TWI620783B - Insulating resin composition for printed circuit board and products using the same - Google Patents
Insulating resin composition for printed circuit board and products using the same Download PDFInfo
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- TWI620783B TWI620783B TW103112070A TW103112070A TWI620783B TW I620783 B TWI620783 B TW I620783B TW 103112070 A TW103112070 A TW 103112070A TW 103112070 A TW103112070 A TW 103112070A TW I620783 B TWI620783 B TW I620783B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/40—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/05—Insulated conductive substrates, e.g. insulated metal substrate
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Abstract
本發明係提供一種用於印刷電路基板之絕緣樹脂組成物及使用其之預浸材、敷銅層板、以及印刷電路基板。由於本發明之絕緣樹脂組成物包含具有聯吡啶構造之硬化劑，故能改善玻璃轉化溫度及熱膨脹係數的耐熱性之特性，並改善金屬層與絕緣層之間的剝離強度的機械性能。 The present invention provides an insulating resin composition for a printed circuit board, a prepreg, a copper-clad laminate, and a printed circuit board using the same. Since the insulating resin composition of the present invention contains a hardener having a bipyridine structure, it can improve the characteristics of the glass transition temperature and the heat resistance of the thermal expansion coefficient, and improve the mechanical properties of the peel strength between the metal layer and the insulating layer.
Description
本發明係有關於一種用於印刷電路基板之絕緣樹脂組成物及使用其之製品。 The present invention relates to an insulating resin composition for a printed circuit board and a product using the same.
隨著電子設備的發展，印刷電路基板的低重量化、薄板化及小型化持續進行中。為因應這樣的趨勢，印刷電路的配線逐漸地更加複雜化及高密度化。對於這樣的基板所要求之電、熱與機械的特性係作為更重要的要素作用著。印刷電路基板主要係由滿足電路配線功能之銅、及滿足層間絕緣功能之高分子所構成。與銅相比，構成絕緣層的高分子被要求熱膨脹係數、玻璃轉化溫度及厚度均一性等各種的特性，特別是，絕緣層的厚度必須要薄薄地製作而成。 With the development of electronic equipment, the weight reduction, thinning, and miniaturization of printed circuit boards continue. In response to such a trend, the wiring of printed circuits is becoming more complicated and denser. Electrical, thermal, and mechanical characteristics required for such a substrate function as more important factors. The printed circuit board is mainly composed of copper that satisfies the function of circuit wiring and a polymer that satisfies the function of interlayer insulation. Compared with copper, the polymers constituting the insulating layer are required to have various characteristics such as thermal expansion coefficient, glass transition temperature, and thickness uniformity. In particular, the thickness of the insulating layer must be made thin.
近年來，隨著被用於環氧樹脂模製化合物(Epoxy Molding Compound,EMC)或基板材料等絕緣層的有機材料之環氧樹脂以外之補強材料的廣泛使用，用作電極之電路層與絕緣層之間的界面黏著力之下降被視為問題。 In recent years, with the widespread use of reinforcing materials other than epoxy resins as organic materials for insulating layers such as epoxy molding compounds (EMC) or substrate materials, they are used as circuit layers and insulation for electrodes. The decrease in interface adhesion between layers is considered a problem.
以往，構成絕緣層之有機物中的環氧樹脂主要的功能是做為與電路層之黏著劑。然而，隨著絕緣層內的環氧樹脂比 例逐漸地減少，電路層與絕緣層之間的黏著強度也逐漸地減少。 In the past, the main function of the epoxy resin in the organic material constituting the insulating layer was as an adhesive with the circuit layer. However, as the epoxy resin ratio in the insulation layer The number of examples gradually decreases, and the adhesion strength between the circuit layer and the insulating layer also gradually decreases.
為提高被廣泛用作環氧樹脂模製化合物或基板材料之環氧樹脂的機械穩定性及熱安定性，而使用雙馬來醯亞胺(bismaleimide)、氰酸酯(cyanate ester)等有機補強材料；此外，為提高材料的玻璃轉化溫度(Tg)，而使用具有全芳香族硬化劑或各種分子量分布之硬化劑等。然而，習知的方式係以在絕緣層包含環氧樹脂的方式而能夠提高與電路層之黏著強度，但由於以絕緣層的組成物包含其它有機補強材料的方式，使得環氧樹脂的添加量減少、且與電路層的黏著強度逐漸地減少。 In order to improve the mechanical stability and thermal stability of epoxy resins widely used as epoxy molding compounds or substrate materials, organic reinforcements such as bismaleimide and cyanate ester are used. In addition, in order to increase the glass transition temperature (Tg) of the material, a wholly aromatic hardener or a hardener having various molecular weight distributions is used. However, the conventional method is to increase the adhesion strength with the circuit layer by including an epoxy resin in the insulating layer, but because the composition of the insulating layer includes other organic reinforcing materials, the amount of epoxy resin is added. The adhesive strength with the circuit layer decreases and gradually decreases.
另一方面，專利文件1雖然已揭示了一種包括含環氧基不飽和化合物之感光性樹脂組成物，然而利用此方式來提高玻璃轉化溫度、熱膨脹係數(CTE)及剝離強度(peel strength)的特性仍有一定的界限。 On the other hand, Patent Document 1 has disclosed a photosensitive resin composition including an epoxy-containing unsaturated compound, but this method is used to improve the glass transition temperature, the coefficient of thermal expansion (CTE), and the peel strength. There are still limits to the characteristics.
〈專利文件1〉韓國專利公開公報第2012-0089947號 <Patent Document 1> Korean Patent Publication Gazette No. 2012-0089947
本發明係用以解決上述習知技術的問題點，本發明的一個目的係提供一種用於印刷電路基板之絕緣樹脂組成物，其係在用於印刷電路基板之絕緣樹脂組成物中，透過環氧樹脂及具有聯吡啶(bipyridine)構造之硬化劑來改善玻璃轉化溫度(Tg)、熱膨脹係數(CTE)及剝離強度(peel strength)的特性。 The present invention is to solve the problems of the above-mentioned conventional technology, and an object of the present invention is to provide an insulating resin composition for a printed circuit board, which is in the insulating resin composition for a printed circuit board, and penetrates the ring. Oxygen resin and hardener with bipyridine structure to improve glass transition temperature (Tg), thermal expansion coefficient (CTE), and peel strength.
本發明的其他目的係提供一種包含前述絕緣樹脂組 成物之預浸材。 Another object of the present invention is to provide an insulating resin group Finished prepreg.
本發明之另一個其他目的係提供一種印刷電路基板，其係使用前述預浸材所製造之敷銅層板上，堆疊疊層所製造而成。 Another object of the present invention is to provide a printed circuit board, which is manufactured by stacking and laminating a copper-clad laminate made of the aforementioned prepreg.
為了達成本發明之一目的，用於印刷電路基板之絕緣樹脂組成物可包含環氧樹脂、以及具有聯吡啶構造之硬化劑。 In order to achieve one of the purposes of the present invention, the insulating resin composition for a printed circuit board may include an epoxy resin and a hardener having a bipyridine structure.
在前述用於印刷電路基板之絕緣樹脂組成物中，相對於100重量份的前述絕緣樹脂組成物而言，可含有25~75重量份的環氧樹脂、及含有10~55重量份的具有聯吡啶構造之硬化劑。 The insulating resin composition for a printed circuit board may contain 25 to 75 parts by weight of an epoxy resin, and 10 to 55 parts by weight of the epoxy resin relative to 100 parts by weight of the insulating resin composition. Pyridine-based hardener.
在前述用於印刷電路基板之絕緣樹脂組成物中，前述環氧樹脂可選自於萘系環氧樹脂、雙酚A型環氧樹脂、酚醛清漆型(phenol novolac)環氧樹脂、甲酚酚醛清漆型(cresol novolac)環氧樹脂、橡膠改性環氧樹脂、磷系環氧樹脂及雙酚F型環氧樹脂中之一種以上者。 In the aforementioned insulating resin composition for a printed circuit board, the aforementioned epoxy resin may be selected from the group consisting of a naphthalene-based epoxy resin, a bisphenol A epoxy resin, a phenol novolac epoxy resin, and a cresol novolac resin. One or more of cresol novolac epoxy resin, rubber-modified epoxy resin, phosphorus-based epoxy resin, and bisphenol F-type epoxy resin.
在前述用於印刷電路基板之絕緣樹脂組成物中，前述聯吡啶構造可以下述式子所表示。 In the insulating resin composition for a printed circuit board, the bipyridine structure can be represented by the following formula.
此處，a為1~10的整數，b為1~13的整數，c為1~13的整數，d為1~21的整數，e為1~21的整數，f為1~10的整數，以及g為1~10的整數。 Here, a is an integer from 1 to 10, b is an integer from 1 to 13, c is an integer from 1 to 13, d is an integer from 1 to 21, e is an integer from 1 to 21, and f is an integer from 1 to 10. , And g is an integer from 1 to 10.
在前述用於印刷電路基板之絕緣樹脂組成物中，前述硬化劑可含有30~60重量%之聯吡啶構造。 In the aforementioned insulating resin composition for a printed circuit board, the aforementioned hardener may contain a bipyridine structure in an amount of 30 to 60% by weight.
在前述用於印刷電路基板之絕緣樹脂組成物中，前述絕緣樹脂組成物可更進一步包含無機填充劑、氰酸酯、雙馬來醯亞胺。 In the aforementioned insulating resin composition for a printed circuit board, the aforementioned insulating resin composition may further include an inorganic filler, a cyanate ester, and bismaleimide.
在前述用於印刷電路基板之絕緣樹脂組成物中，相對於100重量份的前述絕緣樹脂組成物而言，可含有82~488重量份的前述無機填充劑。 The insulating resin composition for a printed circuit board may contain 82 to 488 parts by weight of the inorganic filler with respect to 100 parts by weight of the insulating resin composition.
在前述用於印刷電路基板之絕緣樹脂組成物中，前述無機填充劑可選自於二氧化矽(SiO2)、氧化鋁(Al2O3)、硫酸鋇(BaSO4)、氫氧化鋁(AlOH3)、氫氧化鎂(Mg(OH)2)、碳酸鈣(CaCO3)、碳酸鎂(MgCO3)、氧化鎂(MgO)、氮化硼(BN)、碳化矽(SiC)、硼酸鋁(AlBO3)、鈦酸鋇(BaTiO3)及鋯酸鈣(CaZrO3)中之一種以上者。 In the aforementioned insulating resin composition for a printed circuit board, the aforementioned inorganic filler may be selected from the group consisting of silicon dioxide (SiO 2 ), aluminum oxide (Al 2 O 3 ), barium sulfate (BaSO 4 ), and aluminum hydroxide ( AlOH 3 ), magnesium hydroxide (Mg (OH) 2 ), calcium carbonate (CaCO 3 ), magnesium carbonate (MgCO 3 ), magnesium oxide (MgO), boron nitride (BN), silicon carbide (SiC), aluminum borate (AlBO 3 ), barium titanate (BaTiO 3 ), and calcium zirconate (CaZrO 3 ).
在前述用於印刷電路基板之絕緣樹脂組成物中，相對於100重量份之前述絕緣樹脂組成物，可含有10~65重量份的前述氰酸酯。 The insulating resin composition for a printed circuit board may contain 10 to 65 parts by weight of the cyanate ester relative to 100 parts by weight of the insulating resin composition.
在前述用於印刷電路基板之絕緣樹脂組成物中，前述氰酸酯可選自於雙酚A型氰酸酯、甲酚酚醛清漆型氰酸酯及酚醛清漆型氰酸酯中之一種以上者。 In the foregoing insulating resin composition for a printed circuit board, the cyanate may be selected from one or more of bisphenol A-type cyanate, cresol novolac-type cyanate, and novolac-type cyanate. .
在前述用於印刷電路基板之絕緣樹脂組成物中，相對於100重量份之前述絕緣樹脂組成物而言，可含有10~43重量份的前述雙馬來醯亞胺。 The aforementioned insulating resin composition for a printed circuit board may contain 10 to 43 parts by weight of the aforementioned bismaleimide based on 100 parts by weight of the aforementioned insulating resin composition.
在前述用於印刷電路基板之絕緣樹脂組成物中，前述雙馬來醯亞胺可選自於1,1’-(亞甲基二-4,1-伸苯基)雙馬來醯亞胺(1,1’-(methylenedi-4,1-phenylene)bismaleimide)。 In the aforementioned insulating resin composition for a printed circuit board, the aforementioned bismaleimide may be selected from 1,1 ′-(methylenebis-4,1-phenylene) bismaleimide (1,1 '-(methylenedi-4,1-phenylene) bismaleimide).
用以達成本發明的其他目的之預浸材，係可藉由在包含用以達成本發明的一個目的之絕緣樹脂組成物之清漆(varnish)中，含浸有機纖維或無機纖維並乾燥所製造而成。 The prepreg used for other purposes of the present invention can be produced by impregnating an organic fiber or an inorganic fiber in a varnish containing an insulating resin composition used for the purpose of the present invention and drying the varnish. to make.
在前述預浸材中，前述無機纖維或有機纖維可選自於玻璃纖維、碳纖維、聚對苯撐苯並二嗯唑(poly-p-phenylenebenzobisthiazole)纖維、向熱性(thermotropic)液晶高分子纖維、向液性(lyotropic)液晶高分子纖維、醯胺纖維、聚吡啶並雙咪唑(PIPD)纖維、聚苯並噻唑(polybenzothiazole)纖維、及聚芳基酸酯(polyarylate)纖維中之一種以上者。 In the prepreg, the inorganic or organic fibers may be selected from glass fibers, carbon fibers, poly-p-phenylenebenzobisthiazole fibers, thermotropic liquid crystal polymer fibers, One or more of a lyotropic liquid crystal polymer fiber, amidine fiber, polypyridobisimidazole (PIPD) fiber, polybenzothiazole fiber, and polyarylate fiber.
用以達成本發明之另一個其他目的之印刷電路基板，係可透過在用以達成本發明的其他目的之預浸材的單面或雙面貼附銅箔而得之敷銅層板(Copper-Clad Laminate,CCL)上，堆疊疊層所製造而成。 A printed circuit board used to achieve another purpose of the invention is a copper-clad laminate obtained by attaching copper foil to one or both sides of a prepreg used to achieve the other purpose of the invention. -Clad Laminate (CCL).
按照本發明之用於印刷電路基板之絕緣樹脂組成物及使用其之預浸材、敷銅層板、及印刷電路基板，能夠改善玻璃轉化溫度及熱膨脹係數的耐熱性之特性。 The insulating resin composition for a printed circuit board and the prepreg, copper-clad laminate, and printed circuit board using the same according to the present invention can improve the heat resistance characteristics of the glass transition temperature and the thermal expansion coefficient.
另外，因為前述絕緣樹脂組成物包含具有聯吡啶構造之硬化劑，所以能夠藉由與金屬層之間的配位鍵結來提高金屬層與絕緣層之間的剝離強度之機械性能。 In addition, since the aforementioned insulating resin composition contains a hardener having a bipyridine structure, it is possible to improve the mechanical properties of the peel strength between the metal layer and the insulating layer by coordination bonding with the metal layer.
第1圖係用以說明根據本發明之一實施例的絕緣樹脂組成物之構成示意圖。 FIG. 1 is a schematic diagram illustrating the structure of an insulating resin composition according to an embodiment of the present invention.
本發明之目的、特定優點及新穎的特徴，將因與所附圖式有關之以下的詳細說明、及較佳實施例而更為明瞭清楚。在本說明書中，應當留意的是，各圖式之構成元件上所附之參考標號，只要是相同的構成元件，即使是顯示於不同的圖式上，亦盡可能地附加相同的標號。此外，「一面」、「他面」、「第1」、「第2」等之用語，是為了區別某一構成元件與其他的構成元件而使用的用語，因此構成元件不應因前述用語而受到限定。以下，在說明本發明之際，對於有可能會模糊本發明之主旨的相關習知技術，則省略其詳細說明。 The purpose, specific advantages and novel features of the present invention will be made clearer by the following detailed description and preferred embodiments related to the attached drawings. In this specification, it should be noted that the reference numerals attached to the constituent elements of the drawings are attached with the same reference numerals as much as possible even if they are the same constituent elements even if they are displayed on different diagrams. In addition, the terms "one side", "other side", "first", and "second" are terms used to distinguish one constituent element from other constituent elements. Therefore, constituent elements should not be changed by the aforementioned terms. Limited. Hereinafter, in describing the present invention, detailed descriptions of related conventional technologies that may obscure the gist of the present invention will be omitted.
以下，將參照所附圖式詳細地說明本發明之較佳實施例。 Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.
第1圖係用以說明根據本發明一實施例的絕緣樹脂組成物之構成示意圖。請參照第1圖，本發明中由於絕緣樹脂組成物包含具有使絕緣層與金屬層能配位鍵結之聯吡啶(bipyridine)構造的硬化劑，因此能夠提高熱膨脹係數、玻璃轉化溫度及剝離強度之特性。 FIG. 1 is a schematic diagram illustrating the structure of an insulating resin composition according to an embodiment of the present invention. Please refer to FIG. 1. In the present invention, since the insulating resin composition includes a hardener having a bipyridine structure that enables the insulating layer and the metal layer to coordinately bond, the thermal expansion coefficient, glass transition temperature, and peeling strength can be improved. Of characteristics.
根據本發明一實施例之用於印刷電路基板之絕緣樹脂組成物可包含環氧樹脂，用以提高作為乾燥後的樹脂組成物之黏著膜的處理性能。前述環氧樹脂係指分子內包含1個以上的環氧官能基者，從提高鍵結力來看，較佳為包含4個以上的環氧官能基者。 The insulating resin composition for a printed circuit board according to an embodiment of the present invention may include an epoxy resin to improve the processing performance of the adhesive film as the dried resin composition. The said epoxy resin means the thing which contains one or more epoxy functional groups in a molecule | numerator, From a viewpoint of improving a bonding force, it is preferable that it contains four or more epoxy functional groups.
前述環氧樹脂可選自於萘系環氧樹脂、雙酚A型環 氧樹脂、酚醛清漆型(phenol novolac)環氧樹脂、甲酚酚醛清漆型(cresol novolac)環氧樹脂、橡膠改性環氧樹脂、磷系環氧樹脂及雙酚F型環氧樹脂中之一種以上者，但並非特別限定於此。 The epoxy resin may be selected from a naphthalene-based epoxy resin and a bisphenol A ring One of epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, rubber modified epoxy resin, phosphorus epoxy resin, and bisphenol F epoxy resin The above is not particularly limited thereto.
前述絕緣樹脂組成物中，相對於100重量份的前述絕緣樹脂組成物而言，環氧樹脂的使用量可為25~75重量份。在前述環氧樹脂的使用量未滿25重量份的情況下，會有與金屬層之黏著力降低而使之難以作為基板材料之虞；在超過75重量份的情況下，則會有尚未硬化的環氧樹脂殘存在於組成物內之虞。如此，將減少前述環氧樹脂的硬化密度而減少基板材料的耐熱性，且使熱膨脹係數變高、玻璃轉化溫度變低。 In the foregoing insulating resin composition, the amount of the epoxy resin used may be 25 to 75 parts by weight relative to 100 parts by weight of the insulating resin composition. When the amount of the epoxy resin is less than 25 parts by weight, the adhesion with the metal layer may be reduced, making it difficult to be used as a substrate material. When it exceeds 75 parts by weight, it may not be hardened The epoxy resin may remain in the composition. In this way, the hardened density of the epoxy resin is reduced, the heat resistance of the substrate material is reduced, the thermal expansion coefficient is increased, and the glass transition temperature is reduced.
根據本發明一實施例之用於印刷電路基板之絕緣樹脂組成物可包含具有以下述式子所表示的聯吡啶構造之硬化劑。 The insulating resin composition for a printed circuit board according to an embodiment of the present invention may include a hardener having a bipyridine structure represented by the following formula.
(此處之a係1~10的整數；b係1~13的整數；c係1~13的整數；d係1~21的整數；e係1~21的整數；f係1~10的整數；及g係1~10的整數。) (Here a is an integer from 1 to 10; b is an integer from 1 to 13; c is an integer from 1 to 13; d is an integer from 1 to 21; e is an integer from 1 to 21; f is an integer from 1 to 10 An integer; and g is an integer from 1 to 10.)
前述硬化劑因包含二個以上的苯酚、胺、酸酐等官能基，而能夠與環氧樹脂產生架橋反應。前述絕緣樹脂組成物中，相對於100重量份的絕緣樹脂組成物而言，硬化劑之使用量可以是10~55重量份。在前述硬化劑之使用量未滿10重量份的 情況下，會有與環氧樹脂之硬化度降低而使耐熱性減少之虞；在超過55重量份的情況下，則有組成物內之環氧樹脂的量減少而使耐化學性減少之虞。 Since the hardener contains two or more functional groups such as phenol, amine, and acid anhydride, it can cause a bridging reaction with the epoxy resin. In the foregoing insulating resin composition, the amount of the hardener used may be 10 to 55 parts by weight relative to 100 parts by weight of the insulating resin composition. If the amount of the aforementioned hardener is less than 10 parts by weight In some cases, the degree of hardening with the epoxy resin may be reduced to reduce the heat resistance. When it exceeds 55 parts by weight, the amount of the epoxy resin in the composition may be reduced to reduce the chemical resistance. .
此外，前述硬化劑因其分子內具有能與金屬層配位鍵結之聯吡啶構造，而能提高金屬層與絕緣層之間的剝離強度。前述聯吡啶構造係可在硬化劑內含有30~60重量%。前述聯吡啶構造在硬化劑內未滿30重量%的情況下，無法得到提高與金屬層之剝離強度的效果；超過60重量%的情況下，則會有與環氧樹脂的架橋密度減少而使熱的強度減少之虞。 In addition, the aforementioned hardener has a bipyridine structure capable of coordinating and bonding with the metal layer in its molecule, thereby improving the peel strength between the metal layer and the insulating layer. The bipyridine structure system may contain 30 to 60% by weight in the hardener. When the bipyridine structure is less than 30% by weight in the hardener, the effect of improving the peel strength with the metal layer cannot be obtained; when it exceeds 60% by weight, the bridge density with the epoxy resin is reduced and the There is a concern that the intensity of heat will decrease.
根據本發明一實施例之用於印刷電路基板之絕緣樹脂組成物可更進一步包含用以改善熱膨脹係數之無機填充劑。 The insulating resin composition for a printed circuit board according to an embodiment of the present invention may further include an inorganic filler for improving a thermal expansion coefficient.
前述用於印刷電路基板之絕緣樹脂組成物中，相對於100重量份之絕緣樹脂組成物而言，無機填充劑的使用量可以為82~488重量份。在前述無機填充劑的使用量未滿82重量份的情況下，前述樹脂組成物的熱膨脹係數變高、耐熱性降低而有難以用作基板材料來使用之虞；在超過488重量份的情況下，則有與金屬層的剝離強度降低而難以適用於基板處理之虞。 In the foregoing insulating resin composition for a printed circuit board, the amount of the inorganic filler used may be 82 to 488 parts by weight relative to 100 parts by weight of the insulating resin composition. When the used amount of the inorganic filler is less than 82 parts by weight, the resin composition may have a high thermal expansion coefficient and reduced heat resistance, which may make it difficult to use as a substrate material. , There is a possibility that the peeling strength with the metal layer is reduced and it is difficult to apply it to substrate processing.
前述無機填充劑可選自於二氧化矽(SiO2)、氧化鋁(Al2O3)、硫酸鋇(BaSO4)、氫氧化鋁(AlOH3)、氫氧化鎂(Mg(OH)2)、碳酸鈣(CaCO3)、碳酸鎂(MgCO3)、氧化鎂(MgO)、氮化硼(BN)、碳化矽(SiC)、硼酸鋁(AlBO3)、鈦酸鋇(BaTiO3)及鋯酸鈣(CaZrO3)中之一種以上者，但並非特別限定於此。 The aforementioned inorganic filler may be selected from the group consisting of silicon dioxide (SiO 2 ), aluminum oxide (Al 2 O 3 ), barium sulfate (BaSO 4 ), aluminum hydroxide (AlOH 3 ), and magnesium hydroxide (Mg (OH) 2 ). , Calcium carbonate (CaCO 3 ), magnesium carbonate (MgCO 3 ), magnesium oxide (MgO), boron nitride (BN), silicon carbide (SiC), aluminum borate (AlBO 3 ), barium titanate (BaTiO 3 ), and zirconium One or more types of calcium acid (CaZrO 3 ) are not particularly limited thereto.
為提高耐熱性，根據本發明一實施例之用於印刷電路基板之絕緣樹脂組成物可更進一步包含氰酸酯。 To improve heat resistance, the insulating resin composition for a printed circuit board according to an embodiment of the present invention may further include a cyanate ester.
前述用於印刷電路基板之絕緣樹脂組成物中，相對於100重量份之絕緣樹脂組成物而言，氰酸酯的使用量可為10~65重量份。在前述氰酸酯的使用量未滿10重量份的情況下，使前述樹脂組成物的玻璃轉化溫度變高、耐熱性降低而有難以用作基板材料來使用之虞；在超過65重量份的情況下，則會有與金屬層的剝離強度降低而難以適用於樹脂組成物的基板處理之虞。 In the foregoing insulating resin composition for a printed circuit board, the amount of the cyanate ester used may be 10 to 65 parts by weight relative to 100 parts by weight of the insulating resin composition. When the use amount of the cyanate ester is less than 10 parts by weight, the glass transition temperature of the resin composition may be increased, and the heat resistance may be reduced, making it difficult to use as a substrate material. In this case, there is a possibility that the peeling strength from the metal layer is lowered and it is difficult to apply it to substrate processing of a resin composition.
前述氰酸酯可選自於雙酚A型氰酸酯、甲酚酚醛清漆型氰酸酯及酚醛清漆型氰酸酯中之一種以上者，但並不特別限定於此。 The cyanate may be selected from one or more of bisphenol A cyanate, cresol novolac cyanate, and novolac cyanate, but is not particularly limited thereto.
為提高耐熱性，根據本發明一實施例之用於印刷電路基板之絕緣樹脂組成物可更進一步包含雙馬來亞醯胺。 To improve heat resistance, the insulating resin composition for a printed circuit board according to an embodiment of the present invention may further include bismaleimide.
前述用於印刷電路基板之絕緣樹脂組成物中，相對於100重量份的絕緣樹脂組成物而言，雙馬來亞醯胺的使用量可為10~43重量份。在前述雙馬來亞醯胺的使用量未滿10重量份的情況下，使前述樹脂組成物的玻璃轉化溫度變高而造成耐熱性降低，而有難以用作基板材料來使用之虞；在超過43重量份的情況下，前述樹脂組成物的吸濕率增加而造成材料的可靠性減少，而有難以適用於樹脂組成物的基板處理之虞。 In the foregoing insulating resin composition for a printed circuit board, the amount of bismaleimide used may be 10 to 43 parts by weight relative to 100 parts by weight of the insulating resin composition. In the case where the amount of the bismaleimide used is less than 10 parts by weight, the glass transition temperature of the resin composition is increased to lower the heat resistance, and it may be difficult to use it as a substrate material; When it exceeds 43 weight part, the moisture absorption rate of the said resin composition will increase, and the reliability of a material will fall, and it may become difficult to apply it to the substrate processing of a resin composition.
前述雙馬來亞醯胺可使用1,1’-(亞甲基二-4,1-伸苯基)雙馬來亞醯胺(1,1’-(methylenedi-4,1-phenylene)bismaleimide)，但並非特別限定於此。 As the bismaleimide, 1,1 '-(methylenebis-4,1-phenylene) bismaleimide (1,1'-(methylenedi-4,1-phenylene) bismaleimide can be used. ), But it is not particularly limited to this.
根據本發明一實施例的絕緣樹脂組成物係可以本技術領域中已知的任一普遍方法來製作成半固狀之乾膜。例如，使用輥塗機(roll coater)、淋塗機(curtain coater)、或點塗機(comma coater)等製造成薄膜狀並使其乾燥之後，以堆疊之方式使用於基板上來製造多層印刷電路基板時，可以作為絕緣層(或絕緣膜)或預浸材來使用。這樣的絕緣膜或預浸材係能夠改善熱膨脹係數及玻璃轉化溫度的特性。 The insulating resin composition according to an embodiment of the present invention can be used to make a semi-solid dry film by any of the common methods known in the art. For example, a roll coater, a curtain coater, a comma coater, or the like is used to produce a thin film and then dried, and then stacked on a substrate to manufacture a multilayer printed circuit. In the case of a substrate, it can be used as an insulating layer (or an insulating film) or a prepreg. Such an insulating film or prepreg can improve the characteristics of the coefficient of thermal expansion and the glass transition temperature.
如此，可在包含根據本發明一實施例之用於印刷電路基板之絕緣樹脂組成物的清漆中，含浸並乾燥無機纖維或有機纖維來製造預浸材。 As such, a prepreg can be impregnated and dried in a varnish including an insulating resin composition for a printed circuit board according to an embodiment of the present invention, and dried.
前述無機纖維或有機纖維可選自於玻璃纖維、碳纖維、聚對苯撐苯並二嗯唑(poly-p-phenylenebenzobisthiazole)纖維、向熱性(thermotropic)液晶高分子纖維、向液性(lyotropic)液晶高分子纖維、醯胺纖維、聚吡啶並雙咪唑(PIPD)纖維、聚苯並噻唑(polybenzothiazole)纖維、及聚芳基酸酯(polyarylate)纖維中之一種以上者，但並非特別限定於此。 The inorganic fiber or organic fiber may be selected from glass fiber, carbon fiber, poly-p-phenylenebenzobisthiazole fiber, thermotropic liquid crystal polymer fiber, and lyotropic liquid crystal. One or more of polymer fibers, amidine fibers, polypyridobisimidazole (PIPD) fibers, polybenzothiazole fibers, and polyarylate fibers, but it is not particularly limited thereto.
可於前述預浸材的單面或雙面貼附銅箔來製造敷銅層板(Copper-Clad Laminate,CCL)。藉此，包含有環氧樹脂、及具有聯吡啶構造之硬化劑的絕緣層係能夠提高其與金屬層之剝離強度。 Copper foil can be attached to one or both sides of the prepreg to produce a copper-clad laminate (CCL). Thereby, the insulating layer containing an epoxy resin and a hardener having a bipyridine structure can improve its peel strength from the metal layer.
此外，根據本發明一實施例，由用於印刷電路基板 之絕緣樹脂組成物所構成之絕緣膜或預浸材係可使用在製造印刷電路基板時，用作內層之敷銅層板上疊層之多層印刷電路基板的製造上。例如，可將由前述絕緣樹脂組成物所構成之絕緣膜或預浸材圖型加工後的內層電路基板往上疊層，並使其硬化、進行除膠渣(desmear)製程後，透過電鍍製程形成電路層而製造多層印刷電路基板。 In addition, according to an embodiment of the present invention, a printed circuit board The insulating film or prepreg made of an insulating resin composition can be used for manufacturing a multilayer printed circuit board laminated on a copper-clad laminate used as an inner layer when manufacturing a printed circuit board. For example, an insulating film composed of the aforementioned insulating resin composition or an inner-layer circuit board after pattern processing of the prepreg material may be laminated on top, hardened, and subjected to a desmear process, and then passed through a plating process. A circuit layer is formed to manufacture a multilayer printed circuit board.
以下，將透過實施例及比較例來更具體地說明本發明，然而，本發明的範圍並不限於下述的例子。 Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the scope of the present invention is not limited to the following examples.
於安裝有回流裝置之100ml的圓底燒瓶中，添加7.3g之2,2’-聯吡啶-4,4’-二羧酸(2,2’-bipyridine-4,4’-dicarboxylic acid)、8.7g之4-胺基苯酚(4-aminophenol)、6.6g之間苯二甲酸(isophthalic acid)、6.4g之4-羥基安息香酸(4-hydroxybenzoic acid)、3.1g之6-羥基-2-萘甲酸(6-hydroxy-2-naphthoic acid)、22.4g之醋酸酐。前述燒瓶裝設有密封之機械攪拌機、氮注入管、溫度計及回流電容器。將前述燒瓶的內部以氮氣充分置換後，使燒瓶內部的溫度在氮氣流動下上升至約140℃的溫度，並以此溫度維持燒瓶內部的溫度同時使其回流約1小時。接著，進一步添加5.6g之6-羥基-2-萘甲酸後，除去未與反應副產物之醋酸反應的醋酸酐，將溫度提高至約300℃後，使其發生反應約30分鐘而合成具有聯吡啶構造之硬化劑。 In a 100 ml round bottom flask equipped with a reflux device, 7.3 g of 2,2'-bipyridine-4,4'-dicarboxylic acid (2,2'-bipyridine-4,4'-dicarboxylic acid), 8.7 g of 4-aminophenol, 6.6 g of isophthalic acid, 6.4 g of 4-hydroxybenzoic acid, 3.1 g of 6-hydroxy-2- Naphthoic acid (6-hydroxy-2-naphthoic acid), 22.4 g of acetic anhydride. The aforementioned flask was equipped with a sealed mechanical stirrer, a nitrogen injection tube, a thermometer, and a reflux capacitor. After the inside of the flask was sufficiently replaced with nitrogen, the temperature inside the flask was raised to a temperature of about 140 ° C. under a flow of nitrogen, and the temperature inside the flask was maintained at this temperature while refluxing for about 1 hour. Next, after further adding 5.6 g of 6-hydroxy-2-naphthoic acid, acetic anhydride that has not reacted with acetic acid as a by-product of the reaction was removed, and the temperature was increased to about 300 ° C, and then the reaction was performed for about 30 minutes to synthesize a compound having Pyridine-based hardener.
於安裝有回流裝置的100ml之圓底燒瓶中，添加8.7g之4-胺基苯酚、10.0g之間苯二甲酸、6.4g之4-羥基安息香酸、3.1g之6-羥基-2-萘甲酸、22.4g之醋酸酐。接著，以如前述製造範例1的條件使其發生反應而合成不具有聯吡啶構造之硬化劑。 In a 100 ml round bottom flask equipped with a reflux device, 8.7 g of 4-aminophenol, 10.0 g of m-phthalic acid, 6.4 g of 4-hydroxybenzoic acid, and 3.1 g of 6-hydroxy-2-naphthalene were added. Formic acid, 22.4 g of acetic anhydride. Next, a reaction was performed under the conditions of the aforementioned Production Example 1 to synthesize a hardener having no bipyridine structure.
將33.0g之具有聯吡啶構造的製造範例1之硬化劑、22.0g之環氧樹脂(Araldite MY-721，Huntsmann公司製造)及0.22g之二聚氰胺(DICY)添加至45.0g的N,N’-二甲基乙醯胺(DMAc)中，製成清漆狀之混合溶液，並將玻璃纖維含浸至前述清漆之後，以約200℃將其乾燥5分鐘來製造預浸材。此外，以約220℃的溫度、30kgf/cm2的壓力使前述預浸材硬化約60分鐘來製作敷銅層板。 33.0 g of the hardening agent of Production Example 1 having a bipyridine structure, 22.0 g of an epoxy resin (Araldite MY-721, manufactured by Huntsmann) and 0.22 g of melamine (DICY) were added to 45.0 g of N, N'-dimethylacetamide (DMAc) was prepared into a varnish-like mixed solution, and the glass fiber was impregnated with the varnish, and then dried at about 200 ° C. for 5 minutes to produce a prepreg. In addition, the prepreg was hardened at a temperature of about 220 ° C. and a pressure of 30 kgf / cm 2 for about 60 minutes to produce a copper-clad laminate.
於前述實施例1所製造的混合溶液中，添加312g之粒徑為500μm的球狀二氧化矽(Admatechs公司製造)而製成清漆，並以與前述實施例1相同的方法來製作敷銅層板。 To the mixed solution produced in the foregoing Example 1, 312 g of spherical silicon dioxide (manufactured by Admatechs) having a particle size of 500 μm was added to prepare a varnish, and a copper-clad layer was produced in the same manner as in the foregoing Example 1. board.
將33.0g之不具有聯吡啶構造的製造範例2的硬化 劑、22.0g之環氧樹脂(Araldite MY-721，Huntsmann公司製造)及0.22g之二聚氰胺(DICY)添加至45.0g的N,N’-二甲基乙醯胺(DMAc)，製成清漆狀的混合溶液，並將玻璃纖維含浸至前述清漆之後，以約200℃將其乾燥5分鐘來製造預浸材。此外，以約220℃的溫度、30kgf/cm2的壓力使前述預浸材硬化約60分鐘來製作敷銅層板。 33.0 g of hardener for Production Example 2 without bipyridine structure, 22.0 g of epoxy resin (Araldite MY-721, manufactured by Huntsmann) and 0.22 g of melamine (DICY) were added to 45.0 g of N , N'-dimethylacetamide (DMAc), made into a varnish-like mixed solution, impregnated the glass fiber with the aforementioned varnish, and dried it at about 200 ° C. for 5 minutes to produce a prepreg. In addition, the prepreg was hardened at a temperature of about 220 ° C. and a pressure of 30 kgf / cm 2 for about 60 minutes to produce a copper-clad laminate.
於前述比較例1所製造的混合溶液中，添加312g之粒徑為500μm的球狀二氧化矽(Admatechs公司製造)而製成清漆，並以與前述比較例1相同的方法來製作敷銅層板。 To the mixed solution produced in the aforementioned Comparative Example 1, 312 g of spherical silica with a particle diameter of 500 μm (manufactured by Admatechs) was added to prepare a varnish, and a copper-clad layer was produced in the same manner as in the aforementioned Comparative Example 1. board.
測量由實施例1及2、比較例1及2所製造之敷銅層板除去銅箔後之樣本的熱膨脹係數及玻璃轉化溫度。 The thermal expansion coefficients and glass transition temperatures of the samples after removing the copper foil from the copper-clad laminates produced in Examples 1 and 2 and Comparative Examples 1 and 2 were measured.
為了測量熱膨脹係數，使用TA公司製造的熱機械分析(ThermoMechanical Analysis,TMA)儀器並以拉力模態(Tensile mode)來測量，第1次掃描以每1分鐘每10℃掃描至約300℃，冷卻之後，第2次掃描以每1分鐘每10℃掃描至約310℃，測量2次掃描之結果值的熱膨脹係數。 In order to measure the coefficient of thermal expansion, a thermomechanical analysis (TMA) instrument manufactured by TA Corporation was used to measure in a tensile mode (Tensile mode). The first scan was performed at a temperature of about 300 ° C per 10 ° C every 1 minute, and the cooling After that, the second scan was performed at a temperature of about 310 ° C. per 10 ° C. per minute, and the thermal expansion coefficient of the results of the two scans was measured.
此外，玻璃轉化溫度係使用TA公司製造的示差掃描熱析儀(Differential Scanning Calorimeter,DSC)儀器來測量，將約5mg之各別製造的樣本投入前述儀器中，第1次測量為以每1分鐘每10℃量測至約300℃，冷卻之後，以每1分鐘每10℃量測至300℃來進行第2次測量，利用2次測量之結果值來測量玻璃轉化溫度。 In addition, the glass transition temperature was measured using a Differential Scanning Calorimeter (DSC) instrument manufactured by TA Corporation. About 5 mg of each manufactured sample was put into the aforementioned instrument, and the first measurement was performed every 1 minute. The temperature was measured to about 300 ° C every 10 ° C. After cooling, the second measurement was performed at 300 ° C every 10 ° C every 1 minute, and the glass transition temperature was measured using the results of the two measurements.
最後，將由實施例1及2、比較例1及2所製造的敷銅層板之表面剝離約1cm的銅箔，並使用萬能試驗機(Universal Testing Machine、UTM)來測量銅箔與絕緣層之間的剝離強度。 Finally, the surface of the copper-clad laminates produced in Examples 1 and 2 and Comparative Examples 1 and 2 was stripped of about 1 cm of copper foil, and a universal testing machine (UTM) was used to measure the copper foil and the insulation layer. Peel strength.
由前述表1可明白，與比較例1所製造的預浸材相比，由本發明之不含無機填充劑的絕緣樹脂組成物所構成之實施例1的預浸材係具有改善玻璃轉化溫度、熱膨脹係數及剝離強度的特性之效果。 As is clear from the foregoing Table 1, compared with the prepreg produced in Comparative Example 1, the prepreg of Example 1 composed of the insulating resin composition containing no inorganic filler of the present invention has improved glass transition temperature, Effects of thermal expansion coefficient and peel strength characteristics.
由前述表2可明白，與比較例2所製造之預浸材相比，由本發明之包含無機填充劑的絕緣樹脂組成物所構成之實施例2的預浸材係具有改善玻璃轉化溫度、熱膨脹係數及剝離強度之特性的效果。 As can be understood from the foregoing Table 2, the prepreg of Example 2 composed of the insulating resin composition containing the inorganic filler of the present invention has improved glass transition temperature and thermal expansion compared with the prepreg produced in Comparative Example 2. The effect of coefficient and peel strength characteristics.
綜上，雖然基於具體的實施例來詳細地說明本發明，然而此係用以具體地說明本發明而已，本發明並不限定於此，只要是該具有該領域中之通常知識者，皆能明白在本發明之技術思想內是能夠加以變形或改良的。 In summary, although the present invention is described in detail based on specific embodiments, it is only used to specifically describe the present invention, and the present invention is not limited to this. Anyone who has ordinary knowledge in the field can do so. It is understood that it can be modified or improved within the technical idea of the present invention.
本發明之單純的變形乃至變更皆屬於本發明的領域者，本發明的具體的保護範圍透過所附的申請專利範圍而更加明確。 The simple deformation and even the modification of the present invention belong to those who belong to the field of the present invention, and the specific protection scope of the present invention is made clearer by the scope of the attached patent application.
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| CN109757023B (en) * | 2017-11-08 | 2022-04-26 | 广东生益科技股份有限公司 | Printed circuit board and manufacturing method thereof |
| CN108384234B (en) * | 2018-03-29 | 2019-08-09 | 西北工业大学 | A kind of wave-penetrating composite material and preparation method thereof |
| KR102243041B1 (en) * | 2018-05-30 | 2021-04-22 | 삼성디스플레이 주식회사 | High heat resistant composition and method for preparing three-dimensional substrate using the same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1278288A (en) * | 1997-11-05 | 2000-12-27 | 亨克尔两合股份公司 | Conductive organic coatings |
| CN102224140A (en) * | 2008-11-24 | 2011-10-19 | 巴斯夫欧洲公司 | Curable composition comprising a thermolatent base |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS57174241A (en) * | 1981-04-21 | 1982-10-26 | Hitachi Chemical Co Ltd | Manufacture of fire retardant heatproof copper plated laminated board |
| US4861823A (en) * | 1986-11-20 | 1989-08-29 | Amoco Corporation | Thermoset composition comprising aromatic cyanate ester of allyl ether of bisphenol |
| JPH0196173A (en) * | 1987-10-07 | 1989-04-14 | Hitachi Ltd | Bipyridine-based compound, production and composition thereof |
| EP0508952B1 (en) * | 1991-04-08 | 1996-04-03 | Ciba-Geigy Ag | Epoxy resin blends, especially for the preparation of storable prepregs |
| JP2833433B2 (en) * | 1993-03-24 | 1998-12-09 | 新神戸電機株式会社 | Epoxy resin composition for laminate and method for producing laminate |
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| US7540978B2 (en) * | 2004-08-05 | 2009-06-02 | Novaled Ag | Use of an organic matrix material for producing an organic semiconductor material, organic semiconductor material and electronic component |
| JP2009155354A (en) * | 2006-03-30 | 2009-07-16 | Ajinomoto Co Inc | Resin composition for insulating layer |
| KR100840924B1 (en) | 2007-03-30 | 2008-06-24 | 삼성전기주식회사 | Eucryptite ceramic filler and insulating composite material containing the same |
| KR100835784B1 (en) | 2007-06-26 | 2008-06-09 | 주식회사 두산 | Resine composition for printed circuit board and composite substrate and copper laminates using the same |
| JP5024205B2 (en) * | 2007-07-12 | 2012-09-12 | 三菱瓦斯化学株式会社 | Prepreg and laminate |
| JP5569270B2 (en) | 2010-09-06 | 2014-08-13 | 住友ベークライト株式会社 | Prepreg, metal-clad laminate, printed wiring board, and semiconductor device |
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