的條件下進行了2次熱機械分析(TMA)測量。計算出在50℃至250℃的範圍內之平面方向(XY方向)的線膨脹係數的平均值。另外，線膨脹係數採用了第2次的值。 A test piece of 4 mm × 40 mm was cut out from the obtained cured product. The cut test piece was subjected to a thermomechanical analyzer TMA (manufactured by TA Instruments, Q400) twice under the conditions of a temperature range of 50 to 250 ° C, a temperature increase rate of 10 ° C/min, a load of 10 g, and a tensile mode. Thermomechanical analysis (TMA) measurements. The average value of the linear expansion coefficients in the plane direction (XY direction) in the range of 50 ° C to 250 ° C was calculated. In addition, the linear expansion coefficient uses the second value.
(玻璃轉移溫度、損耗正切tan δ) (glass transition temperature, loss tangent tan δ)
從獲得之硬化物切出了8mm×40mm的試片。對切出之試片，在升溫速度5℃/min、頻率1Hz進行了動態黏彈性測量。藉由動態黏彈性測量裝置(DMA裝置，TA Instruments公司製，Q800)進行了玻璃轉移溫度、損耗正切tan δ的測量。在此，玻璃轉移溫度設為損耗正切tan δ呈現最大值之溫度。並且，依據獲得之損耗正切tan δ的峰值計算出其半值寬。 A test piece of 8 mm × 40 mm was cut out from the obtained cured product. The dynamic viscoelasticity measurement was performed on the cut test piece at a heating rate of 5 ° C/min and a frequency of 1 Hz. The glass transition temperature and the loss tangent tan δ were measured by a dynamic viscoelasticity measuring device (DMA device, manufactured by TA Instruments, Q800). Here, the glass transition temperature is set to a temperature at which the loss tangent tan δ exhibits a maximum value. And, the half value width is calculated from the peak value of the obtained tangent tan δ.
(彎曲試驗) (Bending test)
將獲得之硬化物用作樣品試驗板。樣品試驗板的樣品厚度為100μm。將該樣品試驗板沿著特定直徑的支撐棒折曲180度，並評價了有無斷裂。並且，逐漸減小直徑，將未發生斷裂之最小直徑設為表2中記載之最小直徑。其中，可評價之最小直徑為2mm。 The obtained cured product was used as a sample test plate. The sample thickness of the sample test plate was 100 μm. The sample test plate was bent 180 degrees along a support rod of a specific diameter, and the presence or absence of breakage was evaluated. Further, the diameter was gradually decreased, and the minimum diameter at which no fracture occurred was set to the minimum diameter described in Table 2. Among them, the minimum diameter that can be evaluated is 2 mm.
(面板翹曲) (panel warpage)
在縱250mm×橫250mm見方SUS的支撐基板上配置12μm銅箔，使用2階段真空加壓式層壓裝置(名機製作所股份有限公司製，MVLP-500)，將實施例及比較例中獲得之附載體樹脂膜減壓30秒鐘，並在10hPa以下，作為第1階段條件於溫度120℃、壓力0.8MPa、30秒、作為第2階段條件於溫度120℃、壓力1.0MPa、60秒，利用SUS鏡面板進行了真空加熱加壓成形。接著，從附載體樹脂膜剝離載體基材之後，在180℃、2小時的條件下進行了硬化。將其重複3次而形成三層增建層，並評價了剝離SUS時的面 板翹曲。測量了板端的翹曲。 A 12 μm copper foil was placed on a support substrate of 250 mm long and 250 mm square SUS, and was obtained in the examples and comparative examples using a two-stage vacuum pressure type laminating apparatus (MVLP-500, manufactured by Nago Seisakusho Co., Ltd.). The resin film with a carrier was depressurized for 30 seconds, and was 10 hPa or less, and was used as a first-stage condition at a temperature of 120 ° C, a pressure of 0.8 MPa, and 30 seconds, and as a second-stage condition at a temperature of 120 ° C, a pressure of 1.0 MPa, and 60 seconds. The SUS mirror panel was vacuum heated and formed. Next, the carrier substrate was peeled off from the carrier-attached resin film, and then cured at 180 ° C for 2 hours. This was repeated three times to form a three-layer buildup layer, and the panel warpage at the time of peeling SUS was evaluated. The warpage of the end of the plate was measured.
A：小於15mm A: less than 15mm
B：15mm以上且小於50mm(實質上無問題) B: 15 mm or more and less than 50 mm (substantially no problem)
C：50mm以上 C: 50mm or more
(處理性) (handling)
在進行SUS剝離後，進一步對12μm銅箔進行了蝕刻。然後，評價了面板有無龜裂。 After the SUS peeling, the 12 μm copper foil was further etched. Then, the panel was evaluated for cracks.
A：無龜裂 A: no cracks
B：有龜裂 B: There is crack
可知由上述實施例1~8的熱硬化性樹脂組成物形成之絕緣層，在面板翹曲及處理性方面顯示出良好的結果，強韌性優異。另一方面，由上述比較例1~4的熱硬化性樹脂組成物形成之絕緣層不具有充分的強靭性。另外，依據比較例3的評價結果可知，即使熱硬化性樹脂組成物的硬化物的拉伸伸長率為2%以上，若硬化物的儲存彈性模數E'大於10GPa，則面板翹曲亦會變大，不具有充分的強靭性。並且，依據比較例4的評價結果可知，即使熱硬化性樹脂組成物的硬化物的儲存彈性模數E'為1GPa以上且10GPa以下，若拉伸伸長率小於2%，則面板翹曲亦大，不具有充分的強靭性。 It is understood that the insulating layer formed of the thermosetting resin compositions of the above-described Examples 1 to 8 exhibits excellent results in panel warpage and handleability, and is excellent in toughness. On the other hand, the insulating layer formed of the thermosetting resin compositions of Comparative Examples 1 to 4 described above did not have sufficient toughness. Further, according to the evaluation results of Comparative Example 3, even if the tensile elongation of the cured product of the thermosetting resin composition is 2% or more, if the storage elastic modulus E' of the cured product is more than 10 GPa, the panel warpage will occur. It becomes bigger and does not have sufficient strength and toughness. In addition, according to the evaluation results of the comparative example 4, even if the storage elastic modulus E' of the cured product of the thermosetting resin composition is 1 GPa or more and 10 GPa or less, if the tensile elongation is less than 2%, the panel warpage is large. , does not have sufficient strength and toughness.
以上，基於實施例對本發明進行了進一步具體的說明，但該等為本發明的例示，亦能夠採用除上述以外的各種各樣的構成。 The present invention has been specifically described above based on the embodiments, but these are examples of the present invention, and various configurations other than the above may be employed.
【產業上的可利用性】 [Industrial availability]
本發明的熱硬化性樹脂組成物具有如下特徵：含有熱硬化性 樹脂、硬化劑及無機填充材料，其硬化物在30℃之儲存彈性模數E'30及硬化物的拉伸伸長率在前述特定的範圍內。使用具有該特徵之本發明的熱硬化性樹脂組成物而形成之絕緣膜藉由兼顧低彈性和高伸長度而發揮優異之強靭性。因此，藉由利用於該絕緣層，強韌性優異，因此在製造大面積的面板尺寸封裝體之面板級製程中，能夠抑制面板(無芯基板)的翹曲、搬送時或安裝時之基板龜裂。因此，本發明具有產業上的可利用性。 The thermosetting resin composition of the present invention is characterized in that it contains a thermosetting resin, a curing agent, and an inorganic filler, and the storage elastic modulus E' 30 of the cured product at 30 ° C and the tensile elongation of the cured product are as described above. Within a specific range. The insulating film formed using the thermosetting resin composition of the present invention having such characteristics exhibits excellent toughness by achieving both low elasticity and high elongation. Therefore, since the insulating layer is excellent in toughness, it is possible to suppress warpage of the panel (coreless substrate), warpage during transport, or mounting of the substrate turtle during the panel-level manufacturing process of manufacturing a panel-size package having a large area. crack. Therefore, the present invention has industrial applicability.
Claims (15)
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| US10575401B1 (en) | 2018-08-10 | 2020-02-25 | Taiwan Union Technology Corporation | Dielectric composite and uses thereof |
| TWI821355B (en) * | 2018-08-07 | 2023-11-11 | 日商信越聚合物股份有限公司 | High frequency circuit substrate |
| TWI824889B (en) * | 2022-12-18 | 2023-12-01 | 台光電子材料股份有限公司 | Resin compositions and products thereof |
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| CN110582528A (en) * | 2017-04-28 | 2019-12-17 | 日立化成株式会社 | Sealing film, sealing structure, and methods for producing same |
| US11345784B2 (en) * | 2018-11-09 | 2022-05-31 | Panasonic Intellectual Property Management Co., Ltd. | Resin composition, and resin film, metal foil with resin, metal clad laminate, wiring board, and circuit mount component using same |
| JP7087963B2 (en) * | 2018-11-29 | 2022-06-21 | 信越化学工業株式会社 | Epoxy resin compositions, multilayer printed wiring boards, and semiconductor devices |
| JP2020094212A (en) * | 2018-12-10 | 2020-06-18 | 積水化学工業株式会社 | Resin material and multilayer printed wiring board |
| JP7412413B2 (en) * | 2019-03-27 | 2024-01-12 | 三井金属鉱業株式会社 | Resin compositions, resin-coated copper foils, dielectric layers, copper-clad laminates, capacitor elements, and printed wiring boards with built-in capacitors |
| KR102516291B1 (en) * | 2020-06-30 | 2023-03-31 | (주)이녹스첨단소재 | Insulation film for electronic device manufacturing |
| JP2023144926A (en) * | 2022-03-28 | 2023-10-11 | 株式会社タムラ製作所 | Thermosetting resin composition, cured product of thermosetting resin composition, and solder resist formed of thermosetting resin composition |
| CN115044173B (en) * | 2022-07-11 | 2023-03-21 | 中山超分子新材料有限公司 | Corrosion-resistant high-elasticity composite fiber and preparation method thereof |
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| JPS6092844A (en) * | 1983-10-26 | 1985-05-24 | 鐘淵化学工業株式会社 | Laminated board for electricity and metallic foil lined laminated board |
| JP2006206722A (en) | 2005-01-27 | 2006-08-10 | Admatechs Co Ltd | Lowly reactive silica powder, epoxy resin composition given by using the same, and epoxy resin molded product |
| KR102097847B1 (en) | 2012-12-11 | 2020-04-06 | 미쓰이금속광업주식회사 | Multilayer printed circuit board and manufacturing method thereof |
| JP6229439B2 (en) * | 2013-11-05 | 2017-11-15 | 住友ベークライト株式会社 | Metal-clad laminate, printed wiring board, and semiconductor device |
| JP6358533B2 (en) | 2014-03-27 | 2018-07-18 | パナソニックＩｐマネジメント株式会社 | Prepreg, metal-clad laminate, printed wiring board |
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| TWI821355B (en) * | 2018-08-07 | 2023-11-11 | 日商信越聚合物股份有限公司 | High frequency circuit substrate |
| US10575401B1 (en) | 2018-08-10 | 2020-02-25 | Taiwan Union Technology Corporation | Dielectric composite and uses thereof |
| TWI701685B (en) * | 2018-08-10 | 2020-08-11 | 台燿科技股份有限公司 | Dielectric composite and uses thereof |
| TWI824889B (en) * | 2022-12-18 | 2023-12-01 | 台光電子材料股份有限公司 | Resin compositions and products thereof |
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| WO2018003590A1 (en) | 2018-01-04 |
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