TWI551632B - Prepreg, metal-clad laminate, and printed wiring board,and multilayer printed wiring board - Google Patents
Prepreg, metal-clad laminate, and printed wiring board,and multilayer printed wiring board Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
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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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
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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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- 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
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/021—Fibrous or filamentary layer
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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
- B32B2305/00—Condition, form or state of the layers or laminate
- B32B2305/07—Parts immersed or impregnated in a matrix
- B32B2305/076—Prepregs
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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
- B32B2457/08—PCBs, i.e. printed circuit boards
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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
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/24—Thermosetting resins
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Engineering & Computer Science (AREA)
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Description
本發明係關於預浸材、使用前述預浸材所形成的覆金屬層積板、使用前述覆金屬層積板所形成的印刷配線板、及多層印刷配線板。 The present invention relates to a prepreg, a metal-clad laminate formed using the prepreg, a printed wiring board formed using the metal-clad laminate, and a multilayer printed wiring board.
以往，預浸材係使含有熱硬化性樹脂及無機填充材的樹脂組成物含浸在織布基材，並且至成為半硬化狀態為止進行加熱乾燥所形成(參照例如專利文獻1-3)。接著，可藉由在如上所形成的預浸材層積金屬箔來製造覆金屬層積板，另外藉由在該覆金屬層積板設置導體圖案，來製造印刷配線板。此外，可在該印刷配線板透過預浸材來層積金屬箔，將該金屬箔的不必要部分去除來設置導體圖案，藉此製造多層印刷配線板。之後，藉由在該印刷配線板或多層印刷配線板構裝且封裝半導體元件來製造封裝體(PKG)。 In the past, the prepreg is formed by impregnating a woven fabric substrate with a resin composition containing a thermosetting resin and an inorganic filler, and heating and drying until it is in a semi-cured state (see, for example, Patent Documents 1 to 3). Next, a metal-clad laminate can be produced by laminating a metal foil in the prepreg formed as described above, and a printed wiring board can be produced by providing a conductor pattern on the metal-clad laminate. Further, a multilayer printed wiring board can be manufactured by laminating a metal foil on the printed wiring board through a prepreg, removing unnecessary portions of the metal foil, and providing a conductor pattern. Thereafter, a package (PKG) is manufactured by mounting and packaging a semiconductor element on the printed wiring board or the multilayer printed wiring board.
[專利文獻1]日本特開平8-288416號公報 [Patent Document 1] Japanese Patent Laid-Open No. Hei 8-288416
[專利文獻2]日本特開2003-268136號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2003-268136
[專利文獻3]日本特開2007-246668號公報 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2007-246668
但是，在習知之預浸材中，係會有容易發生樹脂掉粉的問題。此外，若使用如上所示之預浸材來製造覆金屬層積板時，亦會有熱硬化性樹脂與無機填充材分離而容易在覆金屬層積板發生外觀不良的問題。另外亦會有使用如上所示之覆金屬層積板所製造的印刷配線板的絕緣可靠性、導通可靠性降低之虞。 However, in the conventional prepreg, there is a problem that the resin is easily broken. Further, when the metal-clad laminate is produced by using the prepreg as described above, the thermosetting resin and the inorganic filler are separated, and the appearance of the metal-clad laminate is likely to be poor. In addition, there is a possibility that the insulation reliability and the conduction reliability of the printed wiring board manufactured by using the metal-clad laminate shown above are lowered.
本發明係鑑於上述情形而研創者，目的在提供可製造可減低掉粉且外觀良好的層積板的預浸材、外觀良好的覆金屬層積板、印刷配線板、及多層印刷配線板。 The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a prepreg which can produce a laminated board which can reduce powder and has a good appearance, a metal-clad laminate having a good appearance, a printed wiring board, and a multilayer printed wiring board.
本發明之預浸材係使含有熱硬化性樹脂及無機填充材的樹脂組成物含浸在織布基材，並且至成為半硬化狀態為止進行加熱乾燥所形成的預浸材，其特徵為：前述預浸材之藉由動態黏彈性測定所得之玻璃轉化溫度為120~170℃。 The prepreg of the present invention is a prepreg formed by impregnating a woven fabric substrate with a resin composition containing a thermosetting resin and an inorganic filler, and heating and drying it in a semi-hardened state. The pre-dip material has a glass transition temperature of 120 to 170 ° C as measured by dynamic viscoelasticity.
在前述預浸材中，較佳為相對於前述樹脂組成物全量，含有前述無機填充材60~85質量%。 In the prepreg, the inorganic filler is preferably contained in an amount of 60 to 85% by mass based on the total amount of the resin composition.
在前述預浸材中，較佳為相對於前述無機填充材全量，50質量%以上為平均粒徑3μm以下的球狀二氧化矽。 In the prepreg, the spherical cerium oxide having an average particle diameter of 3 μm or less is preferably 50% by mass or more based on the total amount of the inorganic filler.
在前述預浸材中，較佳為前述織布基材的厚度為10~200μm。 In the prepreg, the thickness of the woven base material is preferably 10 to 200 μm.
本發明之覆金屬層積板之特徵為：在前述預浸材層積金屬箔所形成。 The metal-clad laminate of the present invention is characterized in that a metal foil is laminated on the prepreg.
本發明之印刷配線板之特徵為：在前述覆金屬層積板設置導體圖案所形成。 The printed wiring board of the present invention is characterized in that a conductor pattern is formed on the metal-clad laminate.
本發明之多層印刷配線板之特徵為：透過前述預浸材，在印刷配線板層積金屬箔，且將前述金屬箔的不必要部分去除而設置導體圖案所形成。 The multilayer printed wiring board of the present invention is characterized in that a metal foil is laminated on a printed wiring board through the prepreg, and an unnecessary portion of the metal foil is removed to form a conductor pattern.
藉由本發明，藉由預浸材之藉由動態黏彈性測定所得之玻璃轉化溫度為120~170℃，可減低預浸材的掉粉。 此外，若使用該預浸材時，可製造外觀良好的層積板(覆金屬層積板及印刷配線板)。 According to the present invention, the glass transition temperature of the prepreg obtained by dynamic viscoelasticity measurement is 120 to 170 ° C, which can reduce the powder drop of the prepreg. Further, when the prepreg is used, a laminated board (a metal-clad laminate and a printed wiring board) having a good appearance can be produced.
以下說明本發明之實施形態。 Embodiments of the present invention will be described below.
本發明之預浸材係藉由使樹脂組成物含浸在織布基材，並且將此至成為半硬化狀態(B-stage狀態)為止進行加熱乾燥所形成。 The prepreg of the present invention is formed by impregnating a woven fabric substrate with a resin composition and heating and drying the film to a semi-hardened state (B-stage state).
上述之樹脂組成物係含有熱硬化性樹脂及無機填充材。 The above resin composition contains a thermosetting resin and an inorganic filler.
在此，以熱硬化性樹脂而言，係可使用例如環氧樹脂、酚醛樹脂、氰酸酯樹脂、三聚氰胺樹脂、醯亞胺樹脂等。尤其以環氧樹脂而言，可使用例如多官能環氧樹脂、雙酚型環氧樹脂、酚醛型環氧樹脂、聯苯型環氧樹脂等。 Here, as the thermosetting resin, for example, an epoxy resin, a phenol resin, a cyanate resin, a melamine resin, a quinone imide resin, or the like can be used. In particular, as the epoxy resin, for example, a polyfunctional epoxy resin, a bisphenol epoxy resin, a novolac epoxy resin, a biphenyl epoxy resin, or the like can be used.
此外，以無機填充材而言，係可使用例如二氧化矽、氫氧化鋁、氫氧化鎂、碳酸鈣、滑石、氧化鋁等。 Further, as the inorganic filler, for example, cerium oxide, aluminum hydroxide, magnesium hydroxide, calcium carbonate, talc, alumina or the like can be used.
此外，無機填充材係相對於樹脂組成物全量，以含有60~85質量%為佳。如上所示，無機填充材的含有量為60質量%以上，因此可降低預浸材、層積板(覆金屬層積板及印刷配線板)的熱膨脹率(CTE：coefficient of thermal expansion)，或提高彈性率，並且亦可使該等的尺寸安定性提升。此外，若無機填充材的含有量為85質量%以下，可一面抑制黏度上升，一面使樹脂組成物含有無機填充材，並且可更加減低預浸材的掉粉，可得外觀更為良好的層積板(覆金屬層積板及印刷配線板)。 Further, the inorganic filler is preferably contained in an amount of from 60 to 85% by mass based on the total amount of the resin composition. As described above, since the content of the inorganic filler is 60% by mass or more, the coefficient of thermal expansion (CTE) of the prepreg, the laminated board (metal-clad laminate and the printed wiring board) can be lowered, or Increase the modulus of elasticity and also increase the dimensional stability of these. In addition, when the content of the inorganic filler is 85% by mass or less, the resin composition can be made to contain an inorganic filler while suppressing the increase in viscosity, and the powder of the prepreg can be further reduced to obtain a layer having a better appearance. Sheeting (metal-clad laminate and printed wiring board).
此外，相對於無機填充材全量，以50質量%以上(上限為100%)為平均粒徑3μm以下(下限為0.2μm)的球狀二氧化矽為佳，以平均粒徑2μm以下(下限為0.2μm)的球狀二氧化矽為更佳。如上所示，由於無機填充材的一半以上為粒徑小的球狀二氧化矽，因此可抑制無機填充材凝集，可更加抑制熱硬化性樹脂與無機填充材的分離。其中，平均粒徑係可使用雷射繞射式粒度分布測定 裝置，作為中位直徑(50%徑)來進行測定。 In addition, the spherical cerium oxide having an average particle diameter of 3 μm or less (the lower limit is 0.2 μm) is preferably 50% by mass or more (the upper limit is 100%), and the average particle diameter is 2 μm or less (the lower limit is 0.2 μm) of spherical cerium oxide is more preferred. As described above, since half or more of the inorganic filler is spherical cerium oxide having a small particle diameter, aggregation of the inorganic filler can be suppressed, and separation of the thermosetting resin and the inorganic filler can be further suppressed. Among them, the average particle size can be measured by laser diffraction particle size distribution The device was measured as a median diameter (50% diameter).
此外，樹脂組成物亦可含有硬化劑及硬化促進劑。 Further, the resin composition may contain a hardener and a hardening accelerator.
在此，以硬化劑而言，係可使用例如酚系硬化劑、二氰二胺硬化劑等。 Here, as the curing agent, for example, a phenol-based curing agent, a dicyandiamide curing agent, or the like can be used.
此外，以硬化促進劑而言，可使用例如咪唑類、酚化合物、胺類、有機膦類等。 Further, as the hardening accelerator, for example, an imidazole, a phenol compound, an amine, an organic phosphine or the like can be used.
接著，可藉由摻合上述之熱硬化性樹脂、無機填充材，視需要摻合硬化劑、硬化促進劑，來調製樹脂組成物，另外可利用溶劑來將其稀釋，藉此調製樹脂組成物的清漆。以溶劑而言，係可使用例如甲基乙基甲酮、甲苯、苯乙烯、甲氧基丙醇等。 Then, the resin composition can be prepared by blending the above-mentioned thermosetting resin or inorganic filler, if necessary, by blending a curing agent or a curing accelerator, and diluting the solvent with a solvent to prepare a resin composition. Varnish. As the solvent, for example, methyl ethyl ketone, toluene, styrene, methoxypropanol or the like can be used.
以織布基材而言，係可使用例如玻璃布、玻璃紙、玻璃墊等般由無機纖維所成者、或如醯胺布等般由有機纖維所成者。 The woven base material can be made of an inorganic fiber such as a glass cloth, a cellophane, a glass mat or the like, or an organic fiber such as a guanamine cloth.
此外，織布基材的厚度係以10~200μm為佳，以10~100μm為更佳。如上所示，藉由織布基材的厚度為10μm以上，藉此可抑制預浸材、層積板(覆金屬層積板及印刷配線板)發生翹曲。此外，由於織布基材的厚度為200μm以下，因此可達成封裝體的薄型化。 Further, the thickness of the woven base material is preferably 10 to 200 μm, more preferably 10 to 100 μm. As described above, since the thickness of the woven base material is 10 μm or more, warpage of the prepreg and the laminated sheet (metal-clad laminate and printed wiring board) can be suppressed. Further, since the thickness of the woven base material is 200 μm or less, the thickness of the package can be reduced.
接著，本發明之預浸材係可使上述之樹脂組成物含浸在織布基材，並且至此成為半硬化狀態為止進行加熱乾燥來製造，但是如此所得之預浸材之藉由動態黏彈性測定所得之玻璃轉化溫度為120~170℃。較佳為預浸材的玻璃轉化溫度為130~160℃，更佳為140~160℃。為了獲得 顯示如上所示之玻璃轉化溫度的預浸材，若適當調整例如樹脂含有率、加熱溫度、加熱時間等即可。具體而言，若提高加熱溫度且加長加熱時間，則熱硬化性樹脂的硬化進展，預浸材的玻璃轉化溫度係比加熱前為更高。若列舉一例，若將玻璃轉化溫度為100℃的預浸材，在乾燥爐內以100~180℃追加加熱1~6分鐘，即可得玻璃轉化溫度為120~170℃的預浸材。接著，預浸材的玻璃轉化溫度通常可轉用測定覆金屬層積板的玻璃轉化溫度時所使用的DMA法(dynamic mechanical analysis method，動態機械分析法)來進行測定。 Next, the prepreg of the present invention can be produced by impregnating the above-mentioned resin composition on a woven base material and drying and drying it in a semi-hardened state, but the prepreg thus obtained is determined by dynamic viscoelasticity. The resulting glass transition temperature is from 120 to 170 °C. Preferably, the glass transition temperature of the prepreg is from 130 to 160 ° C, more preferably from 140 to 160 ° C. in order to achieve The prepreg showing the glass transition temperature as described above may be appropriately adjusted, for example, in terms of resin content, heating temperature, heating time, and the like. Specifically, when the heating temperature is increased and the heating time is lengthened, the hardening of the thermosetting resin progresses, and the glass transition temperature of the prepreg is higher than that before heating. For example, if a prepreg having a glass transition temperature of 100 ° C is added and heated in a drying oven at 100 to 180 ° C for 1 to 6 minutes, a prepreg having a glass transition temperature of 120 to 170 ° C can be obtained. Next, the glass transition temperature of the prepreg is usually measured by a DMA method (dynamic mechanical analysis method) used for measuring the glass transition temperature of the metal-clad laminate.
如上所述，由於預浸材之藉由動態黏彈性測定所得之玻璃轉化溫度為120~170℃，因此可減低預浸材的樹脂掉粉。亦即，在處理預浸材時，或將預浸材切斷成預定大小時等，不易發生來自預浸材的表面或切剖面等的掉粉。接著，如後所述製造覆金屬層積板時，當將預浸材與金屬箔進行層積時，若樹脂粉混入在該等之間，則該部位即成為刮痕，但是由於如上所述不易發生掉粉，因此可抑制因樹脂粉混入所造成的良率降低。此外，使用玻璃轉化溫度為120~170℃的預浸材所製造的層積板的玻璃轉化溫度會變高。但是，若預浸材的玻璃轉化溫度低於120℃時，與玻璃轉化溫度為120℃以上的預浸材相比，較容易發生掉粉。此外，若使用如上所示之預浸材來製造層積板時，與使用玻璃轉化溫度為120℃以上的預浸材的情形相比，熱硬化性樹脂與無機填充材分離而容易發生外觀不良。尤 其若熱硬化性樹脂與無機填充材分離時，容易在層積板發生裂痕。相反地，若預浸材的玻璃轉化溫度高於170℃時，預浸材會過於硬化，製造層積板時，樹脂流動變差，形成樹脂極端少之處或不存在樹脂之處，容易在層積板發生外觀不良。 As described above, since the glass transition temperature of the prepreg obtained by dynamic viscoelasticity measurement is 120 to 170 ° C, the resin powder of the prepreg can be reduced. That is, when the prepreg is processed, or when the prepreg is cut into a predetermined size, the powder from the surface of the prepreg or the cross section or the like is less likely to occur. Next, when a metal-clad laminate is produced as described later, when the prepreg and the metal foil are laminated, if the resin powder is mixed between the portions, the portion becomes a scratch, but as described above, The powder is less likely to be dropped, so that the decrease in yield due to the incorporation of the resin powder can be suppressed. Further, the glass transition temperature of the laminated board produced using the prepreg having a glass transition temperature of 120 to 170 ° C becomes high. However, when the glass transition temperature of the prepreg is less than 120 ° C, the powder is more likely to be dropped than the prepreg having a glass transition temperature of 120 ° C or higher. Further, when a laminated board is produced by using the prepreg as described above, the thermosetting resin is separated from the inorganic filler and the appearance is poor as compared with the case of using a prepreg having a glass transition temperature of 120 ° C or higher. . especially When the thermosetting resin is separated from the inorganic filler, cracks easily occur in the laminated sheet. On the contrary, if the glass transition temperature of the prepreg is higher than 170 ° C, the prepreg is too hard, and when the laminate is produced, the flow of the resin is deteriorated, and the resin is extremely rare or there is no resin, and it is easy to The laminated board has a poor appearance.
此外，本發明之覆金屬層積板係在上述之預浸材層積金屬箔所形成。預浸材係硬化而成為絕緣層。此時，亦可在1片預浸材的單面或兩面層積金屬箔來進行成形，亦可重疊複數片預浸材，在該單面或兩面層積金屬箔來進行成形。以金屬箔而言，可使用例如銅箔、鋁箔、不銹鋼箔等。上述之層積成形係例如可使用多段真空壓製、雙帶壓製、線壓輥、真空層疊裝置等來加熱/加壓地進行。成形條件係例如溫度為140~350℃、壓力為0.5~6.0MPa、時間為1~240分鐘。針對如上所述所製造的覆金屬層積板，藉由動態黏彈性測定所得之玻璃轉化溫度係成為280~300℃左右，外觀亦為良好。本發明之預浸材的玻璃轉化溫度係比習知者為高，因此若與習知同樣地進行層積成形時，所得之層積板的玻璃轉化溫度係比習知者為高。此外，若以習知之層積板的玻璃轉化溫度為佳，由於本發明之預浸材的玻璃轉化溫度高而可縮短成形時間，因此可使層積板的生產性提升。 Further, the metal-clad laminate of the present invention is formed by laminating a metal foil of the above-mentioned prepreg. The prepreg is hardened to form an insulating layer. In this case, a metal foil may be laminated on one or both sides of one prepreg, or a plurality of prepregs may be stacked, and a metal foil may be laminated on the single or both sides to form. As the metal foil, for example, a copper foil, an aluminum foil, a stainless steel foil, or the like can be used. The above-described laminated forming system can be carried out, for example, by heating, pressurizing using a multi-stage vacuum press, a double belt press, a line press roll, a vacuum lamination apparatus, or the like. The molding conditions are, for example, a temperature of 140 to 350 ° C, a pressure of 0.5 to 6.0 MPa, and a time of 1 to 240 minutes. With respect to the metal-clad laminate produced as described above, the glass transition temperature obtained by dynamic viscoelasticity measurement was about 280 to 300 ° C, and the appearance was also good. Since the glass transition temperature of the prepreg of the present invention is higher than that of the conventional one, when the laminate molding is carried out in the same manner as in the prior art, the glass transition temperature of the obtained laminated sheet is higher than that of the conventional one. Further, if the glass transition temperature of the conventional laminated board is preferred, since the glass transition temperature of the prepreg of the present invention is high, the molding time can be shortened, so that the productivity of the laminated board can be improved.
此外，本發明之印刷配線板係在上述覆金屬層積板設置導體圖案所形成。導體圖案的形成係可藉由例如減成法、加成法等來進行。針對如上所述所製造的印刷配線 板，亦為外觀良好且玻璃轉化溫度高者。 Further, the printed wiring board of the present invention is formed by providing a conductor pattern on the metal-clad laminate. The formation of the conductor pattern can be performed by, for example, a subtractive method, an additive method, or the like. Printed wiring manufactured as described above The board is also good in appearance and high in glass transition temperature.
印刷配線板係通常導體圖案為2層以下，但是亦可如下所示製造導體圖案為3層以上的印刷配線板(多層印刷配線板)。 In the printed wiring board, the conductor pattern is usually two or less layers, but a printed wiring board (multilayer printed wiring board) having three or more conductor patterns may be manufactured as follows.
亦即，本發明之多層印刷配線板係可透過上述預浸材而在印刷配線板層積金屬箔，將該金屬箔的不必要部分去除，設置導體圖案而形成。此時，成為用以形成多層印刷配線板的芯材的印刷配線板係以使用本發明之預浸材所形成為佳，但是亦可使用其他預浸材所形成。此外，透過預浸材來層積金屬箔的，可為印刷配線板的單面，亦可為雙面。以金屬箔而言，係可使用與上述為相同者。層積成形及成形條件係與製造覆金屬層積板時為相同。導體圖案的形成係可與製造印刷配線板時同樣地進行。關於如上所述所製造的多層印刷配線板，亦可為外觀良好且玻璃轉化溫度高者。尤其，若使用本發明之預浸材來製造印刷配線板，且將此作為芯材來製造多層印刷配線板時，該多層印刷配線板係外觀更加良好。其中，導體圖案的層數未被特別限定。 In other words, the multilayer printed wiring board of the present invention can be formed by laminating a metal foil on a printed wiring board through the prepreg, removing unnecessary portions of the metal foil, and providing a conductor pattern. In this case, the printed wiring board which is a core material for forming a multilayer printed wiring board is preferably formed using the prepreg of the present invention, but may be formed using another prepreg. Further, the metal foil may be laminated on the printed wiring board by a prepreg, or may be double-sided. In the case of a metal foil, the same as described above can be used. The lamination forming and forming conditions are the same as in the case of producing a metal clad laminate. The formation of the conductor pattern can be performed in the same manner as in the case of manufacturing a printed wiring board. The multilayer printed wiring board manufactured as described above may have a good appearance and a high glass transition temperature. In particular, when a printed wiring board is manufactured by using the prepreg of the present invention, and the multilayer printed wiring board is manufactured as a core material, the multilayer printed wiring board has a better appearance. Among them, the number of layers of the conductor pattern is not particularly limited.
之後，藉由在上述之印刷配線板或多層印刷配線板構裝且封裝半導體元件，可製造FBGA(Fine pitch Ball Grid Array)等封裝體。 Thereafter, a package such as an FBGA (Fine pitch Ball Grid Array) can be manufactured by mounting and packaging a semiconductor element on the above-described printed wiring board or multilayer printed wiring board.
以下藉由實施例，具體說明本發明。 The invention will be specifically described below by way of examples.
以熱硬化性樹脂而言，使用屬於多官能環氧樹脂的日本化藥股份有限公司製「EPPN502H」。 For the thermosetting resin, "EPPN502H" manufactured by Nippon Kayaku Co., Ltd., which is a multifunctional epoxy resin, is used.
此外，以無機填充材而言，使用屬於球狀二氧化矽的Admatechs股份有限公司製「SO-C6」(平均粒徑2μm)。 Further, as the inorganic filler, "SO-C6" (average particle diameter: 2 μm) manufactured by Admatech Co., Ltd., which is a spherical cerium oxide, was used.
此外，以硬化劑而言，使用屬於酚系硬化劑的明和化成股份有限公司製「MEH7600」。 Further, as the hardener, "MEH7600" manufactured by Minghe Chemical Co., Ltd., which is a phenolic curing agent, was used.
此外，以硬化促進劑而言，使用2-乙基-4-甲咪唑(四國化成工業股份有限公司製)。 Further, as the hardening accelerator, 2-ethyl-4-methylimidazole (manufactured by Shikoku Chemicals Co., Ltd.) was used.
此外，以織布基材而言，使用屬於玻璃布的旭化成股份有限公司製「1037布」(厚度30μm)。 In addition, as the woven fabric substrate, "1037 cloth" (thickness: 30 μm) manufactured by Asahi Kasei Co., Ltd., which is a glass cloth, was used.
接著，以表1所示之摻合量摻合上述之熱硬化性樹脂、無機填充材、硬化劑、硬化促進劑，另外以溶劑(甲基乙基甲酮)稀釋，藉此調製樹脂組成物的清漆。 Next, the above-mentioned thermosetting resin, inorganic filler, hardener, and hardening accelerator were blended in the blending amount shown in Table 1, and diluted with a solvent (methyl ethyl ketone) to prepare a resin composition. Varnish.
接著，使上述之樹脂組成物含浸在織布基材，並且將其至成為半硬化狀態為止，以100~200℃、5~15分鐘，在乾燥爐內進行加熱乾燥(一次加熱)，藉此製造預浸材。此外，將該預浸材，以120℃、2分鐘，追加地進行加熱乾燥(二次加熱)。 Next, the resin composition is impregnated into the woven base material, and is heated and dried (primary heating) in a drying oven at 100 to 200 ° C for 5 to 15 minutes until it is in a semi-hardened state. Manufacturing prepreg. Further, the prepreg was additionally dried by heating (secondary heating) at 120 ° C for 2 minutes.
接著，重疊2枚上述預浸材，在該兩面作為金屬箔而層積銅箔(三井金屬鑛業股份有限公司製「3EC-VLP」，厚度18μm)來進行成形，藉此形成為覆金屬層積板來製造覆銅層積板(CCL)。上述之層積成形係使用多段真空 壓製來加熱/加壓地進行。成形條件係溫度為220℃、壓力為6.0MPa、時間為160分鐘。 Then, two prepregs were stacked, and copper foil ("3EC-VLP" manufactured by Mitsui Mining Co., Ltd., thickness: 18 μm) was laminated on the both surfaces as a metal foil to form a metallized layer. The board is used to make a copper clad laminate (CCL). The above-mentioned laminated forming system uses a multi-stage vacuum Pressing is carried out by heating/pressurization. The molding conditions were a temperature of 220 ° C, a pressure of 6.0 MPa, and a time of 160 minutes.
除了將二次加熱以150℃進行2分鐘以外，與實施例1同樣地製造預浸材及覆金屬層積板。 A prepreg and a metal-clad laminate were produced in the same manner as in Example 1 except that the secondary heating was performed at 150 ° C for 2 minutes.
除了將二次加熱以170℃進行2分鐘以外，與實施例1同樣地製造預浸材及覆金屬層積板。 A prepreg and a metal-clad laminate were produced in the same manner as in Example 1 except that the secondary heating was performed at 170 ° C for 2 minutes.
除了變更熱硬化性樹脂、無機填充材、硬化劑、硬化促進劑的摻合量以外，與實施例2同樣地製造預浸材及覆金屬層積板。 A prepreg and a metal-clad laminate were produced in the same manner as in Example 2 except that the blending amount of the thermosetting resin, the inorganic filler, the curing agent, and the hardening accelerator was changed.
除了變更熱硬化性樹脂、無機填充材、硬化劑、硬化促進劑的摻合量以外，與實施例2同樣地製造預浸材及覆金屬層積板。 A prepreg and a metal-clad laminate were produced in the same manner as in Example 2 except that the blending amount of the thermosetting resin, the inorganic filler, the curing agent, and the hardening accelerator was changed.
與實施例1同樣地製造預浸材。 A prepreg was produced in the same manner as in Example 1.
接著，除了將預浸材設為1枚以外，係與實施例1同 樣地製造覆金屬層積板。 Next, the same as Example 1 except that the prepreg was used as one. A metallized laminated board is produced in a sample.
接著，藉由減成法，僅在覆金屬層積板的單面設置導體圖案來製造印刷配線板。 Next, a printed wiring board was produced by providing a conductor pattern on only one side of the metal-clad laminate by a subtractive method.
之後，在印刷配線板的導體圖案形成面，透過與上述同樣的預浸材，層積銅箔(三井金屬鑛業股份有限公司製「3EC-VLP」，厚度18μm)作為金屬箔來進行成形，藉此製造多層印刷配線板。上述之層積成形係使用多段真空壓製加熱/加壓地進行。成形條件係溫度為220℃、壓力為6.0MPa、時間為160分鐘。 Then, on the conductor pattern forming surface of the printed wiring board, a copper foil ("3EC-VLP" manufactured by Mitsui Mining Co., Ltd., thickness: 18 μm) was laminated as a metal foil by the same prepreg as described above. This manufactures a multilayer printed wiring board. The above-described laminated forming is carried out by heating/pressurizing using a plurality of stages of vacuum pressing. The molding conditions were a temperature of 220 ° C, a pressure of 6.0 MPa, and a time of 160 minutes.
除了未進行二次加熱以外，與實施例1同樣地製造預浸材及覆金屬層積板。 A prepreg and a metal-clad laminate were produced in the same manner as in Example 1 except that the secondary heating was not performed.
除了將二次加熱以180℃進行2分鐘以外，與實施例1同樣地製造預浸材及覆金屬層積板。 A prepreg and a metal-clad laminate were produced in the same manner as in Example 1 except that the secondary heating was performed at 180 ° C for 2 minutes.
將預浸材之藉由動態黏彈性測定所得之玻璃轉化溫度，依據JIS C 6481，藉由DMA法(dynamic mechanical analysis method)來進行測定。具體而言，首先將預浸材切斷成50mm×5mm的大小來製作試料。接著針對該試料，使用動態黏彈性測定裝置(SII Nano Technology股份 有限公司製「DMS6100」)，以5℃/分鐘的條件升溫，將tanδ的峰值位置設為玻璃轉化溫度。 The glass transition temperature of the prepreg obtained by dynamic viscoelasticity measurement was measured by a dynamic mechanical analysis method in accordance with JIS C 6481. Specifically, the prepreg was first cut into a size of 50 mm × 5 mm to prepare a sample. Next, for the sample, a dynamic viscoelasticity measuring device (SII Nano Technology shares) was used. The product "DMS6100" manufactured by the company was heated at a temperature of 5 ° C / min, and the peak position of tan δ was set as the glass transition temperature.
重疊50枚340mm×500mm的大小的預浸材，使其由高度20mm落下至鋼鐵台上，觀察樹脂的掉粉樣子。以所掉落的粉的多寡，如以下判定良否。 50 prepregs of 340 mm × 500 mm size were overlapped, and dropped from a height of 20 mm onto a steel table to observe the powder drop of the resin. The amount of powder dropped is determined as follows.
「○」：幾乎沒有掉粉者。 "○": There is almost no powder drop.
「△」：掉粉少，但是實用上沒有特別問題者。 "△": There is less powder, but there are no special problems in practical use.
「×」：掉粉非常多者。 "X": The powder is very much.
藉由蝕刻來去除覆金屬層積板的金屬箔，藉由觀察去除面來將外觀良否如以下進行判定。 The metal foil of the metal-clad laminate is removed by etching, and the appearance is determined by observing the removal surface as follows.
「○」：未發現因熱硬化性樹脂與無機填充材的分離而起的條紋模樣者。 "○": No streaky pattern was found due to the separation of the thermosetting resin and the inorganic filler.
「△」：局部發現上述之條紋模樣，但是實用上沒有特別問題者。 "△": The above-mentioned stripe pattern was found locally, but there was no particular problem in practical use.
「×(A)」：全體發現上述之條紋模樣者。 "×(A)": All of the above-mentioned stripe patterns were found.
「×(B)」：發現樹脂少之處或不存在樹脂之處者。 "×(B)": It is found that there is little or no resin present.
將覆金屬層積板之藉由動態黏彈性測定所得之玻璃轉化溫度，依據JIS C 6481，藉由DMA法(dynamic mechanical analysis method)來進行測定。具體而言，首先將覆金屬層積板的金屬箔藉由蝕刻進行去除，將此切斷成50mm×5mm的大小來製作試料。接著，針對該試料，使用動態黏彈性測定裝置(SII Nano Technology股份有限公司製「DMS6100」)，以5℃/分鐘的條件進行升溫，將tanδ的峰值位置設為玻璃轉化溫度。 The glass transition temperature of the metal-clad laminate measured by dynamic viscoelasticity, according to JIS C 6481, by DMA method (dynamic mechanical Analysis method) to perform the assay. Specifically, first, the metal foil of the metal-clad laminate was removed by etching, and the sample was cut into a size of 50 mm × 5 mm to prepare a sample. Then, a dynamic viscoelasticity measuring apparatus ("DMS6100" manufactured by SII Nano Technology Co., Ltd.) was used for the sample, and the temperature was raised at 5 ° C /min, and the peak position of tan δ was defined as the glass transition temperature.
由表1可知，藉由動態黏彈性測定所得之玻璃轉化溫度為120~170℃的實施例1~6的預浸材係掉粉被減低。此外，若使用如上所示之預浸材時，亦可製造外觀良好的覆金屬層積板。 As is apparent from Table 1, the prepreg of Examples 1 to 6 having a glass transition temperature of 120 to 170 ° C obtained by dynamic viscoelasticity measurement was reduced. Further, when the prepreg as described above is used, a metal-clad laminate having a good appearance can be produced.
相對於此，在比較例1的預浸材中，由於藉由動態黏彈性測定所得之玻璃轉化溫度為未達120℃，因此發生掉粉。此外，使用如上所示之預浸材所製造的覆金屬層積板的外觀不良。 On the other hand, in the prepreg of Comparative Example 1, since the glass transition temperature obtained by the dynamic viscoelasticity measurement was less than 120 ° C, powder dropping occurred. Further, the metal-clad laminate produced by using the prepreg as shown above has a poor appearance.
此外，在比較例2中，預浸材的掉粉雖然被減低，但是覆金屬層積板的外觀不良。 Further, in Comparative Example 2, although the powder of the prepreg was reduced, the appearance of the metal-clad laminate was poor.
Claims (6)
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| JP2011246516A (en) * | 2010-05-24 | 2011-12-08 | Panasonic Electric Works Co Ltd | Resin composition, resin varnish, prepreg, metal-clad laminate, and printed wiring board |
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| JPH08288416A (en) * | 1995-04-14 | 1996-11-01 | Mitsubishi Gas Chem Co Inc | Plastic semiconductor package |
| JPH11181124A (en) * | 1997-12-25 | 1999-07-06 | Sumitomo Bakelite Co Ltd | Prepreg |
| JP4322463B2 (en) | 2002-03-20 | 2009-09-02 | 住友ベークライト株式会社 | Copper-clad laminate prepreg and copper-clad laminate |
| JP5004483B2 (en) * | 2006-03-15 | 2012-08-22 | 株式会社Ａｄｅｋａ | Epoxy resin curable composition for prepreg |
| JP4926811B2 (en) * | 2006-04-28 | 2012-05-09 | 日立化成工業株式会社 | Resin composition, prepreg, laminate and wiring board |
| JP4971919B2 (en) * | 2007-09-13 | 2012-07-11 | パナソニック株式会社 | Transparent laminate |
| JP5417724B2 (en) * | 2008-03-25 | 2014-02-19 | 味の素株式会社 | A method for producing a multilayer printed wiring board. |
| JP2009231222A (en) * | 2008-03-25 | 2009-10-08 | Ajinomoto Co Inc | Insulating resin sheet |
| JP5493948B2 (en) * | 2010-02-08 | 2014-05-14 | 住友ベークライト株式会社 | Resin composition for printed wiring board, prepreg, laminate, resin sheet, printed wiring board, and semiconductor device |
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| KR20140042738A (en) | 2014-04-07 |
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| JP2014080582A (en) | 2014-05-08 |
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