TW201930463A - Heat curable resin composition, insulation film, interlayer insulation film, multilayer wiring board and semiconductor apparatus - Google Patents

Heat curable resin composition, insulation film, interlayer insulation film, multilayer wiring board and semiconductor apparatus Download PDF

Info

Publication number
TW201930463A
TW201930463A TW107141680A TW107141680A TW201930463A TW 201930463 A TW201930463 A TW 201930463A TW 107141680 A TW107141680 A TW 107141680A TW 107141680 A TW107141680 A TW 107141680A TW 201930463 A TW201930463 A TW 201930463A
Authority
TW
Taiwan
Prior art keywords
resin composition
thermosetting resin
insulating film
cured product
component
Prior art date
Application number
TW107141680A
Other languages
Chinese (zh)
Other versions
TWI772562B (en
Inventor
黒川津与志
佐藤淳也
吉田真樹
寺木慎
Original Assignee
日商納美仕有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日商納美仕有限公司 filed Critical 日商納美仕有限公司
Publication of TW201930463A publication Critical patent/TW201930463A/en
Application granted granted Critical
Publication of TWI772562B publication Critical patent/TWI772562B/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • 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
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5425—Silicon-containing compounds containing oxygen containing at least one C=C bond
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • 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

Abstract

An object of the present invention to provide a heat curable resin composition which is excellent in heat resistance, moisture resistance reliability, and resistance to moisture absorption reflow. Provided is a heat curable resin composition having: (A) a heat curable resin having an unsaturated double bond at its terminal; (B) a silica filler whose surface is treated with a specific long chain spacer type silane coupling agent containing an alkyl group having at least an unsaturated double bond at the end; and (C) a flexibility -providing resin (except component (A)). It is preferable that the unsaturated double bond of the component (B) is a vinyl group.

Description

熱硬化性樹脂組成物、絕緣性膜、層間絕緣性膜、多層配線板及半導體裝置  Thermosetting resin composition, insulating film, interlayer insulating film, multilayer wiring board, and semiconductor device  

本發明係關於熱硬化性樹脂組成物、絕緣性膜、層間絕緣性膜、多層配線板、及半導體裝置。尤其，有關可對應於高頻化之熱硬化性樹脂組成物、絕緣性膜、層間絕緣性膜、多層配線板、及半導體裝置。 The present invention relates to a thermosetting resin composition, an insulating film, an interlayer insulating film, a multilayer wiring board, and a semiconductor device. In particular, it relates to a thermosetting resin composition, an insulating film, an interlayer insulating film, a multilayer wiring board, and a semiconductor device which are compatible with high frequency.

目前，在各種通訊機器等之電子機器中多為要求高頻化。例如，毫米波通訊等高頻用途的印刷配線板，較多要求低傳送損失。該高頻用途之印刷配線板的接著層或被覆層、或基板本身所使用之材料已知有使用熱硬化性聚苯醚(PPE)。 At present, in many electronic devices such as communication devices, high frequency is required. For example, printed wiring boards for high-frequency applications such as millimeter wave communication require low transmission loss. A thermosetting polyphenylene ether (PPE) is known as a material for use in the adhesive layer or the coating layer of the high-frequency use printed wiring board or the substrate itself.

此等高頻用途的印刷配線板適合的用途有期望低熱膨脹率(低CTE)化之情形，例如可藉由在PPE添加氧化矽填充劑而設為所希望之CTE。因此，已提出在PPE中加入既定之中空填充劑(中空氧化矽)而製造低介電率之印刷配線板(專利文獻1)。 A suitable printed wiring board for such high-frequency use has a desired low coefficient of thermal expansion (low CTE), and can be set to a desired CTE by, for example, adding a cerium oxide filler to the PPE. Therefore, it has been proposed to produce a low dielectric constant printed wiring board by adding a predetermined hollow filler (hollow yttrium oxide) to the PPE (Patent Document 1).

在此，上述之接著層、被覆層或基板本身等係要求耐濕可靠性(在溫度：85℃、濕度：85%之環境的長期可靠性)、耐熱性(在本說明書中特別表示焊接時之耐熱性，意指瞬間的耐熱性)、耐吸濕回焊性。 Here, the above-mentioned adhesive layer, the coating layer, the substrate itself, and the like are required to have moisture resistance reliability (long-term reliability in an environment of temperature: 85° C., humidity: 85%), and heat resistance (in the present specification, the welding is particularly indicated. Heat resistance means instantaneous heat resistance) and moisture reflow resistance.

[先前技術文獻]  [Previous Technical Literature]   [專利文獻]  [Patent Literature]  

[專利文獻1]日本特開2007-56170號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2007-56170

然而，若在PPE添加氧化矽填充劑(包含中空氧化矽)，會因耐濕可靠性試驗，使介電損耗正切(tanδ)之變化率增大。又，已知因耐吸濕回焊性試驗，會有在上述之接著層、被覆層、或基板之界面產生剝離或膨脹之缺點。 However, when a cerium oxide filler (including hollow cerium oxide) is added to the PPE, the rate of change in dielectric loss tangent (tan δ) is increased by the moisture resistance reliability test. Further, it is known that there is a disadvantage that peeling or swelling occurs at the interface between the above-mentioned adhesive layer, the coating layer, or the substrate due to the moisture absorption reflow resistance test.

從上述之觀點，本發明之目的在於提供一種耐濕可靠性、耐熱性、及耐吸濕回焊性優異之熱硬化性樹脂組成物。 From the above viewpoints, an object of the present invention is to provide a thermosetting resin composition which is excellent in moisture resistance reliability, heat resistance, and moisture absorption reflow resistance.

發明係關於一種藉由具有以下構成而解決上述問題之熱硬化性樹脂組成物、絕緣性膜、層間絕緣性膜、多層配線板、及半導體裝置。 The invention relates to a thermosetting resin composition, an insulating film, an interlayer insulating film, a multilayer wiring board, and a semiconductor device which solve the above problems by the following constitution.

[1]一種熱硬化性樹脂組成物，係包含：(A)在末端具有不飽和雙鍵之熱硬化性樹脂；(B)經以通式(1)所示之矽烷偶合劑表面處理的氧化矽填充劑 [1] A thermosetting resin composition comprising: (A) a thermosetting resin having an unsaturated double bond at a terminal; (B) an oxidation treatment by a surface treatment of a decane coupling agent represented by the formula (1) Crucible filler

(式中，R1至R3分別獨立地為碳數1至3之烷基，R4係至少在末端具有不飽和雙鍵之官能基，n為5至9)；及(C)賦予柔軟性之樹脂(但不包含(A)成分)。 (wherein R 1 to R 3 are each independently an alkyl group having 1 to 3 carbon atoms, R 4 is a functional group having an unsaturated double bond at least at the terminal, n is 5 to 9); and (C) imparts softness Resin (but not (A)).

[2]如上述[1]所述之熱硬化性樹脂組成物，其中，通式(1)之R4為乙烯基或(甲基)丙烯醯基。 [2] The thermosetting resin composition according to the above [1], wherein R 4 of the formula (1) is a vinyl group or a (meth) acrylonitrile group.

[3]如上述[1]或[2]所述之熱硬化性樹脂組成物，其中，(C)成分為苯乙烯系熱塑性彈性體。 [3] The thermosetting resin composition according to the above [1], wherein the component (C) is a styrene-based thermoplastic elastomer.

[4]一種絕緣性膜，係包含上述[1]至[3]中任一項所述之熱硬化性樹脂組成物。 [4] An insulating film comprising the thermosetting resin composition according to any one of the above [1] to [3].

[5]層間絕緣性膜，係包含上述[1]至[3]中任一項所述之熱硬化性樹脂組成物。 [5] The thermosetting resin composition according to any one of the above [1] to [3].

[6]一種硬化物，係上述[1]至[3]中任一項所述之熱硬化性樹脂組成物的硬化物、上述[4]所述之絕緣性膜或上述[5]所述之層間絕緣性膜的硬化物。 [6] The cured product of the thermosetting resin composition according to any one of the above [1] to [3], the insulating film according to the above [4], or the above [5] A cured product of the interlayer insulating film.

[7]一種多層配線板，係具有：上述[1]至[3]中任一項所述之熱硬化性樹脂組成物的硬化物、上述[4]所述之絕緣性膜或上述[5]所述之層間絕緣性膜的硬化物。 [7] The cured product of the thermosetting resin composition according to any one of the above [1] to [3], the insulating film according to the above [4], or the above [5] The hardened material of the interlayer insulating film described above.

[8]一種半導體裝置，係具有：上述[1]至[3]中任一項所述之熱硬化性樹脂組成物的硬化物、上述[4]所述之絕緣性膜或上述[5]所述之層間絕緣性膜的硬化物。 [8] The cured product of the thermosetting resin composition according to any one of the above [1] to [3], the insulating film according to the above [4], or the above [5] A cured product of the interlayer insulating film.

依據本發明[1]，可提供耐熱性、耐濕可靠性、及耐吸濕回焊性優異之熱硬化性樹脂組成物。 According to the invention [1], a thermosetting resin composition excellent in heat resistance, moisture resistance reliability, and moisture absorption reflow resistance can be provided.

依據本發明[4]，可提供由耐熱性、耐濕可靠性、及耐吸濕回焊性優異之熱硬化性樹脂組成物所形成的絕緣性膜。 According to the invention [4], an insulating film formed of a thermosetting resin composition excellent in heat resistance, moisture resistance reliability, and moisture absorption reflow resistance can be provided.

依據本發明[5]，可提供由耐熱性、耐濕可靠性、及耐吸濕回焊性優異之熱硬化性樹脂組成物所形成的層間絕緣性膜。 According to the invention [5], it is possible to provide an interlayer insulating film formed of a thermosetting resin composition excellent in heat resistance, moisture resistance reliability, and moisture absorption reflow resistance.

依據本發明[6]，可藉由上述熱硬化性樹脂組成物之硬化物、上述絕緣性膜或上述層間絕緣性膜之硬化物而提供耐濕可靠性、及耐吸濕回焊性優異之多層配線板。依據本發明[7]，可藉由上述熱硬化性樹脂組成物之硬化物、上述絕緣性膜或上述層間絕緣性膜之硬化物，而提供耐濕可靠性、及耐吸濕回焊性優異之多層配線板。依據本發明[8]，可藉由上述熱硬化性樹脂組成物之硬化物、上述絕緣性膜或上述層間絕緣性膜之硬化物，而提供耐濕可靠性、及耐吸濕回焊性優異之半導體裝置。 According to the invention [6], the cured product of the thermosetting resin composition, the insulating film or the cured product of the interlayer insulating film can provide a multilayer excellent in moisture resistance reliability and moisture absorption reflow resistance. Wiring board. According to the invention [7], the cured product of the thermosetting resin composition, the insulating film or the cured film of the interlayer insulating film can provide excellent moisture resistance reliability and moisture absorption reflow resistance. Multilayer wiring board. According to the invention [8], the cured product of the thermosetting resin composition, the insulating film or the cured film of the interlayer insulating film can provide excellent moisture resistance reliability and moisture absorption reflow resistance. Semiconductor device.

〔熱硬化性樹脂組成物〕  [thermosetting resin composition]  

本發明之熱硬化性樹脂組成物係包含：(A)在末端具有不飽和雙鍵之熱硬化性樹脂；(B)經以通式(1)所示之矽烷偶合劑表面處理的氧化矽填充劑 The thermosetting resin composition of the present invention comprises: (A) a thermosetting resin having an unsaturated double bond at a terminal; (B) a cerium oxide-filled surface treated with a decane coupling agent represented by the formula (1); Agent

(式中，R1至R3分別獨立地為碳數1至3之烷基，R4係至少在末端具有不飽和雙鍵之官能基，n為5至9)；及(C)賦予柔軟性之樹脂(但不包含(A)成分)。 (wherein R 1 to R 3 are each independently an alkyl group having 1 to 3 carbon atoms, R 4 is a functional group having an unsaturated double bond at least at the terminal, n is 5 to 9); and (C) imparts softness Resin (but not (A)).

(A)成分係對本發明之熱硬化性樹脂組成物(以下，稱為熱硬化性樹脂組成物)賦予接著性、高頻特性、耐熱性者。在此，所謂高頻係指減少在高頻區域之傳送損失的性質。從高頻特性之觀點而言，(A)成分係以在10GHz之比介電率(ε)為3.5以下、介電損耗正切(tanδ)為0.003以下為較佳。(A)成分較佳係在末端具有苯乙烯基之樹脂。又，在末端具有苯乙烯基之樹脂較佳係在末端具有苯乙烯基且在主鏈具有伸苯基醚骨架之熱硬化性樹脂(PPE)。 The component (A) imparts adhesiveness, high frequency characteristics, and heat resistance to the thermosetting resin composition of the present invention (hereinafter referred to as a thermosetting resin composition). Here, the term "high frequency" refers to a property of reducing transmission loss in a high frequency region. From the viewpoint of high-frequency characteristics, the component (A) preferably has a dielectric constant (ε) of 3.5 or less at 10 GHz and a dielectric loss tangent (tan δ) of 0.003 or less. The component (A) is preferably a resin having a styryl group at the terminal. Further, the resin having a styryl group at the terminal is preferably a thermosetting resin (PPE) having a styryl group at the terminal and a phenyl ether skeleton in the main chain.

在末端具有苯乙烯基且在主鏈具有伸苯基醚骨架之熱硬化性樹脂(PPE)由於高頻特性優異且介電特性(尤其為tanδ)之溫度依存性(相對於常溫(25℃)之測定值，在高溫(120℃)之測定值的變化)較小，故以通式(2)所示之化合物為較佳。 A thermosetting resin (PPE) having a styryl group at the terminal and having a phenyl ether skeleton in the main chain is excellent in high frequency characteristics and has a dielectric property (especially tan δ) depending on the temperature (25 ° C) The measured value is small in the change in the measured value at a high temperature (120 ° C), so that the compound represented by the formula (2) is preferred.

(式(2)中，-(O-X-O)-以通式(3)或(4)表示。) (In the formula (2), -(O-X-O)- is represented by the formula (3) or (4).)

(式(3)中，R5、R6、R7、R11、R12可為相同或相異，且為碳數6以下之烷基或苯基。R8、R9、R10可為相同或相異，且為氫原子、碳數6以下之烷基或苯基。) (In the formula (3), R 5 , R 6 , R 7 , R 11 and R 12 may be the same or different and are an alkyl group having 6 or less carbon atoms or a phenyl group. R 8 , R 9 and R 10 may be used. They are the same or different and are a hydrogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group.

(式(4)中，R13、R14、R15、R16、R17、R18、R19、R20可為相同或相異，且為氫原子、碳數6以下之烷基或苯基。-A-為碳數20以下之直鏈狀、分支狀或環狀之2價烴基。) (In the formula (4), R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 and R 20 may be the same or different and are a hydrogen atom, an alkyl group having 6 or less carbon atoms or Phenyl.-A- is a linear, branched or cyclic divalent hydrocarbon group having a carbon number of 20 or less.

(式(2)中，-(Y-O)-係以通式(5)表示，1種類之構造或2種類以上之構造任意排列。) (In the formula (2), the -(Y-O)- is represented by the formula (5), and the structure of one type or the structure of two or more types is arbitrarily arranged.)

(式(5)中，R21、R22可為相同或相異，且為碳數6以下之烷基或苯基。R23、R24可為相同或相異，且為氫原子、碳數6以下之烷基或苯基。) (In the formula (5), R 21 and R 22 may be the same or different and are an alkyl group having 6 or less carbon atoms or a phenyl group. R 23 and R 24 may be the same or different and are a hydrogen atom or a carbon. An alkyl group or a phenyl group of 6 or less.)

(式(2)中，a，b係至少任一者不為0，且表示0至100之整數。) (In the formula (2), at least one of a and b is not 0, and represents an integer of 0 to 100.)

(式(4)中之-A-可舉例如亞甲基、亞乙基、1-甲基亞乙基、 1,1-亞丙基、1,4-伸苯基雙(1-甲基亞乙基)、1,3-伸苯基雙(1-甲基亞乙基)、環亞己基、苯基亞甲基、萘基亞甲基、1-苯基亞乙基等之2價有機基，但不受此等限定。) (-A- in the formula (4) may, for example, be a methylene group, an ethylene group, a 1-methylethylene group, a 1,1-propylene group, a 1,4-phenylene bis(1-methyl group) Ethylene), 1,3-phenylene bis(1-methylethylidene), cyclohexylene, phenylmethylene, naphthylmethylene, 1-phenylethylene, etc. Organic based, but not subject to these restrictions.)

(式(2)所示之化合物係以R5、R6、R7、R11、R12、R21、R22為碳數3以下之烷基，而R8、R9、R10、R13、R14、R15、R16、R17、R18、R19、R20、R23、R24為氫原子或碳數3以下之烷基者為較佳，尤其，更佳係通式(3)或通式(4)所示之-(O-X-O)-為通式(6)、通式(7)或通式(8)，而通式(5)所示之-(Y-O)-為式(9)或式(10)、或式(9)與式(10)為任意排列之構造。) (The compound represented by the formula (2) is such that R 5 , R 6 , R 7 , R 11 , R 12 , R 21 and R 22 are an alkyl group having 3 or less carbon atoms, and R 8 , R 9 and R 10 are R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 23 and R 24 are preferably a hydrogen atom or an alkyl group having 3 or less carbon atoms, and more preferably, more preferably -(OXO)- represented by the formula (3) or the formula (4) is a formula (6), a formula (7) or a formula (8), and a formula (5) - (YO) ) - is a structure in which the formula (9) or the formula (10), or the formulas (9) and (10) are arbitrarily arranged.)

式(2)所示之化合物的製造方法並無特別限定，例如可使由2官能酚化合物與1官能酚化合物氧化偶合所得之2官能伸苯基醚寡聚物的末端酚性羥基進行乙烯基苯甲基醚化而製造。 The method for producing the compound represented by the formula (2) is not particularly limited. For example, the terminal phenolic hydroxyl group of the bifunctional phenyl ether oligomer obtained by oxidative coupling of a bifunctional phenol compound and a monofunctional phenol compound may be vinyl. Benzyl ether is produced by etherification.

(A)成分之熱硬化性樹脂的數平均分子量藉由GPC法經聚苯乙烯換算較佳為500至4,500之範圍，更佳為800至3500之範圍，又更佳為1000至2500之範圍。若數平均分子量為500以上，使本發明之樹脂組成物形成為塗膜狀時不易沾黏，又，若為4,500以下，可防止對溶劑之溶解性的降低。 The number average molecular weight of the thermosetting resin of the component (A) is preferably in the range of from 500 to 4,500 in terms of polystyrene by the GPC method, more preferably in the range of from 800 to 3,500, still more preferably in the range of from 1,000 to 2,500. When the number average molecular weight is 500 or more, when the resin composition of the present invention is formed into a coating film form, it is less likely to be viscous, and if it is 4,500 or less, the solubility in a solvent can be prevented from being lowered.

(A)成分可單獨使用或併用2種以上。 The component (A) may be used singly or in combination of two or more.

(B)成分係對熱硬化性樹脂組成物賦予低熱膨脹性、耐熱性、耐濕可靠性、耐吸濕回焊性者。(B)成分係經以下述通式(1)所示之矽烷偶合劑表面處理的氧化矽填充劑： The component (B) imparts low thermal expansion property, heat resistance, moisture resistance reliability, and moisture absorption reflow resistance to the thermosetting resin composition. The component (B) is a cerium oxide filler which is surface-treated with a decane coupling agent represented by the following formula (1):

(式中，R1至R3分別獨立地為碳數1至3之烷基，R4係至少在末端具有不飽和雙鍵之官能基，n為5至9)。R4具體而言可舉例如乙烯基、或(甲基)丙烯醯基。從反應性所致之與(A)成分的接著性之觀點而言，通式(1)之R4較佳為乙烯基、或(甲基)丙烯醯基，從剝離強度之觀點而言，更佳為乙烯基。 (wherein R 1 to R 3 are each independently an alkyl group having 1 to 3 carbon atoms, and R 4 is a functional group having an unsaturated double bond at least at the terminal, and n is 5 to 9). Specific examples of R 4 include a vinyl group or a (meth) acrylonitrile group. From the viewpoint of reactivity with the adhesion of the component (A), R 4 of the formula (1) is preferably a vinyl group or a (meth) acrylonitrile group, from the viewpoint of peel strength. More preferably vinyl.

使用在(B)成分之矽烷偶合劑可舉例如辛烯基三烷氧基矽烷、(甲基)丙烯醯氧基烷基三烷氧基矽烷。辛烯基三烷氧基矽烷可舉例如辛烯基三甲氧基矽烷、辛烯基三乙氧基矽烷等。(甲基)丙烯醯氧基烷基三烷氧基矽烷可舉例如(甲基)丙烯醯氧基辛基三甲氧基矽烷、(甲基)丙烯醯氧基辛基三乙氧基矽烷等。從提升剝離強度之觀點而言，以辛烯基三甲氧基矽烷為更佳。(B)成分之矽烷偶合劑的市售品可舉例如信越化學工業(股)製辛烯基三甲氧基矽烷(品名：KBM-1083)、信越化學工業(股)製甲基丙烯醯氧基辛基三甲氧基矽烷(品名：KBM-5803)。使用於(B)成分之矽烷偶合劑可為單獨或2種以上。 The decane coupling agent to be used as the component (B) may, for example, be an octenyltrialkoxide or a (meth)acryloxyalkyltrialkoxide. The octenyltrialkoxide may, for example, be octenyltrimethoxydecane or octenyltriethoxydecane. Examples of the (meth) acryloxyalkyltrial alkoxy decane include (meth) propylene oxime octyl trimethoxy decane, (meth) propylene decyl octyl triethoxy decane, and the like. From the viewpoint of enhancing the peel strength, octenyltrimethoxydecane is more preferable. The commercially available product of the decane coupling agent of the component (B) may, for example, be an octenyl trimethoxy decane (product name: KBM-1083) manufactured by Shin-Etsu Chemical Co., Ltd., or a methacryloxy methoxy group manufactured by Shin-Etsu Chemical Co., Ltd. Octyltrimethoxydecane (product name: KBM-5803). The decane coupling agent used in the component (B) may be used alone or in combination of two or more.

使用於(B)成分之氧化矽填充劑可舉例如熔融氧化矽、普通矽石、球狀氧化矽、破碎氧化矽、結晶性氧化矽、非晶質氧化矽等，無特別限定。從氧化矽填充劑之分散性、熱硬化性樹脂組成物之流動性、硬化物之表面平滑性、介電特性、低熱膨脹率、接著性等之觀點而言，以球狀之熔融氧化矽為佳。又，氧化矽填充劑之平均粒径(不為球狀時，為其平均最大徑)無特別限定，但從提升因比表面積較小所致之硬化後的耐濕性的觀點而言，以0.05至20μm為較佳，以0.1至10μm為更佳，以1至10μm為又更佳。在此，氧化矽填充劑之平均粒徑係指藉由雷射散射繞射式粒度分布測定裝置測定得到之體積基準的中位粒徑。使用於(B)成分之氧化矽填充劑可為單獨或2種以上。 The cerium oxide filler to be used in the component (B) is, for example, a molten cerium oxide, a common vermiculite, a spherical cerium oxide, a crushed cerium oxide, a crystalline cerium oxide, or an amorphous cerium oxide, and is not particularly limited. The spherical molten yttrium oxide is used from the viewpoints of the dispersibility of the cerium oxide filler, the fluidity of the thermosetting resin composition, the surface smoothness of the cured product, the dielectric properties, the low thermal expansion coefficient, and the adhesion. good. Further, the average particle diameter of the cerium oxide filler (the average maximum diameter when it is not spherical) is not particularly limited, but from the viewpoint of improving the moisture resistance after curing due to the small specific surface area, More preferably, it is 0.05 to 20 μm, more preferably 0.1 to 10 μm, still more preferably 1 to 10 μm. Here, the average particle diameter of the cerium oxide filler refers to a volume-based median diameter measured by a laser scattering diffraction type particle size distribution analyzer. The cerium oxide filler used in the component (B) may be used alone or in combination of two or more.

使用上述偶合劑而對氧化矽填充劑進行表面處理之方法並無特別限定，可舉例如乾式法、濕式法等。 The method of surface-treating the cerium oxide filler by using the above coupling agent is not particularly limited, and examples thereof include a dry method and a wet method.

乾式法係將氧化矽填充劑、及相對於氧化矽填充劑之表面積 為適當的量之矽烷偶合劑置入攪拌裝置，在適當的條件下攪拌，或者預先將氧化矽填充劑置入攪拌裝置，在適當的條件下攪拌，同時藉由滴下或噴霧等在原液或溶液添加相對於氧化矽填充劑之表面積為適當的量之矽烷偶合劑並藉由攪拌，而使矽烷偶合劑均勻附著在氧化矽填充劑表面以(藉由使其水解)進行表面處理之方法。攪拌裝置可舉例如亨舍爾混合機(Henschel mixer)等可以高速旋轉進行攪拌/混合的混合機，但無特別限定。 In the dry method, a cerium oxide filler and a decane coupling agent having a suitable surface area with respect to the surface area of the cerium oxide filler are placed in a stirring device, stirred under appropriate conditions, or the cerium oxide filler is placed in a stirring device in advance. Stirring under appropriate conditions, while adding a suitable amount of the decane coupling agent to the stock solution or solution by dropping or spraying, etc., and uniformly stirring the decane coupling agent to the cerium oxide by stirring. The surface of the filler is subjected to a surface treatment (by hydrolysis thereof). The stirring device may be, for example, a Henschel mixer or the like which can be stirred and mixed at a high speed, but is not particularly limited.

濕式法係將相對於要進行表面處理之氧化矽填充劑的表面積為充分量之矽烷偶合劑溶解於水或有機溶劑後，於所得的表面處理溶液中添加氧化矽填充劑，並攪拌成為漿液狀，藉此使矽烷偶合劑與氧化矽填充劑充分反應後，使用過濾或離心分離等，將氧化矽填充劑從表面處理溶液分離並加熱乾燥，進行表面處理之方法。 In the wet method, after a sufficient amount of the decane coupling agent is surface-dissolved in water or an organic solvent with respect to the surface area of the cerium oxide filler to be surface-treated, a cerium oxide filler is added to the obtained surface treatment solution, and stirred into a slurry. After the decane coupling agent is sufficiently reacted with the cerium oxide filler, the cerium oxide filler is separated from the surface treatment solution by filtration or centrifugation, and dried by heating to carry out a surface treatment.

(B)成分可為單獨使用或併用2種以上。 The component (B) may be used alone or in combination of two or more.

(C)成分係對熱硬化性樹脂組成物賦予柔軟性之賦予柔軟性的樹脂(但不包含(A)成分)。(C)成分只要與(A)成分相異即可，並無特別限定，可為樹脂或彈性體。 The component (C) is a resin that imparts flexibility to the thermosetting resin composition (but does not contain the component (A)). The component (C) is not particularly limited as long as it differs from the component (A), and may be a resin or an elastomer.

從介電特性之觀點而言，(C)成分係以苯乙烯系熱塑性彈性體為較佳，從相對於介電特性(尤其tanδ)之溫度依存性(相對於在常溫(25℃)的測定值，在高溫(120℃)之測定值的變化)較小之觀點而言，以氫化苯乙烯系熱塑性彈性體為更佳。又，聚丁二烯經氫化者雖然耐熱性變佳，但溫度依存性有增大之情形。 From the viewpoint of dielectric properties, the component (C) is preferably a styrene-based thermoplastic elastomer, and has a temperature dependence with respect to dielectric properties (especially tan δ) (measurement relative to normal temperature (25 ° C)). The hydrogenated styrene-based thermoplastic elastomer is more preferable from the viewpoint that the value is small in the change in the measured value at a high temperature (120 ° C). Further, although the polybutadiene is hydrogenated, the heat resistance is improved, but the temperature dependency is increased.

作為(C)成分較佳之氫化苯乙烯系熱塑性彈性體係分子中之主鏈的不飽和雙鍵經氫化之苯乙烯系嵌段共聚物，該氫化苯乙烯系嵌段共 聚物可舉例苯乙烯-乙烯/丁烯-苯乙烯嵌段共聚物(SEBS)、或苯乙烯-(乙烯-乙烯/丙烯)-苯乙烯嵌段共聚物(SEEPS)、苯乙烯-乙烯/丙烯-苯乙烯嵌段共聚物(SEPS)等，以SEBS、SEEPS為較佳。因為SEBS或SEEPS之介電特性優異，且與屬於(A)成分之選項之聚苯醚(PPE)、改質PPE等的相溶性佳，可形成具有耐熱性之熱硬化性樹脂組成物之故。再者，苯乙烯系嵌段共聚物亦有助於熱硬化性樹脂組成物之低彈性化，故可對絕緣性膜賦予柔軟性，且適宜在對熱硬化性樹脂組成物之硬化物要求3GPa以下之低彈性的用途。 A hydrogenated styrene block copolymer which is a hydrogenated styrene-based block copolymer which is preferably a hydrogenated styrene-based thermoplastic elastomer in a molecule of the (C) component. The hydrogenated styrene block copolymer is exemplified by styrene-ethylene. /butylene-styrene block copolymer (SEBS), or styrene-(ethylene-ethylene/propylene)-styrene block copolymer (SEEPS), styrene-ethylene/propylene-styrene block copolymer ( SEPS), etc., preferably SEBS and SEEPS. Since SEBS or SEEPS has excellent dielectric properties, and has good compatibility with polyphenylene ether (PPE) and modified PPE which are options of component (A), it can form a thermosetting resin composition having heat resistance. . Further, since the styrene block copolymer contributes to the low elasticity of the thermosetting resin composition, it is possible to impart flexibility to the insulating film, and it is preferable to require 3GPa for the cured product of the thermosetting resin composition. The following low-elastic uses.

(C)成分之重量平均分子量以30,000至200,000為較佳，以80,000至120,000為更佳。重量平均分子量係設為藉由凝膠滲透層析法(GPC)並使用藉由標準聚苯乙烯之檢量線而得的值。(C)成分可單獨使用或併用2種以上。 The weight average molecular weight of the component (C) is preferably from 30,000 to 200,000, more preferably from 80,000 to 120,000. The weight average molecular weight is a value obtained by gel permeation chromatography (GPC) and using a calibration curve of standard polystyrene. The component (C) may be used singly or in combination of two or more.

熱硬化性樹脂組成物(但不包含溶劑)中之全樹脂成分較佳係1至65質量%，更佳係10至40質量%，特佳係20至30質量%。(A)成分及(C)成分以外的樹脂例如可併用環氧樹脂、馬來醯亞胺樹脂、氰酸酯樹脂等。 The total resin component in the thermosetting resin composition (but not including the solvent) is preferably from 1 to 65% by mass, more preferably from 10 to 40% by mass, particularly preferably from 20 to 30% by mass. As the resin other than the component (A) and the component (C), for example, an epoxy resin, a maleimide resin, a cyanate resin or the like can be used in combination.

又，(A)成分係相對於(A)成分與(C)成分之合計100質量份，以10至50質量份為較佳，以20至40質量份為更佳。若(A)成分較少，則硬化物之硬化不足，容易產生剝離強度降低或熱膨脹係數(CTE)增加、耐熱性降低等的不佳情形。若(A)成分較多，則膜較硬且脆，變得容易剝離而有損薄膜性，且硬化物亦變硬且脆，容易產生剝離強度降低、因熱衝擊而容易產生龜裂等之不佳情形。 In addition, the component (A) is preferably 10 to 50 parts by mass, more preferably 20 to 40 parts by mass, per 100 parts by mass of the total of the components (A) and (C). When the component (A) is small, the hardening of the cured product is insufficient, and the peel strength is lowered, the coefficient of thermal expansion (CTE) is increased, and the heat resistance is lowered. When the amount of the component (A) is large, the film is hard and brittle, and the film is easily peeled off to impair the film properties, and the cured product is also hard and brittle, and the peel strength is likely to be lowered, and cracks are likely to occur due to thermal shock. Bad situation.

(B)成分係在熱硬化性樹脂組成物(但不包含溶劑)中較佳為45至75體積%(若為固體氧化矽填充劑，為64至88質量%)，更佳為50至70體積%(若為固體氧化矽填充劑，為69至85質量%)。若(B)成分較少，則無法達成所希望之CTE，若(B)成分較多，則容易降低剝離強度。 The component (B) is preferably 45 to 75 vol% in the thermosetting resin composition (but not including the solvent) (64 to 88% by mass in the case of a solid cerium oxide filler), more preferably 50 to 70. % by volume (69 to 85% by mass in the case of a solid cerium oxide filler). If the component (B) is small, the desired CTE cannot be achieved, and if the component (B) is large, the peel strength is likely to be lowered.

(C)成分係相對於(A)成分與(C)成分之合計100質量份，以90至50質量份為較佳，以80至60質量份為更佳。 The component (C) is preferably 90 to 50 parts by mass, more preferably 80 to 60 parts by mass, per 100 parts by mass of the total of the components (A) and (C).

又，在不損及本發明之效果的範圍內，熱硬化性樹脂組成物可包含：作為(A)成分之硬化促進劑的有機過氧化物、矽烷偶合劑等偶合劑(整體摻混)、阻燃劑、增黏劑、消泡劑、流動調整劑、揺變劑、分散劑、抗氧化劑、阻燃劑等添加劑。矽烷偶合劑可舉例如對苯乙烯基三甲氧基矽烷(信越化學工業(股)製、KBM-1403)、雙(三乙氧基矽基丙基)四硫醚(信越化學工業(股)製、KBE-846)、辛烯基三甲氧基矽烷(信越化學工業(股)製、KBM-1083)、甲基丙烯醯氧基辛基三甲氧基矽烷(信越化學工業(股)製、KBM-5803)、3-甲基丙烯醯氧基丙基三甲氧基矽烷(信越化學工業(股)製、KBM-503)、3-甲基丙烯醯氧基丙基三乙氧基矽烷(信越化學工業(股)製、KBE-503)、3-環氧丙氧基丙基三甲氧基矽烷(信越化學工業(股)製、KBM-403)、3-環氧丙氧基丙基三乙氧基矽烷(信越化學工業(股)製、KBE-403)等。阻燃劑可列舉膦酸金屬鹽(Clariant Japan製、OP-935)等。 In addition, the thermosetting resin composition may include a coupling agent such as an organic peroxide or a decane coupling agent as a curing accelerator of the component (A) (integrally blended), and the like, in a range that does not impair the effects of the present invention. Additives such as flame retardants, tackifiers, defoamers, flow regulators, enthalpy modifiers, dispersants, antioxidants, and flame retardants. Examples of the decane coupling agent include p-styryltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-1403) and bis(triethoxymethylpropyl)tetrasulfide (Shin-Etsu Chemical Co., Ltd.). , KBE-846), octenyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-1083), methacryloxymethoxyoctyltrimethoxydecane (Shin-Etsu Chemical Co., Ltd., KBM- 5803), 3-methacryloxypropyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-503), 3-methacryloxypropyltriethoxydecane (Shin-Etsu Chemical Industry) (Stock), KBE-503), 3-glycidoxypropyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403), 3-glycidoxypropyltriethoxy Decane (Shin-Etsu Chemical Industry Co., Ltd., KBE-403), etc. Examples of the flame retardant include a phosphonic acid metal salt (manufactured by Clariant Japan, OP-935).

熱硬化性樹脂組成物可藉由使構成樹脂組成物之(A)、(B)、(C)成分等原料溶解或分散於有機溶劑而製作。此等之原料的溶解或分散等之裝置無特別限定，可使用具備加熱裝置之攪拌機、溶解機、擂潰機、三輥研磨機、球研磨機、行星式混合機、珠磨機等。又，亦可適當組合此等 裝置而使用。 The thermosetting resin composition can be produced by dissolving or dispersing a raw material such as components (A), (B), and (C) constituting the resin composition in an organic solvent. The apparatus for dissolving or dispersing the raw materials is not particularly limited, and a stirrer, a dissolver, a pulverizer, a three-roll mill, a ball mill, a planetary mixer, a bead mill, or the like including a heating device can be used. Further, these devices can be used in combination as appropriate.

就有機溶劑而言，芳香族系溶劑可舉例如甲苯、二甲苯等，酮系溶劑可舉例如甲乙酮、甲基異丁酮等。有機溶劑可單獨或組合2種以上使用。從作業性之點而言，熱硬化性樹脂組成物較佳為黏度在200至3000mPa‧s的範圍。黏度係使用E型黏度計，以旋轉數50rpm、25℃測定之值。 The aromatic solvent may, for example, be toluene or xylene, and the ketone solvent may, for example, be methyl ethyl ketone or methyl isobutyl ketone. The organic solvent may be used singly or in combination of two or more. The thermosetting resin composition preferably has a viscosity in the range of 200 to 3000 mPa‧s from the viewpoint of workability. The viscosity was measured using an E-type viscometer at a number of revolutions of 50 rpm and 25 °C.

所得之熱硬化性樹脂組成物係具有優異之耐熱性、耐濕可靠性、及耐吸濕回焊性。 The obtained thermosetting resin composition has excellent heat resistance, moisture resistance reliability, and moisture absorption reflow resistance.

[絕緣性膜]  [insulating film]  

本發明之絕緣性膜係包含上述之熱硬化性樹脂組成物。絕緣性膜係從熱硬化性樹脂組成物形成為所希望之形狀。具體而言，絕緣性膜係將上述之熱硬化性樹脂組成物塗佈於支撐體上之後，進行乾燥而得。支撐體並無特別限定，可舉例如銅、鋁等之金屬箔、聚酯樹脂、聚乙烯樹脂、聚對苯二甲酸乙二酯樹脂(PET)等之有機膜等。支撐體亦可經聚矽氧系化合物等離型處理。又，熱硬化性樹脂組成物可以各種形狀使用，形狀並無特別限定。 The insulating film of the present invention comprises the above-described thermosetting resin composition. The insulating film is formed into a desired shape from the thermosetting resin composition. Specifically, the insulating film is obtained by applying the above-mentioned thermosetting resin composition onto a support and drying it. The support is not particularly limited, and examples thereof include metal foils such as copper and aluminum, organic resins such as polyester resins, polyethylene resins, and polyethylene terephthalate resins (PET). The support may also be subjected to a release treatment by a polyoxymethylene compound. Further, the thermosetting resin composition can be used in various shapes, and the shape is not particularly limited.

將熱硬化性樹脂組成物塗佈於支撐體之方法並無特別限定，但從薄膜化/控制膜厚之點而言，以凹版法、狹縫式模具法、刮刀法為較佳。藉由狹縫式模具法，可獲得厚度為5至300μm之熱硬化性樹脂組成物的未硬化膜，亦即絕緣性膜。 The method of applying the thermosetting resin composition to the support is not particularly limited, but a gravure method, a slit mold method, or a doctor blade method is preferable from the viewpoint of thin film formation/control film thickness. An uncured film of a thermosetting resin composition having a thickness of 5 to 300 μm, that is, an insulating film, can be obtained by a slit mold method.

乾燥條件係可依照使用於熱硬化性樹脂組成物之有機溶劑的種類、量、塗布之厚度等而適當設定，例如可設為50至120℃、1至60 分鐘左右。如此方式所得之絕緣性膜具有良好的保存安定性。又，絕緣性膜可在所希望之時機從支撐體剝離。 The drying conditions can be appropriately set depending on the type and amount of the organic solvent used in the thermosetting resin composition, the thickness of the coating, and the like, and can be, for example, about 50 to 120 ° C for about 1 to 60 minutes. The insulating film obtained in this manner has good storage stability. Further, the insulating film can be peeled off from the support at a desired timing.

絕緣性膜之硬化係例如可以150至230℃、30至180分鐘之條件進行。本發明之層間絕緣性膜可以與上述同樣之方法製作且進行硬化。使用絕緣性膜作為層間絕緣性膜時，層間絕緣性膜之硬化係可在以銅箔等形成配線之基板間夾住層間絕緣性膜後進行，亦可在將以銅箔等形成配線之層間絕緣性膜適當積層後進行。又，絕緣性膜亦可使用作為保護基板上之配線的被覆層膜，此時之硬化條件亦同樣。又，亦可使熱硬化性樹脂組成物同樣地硬化。又，硬化時，亦可以例如1至5MPa之壓力進行擠壓硬化。 The hardening of the insulating film can be carried out, for example, at 150 to 230 ° C for 30 to 180 minutes. The interlayer insulating film of the present invention can be produced and cured in the same manner as described above. When an insulating film is used as the interlayer insulating film, the curing of the interlayer insulating film may be performed after sandwiching the interlayer insulating film between the substrates on which the wiring is formed, such as copper foil, or between the layers in which wiring is formed by copper foil or the like. The insulating film is formed after lamination. Further, as the insulating film, a coating film as a wiring for protecting the substrate can be used, and the curing conditions at this time are also the same. Further, the thermosetting resin composition can be cured in the same manner. Further, at the time of curing, extrusion hardening may be performed, for example, at a pressure of 1 to 5 MPa.

[多層配線板]  [Multilayer wiring board]  

本發明之多層配線板係具有上述熱硬化性樹脂組成物之硬化物、上述之絕緣性膜或層間絕緣性膜之硬化物。本發明之印刷配線板係使用上述之熱硬化性樹脂組成物、上述之絕緣性膜或層間絕緣性膜，並使此硬化而製作。該印刷配線板係藉由上述熱硬化性樹脂組成物之硬化物、上述絕緣性膜或層間絕緣性膜之硬化物，而具有優異之耐熱性、耐濕可靠性、及耐吸濕回焊性。多層配線板之中，可舉例如微波、毫米波通訊用之基板，尤其是車載用毫米波雷達基板等高頻用途的印刷配線板等。多層配線板之製造方法無特別限定，可採用與使用一般的預浸物而製作印刷配線板時同樣之方法。 The multilayer wiring board of the present invention has a cured product of the above-mentioned thermosetting resin composition, a cured product of the above-mentioned insulating film or interlayer insulating film. The printed wiring board of the present invention is produced by using the above-described thermosetting resin composition, the above-mentioned insulating film or interlayer insulating film, and curing the film. The printed wiring board has excellent heat resistance, moisture resistance reliability, and moisture absorption reflow resistance by the cured product of the thermosetting resin composition, the insulating film or the cured film of the interlayer insulating film. Among the multilayer wiring boards, for example, a substrate for microwave or millimeter wave communication, in particular, a printed wiring board for high frequency use such as a millimeter wave radar substrate for vehicle use. The method for producing the multilayer wiring board is not particularly limited, and the same method as in the case of producing a printed wiring board using a general prepreg can be employed.

[半導體裝置]  [semiconductor device]  

本發明之半導體裝置係使用上述之熱硬化性樹脂組成物、上述之絕緣性膜或層間絕緣性膜，並使此硬化而製作。該半導體裝置係藉由上述熱硬化性樹脂組成物之硬化物、上述絕緣性膜或層間絕緣性膜之硬化物，而具有優異之耐熱性、耐濕可靠性、及耐吸濕回焊性。在此，所謂半導體裝置係指可利用半導體特性而發揮功能之所有裝置，包含電子零件、半導體電路、組裝有此等之模組、電子機器等。 In the semiconductor device of the present invention, the above-mentioned thermosetting resin composition, the above-mentioned insulating film or interlayer insulating film is used and cured. The semiconductor device has excellent heat resistance, moisture resistance reliability, and moisture absorption reflow resistance by the cured product of the thermosetting resin composition, the insulating film or the cured film of the interlayer insulating film. Here, the semiconductor device refers to all devices that can function by using semiconductor characteristics, and includes electronic components, semiconductor circuits, modules in which these are incorporated, electronic devices, and the like.

(實施例)  (Example)  

藉由實施例來說明本發明，但本發明不限定於此。又，在以下之實施例中，只要無特別聲明，份、%表示質量份、質量%。 The present invention will be described by way of examples, but the invention is not limited thereto. Further, in the following examples, the parts and % represent parts by mass and mass% unless otherwise stated.

[實施例1至8、比較例1至6]  [Examples 1 to 8 and Comparative Examples 1 to 6]   〈熱硬化性樹脂組成物之製作〉  <Production of Thermosetting Resin Composition>  

以表1至2所示之配方，在容器中量取各成分，以自轉/公轉式之攪拌機(Mazerustar(註冊商標)、Kurabo製)攪拌混合3分鐘之後，使用珠磨機進行分散，以甲苯調整黏度以調整熱硬化性樹脂組成物。其次，將熱硬化性樹脂組成物藉由塗布機在聚對苯二甲酸乙二酯(PET)基材上塗佈成為50至100μm之厚度，在100至120℃乾燥10至20分鐘，以進行薄膜化。 In the formulation shown in Tables 1 to 2, each component was weighed and stirred in a spinning/revolving mixer (Mazerustar (registered trademark), manufactured by Kurabo) for 3 minutes, and then dispersed using a bead mill to toluene. The viscosity is adjusted to adjust the thermosetting resin composition. Next, the thermosetting resin composition is coated on a polyethylene terephthalate (PET) substrate by a coater to a thickness of 50 to 100 μm, and dried at 100 to 120 ° C for 10 to 20 minutes to carry out Thin film.

在此，表1至2記載之OPE-2St 2200係使用三菱Gas化學(股)製苯乙烯末端改質PPE(分子量(Mn)：2200)，G1652係使用Craton Polymer製SEBS(苯乙烯比30%彈性體)，H1052係使用旭化成(股)製SEBS(苯乙烯比20%彈性體)，FB-3SDX係使用Denka(股)製球狀氧化矽(平均粒径：3.4μm)， MP-8FS係使用龍森(股)製球狀氧化矽(平均粒径：0.5μm)，SFP-130MC係使用Denka(股)製球狀氧化矽(平均粒径：0.7μm)，KBM-1403係使用信越化學(股)製對苯乙烯基三甲氧基矽烷，KBE-846係使用信越化學(股)製雙(三乙氧基矽基丙基)四硫醚，KBM-1083係使用信越化學(股)製7-辛烯基三甲氧基矽烷，KBM-5803係使用信越化學(股)製8-甲基丙烯醯氧基辛基三甲氧基矽烷，KBM-503係使用信越化學(股)製3-甲基丙烯醯氧基丙基三甲氧基矽烷，KBE-3083係使用信越化學(股)製辛基三乙氧基矽烷。 Here, the OPE-2St 2200 described in Tables 1 to 2 is a styrene-terminated PPE (molecular weight (Mn): 2,200) manufactured by Mitsubishi Gas Chemical Co., Ltd., and a SEBS (30% by weight of styrene) is used for the G1652 system. Elastomer), H1052 is made of Asahi Kasei (stock) SEBS (styrene ratio 20% elastomer), FB-3SDX is made of Denka (strand) spherical yttrium oxide (average particle size: 3.4 μm), MP-8FS system Spherical yttrium oxide (average particle size: 0.5 μm) made of Ronson (s), SFP-130MC spheroidal yttrium oxide (average particle size: 0.7 μm) made of Denka (strand), and Shin-Etsu Chemical Co., Ltd. (Fe) compound p-styryl trimethoxy decane, KBE-846 system using Shin-Etsu Chemical Co., Ltd. bis (triethoxymethyl propyl) tetrasulfide, KBM-1083 system using Shin-Etsu Chemical Co., Ltd. 7-octenyltrimethoxydecane, KBM-5803 is 8-methylpropenyloxyoctyltrimethoxydecane manufactured by Shin-Etsu Chemical Co., Ltd., KBM-503 is manufactured by Shin-Etsu Chemical Co., Ltd. 3-A Alkyl methoxy propyl trimethoxy decane, KBE-3083 is a octyl triethoxy decane manufactured by Shin-Etsu Chemical Co., Ltd.

[評估方法]  [evaluation method]   〈剝離強度〉  <stripping strength>  

在2片Cu箔(福田金屬箔粉工業(股)製、品名：CF-T9FZSV)夾住從PET基材剝離之膜，在200℃以3MPa進行擠壓硬化1小時後，切成1cm×10cm而作為試驗片，使用自動繪圖儀(Autograph)測定一者之Cu箔的180°剝離強度。在此，S面係銅箔亮面(光澤面)彼此之間的剝離強度，M面係銅箔霧面(粗化面)彼此之間的剝離強度。S面較佳為2.5N/cm以上，M面較佳為5N/cm以上。 The film peeled off from the PET substrate was sandwiched between two sheets of Cu foil (Fukuda Metal Foil Powder Co., Ltd., product name: CF-T9FZSV), and subjected to press hardening at 3 ° C for 1 hour at 200 ° C, and then cut into 1 cm × 10 cm. As a test piece, the 180° peel strength of one of the Cu foils was measured using an automatic plotter (Autograph). Here, the peeling strength between the glossy faces (glossy faces) of the S-face copper foil and the matte strength of the matte surface (roughened faces) of the M-faced copper foils. The S surface is preferably 2.5 N/cm or more, and the M surface is preferably 5 N/cm or more.

〈熱膨脹係數(Z方向CTE)〉  <Coefficient of Thermal Expansion (Z-direction CTE)>  

將從PET基材剝離之膜積層為約2mm之厚度，在200℃以1MPa進行擠壓硬化1小時後，切成5mm平方而作為試驗片，使用Netzsch Japan(股) 製TMA4000S測定厚度方向之熱膨脹係數(Z方向CTE)。熱膨脹係數以70ppm/℃以下為較佳。 The film laminate peeled off from the PET substrate was a thickness of about 2 mm, and was subjected to press hardening at 1 MPa for 1 hour at 200 ° C, and then cut into a square of 5 mm to prepare a test piece, and the thermal expansion in the thickness direction was measured using a TMS 4000S manufactured by Netzsch Japan Co., Ltd. Coefficient (Z direction CTE). The coefficient of thermal expansion is preferably 70 ppm/°C or less.

〈介電特性〉  <Dielectric properties>  

將從PET基材剝離之膜在200℃以1MPa進行擠壓硬化1小時後，裁切成70×50mm，藉由分離式介電體共振器(split post dielectric resonator：SPDR)以介電體共振頻率10GHz測定常溫常濕之比介電率(ε)、介電損耗正切(tanδ)。若比介電率為3.5以下，介電損耗正切為0.0030以下，則較佳。將結果表示於表1至2中。 The film peeled from the PET substrate was subjected to press hardening at 1 ° C for 1 hour at 200 ° C, and then cut into 70 × 50 mm, and dielectric resonance was performed by a split-post dielectric resonator (SPDR). The specific dielectric constant (ε) and the dielectric loss tangent (tan δ) of the normal temperature and the normal humidity were measured at a frequency of 10 GHz. If the specific dielectric constant is 3.5 or less and the dielectric loss tangent is 0.0030 or less, it is preferable. The results are shown in Tables 1 to 2.

〈耐濕可靠性(tanδ變化)〉  <Humidity resistance reliability (tan δ change)>  

將測定過上述之介電特性的硬化膜放置於85℃/85%RH之恆溫恆濕槽中1000小時後，在常溫常濕藉由SPDR法(10GHz)測定tanδ，求出tanδ之變化量與變化率。若變化率若80%以下，則較佳。將結果表示於表1至2中。 The cured film having the above dielectric properties was placed in a constant temperature and humidity chamber at 85 ° C / 85% RH for 1000 hours, and tan δ was measured by SPDR method (10 GHz) at room temperature and humidity to determine the amount of change in tan δ and Rate of change. It is preferable if the rate of change is 80% or less. The results are shown in Tables 1 to 2.

〈焊料耐熱性〉  <Solder heat resistance>  

在2片Cu箔(CF-T9FZSV)夾住從PET基材剝離之膜，在200℃以3MPa進行擠壓硬化1小時而接著後，切成3cm×3cm而作為試驗片，在焊料浴中以表3所示之各溫度浮游60秒鐘，以目視確認出有無膨脹產生。在膨脹等外觀無變化時判定為「OK」(合格)，觀察到膨脹時判定為「NG」(不合格)。若焊料耐熱性為270℃以上，則較佳。將結果表示於表3。 The film peeled off from the PET substrate was sandwiched between two Cu foils (CF-T9FZSV), and extrusion-hardened at 3 MPa for 1 hour at 200 ° C, and then cut into 3 cm × 3 cm to prepare a test piece in a solder bath. The temperatures shown in Table 3 were floated for 60 seconds, and it was visually confirmed whether or not expansion occurred. When there was no change in appearance such as expansion, it was judged as "OK" (passed), and when expansion was observed, it was judged as "NG" (failed). It is preferable if the solder heat resistance is 270 ° C or more. The results are shown in Table 3.

〈耐吸濕回焊性〉  <Water absorption reflow resistance>  

在2片Cu箔(CF-T9FZSV)夾住從PET基材剝離之膜，在200℃以3MPa進行擠壓硬化1小時而接著後，切成1cm×10cm而作為試驗片，在壓力鍋試驗(PCT：121℃、2氣壓飽和水蒸氣)16小時後，通過焊料回焊爐後剝離Cu箔，以光學顯微鏡照片確認膜有無膨脹產生。膨脹之面積未達5%時判定為「◎」(非常良好)，5%以上且未達30%時判定為「○」(良好)，30%以上時判定為「×」(差)。將結果表示在表4中。又，焊料回焊爐係設置5座加熱器且爐長約2.5m，其中1座設定為峰值溫度的260℃，將爐內設為恆溫狀態後，使試驗片以輸送帶速度0.35m/min通過。 The film peeled off from the PET substrate was sandwiched between two Cu foils (CF-T9FZSV), and subjected to extrusion hardening at 3 ° C for 1 hour at 200 ° C, and then cut into 1 cm × 10 cm to be used as a test piece in a pressure cooker test (PCT). After 16 hours at 121 ° C and 2 atmospheres of saturated water vapor, the Cu foil was peeled off by a solder reflow furnace, and the presence or absence of swelling of the film was confirmed by an optical microscope photograph. When the area of expansion is less than 5%, it is judged as "◎" (very good), and when it is 5% or more and less than 30%, it is judged as "○" (good), and when it is 30% or more, it is judged as "x" (poor). The results are shown in Table 4. In addition, the solder reflow furnace is equipped with five heaters and the furnace length is about 2.5 m, one of which is set to 260 ° C of the peak temperature. After the furnace is set to a constant temperature state, the test piece is conveyed at a conveyor speed of 0.35 m/min. by.

在此，填充劑比率(體積百分率(Vol%))係如以下求出。(填充劑體積)=(氧化矽填充劑質量)/(氧化矽填充劑密度)、(氧化矽填充劑以外原材料之體積)=(氧化矽填充劑以外原材料之質量合計)/(氧化矽填充劑以外原材料之密度)、填充劑比率(體積百分率(Vol%))=[(氧化矽填充劑體積)/{(氧化矽填充劑體積)+(氧化矽填充劑以外原材料之體積)}]×100。又，氧化矽填充劑之密度為2.2g/cm3，氧化矽填充劑以外原材料(有機物) 之密度係大約計算為1.0g/cm3。 Here, the filler ratio (volume percentage (Vol%)) was determined as follows. (filler volume) = (manganese oxide filler mass) / (yttria filler density), (volume of raw materials other than cerium oxide filler) = (total mass of raw materials other than cerium oxide filler) / (yttria filler) Density of raw materials), filler ratio (vol%) ([(矽 矽 矽 矽 体积 / / / / / / + + + + + + + + + + + + + + } } } } } } 100 100 100 100 100 100 100 100 100 100 100 100 100 . Further, the density of the cerium oxide filler was 2.2 g/cm 3 , and the density of the raw material (organic matter) other than the cerium oxide filler was approximately 1.0 g/cm 3 .

從表1至4可知，實施例1至8係在剝離強度、熱膨脹係數、比介電率(ε)、介電損耗正切(tanδ)、耐濕可靠性(tanδ之變化量、變化率)、焊料耐熱性、耐久熱回焊性全部為良好的結果。相對於此，不使用(B)成分之比較例1至3係耐濕可靠性之變化率大。不使用(B)成分之比較例4至6 係焊料耐熱性差。不使用(B)成分之比較例3至6係耐吸濕回焊性之結果亦差。 As is clear from Tables 1 to 4, Examples 1 to 8 are peel strength, thermal expansion coefficient, specific dielectric constant (ε), dielectric loss tangent (tan δ), moisture resistance reliability (change amount of tan δ, rate of change), Solder heat resistance and durable heat reflowability are all good results. On the other hand, in Comparative Examples 1 to 3 in which the component (B) was not used, the rate of change in moisture resistance reliability was large. Comparative Examples 4 to 6 in which the component (B) was not used were inferior in solder heat resistance. The results of Comparative Examples 3 to 6 which did not use the component (B) were also poor in moisture reflow resistance.

[產業上之利用可能性]  [Industry use possibility]  

本發明之熱硬化性樹脂組成物係可形成耐熱性、耐濕可靠性、耐吸濕回焊性優異之絕緣性膜、層間絕緣性膜，為非常有用者。本發明之多層配線板係藉由上述熱硬化性樹脂組成物之硬化物、上述絕緣性膜或層間絕緣性膜之硬化物，而具有優異之耐熱性、耐濕可靠性、耐吸濕回焊性。本發明之半導體裝置係藉由上述熱硬化性樹脂組成物之硬化物、上述絕緣性膜或層間絕緣性膜之硬化物，而具有優異之耐濕可靠性、耐吸濕回焊性，故適宜在高頻用途。 The thermosetting resin composition of the present invention is excellent in heat resistance, moisture resistance reliability, and an insulating film and an interlayer insulating film which are excellent in moisture absorption reflow resistance. The multilayer wiring board of the present invention has excellent heat resistance, moisture resistance reliability, and moisture reflow resistance by the cured product of the thermosetting resin composition, the insulating film or the cured film of the interlayer insulating film. . The semiconductor device of the present invention is excellent in moisture resistance reliability and moisture absorption reflow resistance by the cured product of the thermosetting resin composition, the insulating film or the cured film of the interlayer insulating film. High frequency use.

Claims (8)

一種熱硬化性樹脂組成物，係包含：(A)在末端具有不飽和雙鍵之熱硬化性樹脂；(B)經以通式(1)所示之矽烷偶合劑表面處理的氧化矽填充劑， 式中，R 1至R 3分別獨立地為碳數1至3之烷基，R 4係至少在末端具有不飽和雙鍵之官能基，n為5至9；及(C)賦予柔軟性的樹脂(但不包含(A)成分)。 A thermosetting resin composition comprising: (A) a thermosetting resin having an unsaturated double bond at a terminal; (B) a cerium oxide filler surface-treated with a decane coupling agent represented by the formula (1) , Wherein R 1 to R 3 are each independently an alkyl group having 1 to 3 carbon atoms, R 4 is a functional group having an unsaturated double bond at least at the terminal, n is 5 to 9; and (C) imparts flexibility. Resin (but not (A)). 如申請專利範圍第1項所述之熱硬化性樹脂組成物，其中，通式(1)之R 4為乙烯基或(甲基)丙烯醯基。 The thermosetting resin composition according to claim 1, wherein R 4 of the formula (1) is a vinyl group or a (meth)acryl fluorenyl group. 如申請專利範圍第1或2項所述之熱硬化性樹脂組成物，其中，(C)成分為苯乙烯系熱塑性彈性體。  The thermosetting resin composition according to claim 1 or 2, wherein the component (C) is a styrene-based thermoplastic elastomer.   一種絕緣性膜，係包含申請專利範圍第1至3項中任一項所述之熱硬化性樹脂組成物。  An insulating film comprising the thermosetting resin composition according to any one of claims 1 to 3.   一種層間絕緣性膜，係包含申請專利範圍第1至3項中任一項所述之熱硬化性樹脂組成物。  An interlayer insulating film comprising the thermosetting resin composition according to any one of claims 1 to 3.   一種硬化物，係申請專利範圍第1至3項中任一項所述之熱硬化性樹脂組成物的硬化物、申請專利範圍第4項所述之絕緣性膜或申請專利範圍第5項所述之層間絕緣性膜的硬化物。  A cured product of the thermosetting resin composition according to any one of claims 1 to 3, the insulating film described in claim 4, or the fifth aspect of the patent application. A cured product of the interlayer insulating film.   一種多層配線板，係具有：申請專利範圍第1至3項中任一項所述之熱硬化性樹脂組成物的硬化物、申請專利範圍第4項所述之絕緣性膜或申請專利範圍第5項所述之層間絕緣性膜的硬化物。  A multilayer wiring board comprising: a cured product of a thermosetting resin composition according to any one of claims 1 to 3; an insulating film according to item 4 of the patent application or a patent application scope A cured product of the interlayer insulating film according to item 5.   一種半導體裝置，係具有：申請專利範圍第1至3項中任一項所述之熱硬化性樹脂組成物的硬化物、申請專利範圍第4項所述之絕緣性膜或申請專利範圍第5項所述之層間絕緣性膜的硬化物。  A semiconductor device comprising: a cured product of a thermosetting resin composition according to any one of claims 1 to 3, an insulating film according to claim 4, or a patent application scope 5 A cured product of the interlayer insulating film according to the item.  
TW107141680A 2017-11-24 2018-11-22 Heat curable resin composition, insulation film, interlayer insulation film, multilayer wiring board and semiconductor apparatus TWI772562B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017-225470 2017-11-24
JP2017225470 2017-11-24

Publications (2)

Publication Number Publication Date
TW201930463A true TW201930463A (en) 2019-08-01
TWI772562B TWI772562B (en) 2022-08-01

Family

ID=66631558

Family Applications (1)

Application Number Title Priority Date Filing Date
TW107141680A TWI772562B (en) 2017-11-24 2018-11-22 Heat curable resin composition, insulation film, interlayer insulation film, multilayer wiring board and semiconductor apparatus

Country Status (5)

Country Link
JP (1) JP7204214B2 (en)
KR (1) KR102657819B1 (en)
CN (1) CN111372960B (en)
TW (1) TWI772562B (en)
WO (1) WO2019103082A1 (en)

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6352782B2 (en) * 1999-12-01 2002-03-05 General Electric Company Poly(phenylene ether)-polyvinyl thermosetting resin
JP4561534B2 (en) 2005-08-25 2010-10-13 パナソニック電工株式会社 Polyphenylene ether resin composition, prepreg and laminate
JP5093059B2 (en) * 2008-11-06 2012-12-05 日立化成工業株式会社 Resin composition, prepreg, laminate and printed circuit board
JP2013111758A (en) * 2011-11-25 2013-06-10 Canon Inc Printing apparatus and colorimetry apparatus
JP5885585B2 (en) * 2012-05-21 2016-03-15 昭和電工株式会社 Curable composition and cured product thereof
JP6594054B2 (en) * 2015-06-18 2019-10-23 太陽インキ製造株式会社 Photocurable resin composition, dry film, cured product and printed wiring board
JP6672630B2 (en) * 2015-08-07 2020-03-25 味の素株式会社 Resin composition
JP6638380B2 (en) * 2015-12-22 2020-01-29 日立化成株式会社 Pre-supply type underfill material and cured product thereof, electronic component device and method of manufacturing the same

Also Published As

Publication number Publication date
JPWO2019103082A1 (en) 2020-12-03
CN111372960B (en) 2023-01-24
KR20200079508A (en) 2020-07-03
KR102657819B1 (en) 2024-04-15
CN111372960A (en) 2020-07-03
JP7204214B2 (en) 2023-01-16
WO2019103082A1 (en) 2019-05-31
TWI772562B (en) 2022-08-01

Similar Documents

Publication Publication Date Title
JP7202691B2 (en) Resin compositions, films, laminates and semiconductor devices
US9872382B2 (en) Low dielectric composite material and laminate and printed circuit board thereof
TWI589686B (en) Low-dielectric phosphorus-containing flame retardant resin composition and its preparation method and application
TWI519602B (en) Low dielectric resin composition and the application of its resin film, semi-cured film and circuit board
WO2016076167A1 (en) Resin composition, and insulating film and semiconductor device using same
JP6675183B2 (en) Thermosetting resin composition, thermosetting resin film, printed wiring board, and semiconductor device
JP7264485B2 (en) Thermosetting resin composition, insulating film, interlayer insulating film, multilayer wiring board, and semiconductor device
TWI818994B (en) Thermosetting resin compositions, films containing the same, and multilayer wiring boards using the same
WO2023042578A1 (en) Resin composition, and printed wiring board, cured product, prepreg, and electronic component for high frequency in which same is used
CN109971152B (en) Polyphenylene ether resin composition, prepreg, laminate, and printed wiring board
TW201930463A (en) Heat curable resin composition, insulation film, interlayer insulation film, multilayer wiring board and semiconductor apparatus
WO2024034398A1 (en) Resin composition, cured product in which resin composition is used, prepreg, printed wiring board, and electronic component for high frequencies
KR20240055726A (en) Resin compositions, printed wiring boards, cured products, prepregs, and high-frequency electronic components using the same
KR20160095959A (en) Adhesive resin composition, adhesive film, and flexible metal laminate
TW202411282A (en) Resin compositions, and cured products, prepregs, printed circuit boards and high-frequency electronic components using the same
CN117980362A (en) Resin composition, and printed wiring board, cured product, prepreg, and high-frequency electronic component using same
JP2021054889A (en) Modified hydrogenated polyolefin, resin composition, insulating film, semiconductor device, and method for producing modified hydrogenated polyolefin
JP2004059703A (en) Epoxy resin composition, prepreg and laminate
JP2002128977A (en) Curable polyvinyl benzyl ether resin composition