TWI829708B - Curable resin composition and electronic device - Google Patents

Curable resin composition and electronic device Download PDF

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TWI829708B
TWI829708B TW108120128A TW108120128A TWI829708B TW I829708 B TWI829708 B TW I829708B TW 108120128 A TW108120128 A TW 108120128A TW 108120128 A TW108120128 A TW 108120128A TW I829708 B TWI829708 B TW I829708B
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curable resin
epoxy resin
groups
resin composition
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TW202000767A (en
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中村真也
石黒正
大下毅
遠藤由則
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日商力森諾科股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • 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
    • C08G59/20—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 epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/38—Epoxy compounds containing three or more epoxy groups together with di-epoxy compounds
    • 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
    • C08G59/62—Alcohols or phenols
    • 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
    • C08G59/68—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 catalysts used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape

Abstract

A curable resin composition, comprising a curable resin and a compound represented by the following Formula (1): wherein, in Formula (1), each of R1 to R3 independently represents a monovalent hydrocarbon group.

Description

硬化性樹脂組成物及電子零件裝置Curable resin compositions and electronic components and devices

本發明是有關於一種硬化性樹脂組成物及電子零件裝置。 The present invention relates to a curable resin composition and an electronic component device.

伴隨近年來的電子設備的小型化、輕量化、高性能化等，不斷推進安裝的高密度化。藉此，電子零件裝置的主流自現有的針腳***型的封裝向積體電路(Integrated Circuit，IC)、大型積體電路(Large Scale Integration，LSI)等表面安裝型的封裝變化。 In recent years, with the miniaturization, weight reduction, and performance improvement of electronic equipment, the density of installation has been continuously promoted. As a result, the mainstream of electronic component devices has changed from the existing pin insertion type packaging to surface mounting type packaging such as integrated circuit (IC) and large scale integrated circuit (LSI).

表面安裝型封裝的安裝方法與現有的針腳***型封裝不同。即於將針腳安裝於配線板時，現有的針腳***型封裝是將針腳***配線板後自配線板的背面進行焊接，因此封裝未直接暴露於高溫下。但是，於表面安裝型封裝中，電子零件裝置整體是利用焊料浴、回焊裝置等進行處理，因此封裝直接暴露於焊接溫度(回焊溫度)下。結果，於封裝吸濕的情況下，於焊接時因吸濕而引起水分急遽膨脹，所產生的蒸氣壓作為剝離應力發揮作用，從而於元件、引線框架等***物與密封材之間產生剝離，有 時成為封裝裂紋、電氣特性不良等的原因。因此，期望開發一種相對於***物的接著性優異、進而焊料耐熱性(耐回焊性)優異的密封材料。 The installation method of the surface mount type package is different from the existing pin insertion type package. That is, when the pins are installed on the wiring board, in the existing pin insertion type package, the pins are inserted into the wiring board and then welded from the back of the wiring board, so the package is not directly exposed to high temperature. However, in surface mount packages, the entire electronic component device is processed using a solder bath, a reflow device, etc., so the package is directly exposed to soldering temperature (reflow temperature). As a result, when the package absorbs moisture, moisture absorption causes rapid expansion of the moisture during soldering, and the vapor pressure generated acts as peeling stress, causing peeling between the components, lead frames, and other interposers and the sealing material. have This may cause package cracks, poor electrical characteristics, etc. Therefore, it is desired to develop a sealing material that is excellent in adhesion to the insert and has excellent solder heat resistance (reflow resistance).

為了應對所述要求，作為密封材中所含的無機填充材的改質材，研究使用矽烷偶合劑。具體而言，研究含環氧基的矽烷偶合劑或含胺基的矽烷偶合劑的使用(例如，參照專利文獻1)、含硫原子的矽烷偶合劑的使用(例如，參照專利文獻2)等。 In order to meet the above requirements, the use of a silane coupling agent as a modified material for the inorganic filler contained in the sealing material has been studied. Specifically, the use of epoxy group-containing silane coupling agents or amine group-containing silane coupling agents (for example, refer to Patent Document 1), the use of sulfur atom-containing silane coupling agents (for example, refer to Patent Document 2), and the like are studied. .

[現有技術文獻] [Prior art documents]

[專利文獻] [Patent Document]

[專利文獻1]日本專利特開平11-147939號公報 [Patent Document 1] Japanese Patent Application Laid-Open No. 11-147939

[專利文獻2]日本專利特開2000-103940號公報 [Patent Document 2] Japanese Patent Application Publication No. 2000-103940

但是，在使用含環氧基的矽烷偶合劑或含胺基的矽烷偶合劑的方法中，有時引線框架的表面對金屬的接著性的提高效果不充分。另外，於使用含硫原子的矽烷偶合劑的情況下，存在對金屬(特別是金、銀等貴金屬)的接著性的提高效果不充分的問題。 However, in the method using an epoxy group-containing silane coupling agent or an amine group-containing silane coupling agent, the effect of improving the adhesion of the surface of the lead frame to the metal may not be sufficient. In addition, when a silane coupling agent containing a sulfur atom is used, there is a problem that the effect of improving the adhesion to metals (especially noble metals such as gold and silver) is insufficient.

本發明鑑於所述情況，其課題在於提供於硬化狀態下對金屬的接著性優異的硬化性樹脂組成物、以及包括由此密封的元件的電子零件裝置。 In view of the above-mentioned circumstances, an object of the present invention is to provide a curable resin composition excellent in adhesion to metal in a cured state, and an electronic component device including an element sealed thereby.

用以解決所述課題的手段中包含以下的實施形態。 Means for solving the above problems include the following embodiments.

<1>一種硬化性樹脂組成物，其包含：硬化性樹脂；以及下述通式(1)所表示的化合物。 <1> A curable resin composition containing: a curable resin; and a compound represented by the following general formula (1).

Figure 108120128-A0305-02-0005-1
Figure 108120128-A0305-02-0005-1

通式(1)中，R1~R3分別獨立地表示一價烴基。 In the general formula (1), R 1 to R 3 each independently represent a monovalent hydrocarbon group.

<2>如<1>所述的硬化性樹脂組成物，其中所述通式(1)所表示的化合物含有下述通式(2)所表示的化合物。 <2> The curable resin composition according to <1>, wherein the compound represented by the general formula (1) contains a compound represented by the following general formula (2).

[化2]

Figure 108120128-A0305-02-0006-2
[Chemicalization 2]
Figure 108120128-A0305-02-0006-2

通式(2)中，R4~R6分別獨立地為選自由芳香族烴基、脂肪族烴基、脂肪族烴氧基、芳香族烴氧基、羥基、羧基、鹵素原子、胺基、芳香族烴胺基、脂肪族烴胺基、二芳香族烴胺基、二脂肪族烴胺基及芳香族烴脂肪族烴胺基所組成的群組中的一價基。n分別獨立地為0~5的整數。 In the general formula (2), R 4 to R 6 are independently selected from aromatic hydrocarbon groups, aliphatic hydrocarbon groups, aliphatic hydrocarbon oxygen groups, aromatic hydrocarbon oxygen groups, hydroxyl groups, carboxyl groups, halogen atoms, amine groups, aromatic A monovalent group in the group consisting of a hydrocarbon amine group, an aliphatic hydrocarbon amine group, a diaromatic hydrocarbon amine group, a dialiphatic hydrocarbon amine group and an aromatic hydrocarbon aliphatic hydrocarbon amine group. n is independently an integer from 0 to 5.

<3>如<2>所述的硬化性樹脂組成物，其中所述R4~R6的至少一個為羥基。 <3> The curable resin composition according to <2>, wherein at least one of R 4 to R 6 is a hydroxyl group.

<4>如<1>~<3>中任一項所述的硬化性樹脂組成物，其更包含無機填充材。 <4> The curable resin composition according to any one of <1> to <3>, further containing an inorganic filler.

<5>如<1>~<4>中任一項所述的硬化性樹脂組成物，其中所述硬化性樹脂包含環氧樹脂。 <5> The curable resin composition according to any one of <1> to <4>, wherein the curable resin contains an epoxy resin.

<6>如<5>所述的硬化性樹脂組成物，其中所述環氧樹脂包含選自由聯苯型環氧樹脂、二苯乙烯型環氧樹脂、二苯基甲烷型環氧樹脂、含硫原子型環氧樹脂、酚醛清漆型環氧樹脂、二環戊二烯型環氧樹脂、三苯基甲烷型環氧樹脂、共聚合型環氧樹脂 及芳烷基型環氧樹脂所組成的群組中的至少一種。 <6> The curable resin composition according to <5>, wherein the epoxy resin is selected from the group consisting of biphenyl-type epoxy resin, stilbene-type epoxy resin, diphenylmethane-type epoxy resin, Sulfur atom type epoxy resin, novolak type epoxy resin, dicyclopentadiene type epoxy resin, triphenylmethane type epoxy resin, copolymerized epoxy resin and at least one of the group consisting of aralkyl epoxy resins.

<7>如<1>~<6>中任一項所述的硬化性樹脂組成物，其更包含硬化劑。 <7> The curable resin composition according to any one of <1> to <6>, further containing a curing agent.

<8>如<7>所述的硬化性樹脂組成物，其中所述硬化劑包含選自由芳烷基型酚樹脂、二環戊二烯型酚樹脂、三苯基甲烷型酚樹脂、苯甲醛型酚樹脂與芳烷基型酚樹脂的共聚合型酚樹脂、及酚醛清漆型酚樹脂所組成的群組中的至少一種。 <8> The curable resin composition according to <7>, wherein the curing agent contains an aralkyl phenol resin, a dicyclopentadiene phenol resin, a triphenylmethane phenol resin, and benzaldehyde. At least one of the group consisting of a copolymerized phenol resin of a type phenol resin and an aralkyl type phenol resin, and a novolak type phenol resin.

<9>如<1>~<8>中任一項所述的硬化性樹脂組成物，其更包含硬化促進劑。 <9> The curable resin composition according to any one of <1> to <8>, further comprising a curing accelerator.

<10>如<9>所述的硬化性樹脂組成物，其中所述硬化促進劑含有鏻化合物。 <10> The curable resin composition according to <9>, wherein the curing accelerator contains a phosphonium compound.

<11>如<9>或<10>所述的硬化性樹脂組成物，其中所述硬化促進劑含有下述通式(I-1)所表示的化合物。 <11> The curable resin composition according to <9> or <10>, wherein the curing accelerator contains a compound represented by the following general formula (I-1).

Figure 108120128-A0305-02-0007-3
Figure 108120128-A0305-02-0007-3

式(I-1)中，R1~R3分別獨立地為碳數1~18的烴基，R1 ~R3中的兩個以上可相互鍵結而形成環狀結構；R4~R7分別獨立地為氫原子、羥基或碳數1~18的有機基，R4~R7中的兩個以上可相互鍵結而形成環狀結構。 In formula (I-1), R 1 ~ R 3 are each independently a hydrocarbon group with 1 to 18 carbon atoms. Two or more of R 1 ~ R 3 can be bonded to each other to form a cyclic structure; R 4 ~ R 7 Each is independently a hydrogen atom, a hydroxyl group or an organic group having 1 to 18 carbon atoms, and two or more of R 4 to R 7 may be bonded to each other to form a cyclic structure.

<12>如<11>所述的硬化性樹脂組成物，其中所述通式(I-1)所表示的化合物含有下述通式(I-2)所表示的化合物。 <12> The curable resin composition according to <11>, wherein the compound represented by the general formula (I-1) contains a compound represented by the following general formula (I-2).

Figure 108120128-A0305-02-0008-4
Figure 108120128-A0305-02-0008-4

式(I-2)中，R1~R3分別獨立地為碳數1~18的烴基，R1~R3中的兩個以上可相互鍵結而形成環狀結構；R4~R6分別獨立地為氫原子或碳數1~18的有機基，R4~R6中的兩個以上可相互鍵結而形成環狀結構。 In formula (I-2), R 1 ~ R 3 are each independently a hydrocarbon group with 1 to 18 carbon atoms. Two or more of R 1 ~ R 3 can be bonded to each other to form a cyclic structure; R 4 ~ R 6 They are each independently a hydrogen atom or an organic group having 1 to 18 carbon atoms, and two or more of R 4 to R 6 may be bonded to each other to form a cyclic structure.

<13>一種電子零件裝置，其包括：元件；以及密封所述元件的如<1>~<12>中任一項所述的硬化性樹脂組成物的硬化物。 <13> An electronic component device including: a component; and a hardened product of the curable resin composition according to any one of <1> to <12> that seals the component.

根據本發明，提供於硬化狀態下對金屬的接著性優異的硬化性樹脂組成物、以及包括由此密封的元件的電子零件裝置。 According to the present invention, there are provided a curable resin composition excellent in adhesion to metal in a cured state, and an electronic component device including an element sealed thereby.

以下，對用以實施本發明的形態進行詳細說明。但是，本發明並不限定於以下的實施形態。於以下的實施形態中，其構成要素(亦包括要素步驟等)除了特別明示的情況，並非必須。關於數值及其範圍亦同樣如此，並不限制本發明。 Hereinafter, the form for carrying out the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In the following embodiments, the constituent elements (including element steps, etc.) are not essential unless otherwise expressly stated. The same applies to numerical values and their ranges, which do not limit the present invention.

於本揭示中，「步驟」的用語中，除與其他步驟獨立的步驟以外，即便於無法與其他步驟明確區別的情況下，只要達成該步驟的目的，則亦包含該步驟。 In this disclosure, the term "step" includes steps other than steps that are independent from other steps, even if they cannot be clearly distinguished from other steps, as long as the purpose of the step is achieved.

於本揭示中，使用「~」所表示的數值範圍中包含「~」的前後所記載的數值分別作為最小值及最大值。 In this disclosure, in the numerical range represented by "~", the numerical values recorded before and after "~" are respectively regarded as the minimum value and the maximum value.

於本揭示中階段性記載的數值範圍中，在一個數值範圍中所記載的上限值或下限值亦可置換為其他階段性記載的數值範圍的上限值或下限值。另外，於所記載的數值範圍中，該數值範圍的上限值或下限值亦可置換為實施例中所示的值。 Among the numerical ranges described in stages in this disclosure, the upper limit or lower limit described in one numerical range may also be replaced with the upper limit or lower limit of another numerical range described in stages. In addition, in the numerical range described, the upper limit value or the lower limit value of this numerical range may be replaced with the value shown in the Example.

於本揭示中，關於組成物中的各成分的含有率或含量，於在組成物中存在多種相當於各成分的物質的情況下，只要無特別說明，則是指組成物中所存在的該多種物質的合計含有率或含量。 In this disclosure, the content rate or content of each component in the composition, when there are multiple substances corresponding to each component in the composition, refers to the content of the component present in the composition unless otherwise specified. The total content rate or content of multiple substances.

於本揭示中，組成物中的各成分的粒徑在組成物中存在多種相當於各成分的粒子的情況下，只要無特別說明，則表示關於組成物中所存在的該多種粒子的混合物的值。 In this disclosure, when there are multiple types of particles corresponding to each component in the composition, the particle size of each component in the composition refers to the mixture of the multiple types of particles present in the composition unless otherwise specified. value.

<硬化性樹脂組成物> <Cureable resin composition>

作為本揭示的一實施形態的硬化性樹脂組成物包含：硬化性樹脂；以及下述通式(1)所表示的化合物(以下，亦稱為特定三嗪化合物)。 A curable resin composition according to one embodiment of the present disclosure includes: a curable resin; and a compound represented by the following general formula (1) (hereinafter also referred to as a specific triazine compound).

藉由本發明者等人的研究可知，含有特定三嗪化合物的硬化性樹脂組成物於硬化狀態下對金屬(特別是金、銀等貴金屬)的接著性優異。其原因尚不清楚，但推測原因在於硬化物中的特定三嗪化合物與金屬形成配位鍵。 Research by the present inventors revealed that a curable resin composition containing a specific triazine compound has excellent adhesion to metals (especially noble metals such as gold and silver) in a cured state. The reason for this is not yet clear, but it is speculated that the specific triazine compound in the hardened product forms a coordination bond with the metal.

含有特定三嗪化合物的硬化性樹脂組成物於硬化狀態下對金屬的接著性優異，因此於作為包含至少表面的材質為金屬的引線框架的封裝的密封材使用的情況下，可抑制引線框架與密封材之間的剝離。因此，耐回焊性優異。 The curable resin composition containing a specific triazine compound has excellent adhesion to metal in a cured state. Therefore, when used as a sealing material for a package including a lead frame whose material at least the surface is metal, the lead frame can be suppressed from being Peeling between sealants. Therefore, the reflow resistance is excellent.

(特定三嗪化合物) (specific triazine compounds)

特定三嗪化合物是下述通式(1)所表示的化合物。特定三嗪化合物可單獨使用一種，亦可使用結構不同的兩種以上。 The specific triazine compound is a compound represented by the following general formula (1). A single type of specific triazine compound may be used, or two or more types having different structures may be used.

[化5]

Figure 108120128-A0305-02-0011-5
[Chemistry 5]
Figure 108120128-A0305-02-0011-5

通式(1)中，R1~R3分別獨立地表示一價烴基。R1~R3所表示的一價烴基的結構並無特別限制。例如，可列舉芳香族烴基及脂肪族烴基。 In the general formula (1), R 1 to R 3 each independently represent a monovalent hydrocarbon group. The structure of the monovalent hydrocarbon group represented by R 1 to R 3 is not particularly limited. Examples include aromatic hydrocarbon groups and aliphatic hydrocarbon groups.

作為芳香族烴基，可列舉苯基、萘基等。 Examples of the aromatic hydrocarbon group include phenyl group, naphthyl group, and the like.

作為脂肪族烴基，可列舉碳數1~18的直鏈或分支狀的脂肪族烴基、碳數3~18的脂環式烴基等。 Examples of the aliphatic hydrocarbon group include linear or branched aliphatic hydrocarbon groups having 1 to 18 carbon atoms, alicyclic hydrocarbon groups having 3 to 18 carbon atoms, and the like.

作為碳數1~18的直鏈或分支狀的脂肪族烴基，具體而言可列舉：甲基、乙基、丙基、異丙基、正丁基、第二丁基、第三丁基、戊基、己基、辛基、癸基、十二烷基等烷基、烯丙基、乙烯基等。 Specific examples of linear or branched aliphatic hydrocarbon groups having 1 to 18 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, second butyl, and third butyl. Alkyl groups such as pentyl, hexyl, octyl, decyl, dodecyl, allyl, vinyl, etc.

作為碳數3~18的脂環式烴基，具體而言可列舉：環戊基、環己基、環庚基、環戊烯基、環己烯基等環烷基、金剛烷基、降冰片基、二環戊基等。 Specific examples of the alicyclic hydrocarbon group having 3 to 18 carbon atoms include cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, cyclopentenyl, and cyclohexenyl, adamantyl, and norbornyl. , dicyclopentyl, etc.

R1~R3所表示的一價烴基亦可具有取代基。作為取代基，可列舉：芳香族烴基、脂肪族烴基、脂肪族烴氧基、芳香族 烴氧基、羥基、羧基、鹵素原子、胺基、芳香族烴胺基、脂肪族烴胺基、二芳香族烴胺基、二脂肪族烴胺基、芳香族烴脂肪族烴胺基等。 The monovalent hydrocarbon group represented by R 1 to R 3 may have a substituent. Examples of the substituent include aromatic hydrocarbon group, aliphatic hydrocarbon group, aliphatic hydrocarbonoxy group, aromatic hydrocarbonoxy group, hydroxyl group, carboxyl group, halogen atom, amino group, aromatic hydrocarbon amine group, aliphatic hydrocarbon amine group, di Aromatic hydrocarbon amine group, dialiphatic hydrocarbon amine group, aromatic hydrocarbon aliphatic hydrocarbon amine group, etc.

作為芳香族烴基，可列舉苯基、萘基等。 Examples of the aromatic hydrocarbon group include phenyl group, naphthyl group, and the like.

作為脂肪族烴基，可列舉碳數1~18的直鏈或分支狀的脂肪族烴基、碳數3~18的脂環式烴基等。 Examples of the aliphatic hydrocarbon group include linear or branched aliphatic hydrocarbon groups having 1 to 18 carbon atoms, alicyclic hydrocarbon groups having 3 to 18 carbon atoms, and the like.

作為芳香族烴氧基，可列舉在苯基、萘基等芳香族烴基上鍵結有氧原子的基。 Examples of the aromatic hydrocarbon oxygen group include groups in which an oxygen atom is bonded to an aromatic hydrocarbon group such as a phenyl group or a naphthyl group.

作為脂肪族烴氧基，可列舉在碳數1~18的直鏈或分支狀的脂肪族烴基、碳數3~18的脂環式烴基等脂肪族烴基上鍵結有氧原子的基。 Examples of the aliphatic hydrocarbonoxy group include groups in which an oxygen atom is bonded to an aliphatic hydrocarbon group such as a linear or branched aliphatic hydrocarbon group having 1 to 18 carbon atoms or an alicyclic hydrocarbon group having 3 to 18 carbon atoms.

R1~R3所表示的一價烴基的碳數並無特別限制。例如，較佳為分別獨立地為碳數1~30。於R1~R3所表示的一價烴基具有取代基的情況下，該取代基中所含的碳原子亦包含於「一價碳原子的碳數」中。 The number of carbon atoms in the monovalent hydrocarbon group represented by R 1 to R 3 is not particularly limited. For example, it is preferable that each independently has a carbon number of 1 to 30. When the monovalent hydrocarbon group represented by R 1 to R 3 has a substituent, the carbon atom contained in the substituent is also included in the "carbon number of the monovalent carbon atom".

在某一實施形態中，R1~R3所表示的一價烴基中的至少一個為苯基，另外，在某一實施形態中，R1~R3所表示的一價烴基全部為苯基。特定三嗪化合物亦可為下述通式(2)所表示的化合物。 In a certain embodiment, at least one of the monovalent hydrocarbon groups represented by R 1 to R 3 is a phenyl group. In addition, in a certain embodiment, all of the monovalent hydrocarbon groups represented by R 1 to R 3 are phenyl groups. . The specific triazine compound may be a compound represented by the following general formula (2).

[化6]

Figure 108120128-A0305-02-0013-6
[Chemical 6]
Figure 108120128-A0305-02-0013-6

通式(2)中，R4~R6分別獨立地為選自由芳香族烴基、脂肪族烴基、脂肪族烴氧基、芳香族烴氧基、羥基、羧基、鹵素原子、胺基、芳香族烴胺基、脂肪族烴胺基、二芳香族烴胺基、二脂肪族烴胺基及芳香族烴脂肪族烴胺基所組成的群組中的一價基。n分別獨立地為0~5的整數。 In the general formula (2), R 4 to R 6 are independently selected from aromatic hydrocarbon groups, aliphatic hydrocarbon groups, aliphatic hydrocarbon oxygen groups, aromatic hydrocarbon oxygen groups, hydroxyl groups, carboxyl groups, halogen atoms, amine groups, aromatic A monovalent group in the group consisting of a hydrocarbon amine group, an aliphatic hydrocarbon amine group, a diaromatic hydrocarbon amine group, a dialiphatic hydrocarbon amine group and an aromatic hydrocarbon aliphatic hydrocarbon amine group. n is independently an integer from 0 to 5.

通式(2)中，n可分別獨立地為1~3的整數，亦可為2。在某一實施形態中，通式(2)中的R4~R6中的至少一個為羥基。 In the general formula (2), n may be independently an integer from 1 to 3, or may be 2. In a certain embodiment, at least one of R 4 to R 6 in the general formula (2) is a hydroxyl group.

在某一實施形態中，特定三嗪化合物為通式(1)中的R1~R3中的1個或2個為2,4-二甲基苯基。另外，在某一實施形態中，R1~R3中的2個為2,4-二甲基苯基，1個為2-羥基-4-正辛氧基苯基。作為特定三嗪化合物的具體例，可列舉具有下述式所表示的結構的化合物。 In a certain embodiment, the specific triazine compound is one or two of R 1 to R 3 in the general formula (1) being 2,4-dimethylphenyl. In addition, in a certain embodiment, two of R 1 to R 3 are 2,4-dimethylphenyl, and one is 2-hydroxy-4-n-octyloxyphenyl. Specific examples of the specific triazine compound include compounds having a structure represented by the following formula.

[化7]

Figure 108120128-A0305-02-0014-7
[Chemical 7]
Figure 108120128-A0305-02-0014-7

特定三嗪化合物在硬化性樹脂組成物中的量並無特別限制。就充分獲得對金及銀的接著性的提高效果的觀點而言，例如相對於硬化性樹脂組成物中含有的硬化性樹脂及根據需要使用的硬化劑的合計(以下，亦稱為「樹脂成分」)100質量份，較佳為0.1質量份以上，更佳為1.0質量份以上，進而佳為3.0質量份以上。就硬化性的觀點而言，例如相對於樹脂成分100質量份，較佳為50質量份以下，更佳為30質量份以下，進而佳為20質量份以下。 The amount of the specific triazine compound in the curable resin composition is not particularly limited. From the viewpoint of fully obtaining the effect of improving the adhesion to gold and silver, for example, relative to the total of the curable resin contained in the curable resin composition and the curing agent used if necessary (hereinafter also referred to as "resin component" 》)100 parts by mass, preferably 0.1 parts by mass or more, more preferably 1.0 parts by mass or more, and still more preferably 3.0 parts by mass or more. From the viewpoint of curability, for example, it is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and still more preferably 20 parts by mass or less based on 100 parts by mass of the resin component.

(硬化性樹脂) (hardening resin)

硬化性樹脂若為藉由反應形成三維交聯結構的樹脂，則並無特別限制，可為熱硬化性亦可為光硬化性。就量產性的觀點而言，較佳為熱硬化性。硬化性樹脂可為藉由自聚合而硬化者，亦可為 藉由與硬化劑、交聯劑等的反應而硬化者。 The curable resin is not particularly limited as long as it forms a three-dimensional cross-linked structure by reaction, and may be thermosetting or photocurable. From the viewpoint of mass productivity, thermosetting properties are preferred. The curable resin may be one that hardens by self-polymerization, or it may be Hardened by reaction with hardeners, cross-linking agents, etc.

產生硬化性樹脂的反應的官能基並無特別限制，可列舉：環氧基、氧雜環丁基等環狀醚基、羥基、羧基、胺基、丙烯醯基、異氰酸酯基、馬來醯亞胺基、烯基等。就作為密封材的特性的平衡的觀點而言，較佳為包含環狀醚基的硬化性樹脂，更佳為包含環氧基的硬化性樹脂(環氧樹脂)。 The functional group that reacts to produce a curable resin is not particularly limited, and examples thereof include: epoxy group, cyclic ether group such as oxetanyl group, hydroxyl group, carboxyl group, amine group, acryl group, isocyanate group, and maleic acid group. Amino group, alkenyl group, etc. From the viewpoint of the balance of properties as a sealing material, a curable resin containing a cyclic ether group is preferred, and a curable resin containing an epoxy group (epoxy resin) is more preferred.

於硬化性樹脂為環氧樹脂的情況下，環氧樹脂只要為於1分子中具有兩個以上的環氧基者，則其種類並無特別限制。 When the curable resin is an epoxy resin, the type of the epoxy resin is not particularly limited as long as it has two or more epoxy groups in one molecule.

具體而言可列舉：使選自由苯酚、甲酚、二甲酚、間苯二酚、鄰苯二酚、雙酚A、雙酚F等酚化合物及α-萘酚、β-萘酚、二羥基萘等萘酚化合物所組成的群組中的至少一種酚性化合物與甲醛、乙醛、丙醛等脂肪族醛化合物在酸性觸媒下縮合或共縮合而獲得酚醛清漆樹脂並將該酚醛清漆樹脂進行環氧化而獲得的酚醛清漆型環氧樹脂(苯酚酚醛清漆型環氧樹脂、鄰甲酚酚醛清漆型環氧樹脂等)；使所述酚性化合物與苯甲醛、水楊醛等芳香族醛化合物在酸性觸媒下縮合或共縮合而獲得三苯基甲烷型酚樹脂並將該三苯基甲烷型酚樹脂進行環氧化而獲得的三苯基甲烷型環氧樹脂；使所述酚化合物及萘酚化合物與醛化合物在酸性觸媒下共縮合而獲得酚醛清漆樹脂並將該酚醛清漆樹脂進行環氧化而獲得的共聚合型環氧樹脂；作為雙酚A、雙酚F等的二縮水甘油醚的二苯基甲烷型環氧樹脂；作為烷基取代或未經取代的聯苯酚的二縮水甘油醚的聯苯型環氧樹脂；作為二苯乙烯(stilbene)系酚化合 物的二縮水甘油醚的二苯乙烯型環氧樹脂；作為雙酚S等的二縮水甘油醚的含硫原子的環氧樹脂；作為丁二醇、聚乙二醇、聚丙二醇等醇類的縮水甘油醚的環氧樹脂；作為鄰苯二甲酸、間苯二甲酸、四氫鄰苯二甲酸等多元羧酸化合物的縮水甘油酯的縮水甘油酯型環氧樹脂；將苯胺、二胺基二苯基甲烷、異三聚氰酸等的鍵結於氮原子的活性氫以縮水甘油基取代而獲得的縮水甘油胺型環氧樹脂；將二環戊二烯與酚化合物的共縮合樹脂進行環氧化而獲得的二環戊二烯型環氧樹脂；將分子內的烯烴鍵進行環氧化而獲得的二環氧化乙烯基環己烯、3,4-環氧環己基甲基-3,4-環氧環己烷羧酸酯、2-(3,4-環氧基)環己基-5,5-螺環(3,4-環氧基)環己烷-間二噁烷等脂環型環氧樹脂；作為對二甲苯改質酚樹脂的縮水甘油醚的對二甲苯改質環氧樹脂；作為間二甲苯改質酚樹脂的縮水甘油醚的間二甲苯改質環氧樹脂；作為萜烯改質酚樹脂的縮水甘油醚的萜烯改質環氧樹脂；作為二環戊二烯改質酚樹脂的縮水甘油醚的二環戊二烯改質環氧樹脂；作為環戊二烯改質酚樹脂的縮水甘油醚的環戊二烯改質環氧樹脂；作為多環芳香環改質酚樹脂的縮水甘油醚的多環芳香環改質環氧樹脂；作為含萘環的酚樹脂的縮水甘油醚的萘型環氧樹脂；鹵化酚酚醛清漆型環氧樹脂；對苯二酚型環氧樹脂；三羥甲基丙烷型環氧樹脂；利用過乙酸等過酸將烯烴鍵氧化而獲得的線狀脂肪族環氧樹脂；將苯酚芳烷基樹脂、萘酚芳烷基樹脂等芳烷基型酚樹脂進行環氧化而獲得的芳烷基型環氧樹脂等。進而，亦可列舉矽酮樹脂的環氧化物、丙烯酸 樹脂的環氧化物等作為環氧樹脂。該些環氧樹脂可單獨使用一種，亦可組合使用兩種以上。 Specific examples include: phenol compounds selected from phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, and α-naphthol, β-naphthol, bisphenol, etc. At least one phenolic compound in the group consisting of naphthol compounds such as hydroxynaphthalene and aliphatic aldehyde compounds such as formaldehyde, acetaldehyde, propionaldehyde, etc. are condensed or co-condensed under an acidic catalyst to obtain a novolak resin and the novolak resin Novolak-type epoxy resin (phenol novolak-type epoxy resin, o-cresol novolak-type epoxy resin, etc.) obtained by epoxidation of resin; the phenolic compound is mixed with aromatic compounds such as benzaldehyde and salicylaldehyde. Aldehyde compounds are condensed or co-condensed under an acidic catalyst to obtain a triphenylmethane-type phenol resin, and the triphenylmethane-type phenol resin is epoxidized to obtain a triphenylmethane-type epoxy resin; making the phenolic compound And a copolymerized epoxy resin obtained by co-condensing a naphthol compound and an aldehyde compound under an acidic catalyst to obtain a novolac resin and epoxidizing the novolak resin; as a disacid of bisphenol A, bisphenol F, etc. Diphenylmethane-type epoxy resins as glyceryl ethers; biphenyl-type epoxy resins as diglycidyl ethers of alkyl-substituted or unsubstituted biphenols; stilbene-based phenol compounds stilbene-type epoxy resins that are diglycidyl ethers of bisphenol S, etc.; sulfur atom-containing epoxy resins that are diglycidyl ethers such as bisphenol S; epoxy resins that are alcohols such as butylene glycol, polyethylene glycol, and polypropylene glycol. Epoxy resins of glycidyl ethers; glycidyl ester type epoxy resins which are glycidyl esters of polycarboxylic acid compounds such as phthalic acid, isophthalic acid, tetrahydrophthalic acid, etc.; aniline, diamine dicarboxylic acid Glycidyl amine type epoxy resin obtained by replacing the active hydrogen bonded to the nitrogen atom of phenylmethane, isocycyanuric acid, etc. with a glycidyl group; cyclization of the co-condensation resin of dicyclopentadiene and phenolic compounds Dicyclopentadiene-type epoxy resin obtained by oxidation; diepoxidized vinylcyclohexene and 3,4-epoxycyclohexylmethyl-3,4- obtained by epoxidation of olefin bonds in the molecule Alicyclic types such as epoxycyclohexane carboxylate, 2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane Epoxy resin; p-xylene modified epoxy resin as glycidyl ether of p-xylene modified phenol resin; m-xylene modified epoxy resin as glycidyl ether of m-xylene modified phenol resin; as terpene Terpene-modified epoxy resin as glycidyl ether of dicyclopentadiene-modified phenol resin; dicyclopentadiene-modified epoxy resin as glycidyl ether of dicyclopentadiene-modified phenol resin; as cyclopentadiene-modified epoxy resin Cyclopentadiene-modified epoxy resin is a glycidyl ether of a polycyclic aromatic ring-modified phenol resin; a polycyclic aromatic ring-modified epoxy resin is a glycidyl ether of a polycyclic aromatic ring-modified phenol resin; and a phenol resin containing a naphthalene ring is used. Naphthalene-type epoxy resin of glycidyl ether; halogenated phenol novolak-type epoxy resin; hydroquinone-type epoxy resin; trimethylolpropane-type epoxy resin; obtained by oxidizing olefin bonds using peracids such as peracetic acid. linear aliphatic epoxy resin; aralkyl-type epoxy resin obtained by epoxidizing aralkyl-type phenol resins such as phenol aralkyl resin and naphthol aralkyl resin. Furthermore, epoxides of silicone resins, acrylic resins, etc. Epoxides of resins, etc. are used as epoxy resins. These epoxy resins may be used individually by 1 type, and may be used in combination of 2 or more types.

所述環氧樹脂中，就耐回焊性與流動性的平衡的觀點而言，較佳為選自由聯苯型環氧樹脂、二苯乙烯型環氧樹脂、二苯基甲烷型環氧樹脂、含硫原子型環氧樹脂、酚醛清漆型環氧樹脂、二環戊二烯型環氧樹脂、三苯基甲烷型環氧樹脂、共聚合型環氧樹脂及芳烷基型環氧樹脂所組成的群組中的環氧樹脂(將該些稱為「特定環氧樹脂」)。特定環氧樹脂可單獨使用一種，亦可將兩種以上組合而使用。 Among the epoxy resins, from the viewpoint of the balance between reflow resistance and fluidity, it is preferable to be selected from the group consisting of biphenyl-type epoxy resin, stilbene-type epoxy resin, and diphenylmethane-type epoxy resin. , sulfur atom-containing epoxy resin, novolak-type epoxy resin, dicyclopentadiene-type epoxy resin, triphenylmethane-type epoxy resin, copolymerized epoxy resin and aralkyl-type epoxy resin Epoxy resins in the group consisting of (referred to as "specific epoxy resins"). A specific epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more types.

於環氧樹脂包含特定環氧樹脂的情況下，就發揮特定環氧樹脂的性能的觀點而言，其含有率較佳為環氧樹脂整體的30質量%以上，更佳為50質量%以上。 When the epoxy resin contains a specific epoxy resin, from the viewpoint of exerting the performance of the specific epoxy resin, the content rate is preferably 30 mass% or more of the entire epoxy resin, more preferably 50 mass% or more.

就流動性的觀點而言，特定環氧樹脂中更佳為聯苯型環氧樹脂、二苯乙烯型環氧樹脂、二苯基甲烷型環氧樹脂或含硫原子型環氧樹脂，就耐熱性的觀點而言，較佳為二環戊二烯型環氧樹脂、三苯基甲烷型環氧樹脂或芳烷基型環氧樹脂。以下表示較佳的環氧樹脂的具體例。 From the viewpoint of fluidity, among the specific epoxy resins, biphenyl-type epoxy resin, stilbene-type epoxy resin, diphenylmethane-type epoxy resin or sulfur atom-containing epoxy resin is more preferred in terms of heat resistance. From the viewpoint of stability, dicyclopentadiene-type epoxy resin, triphenylmethane-type epoxy resin or aralkyl-type epoxy resin is preferred. Specific examples of preferred epoxy resins are shown below.

聯苯型環氧樹脂只要為具有聯苯骨架的環氧樹脂，則並無特別限定。例如較佳為下述通式(II)所表示的環氧樹脂。下述通式(II)所表示的環氧樹脂中，R8中氧原子進行取代的位置設為4位及4'位時的3,3',5,5'位為甲基且除此以外的R8為氫原子的YX-4000H(三菱化學股份有限公司，商品名)，所有的R8為氫原 子的4,4'-雙(2,3-環氧基丙氧基)聯苯，所有的R8為氫原子的情況以及R8中氧原子進行取代的位置設為4位及4'位時的3,3',5,5'位為甲基且除此以外的R8為氫原子的情況下的混合品即YL-6121H(三菱化學股份有限公司，商品名)等可作為市售品而獲取。 The biphenyl-type epoxy resin is not particularly limited as long as it is an epoxy resin having a biphenyl skeleton. For example, an epoxy resin represented by the following general formula (II) is preferred. In the epoxy resin represented by the following general formula (II), when the positions where the oxygen atom in R 8 is substituted is the 4-position and the 4'-position, the 3, 3', 5, and 5' positions are methyl groups and in addition YX-4000H (trade name, Mitsubishi Chemical Co., Ltd.) in which R 8 is a hydrogen atom, and 4,4'-bis(2,3-epoxypropoxy)biphenyl in which all R 8 are hydrogen atoms. , in all cases where R 8 is a hydrogen atom and when the oxygen atom in R 8 is substituted at the 4-position and 4'-position, the 3, 3', 5, and 5' positions are methyl groups, and the other R 8 In the case of a hydrogen atom, a mixture such as YL-6121H (trade name of Mitsubishi Chemical Co., Ltd.) is available as a commercial product.

Figure 108120128-A0305-02-0018-8
Figure 108120128-A0305-02-0018-8

式(II)中，R8表示氫原子、碳數1~12的烷基或碳數4~18的芳香族基，可分別均相同亦可不同。n為平均值，表示0~10的數。 In formula (II), R 8 represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an aromatic group having 4 to 18 carbon atoms, and they may be the same or different. n is the average value, representing a number from 0 to 10.

二苯乙烯型環氧樹脂只要為具有二苯乙烯骨架的環氧樹脂，則並無特別限定。例如較佳為下述通式(III)所表示的環氧樹脂。下述通式(III)所表示的環氧樹脂中，R9中氧原子進行取代的位置設為4位及4'位時的3,3',5,5'位為甲基且除此以外的R9為氫原子、R10均為氫原子的情況，以及R9中3,3',5,5'位中的3個為甲基、1個為第三丁基且除此以外的R9為氫原子、R10均為氫原子的情況下的混合品即ESLV-210(住友化學股份有限公司，商品名)等可作為市售品而獲取。 The stilbene-type epoxy resin is not particularly limited as long as it is an epoxy resin having a stilbene skeleton. For example, an epoxy resin represented by the following general formula (III) is preferred. In the epoxy resin represented by the following general formula (III), when the positions where the oxygen atom in R 9 is substituted are the 4-position and the 4'-position, the 3, 3', 5, and 5' positions are methyl groups and in addition Except for the case where R 9 is a hydrogen atom and R 10 are all hydrogen atoms, and among R 9 , 3 of the 3, 3', 5, and 5' positions are methyl and 1 is the tert-butyl group, and other than A mixture product in which R 9 is a hydrogen atom and R 10 are both hydrogen atoms, namely ESLV-210 (trade name of Sumitomo Chemical Co., Ltd.), is available as a commercial product.

[化9]

Figure 108120128-A0305-02-0019-9
[Chemical 9]
Figure 108120128-A0305-02-0019-9

式(III)中，R9及R10表示氫原子或碳數1~18的一價有機基，可分別均相同亦可不同。n為平均值，表示0~10的數。 In formula (III), R 9 and R 10 represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. n is the average value, representing a number from 0 to 10.

二苯基甲烷型環氧樹脂只要為具有二苯基甲烷骨架的環氧樹脂，則並無特別限定。例如較佳為下述通式(IV)所表示的環氧樹脂。下述通式(IV)所表示的環氧樹脂中，R11均為氫原子、R12中氧原子進行取代的位置設為4位及4'位時的3,3',5,5'位為甲基且除此以外的R12為氫原子的YSLV-80XY(新日鐵住金化學股份有限公司，商品名)等可作為市售品而獲取。 The diphenylmethane-type epoxy resin is not particularly limited as long as it is an epoxy resin having a diphenylmethane skeleton. For example, an epoxy resin represented by the following general formula (IV) is preferred. In the epoxy resin represented by the following general formula (IV), R 11 is a hydrogen atom, and the position where the oxygen atom in R 12 is substituted is 3, 3', 5, 5' when the 4-position and 4'-position are YSLV-80XY (trade name, Nippon Steel & Sumitomo Metal Chemical Co., Ltd.), in which R 12 is a methyl group and the other R 12 is a hydrogen atom, is available as a commercial product.

Figure 108120128-A0305-02-0019-10
Figure 108120128-A0305-02-0019-10

式(IV)中，R11及R12表示氫原子或碳數1~18的一價有機基，可分別均相同亦可不同。n為平均值，表示0~10的數。 In formula (IV), R 11 and R 12 represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. n is the average value, representing a number from 0 to 10.

含硫原子型環氧樹脂只要為含有硫原子的環氧樹脂，則並無特別限定。例如可列舉下述通式(V)所表示的環氧樹脂。下述通式(V)所表示的環氧樹脂中，R13中氧原子進行取代的位置 設為4位及4'位時的3,3'位為第三丁基、6,6'位為甲基且除此以外的R13為氫原子的YSLV-120TE(新日鐵住金化學股份有限公司，商品名)等可作為市售品而獲取。 The sulfur atom-containing epoxy resin is not particularly limited as long as it is an epoxy resin containing sulfur atoms. Examples thereof include epoxy resins represented by the following general formula (V). In the epoxy resin represented by the following general formula (V), when the positions where the oxygen atom in R 13 is substituted are the 4-position and the 4'-position, the 3,3'-position is the tert-butyl group and the 6,6'-position YSLV-120TE (trade name, Nippon Steel & Sumitomo Metal Chemical Co., Ltd.) in which R 13 is a methyl group and the other R 13 is a hydrogen atom is available as a commercial product.

Figure 108120128-A0305-02-0020-11
Figure 108120128-A0305-02-0020-11

式(V)中，R13表示氫原子或碳數1~18的一價有機基，可分別均相同亦可不同。n為平均值，表示0~10的數。 In formula (V), R 13 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and they may be the same or different. n is the average value, representing a number from 0 to 10.

酚醛清漆型環氧樹脂只要為使酚醛清漆型酚樹脂進行環氧化而獲得的環氧樹脂，則並無特別限定。例如較佳為使用縮水甘油醚化等方法使苯酚酚醛清漆樹脂、甲酚酚醛清漆樹脂、萘酚酚醛清漆樹脂等酚醛清漆型酚樹脂進行環氧化而獲得的環氧樹脂，更佳為下述通式(VI)所表示的環氧樹脂。在下述通式(VI)所表示的環氧樹脂中，R14全部為氫原子、R15為甲基、i=1的ESCN-190、ESCN-195(住友化學股份有限公司，商品名)；R14全部為氫原子、i=0的N-770、N-775(迪愛生(DIC)股份有限公司，商品名)；具有R14全部為氫原子、i=0的部分與i=1、R15為-CH(CH3)-Ph的部分的苯乙烯改質苯酚酚醛清漆型環氧樹脂、即、YDAN-1000-10C(新日鐵住金化學股份有限公司，商品名)；作為 具有R14全部為氫原子、i=1、R15為甲基的部分與i=2、R15中的一個為甲基、一個為苄基的部分的苄基改質甲酚酚醛清漆型環氧樹脂、即、HP-5600(迪愛生(DIC)股份有限公司，商品名)等可作為市售品而獲取。 The novolak-type epoxy resin is not particularly limited as long as it is an epoxy resin obtained by epoxidizing a novolak-type phenol resin. For example, an epoxy resin obtained by epoxidizing a novolak-type phenol resin such as a phenol novolac resin, a cresol novolac resin, and a naphthol novolac resin using a method such as glycidyl etherification is preferred, and more preferably the following general Epoxy resin represented by formula (VI). In the epoxy resin represented by the following general formula (VI), all R 14 are hydrogen atoms, R 15 is a methyl group, and i=1, ESCN-190 and ESCN-195 (trade name of Sumitomo Chemical Co., Ltd.); N- 770 and N-775 (trade name of DIC Co., Ltd.) in which all R 14 are hydrogen atoms and i=0; the part in which all R 14 are hydrogen atoms and i=0 is the same as i=1, A styrene-modified phenol novolak-type epoxy resin in which R 15 is -CH(CH 3 )-Ph, that is, YDAN-1000-10C (trade name of Nippon Steel & Sumitomo Metal Chemical Co., Ltd.); as having R Benzyl modified cresol novolak type epoxy resin where all 14 are hydrogen atoms, i=1, R15 is methyl group and i=2, one of R15 is methyl group and one is benzyl group , that is, HP-5600 (trade name of DIC Co., Ltd.) and the like are available as commercial products.

Figure 108120128-A0305-02-0021-12
Figure 108120128-A0305-02-0021-12

式(VI)中，R14表示氫原子或碳數1~18的一價有機基，可分別均相同亦可不同。R15表示碳數1~18的一價有機基，可分別均相同亦可不同。i分別獨立地表示0~3的整數。n為平均值，表示0~10的數。 In formula (VI), R 14 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. R 15 represents a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. i independently represents an integer from 0 to 3. n is the average value, representing a number from 0 to 10.

二環戊二烯型環氧樹脂只要為將具有二環戊二烯骨架的化合物作為原料來進行環氧化而獲得的環氧樹脂，則並無特別限定。例如較佳為下述通式(VII)所表示的環氧樹脂。下述通式(VII)所表示的環氧樹脂中，i=0的HP-7200(迪愛生(DIC)股份有限公司，商品名)等可作為市售品而獲取。 The dicyclopentadiene-type epoxy resin is not particularly limited as long as it is an epoxy resin obtained by epoxidizing a compound having a dicyclopentadiene skeleton as a raw material. For example, an epoxy resin represented by the following general formula (VII) is preferred. Among the epoxy resins represented by the following general formula (VII), HP-7200 (trade name of DIC Co., Ltd.) in which i=0 is available as a commercial product.

[化13]

Figure 108120128-A0305-02-0022-13
[Chemical 13]
Figure 108120128-A0305-02-0022-13

式(VII)中，R16表示碳數1~18的一價有機基，可分別均相同亦可不同。i分別獨立地表示0~3的整數。n為平均值，表示0~10的數。 In formula (VII), R 16 represents a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. i independently represents an integer from 0 to 3. n is the average value, representing a number from 0 to 10.

三苯基甲烷型環氧樹脂只要為將具有三苯基甲烷骨架的化合物作為原料的環氧樹脂，則並無特別限制。例如較佳為將具有三苯基甲烷骨架的化合物與具有酚性羥基的化合物的酚醛清漆型酚樹脂等三苯基甲烷型酚樹脂進行縮水甘油醚化而獲得的環氧樹脂，更佳為下述通式(VIII)所表示的環氧樹脂。下述通式(VIII)所表示的環氧樹脂中，i為0且k為0的1032H60(三菱化學股份有限公司，商品名)、EPPN-502H(日本化藥股份有限公司，商品名)等可作為市售品而獲取。 The triphenylmethane-type epoxy resin is not particularly limited as long as it is an epoxy resin using a compound having a triphenylmethane skeleton as a raw material. For example, an epoxy resin obtained by glycidyl etherifying a novolac-type phenol resin such as a novolak-type phenol resin of a compound having a triphenylmethane skeleton and a compound having a phenolic hydroxyl group is preferred, and the following is more preferred. Epoxy resin represented by general formula (VIII). Among the epoxy resins represented by the following general formula (VIII), 1032H60 (trade name of Mitsubishi Chemical Co., Ltd.), EPPN-502H (trade name of Nippon Kayaku Co., Ltd.), etc., in which i is 0 and k is 0 It is available as a commercial product.

Figure 108120128-A0305-02-0022-14
Figure 108120128-A0305-02-0022-14

式(VIII)中，R17及R18表示碳數1~18的一價有機基，可分別均相同亦可不同。i分別獨立地表示0~3的整數，k分別獨立地表示0~4的整數。n為平均值，表示0~10的數。 In formula (VIII), R 17 and R 18 represent a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. i independently represents an integer from 0 to 3, and k represents an integer from 0 to 4 independently. n is the average value, representing a number from 0 to 10.

使由萘酚化合物及苯酚化合物與醛化合物所獲得的酚醛清漆樹脂進行環氧化而成的共聚合型環氧樹脂只要為將具有萘酚骨架的化合物及具有苯酚骨架的化合物作為原料的環氧樹脂，則並無特別限定。例如較佳為使利用具有萘酚骨架的化合物及具有苯酚骨架的化合物的酚醛清漆型酚樹脂進行縮水甘油醚化而獲得的環氧樹脂，更佳為下述通式(IX)所表示的環氧樹脂。下述通式(IX)所表示的環氧樹脂中，R21為甲基且i為1、j為0、k為0的NC-7300(日本化藥股份有限公司，商品名)等可作為市售品而獲取。 The copolymerized epoxy resin obtained by epoxidizing a novolac resin obtained from a naphthol compound, a phenol compound, and an aldehyde compound may be an epoxy resin using a compound having a naphthol skeleton and a compound having a phenol skeleton as raw materials. , there are no special restrictions. For example, an epoxy resin obtained by glycidyl etherification of a novolak-type phenol resin using a compound having a naphthol skeleton and a compound having a phenol skeleton is preferable, and an epoxy resin represented by the following general formula (IX) is more preferable. Oxygen resin. Among the epoxy resins represented by the following general formula (IX), NC-7300 (trade name of Nippon Kayaku Co., Ltd., trade name), etc., in which R 21 is a methyl group, i is 1, j is 0, and k is 0, can be used. Obtained from commercially available products.

Figure 108120128-A0305-02-0023-15
Figure 108120128-A0305-02-0023-15

式(IX)中，R19~R21表示碳數1~18的一價有機基，可分別均相同亦可不同。i分別獨立地表示0~3的整數，j分別獨立地表示0~2的整數，k分別獨立地表示0~4的整數。l及m分 別為平均值，為0~10的數，(l+m)表示0~10的數。式(IX)所表示的環氧樹脂的末端為下述式(IX-1)或式(IX-2)的任一者。式(IX-1)及式(IX-2)中，R19~R21中的i、j及k的定義與式(IX)中的R19~R21中的i、j及k的定義相同。n為1(經由亞甲基而鍵結的情況)或0(不經由亞甲基而鍵結的情況)。 In formula (IX), R 19 to R 21 represent monovalent organic groups having 1 to 18 carbon atoms, and may be the same or different. i independently represents an integer from 0 to 3, j independently represents an integer from 0 to 2, and k represents an integer from 0 to 4 independently. l and m are respectively the average value and a number from 0 to 10, and (l+m) represents a number from 0 to 10. The terminal of the epoxy resin represented by formula (IX) is either formula (IX-1) or formula (IX-2) below. In formula (IX-1) and formula (IX-2), the definitions of i, j and k in R 19 ~ R 21 are the same as the definitions of i, j and k in R 19 ~ R 21 in formula (IX). same. n is 1 (when bonding via a methylene group) or 0 (when bonding is not via a methylene group).

Figure 108120128-A0305-02-0024-16
Figure 108120128-A0305-02-0024-16

作為所述通式(IX)所表示的環氧樹脂，可列舉：無規地包含1個構成單元及m個構成單元的無規共聚物、交替地包含1個構成單元及m個構成單元的交替共聚物、有規則地包含1個構成單元及m個構成單元的共聚物、以嵌段狀包含1個構成單元及m個構成單元的嵌段共聚物等。可單獨使用該些的任一種，亦可將兩種以上組合而使用。 Examples of the epoxy resin represented by the general formula (IX) include a random copolymer including one structural unit and m structural units randomly, and a random copolymer including one structural unit and m structural units alternately. Alternating copolymers, copolymers including one structural unit and m structural units regularly, block copolymers including one structural unit and m structural units in block form, etc. Any one of these may be used alone, or two or more types may be used in combination.

作為共聚合型環氧樹脂，另外亦較佳為以無規、交替或嵌段的順序含有下述2種結構單元的甲氧基萘．甲酚甲醛共縮合型環氧樹脂、即、下述通式表示的艾比克隆(EPICLON)HP-5000(迪愛生(DIC)股份有限公司，商品名)。下述通式中，n及m分別為平均值，為0~10的數，(n+m)表示0~10的數，較佳為n及m分別為平均值，為1~9的數，(n+m)表示2~10的數。 As a copolymerized epoxy resin, methoxynaphthalene containing the following two structural units in random, alternating or block order is also preferred. The cresol-formaldehyde co-condensation type epoxy resin is EPICLON HP-5000 (trade name of DIC Co., Ltd.) represented by the following general formula. In the following general formula, n and m are respectively an average value and a number from 0 to 10, (n+m) represents a number from 0 to 10, preferably n and m are respectively an average value and a number from 1 to 9. , (n+m) represents a number from 2 to 10.

Figure 108120128-A0305-02-0025-17
Figure 108120128-A0305-02-0025-17

芳烷基型環氧樹脂只要為將由選自由苯酚、甲酚等酚化合物及萘酚、二甲基萘酚等萘酚化合物所組成的群組中的至少一種，與由二甲氧基對二甲苯、雙(甲氧基甲基)聯苯或該些的衍生物所合成的酚樹脂作為原料的環氧樹脂，則並無特別限定。例如較佳為對由選自由苯酚、甲酚等酚化合物及萘酚、二甲基萘酚等萘酚化合物所組成的群組中的至少一種與二甲氧基對二甲苯、雙(甲氧基甲基)聯苯或該些的衍生物所合成的酚樹脂進行縮水甘油醚化而獲得的環氧樹脂，更佳為下述通式(X)及通式(XI)所表示 的環氧樹脂。 The aralkyl-type epoxy resin is at least one selected from the group consisting of phenol compounds such as phenol and cresol and naphthol compounds such as naphthol and dimethylnaphthol, and is composed of dimethoxy-dimethoxy The epoxy resin using a phenol resin synthesized from toluene, bis(methoxymethyl)biphenyl or their derivatives as a raw material is not particularly limited. For example, it is preferable to combine at least one compound selected from the group consisting of phenol compounds such as phenol and cresol and naphthol compounds such as naphthol and dimethylnaphthol with dimethoxy-p-xylene, bis(methoxy-p-xylene, etc.) An epoxy resin obtained by glycidyl etherification of a phenol resin synthesized from methyl)biphenyl or these derivatives is more preferably represented by the following general formula (X) and general formula (XI) of epoxy resin.

下述通式(X)所表示的環氧樹脂中，i為0且R38為氫原子的NC-3000S(日本化藥股份有限公司，商品名)，以質量比80：20將i為0且R38為氫原子的環氧樹脂與通式(II)的所有的R8為氫原子的環氧樹脂混合而成的CER-3000(日本化藥股份有限公司，商品名)等可作為市售品而獲取。另外，下述通式(XI)所表示的環氧樹脂中，i為0、j為0、k為0的ESN-175(新日鐵住金化學股份有限公司，商品名)等可作為市售品而獲取。 In the epoxy resin represented by the following general formula (X), in which i is 0 and R 38 is a hydrogen atom, NC-3000S (trade name of Nippon Kayaku Co., Ltd.) is used, with i being 0 at a mass ratio of 80:20. In addition, CER-3000 (trade name of Nippon Kayaku Co., Ltd.), which is a mixture of an epoxy resin in which R 38 is a hydrogen atom and an epoxy resin in which all R 8 is a hydrogen atom in the general formula (II), is available on the market. Obtained from the sale of goods. In addition, among the epoxy resins represented by the following general formula (XI), ESN-175 (trade name of Nippon Steel & Sumitomo Metal Chemical Co., Ltd.), etc., in which i is 0, j is 0, and k is 0, is commercially available as Obtained by product.

Figure 108120128-A0305-02-0026-18
Figure 108120128-A0305-02-0026-18

式(X)及式(XI)中，R38表示氫原子或碳數1~18的一價有機基，可分別均相同亦可不同。R37、R39~R41表示碳數1~18的一價有機基，可分別均相同亦可不同。i分別獨立地為0~3的整數，j分別獨立地為0~2的整數，k分別獨立地為0~4的整數，l分別獨立地表示0~6的整數。n為平均值，分別獨立地為0~10的數。 In Formula (X) and Formula (XI), R 38 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. R 37 and R 39 to R 41 represent monovalent organic groups having 1 to 18 carbon atoms, and may be the same or different. i is an integer from 0 to 3, j is an integer from 0 to 2, k is an integer from 0 to 4, and l is an integer from 0 to 6. n is the average value, each independently a number from 0 to 10.

關於所述通式(II)~通式(XI)中的R8~R21及R37~R41，所謂「可分別均相同亦可不同」例如是指式(II)中的8個~88個R8可均相同亦可不同。關於其他的R9~R21及R37~R41，是指式中所含的各自的個數可均相同亦可不同。另外，R8~R21及R37~R41可分別相同亦可不同。例如，R9與R10可均相同亦可不同。 Regarding R 8 to R 21 and R 37 to R 41 in the general formula (II) to the general formula (XI), the so-called "can be the same or different" means, for example, 8 ~ in the formula (II). The 88 R 8s can all be the same or different. Regarding the other R 9 to R 21 and R 37 to R 41 , the respective numbers included in the formula may be the same or different. In addition, R 8 to R 21 and R 37 to R 41 may be the same or different, respectively. For example, R 9 and R 10 may both be the same or different.

另外，通式(III)~通式(XI)中的碳數1~18的有機基較佳為烷基或芳基。 In addition, the organic group having 1 to 18 carbon atoms in the general formulas (III) to (XI) is preferably an alkyl group or an aryl group.

所述通式(II)~通式(XI)中的n為平均值，較佳為分別獨立地為0~10的範圍。若n為10以下，則樹脂成分的熔融黏度不會過高，硬化性樹脂組成物的熔融成形時的黏度下降，有抑制產生填充不良、接合線(連接元件與引線的金屬線)的變形等的傾向。n更佳為設定為0~4的範圍。 n in the general formulas (II) to (XI) is an average value, preferably in the range of 0 to 10 independently. If n is 10 or less, the melt viscosity of the resin component will not be too high, the viscosity of the curable resin composition during melt molding will be reduced, and the occurrence of filling defects, deformation of bonding wires (metal wires connecting components and leads), etc. will be suppressed. tendency. It is more preferable that n is set in the range of 0~4.

硬化性樹脂的官能基當量(於環氧樹脂的情況下為環氧當量)並無特別限制。就成形性、耐回焊性及電氣可靠性等各種特性平衡的觀點而言，硬化性樹脂的官能基當量較佳為100g/eq~1000g/eq，更佳為150g/eq~500g/eq。 The functional group equivalent of the curable resin (epoxy equivalent in the case of epoxy resin) is not particularly limited. From the viewpoint of balancing various characteristics such as formability, reflow resistance, and electrical reliability, the functional group equivalent weight of the curable resin is preferably 100g/eq~1000g/eq, and more preferably 150g/eq~500g/eq.

硬化性樹脂的軟化點或熔點並無特別限制。就成形性與耐回焊性的觀點而言，較佳為40℃~180℃，就硬化性樹脂組成物的製備時的操作性的觀點而言，更佳為50℃~130℃。 The softening point or melting point of the curable resin is not particularly limited. From the viewpoint of formability and reflow resistance, 40°C to 180°C is preferred, and from the viewpoint of workability during preparation of the curable resin composition, 50°C to 130°C is more preferred.

就強度、流動性、耐熱性、成形性等的觀點而言，硬化性樹脂組成物中的硬化性樹脂的含有率較佳為0.5質量%~50質量%，更佳為2質量%~30質量%。 From the viewpoints of strength, fluidity, heat resistance, formability, etc., the curable resin content in the curable resin composition is preferably 0.5% by mass to 50% by mass, more preferably 2% by mass to 30% by mass. %.

(硬化劑) (hardener)

硬化性樹脂組成物亦可包含硬化劑。硬化劑的種類並無特別限制，可對應於硬化性樹脂的種類、硬化性樹脂組成物的所期望的特性等來選擇。 The curable resin composition may also contain a curing agent. The type of curing agent is not particularly limited and can be selected according to the type of curable resin, desired properties of the curable resin composition, and the like.

作為硬化性樹脂為環氧樹脂時的硬化劑，可列舉：酚硬化劑、胺硬化劑、酸酐硬化劑、聚硫醇硬化劑、聚胺基醯胺硬化劑、異氰酸酯硬化劑、嵌段異氰酸酯硬化劑等。就硬化性及適用期併存的觀點而言，較佳為選自由酚硬化劑、胺硬化劑及酸酐硬化劑所組成的群組中的至少一種，就電氣可靠性的觀點而言，更佳為酚硬化劑。 When the curable resin is an epoxy resin, examples of the curing agent include phenol curing agents, amine curing agents, acid anhydride curing agents, polythiol curing agents, polyaminoamide curing agents, isocyanate curing agents, and block isocyanate curing agents. Agents, etc. From the viewpoint of both hardening properties and pot life, at least one selected from the group consisting of phenol hardeners, amine hardeners and acid anhydride hardeners is preferred, and from the viewpoint of electrical reliability, it is more preferred Phenol hardener.

作為酚硬化劑，例如可列舉於1分子中具有兩個以上的酚性羥基的酚樹脂及多元酚化合物。具體而言，可列舉：間苯二酚、鄰苯二酚、雙酚A、雙酚F、經取代或未經取代的聯苯酚等多元酚化合物；使選自由苯酚、甲酚、二甲酚、間苯二酚、鄰苯二酚、雙酚A、雙酚F、苯基苯酚、胺基苯酚等苯酚化合物及α-萘酚、β-萘酚、二羥基萘等萘酚化合物所組成的群組中的至少一種酚性化合物、與甲醛、乙醛、丙醛、苯甲醛、水楊醛等醛化合物於酸性觸媒下縮合或共縮合而獲得的酚醛清漆型酚樹脂；由所述酚性化合物與二甲氧基對二甲苯、雙(甲氧基甲基)聯苯等所合成的苯酚芳烷基樹脂、萘酚芳烷基樹脂等芳烷基型酚樹脂；對二甲苯及/或間二甲苯改質酚樹脂；三聚氰胺改質酚樹脂；萜烯改質酚樹脂；由所述酚性化合物與二環戊二烯藉由共聚合而合成的二環戊 二烯型苯酚樹脂及二環戊二烯型萘酚樹脂；環戊二烯改質酚樹脂；多環芳香環改質酚樹脂；聯苯型酚樹脂；使所述酚性化合物與苯甲醛、水楊醛等芳香族醛化合物於酸性觸媒下縮合或共縮合而獲得的三苯基甲烷型酚樹脂；將該些的兩種以上共聚合而獲得的酚樹脂等。該些酚硬化劑可單獨使用一種，亦可將兩種以上組合而使用。 Examples of the phenol curing agent include phenol resins and polyhydric phenol compounds having two or more phenolic hydroxyl groups in one molecule. Specifically, polyphenol compounds such as resorcin, catechol, bisphenol A, bisphenol F, and substituted or unsubstituted biphenol may be listed; selected from the group consisting of phenol, cresol, and xylenol. , resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol and other phenol compounds and α-naphthol, β-naphthol, dihydroxynaphthol and other naphthol compounds A novolac-type phenolic resin obtained by condensing or co-condensing at least one phenolic compound in the group with formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde and other aldehyde compounds under an acidic catalyst; made from the phenol Aralkyl-type phenol resins such as phenol aralkyl resin and naphthol aralkyl resin synthesized from chemical compounds and dimethoxy-p-xylene, bis(methoxymethyl)biphenyl, etc.; p-xylene and/ Or m-xylene modified phenol resin; melamine modified phenol resin; terpene modified phenol resin; dicyclopentadiene synthesized by copolymerization of the phenolic compound and dicyclopentadiene Diene-type phenol resin and dicyclopentadiene-type naphthol resin; cyclopentadiene-modified phenol resin; polycyclic aromatic ring-modified phenol resin; biphenyl-type phenol resin; making the phenolic compound and benzaldehyde, Triphenylmethane-type phenol resin obtained by condensation or co-condensation of aromatic aldehyde compounds such as salicylaldehyde under an acidic catalyst; phenol resin obtained by copolymerizing two or more of these, etc. These phenol hardeners may be used individually by 1 type, or in combination of 2 or more types.

酚硬化劑中，就耐回焊性的觀點而言，較佳為選自由芳烷基型酚樹脂、二環戊二烯型酚樹脂、三苯基甲烷型酚樹脂、苯甲醛型酚樹脂與芳烷基型酚樹脂的共聚合型酚樹脂、及酚醛清漆型酚樹脂所組成的群組中的至少一種(將該些稱為「特定酚硬化劑」)。特定酚硬化劑可單獨使用一種，亦可將兩種以上組合而使用。 Among the phenol hardeners, from the viewpoint of reflow resistance, it is preferable to select one selected from the group consisting of aralkyl type phenol resin, dicyclopentadiene type phenol resin, triphenylmethane type phenol resin, benzaldehyde type phenol resin and At least one of the group consisting of a copolymerized phenol resin of an aralkyl-type phenol resin and a novolak-type phenol resin (these are referred to as "specific phenol hardeners"). A specific phenol hardener may be used individually by 1 type, and may be used in combination of 2 or more types.

於硬化劑包含特定酚硬化劑的情況下，就充分地發揮該些的性能的觀點而言，特定酚硬化劑的含有率較佳為硬化劑整體的30質量%以上，更佳為50質量%以上 When the hardener contains a specific phenol hardener, from the viewpoint of fully utilizing these properties, the content rate of the specific phenol hardener is preferably 30% by mass or more of the entire hardener, more preferably 50% by mass. above

作為芳烷基型酚樹脂，可列舉由酚性化合物與二甲氧基對二甲苯、雙(甲氧基甲基)聯苯等所合成的苯酚芳烷基樹脂、萘酚芳烷基樹脂等。芳烷基型酚樹脂亦可進而與其他酚樹脂共聚合。作為共聚合的芳烷基型酚樹脂，可列舉：苯甲醛型酚樹脂與芳烷基型酚樹脂的共聚合型酚樹脂、水楊醛型酚樹脂與芳烷基型酚樹脂的共聚合型酚樹脂、酚醛清漆型酚樹脂與芳烷基型酚樹脂的共聚合型酚樹脂等。 Examples of the aralkyl-type phenol resin include phenol aralkyl resin, naphthol aralkyl resin, etc. synthesized from a phenolic compound and dimethoxyp-xylene, bis(methoxymethyl)biphenyl, etc. . Aralkyl phenol resins can also be copolymerized with other phenol resins. Examples of the copolymerized aralkyl phenol resin include a copolymerized phenol resin of a benzaldehyde phenol resin and an aralkyl phenol resin, a copolymerized salicylaldehyde phenol resin and an aralkyl phenol resin. Phenol resin, copolymerized phenol resin of novolak type phenol resin and aralkyl type phenol resin, etc.

芳烷基型酚樹脂只要為由選自由苯酚化合物及萘酚化合物所組成的群組中的至少一種與二甲氧基對二甲苯、雙(甲氧基甲基)聯苯或該些的衍生物所合成的酚樹脂，則並無特別限定。例如較佳為下述通式(XII)~通式(XIV)所表示的酚樹脂。 The aralkyl-type phenol resin is composed of at least one selected from the group consisting of phenol compounds and naphthol compounds, dimethoxy-p-xylene, bis(methoxymethyl)biphenyl, or derivatives thereof. The phenol resin synthesized is not particularly limited. For example, phenol resins represented by the following general formulas (XII) to (XIV) are preferred.

Figure 108120128-A0305-02-0030-19
Figure 108120128-A0305-02-0030-19

式(XII)~式(XIV)中，R23表示氫原子或碳數1~18的一價有機基，可分別均相同亦可不同。R22、R24、R25及R28表示碳數1~18的一價有機基，可分別均相同亦可不同。R26及R27表示羥基或碳數1~18的一價有機基，可分別均相同亦可不同。i分別獨立地為0~3的整數，j分別獨立地為0~2的整數，k分別獨立地為0~4的整數，p分別獨立地為0~4的整數。n為平均值，分別獨立地為0~10的數。 In formulas (XII) to (XIV), R 23 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. R 22 , R 24 , R 25 and R 28 represent a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. R 26 and R 27 represent a hydroxyl group or a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. i is an integer from 0 to 3, j is an integer from 0 to 2, k is an integer from 0 to 4, and p is an integer from 0 to 4. n is the average value, each independently a number from 0 to 10.

所述通式(XII)所表示的酚樹脂中，i為0且R23均為氫原子的MEH-7851(明和化成股份有限公司，商品名)等可作為 市售品而獲取。 Among the phenol resins represented by the general formula (XII), MEH-7851 (trade name of Meiwa Kasei Co., Ltd.) in which i is 0 and R 23 is a hydrogen atom is available as a commercial product.

所述通式(XIII)所表示的酚樹脂中，i為0且k為0的XL-225、XLC(三井化學股份有限公司，商品名)、MEH-7800(明和化成股份有限公司，商品名)等可作為市售品而獲取。 Among the phenol resins represented by the general formula (XIII), XL-225, XLC (trade name of Mitsui Chemicals Co., Ltd.), MEH-7800 (trade name of Meiwa Chemicals Co., Ltd.) in which i is 0 and k is 0 ), etc. are available as commercial products.

所述通式(XIV)所表示的酚樹脂中，j為0、k為0且p為0的SN-170(新日鐵住金化學股份有限公司，商品名)、j為0、k為1、R27為羥基且p為0的SN-395(新日鐵住金化學股份有限公司，商品名)等可作為市售品而獲取。 In the phenol resin represented by the general formula (XIV), j is 0, k is 0, and p is 0, SN-170 (trade name of Nippon Steel & Sumitomo Metal Chemical Co., Ltd.), j is 0, and k is 1 , SN-395 (trade name, Nippon Steel & Sumitomo Metal Chemical Co., Ltd.) in which R 27 is a hydroxyl group and p is 0 is available as a commercial product.

二環戊二烯型酚樹脂只要為將具有二環戊二烯骨架的化合物作為原料而獲得的酚樹脂，則並無特別限定。例如較佳為下述通式(XV)所表示的酚樹脂。下述通式(XV)所表示的酚樹脂中，i為0的DPP(新日本石油化學股份有限公司，商品名)等可作為市售品而獲取。 The dicyclopentadiene-type phenol resin is not particularly limited as long as it is a phenol resin obtained by using a compound having a dicyclopentadiene skeleton as a raw material. For example, a phenol resin represented by the following general formula (XV) is preferred. Among the phenol resins represented by the following general formula (XV), DPP (trade name of New Nippon Petrochemical Co., Ltd.), etc., in which i is 0, are available as commercial products.

Figure 108120128-A0305-02-0031-20
Figure 108120128-A0305-02-0031-20

式(XV)中，R29表示碳數1~18的一價有機基，可分別均相同亦可不同。i分別獨立地表示0~3的整數。n為平均值， 表示0~10的數。 In formula (XV), R 29 represents a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. i independently represents an integer from 0 to 3. n is the average value, representing a number from 0 to 10.

三苯基甲烷型酚樹脂只要為將具有三苯基甲烷骨架的化合物作為原料而獲得的酚樹脂，則並無特別限定。例如較佳為下述通式(XVI)所表示的酚樹脂。 The triphenylmethane-type phenol resin is not particularly limited as long as it is a phenol resin obtained by using a compound having a triphenylmethane skeleton as a raw material. For example, a phenol resin represented by the following general formula (XVI) is preferred.

下述通式(XVI)所表示的酚樹脂中，i為0且k為0的MEH-7500(明和化成股份有限公司，商品名)等可作為市售品而獲取。 Among the phenol resins represented by the following general formula (XVI), MEH-7500 (trade name of Meiwa Kasei Co., Ltd.) in which i is 0 and k is 0 is available as a commercial product.

Figure 108120128-A0305-02-0032-21
Figure 108120128-A0305-02-0032-21

式(XVI)中，R30及R31表示碳數1~18的一價有機基，可分別均相同亦可不同。i分別獨立地為0~3的整數，k分別獨立地為0~4的整數。n為平均值，為0~10的數。 In formula (XVI), R 30 and R 31 represent a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. i is an integer from 0 to 3 independently, and k is an integer from 0 to 4 independently. n is the average value, which is a number from 0 to 10.

苯甲醛型酚樹脂與芳烷基型酚樹脂的共聚合型酚樹脂只要為將具有苯甲醛骨架的化合物作為原料而獲得的酚樹脂與芳烷基型酚樹脂的共聚合型酚樹脂，則並無特別限定。例如較佳為下述通式(XVII)所表示的酚樹脂。 The copolymer-type phenol resin of a benzaldehyde-type phenol resin and an aralkyl-type phenol resin can be used as long as it is a copolymer-type phenol resin of a phenol resin and an aralkyl-type phenol resin obtained by using a compound having a benzaldehyde skeleton as a raw material. No special restrictions. For example, a phenol resin represented by the following general formula (XVII) is preferred.

下述通式(XVII)所表示的酚樹脂中，i為0、k為0且q為0的HE-510(空氣水化學(Air Water Chemical)股份有限公司，商品名)等可作為市售品而獲取。 Among the phenol resins represented by the following general formula (XVII), HE-510 (trade name, Air Water Chemical Co., Ltd.), etc., in which i is 0, k is 0, and q is 0, is commercially available. Obtained by product.

Figure 108120128-A0305-02-0033-22
Figure 108120128-A0305-02-0033-22

式(XVII)中，R32~R34表示碳數1~18的一價有機基，可分別均相同亦可不同。i分別獨立地為0~3的整數，k分別獨立地為0~4的整數，q分別獨立地為0~5的整數。l及m分別為平均值，分別獨立地為0~11的數。其中，l與m的合計為1~11的數。 In formula (XVII), R 32 to R 34 represent monovalent organic groups having 1 to 18 carbon atoms, and may be the same or different. i is an integer from 0 to 3, k is an integer from 0 to 4, and q is an integer from 0 to 5. l and m are respectively average values, and are independently numbers from 0 to 11. Among them, the total of l and m is a number from 1 to 11.

酚醛清漆型酚樹脂只要為使選自由苯酚化合物及萘酚化合物所組成的群組中的至少一種酚性化合物與醛化合物於酸性觸媒下縮合或共縮合而獲得的酚樹脂，則並無特別限定。例如較佳為下述通式(XVIII)所表示的酚樹脂。 The novolac-type phenol resin is not particularly limited as long as it is a phenol resin obtained by condensing or co-condensing at least one phenolic compound selected from the group consisting of phenol compounds and naphthol compounds and an aldehyde compound under an acidic catalyst. limited. For example, a phenol resin represented by the following general formula (XVIII) is preferred.

下述通式(XVIII)所表示的酚樹脂中，i為0、R35均為氫原子的特瑪諾爾(Tamanol)758、759(荒川化學工業股份有限公司，商品名)、HP-850N(日立化成股份有限公司，商品名)等 可作為市售品而獲取。 Among the phenol resins represented by the following general formula (XVIII), Tamanol 758 and 759 (trade name of Arakawa Chemical Industry Co., Ltd.), HP-850N ( Hitachi Chemical Co., Ltd., trade name) and the like are available as commercial products.

Figure 108120128-A0305-02-0034-23
Figure 108120128-A0305-02-0034-23

式(XVIII)中，R35表示氫原子或碳數1~18的一價有機基，可分別均相同亦可不同。R36表示碳數1~18的一價有機基，可分別均相同亦可不同。i分別獨立地表示0~3的整數。n為平均值，表示0~10的數。 In formula (XVIII), R 35 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and they may be the same or different. R 36 represents a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. i independently represents an integer from 0 to 3. n is the average value, representing a number from 0 to 10.

所述通式(XII)~通式(XVIII)中的R22~R36中記載的「可分別均相同亦可不同」例如是指式(XII)中的i個R22可均相同亦可相互不同。關於其他的R23~R36，是指式中所含的各自的個數可均相同亦可相互不同。另外，R22~R36分別可相同亦可不同。例如，R22及R23可均相同亦可不同，R30及R31可均相同亦可不同。 The words "may be the same or different" described in the R 22 to R 36 in the general formula (XII) to the general formula (XVIII), for example, means that i R 22 in the formula (XII) may be all the same or different. different from each other. Regarding the other R 23 to R 36 , it means that the respective numbers contained in the formula may be the same or different from each other. In addition, R 22 to R 36 may be the same or different, respectively. For example, R 22 and R 23 may be the same or different, and R 30 and R 31 may be the same or different.

所述通式(XII)~通式(XVIII)中的n較佳為0~10的範圍。若為10以下，則樹脂成分的熔融黏度不會過高，硬化性樹脂組成物的熔融成形時的黏度亦變低，未發生填充不良或難以產生接合線(連接元件與引線的金屬線)的變形。1分子中的平均 n較佳為設定為0~4的範圍。 n in the general formulas (XII) to (XVIII) is preferably in the range of 0 to 10. If it is 10 or less, the melt viscosity of the resin component will not be too high, the viscosity of the curable resin composition during melt molding will also be low, and filling defects will not occur or bonding wires (metal wires that connect components and leads) will not easily occur. Deformation. average in 1 molecule n is preferably set in the range of 0 to 4.

硬化劑的官能基當量(於酚硬化劑的情況下為羥基當量)並無特別限制。就成形性、耐回焊性、電氣可靠性等各種特性平衡的觀點而言，較佳為70g/eq~1000g/eq，更佳為80g/eq~500g/eq。 The functional group equivalent of the hardener (hydroxyl equivalent in the case of a phenol hardener) is not particularly limited. From the viewpoint of the balance of various characteristics such as formability, reflow resistance, and electrical reliability, 70g/eq to 1000g/eq is preferred, and 80g/eq to 500g/eq is more preferred.

硬化劑的軟化點或熔點並無特別限制。就成形性與耐回焊性的觀點而言，較佳為40℃~180℃，就硬化性樹脂組成物的製造時的操作性的觀點而言，更佳為50℃~130℃。 The softening point or melting point of the hardener is not particularly limited. From the viewpoint of formability and reflow resistance, 40°C to 180°C is preferred, and from the viewpoint of workability during production of the curable resin composition, 50°C to 130°C is more preferred.

硬化性樹脂與硬化劑的當量比、即硬化劑中的官能基數相對於硬化性樹脂中的官能基數的比(硬化劑中的官能基數/硬化性樹脂中的官能基數)並無特別限制。就將各自的未反應成分抑制得少的觀點而言，較佳為設定為0.5~2.0的範圍，更佳為設定為0.6~1.3的範圍。就成形性與耐回焊性的觀點而言，進而佳為設定為0.8~1.2的範圍。 The equivalent ratio of the curable resin to the curing agent, that is, the ratio of the number of functional groups in the curing agent to the number of functional groups in the curable resin (number of functional groups in the curing agent/number of functional groups in the curing resin) is not particularly limited. From the viewpoint of suppressing each unreacted component to a small amount, it is preferably set to the range of 0.5 to 2.0, and more preferably set to the range of 0.6 to 1.3. From the viewpoint of formability and reflow resistance, it is more preferable to set it in the range of 0.8 to 1.2.

(硬化促進劑) (hardening accelerator)

硬化性樹脂組成物亦可包含硬化促進劑。硬化促進劑的種類並無特別限制，可根據硬化性樹脂的種類、硬化性樹脂組成物的所期望的特性等選擇。 The curable resin composition may also contain a curing accelerator. The type of curing accelerator is not particularly limited and can be selected according to the type of curable resin, desired properties of the curable resin composition, and the like.

就硬化性及流動性的觀點而言，硬化促進劑較佳為含有鏻化合物。作為鏻化合物，具體而言可列舉：三苯基膦、二苯基(對甲苯)膦、三(烷基苯基)膦、三(烷氧基苯基)膦、三(烷基．烷氧基苯基)膦、三(二烷基苯基)膦、三(三烷基苯基)膦、三(四烷基苯基)膦、 三(二烷氧基苯基)膦、三(三烷氧基苯基)膦、三(四烷氧基苯基)膦、三烷基膦、二烷基芳基膦、烷基二芳基膦等三級膦；馬來酸酐、1,4-苯醌、2,5-甲苯醌、1,4-萘醌、2,3-二甲基苯醌、2,6-二甲基苯醌、2,3-二甲氧基-5-甲基-1,4-苯醌、2,3-二甲氧基-1,4-苯醌、苯基-1,4-苯醌等醌化合物、重氮苯基甲烷等具有π鍵的化合物加成而形成的具有分子內極化的化合物；於使所述三級膦或所述膦化合物與4-溴苯酚、3-溴苯酚、2-溴苯酚、4-氯苯酚、3-氯苯酚、2-氯苯酚、4-碘苯酚、3-碘苯酚、2-碘苯酚、4-溴-2-甲基苯酚、4-溴-3-甲基苯酚、4-溴-2,6-二甲基苯酚、4-溴-3,5-二甲基苯酚、4-溴-2,6-二-第三丁基苯酚、4-氯-1-萘酚、1-溴-2-萘酚、6-溴-2-萘酚、4-溴-4'-羥基聯苯等鹵化苯酚化合物反應後經過脫鹵化氫的步驟而獲得的具有分子內極化的化合物；四苯基鏻等四取代鏻、四-對甲苯硼酸鹽等不存在與硼原子鍵結的苯基的四取代鏻及四取代硼酸鹽；四取代鏻與自酚化合物脫離質子後的陰離子的鹽、四取代鏻與自羧酸化合物脫離質子後的陰離子的鹽等。 From the viewpoint of hardening properties and fluidity, the hardening accelerator preferably contains a phosphonium compound. Specific examples of the phosphonium compound include triphenylphosphine, diphenyl(p-toluene)phosphine, tris(alkylphenyl)phosphine, tris(alkoxyphenyl)phosphine, and tris(alkyl.alkoxy)phosphine. phenyl)phosphine, tris(dialkylphenyl)phosphine, tris(trialkylphenyl)phosphine, tris(tetraalkylphenyl)phosphine, Tris(dialkoxyphenyl)phosphine, tris(trialkoxyphenyl)phosphine, tris(tetraalkoxyphenyl)phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiaryl Tertiary phosphine such as phosphine; maleic anhydride, 1,4-benzoquinone, 2,5-toluoquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone , 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone and other quinone compounds A compound with intramolecular polarization formed by the addition of compounds with π bonds such as diazophenylmethane; in making the tertiary phosphine or the phosphine compound and 4-bromophenol, 3-bromophenol, 2- Bromophenol, 4-chlorophenol, 3-chlorophenol, 2-chlorophenol, 4-iodophenol, 3-iodophenol, 2-iodophenol, 4-bromo-2-methylphenol, 4-bromo-3-methyl phenol, 4-bromo-2,6-dimethylphenol, 4-bromo-3,5-dimethylphenol, 4-bromo-2,6-di-tert-butylphenol, 4-chloro-1 -Naphthol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, 4-bromo-4'-hydroxybiphenyl and other halogenated phenol compounds are obtained through the dehydrohalogenation step and have intramolecular properties. Polarized compounds; tetraphenylphosphonium and other tetrasubstituted phosphoniums, tetra-p-toluene borate and other tetrasubstituted phosphoniums and tetrasubstituted borates that do not have a phenyl group bonded to the boron atom; tetrasubstituted phosphoniums and phenolic compounds that are free of protons The salt of the anion after the tetrasubstituted phosphonium and the anion after removing the proton from the carboxylic acid compound, etc.

所述鏻化合物中，較佳為下述通式(I-1)所表示的化合物(以下，亦稱為特定硬化促進劑)。 Among the phosphonium compounds, a compound represented by the following general formula (I-1) (hereinafter also referred to as a specific hardening accelerator) is preferred.

[化24]

Figure 108120128-A0305-02-0037-24
[Chemistry 24]
Figure 108120128-A0305-02-0037-24

式(I-1)中，R1~R3分別獨立地為碳數1~18的烴基，R1~R3中的兩個以上可相互鍵結而形成環狀結構，R4~R7分別獨立地為氫原子、羥基或碳數1~18的有機基，R4~R7中的兩個以上可相互鍵結而形成環狀結構。 In formula (I-1), R 1 ~ R 3 are each independently a hydrocarbon group with 1 to 18 carbon atoms. Two or more of R 1 ~ R 3 can be bonded to each other to form a cyclic structure. R 4 ~ R 7 Each is independently a hydrogen atom, a hydroxyl group or an organic group having 1 to 18 carbon atoms, and two or more of R 4 to R 7 may be bonded to each other to form a cyclic structure.

作為通式(I-1)的R1~R3記載的「碳數1~18的烴基」包括碳數為1~18的脂肪族烴基及碳數為6~18的芳香族烴基。 The "hydrocarbon group having 1 to 18 carbon atoms" described as R 1 to R 3 in the general formula (I-1) includes an aliphatic hydrocarbon group having 1 to 18 carbon atoms and an aromatic hydrocarbon group having 6 to 18 carbon atoms.

就流動性的觀點而言，碳數1~18的脂肪族烴基較佳為碳數1~8，更佳為2~6，進而佳為4~6。 From the viewpoint of fluidity, the aliphatic hydrocarbon group having 1 to 18 carbon atoms is preferably 1 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 4 to 6 carbon atoms.

碳數1~18的脂肪族烴基可為碳數1~18的直鏈或分支狀的脂肪族烴基，亦可為碳數3~18的脂環式烴基。就容易製造的觀點而言，較佳為直鏈或分支狀的脂肪族烴基。 The aliphatic hydrocarbon group having 1 to 18 carbon atoms may be a linear or branched aliphatic hydrocarbon group having 1 to 18 carbon atoms, or may be an alicyclic hydrocarbon group having 3 to 18 carbon atoms. From the viewpoint of ease of production, a linear or branched aliphatic hydrocarbon group is preferred.

作為碳數1~18的直鏈或分支狀的脂肪族烴基，具體而言可列舉：甲基、乙基、丙基、異丙基、正丁基、第二丁基、第三丁基、戊基、己基、辛基、癸基、十二烷基等烷基、烯丙基、乙烯基等。直鏈或分支狀的脂肪族烴基可具有取代基，亦可不具有取代基。作為取代基，可列舉：甲氧基、乙氧基、丁氧基、第 三丁氧基等烷氧基、苯基、萘基等芳基、羥基、胺基、鹵素原子等。直鏈或分支狀的脂肪族烴基可具有兩個以上的取代基，此時的取代基可相同亦可不同。於直鏈或分支狀的脂肪族烴基具有取代基的情況下，脂肪族烴基與取代基中所含的碳數的合計較佳為1~18。就硬化性的觀點而言，較佳為未經取代的烷基，更佳為碳數1~8的未經取代的烷基，進而佳為正丁基、異丁基、正戊基、正己基及正辛基。 Specific examples of linear or branched aliphatic hydrocarbon groups having 1 to 18 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, second butyl, and third butyl. Alkyl groups such as pentyl, hexyl, octyl, decyl, dodecyl, allyl, vinyl, etc. The linear or branched aliphatic hydrocarbon group may or may not have a substituent. Examples of substituents include: methoxy, ethoxy, butoxy, Alkoxy groups such as tributoxy group, aryl groups such as phenyl and naphthyl groups, hydroxyl groups, amine groups, halogen atoms, etc. The linear or branched aliphatic hydrocarbon group may have two or more substituents, and the substituents in this case may be the same or different. When the linear or branched aliphatic hydrocarbon group has a substituent, the total number of carbon atoms contained in the aliphatic hydrocarbon group and the substituent is preferably 1 to 18. From the viewpoint of hardening properties, an unsubstituted alkyl group is preferred, an unsubstituted alkyl group having 1 to 8 carbon atoms is more preferred, and n-butyl, isobutyl, n-pentyl, and n-hexyl are further preferred. base and n-octyl.

作為碳數3~18的脂環式烴，具體而言可列舉：環戊基、環己基、環庚基等環烷基、環戊烯基、環己烯基等環烯基等。脂環式烴基可具有取代基，亦可不具有取代基。作為取代基，可列舉：甲基、乙基、丁基、第三丁基等烷基、甲氧基、乙氧基、丁氧基、第三丁氧基等烷氧基、苯基、萘基等芳基、羥基、胺基、鹵素原子等。脂環式烴基可具有兩個以上的取代基，此時的取代基可相同亦可不同。於脂環式烴基具有取代基的情況下，脂環式烴基與取代基中所含的碳數的合計較佳為3~18。於脂環式烴基具有取代基的情況下，取代基的位置並無特別限定。就硬化性的觀點而言，較佳為未經取代的環烷基，更佳為碳數4~10的未經取代的環烷基，進而佳為環己基、環戊基及環庚基。 Specific examples of alicyclic hydrocarbons having 3 to 18 carbon atoms include cycloalkyl groups such as cyclopentyl, cyclohexyl, and cycloheptyl, and cycloalkenyl groups such as cyclopentenyl and cyclohexenyl. The alicyclic hydrocarbon group may or may not have a substituent. Examples of substituents include: alkyl groups such as methyl, ethyl, butyl, and tert-butyl; alkoxy groups such as methoxy, ethoxy, butoxy, and tert-butoxy; phenyl; naphthalene; Aryl groups, hydroxyl groups, amine groups, halogen atoms, etc. The alicyclic hydrocarbon group may have two or more substituents, and the substituents in this case may be the same or different. When the alicyclic hydrocarbon group has a substituent, the total number of carbon atoms contained in the alicyclic hydrocarbon group and the substituent is preferably 3 to 18. When the alicyclic hydrocarbon group has a substituent, the position of the substituent is not particularly limited. From the viewpoint of hardening properties, an unsubstituted cycloalkyl group is preferred, an unsubstituted cycloalkyl group having 4 to 10 carbon atoms is more preferred, and a cyclohexyl group, a cyclopentyl group and a cycloheptyl group are further preferred.

碳數為6~18的芳香族烴基較佳為碳數6~14，更佳為6~10。芳香族烴基可具有取代基，亦可不具有取代基。作為取代基，可列舉：甲基、乙基、丁基、第三丁基等烷基、甲氧基、乙氧基、丁氧基、第三丁氧基等烷氧基、苯基、萘基等芳基、羥基、 胺基、鹵素原子等。芳香族烴基可具有兩個以上的取代基，此時的取代基可相同亦可不同。於芳香族烴基具有取代基的情況下，芳香族烴基與取代基中所含的碳數的合計較佳為6~18。於芳香族烴基具有取代基的情況下，取代基的位置並無特別限定。 The aromatic hydrocarbon group having 6 to 18 carbon atoms is preferably 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms. The aromatic hydrocarbon group may or may not have a substituent. Examples of substituents include: alkyl groups such as methyl, ethyl, butyl, and tert-butyl; alkoxy groups such as methoxy, ethoxy, butoxy, and tert-butoxy; phenyl; naphthalene; Aryl groups, hydroxyl groups, etc. Amino groups, halogen atoms, etc. The aromatic hydrocarbon group may have two or more substituents, and the substituents in this case may be the same or different. When the aromatic hydrocarbon group has a substituent, the total number of carbon atoms contained in the aromatic hydrocarbon group and the substituent is preferably 6 to 18. When the aromatic hydrocarbon group has a substituent, the position of the substituent is not particularly limited.

作為碳數為6~18的芳香族烴基，具體而言可列舉：苯基、1-萘基、2-萘基、甲苯基、二甲基苯基、乙基苯基、丁基苯基、第三丁基苯基、甲氧基苯基、乙氧基苯基、丁氧基苯基、第三丁氧基苯基。該些芳香族烴基中的取代基的位置可為鄰位、間位及對位中的任一種。就流動性的觀點而言，較佳為未經取代且碳數為6~12或包含取代基的碳數為6~12的芳基，更佳為未經取代且碳數為6~10或包含取代基的碳數為6~10的芳基，進而佳為苯基、對甲苯基及對甲氧基苯基。 Specific examples of the aromatic hydrocarbon group having 6 to 18 carbon atoms include phenyl, 1-naphthyl, 2-naphthyl, tolyl, dimethylphenyl, ethylphenyl, butylphenyl, tert-butylphenyl, methoxyphenyl, ethoxyphenyl, butoxyphenyl, tert-butoxyphenyl. The position of the substituents in these aromatic hydrocarbon groups may be any of ortho, meta and para. From the viewpoint of fluidity, an unsubstituted aryl group with 6 to 12 carbon atoms or a substituent-containing aryl group with 6 to 12 carbon atoms is preferred, and an unsubstituted aryl group with 6 to 10 carbon atoms or a substituent is more preferred. The aryl group having 6 to 10 carbon atoms including a substituent is more preferably a phenyl group, a p-tolyl group and a p-methoxyphenyl group.

作為通式(I-1)的R1~R3所記載的用語「R1~R3中的兩個以上可相互鍵結而形成環狀結構」是指R1~R3中的2個或3個鍵結，整體成為一個二價或三價烴基的情況。作為此時的R1~R3的例子，可列舉可與磷原子鍵結而形成環狀結構的伸乙基、伸丙基、伸丁基、伸戊基、伸己基等伸烷基、伸乙炔基、伸丙炔基、伸丁炔基等伸烯基、亞甲基伸苯基等伸芳烷基、伸苯基、伸萘基、伸蒽基等伸芳基等、可與磷原子鍵結而形成環狀結構的取代基。該些取代基亦可進一步經烷基、烷氧基、芳基、芳氧基、胺基、羥基、鹵素原子等取代。 The term "two or more of R 1 to R 3 may be bonded to each other to form a cyclic structure" described as R 1 to R 3 in the general formula (I-1) means two of R 1 to R 3 Or three bonds, the whole becomes a divalent or trivalent hydrocarbon group. Examples of R 1 to R 3 at this time include alkylene groups such as ethylene group, propylene group, butylene group, pentylene group, and hexylene group, which can be bonded to a phosphorus atom to form a cyclic structure. Alkenylene groups such as ethynyl, propynyl and butynyl groups, aralkyl groups such as methylene phenylene group, arylyl groups such as phenylene group, naphthylene group, anthracenyl group, etc., can be combined with phosphorus atoms A substituent that bonds to form a cyclic structure. These substituents may also be further substituted by alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, hydroxyl groups, halogen atoms, etc.

作為所述通式(I-1)中的R4~R7所記載的「碳數1~ 18的有機基」是指包含碳數為1~18且可經取代亦可未經取代的脂肪族烴基、芳香族烴基、脂肪族烴氧基、芳香族烴氧基、醯基、烴氧基羰基、以及醯氧基。 The "organic group having 1 to 18 carbon atoms" described as R 4 to R 7 in the general formula (I-1) refers to a fat containing 1 to 18 carbon atoms that may or may not be substituted. aliphatic hydrocarbon group, aromatic hydrocarbon group, aliphatic hydrocarbonoxy group, aromatic hydrocarbonoxy group, acyl group, alkoxycarbonyl group, and acyloxy group.

作為所述脂肪族烴基及芳香族烴基的例子，可列舉作為R1~R3所表示的脂肪族烴基及芳香族烴基的例子在上文敘述者。 Examples of the aliphatic hydrocarbon group and aromatic hydrocarbon group include those described above as examples of the aliphatic hydrocarbon group and aromatic hydrocarbon group represented by R 1 to R 3 .

作為所述脂肪族烴氧基，可列舉：甲氧基、乙氧基、丙氧基、異丙氧基、正丁氧基、2-丁氧基、第三丁氧基、環丙氧基、環己氧基、環戊氧基、烯丙氧基、乙烯氧基等所述脂肪族烴基上鍵結有氧原子的結構的氧基；該些脂肪族烴氧基進一步被烷基、烷氧基、芳基、芳氧基、胺基、羥基、鹵素原子等取代的基等。 Examples of the aliphatic hydrocarbonoxy group include: methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, 2-butoxy group, tert-butoxy group, and cyclopropoxy group , cyclohexyloxy, cyclopentyloxy, allyloxy, vinyloxy and other aliphatic hydrocarbon groups with oxygen atoms bonded to the structure of the structure; these aliphatic hydrocarbon oxygen groups are further alkyl, alkyl Substituted groups such as oxygen group, aryl group, aryloxy group, amine group, hydroxyl group, halogen atom, etc.

作為所述芳香族烴氧基，可列舉：苯氧基、甲基苯氧基、乙基苯氧基、甲氧基苯氧基、丁氧基苯氧基、苯氧基苯氧基等所述芳香族烴基上鍵結有氧原子的結構的氧基；該些芳香族烴氧基進一步被烷基、烷氧基、芳基、芳氧基、胺基、鹵素原子等取代的基等。 Examples of the aromatic hydrocarbonoxy group include phenoxy group, methylphenoxy group, ethylphenoxy group, methoxyphenoxy group, butoxyphenoxy group, phenoxyphenoxy group and the like. The aromatic hydrocarbon group is an oxygen group having an oxygen atom bonded to the structure; the aromatic hydrocarbon oxygen group is further substituted by an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amine group, a halogen atom, etc.

作為所述醯基，可列舉：甲醯基、乙醯基、乙基羰基、丁醯基、環己基羰基、烯丙基羰基等脂肪族烴羰基、苯基羰基、甲基苯基羰基等芳香族烴羰基等；該些脂肪族烴羰基或芳香族烴羰基進一步被烷基、烷氧基、芳基、芳氧基、胺基、鹵素原子等取代的基等。 Examples of the hydroxyl group include aliphatic hydrocarbon carbonyl groups such as a formyl group, acetyl carbonyl group, ethyl carbonyl group, butyl carbonyl group, cyclohexyl carbonyl group, and allyl carbonyl group, and aromatic hydrocarbon groups such as a phenyl carbonyl group and methylphenyl carbonyl group. Carbonyl groups, etc.; these aliphatic hydrocarbon carbonyl groups or aromatic hydrocarbon carbonyl groups are further substituted by alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amine groups, halogen atoms, etc.

作為所述烴氧羰基，可列舉：甲氧基羰基、乙氧基羰基、丁氧基羰基、烯丙氧基羰基、環己基氧基羰基等脂肪族烴氧羰基、 苯氧基羰基、甲基苯氧基羰基等芳香族烴氧羰基、該些脂肪族烴氧羰基或芳香族烴氧羰基進一步被烷基、烷氧基、芳基、芳氧基、胺基、鹵素原子等取代的基等。 Examples of the hydrocarbonoxycarbonyl group include aliphatic hydrocarbonoxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, allyloxycarbonyl group, and cyclohexyloxycarbonyl group; Aromatic hydrocarbonoxycarbonyl groups such as phenoxycarbonyl group and methylphenoxycarbonyl group, these aliphatic hydrocarbonoxycarbonyl groups or aromatic hydrocarbonoxycarbonyl groups are further substituted by alkyl group, alkoxy group, aryl group, aryloxy group, amine group, Substituted groups such as halogen atoms and the like.

作為所述醯氧基，可列舉：甲基羰氧基、乙基羰氧基、丁基羰氧基、烯丙基羰氧基、環己基羰氧基等脂肪族烴羰氧基、苯基羰氧基、甲基苯基羰氧基等芳香族烴羰氧基、該些脂肪族烴羰氧基或芳香族烴羰氧基進一步被烷基、烷氧基、芳基、芳氧基、胺基、鹵素原子等取代的基等。 Examples of the hydroxyl group include aliphatic hydrocarbon carbonyloxy groups such as methylcarbonyloxy, ethylcarbonyloxy, butylcarbonyloxy, allylcarbonyloxy, cyclohexylcarbonyloxy, and the like, and phenyl Aromatic hydrocarbon carbonyloxy groups such as carbonyloxy and methylphenylcarbonyloxy, these aliphatic hydrocarbon carbonyloxy or aromatic hydrocarbon carbonyloxy groups are further substituted by alkyl, alkoxy, aryl, aryloxy, Substituted groups such as amine group and halogen atom, etc.

作為所述通式(I-1)的R4~R7所記載的用語「兩個以上的R4~R7可相互鍵結而形成環狀結構」是指2個~4個R4~R7鍵結，作為整體可形成一個2價~4價的有機基。作為此時的R4~R7，可列舉伸乙基、伸丙基、伸丁基、伸戊基、伸己基等伸烷基、伸乙炔基、伸丙炔基、伸丁炔基等伸烯基、亞甲基伸苯基等伸芳烷基、伸苯基、伸萘基、伸蒽基等伸芳基等可形成環狀結構的取代基、該些的氧基或雙氧基等。該些取代基亦可進一步經烷基、烷氧基、芳基、芳氧基、胺基、羥基、鹵素原子等取代。 The term "two or more R 4 to R 7 can be bonded to each other to form a cyclic structure" described as R 4 to R 7 in the general formula (I-1) means 2 to 4 R 4 to R 7 bond, as a whole can form a 2- to 4-valent organic group. Examples of R 4 to R 7 in this case include alkylene groups such as ethylene, propylene, butylene, pentylene, and hexylene, and alkylene groups such as ethynyl, propynyl, and butynyl. arylalkylene groups such as alkenyl and methylene phenylene groups, arylalkylene groups such as phenylene groups, naphthylene groups, and anthracenyl groups, and other substituents that can form a cyclic structure, and their oxy or dioxy groups, etc. . These substituents may also be further substituted by alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, hydroxyl groups, halogen atoms, etc.

作為所述通式(I-1)的R4~R7，並無特別限定。例如較佳為分別獨立地選自氫原子、羥基、經取代或未經取代的烷基、經取代或未經取代的芳基、經取代或未經取代的烷氧基、或經取代或未經取代的芳氧基。其中，就原料的獲取容易性的觀點而言，較佳為氫原子、羥基、未經取代或經選自由烷基及烷氧基所組成的群組中的至少一種取代的芳基、或者鏈狀或環狀的烷基。作為 未經取代或經選自由烷基及烷氧基所組成的群組中的至少一種取代的芳基，可列舉苯基、對甲苯基、間甲苯基、鄰甲苯基、對甲氧基苯基等。作為鏈狀或環狀的烷基，可列舉甲基、乙基、丙基、異丙基、丁基、2-丁基、第三丁基、辛基、環己基等。就硬化性的觀點而言，較佳為R4~R7全部為氫原子的情況、或者R4~R7中的至少一個為羥基、其餘全部為氫原子的情況。 R 4 to R 7 in the general formula (I-1) are not particularly limited. For example, it is preferable to be independently selected from a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted alkoxy group. Substituted aryloxy. Among them, from the viewpoint of easy acquisition of raw materials, a hydrogen atom, a hydroxyl group, an aryl group that is unsubstituted or substituted with at least one selected from the group consisting of an alkyl group and an alkoxy group, or a chain Shape or cyclic alkyl group. Examples of the aryl group that is unsubstituted or substituted with at least one selected from the group consisting of an alkyl group and an alkoxy group include phenyl, p-tolyl, m-tolyl, o-tolyl, and p-methoxybenzene Key et al. Examples of the chain or cyclic alkyl group include methyl, ethyl, propyl, isopropyl, butyl, 2-butyl, tert-butyl, octyl, cyclohexyl, and the like. From the viewpoint of hardenability, it is preferable that all R 4 to R 7 are hydrogen atoms, or that at least one of R 4 to R 7 is a hydroxyl group and the rest are all hydrogen atoms.

通式(I-1)中，更佳為R1~R3中的兩個以上為碳數1~18的烷基或碳數3~18的環烷基，R4~R7全部為氫原子或至少一個為羥基，其餘全部為氫原子。進而佳為R1~R3中的全部為碳數1~18的烷基或碳數3~18的環烷基，R4~R7全部為氫原子或至少一個為羥基，其餘全部為氫原子。 In the general formula (I-1), it is more preferable that two or more of R 1 to R 3 are alkyl groups having 1 to 18 carbon atoms or cycloalkyl groups having 3 to 18 carbon atoms, and all R 4 to R 7 are hydrogen. At least one of the atoms is a hydroxyl group, and all the others are hydrogen atoms. More preferably, all of R 1 to R 3 are alkyl groups with 1 to 18 carbon atoms or cycloalkyl groups with 3 to 18 carbon atoms, all of R 4 to R 7 are hydrogen atoms or at least one is a hydroxyl group, and the rest are all hydrogen atoms. atom.

就快速硬化性的觀點而言，特定硬化促進劑較佳為下述通式(I-2)所表示的化合物。 From the viewpoint of rapid hardening properties, the specific hardening accelerator is preferably a compound represented by the following general formula (I-2).

Figure 108120128-A0305-02-0042-25
Figure 108120128-A0305-02-0042-25

式(I-2)中，R1~R3分別獨立地為碳數1~18的烴基，R1~R3中的兩個以上可相互鍵結而形成環狀結構，R4~R6分別獨立地為氫原子或碳數1~18的有機基，R4~R6中的兩個以上可相互鍵結而形成環狀結構。 In formula (I-2), R 1 ~ R 3 are each independently a hydrocarbon group with 1 to 18 carbon atoms. Two or more of R 1 ~ R 3 can be bonded to each other to form a cyclic structure. R 4 ~ R 6 They are each independently a hydrogen atom or an organic group having 1 to 18 carbon atoms, and two or more of R 4 to R 6 may be bonded to each other to form a cyclic structure.

通式(I-2)中的R1~R6的具體例分別與通式(I-1)中的R1~R6的具體例相同，較佳範圍亦相同。 Specific examples of R 1 to R 6 in the general formula (I-2) are the same as those of R 1 to R 6 in the general formula (I-1), and the preferred ranges are also the same.

作為特定硬化促進劑的具體例，可列舉：三苯基膦與1,4-苯醌的加成反應物、三正丁基膦與1,4-苯醌的加成反應物、三環己基膦與1,4-苯醌的加成反應物、二環己基苯基膦與1,4-苯醌的加成反應物、環己基二苯基膦與1,4-苯醌的加成反應物、三異丁基膦與1,4-苯醌的加成反應物、三環戊基膦與1,4-苯醌的加成反應物等。 Specific examples of the specific hardening accelerator include an addition reaction product of triphenylphosphine and 1,4-benzoquinone, an addition reaction product of tri-n-butylphosphine and 1,4-benzoquinone, and tricyclohexyl Addition reaction product of phosphine and 1,4-benzoquinone, addition reaction product of dicyclohexylphenylphosphine and 1,4-benzoquinone, addition reaction of cyclohexyldiphenylphosphine and 1,4-benzoquinone substance, the addition reaction product of triisobutylphosphine and 1,4-benzoquinone, the addition reaction product of tricyclopentylphosphine and 1,4-benzoquinone, etc.

特定硬化促進劑例如可作為第三膦化合物與醌化合物的加成物而獲得。 Specific hardening accelerators are available, for example, as adducts of third phosphine compounds and quinone compounds.

作為第三膦化合物，具體而言可列舉：三苯基膦、三丁基膦、二丁基苯基膦、丁基二苯基膦、乙基二苯基膦、三苯基膦、三(4-甲基苯基)膦、三(4-乙基苯基)膦、三(4-丙基苯基)膦、三(4-丁基苯基)膦、三(異丙基苯基)膦、三(第三丁基苯基)膦、三(2,4-二甲基苯基)膦、三(2,6-二甲基苯基)膦、三(2,4,6-三甲基苯基)膦、三(2,6-二甲基-4-乙氧基苯基)膦、三(4-甲氧基苯基)膦、三(4-乙氧基苯基)膦等。就成形性的觀點而言，較佳為三苯基膦及三丁基膦。 Specific examples of the third phosphine compound include triphenylphosphine, tributylphosphine, dibutylphenylphosphine, butyldiphenylphosphine, ethyldiphenylphosphine, triphenylphosphine, tris( 4-methylphenyl)phosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-butylphenyl)phosphine, tris(isopropylphenyl) Phosphine, tris(tert-butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, tris(2,6-dimethylphenyl)phosphine, tris(2,4,6-tris Methylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(4-ethoxyphenyl)phosphine wait. From the viewpoint of formability, triphenylphosphine and tributylphosphine are preferred.

作為醌化合物，具體而言，可列舉：鄰苯醌、對苯醌、 聯苯醌、1,4-萘醌、蒽醌等。就耐濕性與保存穩定性的觀點而言，較佳為對苯醌。 Specific examples of the quinone compound include o-benzoquinone, p-benzoquinone, Diphenoquinone, 1,4-naphthoquinone, anthraquinone, etc. From the viewpoint of moisture resistance and storage stability, p-benzoquinone is preferred.

硬化性樹脂組成物亦可包含鏻化合物以外的硬化促進劑。 The curable resin composition may contain a curing accelerator other than the phosphonium compound.

作為鏻化合物以外的硬化促進劑，具體而言可列舉：1,5-二氮雜雙環[4.3.0]壬烯-5(1,5-Diazabicyclo[4.3.0]nonene-5，DBN)、1,8-二氮雜雙環[5.4.0]十一烯-7(1,8-Diazabicyclo[5.4.0]undecene-7，DBU)等二氮雜雙環烯烴、2-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、2-十七烷基咪唑等環狀脒化合物；所述環狀脒化合物的衍生物；所述環狀脒化合物或其衍生物的苯酚酚醛清漆鹽；於該些化合物上加成馬來酸酐、1,4-苯醌、2,5-甲苯醌、1,4-萘醌、2,3-二甲基苯醌、2,6-二甲基苯醌、2,3-二甲氧基-5-甲基-1,4-苯醌、2,3-二甲氧基-1,4-苯醌、苯基-1,4-苯醌等醌化合物、重氮苯基甲烷等具有π鍵的化合物而形成的具有分子內極化的化合物；DBU的四苯基硼鹽、DBN的四苯基硼鹽、2-乙基-4-甲基咪唑的四苯基硼鹽、N-甲基嗎啉的四苯基硼鹽等環狀脒鎓化合物；吡啶、三乙胺、三乙二胺、苄基二甲基胺、三乙醇胺、二甲基胺基乙醇、三(二甲基胺基甲基)苯酚等三級胺化合物；所述三級胺化合物的衍生物；乙酸四正丁基銨、磷酸四正丁基銨、乙酸四乙基銨、苯甲酸四正己基銨、氫氧化四丙基銨等銨鹽化合物等。 Specific examples of hardening accelerators other than phosphonium compounds include: 1,5-Diazabicyclo[4.3.0]nonene-5 (DBN), 1,8-Diazabicyclo[5.4.0]undecene-7 (1,8-Diazabicyclo[5.4.0]undecene-7, DBU) and other diazabicycloalkenes, 2-methylimidazole, 2- Cyclic amidine compounds such as phenylimidazole, 2-phenyl-4-methylimidazole, and 2-heptadecylimidazole; derivatives of the cyclic amidine compound; phenol of the cyclic amidine compound or its derivatives Novolac salt; maleic anhydride, 1,4-benzoquinone, 2,5-toluoquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6- Dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4- Compounds with intramolecular polarization formed from quinone compounds such as benzoquinone and compounds with π bonds such as diazophenylmethane; DBU tetraphenylboron salt, DBN tetraphenylboron salt, 2-ethyl-4 - Cyclic amidinium compounds such as tetraphenylboron salt of methylimidazole and tetraphenylboron salt of N-methylmorpholine; pyridine, triethylamine, triethylenediamine, benzyldimethylamine, and triethanolamine , dimethylaminoethanol, tris(dimethylaminomethyl)phenol and other tertiary amine compounds; derivatives of the tertiary amine compounds; tetra-n-butylammonium acetate, tetra-n-butylammonium phosphate, acetic acid Ammonium salt compounds such as tetraethylammonium, tetra-n-hexylammonium benzoate, tetrapropylammonium hydroxide, etc.

於硬化性樹脂組成物含有特定硬化促進劑作為硬化促 進劑的情況下，特定硬化促進劑的含有率較佳為硬化促進劑整體的30質量%以上，更佳為50質量%以上，進而佳為70質量%以上。 The curable resin composition contains a specific hardening accelerator as a hardening accelerator. When adding an agent, the content rate of the specific hardening accelerator is preferably 30 mass% or more of the entire hardening accelerator, more preferably 50 mass% or more, and still more preferably 70 mass% or more.

於硬化性樹脂組成物包含硬化促進劑的情況下，硬化促進劑的量較佳為相對於樹脂成分100質量份而為0.1質量份~30質量份，更佳為1質量份~15質量份。若硬化促進劑的量相對於樹脂成分100質量份而為0.1質量份以上，則存在短時間內良好地硬化的傾向。若硬化促進劑的量相對於樹脂成分100質量份而為30質量份以下，則存在可獲得硬化速度不會過快的良好的成形品的傾向。 When the curable resin composition contains a hardening accelerator, the amount of the hardening accelerator is preferably 0.1 to 30 parts by mass, and more preferably 1 to 15 parts by mass relative to 100 parts by mass of the resin component. If the amount of the curing accelerator is 0.1 parts by mass or more with respect to 100 parts by mass of the resin component, there is a tendency for good curing in a short time. When the amount of the curing accelerator is 30 parts by mass or less based on 100 parts by mass of the resin component, a good molded article in which the curing speed is not too fast tends to be obtained.

(無機填充材) (Inorganic filler material)

硬化性樹脂組成物亦可含有無機填充材。特別是於將硬化性樹脂組成物用作半導體封裝的密封材的情況下，較佳為包含無機填充材。 The curable resin composition may contain an inorganic filler. Particularly when the curable resin composition is used as a sealing material for a semiconductor package, it is preferable to contain an inorganic filler.

無機填充材的種類並無特別限制。具體而言，可列舉：熔融二氧化矽、晶體二氧化矽、玻璃、氧化鋁、碳酸鈣、矽酸鋯、矽酸鈣、氮化矽、氮化鋁、氮化硼、氧化鈹、氧化鋯、鋯石、鎂橄欖石、塊滑石、尖晶石、富鋁紅柱石、氧化鈦、滑石、黏土、雲母等無機材料。亦可使用具有阻燃效果的無機填充材。作為具有阻燃效果的無機填充材，可列舉：氫氧化鋁、氫氧化鎂、鎂與鋅的複合氫氧化物等複合金屬氫氧化物、硼酸鋅等。其中，就線膨脹係數減少的觀點而言，較佳為熔融二氧化矽，就高導熱性的 觀點而言，較佳為氧化鋁。無機填充材可單獨使用一種，亦可將兩種以上組合而使用。作為無機填充材的狀態，可列舉粉末、將粉末球形化的顆粒、纖維等。 The type of inorganic filler is not particularly limited. Specific examples include: fused silica, crystalline silica, glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, beryllium oxide, and zirconium oxide. , zircon, forsterite, talc, spinel, mullite, titanium oxide, talc, clay, mica and other inorganic materials. Inorganic fillers with flame retardant effects can also be used. Examples of inorganic fillers having a flame retardant effect include aluminum hydroxide, magnesium hydroxide, composite metal hydroxides such as magnesium and zinc composite hydroxides, zinc borate, and the like. Among them, from the viewpoint of reducing the linear expansion coefficient, fused silica is preferred, and from the viewpoint of high thermal conductivity From a viewpoint, alumina is preferred. One type of inorganic filler may be used alone, or two or more types may be used in combination. Examples of the state of the inorganic filler include powder, particles obtained by spheroidizing the powder, and fibers.

於硬化性樹脂組成物包含無機填充材的情況下，其含有率並無特別限制。就流動性及強度的觀點而言，較佳為硬化性樹脂組成物整體的30體積%~90體積%，更佳為35體積%~80體積%，進而佳為40體積%~70體積%。若無機填充材的含有率為硬化性樹脂組成物整體的30體積%以上，則存在硬化物的熱膨脹係數、熱傳導率、彈性係數等特性進一步提高的傾向。若無機填充材的含有率為硬化性樹脂組成物整體的90體積%以下，則存在硬化性樹脂組成物的黏度的上昇得到抑制、流動性進一步提高且成形性變得更良好的傾向。 When the curable resin composition contains an inorganic filler, its content rate is not particularly limited. From the viewpoint of fluidity and strength, it is preferably 30 volume % to 90 volume % of the entire curable resin composition, more preferably 35 volume % to 80 volume %, and still more preferably 40 volume % to 70 volume %. If the content rate of the inorganic filler is 30 volume % or more of the entire curable resin composition, properties such as thermal expansion coefficient, thermal conductivity, and elastic modulus of the cured product tend to further improve. When the content rate of the inorganic filler is 90 volume % or less of the entire curable resin composition, an increase in the viscosity of the curable resin composition is suppressed, the fluidity is further improved, and the moldability tends to become better.

無機填充材的平均粒徑並無特別限制。例如，體積平均粒徑較佳為0.2μm~10μm，更佳為0.5μm~5μm。若體積平均粒徑為0.2μm以上，則存在模塑填底膠用樹脂組成物的黏度的上升進一步得到抑制的傾向。若體積平均粒徑為10μm以下，則存在對狹小的縫隙的填充性進一步提高的傾向。無機填充材的體積平均粒徑可藉由雷射繞射散射法粒度分佈測定裝置以體積平均粒徑(D50)的形式測定。 The average particle diameter of the inorganic filler is not particularly limited. For example, the volume average particle size is preferably 0.2 μm to 10 μm, more preferably 0.5 μm to 5 μm. If the volume average particle diameter is 0.2 μm or more, an increase in the viscosity of the resin composition for mold primers tends to be further suppressed. When the volume average particle diameter is 10 μm or less, the filling property of narrow gaps tends to be further improved. The volume average particle diameter of the inorganic filler can be measured as the volume average particle diameter (D50) using a laser diffraction scattering particle size distribution measuring device.

硬化性樹脂組成物或其硬化物中的無機填充材的體積平均粒徑可利用公知的方法來進行測定。例如，使用有機溶劑、硝酸、王水等自硬化性樹脂組成物或硬化物中萃取無機填充材， 利用超音波分散機等充分地分散而製備分散液。可使用該分散液，並根據利用雷射繞射散射法粒度分佈測定裝置而測定的體積基準的粒度分佈來測定無機填充材的體積平均粒徑。或者，可將硬化物埋入至透明的環氧樹脂等中，進行研磨而獲得剖面，根據利用掃描式電子顯微鏡觀察所獲得的剖面而獲得的體積基準的粒度分佈來測定無機填充材的體積平均粒徑。進而，亦可藉由如下方式來測定：使用FIB裝置(聚焦離子束SEM)等連續進行硬化物的二維的剖面觀察，並進行三維結構分析。 The volume average particle diameter of the inorganic filler in the curable resin composition or its cured product can be measured by a known method. For example, organic solvents, nitric acid, aqua regia and other self-curing resin compositions or hardened materials are used to extract inorganic fillers. Disperse thoroughly using an ultrasonic disperser or the like to prepare a dispersion liquid. The volume average particle diameter of the inorganic filler can be measured based on the volume-based particle size distribution measured using a laser diffraction scattering particle size distribution measuring device using this dispersion liquid. Alternatively, the hardened material can be embedded in transparent epoxy resin, etc., polished to obtain a cross-section, and the volume-based particle size distribution obtained by observing the obtained cross-section with a scanning electron microscope can be used to measure the volume average of the inorganic filler. particle size. Furthermore, it can also be measured by continuously observing the two-dimensional cross-section of the hardened material using a FIB device (focused ion beam SEM) or the like, and performing a three-dimensional structural analysis.

就硬化性樹脂組成物的流動性的觀點而言，關於無機填充材的粒子形狀，球形優於角形，且較佳為無機填充材的粒度分佈以廣範圍進行分佈。 From the viewpoint of the fluidity of the curable resin composition, the particle shape of the inorganic filler is preferably spherical rather than angular, and it is preferable that the particle size distribution of the inorganic filler is distributed in a wide range.

[各種添加劑] [Various additives]

硬化性樹脂組成物除了所述成分以外，亦可包含以下例示的偶合劑、離子交換體、脫模劑、阻燃劑、著色劑、應力緩和劑等各種添加劑。硬化性樹脂組成物除了以下例示的添加劑以外，亦可視需要包含在本技術領域中周知的各種添加劑。 In addition to the above-mentioned components, the curable resin composition may also contain various additives such as coupling agents, ion exchangers, release agents, flame retardants, colorants, and stress relaxants exemplified below. In addition to the additives exemplified below, the curable resin composition may optionally contain various additives well known in the art.

(偶合劑) (coupling agent)

於硬化性樹脂組成物包含無機填充材的情況下，為了提高樹脂成分與無機填充材的接著性，亦可包含偶合劑。作為偶合劑，可列舉：環氧基矽烷、巰基矽烷、胺基矽烷、烷基矽烷、醯脲矽烷、乙烯基矽烷等矽烷系化合物、鈦系化合物、鋁螯合物化合物、鋁/鋯系化合物等公知的偶合劑。 When the curable resin composition contains an inorganic filler, a coupling agent may be included in order to improve the adhesiveness between the resin component and the inorganic filler. Examples of the coupling agent include silane-based compounds such as epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureasilane, and vinylsilane, titanium-based compounds, aluminum chelate compounds, and aluminum/zirconium-based compounds. and other well-known coupling agents.

於硬化性樹脂組成物包含偶合劑的情況下，偶合劑的量較佳為相對於無機填充材100質量份而為0.05質量份~5質量份，更佳為0.1質量份~2.5質量份。若偶合劑的量相對於無機填充材100質量份而為0.05質量份以上，則存在與框架(frame)的接著性進一步提高的傾向。若偶合劑的量相對於無機填充材100質量份而為5質量份以下，則存在封裝的成形性進一步提高的傾向。 When the curable resin composition contains a coupling agent, the amount of the coupling agent is preferably 0.05 to 5 parts by mass, and more preferably 0.1 to 2.5 parts by mass relative to 100 parts by mass of the inorganic filler. When the amount of the coupling agent is 0.05 parts by mass or more based on 100 parts by mass of the inorganic filler, the adhesiveness to the frame tends to be further improved. When the amount of the coupling agent is 5 parts by mass or less based on 100 parts by mass of the inorganic filler, the formability of the package tends to be further improved.

(離子交換體) (ion exchanger)

硬化性樹脂組成物亦可包含離子交換體。尤其，於將硬化性樹脂組成物用做密封用成形材料的情況下，就使包括進行了密封的元件的電子零件裝置的耐濕性及高溫放置特性提高的觀點而言，較佳為包含離子交換體。離子交換體並無特別限制，可使用現有公知者。具體而言，可列舉水滑石化合物、以及含有選自由鎂、鋁、鈦、鋯及鉍所組成的群組中的至少一種元素的氫氧化物等。離子交換體可單獨使用一種，亦可組合使用兩種以上。其中，較佳為下述通式(A)所表示的水滑石。 The curable resin composition may contain an ion exchanger. In particular, when a curable resin composition is used as a sealing molding material, from the viewpoint of improving the moisture resistance and high-temperature storage characteristics of an electronic component device including a sealed element, it is preferable to contain ions. Exchange body. The ion exchanger is not particularly limited, and conventionally known ones can be used. Specific examples include hydrotalcite compounds, hydroxides containing at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium and bismuth. One type of ion exchanger may be used alone, or two or more types of ion exchangers may be used in combination. Among them, hydrotalcite represented by the following general formula (A) is preferred.

Mg(1-X)AlX(OH)2(CO3)X/2．mH2O．．．．．．(A) Mg (1-X) Al X (OH) 2 (CO 3 ) X/2 ． mH 2 O． ． ． ． ． ． (A)

(0<X≦0.5，m為正數) (0<X≦0.5, m is a positive number)

於硬化性樹脂組成物包含離子交換體的情況下，只要離子交換體的含量為對於捕捉鹵素離子等離子而言充分的量，則並無特別限制。例如相對於樹脂成分100質量份而較佳為0.1質量份~30質量份，更佳為1質量份~15質量份。 When the curable resin composition contains an ion exchanger, there is no particular limitation as long as the content of the ion exchanger is a sufficient amount to capture halogen ion plasma. For example, it is preferably 0.1 to 30 parts by mass, and more preferably 1 to 15 parts by mass based on 100 parts by mass of the resin component.

(脫模劑) (release agent)

就獲得成形時的與模具的良好的脫模性的觀點而言，硬化性樹脂組成物亦可包含脫模劑。脫模劑並無特別限制，可使用現有公知者。具體可列舉：棕櫚蠟(carnauba wax)、二十八酸、硬脂酸等高級脂肪酸、高級脂肪酸金屬鹽、二十八酸酯等酯系蠟、氧化聚乙烯、非氧化聚乙烯等聚烯烴系蠟等。脫模劑可單獨使用一種，亦可組合使用兩種以上。 From the viewpoint of obtaining good releasability from the mold during molding, the curable resin composition may contain a release agent. The release agent is not particularly limited, and conventionally known ones can be used. Specific examples include: carnauba wax, higher fatty acids such as beocyanic acid and stearic acid, higher fatty acid metal salts, ester waxes such as beocyanate esters, and polyolefins such as oxidized polyethylene and non-oxidized polyethylene. Wax etc. One type of release agent may be used alone, or two or more types may be used in combination.

於硬化性樹脂組成物包含脫模劑的情況下，相對於樹脂成分100質量份，所述脫模劑的量較佳為0.01質量份~15質量份，更佳為0.1質量份~10質量份。若脫模劑的量相對於樹脂成分100質量份而為0.01質量份以上，則存在可充分獲得脫模性的傾向。若為15質量份以下，則存在可獲得更良好的接著性的傾向。 When the curable resin composition contains a release agent, the amount of the release agent is preferably 0.01 to 15 parts by mass, and more preferably 0.1 to 10 parts by mass relative to 100 parts by mass of the resin component. . When the amount of the release agent is 0.01 parts by mass or more relative to 100 parts by mass of the resin component, sufficient release properties tend to be obtained. If it is 15 parts by mass or less, better adhesiveness tends to be obtained.

(阻燃劑) (Flame retardant)

硬化性樹脂組成物亦可包含阻燃劑。阻燃劑並無特別限制，可使用現有公知者。具體而言，可列舉包含鹵素原子、銻原子、氮原子或磷原子的有機化合物或無機化合物、金屬氫氧化物等。阻燃劑可單獨使用一種，亦可組合使用兩種以上。 The curable resin composition may also contain a flame retardant. The flame retardant is not particularly limited, and conventionally known ones can be used. Specific examples include organic compounds or inorganic compounds containing halogen atoms, antimony atoms, nitrogen atoms, or phosphorus atoms, metal hydroxides, and the like. One type of flame retardant may be used alone, or two or more types may be used in combination.

於硬化性樹脂組成物包含阻燃劑的情況下，只要阻燃劑的量為對於獲得所需的阻燃效果而言充分的量，則並無特別限制。例如相對於樹脂成分100質量份而較佳為1質量份~300質量份，更佳為2質量份~150質量份。 When the curable resin composition contains a flame retardant, the amount of the flame retardant is not particularly limited as long as it is a sufficient amount to obtain the desired flame retardant effect. For example, it is preferably 1 to 300 parts by mass, and more preferably 2 to 150 parts by mass based on 100 parts by mass of the resin component.

(著色劑) (colorant)

硬化性樹脂組成物亦可進一步包含著色劑。作為著色劑，可列舉碳黑、有機染料、有機顏料、氧化鈦、鉛丹、氧化鐵等公知的著色劑。著色劑的含量可根據目的等適宜選擇。著色劑可單獨使用一種，亦可組合使用兩種以上。 The curable resin composition may further contain a colorant. Examples of the colorant include known colorants such as carbon black, organic dyes, organic pigments, titanium oxide, lead, and iron oxide. The content of the colorant can be appropriately selected depending on the purpose and the like. A colorant may be used individually by 1 type, and may be used in combination of 2 or more types.

(應力緩和劑) (stress reliever)

硬化性樹脂組成物亦可包含矽油、矽橡膠粒子等應力緩和劑。藉由包含應力緩和劑，可進一步減少封裝的翹曲變形及封裝裂紋的發生。作為應力緩和劑，可列舉通常使用的公知的應力緩和劑(可撓劑)。具體而言，可列舉矽酮系、苯乙烯系、烯烴系、胺基甲酸酯系、聚酯系、聚醚系、聚醯胺系、聚丁二烯系等熱塑性彈性體，天然橡膠(natural rubber，NR)、丙烯腈-丁二烯橡膠(acrylonitrile butadiene rubber，NBR)、丙烯酸橡膠、胺基甲酸酯橡膠、矽酮粉末等橡膠粒子，甲基丙烯酸甲酯-苯乙烯-丁二烯共聚物(Methacrylate methyl styrene butadiene，MBS)、甲基丙烯酸甲酯-矽酮共聚物、甲基丙烯酸甲酯-丙烯酸丁酯共聚物等具有核-殼結構的橡膠粒子等。應力緩和劑可單獨使用一種，亦可組合使用兩種以上。其中，較佳為矽酮系應力緩和劑。作為矽酮系應力緩和劑，可列舉具有環氧基者、具有胺基者、將該些進行聚醚改質而成者等。 The curable resin composition may also contain stress relieving agents such as silicone oil and silicone rubber particles. By including a stress reliever, the occurrence of package warpage and package cracks can be further reduced. Examples of the stress relieving agent include commonly used known stress relieving agents (flexibility agents). Specifically, thermoplastic elastomers such as silicone type, styrene type, olefin type, urethane type, polyester type, polyether type, polyamide type, polybutadiene type, etc., natural rubber ( natural rubber (NR), acrylonitrile butadiene rubber (NBR), acrylic rubber, urethane rubber, silicone powder and other rubber particles, methyl methacrylate-styrene-butadiene Rubber particles with core-shell structure such as copolymer (Methacrylate methyl styrene butadiene, MBS), methyl methacrylate-silicone copolymer, methyl methacrylate-butyl acrylate copolymer, etc. One type of stress reliever may be used alone, or two or more types may be used in combination. Among them, silicone-based stress relieving agents are preferred. Examples of silicone-based stress relieving agents include those having an epoxy group, those having an amine group, those obtained by polyether modification, and the like.

(硬化性樹脂組成物的製備方法) (Preparation method of curable resin composition)

硬化性樹脂組成物的製備方法並無特別限制。作為一般的方法，可列舉如下方法：於藉由混合機等將規定調配量的成分充分 混合後，藉由研磨輥、擠出機等熔融混煉，進行冷卻並粉碎。更具體而言，例如可列舉如下方法：將所述成分的規定量均勻地攪拌及混合，利用預先加熱為70℃~140℃的捏合機、輥、擠壓機等進行混煉並冷卻，進行粉碎。 The preparation method of the curable resin composition is not particularly limited. As a general method, the following method can be cited: using a mixer, etc., to mix ingredients in a predetermined amount After mixing, the mixture is melt-kneaded using a grinding roller, an extruder, etc., then cooled and pulverized. More specifically, for example, the following method can be cited: uniformly stirring and mixing a predetermined amount of the above ingredients, kneading and cooling using a kneader, roller, extruder, etc. that has been preheated to 70°C to 140°C, and then cooling. Crush.

硬化性樹脂組成物較佳為於常溫常壓下(例如，25℃、大氣壓下)為固體。硬化性樹脂組成物為固體時的形狀並無特別限制，可列舉粉狀、粒狀、片狀等。就操作性的觀點而言，硬化性樹脂組成物為片狀時的尺寸及質量較佳為成為與封裝的成形條件相符的尺寸及質量。 The curable resin composition is preferably solid at normal temperature and pressure (for example, 25° C. and atmospheric pressure). The shape of the curable resin composition when it is solid is not particularly limited, and examples include powder, granular, flake, and the like. From the viewpoint of operability, the size and quality of the curable resin composition in the form of a sheet are preferably those that match the molding conditions of the package.

<電子零件裝置> <Electronic component device>

作為本揭示的一實施形態的電子零件裝置包括：元件；以及密封所述元件的所述硬化性樹脂組成物的硬化物。 An electronic component device according to an embodiment of the present disclosure includes: a component; and a cured product of the curable resin composition that seals the component.

作為電子零件裝置，可列舉利用硬化性樹脂組成物對如下元件部進行密封而得者，所述元件部是於引線框架、已配線的輸送膠帶、配線板、玻璃、矽晶圓、有機基板等支撐構件上搭載元件(半導體晶片、電晶體、二極體、閘流體等主動元件、電容器、電阻體、線圈等被動元件等)而獲得。 Examples of electronic component devices include those obtained by sealing element portions such as lead frames, wired conveyor tapes, wiring boards, glass, silicon wafers, organic substrates, etc., with curable resin compositions. It is obtained by mounting components (active components such as semiconductor wafers, transistors, diodes, and thyristors, passive components such as capacitors, resistors, and coils, etc.) on the supporting member.

更具體而言，可列舉：雙列直插式封裝(Dual Inline Package，DIP)、塑膠引線晶片載體(Plastic Leaded Chip Carrier，PLCC)、四面扁平封裝(Quad Flat Package，QFP)、小外型封裝(Small Outline Package，SOP)、小外型J-引線封裝(Small Outline J-lead package，SOJ)、薄小外型封裝(Thin Small Outline Package， TSOP)、薄型四面扁平封裝(Thin Quad Flat Package，TQFP)等一般的樹脂密封型IC，其具有在將元件固定在引線框架上且以打線接合、凸塊等連接接合墊等元件的端子部與引線部後，使用硬化性樹脂組成物並藉由轉移成形等進行密封的結構；載帶封裝(Tape Carrier Package，TCP)，其具有利用硬化性樹脂組成物對以凸塊連接於載帶上的元件進行密封的結構；基板覆晶(Chip On Board，COB)模組、混合IC、多晶模組等，其具有利用硬化性樹脂組成物對以打線接合、倒裝晶片接合、焊料等連接於支撐構件上所形成的配線上的元件進行密封的結構；球形陣列(Ball Grid Array，BGA)、晶片尺寸封裝(Chip Size Package，CSP)、多晶片封裝(Multi Chip Package，MCP)等，其具有於背面形成配線板連接用端子的支撐構件的表面上搭載元件，並藉由凸塊或打線接合將元件與支撐構件上形成的配線連接後，利用硬化性樹脂組成物密封元件的結構。另外，於印刷配線板中亦可較佳地使用硬化性樹脂組成物。 More specifically, they can be listed: Dual Inline Package (DIP), Plastic Leaded Chip Carrier (PLCC), Quad Flat Package (QFP), Small Outline Package (Small Outline Package, SOP), Small Outline J-lead package (SOJ), Thin Small Outline Package, General resin-sealed ICs such as TSOP (TSOP) and Thin Quad Flat Package (TQFP) have components such as terminals and bonding pads that are fixed to the lead frame and connected by wire bonding, bumps, etc. After the lead part, a curable resin composition is used and sealed by transfer molding, etc.; a tape carrier package (TCP), which has a curable resin composition that is connected to the carrier tape with bumps A structure in which components are sealed; Chip On Board (COB) modules, hybrid ICs, polycrystalline modules, etc., which use a curable resin composition to connect to the Structures that seal components on the wiring formed on the support member; Ball Grid Array (BGA), Chip Size Package (CSP), Multi Chip Package (MCP), etc., which have A structure in which components are mounted on the surface of a support member with wiring board connection terminals formed on the back side, and the components are connected to wiring formed on the support member through bumps or wire bonding, and then the components are sealed with a curable resin composition. In addition, the curable resin composition can also be preferably used in printed wiring boards.

作為使用硬化性樹脂組成物來密封電子零件裝置的方法，可列舉低壓轉移成形法、噴射成形法、壓縮成形法等。該些中，通常為低壓轉移成形法。 Examples of methods for sealing electronic component devices using curable resin compositions include low-pressure transfer molding, injection molding, and compression molding. Among these, the low-pressure transfer molding method is usually used.

[實施例] [Example]

以下，藉由實施例對所述實施形態進行具體說明，但所述實施形態的範圍並不限定於該些實施例。 Hereinafter, the embodiment will be described in detail using examples, but the scope of the embodiment is not limited to these examples.

[硬化性樹脂組成物的製備] [Preparation of curable resin composition]

將下述材料以表1~表3中記載的組成(質量份)混合，在混煉溫度為80℃、混煉時間15分鐘的條件下進行輥混煉，藉此製備實施例1~實施例21、比較例1~比較例10的硬化性樹脂組成物。 The following materials were mixed with the compositions (mass parts) described in Tables 1 to 3, and roller kneading was performed at a kneading temperature of 80° C. and a kneading time of 15 minutes to prepare Examples 1 to 1. 21. The curable resin compositions of Comparative Examples 1 to 10.

(環氧樹脂) (epoxy resin)

．環氧樹脂1：環氧當量196、熔點106℃的聯苯型環氧樹脂(三菱化學股份有限公司，商品名「YX-4000H」) ． Epoxy resin 1: biphenyl-type epoxy resin with an epoxy equivalent of 196 and a melting point of 106°C (Mitsubishi Chemical Co., Ltd., trade name "YX-4000H")

環氧樹脂2：環氧當量282、軟化點59℃的苯乙烯改質苯酚酚醛清漆型環氧樹脂(新日鐵住金化學股份有限公司，商品名「YDAN-1000-10C」) Epoxy resin 2: styrene-modified phenol novolak-type epoxy resin with an epoxy equivalent of 282 and a softening point of 59°C (Nippon Steel & Sumitomo Metal Chemical Co., Ltd., trade name "YDAN-1000-10C")

環氧樹脂3：環氧當量250、軟化點58℃的甲氧基萘．甲酚甲醛共縮合型環氧樹脂(迪愛生(DIC)股份有限公司，商品名「HP-5000」) Epoxy Resin 3: Methoxynaphthalene with an epoxy equivalent of 250 and a softening point of 58°C. Cresol-formaldehyde co-condensation type epoxy resin (DIC Co., Ltd., trade name "HP-5000")

．環氧樹脂4：環氧當量282、軟化點56℃的含有伸聯苯基骨架的芳烷基型環氧樹脂(日本化藥股份有限公司，商品名「NC-3000」) ． Epoxy Resin 4: Aralkyl-type epoxy resin containing an extended biphenyl skeleton with an epoxy equivalent of 282 and a softening point of 56°C (Nippon Kayaku Co., Ltd., trade name "NC-3000")

(硬化劑) (hardener)

硬化劑1：羥基當量176、軟化點70℃的苯酚芳烷基樹脂(明和化成股份有限公司，商品名「MEH-7800」) Hardener 1: Phenol aralkyl resin with a hydroxyl equivalent of 176 and a softening point of 70°C (Meiwa Chemical Co., Ltd., trade name "MEH-7800")

硬化劑2：羥基當量199、軟化點89℃的聯苯基骨架型苯酚芳烷基樹脂(明和化成股份有限公司，商品名「MEH-7851」) Hardener 2: Biphenyl skeleton type phenol aralkyl resin with a hydroxyl equivalent of 199 and a softening point of 89°C (Meiwa Chemical Co., Ltd., trade name "MEH-7851")

(三嗪化合物) (triazine compound)

三嗪化合物1：2-(4,6-雙-(2,4-二甲基苯基)-1,3,5-三嗪-2-基)-5-(辛氧基)-苯酚(氰特(Cytec)公司，商品名「UV-1164」) Triazine compound 1: 2-(4,6-bis-(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-(octyloxy)-phenol ( Cytec Corporation, trade name "UV-1164")

三嗪化合物2：2-[4,6-雙(2,4-二甲基苯基)-1,3,5-三嗪-2-基]-5-[3-[(2-乙基苯基)氧基]-2-羥基丙氧基]苯酚(巴斯夫(BASF)公司製造，商品名「帝奴彬(Tinuvin)405」) Triazine compound 2: 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-[(2-ethyl) Phenyl)oxy]-2-hydroxypropoxy]phenol (manufactured by BASF, trade name "Tinuvin 405")

三嗪化合物3：2,4,6-三(2-羥基-4-己氧基-3-甲基苯基)-1,3,5-三嗪(艾迪科(ADEKA)股份有限公司、商品名「艾迪科斯塔波(Adekastab)LA-F70」) Triazine compound 3: 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine (ADEKA Co., Ltd., Product name "Adekastab LA-F70")

三嗪化合物4：2-(4,6-二苯基-1,3,5-三嗪-2-基)-5-[(己基)氧基-苯酚(巴斯夫(BASF)公司，商品名「帝奴彬(Tinuvin)1577」) Triazine compound 4: 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy-phenol (BASF Company, trade name " Tinuvin1577")

三嗪化合物5：2-(4,6-二苯基-1,3,5-三嗪-2-基)-5-[2-(2-乙基己醯氧基)乙氧基]苯酚(艾迪科(ADEKA)股份有限公司、商品名「艾迪科斯塔波(Adekastab)LA-46」) Triazine compound 5: 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexyloxy)ethoxy]phenol (ADEKA Co., Ltd., trade name "Adekastab LA-46")

三嗪化合物6：2-[4-[4,6-雙[(1,1'-聯苯基)-4-基]-1,3,5-三嗪-2-基]-3-羥基苯氧基]異辛基丙酸酯(巴斯夫(BASF)公司，商品名「帝奴彬(Tinuvin)479」) Triazine compound 6: 2-[4-[4,6-bis[(1,1'-biphenyl)-4-yl]-1,3,5-triazin-2-yl]-3-hydroxy Phenoxy]isooctylpropionate (BASF, trade name "Tinuvin 479")

三嗪化合物7：2-(2,4-二羥基苯基)-4,6-雙(2,4-二甲基苯基)-1,3,5-三嗪(東京化成工業股份有限公司、試劑) Triazine compound 7: 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine (Tokyo Chemical Industry Co., Ltd. , reagent)

三嗪化合物8：2-(2,4-二羥基苯基)-4,6-二苯基-1,3,5-三嗪(東京化成工業股份有限公司、試劑) Triazine compound 8: 2-(2,4-dihydroxyphenyl)-4,6-diphenyl-1,3,5-triazine (Tokyo Chemical Industry Co., Ltd., reagent)

三嗪化合物9：2-(2-羥基-4-甲氧基苯基)-4,6-二苯基-1,3,5-三嗪(東京化成工業股份有限公司、試劑) Triazine compound 9: 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine (Tokyo Chemical Industry Co., Ltd., reagent)

三嗪化合物10：2,4,6-三苯基-1,3,5-三嗪(東京化成工業股份有限公司、試劑) Triazine compound 10: 2,4,6-triphenyl-1,3,5-triazine (Tokyo Chemical Industry Co., Ltd., reagent)

三嗪化合物A：三聚氰胺(東京化成工業股份有限公司、試劑) Triazine compound A: Melamine (Tokyo Chemical Industry Co., Ltd., reagent)

三嗪化合物B：苯並胍胺(東京化成工業股份有限公司、試劑) Triazine compound B: benzoguanamine (Tokyo Chemical Industry Co., Ltd., reagent)

(硬化促進劑) (hardening accelerator)

硬化促進劑：三苯基膦與1,4-苯醌的加成反應物 Hardening accelerator: addition reaction product of triphenylphosphine and 1,4-benzoquinone

(無機填充材) (Inorganic filler material)

球狀熔融二氧化矽(平均粒徑17.5μm，比表面積3.8m2/g) Spherical fused silica (average particle size 17.5μm, specific surface area 3.8m 2 /g)

(偶合劑) (coupling agent)

環氧矽烷(γ-縮水甘油氧基丙基三甲氧基矽烷) Epoxysilane (γ-glycidoxypropyltrimethoxysilane)

(著色劑) (colorant)

碳黑(三菱化學股份有限公司，商品名「MA-100」) Carbon black (Mitsubishi Chemical Co., Ltd., trade name "MA-100")

(脫模劑) (release agent)

棕櫚蠟(馨樂野田(Cera NODA)股份有限公司) Palm wax (Cera NODA Co., Ltd.)

Figure 108120128-A0305-02-0056-26
Figure 108120128-A0305-02-0056-26

Figure 108120128-A0305-02-0057-27
Figure 108120128-A0305-02-0057-27

Figure 108120128-A0305-02-0057-28
Figure 108120128-A0305-02-0057-28

[密封用環氧樹脂成形材料的評價] [Evaluation of epoxy resin molding materials for sealing]

藉由以下的特性試驗來評價實施例1~實施例21及比較例1~比較例10中製備的密封用環氧樹脂成形材料的特性。將評價結果示於下述表4~表6中。再者，只要未標明，則密封用環氧樹脂成形材料的成形是藉由轉移成形機並於模具溫度175℃、成形壓力6.9MPa、硬化時間90秒下成形。另外，視需要於175℃、5小時的條件下進行後硬化。 The characteristics of the sealing epoxy resin molding materials prepared in Examples 1 to 21 and Comparative Examples 1 to 10 were evaluated by the following characteristic tests. The evaluation results are shown in Tables 4 to 6 below. In addition, unless otherwise specified, the sealing epoxy resin molding material is molded by a transfer molding machine at a mold temperature of 175°C, a molding pressure of 6.9 MPa, and a curing time of 90 seconds. In addition, if necessary, post-hardening is performed at 175°C for 5 hours.

(1)旋流 (1) Swirl

使用依據EMMI-1-66的旋流測定用模具，於所述條件下將密封用環氧樹脂成形材料成形並求出流動距離(cm)。 Using a swirl flow measurement mold conforming to EMMI-1-66, the sealing epoxy resin molding material was molded under the conditions described above, and the flow distance (cm) was determined.

(2)熱時硬度 (2)Hot hardness

將密封用環氧樹脂成形材料於所述條件下成形為直徑50mm×厚度3mm的圓板，成形後立即使用蕭氏D型硬度計(上島製作所股份有限公司製造，HD-1120(D型))來進行測定。 The sealing epoxy resin molding material was formed into a circular plate with a diameter of 50 mm x a thickness of 3 mm under the above conditions, and a Shore D type hardness tester (manufactured by Uejima Seisakusho Co., Ltd., HD-1120 (D type)) was used immediately after forming. to measure.

(3)260℃剪切接著力 (3) Shear bonding strength at 260℃

於所述條件下在鍍銀的銅板上以底面直徑4mm、上表面直徑3mm、高度4mm的尺寸將密封用環氧樹脂成形材料成形，並於所述條件下進行後硬化。之後，使用粘接測試儀(Bondtester)(諾信先進技術(Nordson advanced Technology)股份有限公司製造的Series 4000)，將銅板的溫度保持為260℃並以剪切速度50μm/s求出剪切接著力(MPa)。 Under the above conditions, the sealing epoxy resin molding material was formed on a silver-plated copper plate with a bottom surface diameter of 4 mm, an upper surface diameter of 3 mm, and a height of 4 mm, and was post-hardened under the above conditions. Thereafter, a bond tester (Bondtester) (Series 4000 manufactured by Nordson Advanced Technology Co., Ltd.) was used to determine the shear bonding strength at a shear speed of 50 μm/s while maintaining the temperature of the copper plate at 260°C. Force (MPa).

(4)吸水率 (4)Water absorption rate

於所述條件下對所述(2)中成形的圓板進行後硬化。之後，於85℃、60%RH(相對濕度)的條件下將所獲得的圓板放置168小時，並測定放置前後的質量變化。根據測定結果並藉由下述式來計算吸水率。 The circular plate formed in (2) is post-hardened under the above conditions. Thereafter, the obtained disc was left standing for 168 hours under the conditions of 85° C. and 60% RH (relative humidity), and the mass change before and after the standing was measured. Based on the measurement results, the water absorption rate is calculated by the following formula.

吸水率(質量%)=(放置後的圓板質量-放置前的圓板質量)/放置前的圓板質量×100 Water absorption rate (mass %) = (mass of the disc after placement - mass of the disc before placement)/mass of the disc before placement × 100

(5)耐回焊性 (5)Reflow resistance

針對搭載有8mm×10mm×0.4mm的矽晶片的外形尺寸20mm×14mm×2mm的80針腳扁平封裝(QFP)(引線框架材質：銅合金，晶片墊部上表面及引線前端鍍銀的處理品)，使用密封用環氧樹脂成形材料於所述條件下進行成形，於所述條件下進行後硬化。將所獲得的封裝於85℃、85%RH的條件下加濕168小時。之後，於規定溫度(250℃、260℃、270℃)下分別以10秒的條件分別進行回焊處理，以目視觀察封裝外部的裂紋的有無，並利用超音波探傷裝置(日立建機股份有限公司製造，HYE-FOCUS)觀察封裝內部的剝離產生的有無。以相對於試驗封裝數(10)的產生裂紋及剝離的任一者的封裝數的總和來評價耐回焊性。 For an 80-pin flat package (QFP) with an external size of 20mm×14mm×2mm and equipped with a silicon chip of 8mm×10mm×0.4mm (lead frame material: copper alloy, the upper surface of the chip pad and the lead tip are silver-plated) , use the sealing epoxy resin molding material to perform molding under the above conditions, and perform post-hardening under the above conditions. The obtained package was humidified under conditions of 85°C and 85%RH for 168 hours. After that, reflow processing was performed at specified temperatures (250°C, 260°C, and 270°C) for 10 seconds each to visually observe the presence of cracks on the outside of the package and use an ultrasonic flaw detection device (Hitachi Construction Machinery Co., Ltd. Manufactured by HYE-FOCUS), observe whether peeling occurs inside the package. Reflow resistance was evaluated based on the total number of packages in which either cracking or peeling occurred relative to the number of test packages (10).

Figure 108120128-A0305-02-0060-29
Figure 108120128-A0305-02-0060-29

Figure 108120128-A0305-02-0060-35
Figure 108120128-A0305-02-0060-35

Figure 108120128-A0305-02-0060-30
Figure 108120128-A0305-02-0060-30

如表4~表6所示，含有相當於特定三嗪化合物的三嗪化合物1~三嗪化合物10的實施例1~實施例21與不含三嗪化合物的比較例1~比較例8相比，對金屬(銀)的接著力提高，耐回 焊性亦提高。 As shown in Tables 4 to 6, Examples 1 to 21 containing triazine compounds 1 to 10 corresponding to specific triazine compounds are compared with Comparative Examples 1 to 8 which do not contain a triazine compound. , improved adhesion to metal (silver), durable The weldability is also improved.

含有不相當於特定三嗪化合物的三嗪化合物A、三嗪化合物B的比較例9、比較例10與不含三嗪化合物的比較例1~比較例8相比，未觀察到對金屬(銀)的接著力及耐回焊性提高。 In Comparative Examples 9 and 10 containing triazine compound A and triazine compound B that are not equivalent to the specific triazine compound, compared with Comparative Examples 1 to 8 that do not contain a triazine compound, no reaction to the metal (silver) was observed. ), the bonding strength and reflow resistance are improved.

Claims (11)

一種硬化性樹脂組成物，其包含：硬化性樹脂；硬化劑，所述硬化劑包含選自由芳烷基型酚樹脂、二環戊二烯型酚樹脂、三苯基甲烷型酚樹脂、苯甲醛型酚樹脂與芳烷基型酚樹脂的共聚合型酚樹脂、及酚醛清漆型酚樹脂所組成的群組中的至少一種；以及下述通式(1)所表示的化合物；
Figure 108120128-A0305-02-0062-31
 [通式(1)中，R1~R3分別獨立地表示一價烴基]，且所述通式(1)中的R1~R3中的1個或2個為2,4-二甲基苯基。 A curable resin composition comprising: a curable resin; a hardener, the hardener being selected from the group consisting of aralkyl phenol resin, dicyclopentadiene phenol resin, triphenylmethane phenol resin, benzaldehyde At least one of the group consisting of a copolymerized phenol resin of a type phenol resin and an aralkyl type phenol resin, and a novolak type phenol resin; and a compound represented by the following general formula (1);
Figure 108120128-A0305-02-0062-31
 [In the general formula (1), R 1 to R 3 each independently represent a monovalent hydrocarbon group], and one or two of R 1 to R 3 in the general formula (1) is 2,4-bis Methylphenyl. 如申請專利範圍第1項所述的硬化性樹脂組成物，其中所述通式(1)所表示的化合物含有下述通式(2)所表示的化合物；
Figure 108120128-A0305-02-0063-32
 [通式(2)中，R4~R6分別獨立地為選自由芳香族烴基、脂肪族烴基、脂肪族烴氧基、芳香族烴氧基、羥基、羧基、鹵素原子、胺基、芳香族烴胺基、脂肪族烴胺基、二芳香族烴胺基、二脂肪族烴胺基及芳香族烴脂肪族烴胺基所組成的群組中的一價基；n分別獨立地為0~5的整數]。 The curable resin composition as described in claim 1, wherein the compound represented by the general formula (1) contains a compound represented by the following general formula (2);
Figure 108120128-A0305-02-0063-32
 [In the general formula (2), R 4 to R 6 are independently selected from aromatic hydrocarbon groups, aliphatic hydrocarbon groups, aliphatic hydrocarbon oxygen groups, aromatic hydrocarbon oxygen groups, hydroxyl groups, carboxyl groups, halogen atoms, amine groups, aromatic A monovalent group in the group consisting of an aliphatic hydrocarbon amine group, an aliphatic hydrocarbon amine group, a diaromatic hydrocarbon amine group, a dialiphatic hydrocarbon amine group and an aromatic hydrocarbon aliphatic hydrocarbon amine group; n is independently 0 ~5 integers]. 如申請專利範圍第2項所述的硬化性樹脂組成物，其中所述R4~R6的至少一個為羥基。 The curable resin composition described in item 2 of the patent application, wherein at least one of R 4 to R 6 is a hydroxyl group. 如申請專利範圍第1項至第3項中任一項所述的硬化性樹脂組成物，其更包含無機填充材。 The curable resin composition as described in any one of items 1 to 3 of the patent application further includes an inorganic filler. 如申請專利範圍第1項所述的硬化性樹脂組成物，其中所述硬化性樹脂包含環氧樹脂。 The curable resin composition according to claim 1, wherein the curable resin includes epoxy resin. 如申請專利範圍第5項所述的硬化性樹脂組成物，其中所述環氧樹脂包含選自由聯苯型環氧樹脂、二苯乙烯型環氧樹 脂、二苯基甲烷型環氧樹脂、含硫原子型環氧樹脂、酚醛清漆型環氧樹脂、二環戊二烯型環氧樹脂、三苯基甲烷型環氧樹脂、共聚合型環氧樹脂及芳烷基型環氧樹脂所組成的群組中的至少一種。 The curable resin composition as described in Item 5 of the patent application, wherein the epoxy resin includes a biphenyl-type epoxy resin, a stilbene-type epoxy resin. Grease, diphenylmethane type epoxy resin, sulfur atom-containing epoxy resin, novolak type epoxy resin, dicyclopentadiene type epoxy resin, triphenylmethane type epoxy resin, copolymerized epoxy At least one of the group consisting of resin and aralkyl epoxy resin. 如申請專利範圍第1項所述的硬化性樹脂組成物，其更包含硬化促進劑。 The curable resin composition described in claim 1 of the patent application further includes a curing accelerator. 如申請專利範圍第7項所述的硬化性樹脂組成物，其中所述硬化促進劑含有鏻化合物。 The curable resin composition according to claim 7, wherein the curing accelerator contains a phosphonium compound. 如申請專利範圍第7項或第8項所述的硬化性樹脂組成物，其中所述硬化促進劑含有下述通式(I-1)所表示的化合物；
Figure 108120128-A0305-02-0064-33
 [式(I-1)中，R1~R3分別獨立地為碳數1~18的烴基，R1~R3中的兩個以上可相互鍵結而形成環狀結構；R4~R7分別獨立地為氫原子、羥基或碳數1~18的有機基，R4~R7中的兩個以上可相互鍵結而形成環狀結構]。 The curable resin composition as described in Item 7 or Item 8 of the patent application, wherein the hardening accelerator contains a compound represented by the following general formula (I-1);
Figure 108120128-A0305-02-0064-33
 [In formula (I-1), R 1 to R 3 are each independently a hydrocarbon group with 1 to 18 carbon atoms, and two or more of R 1 to R 3 can be bonded to each other to form a cyclic structure; R 4 to R 7 are each independently a hydrogen atom, a hydroxyl group or an organic group having 1 to 18 carbon atoms, and two or more of R 4 to R 7 may be bonded to each other to form a cyclic structure]. 如申請專利範圍第9項所述的硬化性樹脂組成物，其中所述通式(I-1)所表示的化合物含有下述通式(I-2)所表示的化合物；
Figure 108120128-A0305-02-0065-34
 [式(I-2)中，R1~R3分別獨立地為碳數1~18的烴基，R1~R3中的兩個以上可相互鍵結而形成環狀結構；R4~R6分別獨立地為氫原子或碳數1~18的有機基，R4~R6中的兩個以上可相互鍵結而形成環狀結構]。 The curable resin composition as described in claim 9, wherein the compound represented by the general formula (I-1) contains a compound represented by the following general formula (I-2);
Figure 108120128-A0305-02-0065-34
 [In formula (I-2), R 1 ~ R 3 are each independently a hydrocarbon group with 1 to 18 carbon atoms, and two or more of R 1 ~ R 3 can be bonded to each other to form a cyclic structure; R 4 ~ R 6 are each independently a hydrogen atom or an organic group having 1 to 18 carbon atoms, and two or more of R 4 to R 6 may be bonded to each other to form a cyclic structure]. 一種電子零件裝置，其包括：元件；以及密封所述元件的如申請專利範圍第1項至第10項中任一項所述的硬化性樹脂組成物的硬化物。 An electronic component device includes: a component; and a cured product of the curable resin composition as described in any one of items 1 to 10 of the patent application for sealing the component.
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EP3916773A4 (en) * 2019-01-23 2022-03-23 FUJIFILM Corporation Composition, thermally-conductive sheet, and device equipped with thermally-conductive layer
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101223207A (en) * 2005-07-29 2008-07-16 住友电木株式会社 Epoxy resin composition and semiconductor device
JP2014136779A (en) * 2013-01-18 2014-07-28 Ajinomoto Co Inc Resin composition
WO2017112766A1 (en) * 2015-12-22 2017-06-29 Cytec Industries Inc. Mold-releasable surfacing materials for composite parts

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3478315B2 (en) * 1995-12-06 2003-12-15 日立化成工業株式会社 Epoxy resin composition for semiconductor encapsulation and semiconductor device encapsulated with the resin composition
JPH11147939A (en) 1997-11-14 1999-06-02 Toshiba Chem Corp Epoxy resin composition and semiconductor device sealed therewith
JP2000103940A (en) 1998-09-25 2000-04-11 Toshiba Chem Corp Epoxy resin composition and semiconductor sealing device
JP3659150B2 (en) * 2000-07-31 2005-06-15 日立化成工業株式会社 Epoxy resin molding material for sealing and electronic component device
GB2497906B (en) * 2010-11-17 2016-05-04 Nippon Kayaku Kk Epoxy resin composition for transparent sheets and cured product thereof
JP2016074849A (en) * 2014-10-08 2016-05-12 太陽インキ製造株式会社 Dry film, cured product, and printed wiring board
JP2017137434A (en) * 2016-02-04 2017-08-10 株式会社Adeka Curable composition, method for curing curable composition, cured product thereof, and display element using the same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101223207A (en) * 2005-07-29 2008-07-16 住友电木株式会社 Epoxy resin composition and semiconductor device
JP2014136779A (en) * 2013-01-18 2014-07-28 Ajinomoto Co Inc Resin composition
WO2017112766A1 (en) * 2015-12-22 2017-06-29 Cytec Industries Inc. Mold-releasable surfacing materials for composite parts

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