TW201718798A - Resin sheet and electronic device - Google Patents
Resin sheet and electronic device Download PDFInfo
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- TW201718798A TW201718798A TW105128121A TW105128121A TW201718798A TW 201718798 A TW201718798 A TW 201718798A TW 105128121 A TW105128121 A TW 105128121A TW 105128121 A TW105128121 A TW 105128121A TW 201718798 A TW201718798 A TW 201718798A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
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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
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J201/00—Adhesives based on unspecified macromolecular compounds
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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
- B32B2457/00—Electrical equipment
- B32B2457/16—Capacitors
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本發明係關於一種樹脂片材及電子裝置。 The present invention relates to a resin sheet and an electronic device.
於電子裝置之製造中,存在於絕緣層之一面搭載並固定電子零件之情形。例如存在如下技術:於製造內藏有陶瓷電容器等電子零件之佈線基板時,將電子零件形成於增層上。作為此種技術,例如可列舉專利文獻1中記載之技術。 In the manufacture of an electronic device, there is a case where an electronic component is mounted and fixed on one surface of an insulating layer. For example, there is a technique in which an electronic component is formed on a buildup layer when manufacturing a wiring board in which an electronic component such as a ceramic capacitor is built. As such a technique, for example, the technique described in Patent Document 1 can be cited.
於專利文獻1中記載有如下內容:於具有包含本體部及外部電極之電子零件之電子零件內藏佈線板中,將外部電極之至少一部分形成於開口部,該開口部係形成於本體部。 Patent Document 1 discloses that in an electronic component-embedded wiring board having an electronic component including a main body portion and an external electrode, at least a part of the external electrode is formed in the opening portion, and the opening portion is formed in the main body portion.
[專利文獻1]日本專利特開2013-183028號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2013-183028
於製造在絕緣層上搭載有電子零件之電子裝置時,由本發明人研究出進行例如如下製程:於設置有電路之基底層上形成樹脂片材,於將電子零件載置於樹脂片材上之後,使樹脂片材硬化。然而,伴隨著電路佈線之微細化,樹脂片材對基底層之電路之 嵌入性變得更為重要。另一方面,已判明於該製程中,對於該樹脂片材,亦要求提高對電子零件之密接性。迄今為止,難以實現可提高對基底層之電路之嵌入性、與對電子零件之密接性之平衡的樹脂片材。 When manufacturing an electronic device in which an electronic component is mounted on an insulating layer, the inventors have studied, for example, a process of forming a resin sheet on a base layer provided with a circuit, and placing the electronic component on the resin sheet. To harden the resin sheet. However, with the miniaturization of the circuit wiring, the circuit of the resin sheet to the base layer Embeddedness becomes more important. On the other hand, it has been found that in the process, it is also required to improve the adhesion to electronic parts of the resin sheet. Heretofore, it has been difficult to realize a resin sheet which can improve the embedding property to the circuit of the underlying layer and the balance with the adhesion to the electronic component.
根據本發明,提供一種樹脂片材,其係用於接著電子零件之樹脂片材,且25℃之黏著力為80gf/5mm 以上,於對該樹脂片材使用動態黏彈性測定裝置以頻率62.83rad/sec、測定溫度範圍50℃~200℃之條件進行測定時,該樹脂片材之最低熔融黏度為300Pa.s以上且1000Pa.s以下。 According to the present invention, there is provided a resin sheet which is used for a resin sheet which is followed by an electronic part, and has an adhesive force of 80 gf/5 mm at 25 ° C. As described above, when the resin sheet is measured using a dynamic viscoelasticity measuring apparatus at a frequency of 62.83 rad/sec and a measurement temperature range of 50 ° C to 200 ° C, the lowest melt viscosity of the resin sheet is 300 Pa. s above and 1000Pa. s below.
又,根據本發明,提供一種電子裝置,其具備上述樹脂片材之硬化膜、及接著於該硬化膜之一個面上之電子零件。 Moreover, according to the present invention, there is provided an electronic device comprising the cured film of the resin sheet and an electronic component attached to one surface of the cured film.
根據本發明,可實現可提高對電路之嵌入性、與對電子零件之密接性之平衡的樹脂片材。 According to the present invention, it is possible to realize a resin sheet which can improve the embedding property to a circuit and the balance with the adhesion to an electronic component.
1‧‧‧電路基板 1‧‧‧ circuit substrate
10‧‧‧樹脂片材 10‧‧‧Resin sheet
12‧‧‧增層 12‧‧‧Additional
14‧‧‧第1樹脂層 14‧‧‧1st resin layer
16‧‧‧第2樹脂層 16‧‧‧2nd resin layer
20‧‧‧載體 20‧‧‧ Carrier
30‧‧‧剝離層 30‧‧‧ peeling layer
40‧‧‧佈線 40‧‧‧Wiring
50‧‧‧陶瓷電容器 50‧‧‧Ceramic capacitors
52‧‧‧本體部 52‧‧‧ Body Department
54‧‧‧電極 54‧‧‧Electrode
60‧‧‧預浸體 60‧‧‧Prepreg
62‧‧‧絕緣層 62‧‧‧Insulation
64、68‧‧‧阻焊膜 64, 68‧‧‧ solder mask
70、72‧‧‧通孔 70, 72‧‧‧through holes
74、76‧‧‧佈線 74, 76‧‧‧ wiring
78‧‧‧金屬鍍層 78‧‧‧Metal plating
80‧‧‧半導體晶片 80‧‧‧Semiconductor wafer
82‧‧‧凸塊 82‧‧‧Bumps
84‧‧‧底部填充樹脂 84‧‧‧ underfill resin
86‧‧‧外部連接端子 86‧‧‧External connection terminal
90‧‧‧開口部 90‧‧‧ openings
100‧‧‧電子裝置 100‧‧‧Electronic devices
A、B‧‧‧原點 A, B‧‧‧ origin
W、X、Y、Z‧‧‧平面距離 W, X, Y, Z‧‧‧ plane distance
圖1係表示本實施形態之樹脂片材之剖面示意圖。 Fig. 1 is a schematic cross-sectional view showing a resin sheet of the embodiment.
圖2(a)至(c)係表示本實施形態之電路基板之製造方法之剖面示意圖。 2(a) to 2(c) are schematic cross-sectional views showing a method of manufacturing the circuit board of the embodiment.
圖3(a)至(c)係表示本實施形態之電路基板之製造方法之剖面示意圖。 3(a) to 3(c) are schematic cross-sectional views showing a method of manufacturing the circuit board of the embodiment.
圖4(a)至(c)係表示本實施形態之電子裝置之製造方法之剖面 示意圖。 4(a) to 4(c) are sectional views showing the manufacturing method of the electronic device of the embodiment. schematic diagram.
圖5係表示本實施形態之樹脂片材之變形例之剖面示意圖。 Fig. 5 is a schematic cross-sectional view showing a modified example of the resin sheet of the embodiment.
圖6係表示位置偏移量之測定方法之平面示意圖。 Fig. 6 is a schematic plan view showing a method of measuring the positional shift amount.
圖7(a)至(c)係表示陶瓷電容器之變形例之剖面示意圖。 7(a) to 7(c) are schematic cross-sectional views showing a modification of the ceramic capacitor.
以下,使用圖式對本發明之較佳實施形態進行說明。再者,於所有圖式中,對相同之構成要素標註相同之符號,並適當省略說明。 Hereinafter, preferred 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.
首先,對本發明之樹脂片材之概要進行說明。 First, the outline of the resin sheet of the present invention will be described.
本發明之樹脂片材係滿足如下構成要件:構成要件A,其係25℃之黏著力為80gf/5mm 以上;及構成要件B,其係於使用動態黏彈性測定裝置以頻率62.83rad/sec、測定溫度範圍50℃~200℃之條件進行測定時之最低熔融黏度為300Pa.s以上且1000Pa.s以下。 The resin sheet of the present invention satisfies the following constituent elements: constituent element A, which has an adhesive force of 80 gf/5 mm at 25 ° C. And the constitutive requirement B is the lowest melt viscosity of 300 Pa when measured by a dynamic viscoelasticity measuring device at a frequency of 62.83 rad/sec and a measurement temperature range of 50 ° C to 200 ° C. s above and 1000Pa. s below.
本發明之樹脂片材可用於在其一個面上接著電子零件。另一方面,另一面可接著於形成有電路圖案之基板之電路面。 The resin sheet of the present invention can be used to follow electronic parts on one side thereof. On the other hand, the other side may follow the circuit surface of the substrate on which the circuit pattern is formed.
於本發明中,藉由滿足構成要件A,樹脂片材係對接著於上側之電子零件具有充分之密接力。藉由使構成要件A之黏著力變大,可提高樹脂片材對電子零件之密接力,且抑制於樹脂片材之硬化後,該電子零件發生位置偏移。 In the present invention, by satisfying the constitution A, the resin sheet has sufficient adhesion to the electronic component following the upper side. By increasing the adhesive force of the constituent A, the adhesion of the resin sheet to the electronic component can be improved, and the position of the electronic component can be prevented from shifting after the resin sheet is cured.
又,於本發明中,藉由滿足構成要件B,樹脂片材係對配置於下側之電路具有良好之嵌入特性。藉由將構成要件B之最低熔融黏度以成為上述範圍內之方式設為相對較低,硬化前之樹脂片材變得易嵌入至電路之間隙等。 Further, in the present invention, by satisfying the constitution B, the resin sheet has good embedding characteristics for the circuit disposed on the lower side. By setting the lowest melt viscosity of the constituent B to be within the above range, the resin sheet before curing becomes easy to be inserted into the gap of the circuit or the like.
本發明人進行了研究,結果發現,伴隨著電路佈線之微細化,樹脂片材對下側之電路(基板之電路)之嵌入性變得更為重要,另一方面,於該製程中,亦必須提高對電子零件之密接性。基於此種見解進一步進行了研究,結果為,藉由兼具構成要件A與構成要件B,以至實現了可提高對基板之電路之嵌入性、與對電子零件之密接性之平衡的樹脂片材。 As a result of research, the inventors have found that the embedding property of the resin sheet on the lower circuit (circuit of the substrate) becomes more important as the circuit wiring is miniaturized. On the other hand, in the process, The adhesion to electronic components must be improved. Further, based on such a finding, the resin sheet having a balance between the embedding property of the substrate and the adhesion to the electronic component is realized by combining the constituent element A and the constituent element B. .
本發明之樹脂片材可使對基板之電路之嵌入性、及對電子零件之密接性均提高,可取得嵌入性與密接性之平衡。又,使用該樹脂片材之電路基板或電子裝置係可靠性高,且良率優異。 The resin sheet of the present invention can improve the embedding property to the circuit of the substrate and the adhesion to the electronic component, and can achieve a balance between embedding property and adhesion. Further, the circuit board or the electronic device using the resin sheet is highly reliable and excellent in yield.
以下,對本實施形態之樹脂片材、電路基板、電路基板之製造方法及電子裝置詳細地進行說明。 Hereinafter, the resin sheet, the circuit board, the method of manufacturing the circuit board, and the electronic device of the present embodiment will be described in detail.
首先,對用以形成本實施形態之樹脂片材之樹脂片材用樹脂組成物進行說明。 First, a resin composition for a resin sheet for forming the resin sheet of the present embodiment will be described.
樹脂片材用樹脂組成物為清漆狀之樹脂組成物。藉由將該樹脂片材用樹脂組成物設為薄膜狀,可獲得本實施形態之樹脂片材。此種樹脂片材用樹脂組成物係包含熱硬化性樹脂之熱硬化性樹脂組成物。作為本實施形態之樹脂片材,可使用利用該熱硬化性樹脂組成物而形成之樹脂膜。 The resin composition for a resin sheet is a varnish-like resin composition. The resin sheet of the present embodiment can be obtained by forming the resin sheet resin composition into a film form. The resin composition for a resin sheet contains a thermosetting resin composition of a thermosetting resin. As the resin sheet of the present embodiment, a resin film formed using the thermosetting resin composition can be used.
作為上述熱硬化性樹脂,並無特別限定,例如可列舉:酚樹脂、具有苯并環之樹脂、環氧樹脂、三聚氰胺樹脂、不飽和聚酯樹脂、順丁烯二醯亞胺樹脂、聚胺基甲酸乙酯樹脂、鄰苯二甲酸二烯丙酯樹脂、聚矽氧樹脂、氰酸酯樹脂、具有甲基丙烯 醯基之樹脂等。例如,熱硬化性樹脂亦可包含於室溫(25℃)下為液狀之液狀樹脂。該等可使用1種或組合使用2種以上。於本實施形態中,熱硬化性樹脂較佳為包含環氧樹脂。 The thermosetting resin is not particularly limited, and examples thereof include a phenol resin and a benzoic acid. Ring resin, epoxy resin, melamine resin, unsaturated polyester resin, maleimide resin, polyurethane resin, diallyl phthalate resin, polyoxyn resin, cyanide An acid ester resin, a resin having a methacrylonitrile group, or the like. For example, the thermosetting resin may contain a liquid resin which is liquid at room temperature (25 ° C). These may be used alone or in combination of two or more. In the present embodiment, the thermosetting resin preferably contains an epoxy resin.
環氧樹脂(A)例如可包含選自如下樹脂中之一種或兩種以上: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(4,4'-(1,3-伸苯基二亞異丙基)雙酚型環氧樹脂)、雙酚P型環氧樹脂(4,4'-(1,4-伸苯基二亞異丙基)雙酚型環氧樹脂)、雙酚Z型環氧樹脂(4,4'-亞環己基雙酚型環氧樹脂)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、四苯酚基乙烷型酚醛清漆型環氧樹脂、具有縮合環芳香族烴構造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;苯二甲基型環氧樹脂、聯苯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、萘改質甲酚酚醛清漆環氧樹脂等具有萘骨架之環氧樹脂;蒽型環氧樹脂;苯氧基型環氧樹脂;二環戊二烯型環氧樹脂;降烯型環氧樹脂;金剛烷型環氧樹脂;茀型環氧樹脂、烯丙基化環氧樹脂、環氧丙胺型環氧樹脂、環氧丙酯型環氧樹脂、脂環式環氧樹脂。該等中,就提高樹脂片材之嵌入性、或表面平滑性之觀點而言,更佳為包含具有萘骨架之環氧樹脂。藉此,亦可實現樹脂片材之低線膨脹化及高彈性模數化。又,亦可提高電路基板之剛性而有助於作業性之提高,或實現半導體封裝之耐回焊性之提高及翹曲 之抑制。再者,就提高樹脂片材之嵌入性之觀點而言,尤佳為包含3官能以上之具有萘骨架之環氧樹脂。 The epoxy resin (A) may, for example, comprise one or more selected from the group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, and bisphenol S type ring. Oxygen resin, bisphenol M type epoxy resin (4,4'-(1,3-phenylene diisopropylidene) bisphenol type epoxy resin), bisphenol P type epoxy resin (4,4' -(1,4-1,4-phenylene diisopropylidene) bisphenol epoxy resin), bisphenol Z epoxy resin (4,4'-cyclohexylene bisphenol epoxy resin) and other bisphenols Epoxy resin; phenol novolak type epoxy resin, cresol novolak type epoxy resin, tetraphenol ethane novolak type epoxy resin, phenolic aldehyde type epoxy resin having a condensed ring aromatic hydrocarbon structure, etc. Varnish type epoxy resin; biphenyl type epoxy resin; arylene type epoxy resin, biphenyl aralkyl type epoxy resin and other aralkyl type epoxy resin; n-naphthyl ether type epoxy resin, naphthalene Phenolic epoxy resin, naphthalene diphenol epoxy resin, 2-functional to 4-functional naphthalene epoxy resin, binaphthyl epoxy resin, naphthalene aralkyl epoxy resin, naphthalene modified cresol novolac epoxy Resin or the like having a naphthalene skeleton Epoxy resin; anthracene-type epoxy resins; phenoxy type epoxy resins; dicyclopentadiene type epoxy resins; drop Ethylene type epoxy resin; adamantane type epoxy resin; bismuth type epoxy resin, allylated epoxy resin, epoxidized epoxide type epoxy resin, propylene acrylate type epoxy resin, alicyclic epoxy resin . In the above, from the viewpoint of improving the embedding property of the resin sheet or the surface smoothness, it is more preferable to include an epoxy resin having a naphthalene skeleton. Thereby, the low-line expansion of the resin sheet and the high elastic modulus can be achieved. Moreover, the rigidity of the circuit board can be improved, the workability can be improved, or the reflow resistance of the semiconductor package can be improved and the warpage can be suppressed. Further, from the viewpoint of improving the embedding property of the resin sheet, an epoxy resin having a trifunctional or higher naphthalene skeleton is particularly preferable.
關於環氧樹脂(A),可列舉包含以下之通式(1)所示之環氧樹脂作為較佳樣態之一例。 The epoxy resin (A) is exemplified by an epoxy resin represented by the following formula (1).
(式(1)中,n為0~10之整數,R1及R2相互獨立為氫原子、碳數1~6之烷基、或碳數1~6之烷氧基) (In the formula (1), n is an integer of 0 to 10, and R 1 and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms)
環氧樹脂(A)之含量較佳為例如相對於熱硬化性樹脂組成物之總固形份而為3重量%以上,更佳為5重量%以上。藉由將環氧樹脂(A)之含量設為上述下限值以上,可有助於提高使用熱硬化性樹脂組成物而形成之樹脂片材之嵌入性或平滑性。另一方面,環氧樹脂(A)之含量較佳為例如相對於熱硬化性樹脂組成物之總固形份而為40重量%以下,更佳為35重量%以下。藉由將環氧樹脂(A)之含量設為上述上限值以下,可實現使用熱硬化性樹脂組成物而形成之樹脂片材之耐熱性或耐濕性之提高。上述環氧樹脂(A)亦可為包含液狀環氧樹脂者。液狀環氧樹脂之含量係相對於熱硬化性樹脂組成物之總固形份,可設為15重量%以下,亦可設為10重量%以下。藉由減少液狀環氧樹脂之含量,可抑制因黏著力變得過強所致之載體剝離性之劣化。 The content of the epoxy resin (A) is preferably 3% by weight or more, and more preferably 5% by weight or more based on the total solid content of the thermosetting resin composition. When the content of the epoxy resin (A) is at least the above lower limit value, it is possible to contribute to improvement in embedding property or smoothness of the resin sheet formed using the thermosetting resin composition. On the other hand, the content of the epoxy resin (A) is preferably 40% by weight or less, and more preferably 35% by weight or less based on the total solid content of the thermosetting resin composition. When the content of the epoxy resin (A) is at most the above upper limit value, the heat resistance or moisture resistance of the resin sheet formed using the thermosetting resin composition can be improved. The epoxy resin (A) may be one containing a liquid epoxy resin. The content of the liquid epoxy resin may be 15% by weight or less, or may be 10% by weight or less, based on the total solid content of the thermosetting resin composition. By reducing the content of the liquid epoxy resin, deterioration of the carrier peelability due to excessive adhesion can be suppressed.
再者,所謂熱硬化性樹脂組成物之總固形份,係指熱硬化性樹脂組成物中包含之除溶劑以外之所有成分。以下,於本說明書中相 同。 In addition, the total solid content of the thermosetting resin composition means all components except the solvent contained in the thermosetting resin composition. Hereinafter, in this specification with.
又,熱硬化性樹脂組成物較佳為進而包含選自氰酸酯樹脂、烯丙基苯酚化合物、丙烯基苯酚化合物、活性酯化合物、烷氧基矽烷改質酚化合物、碳二醯亞胺化合物中之至少一種液狀、或半固形狀之樹脂。藉由包含該等樹脂,可一面將樹脂片材之最低熔融黏度設為上述範圍內,一面提高其黏著力。尤其熱硬化性樹脂組成物較佳為包含上述樹脂中之氰酸酯樹脂。 Further, the thermosetting resin composition preferably further comprises a cyanate resin, an allylphenol compound, a propenylphenol compound, an active ester compound, an alkoxydecane-modified phenol compound, or a carbodiimide compound. At least one liquid or semi-solid resin. By including these resins, the adhesiveness of the resin sheet can be improved while the lowest melt viscosity of the resin sheet is within the above range. In particular, the thermosetting resin composition preferably contains a cyanate resin in the above resin.
藉由熱硬化性樹脂組成物包含氰酸酯樹脂,可對樹脂片材賦予適度之黏性,並且實現樹脂片材之低線膨脹化、或彈性模數及剛性之提高。又,亦可有助於所獲得之半導體裝置之耐熱性或耐濕性之提高。 When the thermosetting resin composition contains a cyanate resin, it is possible to impart a moderate viscosity to the resin sheet, and to achieve a low-line expansion of the resin sheet or an increase in the modulus of elasticity and rigidity. Moreover, it can also contribute to an improvement in heat resistance or moisture resistance of the obtained semiconductor device.
氰酸酯樹脂(B1)係於分子內具有氰酸酯基(-O-CN)之樹脂。尤其較佳為使用於分子內具有2個以上之氰酸酯基之氰酸酯樹脂。作為上述氰酸酯樹脂(B1),並無特別限定,例如可列舉:二環戊二烯型氰酸酯樹脂,苯酚酚醛清漆型氰酸酯樹脂,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,及萘酚芳烷基型氰酸酯樹脂等。 The cyanate resin (B1) is a resin having a cyanate group (-O-CN) in the molecule. It is especially preferable to use a cyanate resin having two or more cyanate groups in the molecule. The cyanate resin (B1) is not particularly limited, and examples thereof include a dicyclopentadiene type cyanate resin, a phenol novolak type cyanate resin, a novolac type cyanate resin, and a bisphenol A. A bisphenol type cyanate resin such as a cyanate resin, a bisphenol E type cyanate resin, a tetramethyl bisphenol F type cyanate resin, or a naphthol aralkyl type cyanate resin.
又,上述氰酸酯樹脂(B1)並無特別限定,例如可使鹵化氰化合物、與苯酚類或萘酚類反應而獲得。作為此種上述氰酸酯樹脂,例如可列舉:藉由苯酚酚醛清漆型多酚類與鹵化氰之反應而獲得之氰酸酯樹脂、藉由甲酚酚醛清漆型多酚類與鹵化氰之反應而獲得之氰酸酯樹脂、及藉由萘酚芳烷基型多元萘酚類與鹵化氰之反應而獲得 之氰酸酯樹脂等。上述氰酸酯樹脂(B1)亦可使用一種或組合使用兩種以上。 Further, the cyanate resin (B1) is not particularly limited, and may be obtained, for example, by reacting a cyanogen halide compound with a phenol or a naphthol. Examples of such a cyanate resin include a cyanate resin obtained by a reaction of a phenol novolak type polyphenol and a cyanogen halide, and a reaction of a cresol novolak type polyphenol with a cyanogen halide. The obtained cyanate resin and the reaction of the naphthol aralkyl type polynaphthol and the cyanogen halide are obtained. Cyanate resin and the like. The cyanate resin (B1) may be used alone or in combination of two or more.
該等中,就樹脂片材之低線膨脹化、或提高彈性模數及剛性之觀點而言,更佳為包含苯酚酚醛清漆型氰酸酯樹脂、二環戊二烯型氰酸酯樹脂、或萘酚芳烷基型氰酸酯樹脂,尤佳為包含苯酚酚醛清漆型氰酸酯樹脂。 In view of the low-line expansion of the resin sheet or the improvement of the modulus of elasticity and the rigidity, the phenol novolac type cyanate resin and the dicyclopentadiene type cyanate resin are more preferably contained. Or a naphthol aralkyl type cyanate resin, particularly preferably a phenol novolac type cyanate resin.
上述氰酸酯樹脂(B1)之含量較佳為例如相對於熱硬化性樹脂組成物之總固形份而為3重量%以上,更佳為5重量%以上。藉由將氰酸酯樹脂(B1)之含量設為上述下限值以上,可實現使用熱硬化性樹脂組成物而形成之樹脂片材之更有效之低線膨脹化、及高彈性模數化。又,可有助於嵌入性或平滑性之提高。另一方面,氰酸酯樹脂(B1)之含量較佳為例如相對於熱硬化性樹脂組成物之總固形份而為40重量%以下,更佳為35重量%以下。藉由將氰酸酯樹脂(B1)之含量設為上述上限值以下,可實現使用熱硬化性樹脂組成物而形成之樹脂片材之耐熱性或耐濕性之提高。 The content of the cyanate resin (B1) is preferably 3% by weight or more, and more preferably 5% by weight or more based on the total solid content of the thermosetting resin composition. When the content of the cyanate resin (B1) is at least the above lower limit value, more effective low-line expansion and high elastic modulus of the resin sheet formed using the thermosetting resin composition can be achieved. . Moreover, it can contribute to the improvement of embedding property or smoothness. On the other hand, the content of the cyanate resin (B1) is preferably 40% by weight or less, and more preferably 35% by weight or less based on the total solid content of the thermosetting resin composition. When the content of the cyanate resin (B1) is at most the above upper limit value, the heat resistance or moisture resistance of the resin sheet formed using the thermosetting resin composition can be improved.
熱硬化性樹脂組成物較佳為進而包含填充材料(C)。 The thermosetting resin composition preferably further contains a filler (C).
作為填充材料(C),可使用無機填充材料。作為上述無機填充材料,並無特別限定,例如可列舉:滑石、煅燒黏土、未煅燒黏土、雲母、玻璃等矽酸鹽;氧化鈦、氧化鋁、水鋁土、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。該等中,較佳為滑石、氧化鋁、玻璃、二氧化矽、雲母、氫氧化鋁、氫氧化鎂,尤佳為二氧化矽。 As the filler (C), an inorganic filler can be used. The inorganic filler is not particularly limited, and examples thereof include talc, calcined clay, uncalcined clay, mica, glass, etc.; titanium oxide, aluminum oxide, bauxite, cerium oxide, and molten cerium oxide. 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; boric acid Zinc, barium metaborate, aluminum borate, calcium borate, sodium borate, etc. Borate; nitride such as aluminum nitride, boron nitride, tantalum nitride or carbon nitride; titanate such as barium titanate or barium titanate. Among these, talc, alumina, glass, cerium oxide, mica, aluminum hydroxide, magnesium hydroxide, and preferably cerium oxide are preferable.
二氧化矽並無特別限定,例如亦可包含球狀二氧化矽、及破碎二氧化矽中之至少一者。就提高樹脂片材之嵌入性或表面平滑性之觀點而言,更佳為包含球狀二氧化矽。又,二氧化矽例如亦可為熔融球狀二氧化矽。 The cerium oxide is not particularly limited, and may include, for example, at least one of spherical cerium oxide and crushed cerium oxide. It is more preferable to contain spherical cerium oxide from the viewpoint of improving the embedding property or surface smoothness of the resin sheet. Further, the cerium oxide may be, for example, a molten spherical cerium oxide.
上述填充材料(C)之平均粒徑D50並無特別限定,較佳為0.01μm以上且5.0μm以下,更佳為0.05μm以上且2.0μm以下。 The average particle diameter D 50 of the filler (C) is not particularly limited, but is preferably 0.01 μm or more and 5.0 μm or less, and more preferably 0.05 μm or more and 2.0 μm or less.
上述填充材料(C)之平均粒徑D50可使用例如雷射繞射式粒度分佈測定裝置(HORIBA公司製造之LA-500)進行測定。又,填充材料亦可包含1種或2種以上。 The average particle diameter D 50 of the above-mentioned filler (C) can be measured using, for example, a laser diffraction type particle size distribution measuring apparatus (LA-500 manufactured by HORIBA). Further, the filler may contain one type or two or more types.
上述填充材料(C)之含量較佳為例如相對於熱硬化性樹脂組成物之總固形份而為40重量%以上,更佳為50重量%以上。藉由將填充材料(C)之含量設為上述下限值以上,可有效地提高使用熱硬化性樹脂組成物而獲得之樹脂片材之耐熱性或耐濕性。又,亦可使樹脂片材低線膨脹化及高彈性模數化,有助於減少所獲得之半導體封裝之翹曲。另一方面,填充材料(C)之含量較佳為例如相對於熱硬化性樹脂組成物之總固形份而為90重量%以下,更佳為85重量%以下。藉由將填充材料(B)之含量設為上述上限值以下,可更有效地提高樹脂片材之嵌入性。 The content of the filler (C) is preferably, for example, 40% by weight or more, and more preferably 50% by weight or more based on the total solid content of the thermosetting resin composition. When the content of the filler (C) is at least the above lower limit value, the heat resistance or moisture resistance of the resin sheet obtained by using the thermosetting resin composition can be effectively improved. Further, the resin sheet can be made to have a low linear expansion and a high elastic modulus, which contributes to reduction in warpage of the obtained semiconductor package. On the other hand, the content of the filler (C) is preferably, for example, 90% by weight or less, and more preferably 85% by weight or less based on the total solid content of the thermosetting resin composition. By setting the content of the filler (B) to be equal to or less than the above upper limit value, the embedding property of the resin sheet can be more effectively improved.
熱硬化性樹脂組成物較佳為進而包含例如硬化促進劑(D)。藉此,可提高熱硬化性樹脂組成物之硬化性。 The thermosetting resin composition preferably further contains, for example, a curing accelerator (D). Thereby, the hardenability of the thermosetting resin composition can be improved.
作為硬化促進劑(D),可使用促進環氧樹脂(A)之硬化反應者,其種類並無特別限定。作為硬化促進劑(D),並無特別限定,例如可包含選自如下化合物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]辛烷等三級胺類;如四苯基鏻-四苯基硼酸鹽(TPP-K)、四苯基鏻-四(4-甲基苯基)硼酸鹽(TPP-MK)般之四級鏻系化合物;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-4,5-二羥基咪唑等咪唑類;苯酚、雙酚A、壬基苯酚等酚化合物;乙酸、苯甲酸、水楊酸、對甲苯磺酸等有機酸;及鎓鹽化合物。該等中,就更有效地提高硬化性之觀點而言,更佳為包含鎓鹽化合物。 As the curing accelerator (D), a curing reaction for promoting the epoxy resin (A) can be used, and the type thereof is not particularly limited. The curing accelerator (D) is not particularly limited, and may, for example, include one or more selected from the group consisting of zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octoate, zinc octoate, and diacetyl hydrazine. An organic metal salt such as acetone cobalt (II), triethyl hydrazine acetone (III); a tertiary amine such as triethylamine, tributylamine or diazabicyclo[2.2.2]octane; such as tetraphenylphosphonium- Tetraphenylborate (TPP-K), tetraphenylphosphonium-tetrakis(4-methylphenyl)borate (TPP-MK), a tetradecyl quinone compound; 2-phenyl-4-methylimidazole , 2-ethyl-4-ethylimidazole, 2-phenyl-4-ethylimidazole, 2-phenyl-4-methyl-5-hydroxyimidazole, 2-phenyl-4,5-dihydroxyimidazole Imidazoles; phenolic compounds such as phenol, bisphenol A, nonylphenol; organic acids such as acetic acid, benzoic acid, salicylic acid, p-toluenesulfonic acid; Among these, it is more preferable to contain an onium salt compound from the viewpoint of more effectively improving the hardenability.
作為上述硬化促進劑(D)而使用之鎓鹽化合物並無特別限定,例如可使用下述通式(2)所表示之化合物。 The onium salt compound to be used as the curing accelerator (D) is not particularly limited, and for example, a compound represented by the following formula (2) can be used.
(式(2)中,P為磷原子,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、或者經取代或未經取代之脂肪族基,且可彼此相同亦可不同;A-表示於分子內具有至少1個以 上之可釋出至分子外之質子的n(n≧1)價質子供體之陰離子、或其錯陰離子) (In the formula (2), P is 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 Aliphatic groups, which may be the same or different from each other; A - represents an anion of an n(n≧1) valence proton donor having at least one or more protons released to the outside of the molecule, or a wrong anion thereof )
上述硬化促進劑(D)之含量較佳為例如相對於熱硬化性樹脂組成物之總固形份而為0.1重量%以上,更佳為0.3重量%以上。藉由將硬化促進劑(D)之含量設為上述下限值以上,可更有效地提高熱硬化性樹脂組成物之硬化性。另一方面,硬化促進劑(D)之含量較佳為例如相對於熱硬化性樹脂組成物之總固形份而為10重量%以下,更佳為5重量%以下。藉由將硬化促進劑(D)之含量設為上述上限值以下,可提高熱硬化性樹脂組成物之保存性。 The content of the hardening accelerator (D) is preferably 0.1% by weight or more, and more preferably 0.3% by weight or more based on the total solid content of the thermosetting resin composition. When the content of the curing accelerator (D) 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 content of the curing accelerator (D) is preferably, for example, 10% by weight or less, and more preferably 5% by weight or less based on the total solid content of the thermosetting resin composition. When the content of the curing accelerator (D) is at most the above upper limit value, the storage stability of the thermosetting resin composition can be improved.
熱硬化性樹脂組成物可進而包含例如著色劑(E)。著色劑(E)例如包含選自綠色、紅色、藍色、黃色、及黑色等之染料、顏料、以及色素中之一種或兩種以上。該等中,就提高開口部之視認性等之觀點而言,可使用綠色之著色劑,亦可使用綠色染料。作為該綠色著色劑,例如可包含蒽醌系、酞菁系、及苝系等公知之著色劑中之一種或兩種以上。 The thermosetting resin composition may further contain, for example, a color former (E). The colorant (E) contains, for example, one or more selected from the group consisting of dyes, pigments, and pigments such as green, red, blue, yellow, and black. In the above, a green coloring agent or a green dye may be used from the viewpoint of improving the visibility of the opening and the like. The green coloring agent may, for example, comprise one or more of known known coloring agents such as an anthraquinone, a phthalocyanine, and an anthraquinone.
上述著色劑(E)之含量較佳為例如相對於熱硬化性樹脂組成物之總固形份而為0.05重量%以上,更佳為0.1重量%以上。藉由將著色劑(E)之含量設為上述下限值以上,可更有效地提高使用熱硬化性樹脂組成物而獲得之樹脂片材之開口部之視認性或隱蔽性。另一方面,著色劑(E)之含量較佳為例如相對於熱硬化性樹脂組成物之總固形份而為5重量%以下,更佳為3重量%以下。藉由將著色劑(E)之含量設為上述上限值以下,可更有效地提高熱硬化性樹 脂組成物之硬化性等。 The content of the coloring agent (E) is preferably 0.05% by weight or more, and more preferably 0.1% by weight or more based on the total solid content of the thermosetting resin composition. When the content of the coloring agent (E) is at least the above lower limit value, the visibility or concealability of the opening portion of the resin sheet obtained by using the thermosetting resin composition can be more effectively improved. On the other hand, the content of the coloring agent (E) is preferably 5% by weight or less, and more preferably 3% by weight or less based on the total solid content of the thermosetting resin composition. By setting the content of the colorant (E) to be equal to or less than the above upper limit, the thermosetting tree can be more effectively improved. The hardening property of the lipid composition, and the like.
於熱硬化性樹脂組成物中,除上述各成分以外,亦可視需要添加選自偶合劑、調平劑、硬化劑、感光劑、消泡劑、紫外線吸收劑、發泡劑、抗氧化劑、難燃劑、及離子捕捉劑等中之一種或兩種以上之添加物。 In the thermosetting resin composition, in addition to the above components, a coupling agent, a leveling agent, a hardener, a sensitizer, an antifoaming agent, an ultraviolet absorber, a foaming agent, an antioxidant, and a hardening may be added as needed. One or more additives of a fuel, an ion trapping agent, and the like.
作為上述偶合劑,例如可列舉:環氧矽烷偶合劑、陽離子矽烷偶合劑、胺基矽烷偶合劑等矽烷偶合劑,鈦酸酯系偶合劑,以及聚矽氧油型偶合劑等。作為調平劑,可列舉丙烯酸系共聚合物等。上述偶合劑之含量並無特別限定,例如較佳為相對於熱硬化性樹脂組成物之總固形份而為0.05~5重量%,更佳為0.2~3重量%。 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 a polyasoxy oil type coupling agent. Examples of the leveling agent include an acrylic copolymer and the like. The content of the above-mentioned coupling agent is not particularly limited, and is, for example, preferably 0.05 to 5% by weight, and more preferably 0.2 to 3% by weight based on the total solid content of the thermosetting resin composition.
作為上述硬化劑,例如可列舉:苯酚酚醛清漆樹脂、甲酚酚醛清漆樹脂、芳基伸烷基型酚醛清漆樹脂等酚樹脂等。上述硬化劑之含量並無特別限定,例如較佳為相對於熱硬化性樹脂組成物之總固形份而為0.05~10重量%,更佳為0.2~5重量%。 Examples of the curing agent include a phenol resin such as a phenol novolak resin, a cresol novolak resin, and an aryl alkylene novolak resin. The content of the curing agent is not particularly limited. For example, it is preferably 0.05 to 10% by weight, and more preferably 0.2 to 5% by weight based on the total solid content of the thermosetting resin composition.
本實施形態之樹脂片材係藉由使用含有既定量之上述各成分之熱硬化性樹脂組成物,而滿足構成要件A及B。尤其藉由使用包含3~40重量%之環氧樹脂(A),3~40重量%之選自氰酸酯樹脂(B1)、烯丙基苯酚化合物、丙烯基苯酚化合物、活性酯化合物、烷氧基矽烷改質酚化合物、碳二醯亞胺化合物中之至少一種液狀、或半固形狀之樹脂,40~80重量%之填充劑(C),以及0.1~5重量%之硬化促進劑(D)之熱硬化性樹脂組成物,可獲得更確實地滿足構 成要件A及B之樹脂片材。又,就獲得滿足構成要件A及B、且嵌入性與密接性之平衡特別優異的樹脂片材之觀點而言,更佳為使用如下熱硬化性樹脂組成物,即,其包含:5~35重量%之環氧樹脂(A);10~35重量%之選自氰酸酯樹脂(B1)、烯丙基苯酚化合物、丙烯基苯酚化合物、活性酯化合物、烷氧基矽烷改質酚化合物、碳二醯亞胺化合物中之至少一種液狀、或半固形狀之樹脂;50~85重量%之填充劑(C);以及0.3~5重量%之硬化促進劑(D)。 The resin sheet of the present embodiment satisfies the constitutional requirements A and B by using a thermosetting resin composition containing a predetermined amount of each component. In particular, by using 3 to 40% by weight of epoxy resin (A), 3 to 40% by weight of a cyanate resin (B1), an allylphenol compound, a propenylphenol compound, an active ester compound, an alkane At least one liquid or semi-solid resin of the oxydecane-modified phenol compound or the carbodiimide compound, 40 to 80% by weight of the filler (C), and 0.1 to 5% by weight of the hardening accelerator The thermosetting resin composition of (D) can be more reliably satisfied A resin sheet of the parts A and B. Moreover, it is more preferable to use the following thermosetting resin composition from the viewpoint of obtaining a resin sheet which satisfies the constituent elements A and B and which is particularly excellent in the balance between the embedding property and the adhesiveness, that is, it contains: 5 to 35 5% by weight of epoxy resin (A); 10 to 35% by weight selected from the group consisting of cyanate resin (B1), allyl phenol compound, propylene phenol compound, active ester compound, alkoxy decane modified phenol compound, At least one liquid or semi-solid resin of the carbodiimide compound; 50 to 85% by weight of the filler (C); and 0.3 to 5% by weight of the hardening accelerator (D).
又,上述熱硬化性樹脂組成物為清漆狀之樹脂組成物。藉由將清漆狀之熱硬化性樹脂組成物製成薄膜狀,可獲得本實施形態之樹脂片材。 Further, the thermosetting resin composition is a varnish-like resin composition. The resin sheet of this embodiment can be obtained by forming a varnish-like thermosetting resin composition into a film form.
本實施形態之樹脂片材可藉由例如對塗佈清漆狀之熱硬化性樹脂組成物而獲得之塗佈膜(樹脂膜)進行溶劑去除處理而獲得。上述樹脂片材可定義為溶劑含有率相對於熱硬化性樹脂組成物總體而為5重量%以下。於本實施形態中,例如可以100℃~150℃、1分鐘~5分鐘之條件進行溶劑去除處理。藉此,可一面抑制熱硬化性樹脂膜之硬化進行,一面充分地去除溶劑。 The resin sheet of the present embodiment can be obtained, for example, by subjecting a coating film (resin film) obtained by coating a varnish-like thermosetting resin composition to a solvent removal treatment. The resin sheet can be defined as a solvent content ratio of 5% by weight or less based on the total amount of the thermosetting resin composition. In the present embodiment, for example, the solvent removal treatment can be carried out at 100 ° C to 150 ° C for 1 minute to 5 minutes. Thereby, the solvent can be sufficiently removed while suppressing the hardening of the thermosetting resin film.
於本實施形態中,作為將熱硬化性樹脂組成物形成於載體基材上之方法,並無特別限定,可列舉如下所述之方法。例如可列舉如下方法等:首先,使熱硬化性樹脂溶解、分散於溶劑等中而製備樹脂清漆,於使用各種塗佈裝置將樹脂清漆塗佈於載體基材後將其乾燥之方法;以及於使用噴霧裝置將樹脂清漆噴霧塗佈於載體基材後將其乾燥之方法。該等中,較佳為如下方法:於使用缺角輪塗佈機、模嘴塗佈機等各種塗佈裝置將樹脂清漆塗佈於載體基材上後,將其乾燥之方法。藉此,可效率良好地製造具備無空隙且具 有均勻厚度之樹脂片材的附載體基材之樹脂片材。 In the present embodiment, the method of forming the thermosetting resin composition on the carrier substrate is not particularly limited, and the following methods can be mentioned. For example, a method of preparing a resin varnish by dissolving and dispersing a thermosetting resin in a solvent or the like, and applying the resin varnish to a carrier substrate using various coating apparatuses, and drying the resin varnish; A method in which a resin varnish is spray-coated on a carrier substrate using a spray device and then dried. Among these, a method in which a resin varnish is applied onto a carrier substrate by various coating apparatuses such as a comma coater or a die coater, and then dried is used. Thereby, it is possible to efficiently manufacture a void-free device A resin sheet with a carrier substrate of a resin sheet having a uniform thickness.
上述清漆狀之熱硬化性樹脂組成物可包含例如溶劑。 The varnish-like thermosetting resin composition may contain, for example, a solvent.
作為上述溶劑,例如可包含選自如下溶劑中之一種或兩種以上:丙酮、甲基乙基酮、甲基異丁基酮、甲苯、乙酸乙酯、環己烷、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、大茴香醚、及N-甲基吡咯啶酮等有機溶劑。 The solvent may, for example, comprise one or more selected from the group consisting of acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, ethyl acetate, cyclohexane, heptane, cyclohexane. , cyclohexanone, tetrahydrofuran, dimethylformamide, dimethylacetamide, dimethyl hydrazine, ethylene glycol, serotonin, carbitol, anisole, and N-methyl An organic solvent such as pyrrolidone.
於清漆狀之熱硬化性樹脂組成物中,熱硬化性樹脂組成物之固形份含量例如較佳為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,可獲得作業性或成膜性非常優異之熱硬化性樹脂組成物。再者,清漆狀之熱硬化性樹脂組成物可藉由例如使用超音波分散方式、高壓碰撞式分散方式、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之各種混合機,將上述各成分於溶劑中溶解、混合、攪拌而製備。 In the varnish-like thermosetting resin composition, 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. Further, the varnish-like thermosetting resin composition can be, for example, an ultrasonic dispersion method, a high-pressure collision type dispersion method, a high-speed rotation dispersion method, a bead milling method, a high-speed shear dispersion method, and a self-rotating revolution dispersion method. Each of the above-mentioned mixers was prepared by dissolving, mixing, and stirring the above components in a solvent.
再者,熱硬化性樹脂組成物較佳為製成例如不含玻璃纖維基材等纖維基材或紙基材之組成物。藉由不含此種基材,電路之嵌入性提高,可實現特別適於形成樹脂片材之熱硬化性樹脂組成物。 Further, the thermosetting resin composition is preferably a composition which is, for example, a fiber substrate or a paper substrate which does not contain a glass fiber substrate. By not including such a substrate, the embedding property of the circuit is improved, and a thermosetting resin composition which is particularly suitable for forming a resin sheet can be realized.
本實施形態之樹脂片材可包含由上述樹脂片材用樹脂組成物 所獲得之薄膜。於本實施形態中,樹脂片材可為薄片形狀,亦可為可捲取之捲筒形狀。 The resin sheet of the present embodiment may contain the resin composition for the resin sheet described above. The film obtained. In the present embodiment, the resin sheet may have a sheet shape or a roll shape that can be wound up.
如上所述,本實施形態之樹脂片材之25℃之黏著力為80gf/5mm 以上。上述樹脂片材之黏著力之下限值為80gf/5mm 以上,較佳為90gf/5mm 以上,更佳為100gf/5mm 以上。上述樹脂片材之黏著力之上限值並無特別限定,例如較佳為1000gf/5mm 以下,更佳為900gf/5mm 以下,進而較佳為800gf/5mm 以下。藉由將黏著力設為上述下限值以上,可提高對電子零件之密接力。藉此,於製造電子裝置時,可抑制於樹脂片材硬化之前,因乾燥或追加步驟之影響而引起之電子零件之位置偏移。藉由將黏著力設為上述上限值以下,可容易地剝離載體或載體基材,樹脂片材之使用變得良好。 As described above, the adhesive sheet of the present embodiment has an adhesion at 25 ° C of 80 gf / 5 mm. the above. The lower limit of the adhesion of the above resin sheet is 80gf/5mm Above, preferably 90gf/5mm Above, more preferably 100gf/5mm the above. The upper limit of the adhesive force of the above resin sheet is not particularly limited, and is preferably, for example, 1000 gf/5 mm. Below, more preferably 900gf/5mm Hereinafter, it is further preferably 800 gf/5 mm the following. By setting the adhesive force to be equal to or higher than the above lower limit value, the adhesion to the electronic component can be improved. Thereby, when manufacturing an electronic device, it is possible to suppress the positional shift of the electronic component due to the influence of the drying or the additional step before the resin sheet is cured. By setting the adhesive force to the above upper limit or less, the carrier or the carrier substrate can be easily peeled off, and the use of the resin sheet becomes good.
於本實施形態中,樹脂片材之黏著力例如可藉由以下順序而進行測定。首先,準備附載體基材之樹脂片材。將該附載體基材之樹脂片材的樹脂片材於80℃貼合於芯材。其次,將經貼合之附載體基材之樹脂片材及芯材切割成約10cm見方,將載體基材剝離,而製成測定樣品。隨後,以芯材成為下之方式將測定樣品載置於經設定為25℃之黏著(tacking)試驗機(Rhesca公司製造)之台上,將探針(5mm )以100gf/5mm 、5sec之條件按壓於測定樣品。其後,使探針以2mm/sec之條件自測定樣品脫離。此時,測定探針自測定樣品承受之拉力,並將其峰值作為黏著力(gf/5mm )。藉由以上操作,可測定將載體基材剝離後之樹脂片材之剝離面之黏著力。 In the present embodiment, the adhesion of the resin sheet can be measured, for example, by the following procedure. First, a resin sheet with a carrier substrate is prepared. The resin sheet of the resin sheet with a carrier substrate was bonded to the core material at 80 °C. Next, the resin sheet and the core material of the bonded carrier substrate were cut into about 10 cm square, and the carrier substrate was peeled off to prepare a measurement sample. Subsequently, the measurement sample was placed on a table of a tacking tester (manufactured by Rhesca) set to a temperature of 25 ° C in the following manner, and the probe (5 mm) was placed. ) at 100gf/5mm The condition of 5 sec was pressed against the measurement sample. Thereafter, the probe was detached from the measurement sample under the condition of 2 mm/sec. At this time, the tensile force of the probe from the measured sample is measured, and the peak value is used as the adhesive force (gf/5 mm). ). By the above operation, the adhesion of the peeling surface of the resin sheet after peeling off the carrier substrate can be measured.
於本實施形態之樹脂片材中,藉由測定頻率62.83 rad/sec、升溫速度3℃/min之條件之動態黏彈性試驗所測得之50~200℃之最低熔融黏度為2000Pa.s以下。上述最低熔融黏度之上限值為2000Pa.s以下,較佳為900Pa.s以下,更佳為800Pa.s以下。藉由將最低熔融黏度設為上述上限值以下,如上所述般可提高樹脂片材之嵌入性。另一方面,上述最低熔融黏度之下限值為300Pa.s以上,較佳為400Pa.s以上,更佳為500Pa.s以上。藉由將最低熔融黏度設為上述下限值以上,可提高樹脂片材之表面平滑性。 In the resin sheet of the present embodiment, by measuring the frequency of 62.83 The minimum melt viscosity of 50~200 °C measured by dynamic viscoelasticity test of rad/sec and heating rate of 3 °C/min is 2000 Pa. s below. The upper limit of the above minimum melt viscosity is 2000 Pa. Below s, preferably 900Pa. Below s, more preferably 800Pa. s below. By setting the minimum melt viscosity to be equal to or less than the above upper limit value, the embedding property of the resin sheet can be improved as described above. On the other hand, the lower limit of the above minimum melt viscosity is 300 Pa. Above s, preferably 400 Pa. Above s, more preferably 500Pa. s above. By setting the minimum melt viscosity to be equal to or higher than the above lower limit value, the surface smoothness of the resin sheet can be improved.
於本實施形態中,動態黏彈性試驗可使用例如動態黏彈性測定裝置以下述條件進行。又,作為動態黏彈性測定裝置,並無特別限定,例如可使用Anton Paar公司製造之Physica MCR-301。 In the present embodiment, the dynamic viscoelasticity test can be carried out under the following conditions using, for example, a dynamic viscoelasticity measuring device. Further, the dynamic viscoelasticity measuring device is not particularly limited, and for example, Physica MCR-301 manufactured by Anton Paar Co., Ltd. can be used.
頻率:62.83rad/sec Frequency: 62.83 rad/sec
測定溫度:50~200℃ Measuring temperature: 50~200°C
升溫速度:3℃/min Heating rate: 3 ° C / min
幾何形狀:平行板 Geometric shape: parallel plate
板直徑:10mm Plate diameter: 10mm
板間隔:0.1mm Board spacing: 0.1mm
負重(法線力(normal force)):0N(固定) Load (normal force): 0N (fixed)
應變:0.3% Strain: 0.3%
測定氣氛:空氣 Measuring atmosphere: air
於本實施形態中,例如可藉由適當地選擇熱硬化性樹脂組成物中所包含之各成分之種類或調配量、及熱硬化性樹脂組成物之製備方法等,而控制上述黏著力及最低熔融黏度。該等中,例如可列舉於液狀環氧樹脂之含量較少之範圍(相對於熱硬化性樹脂組成物之總固形份而為15重量%以下)內,藉由加溫等調製方法、 偶合劑處理、攪拌方法而提高填料之分散性等,作為用以將上述黏著力及最低熔融黏度設為所期望之數值範圍之要素。進而,可列舉於液狀環氧樹脂之含量較少之範圍內,將填充材料之含量設為上述下限值以上(相對於熱硬化性樹脂組成物之總固形份而為40重量%以上),並且藉由適當之攪拌方法提高填充材料之分散性,作為用以控制上述黏著力及最低熔融黏度之特別重要之要素。 In the present embodiment, for example, the adhesion and the minimum amount can be controlled by appropriately selecting the type or amount of each component contained in the thermosetting resin composition, the preparation method of the thermosetting resin composition, and the like. Melt viscosity. In the above, for example, in a range in which the content of the liquid epoxy resin is small (15% by weight or less based on the total solid content of the thermosetting resin composition), a preparation method such as heating or the like is used. The coupling agent treatment and the stirring method are used to improve the dispersibility of the filler and the like, and are used as elements for setting the adhesion and the minimum melt viscosity to a desired numerical range. Furthermore, the content of the filler is set to be less than or equal to the lower limit value (40% by weight or more based on the total solid content of the thermosetting resin composition) in a range in which the content of the liquid epoxy resin is small. And the dispersibility of the filler material is improved by a suitable stirring method as a particularly important factor for controlling the above adhesion and the lowest melt viscosity.
於本實施形態中,於對樹脂片材以200℃、1小時進行熱處理而獲得硬化物時,樹脂片材之硬化物之25℃之儲存模數較佳為7GPa以上。藉此,可實現具備使用熱硬化性樹脂組成物而獲得之樹脂片材之電路基板之撓曲抑制或強度提高、以及具備該電路基板之半導體封裝之翹曲抑制等。上述儲存模數更佳為10GPa以上。另一方面,上述儲存模數之上限值並無特別限定,例如可設為50GPa以下。 In the present embodiment, when the resin sheet is heat-treated at 200 ° C for 1 hour to obtain a cured product, the storage modulus at 25 ° C of the cured product of the resin sheet is preferably 7 GPa or more. Thereby, it is possible to achieve the deflection suppression or the strength improvement of the circuit board including the resin sheet obtained by using the thermosetting resin composition, and the warpage suppression of the semiconductor package including the circuit board. The above storage modulus is more preferably 10 GPa or more. On the other hand, the upper limit of the storage modulus is not particularly limited, and may be, for example, 50 GPa or less.
於本實施形態中,於對樹脂片材以200℃、1小時進行熱處理而獲得硬化物時,樹脂片材之硬化物之玻璃轉移溫度較佳為160℃以上。藉此,可實現使用熱硬化性樹脂組成物而獲得之樹脂片材之耐熱性及耐回焊性之提高等。上述玻璃轉移溫度更佳為200℃以上。另一方面,上述玻璃轉移溫度之上限值並無特別限定,例如可設為350℃以下。 In the present embodiment, when the resin sheet is heat-treated at 200 ° C for 1 hour to obtain a cured product, the glass transition temperature of the cured product of the resin sheet is preferably 160 ° C or higher. Thereby, the heat resistance and the reflow resistance of the resin sheet obtained by using the thermosetting resin composition can be improved. The above glass transition temperature is more preferably 200 ° C or higher. On the other hand, the upper limit of the glass transition temperature is not particularly limited, and may be, for example, 350 ° C or lower.
於本實施形態中,上述儲存模數及上述玻璃轉移溫度例如可根據藉由如下方式所獲得之測定結果而算出,即,對上述硬化物,使用動態黏彈性測定裝置以頻率1Hz、升溫速度5℃/min之條件進行動態黏彈性試驗。作為動態黏彈性測定裝置,並無特別限定,例如可使用Seiko Instruments公司製造之DMS6100。 In the present embodiment, the storage modulus and the glass transition temperature can be calculated, for example, based on measurement results obtained by using a dynamic viscoelasticity measuring device at a frequency of 1 Hz and a temperature increase rate of 5 for the cured product. Dynamic viscoelasticity test was carried out under the conditions of °C/min. The dynamic viscoelasticity measuring device is not particularly limited, and for example, DMS6100 manufactured by Seiko Instruments Co., Ltd. can be used.
於本實施形態中,於對樹脂片材以200℃、1小時進行熱處理而獲得硬化物時,樹脂片材之硬化物之未達玻璃轉移溫度之線膨脹係數較佳為30ppm/℃以下。藉此,可實現具備使用熱硬化性樹脂組成物而獲得之樹脂片材之半導體封裝之翹曲抑制等。上述線膨脹係數更佳為28ppm/℃以下。另一方面,上述線膨脹係數之下限值並無特別限定,例如可設為3ppm/℃以上。 In the present embodiment, when the resin sheet is heat-treated at 200 ° C for 1 hour to obtain a cured product, the linear expansion coefficient of the cured product of the resin sheet which is less than the glass transition temperature is preferably 30 ppm/° C. or less. Thereby, warpage suppression of a semiconductor package including a resin sheet obtained by using a thermosetting resin composition can be achieved. The above linear expansion coefficient is more preferably 28 ppm/° C. or less. On the other hand, the lower limit of the linear expansion coefficient is not particularly limited, and may be, for example, 3 ppm/° C. or more.
於本實施形態中,例如可對上述硬化物使用熱機械分析儀(TMA,thermomechanical analyzer)(熱分析裝置)以升溫速度10℃/min之條件進行測定,並算出藉此獲得之線膨脹係數之25~50℃之平均,將其作為未達玻璃轉移溫度下之上述線膨脹係數。 In the present embodiment, for example, the cured product can be measured using a thermomechanical analyzer (TMA) (thermal analyzer) at a temperature increase rate of 10 ° C/min, and the coefficient of linear expansion obtained thereby can be calculated. The average of 25 to 50 ° C is taken as the above linear expansion coefficient at a glass transition temperature.
再者,於本實施形態中,例如可藉由適當地選擇熱硬化性樹脂組成物中所包含之各成分之種類或調配量、及熱硬化性樹脂組成物之製備方法等,而控制上述儲存模數、上述玻璃轉移溫度、及上述線膨脹係數。 In the present embodiment, for example, the storage can be controlled by appropriately selecting the type or amount of each component contained in the thermosetting resin composition, the preparation method of the thermosetting resin composition, and the like. Modulus, the above glass transition temperature, and the above linear expansion coefficient.
又,可藉由將本實施形態之樹脂片材積層於載體基材上,而構成附載體基材之樹脂片材。藉此,可提高樹脂片材之處理性。 Further, the resin sheet of the present embodiment can be laminated on the carrier substrate to form a resin sheet with a carrier substrate. Thereby, the rationality of the resin sheet can be improved.
於本實施形態中,作為載體基材,例如可使用高分子薄膜。作為該高分子薄膜,並無特別限定,例如可列舉:聚乙烯、聚丙烯等聚烯烴,聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯等聚酯,聚碳酸酯,聚矽氧片材等脫模紙,氟系樹脂、聚醯亞胺樹脂等具有耐熱性之熱塑性樹脂片材等。該等中,包含聚對苯二甲酸乙二酯之片材由於價廉及剝離強度之調節簡便,故而最佳。藉此,變得容易自上述樹脂片材以適度之強度進行剝離。 In the present embodiment, as the carrier substrate, for example, a polymer film 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, and polycarbonate. A release paper such as a xenon sheet, a thermoplastic resin sheet having heat resistance such as a fluorine resin or a polyimide resin. Among these, the sheet containing polyethylene terephthalate is preferable because it is inexpensive and the peel strength is easily adjusted. Thereby, it becomes easy to peel from the said resin sheet with moderate intensity|strength.
上述載體基材之厚度並無特別限定,例如可設為10~100μm,亦可設為10~70μm。藉此,製造樹脂片材時之處理性良好而較佳。 The thickness of the carrier substrate is not particularly limited, and may be, for example, 10 to 100 μm or 10 to 70 μm. Thereby, it is rational and preferable to manufacture a resin sheet.
本發明之樹脂片材可為單層亦可為多層,且可包含1種或2種以上之上述薄膜。於該樹脂片材為多層之情形時,可由同種構成,亦可由不同種構成。 The resin sheet of the present invention may be a single layer or a plurality of layers, and may contain one or more of the above films. When the resin sheet is a plurality of layers, it may be composed of the same kind or may be composed of different types.
本實施形態之樹脂片材可設為包含第1樹脂片材(第1樹脂層)、及配置於第1樹脂片材之下之第2樹脂片材(第2樹脂層)之構成。再者,第1樹脂片材及第2樹脂片材具有與上述樹脂片材相同之構成。 The resin sheet of the present embodiment may have a configuration including a first resin sheet (first resin layer) and a second resin sheet (second resin layer) disposed under the first resin sheet. In addition, the first resin sheet and the second resin sheet have the same configuration as the above resin sheet.
亦可使上述第1樹脂片材較第2樹脂片材而對電子零件之密接性更高。即,於本實施形態中,可將第1樹脂片材之上述黏著力設為較上述第2樹脂片材之黏著力更大。另一方面,亦可使上述第2樹脂片材較第1樹脂片材而對下層之電路之嵌入特性更高。即,於本實施形態中,可將第2樹脂片材之上述最低熔融黏度設為較第1樹脂片材之最低熔融黏度更大。藉由使用2層以上之樹脂片材,可使上層與電子零件之密接性進一步提高,並且亦使下層對電路之嵌入更良好。即,可進一步提高對電子零件之密接性與對下層之電路之嵌入特性之平衡。 The first resin sheet may have higher adhesion to the electronic component than the second resin sheet. In other words, in the present embodiment, the adhesion of the first resin sheet can be made larger than the adhesion of the second resin sheet. On the other hand, the second resin sheet may have higher embedding characteristics to the lower layer circuit than the first resin sheet. That is, in the present embodiment, the lowest melt viscosity of the second resin sheet can be made larger than the lowest melt viscosity of the first resin sheet. By using two or more resin sheets, the adhesion between the upper layer and the electronic component can be further improved, and the lower layer can be better embedded in the circuit. That is, the balance between the adhesion to the electronic component and the embedding property to the circuit of the lower layer can be further improved.
於本實施形態中,形成2層以上之樹脂片材(樹脂層)之方法並無特別限定,例如,首先使將熱硬化性樹脂組成物塗佈於載體基材上而獲得之第1樹脂層及第2樹脂層以第1樹脂層與第2樹脂層對向之方式貼合,並加以乾燥。其後,藉由自第1樹脂層及第2樹脂層將載體基材去除,而獲得2層構成之樹脂片材。此外,可列舉如下方法:藉由將熱硬化性樹脂組成物塗佈於載體基材上並 加以乾燥,而獲得第1樹脂片材。其後,藉由在第1樹脂片材上塗佈熱硬化性樹脂組成物並加以乾燥,而將第2樹脂片材形成於第1樹脂片材上。又,亦可使用如下方法:藉由將2層同時塗佈於載體基材上並加以乾燥,而獲得2層之樹脂片材。 In the present embodiment, a method of forming a resin sheet (resin layer) of two or more layers is not particularly limited. For example, first, a first resin layer obtained by applying a thermosetting resin composition onto a carrier substrate is used. The second resin layer is bonded to the first resin layer and the second resin layer, and dried. Thereafter, the carrier substrate is removed from the first resin layer and the second resin layer to obtain a resin sheet having a two-layer structure. Further, a method of applying a thermosetting resin composition onto a carrier substrate and It was dried to obtain a first resin sheet. Thereafter, the thermosetting resin composition is applied onto the first resin sheet and dried to form the second resin sheet on the first resin sheet. Further, a method in which two layers are simultaneously coated on a carrier substrate and dried to obtain two layers of a resin sheet can be used.
又,於本實施形態中,於上述第2樹脂片材之製造中,藉由使環氧樹脂之含量較第1樹脂片材進一步減少、或者不調配液狀環氧樹脂,可提高第2樹脂片材與載體基材之剝離性。 Further, in the present embodiment, in the production of the second resin sheet, the second resin can be improved by further reducing the content of the epoxy resin to the first resin sheet or without disposing the liquid epoxy resin. Peelability of the sheet from the carrier substrate.
本實施形態之電路基板可包含上述樹脂片材之硬化膜、及接著於上述硬化膜之一面上之電子零件。 The circuit board of the present embodiment may include a cured film of the resin sheet and an electronic component that is next to one surface of the cured film.
圖3(c)表示本實施形態之電路基板1之一例。該電路基板1亦可具備增層12、絕緣層62、佈線40、及電子零件(陶瓷電容器50)。佈線40係嵌入至下層之增層12中。於下層之增層12之上表面固定有陶瓷電容器50。於下層之增層12上,以形成同一層之方式配置有陶瓷電容器50及絕緣層62。絕緣層62可使用預浸體之硬化物。該預浸體亦可不含基材。於陶瓷電容器50及絕緣層62上,配置有上層之增層12。於本實施形態之電路基板1中,內藏電子零件,並且絕緣層62亦可不使用包含基材之芯層而由無芯層形成。可製成此種電子零件內藏型空心基板。 Fig. 3 (c) shows an example of the circuit board 1 of the present embodiment. The circuit board 1 may include a buildup layer 12, an insulating layer 62, a wiring 40, and an electronic component (ceramic capacitor 50). The wiring 40 is embedded in the buildup layer 12 of the lower layer. A ceramic capacitor 50 is fixed to the upper surface of the buildup layer 12 of the lower layer. On the buildup layer 12 of the lower layer, the ceramic capacitor 50 and the insulating layer 62 are disposed so as to form the same layer. As the insulating layer 62, a cured product of a prepreg can be used. The prepreg may also be free of a substrate. On the ceramic capacitor 50 and the insulating layer 62, an upper layer 12 is disposed. In the circuit board 1 of the present embodiment, an electronic component is housed, and the insulating layer 62 may be formed of a coreless layer without using a core layer including a substrate. The hollow substrate embedded in the electronic component can be made.
於本實施形態中,由於增層12包含上述樹脂片材,故而佈線之嵌入良好,且電子零件之位置偏移得以抑制,因此可獲得可靠性優異之構造之電路基板。 In the present embodiment, since the buildup layer 12 includes the resin sheet, the wiring is well embedded, and the positional deviation of the electronic component is suppressed. Therefore, a circuit board having a structure excellent in reliability can be obtained.
本實施形態之電子裝置可使用於上述電路基板上安裝有電子元件之電子裝置。作為電子元件,例如可列舉半導體元件等。 The electronic device of the present embodiment can be used for an electronic device in which an electronic component is mounted on the circuit board. Examples of the electronic component include a semiconductor device and the like.
圖4(c)表示上述電子裝置100之一例。其係於電路基板1上覆晶連接有半導體晶片80之例。該電子裝置100可包含電路基板1、佈線層、外部連接端子、與半導體元件之電極凸塊連接之連接部(佈線74、金屬鍍層78)、及半導體晶片80。 FIG. 4(c) shows an example of the electronic device 100 described above. This is an example in which the semiconductor wafer 80 is flip-chip bonded to the circuit board 1. The electronic device 100 may include a circuit board 1, a wiring layer, external connection terminals, a connection portion (wiring 74, metal plating layer 78) connected to the electrode bumps of the semiconductor element, and a semiconductor wafer 80.
於電路基板1之兩面形成有佈線層。佈線層之層數為任意。下層之佈線層之佈線76係與外部連接端子86電性連接。上層之佈線層之佈線74係與半導體晶片80之凸塊82電性連接。佈線74、76之周圍分別被阻焊膜64、68覆蓋。於半導體晶片80與阻焊膜64之間隙中,填充有底部填充樹脂84。 A wiring layer is formed on both surfaces of the circuit board 1. The number of layers of the wiring layer is arbitrary. The wiring 76 of the lower wiring layer is electrically connected to the external connection terminal 86. The wiring 74 of the upper wiring layer is electrically connected to the bump 82 of the semiconductor wafer 80. The periphery of the wirings 74, 76 is covered by the solder resist films 64, 68, respectively. In the gap between the semiconductor wafer 80 and the solder resist film 64, an underfill resin 84 is filled.
於本實施形態中,藉由利用可靠性優異之構造之電路基板,可實現具有穩定地獲得可靠性、並且良率優異之構造之電子裝置。 In the present embodiment, an electronic device having a structure in which reliability is obtained stably and excellent in yield can be realized by using a circuit board having a structure excellent in reliability.
使用圖1~3對本實施形態之電路基板之製造步驟進行說明。 The manufacturing steps of the circuit board of the present embodiment will be described with reference to Figs.
圖1係表示本實施形態之樹脂片材10之構造之剖面圖,圖2及圖3係表示本實施形態之電路基板1之製造順序之步驟剖面圖。 1 is a cross-sectional view showing a structure of a resin sheet 10 of the present embodiment, and FIGS. 2 and 3 are step sectional views showing a manufacturing procedure of the circuit board 1 of the present embodiment.
首先,準備圖1所示之樹脂片材10。作為該樹脂片材10,可使用由本實施形態之樹脂片材用樹脂組成物形成之樹脂片材10。該樹脂片材10係形成於載體基材(未圖示)之一個面上。 First, the resin sheet 10 shown in Fig. 1 is prepared. As the resin sheet 10, the resin sheet 10 formed of the resin composition for a resin sheet of the present embodiment can be used. The resin sheet 10 is formed on one surface of a carrier substrate (not shown).
繼而,準備於一個面上形成有剝離層30之載體20。作為載體 20,只要為強度高之基板則並無特別限定,例如可使用銅板等金屬板。於該載體20上,藉由微影而形成經圖案化之抗蝕劑。隨後,形成金屬障壁層,藉由電解鍍敷處理形成電解鍍膜。隨後,使用抗蝕劑剝離液將上述抗蝕劑去除,藉此形成經圖案化之作為導電電路而發揮功能之佈線40(佈線圖案)(圖2(a))。 Then, the carrier 20 having the peeling layer 30 formed on one surface is prepared. As a carrier 20 is not particularly limited as long as it is a substrate having high strength, and for example, a metal plate such as a copper plate can be used. On the carrier 20, a patterned resist is formed by lithography. Subsequently, a metal barrier layer is formed, and an electrolytic plating film is formed by electrolytic plating. Subsequently, the resist is removed using a resist stripper, thereby forming a patterned wiring 40 (wiring pattern) functioning as a conductive circuit (FIG. 2(a)).
其次,於使未配置載體基材之樹脂片材10之一個面、與載體20之形成有佈線40之佈線面對向之狀態下,使樹脂片材10壓接於剝離層30上。藉此,將樹脂片材10與載體20接合。即,將樹脂片材接合於形成有導電電路(佈線40)之側之基板(載體20)之面。藉此,可將樹脂片材10嵌入至佈線40之周圍或佈線間之間隙中。其後,自樹脂片材10將載體基材剝離(圖2(b))。 Next, the resin sheet 10 is pressure-bonded to the release layer 30 in a state in which one surface of the resin sheet 10 on which the carrier substrate is not disposed and the wiring on which the wiring 40 of the carrier 20 are formed are faced. Thereby, the resin sheet 10 is bonded to the carrier 20. That is, the resin sheet is bonded to the surface of the substrate (carrier 20) on the side where the conductive circuit (wiring 40) is formed. Thereby, the resin sheet 10 can be embedded in the periphery of the wiring 40 or in the gap between the wirings. Thereafter, the carrier substrate is peeled off from the resin sheet 10 (Fig. 2(b)).
其次,於樹脂片材10之剝離面上,積層電子零件(例如,陶瓷電容器50)(圖2(c))。 Next, an electronic component (for example, a ceramic capacitor 50) is laminated on the peeling surface of the resin sheet 10 (Fig. 2(c)).
其次,於樹脂片材10及陶瓷電容器50上積層預浸體60。其後,藉由例如雷射照射、電漿蝕刻、或機械鑽孔,於預浸體60中形成使陶瓷電容器50露出之開口部90(圖3(a))。藉此,可選擇最適於B-階段狀態之樹脂片材10之開口處理。作為預浸體60,例如可使用使普通之熱硬化性樹脂組成物半硬化所得之預浸體,亦可使用利用構成本實施形態之樹脂片材20之樹脂片材用樹脂組成物之預浸體。上述預浸體60之膜厚例如較佳為10~100μm,更佳為10~70μm。 Next, a prepreg 60 is laminated on the resin sheet 10 and the ceramic capacitor 50. Thereafter, an opening portion 90 through which the ceramic capacitor 50 is exposed is formed in the prepreg 60 by, for example, laser irradiation, plasma etching, or mechanical drilling (Fig. 3(a)). Thereby, the opening treatment of the resin sheet 10 which is most suitable for the B-stage state can be selected. For the prepreg 60, for example, a prepreg obtained by semi-curing a conventional thermosetting resin composition, or a prepreg using a resin composition for a resin sheet constituting the resin sheet 20 of the present embodiment may be used. body. The film thickness of the prepreg 60 is preferably, for example, 10 to 100 μm, more preferably 10 to 70 μm.
其次,於陶瓷電容器50及預浸體60上,藉由熱壓接而積層附載體基材之樹脂片材10。藉此,可利用樹脂片材10埋設上述開口部之內部中之陶瓷電容器50之周圍及上部。又,可於預 浸體60上配置樹脂片材10。其後,將載體基材自樹脂片材10剝離。變得於樹脂片材10之剝離面上殘留剝離層30(圖3(b))。此時,作為樹脂片材10之載體基材,亦可使用金屬箔。作為金屬箔,例如可使用銅箔等。又,亦可使用包含與構成樹脂片材10之樹脂片材用樹脂組成物不同之組成物的普通預浸體,代替於圖3(b)中使用之樹脂片材10。該預浸體可以附載體基材之樹脂片材之形態使用。例如,亦可使用附銅箔之預浸體,埋設陶瓷電容器50。 Next, on the ceramic capacitor 50 and the prepreg 60, the resin sheet 10 with the carrier substrate is laminated by thermocompression bonding. Thereby, the periphery and the upper portion of the ceramic capacitor 50 in the inside of the opening can be buried in the resin sheet 10. Also, can be pre- The resin sheet 10 is placed on the infusion body 60. Thereafter, the carrier substrate is peeled off from the resin sheet 10. The peeling layer 30 remains on the peeling surface of the resin sheet 10 (FIG. 3 (b)). At this time, as the carrier substrate of the resin sheet 10, a metal foil can also be used. As the metal foil, for example, a copper foil or the like can be used. Further, instead of the resin sheet 10 used in Fig. 3(b), a general prepreg containing a composition different from the resin composition for the resin sheet constituting the resin sheet 10 may be used. The prepreg can be used in the form of a resin sheet of a carrier substrate. For example, a prepreg with a copper foil may be used to embed the ceramic capacitor 50.
其次,對圖3(b)所示之構造體進行熱處理。藉此,可使下層之樹脂片材10、預浸體60、及上層之樹脂片材10一次硬化。於本實施形態中,由於可使固定陶瓷電容器50之下層之樹脂片材10、及嵌入陶瓷電容器50之上層之樹脂片材10一次硬化,故而可削減步驟數或製造時間等而提高製程之生產性。又,關於下層之樹脂片材10,藉由不僅將黏著力設為上述下限值以上,而且將最低熔融黏度設為上述下限值以上,即便於未硬化之狀態下亦可有效地抑制陶瓷電容器50之位置偏移量。因此,於圖2(c)至圖3(b)之製程中,換言之,於自將陶瓷電容器50配置於樹脂片材10之上起至使該樹脂片材10硬化為止之期間中,未硬化之樹脂片材10可抑制陶瓷電容器50之位置偏移。 Next, the structure shown in Fig. 3(b) is subjected to heat treatment. Thereby, the resin sheet 10 of the lower layer, the prepreg 60, and the resin sheet 10 of the upper layer can be hardened once. In the present embodiment, the resin sheet 10 on the lower layer of the ceramic capacitor 50 and the resin sheet 10 embedded in the upper layer of the ceramic capacitor 50 can be hardened at one time, so that the number of steps, the manufacturing time, and the like can be reduced to improve the production process. Sex. In addition, the resin sheet 10 of the lower layer is effective in suppressing ceramics even in an unhardened state by setting not only the adhesive force to the lower limit or more but also the lowest melt viscosity. The positional offset of the capacitor 50. Therefore, in the process of FIGS. 2(c) to 3(b), in other words, during the period from when the ceramic capacitor 50 is disposed on the resin sheet 10 until the resin sheet 10 is hardened, it is not hardened. The resin sheet 10 can suppress the positional shift of the ceramic capacitor 50.
再者,於上述說明中,於圖3(b)中對進行一次硬化之例進行了說明,但並不限定於此。例如,於將陶瓷電容器50配置於樹脂片材10上時(圖2(c)),亦可使該樹脂片材10稍微硬化。例如,於圖2(c)所示之狀態下,以樹脂片材10不完全硬化之程度進行熱處理。藉此,可進一步減小樹脂片材10之位置偏移。又,與使其完全硬化之情形時相比,可實現製程之時間縮短,生產性提高。 In the above description, an example in which primary hardening is performed in FIG. 3(b) has been described, but the invention is not limited thereto. For example, when the ceramic capacitor 50 is placed on the resin sheet 10 (Fig. 2(c)), the resin sheet 10 can be slightly cured. For example, in the state shown in Fig. 2(c), heat treatment is performed to such an extent that the resin sheet 10 is not completely cured. Thereby, the positional deviation of the resin sheet 10 can be further reduced. Further, compared with the case where it is completely hardened, the time for the process can be shortened and the productivity can be improved.
又,於圖2(c)中,亦可使配置有陶瓷電容器50之樹脂片材10完全硬化。藉此,可進一步抑制陶瓷電容器50之位置偏移。 Further, in FIG. 2(c), the resin sheet 10 on which the ceramic capacitor 50 is placed may be completely cured. Thereby, the positional shift of the ceramic capacitor 50 can be further suppressed.
此處,於使用最低熔融黏度未達上述下限值者作為樹脂片材10之情形時,因預浸體60或上層之樹脂片材10等之積層時之熱壓接,而有下層之樹脂片材10之黏度變低、陶瓷電容器50變得易偏移之虞。於該情形時,亦可藉由在圖2(c)中進行完全硬化,而抑制位置偏移,但若使其完全硬化,則有於陶瓷電容器50之下部與樹脂片材10之界面產生空隙之擔憂。相對於此,於進行一次硬化之情形時,於利用樹脂埋入電容器周圍之空間時,上層之樹脂片材與下層之樹脂片材均係樹脂之黏度下降而流動,故而產生空隙之擔憂變少。 Here, when the resin sheet 10 is used as the resin sheet 10 having the lowest melt viscosity, the lower layer of the resin is formed by the thermocompression bonding of the prepreg 60 or the upper resin sheet 10 or the like. The viscosity of the sheet 10 becomes low, and the ceramic capacitor 50 becomes easy to shift. In this case, the positional shift can be suppressed by performing the complete hardening in FIG. 2(c), but if it is completely cured, a gap is formed in the interface between the lower portion of the ceramic capacitor 50 and the resin sheet 10. Worry. On the other hand, in the case where the primary curing is performed, when the resin is buried in the space around the capacitor, the resin layer of the upper layer and the resin sheet of the lower layer are both reduced in viscosity and flow, so that there is less concern that voids are generated. .
於本實施形態中,熱硬化處理之條件並無特別限定,例如可設為200~220℃、約1小時之條件。藉由硬化處理,形成包含樹脂片材10之硬化物之增層12(絕緣層)、及包含預浸體60之硬化物之絕緣層62。藉此,可於下層之增層12上固定陶瓷電容器50。接著,將載體20自剝離層30剝離(圖3(c))。 In the present embodiment, the conditions of the thermosetting treatment are not particularly limited, and for example, it can be set to 200 to 220 ° C for about 1 hour. By the hardening treatment, the buildup layer 12 (insulating layer) including the cured product of the resin sheet 10, and the insulating layer 62 containing the cured product of the prepreg 60 are formed. Thereby, the ceramic capacitor 50 can be fixed on the buildup layer 12 of the lower layer. Next, the carrier 20 is peeled off from the peeling layer 30 (Fig. 3(c)).
藉由以上處理,可獲得本實施形態之電路基板1。再者,於預浸體60不含基材之情形時,可獲得不具有芯層之無芯電路基板1。 By the above processing, the circuit board 1 of the present embodiment can be obtained. Further, in the case where the prepreg 60 does not contain a substrate, the coreless circuit substrate 1 having no core layer can be obtained.
使用圖4對本實施形態之電子裝置100之製造步驟進行說明。 The manufacturing steps of the electronic device 100 of the present embodiment will be described with reference to Fig. 4 .
圖4係表示本實施形態之電子裝置100之製造順序之步驟剖面 圖。 4 is a cross-sectional view showing the steps of manufacturing the electronic device 100 of the present embodiment. Figure.
使用藉由上述電路基板之製造步驟而獲得之電路基板1。首先,例如藉由對電路基板1之兩面進行雷射照射,而形成開口部(通孔70、72)(圖4(a))。於通孔70之底部,陶瓷電容器50之電極54之一部分露出。另一方面,於通孔72之底部,佈線40之一部分露出。 The circuit board 1 obtained by the above-described manufacturing steps of the circuit board is used. First, the openings (through holes 70, 72) are formed by, for example, performing laser irradiation on both surfaces of the circuit board 1 (FIG. 4(a)). At the bottom of the via 70, a portion of the electrode 54 of the ceramic capacitor 50 is partially exposed. On the other hand, at the bottom of the through hole 72, a part of the wiring 40 is partially exposed.
其次,於電路基板1之兩面側形成佈線層。於本實施形態中,示出佈線層為1層之例,但並不限定於此,佈線層之積層數可任意設定(圖4(b))。 Next, a wiring layer is formed on both sides of the circuit board 1. In the present embodiment, the wiring layer is one layer. However, the number of layers of the wiring layer can be arbitrarily set (FIG. 4(b)).
佈線層之佈線74、76之形成方法並無特別限定,例如可使用藉由微影處理及選擇性蝕刻而形成佈線之方法。 The method of forming the wirings 74 and 76 of the wiring layer is not particularly limited, and for example, a method of forming wiring by lithography and selective etching can be used.
其次,於電路基板1之上表面側形成阻焊膜64。藉由例如雷射照射、電漿蝕刻、化學蝕刻、或微影處理,而於阻焊膜64中形成使佈線74之一部分露出之開口部。接著,藉由電鍍處理等,於該開口部內之佈線74之上表面形成金屬鍍層78。金屬鍍層78係作為與半導體晶片80之電極凸塊(凸塊82)連接之連接部而發揮功能。 Next, a solder resist film 64 is formed on the upper surface side of the circuit substrate 1. An opening portion exposing a portion of the wiring 74 is formed in the solder resist film 64 by, for example, laser irradiation, plasma etching, chemical etching, or lithography. Next, a metal plating layer 78 is formed on the upper surface of the wiring 74 in the opening portion by a plating treatment or the like. The metal plating layer 78 functions as a connection portion to the electrode bumps (bumps 82) of the semiconductor wafer 80.
另一方面,於電路基板1之下表面側,亦形成阻焊膜68。同樣地於阻焊膜68中形成使佈線76之一部分露出之開口部。接著,藉由在該開口部內之佈線76上搭載焊錫球等,而形成外部連接端子86。 On the other hand, on the lower surface side of the circuit board 1, a solder resist film 68 is also formed. Similarly, an opening portion for exposing a portion of the wiring 76 is formed in the solder resist film 68. Next, an external connection terminal 86 is formed by mounting a solder ball or the like on the wiring 76 in the opening.
其次,於電路基板1之上表面側之連接部(佈線74、金屬鍍層78),覆晶連接半導體晶片80之凸塊82。進而,於半導體晶片80之下側填充底部填充樹脂84。藉由以上處理,可獲得半 導體裝置(電子裝置100)(圖4(c))。 Next, the bumps 82 of the semiconductor wafer 80 are flip-chip bonded to the connection portions (wiring 74, metal plating layer 78) on the upper surface side of the circuit board 1. Further, the underfill resin 84 is filled on the lower side of the semiconductor wafer 80. With the above processing, half can be obtained Conductor device (electronic device 100) (Fig. 4(c)).
於本實施形態之製造步驟中,使用圖1對樹脂片材10為單層之例進行了說明,但並不限定於單層,亦可為2層以上之數層。於圖5中,示出本實施形態之樹脂片材為2層之例。樹脂片材10包含第1樹脂層14(第1樹脂片材)及第2樹脂層16(第2樹脂片材)。上層之第1樹脂層14具有穩定地固定陶瓷電容器50之特性,下層之第2樹脂層16具有易於嵌入佈線40等電路圖案之特性。藉由將上述樹脂片材設為2層以上,可進一步提高對下層之電路之嵌入性、與對上層之電子零件之密接性之平衡。 In the manufacturing step of the present embodiment, an example in which the resin sheet 10 is a single layer has been described with reference to FIG. 1. However, the resin sheet 10 is not limited to a single layer, and may be two or more layers. Fig. 5 shows an example in which the resin sheet of the present embodiment has two layers. The resin sheet 10 includes a first resin layer 14 (first resin sheet) and a second resin layer 16 (second resin sheet). The first resin layer 14 of the upper layer has the property of stably fixing the ceramic capacitor 50, and the second resin layer 16 of the lower layer has characteristics of being easily embedded in a circuit pattern such as the wiring 40. By setting the resin sheet to two or more layers, the balance between the embedding property to the lower layer and the adhesion to the electronic component of the upper layer can be further improved.
圖7係表示陶瓷電容器50之變形例之圖。於上述說明中,如圖3(c)所示,示出了利用於本體部52之長度方向之兩端形成有電極54之陶瓷電容器50之例,但並不限定於此,可利用具有各種構造之陶瓷電容器50。例如可列舉具有如下構成之電容器50,即,將電極54僅配置於本體部52之一面側之構成,即,將電極54配置於本體部52之下側之構成(圖7(a))、或將電極54配置於本體部52之上側之構成(圖7(b))。該等電極54具有電極圖案。又,如圖7(c)所示,亦可使用將電極54形成於本體部52之兩面、且遍及其表面而整體地形成之電容器50。 FIG. 7 is a view showing a modification of the ceramic capacitor 50. In the above description, as shown in FIG. 3(c), the ceramic capacitor 50 in which the electrodes 54 are formed at both ends in the longitudinal direction of the main body portion 52 is shown. However, the present invention is not limited thereto, and various types of materials can be used. A ceramic capacitor 50 is constructed. For example, a capacitor 50 having a configuration in which the electrode 54 is disposed only on one surface side of the main body portion 52, that is, a configuration in which the electrode 54 is disposed on the lower side of the main body portion 52 (FIG. 7(a)), Or the electrode 54 is disposed on the upper side of the main body portion 52 (Fig. 7(b)). The electrodes 54 have an electrode pattern. Further, as shown in FIG. 7(c), a capacitor 50 in which the electrode 54 is formed on both surfaces of the main body portion 52 and formed integrally over the entire surface thereof may be used.
於本實施形態中,對覆晶連接之例進行了說明,但並不限定於此,可利用各種連接方法。例如,亦可利用打線接合方法。 In the present embodiment, an example of flip chip connection has been described. However, the present invention is not limited thereto, and various connection methods can be utilized. For example, a wire bonding method can also be utilized.
再者,本發明不受上述實施形態所限定,可達成本發明之目的之範圍內之變形、改良等包含於本發明內。 Further, the present invention is not limited to the above-described embodiments, and modifications, improvements, etc. within the scope of the object of the invention are included in the present invention.
其次,對本發明之實施例進行說明。再者,本發明並 不限定於此。 Next, an embodiment of the present invention will be described. Furthermore, the present invention It is not limited to this.
針對各實施例及各比較例,製備清漆狀之熱硬化性樹脂組成物。清漆狀之熱硬化性樹脂組成物係藉由使根據表1所調配之各成分之原料溶解、分散於下述溶劑1後,使用高速攪拌裝置攪拌1小時而獲得。再者,表1中之表示各成分之調配比率之數值係表示相對於熱硬化性樹脂組成物之固形份總體的各成分之調配比率(重量%)。 For each of the examples and the comparative examples, a varnish-like thermosetting resin composition was prepared. The varnish-like thermosetting resin composition was obtained by dissolving and dispersing the raw materials of the respective components prepared in accordance with Table 1 in the following solvent 1, followed by stirring for 1 hour using a high-speed stirring device. In addition, the numerical value of the compounding ratio of each component in Table 1 shows the compounding ratio (% by weight) of each component with respect to the solid content of the thermosetting resin composition.
表1中之各成分之原料之詳細情況係如下所述。 The details of the raw materials of the respective components in Table 1 are as follows.
熱硬化性樹脂1:萘改質甲酚酚醛清漆環氧樹脂(DIC公司製造之HP-5000) Thermosetting resin 1: naphthalene modified cresol novolac epoxy resin (HP-5000 manufactured by DIC Corporation)
熱硬化性樹脂2:伸萘基醚型環氧樹脂(DIC公司製造之HP-6000) Thermosetting resin 2: Naphthyl ether type epoxy resin (HP-6000 manufactured by DIC Corporation)
熱硬化性樹脂3:4官能萘型環氧樹脂(DIC公司製造之EPICLON HP-4710) Thermosetting resin 3: 4-functional naphthalene type epoxy resin (EPICLON HP-4710 manufactured by DIC Corporation)
熱硬化性樹脂4:雙酚F型環氧樹脂(DIC公司製造之EPICLON、830S) Thermosetting resin 4: bisphenol F type epoxy resin (EPICLON, 830S manufactured by DIC Corporation)
熱硬化性樹脂5:苯酚酚醛清漆型氰酸酯樹脂(LONZA公司製造之Primaset PT-30) Thermosetting resin 5: phenol novolac type cyanate resin (Primaset PT-30 manufactured by LONZA Corporation)
熱硬化性樹脂6:碳二醯亞胺(日清紡化學公司製造之V-05) Thermosetting resin 6: carbodiimide (V-05 manufactured by Nisshinbo Chemical Co., Ltd.)
熱硬化性樹脂7:3官能烷氧基矽烷改質苯酚酚醛清漆(荒川化 學公司製造之P501) Thermosetting resin 7: 3-functional alkoxy decane modified phenol novolac (Arakawa Learned by the company P501)
熱硬化性樹脂8:丙烯酸酯化合物(2-丙烯酸-2-[4-(乙醯氧基)苯基]乙酯) Thermosetting Resin 8: Acrylate Compound (2-Acetyl-2-[4-(ethyloxy)phenyl]ethyl)
填充材料1:球狀二氧化矽(Admatechs公司製造之SO-C4,平均粒徑1.0μm,經苯基胺基矽烷處理) Filler 1: spherical cerium oxide (SO-C4 manufactured by Admatechs, average particle size 1.0 μm, treated with phenylamino decane)
填充材料2:球狀二氧化矽(Admatechs公司製造之SO-C4,平均粒徑1.0μm,未經處理) Filler 2: Spherical cerium oxide (SO-C4 manufactured by Admatechs, average particle size 1.0 μm, untreated)
硬化促進劑1:四苯基鏻-四(4-甲基苯基)硼酸鹽(TPP-MK) Hardening accelerator 1: tetraphenylphosphonium-tetrakis(4-methylphenyl)borate (TPP-MK)
偶合劑1:環氧矽烷(信越化學工業公司製造之KBM-403) Coupling agent 1: epoxy decane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.)
溶劑1:甲基乙基酮 Solvent 1: methyl ethyl ketone
關於實施例1~8、及比較例1~4,將所獲得之熱硬化性樹脂組成物塗佈於作為載體基材之聚對苯二甲酸乙二酯(PET,polyethylene terephthalate)薄膜(38μm厚)上之後,以140℃、2分鐘之條件去除溶劑,形成厚度30μm之附載體基材之樹脂片材。 In Examples 1 to 8 and Comparative Examples 1 to 4, the obtained thermosetting resin composition was applied to a polyethylene terephthalate (PET) film as a carrier substrate (38 μm thick). After the above, the solvent was removed at 140 ° C for 2 minutes to form a resin sheet of a carrier substrate having a thickness of 30 μm.
又,關於實施例4,以如下方式製作樹脂片材。將所獲得之熱硬化性樹脂組成物塗佈於作為載體基材之PET薄膜(38μm厚)上之後,以140℃、2分鐘之條件去除溶劑,形成第1層之第1樹脂層。同樣地獲得第2層之第2樹脂層。藉由使第1樹脂層與第2樹脂層貼合,而形成2層之樹脂層。其後,自第2樹脂層將載體基材剝離,而形成將厚度30μm之第1樹脂片材與厚度30μm之第2樹脂片材積層而成的附載體基材之樹脂片材。 Further, in Example 4, a resin sheet was produced in the following manner. After the obtained thermosetting resin composition was applied onto a PET film (38 μm thick) as a carrier substrate, the solvent was removed at 140 ° C for 2 minutes to form a first resin layer of the first layer. Similarly, the second resin layer of the second layer was obtained. Two layers of the resin layer are formed by bonding the first resin layer and the second resin layer. Then, the carrier substrate is peeled off from the second resin layer, and a resin sheet with a carrier substrate obtained by laminating a first resin sheet having a thickness of 30 μm and a second resin sheet having a thickness of 30 μm is formed.
針對各實施例及各比較例,以如下方式測定樹脂片材之黏著力。首先,使附載體基材之樹脂片材於80℃貼合於芯材(FR-4基材)。其次,將經貼合之附載體基材之樹脂片材及芯材切割成約10cm見方,將載體基材(PET薄膜)剝離,製作測定樣品。隨後,以芯材成為下之方式將測定樣品載置於經設定為25℃之黏著試驗機(Rhesca公司製造)之台上,以100gf/5mm 、5sec之條件將探針(5mm )按壓於測定樣品。其後,使探針以2mm/sec之條件自測定樣品脫離。此時,測定探針自測定樣品承受之拉力,並將其峰值作為黏著力(gf/5mm )。藉由以上操作,測定將PET薄膜剝離後 之樹脂片材之剝離面之黏著力。將結果示於表1。 The adhesion of the resin sheet was measured in the following manner for each of the examples and the comparative examples. First, the resin sheet with a carrier substrate was bonded to a core material (FR-4 substrate) at 80 °C. Next, the resin sheet and the core material of the bonded carrier substrate were cut into about 10 cm square, and the carrier substrate (PET film) was peeled off to prepare a measurement sample. Subsequently, the measurement sample was placed on a table of an adhesion tester (manufactured by Rhesca Co., Ltd.) set to 25 ° C in a manner that the core material was the next, at 100 gf / 5 mm. 5 sec conditions probe (5mm ) pressed against the assay sample. Thereafter, the probe was detached from the measurement sample under the condition of 2 mm/sec. At this time, the tensile force of the probe from the measured sample is measured, and the peak value is used as the adhesive force (gf/5 mm). ). By the above operation, the adhesion of the peeling surface of the resin sheet after peeling off the PET film was measured. The results are shown in Table 1.
針對各實施例及各比較例,以如下方式測定樹脂片材之最低熔融黏度。首先,準備自上述所獲得之附載體基材之樹脂片材將作為載體基材之PET薄膜剝離而獲得之樹脂片材,作為測定樣品。隨後,對該測定樣品使用動態黏彈性測定裝置(Anton Paar公司製造之裝置名Physica MCR-301),以下述條件進行熔融黏度之測定。根據所獲得之測定結果,算出50~200℃之最低熔融黏度(Pa.s)。將結果示於表1。 For each of the examples and the comparative examples, the lowest melt viscosity of the resin sheet was measured in the following manner. First, a resin sheet obtained by peeling off a PET film as a carrier substrate from the resin sheet with a carrier substrate obtained above was prepared as a measurement sample. Subsequently, a dynamic viscoelasticity measuring apparatus (device name Physica MCR-301 manufactured by Anton Paar Co., Ltd.) was used for the measurement sample, and the melt viscosity was measured under the following conditions. Based on the obtained measurement results, the lowest melt viscosity (Pa.s) of 50 to 200 ° C was calculated. The results are shown in Table 1.
頻率:62.83rad/sec Frequency: 62.83 rad/sec
測定溫度:50~200℃ Measuring temperature: 50~200°C
升溫速度:3℃/min Heating rate: 3 ° C / min
幾何形狀:平行板 Geometric shape: parallel plate
板直徑:10mm Plate diameter: 10mm
板間隔:0.1mm Board spacing: 0.1mm
負重(法線力):0N(固定) Load (normal force): 0N (fixed)
應變:0.3% Strain: 0.3%
測定氣氛:空氣 Measuring atmosphere: air
針對各實施例及各比較例,將自所獲得之附載體基材之樹脂片材將作為載體基材之PET薄膜剝離而獲得之樹脂片材積層3片,製作厚度90μm之樹脂片材。隨後,對該樹脂片材以200℃、1小時 進行熱處理之後,切出寬度8mm×長度50mm×厚度90μm而製成測定樣品。對該測定樣品使用動態黏彈性測定裝置(Seiko Instruments公司製造之DMS6100),以頻率1Hz、升溫速度5℃/min之條件進行動態黏彈性試驗。隨後,根據所獲得之測定結果,算出玻璃轉移溫度(℃)、及25℃之儲存模數(GPa)。玻璃轉移溫度係根據tan β之峰值而判定。將結果示於表1。 For each of the examples and the comparative examples, a resin sheet obtained by peeling off a PET film as a carrier substrate from a resin sheet with a carrier substrate obtained was laminated to prepare a resin sheet having a thickness of 90 μm. Subsequently, the resin sheet was heated at 200 ° C for 1 hour. After the heat treatment, a measurement sample was prepared by cutting out a width of 8 mm, a length of 50 mm, and a thickness of 90 μm. A dynamic viscoelasticity test was carried out on the measurement sample using a dynamic viscoelasticity measuring apparatus (DMS6100 manufactured by Seiko Instruments Co., Ltd.) at a frequency of 1 Hz and a temperature elevation rate of 5 ° C/min. Subsequently, based on the obtained measurement results, the glass transition temperature (° C.) and the storage modulus (GPa) at 25° C. were calculated. The glass transition temperature is determined based on the peak of tan β. The results are shown in Table 1.
針對各實施例及各比較例,將自所獲得之附載體基材之樹脂片材將作為載體基材之PET薄膜剝離而獲得之樹脂片材積層3片,製作厚度90μm之樹脂片材。隨後,對該樹脂片材以200℃、1小時進行熱處理之後,切出寬度4mm×長度20mm×厚度90μm而製成測定樣品。對該測定樣品使用TMA(TA Instruments(股)製造),以升溫速度10℃/min之條件進行線膨脹係數之測定。隨後,算出25~50℃之測定結果之平均,將其作為未達玻璃轉移溫度之線膨脹係數(ppm/℃)。將結果示於表1。 For each of the examples and the comparative examples, a resin sheet obtained by peeling off a PET film as a carrier substrate from a resin sheet with a carrier substrate obtained was laminated to prepare a resin sheet having a thickness of 90 μm. Subsequently, the resin sheet was heat-treated at 200 ° C for 1 hour, and then a width of 4 mm × a length of 20 mm × a thickness of 90 μm was cut out to prepare a measurement sample. For the measurement sample, TMA (manufactured by TA Instruments) was used, and the linear expansion coefficient was measured under the conditions of a temperature increase rate of 10 ° C/min. Subsequently, the average of the measurement results at 25 to 50 ° C was calculated, and this was taken as the linear expansion coefficient (ppm / ° C) which did not reach the glass transition temperature. The results are shown in Table 1.
針對各實施例及各比較例,以如下方式評價電路嵌入性、及對積層陶瓷電容器之密接性。首先,於作為載體之銅板上,藉由微影而形成經圖案化之抗蝕劑。隨後,形成鎳障壁層,隨後,藉由電解鍍敷處理形成電解銅鍍膜(厚度12μm),形成L/S=12/12μm之佈線圖案。其次,使用抗蝕劑剝離液將抗蝕劑去除。其次,將上述所獲得之附載體基材之樹脂片材以樹脂片材嵌入佈線之方式積層於 剝離層上之後,自樹脂片材將載體基材剝離。隨後,於樹脂片材上載置陶瓷電容器。隨後,使樹脂片材以200℃、1小時之條件硬化,而形成包含樹脂片材之硬化物之絕緣層。藉此,獲得評價樣品。 For each of the examples and the comparative examples, the circuit embedding property and the adhesion to the multilayer ceramic capacitor were evaluated as follows. First, a patterned resist is formed by lithography on a copper plate as a carrier. Subsequently, a nickel barrier layer was formed, and then an electrolytic copper plating film (thickness: 12 μm) was formed by electrolytic plating to form a wiring pattern of L/S = 12/12 μm. Next, the resist is removed using a resist stripper. Next, the resin sheet with the carrier substrate obtained above is laminated in such a manner that the resin sheet is embedded in the wiring. After peeling off the layer, the carrier substrate was peeled off from the resin sheet. Subsequently, a ceramic capacitor was placed on the resin sheet. Subsequently, the resin sheet was cured at 200 ° C for 1 hour to form an insulating layer containing a cured product of the resin sheet. Thereby, an evaluation sample was obtained.
針對上述所獲得之評價樣品內之任意10個部位,藉由顯微鏡觀察絕緣層之表面,確認於佈線圖案間是否嵌入有絕緣層,並依據以下基準對電路嵌入性進行評價。 The surface of the insulating layer was observed with a microscope by observing the surface of the insulating layer in any of the ten portions of the evaluation sample obtained above, and the circuit embedding property was evaluated based on the following criteria.
◎:於樣品之所有部位,於佈線圖案間完全未觀察到空隙。 ◎: No void was observed at all in the wiring pattern between the wiring patterns.
○:於樣品之所有部位,於佈線圖案間未觀察到空隙,但於絕緣層之表面觀察到若干起伏。 ○: No void was observed between the wiring patterns in all portions of the sample, but several undulations were observed on the surface of the insulating layer.
×:於樣品之至少一個部位,於佈線圖案間觀察到空隙。 ×: A void was observed between the wiring patterns at at least one portion of the sample.
將結果示於表1。 The results are shown in Table 1.
又,對於上述所獲得之評價樣品,利用推挽試驗藉由晶片剪切強度測定依據以下基準進行積層陶瓷電容器之密接性之評價。 Further, with respect to the evaluation sample obtained above, the adhesion of the multilayer ceramic capacitor was evaluated by the wafer shear strength measurement by the push-pull test according to the following criteria.
◎:20N/mm2以上。 ◎: 20 N/mm 2 or more.
○:15N/mm2以上且未達20N/mm2。 ○: 15 N/mm 2 or more and less than 20 N/mm 2 .
×:未達15N/mm2。 ×: Less than 15 N/mm 2 .
將結果示於表1。 The results are shown in Table 1.
針對各實施例及各比較例,以如下方式對樹脂片材之載體剝離性進行評價。首先,於附載體基材之樹脂片材中之未設置PET薄膜(厚度38μm)之側之面上,積層厚度25μm之PET薄膜,獲得積層體。隨後,將該積層體切出約10cm見方而製成測定樣品。隨後, 將測定樣品中之厚度38μm之PET薄膜固定於台。隨後,於25℃之溫度條件下,對於測定樣品中之厚度25μm之PET薄膜,將四角中之一個部位相對於測定樣品向垂直方向拉伸5cm,依據以下基準對載體剝離性進行評價。 The carrier peelability of the resin sheet was evaluated in the following manner for each of the examples and the comparative examples. First, a PET film having a thickness of 25 μm was laminated on the surface of the resin sheet with a carrier substrate on the side where the PET film (thickness: 38 μm) was not provided, and a laminate was obtained. Subsequently, the laminate was cut out to a thickness of about 10 cm to prepare a measurement sample. Subsequently, A PET film having a thickness of 38 μm in the measurement sample was fixed to the stage. Subsequently, at a temperature of 25 ° C, one of the four corners was stretched by 5 cm in the vertical direction with respect to the measurement sample for the PET film having a thickness of 25 μm in the measurement sample, and the carrier peelability was evaluated in accordance with the following criteria.
◎:於厚度25μm之PET薄膜與樹脂片材之間發生剝離。 ◎: Peeling occurred between the PET film having a thickness of 25 μm and the resin sheet.
○:於厚度38μm之PET薄膜與樹脂片材之間發生局部剝離,但於厚度25μm之PET薄膜與樹脂片材之間剝離。 ○: Partial peeling occurred between the PET film having a thickness of 38 μm and the resin sheet, but peeled off between the PET film having a thickness of 25 μm and the resin sheet.
×:於厚度25μm之PET薄膜與樹脂片材之間未剝離,而於厚度38μm之PET薄膜與樹脂片材之間剝離,或測定樣品自固定台剝離。將結果示於表1。 X: The PET film having a thickness of 25 μm and the resin sheet were not peeled off, and the PET film having a thickness of 38 μm was peeled off from the resin sheet, or the sample was peeled off from the fixing table. The results are shown in Table 1.
針對各實施例及各比較例,以如下方式對陶瓷電容器之位置偏移量進行測定。首先,將附載體基材之樹脂片材以銅板與樹脂片材對向之方式積層於銅板上,使用批次式真空加壓貼合機進行真空抽吸30秒鐘。其後,使用耐壓橡膠以30秒鐘、壓力1kg/cm2之條件進行加壓。隨後,自附載體基材之樹脂片材將載體基材剝離。隨後,將陶瓷電容器(1608尺寸)載置於樹脂片材上。 For each of the examples and the comparative examples, the positional shift amount of the ceramic capacitor was measured as follows. First, the resin sheet with the carrier substrate was laminated on the copper plate so that the copper plate and the resin sheet were opposed to each other, and vacuum suction was performed for 30 seconds using a batch type vacuum pressure bonding machine. Thereafter, pressurization was carried out using a pressure resistant rubber under the conditions of 30 seconds and a pressure of 1 kg/cm 2 . Subsequently, the resin sheet attached to the carrier substrate peels off the carrier substrate. Subsequently, a ceramic capacitor (size 1608) was placed on the resin sheet.
隨後,將具有與陶瓷電容器部分對應地形成之開口部之預浸體載置於樹脂片材上。 Subsequently, a prepreg having an opening portion formed corresponding to the ceramic capacitor portion is placed on the resin sheet.
隨後,積層樹脂片材,使用真空加壓機以壓力30kg/cm2、200℃進行30分鐘處理,將陶瓷電容器固定於樹脂片材,並使樹脂片材硬化。藉此,獲得測定樣品。 Subsequently, the laminated resin sheet was treated by a vacuum press at a pressure of 30 kg/cm 2 and 200 ° C for 30 minutes to fix the ceramic capacitor to the resin sheet and to cure the resin sheet. Thereby, a measurement sample is obtained.
圖6係表示位置偏移量之測定方法之平面示意圖。於 載置預浸體之後,分別測定原點A、B與陶瓷電容器之四角之平面距離(X、Y、Z、W)。圖6中之開口部90表示形成於預浸體中之開口部。 Fig. 6 is a schematic plan view showing a method of measuring the positional shift amount. to After the prepreg was placed, the plane distances (X, Y, Z, W) of the four corners of the origins A and B and the ceramic capacitor were measured. The opening portion 90 in Fig. 6 indicates an opening formed in the prepreg.
其次,使樹脂片材硬化。再次測定硬化後之測定樣品之原點A、B與陶瓷電容器之四角之平面距離(X、Y、Z、W)。然後,針對X、Y、Z、W中之於使樹脂片材硬化之上述步驟中發生最大偏移之電容器之四角中之任一者之地點,將其偏移量設為位置偏移量。將結果示於表1。 Next, the resin sheet is hardened. The plane distances (X, Y, Z, W) of the origins A and B of the sample after hardening and the four corners of the ceramic capacitor were measured again. Then, the offset amount is set as the position shift amount for the position of any of the four corners of the capacitor in which the maximum deviation occurs in the above-described step of hardening the resin sheet in X, Y, Z, and W. The results are shown in Table 1.
再者,於比較例3中,由於黏著力高,故而將樹脂片材積層於銅板上之後,於自樹脂片材將載體基材剝離時,於銅板與樹脂片材間剝離,或樹脂片材之內部破裂而剝離,因此無法正常地進行載體基材之剝離。因此,將比較例3之位置偏移量視為無法評價。 Further, in Comparative Example 3, since the adhesive sheet was high, the resin sheet was laminated on the copper plate, and after peeling off the carrier substrate from the resin sheet, the copper sheet and the resin sheet were peeled off, or the resin sheet was peeled off. Since the inside is ruptured and peeled off, peeling of the carrier substrate cannot be performed normally. Therefore, the positional shift amount of Comparative Example 3 was regarded as unevaluable.
10‧‧‧樹脂片材 10‧‧‧Resin sheet
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