TWI693250B - Composition, epoxy resin curing agent, epoxy resin composition, thermosetting composition, cured product, semiconductor device, and interlayer insulating material - Google Patents

Composition, epoxy resin curing agent, epoxy resin composition, thermosetting composition, cured product, semiconductor device, and interlayer insulating material Download PDF

Info

Publication number
TWI693250B
TWI693250B TW105110535A TW105110535A TWI693250B TW I693250 B TWI693250 B TW I693250B TW 105110535 A TW105110535 A TW 105110535A TW 105110535 A TW105110535 A TW 105110535A TW I693250 B TWI693250 B TW I693250B
Authority
TW
Taiwan
Prior art keywords
epoxy resin
composition
compound
chemical formula
resin composition
Prior art date
Application number
TW105110535A
Other languages
Chinese (zh)
Other versions
TW201638175A (en
Inventor
高橋航
村田清貴
Original Assignee
日商愛沃特股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日商愛沃特股份有限公司 filed Critical 日商愛沃特股份有限公司
Publication of TW201638175A publication Critical patent/TW201638175A/en
Application granted granted Critical
Publication of TWI693250B publication Critical patent/TWI693250B/en

Links

Classifications

    • 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
    • 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
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014—Nitrogen containing compounds
    • C08G59/4042—Imines; Imides
    • 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
    • C08G59/50—Amines
    • C08G59/5033—Amines aromatic
    • 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
    • C08G59/50—Amines
    • C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
    • 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
    • C08G59/50—Amines
    • C08G59/5046—Amines heterocyclic
    • C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
    • C08G59/506—Amines heterocyclic containing only nitrogen as a heteroatom having one nitrogen atom in the ring
    • 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
    • C08G59/50—Amines
    • C08G59/56—Amines together with other curing agents
    • 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
    • C08G59/621—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
    • C08G59/686—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 containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/21—Urea; Derivatives thereof, e.g. biuret
    • 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
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3445—Five-membered rings
    • C08K5/3447—Five-membered rings condensed with carbocyclic rings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/40—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes epoxy resins
    • 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
    • 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
    • H01L23/293—Organic, e.g. plastic
    • 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
    • H01L23/293—Organic, e.g. plastic
    • H01L23/295—Organic, e.g. plastic containing a filler
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts

Abstract

本發明提供一種組成物，適於作為能夠滿足高阻燃性、高耐熱性以及高溫下低分解特性的環氧樹脂組成物的固化劑。該組成物含有下述化學式(1)所表示的馬來醯亞胺化合物(A)、下述化學式(2)所表示的芳香族胺化合物(B)、以及下述化學式(3)所表示的酚化合物(C)：

Figure 105110535-A0305-02-0001-1
The present invention provides a composition suitable as a curing agent for an epoxy resin composition that can satisfy high flame retardancy, high heat resistance, and low decomposition characteristics at high temperatures. The composition contains a maleimide compound (A) represented by the following chemical formula (1), an aromatic amine compound (B) represented by the following chemical formula (2), and a compound represented by the following chemical formula (3) Phenol compound (C):
Figure 105110535-A0305-02-0001-1

化學式(1)中，Ar1為可存在取代基的碳數6~12的亞芳基，X1為直接鍵結、碳數1~6的二價烴基、O、S或SO2，p為0~2的整數；

Figure 105110535-A0305-02-0001-2
In the chemical formula (1), Ar 1 is an arylene group having 6 to 12 carbon atoms in which substituents may be present, X 1 is a direct bond, a divalent hydrocarbon group having 1 to 6 carbon atoms, O, S or SO 2 , and p is Integer of 0~2;
Figure 105110535-A0305-02-0001-2

化學式(2)中，Ar2為包含0個~2個的範圍的一級氨基且可存在烴的取代基的碳數6~12的亞芳基，X2為直接鍵結、碳數1~6的二價烴基、O、S或SO2，q為0~2的整數；

Figure 105110535-A0305-02-0002-3
In the chemical formula (2), Ar 2 is an arylene group having 6 to 12 carbon atoms, which contains a primary amino group in the range of 0 to 2, and a hydrocarbon substituent may be present, X 2 is a direct bond, and the carbon number is 1 to 6 Divalent hydrocarbon group, O, S or SO 2 , q is an integer of 0~2;
Figure 105110535-A0305-02-0002-3

化學式(3)中，Ar3為以一分子內的烯丙基數成為2個~4個的範圍的方式包含烯丙基，並且包含0個~2個的範圍的羥基的碳數6~24的亞芳基，X3為直接鍵結、碳數1~6的二價烴基、O、S或SO2，r為0~2的整數。 In the chemical formula (3), Ar 3 contains allyl groups so that the number of allyl groups in one molecule is in the range of 2 to 4 and contains 6 to 24 carbon atoms including hydroxyl groups in the range of 0 to 2 Arylene, X 3 is a direct bond, a divalent hydrocarbon group having 1 to 6 carbon atoms, O, S, or SO 2 , and r is an integer of 0 to 2.

Description

組成物、環氧樹脂固化劑、環氧樹脂組成物、熱固化性組成物、固化物、半導體裝置以及層間絕緣材料 Composition, epoxy resin curing agent, epoxy resin composition, thermosetting composition, cured product, semiconductor device, and interlayer insulating material

本發明關於一種適於作為環氧樹脂的固化劑的成分或熱固性組成物的成分的組成物、含有該組成物的環氧樹脂固化劑、包含該環氧樹脂固化劑的環氧樹脂組成物、該環氧樹脂組成物的固化物、包含該組成物的熱固性組成物、該熱固性組成物的固化物、利用該環氧樹脂組成物或該熱固性組成物密封的半導體裝置、以及含有該環氧樹脂組成物或該熱固性組成物的層間絕緣材料。另外，本說明書中，「熱固性組成物」是指具有熱固性的組成物，「環氧樹脂組成物」是指含有具有環氧基的樹脂的組成物，且「熱固性組成物」的用語概念與「環氧樹脂組成物」的用語概念有重複部分。 The present invention relates to a composition suitable as a component of a curing agent for an epoxy resin or a component of a thermosetting composition, an epoxy resin curing agent containing the composition, an epoxy resin composition containing the epoxy resin curing agent, The cured product of the epoxy resin composition, the thermosetting composition containing the composition, the cured product of the thermosetting composition, a semiconductor device sealed with the epoxy resin composition or the thermosetting composition, and the epoxy resin The composition or the interlayer insulating material of the thermosetting composition. In addition, in this specification, "thermosetting composition" refers to a composition having thermosetting properties, "epoxy resin composition" refers to a composition containing a resin having an epoxy group, and the terms "thermosetting composition" and " The term "epoxy resin composition" has repeated parts.

在環氧樹脂的固化劑中占較大一群的酚系固化劑除種類豐富以外，還因低成本等特徵而被用於各種產業。為了滿足伴隨產業技術進步所產生的各種要求性能，至今為止開發了多種該固化劑。 The phenolic curing agent, which accounts for a larger group of epoxy resin curing agents, is used in various industries due to its low cost and other characteristics in addition to its rich variety. In order to meet the various required performances accompanying the technological advancement of the industry, various curing agents have been developed so far.

在電子材料領域中，近年來，隨著半導體封裝的小型、薄型化以及形狀的複雜化，日益要求半導體密封材料用樹脂為低黏度。如果為低黏度，那麼通過樹脂的流動性提升，也能夠應對複雜形狀的封裝，例如BGA(Ball Grid Array，球柵陣列)等，而且，通過實現填料的高填充化，在所述用途所求的阻燃性、焊料耐熱性、耐濕可靠性的方面也變得有利。 In the field of electronic materials, in recent years, as semiconductor packages have become smaller, thinner, and more complicated in shape, resins for semiconductor sealing materials have been increasingly required to have low viscosity. If the viscosity is low, the flowability of the resin can be improved, and it is possible to cope with packages of complex shapes, such as BGA (Ball Grid Array). Furthermore, by increasing the filling of fillers, it is required in the above-mentioned applications. The flame retardancy, solder heat resistance, and moisture resistance reliability also become favorable.

另外，出於對地球環境的考慮，讓新穎的阻燃性環氧樹脂組成物代替至今為止所利用的含鹵素系化合物或銻化合物等阻燃劑的需求正在增長，對於從通用封裝到先進封裝用的用途中一直使用的苯酚芳烷基樹脂，也要求即便不使用鹵素系阻燃劑及銻化合物，也具有優異的阻燃性(例如專利文獻1等)。其中，已知導入有聯苯骨架的苯酚芳烷基樹脂為高阻燃性，且正被使用於先進封裝用途(例如專利文獻2等)。 In addition, in consideration of the global environment, the demand for new flame-retardant epoxy resin compositions to replace the flame retardants such as halogen-containing compounds or antimony compounds that have been used so far is increasing. For general packaging to advanced packaging Phenol aralkyl resins that have been used for various applications have been required to have excellent flame retardancy without using halogen-based flame retardants and antimony compounds (for example, Patent Document 1 and the like). Among them, it is known that the phenol aralkyl resin introduced with a biphenyl skeleton is highly flame-retardant and is being used for advanced packaging applications (for example, Patent Document 2 etc.).

[現有技術文獻] [Prior Art Literature] [專利文獻] [Patent Literature]

專利文獻1：日本專利特開平5-97965號公報。 Patent Document 1: Japanese Patent Laid-Open No. 5-97965.

專利文獻2：日本專利特開2000-129092號公報。 Patent Document 2: Japanese Patent Laid-Open No. 2000-129092.

然而，專利文獻2所記載的阻燃性環氧樹脂組成物有玻璃化轉變溫度(Tg)變低的傾向。Tg的下降通常會引起高溫可靠性與耐熱性的下降，因此期望提供能夠將所述方面改善的環氧樹脂固化劑。尤其是對於預想今後會越來越普及的電動汽車或混合動力車中所搭載的功率元件(power device)的密封材料，要求具有高耐熱性。此外，就近年來對密封材料的物性需求而言，與耐熱性相關聯地也要求具有高溫下的熱分解性低的特性(以下稱為「高溫下低分解特性」)。 However, the flame-retardant epoxy resin composition described in Patent Document 2 tends to have a low glass transition temperature (Tg). The decrease in Tg usually causes a decrease in high-temperature reliability and heat resistance, and therefore it is desired to provide an epoxy resin curing agent that can improve the above aspects. In particular, high heat resistance is required for sealing materials of power devices (power devices) that are expected to be increasingly popularized in electric vehicles or hybrid vehicles in the future. In addition, in recent years, with regard to the physical properties of sealing materials, in association with heat resistance, it is also required to have a characteristic of low thermal decomposition at high temperature (hereinafter referred to as "low decomposition characteristic at high temperature").

本發明的目的在於提供一種組成物，適於作為能夠滿足高阻燃性、高耐熱性以及高溫下低分解特性的環氧樹脂的固化劑的成分或熱固性組成物的成分。此外，本發明的目的在於提供一種含有該組成物的環氧樹脂固化劑、包含該環氧樹脂固化劑的環氧樹脂組成物、該環氧樹脂組成物的固化物、包含該組成物的熱固性組成物、該熱固性組成物的固化物、利用該環氧樹脂組成物或該熱固性組成物密封的半導體裝置、以及含有該環氧樹脂組成物或該熱固性組成物的層間絕緣材料。 An object of the present invention is to provide a composition suitable as a component of a curing agent for an epoxy resin capable of satisfying high flame retardancy, high heat resistance, and low decomposition characteristics at high temperatures or a component of a thermosetting composition. In addition, an object of the present invention is to provide an epoxy resin curing agent containing the composition, an epoxy resin composition containing the epoxy resin curing agent, a cured product of the epoxy resin composition, and a thermosetting composition containing the composition A composition, a cured product of the thermosetting composition, a semiconductor device sealed with the epoxy resin composition or the thermosetting composition, and an interlayer insulating material containing the epoxy resin composition or the thermosetting composition.

本發明者們為瞭解決所述課題而進行了努力研究，結果發現，除馬來醯亞胺化合物以及芳香族胺化合物以外還以一定比率熔融混合特定的酚化合物所得的新穎的組成物 適於用作環氧樹脂固化劑的成分等熱固性組成物的成分，通過使用該組成物，可獲得能夠形成具有高阻燃性、高耐熱性以及高溫下低分解特性的固化物的熱固性組成物。 The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have found that in addition to the maleimide compound and the aromatic amine compound, a novel composition obtained by melt-mixing a specific phenol compound at a certain ratio A component suitable for a thermosetting composition such as a component of an epoxy resin curing agent. By using this composition, a thermosetting composition capable of forming a cured product having high flame retardancy, high heat resistance, and low decomposition characteristics at high temperatures can be obtained .

本發明的一個技術方案提供一種組成物，含有下述化學式(1)所表示的馬來醯亞胺化合物(A)、下述化學式(2)所表示的芳香族胺化合物(B)、以及下述化學式(3)。 A technical solution of the present invention provides a composition containing a maleimide compound (A) represented by the following chemical formula (1), an aromatic amine compound (B) represented by the following chemical formula (2), and the following Describe the chemical formula (3).

Figure 105110535-A0305-02-0007-6
Figure 105110535-A0305-02-0007-6

化學式(1)中，Ar1為可存在取代基的碳數6~12的亞芳基，X1為直接鍵結、碳數1~6的二價烴基、O、S或SO2，p為0~2的整數。 In the chemical formula (1), Ar 1 is an arylene group having 6 to 12 carbon atoms in which substituents may be present, X 1 is a direct bond, a divalent hydrocarbon group having 1 to 6 carbon atoms, O, S or SO 2 , and p is An integer from 0 to 2.

Figure 105110535-A0305-02-0007-7
Figure 105110535-A0305-02-0007-7

化學式(2)中，Ar2為包含0個~2個的範圍的一級氨 基且可存在烴的取代基的碳數6~12的亞芳基，X2為直接鍵結、碳數1~6的二價烴基、O、S或SO2，q為0~2的整數。 In the chemical formula (2), Ar 2 is an arylene group having 6 to 12 carbon atoms, which contains a primary amino group in the range of 0 to 2, and a hydrocarbon substituent may be present, X 2 is a direct bond, and the carbon number is 1 to 6 , The divalent hydrocarbon group, O, S or SO 2 , q is an integer of 0~2.

Figure 105110535-A0305-02-0008-8
Figure 105110535-A0305-02-0008-8

化學式(3)中，Ar3為以一分子內的烯丙基數成為2個~4個的範圍的方式包含烯丙基，並且包含0個~2個的範圍的羥基的碳數6~24的亞芳基，X3為直接鍵結、碳數1~6的二價烴基、O、S或SO2，r為0~2的整數。 In the chemical formula (3), Ar 3 contains allyl groups so that the number of allyl groups in one molecule is in the range of 2 to 4 and contains 6 to 24 carbon atoms including hydroxyl groups in the range of 0 to 2 Arylene, X 3 is a direct bond, a divalent hydrocarbon group having 1 to 6 carbon atoms, O, S, or SO 2 , and r is an integer of 0 to 2.

該組成物較佳150℃熔融黏度為50mPa‧s以上1000mPa‧s以下，且羥基當量為300g/eq以上1500g/eq以下。 The composition preferably has a melt viscosity at 150° C. of 50 mPa‧s or more and 1000 mPa‧s or less, and a hydroxyl equivalent of 300 g/eq or more and 1500 g/eq or less.

該組成物可還含有馬來醯亞胺化合物(A)與芳香族胺化合物(B)的反應產物。該反應產物可為該馬來醯亞胺化合物(A)與該芳香族胺化合物(B)的邁克爾(Michael)加成物。 The composition may further contain the reaction product of the maleimide compound (A) and the aromatic amine compound (B). The reaction product may be a Michael adduct of the maleimide compound (A) and the aromatic amine compound (B).

該組成物可為包含該馬來醯亞胺化合物(A)、該芳香族胺化合物(B)以及該酚化合物(C)的組成物的熔融混合體。 The composition may be a melt mixture of a composition containing the maleimide compound (A), the aromatic amine compound (B), and the phenol compound (C).

該組成物中，基於源自該馬來醯亞胺化合物(A)的馬來 醯亞胺基的部分結構的總數可為基於源自該芳香族胺化合物(B)的一級氨基的部分結構與基於源自該酚化合物(C)的烯丙基的部分結構的總數的1.5倍以上2.5倍以下。 In this composition, based on the male derived from the maleimide compound (A) The total number of partial structures of the amide imino group may be 1.5 times the total number of partial structures based on the primary amino group derived from the aromatic amine compound (B) and the partial structure based on the allyl group derived from the phenol compound (C) Above 2.5 times.

該酚化合物(C)較佳包含下述化學式(4)所表示的雙酚化合物(C1)。 The phenol compound (C) preferably contains the bisphenol compound (C1) represented by the following chemical formula (4).

Figure 105110535-A0305-02-0009-9
Figure 105110535-A0305-02-0009-9

化學式(4)中，R4及R5分別獨立為碳數1~4的烴基，R6及R7分別獨立為氫原子、甲基、苯基，c及d分別獨立為0~3的整數。 In the chemical formula (4), R 4 and R 5 are independently C 1-4 hydrocarbon groups, R 6 and R 7 are independently hydrogen atoms, methyl groups, and phenyl groups, and c and d are independently integers of 0 to 3 .

該馬來醯亞胺化合物(A)較佳為該化學式(1)中的p為0或1。而且，該芳香族胺化合物(B)較佳為下述化學式(5)所表示的苯二胺化合物(B1)。 In the maleimide compound (A), it is preferable that p in the chemical formula (1) is 0 or 1. Furthermore, the aromatic amine compound (B) is preferably a phenylenediamine compound (B1) represented by the following chemical formula (5).

Figure 105110535-A0305-02-0009-11
Figure 105110535-A0305-02-0009-11

化學式(5)中，R2為碳數1~4的烴基，b為0~4的整數。 In the chemical formula (5), R 2 is a hydrocarbon group having 1 to 4 carbon atoms, and b is an integer of 0 to 4.

本發明的另一個技術方案提供一種環氧樹脂固化劑，其包含所述本發明的組成物。 Another technical solution of the present invention provides an epoxy resin curing agent comprising the composition of the present invention.

本發明的又另一個技術方案提供一種環氧樹脂組成物，其包含所述本發明的環氧樹脂固化劑與環氧樹脂。 Yet another technical solution of the present invention provides an epoxy resin composition comprising the epoxy resin curing agent of the present invention and an epoxy resin.

所述本發明的環氧樹脂組成物可還包含固化促進劑。這時，該固化促進劑較佳包含選自咪唑系化合物、脲系化合物、以及鏻鹽所組成的群中的一種或兩種以上，該固化促進劑更佳包含咪唑系化合物以及脲系化合物。 The epoxy resin composition of the present invention may further contain a curing accelerator. In this case, the curing accelerator preferably contains one or more selected from the group consisting of imidazole-based compounds, urea-based compounds, and phosphonium salts, and the curing accelerator more preferably contains imidazole-based compounds and urea-based compounds.

所述本發明的環氧樹脂組成物可還包含無機填充材料。 The epoxy resin composition of the present invention may further contain an inorganic filler.

本發明的進而又另一個技術方案提供一種固化物，其為所述本發明的環氧樹脂組成物的固化物。 Yet another technical solution of the present invention provides a cured product which is the cured product of the epoxy resin composition of the present invention.

本發明的進而又另一個技術方案提供一種熱固性組成物，其包含所述本發明的組成物。該熱固性組成物可還包含無機填充材料。 Yet another technical solution of the present invention provides a thermosetting composition including the composition of the present invention. The thermosetting composition may further contain an inorganic filler.

本發明的進而又另一個技術方案提供一種固化物，其為所述本發明的熱固性組成物的固化物。 Still another technical solution of the present invention provides a cured product which is the cured product of the thermosetting composition of the present invention.

本發明的進而又另一個技術方案提供一種半導體裝置以及層間絕緣材料，該半導體裝置是利用所述本發明的環氧樹脂組成物或所述本發明的熱固性組成物而密封，該層間絕緣材料含有所述本發明的環氧樹脂組成物或所述本發明的熱固性組成物。 Yet another technical solution of the present invention provides a semiconductor device and an interlayer insulating material, the semiconductor device is sealed with the epoxy resin composition of the present invention or the thermosetting composition of the present invention, the interlayer insulating material contains The epoxy resin composition of the present invention or the thermosetting composition of the present invention.

根據本發明，可提供一種組成物，適於作為滿足高阻燃性、高耐熱性以及高溫下低分解特性的環氧樹脂的固化劑的成分或熱固性組成物的成分。此外，根據本發明，可提供一種含有該組成物的環氧樹脂固化劑、包含該環氧樹脂固化劑的環氧樹脂組成物、該環氧樹脂組成物的環氧樹脂固化物、包含該組成物的熱固性組成物、該熱固性組成物的固化物、利用該環氧樹脂組成物或該熱固性組成物密封的半導體裝置、以及含有該環氧樹脂組成物或該熱固性組成物的層間絕緣材料。 According to the present invention, it is possible to provide a composition suitable as a component of a curing agent for an epoxy resin satisfying high flame retardancy, high heat resistance, and low decomposition characteristics at high temperature or a component of a thermosetting composition. Furthermore, according to the present invention, an epoxy resin curing agent containing the composition, an epoxy resin composition containing the epoxy resin curing agent, an epoxy resin cured product of the epoxy resin composition, and the composition can be provided Thermosetting composition, cured product of the thermosetting composition, semiconductor device sealed with the epoxy resin composition or the thermosetting composition, and interlayer insulating material containing the epoxy resin composition or the thermosetting composition.

以下，對本發明的實施方式進行說明。 Hereinafter, embodiments of the present invention will be described.

本發明的一實施方式的組成物(以下，也將該組成物稱為「本組成物」)含有該化學式(1)所表示的馬來醯亞胺化合物(A)、該化學式(2)所表示的芳香族胺化合物(B)、以及 該化學式(3)所表示的酚化合物(C)。在一實施方式中，本組成物是包含該馬來醯亞胺化合物(A)、芳香族胺化合物(B)、以及酚化合物(C)的組成物的熔融混合體。 The composition of one embodiment of the present invention (hereinafter, this composition is also referred to as "this composition") contains the maleimide compound (A) represented by the chemical formula (1) and the chemical formula (2). Represented aromatic amine compound (B), and The phenol compound (C) represented by the chemical formula (3). In one embodiment, the present composition is a melt-mixture of a composition containing the maleimide compound (A), aromatic amine compound (B), and phenol compound (C).

馬來醯亞胺化合物(A)的較佳例能夠通過使馬來酸酐與二官能型芳香族胺類縮合而容易地獲得(例如參照日本專利特開昭60-260623號公報等)。本組成物所含有的馬來醯亞胺化合物(A)較佳具有熔點為100℃~250℃的物性。 Preferred examples of the maleimide compound (A) can be easily obtained by condensing maleic anhydride and a difunctional aromatic amine (for example, refer to Japanese Patent Laid-Open No. 60-260623, etc.). The maleimide compound (A) contained in the present composition preferably has physical properties with a melting point of 100°C to 250°C.

作為馬來醯亞胺化合物(A)的具體例，可列舉：N,N'-4,4'-二苯基甲烷雙馬來醯亞胺、N,N'-間亞苯基雙馬來醯亞胺、N,N'-4,4'-二苯基醚雙馬來醯亞胺、N,N'-間二甲苯雙馬來醯亞胺等。 Specific examples of the maleimide compound (A) include: N,N'-4,4'-diphenylmethane bismaleimide, N,N'-m-phenylene bismaleimide Acetylene imide, N,N'-4,4'-diphenyl ether bismaleimide, N,N'-m-xylene bismaleimide, etc.

其中，就賦予耐熱性的觀點而言，馬來醯亞胺化合物(A)較佳為該化學式(1)中的p為0或1，更佳含有作為該化學式(1)中的p為1時的物質的一例的N,N'-4,4'-二苯基甲烷雙馬來醯亞胺，進一步較佳由該物質形成。另外，N,N'-4,4'-二苯基甲烷雙馬來醯亞胺在該化學式(1)中，Ar1為亞苯基，X1為亞甲基。 Among them, from the viewpoint of imparting heat resistance, the maleimide compound (A) preferably has p in the chemical formula (1) of 0 or 1, and more preferably contains p as 1 in the chemical formula (1) N,N'-4,4'-diphenylmethane bismaleimide, which is an example of the substance at the time, is more preferably formed from this substance. In addition, N,N'-4,4'-diphenylmethane bismaleimide In this chemical formula (1), Ar 1 is phenylene and X 1 is methylene.

作為芳香族胺化合物(B)的具體例，可列舉：鄰苯二胺、間苯二胺、對苯二胺、4-甲基-1,2-苯二胺、2,4-二氨基甲苯、2,3,5,6-四甲基-1,4-苯二胺、二(4-氨基苯基)碸、3,3'-二氨基聯苯胺、2,2'-亞甲基雙(4-甲基-1,5-苯二胺)等。其 中，就獲取的容易度而言，芳香族胺化合物(B)中的Ar2可包含的一級氨基的個數較佳為0。而且，就賦予耐熱性的觀點而言，芳香族胺化合物(B)較佳為該化學式(5)所表示的苯二胺化合物(B1)。作為苯二胺化合物(B1)的具體例，可列舉：鄰苯二胺、間苯二胺及對苯二胺、4-甲基-1,2-苯二胺等。 Specific examples of the aromatic amine compound (B) include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4-methyl-1,2-phenylenediamine, and 2,4-diaminotoluene , 2,3,5,6-tetramethyl-1,4-phenylenediamine, bis (4-aminophenyl) sulfone, 3,3'-diamino benzidine, 2,2 '- methylene bis (4-methyl-1,5-phenylenediamine) etc. Among them, in terms of ease of acquisition, the number of primary amino groups that Ar 2 in the aromatic amine compound (B) may contain is preferably 0. Furthermore, from the viewpoint of imparting heat resistance, the aromatic amine compound (B) is preferably the phenylenediamine compound (B1) represented by the chemical formula (5). Specific examples of the phenylenediamine compound (B1) include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4-methyl-1,2-phenylenediamine, and the like.

作為酚化合物(C)，可例示：雙酚化合物的烯丙基化化合物、烯丙基化酚系酚醛清漆樹脂等。其中，酚化合物(C)較佳包含該化學式(4)所表示的雙酚化合物(C1)，更佳由雙酚化合物(C1)形成。雙酚化合物(C1)的具體結構並無限定。可例示：雙酚A結構、雙酚F結構、雙酚AP結構、雙酚BP結構等。通過具有所述結構，能夠確保成形時的適度流動性與成形品的適度耐熱性。作為雙酚化合物(C1)的具體例，可列舉：4,4'-(二甲基亞甲基)雙[2-(2-丙烯基)苯酚]、4,4'-亞甲基雙[2-(2-丙烯基)苯酚]、4,4'-(二甲基亞甲基)雙[2-(2-丙烯基)-6-甲基苯酚]等。在酚化合物(C)含有雙酚化合物(C1)時，雙酚化合物(C1)較佳含有4,4'-(二甲基亞甲基)雙[2-(2-丙烯基)苯酚]，更較佳酚化合物(C)由4,4'-(二甲基亞甲基)雙[2-(2-丙烯基)苯酚]形成。 Examples of the phenol compound (C) include an allylated compound of a bisphenol compound, an allylated phenol-based novolak resin, and the like. Among them, the phenol compound (C) preferably contains the bisphenol compound (C1) represented by the chemical formula (4), and more preferably is formed of the bisphenol compound (C1). The specific structure of the bisphenol compound (C1) is not limited. Exemplary: bisphenol A structure, bisphenol F structure, bisphenol AP structure, bisphenol BP structure, etc. By having the above structure, it is possible to ensure appropriate fluidity during molding and moderate heat resistance of the molded product. Specific examples of the bisphenol compound (C1) include 4,4'-(dimethylmethylene)bis[2-(2-propenyl)phenol] and 4,4'-methylenebis[ 2-(2-propenyl)phenol], 4,4'-(dimethylmethylene)bis[2-(2-propenyl)-6-methylphenol], etc. When the phenol compound (C) contains the bisphenol compound (C1), the bisphenol compound (C1) preferably contains 4,4′-(dimethylmethylene)bis[2-(2-propenyl)phenol], More preferably, the phenol compound (C) is formed of 4,4'-(dimethylmethylene)bis[2-(2-propenyl)phenol].

本組成物可還含有馬來醯亞胺化合物(A)與芳香族胺化合物(B)的反應產物。這時，反應產物可為馬來醯亞胺化合物(A)與芳香族胺化合物(B)的邁克爾加成物。 The present composition may further contain the reaction product of the maleimide compound (A) and the aromatic amine compound (B). At this time, the reaction product may be a Michael adduct of maleimide compound (A) and aromatic amine compound (B).

就容易獲得該反應產物的觀點等而言，本組成物可為包含馬來醯亞胺化合物(A)、芳香族胺化合物(B)、以及酚化合物(C)的組成物的熔融混合體。 From the viewpoint of easily obtaining the reaction product, the present composition may be a melt-mixture of a composition containing a maleimide compound (A), an aromatic amine compound (B), and a phenol compound (C).

本組成物存在如下情況：就使包含本組成物作為成分的熱固性組成物的固化物的耐熱特性提升的觀點而言，較佳基於源自馬來醯亞胺化合物(A)的馬來醯亞胺基的部分結構的總數為基於源自芳香族胺化合物(B)的一級氨基的部分結構與基於源自酚化合物(C)的烯丙基的部分結構的總數的1.5倍以上2.5倍以下。關於所述比(基於源自馬來醯亞胺化合物(A)的馬來醯亞胺基的部分結構的總數相對於基於源自芳香族胺化合物(B)的一級氨基的部分結構與基於源自酚化合物(C)的烯丙基的部分結構的總數的比)，存在更佳為1.8以上2.2以下的情況，且存在尤其較佳為1.9以上2.1以下的情況。 The present composition may be such that, from the viewpoint of improving the heat resistance characteristics of the cured product of the thermosetting composition containing the present composition as a component, it is preferably based on maleimide derived from the maleimide compound (A) The total number of partial structures of the amine group is 1.5 times or more and 2.5 times or less the total number of partial structures based on the primary amino group derived from the aromatic amine compound (B) and the partial structures based on the allyl group derived from the phenol compound (C). Regarding the ratio (the total number of partial structures based on the maleimide group derived from the maleimide compound (A) relative to the partial structure based on the primary amino group derived from the aromatic amine compound (B) and based on the source From the ratio of the total number of allyl partial structures of the phenol compound (C), there are cases where it is more preferably 1.8 or more and 2.2 or less, and there are cases where particularly preferably 1.9 or more and 2.1 or less.

在本組成物為該熔融混合體時，可利用使源自馬來醯亞胺化合物(A)的馬來醯亞胺基的總數成為源自芳香族胺化合物(B)的一級氨基與源自酚化合物(C)的烯丙基的總數的1.5倍以上2.5倍以下的成分混合比進行熔融混合。通過在這種條件下進行熔融混合，存在能夠使包含本組成物作為成分的熱固性組成物的固化物的耐熱特性提升的情況。所述成分混合比較佳為1.8以上2.2以下，更佳為1.9以上2.1以下。 When the present composition is the melt mixture, the total number of maleimide groups derived from the maleimide compound (A) can be used as the primary amino group derived from the aromatic amine compound (B) and derived from The component mixing ratio of 1.5 times or more and 2.5 times or less of the total number of allyl groups of the phenol compound (C) is melt-mixed. By performing melt mixing under such conditions, there may be a case where the heat resistance characteristics of the cured product of the thermosetting composition containing the present composition as a component can be improved. The mixing of the components is preferably 1.8 or more and 2.2 or less, and more preferably 1.9 or more and 2.1 or less.

該熔融混合的具體方法並無限定。能夠通過在加熱條件下且較佳在攪拌條件下，將馬來醯亞胺化合物(A)、芳香族胺化合物(B)以及酚化合物(C)等各成分在通常的混合容器中混合而獲得。作為將這些成分混合成組成物的方法，可例示：將馬來醯亞胺化合物(A)、芳香族胺化合物(B)以及酚化合物(C)一起熔融混合的方法；將芳香族胺化合物(B)與酚化合物(C)熔融混合之後混合馬來醯亞胺化合物(A)的方法等。就提升組成物的物性的穩定性的觀點而言，較佳首先將馬來醯亞胺化合物(A)以外的成分熔融混合，進一步在所得的混合物中混合馬來醯亞胺化合物(A)而製成熔融混合物。 The specific method of this melt mixing is not limited. It can be obtained by mixing the components such as the maleimide compound (A), the aromatic amine compound (B) and the phenol compound (C) in a general mixing container under heating conditions and preferably under stirring conditions. . As a method of mixing these components into a composition, a method of melt-mixing a maleimide compound (A), an aromatic amine compound (B), and a phenol compound (C) together; an aromatic amine compound ( B) The method of mixing the maleimide compound (A) after melt mixing with the phenol compound (C), etc. From the viewpoint of improving the stability of the physical properties of the composition, it is preferable to melt-mix the components other than the maleimide compound (A) first, and further mix the maleimide compound (A) in the resulting mixture. Make a molten mixture.

該熔融混合的條件並無限定。如果進行並無限定的例示，那麼可列舉在100℃~200℃的溫度範圍攪拌混合15分鐘~60分鐘左右。本組成物的150℃熔融黏度較佳為50mPa‧s以上1000mPa‧s以下，更佳為10mPa‧s以上600mPa‧s以下。而且，本組成物的羥基當量較佳為300g/eq以上1500g/eq以下，更佳為600g/eq以上1200g/eq以下。 The conditions of this melt mixing are not limited. If the example is not limited, it may be agitated and mixed in a temperature range of 100°C to 200°C for about 15 minutes to 60 minutes. The 150°C melt viscosity of the composition is preferably 50 mPa‧s or more and 1000 mPa‧s or less, and more preferably 10 mPa‧s or more and 600 mPa‧s or less. In addition, the hydroxyl equivalent of the present composition is preferably 300 g/eq or more and 1500 g/eq or less, and more preferably 600 g/eq or more and 1200 g/eq or less.

關於本發明的混合產物，推定混合成分是各成分以相溶狀態或成分彼此一部分已反應的狀態相溶而成。如所述那樣可包含邁克爾加成物。 Regarding the mixed product of the present invention, it is presumed that the mixed components are the components dissolved in a compatible state or in a state where a part of the components have reacted with each other. As described, Michael adducts may be included.

在本發明的一實施方式中，本組成物被用作環氧樹脂固化物的成分。本發明的一實施方式的環氧樹脂固化物包含本組成物，較佳由本組成物形成。本發明的一實施方式的環氧樹脂固化劑的成形溫度區域內的熔融黏度低，加工性優異，且阻燃性、耐熱性優異，因此能夠用於成形材料、各種黏合劑、塗布材料、層疊材料等。 In one embodiment of the present invention, the present composition is used as a component of a cured epoxy resin. The cured epoxy resin according to an embodiment of the present invention includes the present composition, and is preferably formed from the present composition. The epoxy resin curing agent according to an embodiment of the present invention has a low melt viscosity in the molding temperature range, is excellent in workability, and is excellent in flame retardancy and heat resistance. Therefore, it can be used for molding materials, various adhesives, coating materials, and lamination Materials etc.

本發明的一實施方式的環氧樹脂組成物是包含所述本發明的一實施方式的環氧樹脂固化劑與環氧樹脂的環氧樹脂組成物。在環氧樹脂組成物中，作為能夠與本發明的一實施方式的環氧樹脂固化劑一起使用的環氧樹脂，例如可列舉：雙酚A型環氧樹脂、雙酚F型環氧樹脂、甲酚酚醛清漆型環氧樹脂、苯酚酚醛清漆型環氧樹脂、聯苯型環氧樹脂、苯酚聯苯芳烷基型環氧樹脂、通過苯酚、萘酚等與亞二甲苯基鍵結而成的芳烷基樹脂的環氧化物、二環戊二烯型環氧樹脂、二羥基萘型環氧樹脂、三苯酚甲烷型環氧樹脂等縮水甘油醚型環氧樹脂、縮水甘油酯型環氧樹脂、縮水甘油胺型環氧樹脂等在一分子中具有兩個以上環氧基的環氧化合物。這些環氧樹脂可單獨使用，也可並用兩種以上。如果考慮耐濕性、熱時低彈性模量、阻燃性，那麼較佳使用雙酚F型環氧樹脂、聯苯型環氧樹脂等二官能型環氧樹脂、或者選自苯酚聯苯芳烷基型環氧樹脂、通過苯酚、萘酚等與亞二甲苯基鍵結而成的芳烷基樹脂的環氧化物等中的芳香環較多的多官能型環氧樹脂。 The epoxy resin composition of one embodiment of the present invention is an epoxy resin composition containing the epoxy resin curing agent and epoxy resin of one embodiment of the present invention. In the epoxy resin composition, examples of the epoxy resin that can be used with the epoxy resin curing agent of one embodiment of the present invention include bisphenol A epoxy resin, bisphenol F epoxy resin, Cresol novolac type epoxy resin, phenol novolac type epoxy resin, biphenyl type epoxy resin, phenol biphenyl aralkyl type epoxy resin, formed by bonding with xylylene group by phenol, naphthol, etc. Epoxy resins of aralkyl resins, dicyclopentadiene type epoxy resins, dihydroxynaphthalene type epoxy resins, triphenol methane type epoxy resins and other glycidyl ether type epoxy resins and glycidyl ester type epoxy resins Epoxy compounds such as resins and glycidylamine-type epoxy resins having more than two epoxy groups in one molecule. These epoxy resins may be used alone or in combination of two or more. If moisture resistance, low modulus of elasticity at heat, and flame retardancy are considered, it is preferable to use difunctional epoxy resins such as bisphenol F type epoxy resin and biphenyl type epoxy resin, or selected from phenol biphenyl aryl Multifunctional epoxy resins with many aromatic rings in alkyl type epoxy resins, epoxides of aralkyl resins bonded to xylylene groups such as phenol and naphthol.

在環氧樹脂的固化時，較佳並用固化促進劑。作為固化促進劑，可使用用於利用酚系固化劑使環氧樹脂固化的公知的固化促進劑，例如可列舉：三級胺化合物、四級銨鹽、咪唑類、脲系化合物、膦化合物、鏻鹽等。更具體而言，可列舉：三乙胺、三乙二胺、苄基二甲基胺、2,4,6-三(二甲基氨基甲基)苯酚、1,8-二氮雜雙環(5,4,0)十一烯-7等三級胺化合物；2-甲基咪唑、2,4-二甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑等咪唑類；3-苯基-1,1-二甲基脲、3-(鄰甲基苯基)-1,1-二甲基脲、3-(對甲基苯基)-1,1-二甲基脲、1,1'-亞苯基雙(3,3-二甲基脲)、1,1'-(4-甲基-間亞苯基)-雙(3,3-二甲基脲)等脲系化合物；三苯基膦、三丁基膦、三(對甲基苯基)膦、三(壬基苯基)膦等膦化合物；三苯基鏻酚鹽、四苯基鏻四苯基硼酸鹽、四苯基鏻四萘甲酸硼酸鹽等鏻鹽等。較佳使用包含選自對環氧樹脂的固化與雙馬來醯亞胺的聚合的兩者均顯示高活性的咪唑類、脲系化合物、以及鏻鹽所組成的群中的一種或兩種以上的固化促進劑。固化促進劑更佳包含咪唑系化合物及脲系化合物的至少一者，尤其較佳包含咪唑系化合物及脲系化合物，即，並用咪唑系化合物與脲系化合物。 When curing the epoxy resin, a curing accelerator is preferably used in combination. As the curing accelerator, a known curing accelerator for curing an epoxy resin with a phenolic curing agent can be used, and examples thereof include tertiary amine compounds, quaternary ammonium salts, imidazoles, urea compounds, and phosphine compounds. Phosphonium salt, etc. More specifically, triethylamine, triethylenediamine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo( 5,4,0) undecene-7 and other tertiary amine compounds; 2-methylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2 -Phenyl-4-methylimidazole and other imidazoles; 3-phenyl-1,1-dimethylurea, 3-(o-methylphenyl)-1,1-dimethylurea, 3-(p Methylphenyl)-1,1-dimethylurea, 1,1'-phenylene bis(3,3-dimethylurea), 1,1'-(4-methyl-m-phenylene )-Bis(3,3-dimethylurea) and other urea compounds; triphenylphosphine, tributylphosphine, tri(p-methylphenyl)phosphine, tri(nonylphenyl)phosphine and other phosphine compounds; Phosphonium salts such as triphenylphosphonium phenolate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetranaphthoate borate, etc. It is preferable to use one or more selected from the group consisting of imidazoles, urea compounds, and phosphonium salts that exhibit high activity both for curing epoxy resins and for polymerization of bismaleimide. Curing accelerator. The curing accelerator more preferably contains at least one of an imidazole-based compound and a urea-based compound, and particularly preferably contains an imidazole-based compound and a urea-based compound, that is, an imidazole-based compound and a urea-based compound are used in combination.

在本發明的一實施方式的環氧樹脂組成物中，可視需要添加或預先進行反應地使用無機填充劑、偶聯劑、脫模劑、著色劑、阻燃劑、低應力劑等。而且，也可並用其他 固化劑。作為所述其他固化劑的例子，可列舉：苯酚酚醛清漆樹脂、苯酚芳烷基樹脂、苯酚聯苯芳烷基樹脂、苯酚萘基芳烷基樹脂、萘酚芳烷基樹脂、三苯酚甲烷型酚醛清漆樹脂等。 In the epoxy resin composition according to an embodiment of the present invention, an inorganic filler, a coupling agent, a mold release agent, a coloring agent, a flame retardant, a low-stress agent, etc. may be used as needed or added or reacted in advance. Moreover, other Hardener. Examples of the other curing agent include phenol novolak resin, phenol aralkyl resin, phenol biphenyl aralkyl resin, phenol naphthyl aralkyl resin, naphthol aralkyl resin, and triphenol methane type. Novolac resin, etc.

作為無機填充劑的例子，可列舉非晶性二氧化矽、結晶性二氧化矽、氧化鋁、玻璃、矽酸鈣、菱鎂礦、黏土、滑石、雲母、氧化鎂、硫酸鋇等，尤其較佳為非晶性二氧化矽、結晶性二氧化矽、硫酸鋇。而且，在想要維持優異的成形性且提高填充劑的調配量時，較佳使用如能細密填充的細微性分佈廣的球形填充劑。 Examples of inorganic fillers include amorphous silica, crystalline silica, alumina, glass, calcium silicate, magnesite, clay, talc, mica, magnesium oxide, barium sulfate, etc. Amorphous silicon dioxide, crystalline silicon dioxide, and barium sulfate are preferred. In addition, when it is desired to maintain excellent moldability and increase the amount of filler to be filled, it is preferable to use a spherical filler with a wide distribution of fineness such as fine filling.

作為偶聯劑的例子，可例示巰基矽烷系、乙烯基矽烷系、氨基矽烷系、環氧矽烷系等的矽烷偶聯劑或鈦偶聯劑；作為脫模劑的例子，可例示巴西棕櫚蠟、石蠟等，另外，著色劑可例示碳黑等。作為阻燃劑的例子，可列舉磷化合物、金屬氫氧化物等，作為低應力劑的例子，可列舉矽橡膠、改性腈橡膠、改性丁二烯橡膠、改性矽油等。 As an example of the coupling agent, a silane coupling agent or a titanium coupling agent such as mercaptosilane-based, vinylsilane-based, aminosilane-based, epoxysilane-based, etc. can be exemplified; as an example of the release agent, carnauba wax can be exemplified. , Paraffin, etc. In addition, the coloring agent can be exemplified by carbon black and the like. Examples of flame retardants include phosphorus compounds and metal hydroxides. Examples of low-stress agents include silicone rubber, modified nitrile rubber, modified butadiene rubber, and modified silicone oil.

關於本發明的一實施方式的環氧樹脂固化劑與環氧樹脂的調配比，如果考慮耐熱性、機械特性等，那麼環氧基/羥基的當量比較佳處於0.5~1.5的範圍，尤其是0.8~1.2的範圍。而且，在與其他固化劑並用時，也較佳使環氧基/羥基的當量比成為該比率。關於固化促進劑，如果考慮固 化特性及各物性，那麼較佳在相對於環氧樹脂100重量份而為0.1重量份~10重量份的範圍內使用。在並用多種固化促進劑時，也較佳使相對於環氧樹脂100重量份的品質份成為所述範圍。無機填充劑的調配率雖也因種類而不同，但如果考慮焊料耐熱性、成形性(熔融黏度、流動性)、低應力性、低吸水性等，那麼較佳以如占組成物整體的60重量%~93重量%的比率調配無機填充劑。 Regarding the blending ratio of the epoxy resin curing agent and epoxy resin according to an embodiment of the present invention, considering heat resistance, mechanical properties, etc., the epoxy/hydroxyl equivalent is preferably in the range of 0.5 to 1.5, especially 0.8 ~1.2 range. In addition, when used in combination with other curing agents, it is also preferable to make the equivalent ratio of epoxy group/hydroxyl group to this ratio. Regarding the curing accelerator, if you consider Chemical properties and various physical properties are preferably used in the range of 0.1 to 10 parts by weight relative to 100 parts by weight of epoxy resin. When a plurality of curing accelerators are used in combination, it is also preferable to make the mass part relative to 100 parts by weight of the epoxy resin fall within the above range. Although the compounding ratio of the inorganic filler also varies depending on the type, if considering the solder heat resistance, formability (melt viscosity, fluidity), low stress, low water absorption, etc., it is preferable to account for 60% of the entire composition The inorganic filler is blended in the ratio of wt% to 93 wt%.

本發明的一實施方式的熱固性組成物包含本組成物。本組成物不僅能夠如所述那樣作為固化劑使用，且自身能作為固化性物質發揮功能。這時，可通過使本發明的一實施方式的熱固性組成物中所含的本組成物自聚而獲得固化物。在該情況下，本發明的一實施方式的熱固性組成物除了本組成物以外可以還含有其他固化性物質。 The thermosetting composition according to an embodiment of the present invention includes the present composition. Not only can the present composition be used as a curing agent as described above, but it can also function as a curable substance itself. At this time, a cured product can be obtained by self-polymerizing the present composition contained in the thermosetting composition of one embodiment of the present invention. In this case, the thermosetting composition according to an embodiment of the present invention may contain other curable substances in addition to the present composition.

在本發明的一實施方式的熱固性組成物中，可視需要添加或預先進行反應地使用無機填充劑、偶聯劑、脫模劑、著色劑、阻燃劑、低應力劑等。 In the thermosetting composition according to an embodiment of the present invention, an inorganic filler, a coupling agent, a mold release agent, a coloring agent, a flame retardant, a low-stress agent, etc. may be added or reacted in advance if necessary.

作為無機填充劑的例子，可列舉非晶性二氧化矽、結晶性二氧化矽、氧化鋁、玻璃、矽酸鈣、菱鎂礦、黏土、滑石、雲母、氧化鎂、硫酸鋇等，尤其較佳為非晶性二氧化矽、結晶性二氧化矽、硫酸鋇。而且，在想要維持優異的成形性且提高填充劑的調配量時，較佳使用如能細密填 充的細微性分佈廣的球形填充劑。 Examples of inorganic fillers include amorphous silica, crystalline silica, alumina, glass, calcium silicate, magnesite, clay, talc, mica, magnesium oxide, barium sulfate, etc. Amorphous silicon dioxide, crystalline silicon dioxide, and barium sulfate are preferred. Moreover, when it is desired to maintain excellent formability and increase the amount of filler, it is preferable to use Spherical filler with wide distribution of fineness.

作為將本發明的一實施方式的環氧樹脂組成物或本發明的一實施方式的熱固性組成物作為成形材料製備時的一般方法，可列舉如下等方法：利用例如混合器將規定比率的各原料充分混合後，利用熱輥或捏合機等施予混煉處理，進一步進行冷卻固化後，粉碎成適當大小，且視需要進行片狀化。如此所得的成形材料可通過例如低壓轉移成形等密封半導體而製造半導體裝置。 As a general method for preparing an epoxy resin composition according to an embodiment of the present invention or a thermosetting composition according to an embodiment of the present invention as a molding material, the following methods may be mentioned: each raw material at a predetermined ratio is prepared using, for example, a mixer After fully mixed, it is subjected to kneading treatment with a hot roller, a kneader, or the like, and after further cooling and solidification, it is pulverized to an appropriate size and, if necessary, is sheeted. The molding material thus obtained can manufacture a semiconductor device by sealing a semiconductor, for example, low-pressure transfer molding.

作為將本發明的一實施方式的環氧樹脂組成物或本發明的一實施方式的熱固性組成物作為絕緣層材料製備時的一般方法，可使規定比率的各原料溶解至溶劑中，製成用於將所得的溶液塗布在電路基板上的層間絕緣用清漆；可通過使玻璃纖維含浸該溶液並進行加熱處理而製成所述用途的預浸體；或者可在支撐膜上將該溶液加熱處理而製成膜狀的所述用途的黏接片。所述各者以任一形態使用均可製成層間絕緣層。 As a general method for preparing an epoxy resin composition according to an embodiment of the present invention or a thermosetting composition according to an embodiment of the present invention as an insulating layer material, a predetermined ratio of each raw material can be dissolved in a solvent to produce Varnish for interlayer insulation that applies the obtained solution on a circuit board; the prepreg for the purpose can be made by impregnating the solution with glass fiber and performing heat treatment; or the solution can be heat-treated on the support film Instead, it is made into a film-like adhesive sheet for the purpose. Each of the above can be used as an interlayer insulating layer in any form.

關於包含本組成物的環氧樹脂組成物的固化或包含本製品的熱固性組成物的固化，不論為所述哪一製品形態均在例如100℃~250℃的溫度範圍內進行。 Regarding the curing of the epoxy resin composition containing the present composition or the curing of the thermosetting composition containing the present product, regardless of the form of the product, the temperature range is, for example, 100°C to 250°C.

以上所說明的實施方式是為了易於理解本發明而記載 的，並非為了限定本發明而記載的。因此，所述實施方式所公開的各要素也包括屬於本發明的技術範圍的所有設計變更及均等物的概念。 The embodiments described above are described for easy understanding of the present invention Is not intended to limit the invention. Therefore, each element disclosed in the above-described embodiment also includes all design changes and concepts of equivalents that fall within the technical scope of the present invention.

[實施例] [Example]

以下，利用實施例及比較例對本發明更具體地進行說明，但本發明並不受這些例子任何的限制。 Hereinafter, the present invention will be described more specifically using examples and comparative examples, but the present invention is not limited to these examples.

[實施例1] [Example 1]

將4,4'-(二甲基亞甲基)雙[2-(2-丙烯基)苯酚]30.8g(0.10莫耳)(大和化成工業公司製造，DABPA，羥基當量為159g/eq)、1,3-苯二胺10.8g(0.10莫耳)、以及4,4'-二苯基甲烷雙馬來醯亞胺143.2g(0.40莫耳)在150℃攪拌20分鐘後進行常溫冷卻，由此獲得作為混合產物的均質的紅褐色的玻璃狀熔融物184.5g(混合產物1)。 4,4'-(dimethylmethylene)bis[2-(2-propenyl)phenol] 30.8g (0.10 mole) (made by Daiwa Chemical Industry Co., Ltd., DABPA, hydroxyl equivalent 159g/eq), 1,3-Phenylenediamine 10.8g (0.10 mol) and 4,4'-diphenylmethane bismaleimide 143.2g (0.40 mol) were stirred at 150°C for 20 minutes and then cooled at room temperature by This obtained 184.5 g of a homogeneous red-brown glassy melt as a mixed product (mixed product 1).

利用ICI熔融黏度計測定出的150℃下的混合產物1的熔融黏度為480mPa‧s。而且，根據DABPA的羥基當量及其成分濃度而算出混合產物1的羥基當量為924g/eq。將本實施例1中所得的混合產物1設為組成物1，在作為固化劑使用時有稱為「固化劑1」的情況。 The melt viscosity of the mixed product 1 at 150°C measured by an ICI melt viscosity meter was 480 mPa‧s. Furthermore, the hydroxyl equivalent of the mixed product 1 was calculated based on the hydroxyl equivalent of DABPA and its component concentration to be 924 g/eq. The mixed product 1 obtained in this Example 1 is referred to as composition 1, and when used as a curing agent, it may be referred to as "curing agent 1".

[實施例2] [Example 2]

將下述化學式(6)所表示的環氧樹脂(日本化藥公司製造的「NC3000」，苯酚聯苯芳烷基型，環氧當量為275 g/eq)、實施例1中所得的固化劑1、熔融二氧化矽、以及包含咪唑系固化促進劑(四國化成公司製造的「Curezol C11Z-A」)的固化促進劑以表2所示的比率(表2中的數值為品質份，以下相同)調配且充分混合後，利用85℃±3℃的兩根輥混煉3分鐘，且進行冷卻、粉碎，由此獲得成形用組成物作為環氧樹脂組成物。利用轉移成形機將該環氧樹脂組成物以壓力100kgf/cm2在175℃成形2分鐘後，在230℃進行6小時的後烘焙(post cure)，而製備玻璃化轉變溫度測定用、350℃重量減少率測定用、以及阻燃性試驗用的試片且進行其評價。將其結果示於表2。 The epoxy resin represented by the following chemical formula (6) ("NC3000" manufactured by Nippon Kayaku Co., Ltd., phenol biphenyl aralkyl type, epoxy equivalent is 275 g/eq), the curing agent 1 obtained in Example 1, fused silica, and the curing accelerator containing an imidazole curing accelerator ("Curezol C11Z-A" manufactured by Shikoku Chemicals Co., Ltd.) are shown in Table 2. The ratio (values in Table 2 are parts by mass, the same below) is prepared and thoroughly mixed, kneaded with two rollers at 85°C±3°C for 3 minutes, and cooled and pulverized, thereby obtaining a molding composition as Epoxy resin composition. This epoxy resin composition was molded at a pressure of 100 kgf/cm2 at 175°C for 2 minutes using a transfer molding machine, and post-bake was performed at 230°C for 6 hours to prepare a 350°C weight for glass transition temperature measurement Test pieces for reduction rate measurement and flame retardancy test were evaluated. The results are shown in Table 2.

Figure 105110535-A0305-02-0022-12
Figure 105110535-A0305-02-0022-12

化學式(6)中，G為縮水甘油基，n為1~10的自然數。 In the chemical formula (6), G is a glycidyl group, and n is a natural number of 1-10.

[實施例3] [Example 3]

以表2所示的調配比率使用包含咪唑系固化促進劑(四國化成公司製造的「Curezol C11Z-A」)以及脲系固化促進劑(三亞普羅(San-Apro)公司製造的「U-CAT 3513N」)的固化促進劑，除此以外，以與實施例2同樣的方式製備成形用組成物且作為環氧樹脂組成物獲得。將進行其評價所 得的結果示於表2。 Use imidazole-based curing accelerator ("Curezol C11Z-A" manufactured by Shikoku Chemicals) and urea-based curing accelerator ("U-CAT" manufactured by San-Apro) at the blending ratio shown in Table 2. 3513N"), except that the curing accelerator was prepared in the same manner as in Example 2 and obtained as an epoxy resin composition. Will evaluate its place The results obtained are shown in Table 2.

[實施例4] [Example 4]

代替咪唑系固化促進劑而以表2所示的調配比率使用脲系固化促進劑(三亞普羅(San-Apro)公司製造的「U-CAT 3512T」)，除此以外，以與實施例2同樣的方式製備成形用組成物且作為環氧樹脂組成物獲得，將進行其評價所得的結果示於表2。 Instead of the imidazole-based curing accelerator, the urea-based curing accelerator ("U-CAT 3512T" manufactured by San-Apro) was used in the formulation ratio shown in Table 2, except that it was the same as in Example 2. The composition for molding was prepared and obtained as an epoxy resin composition, and the results of the evaluation thereof are shown in Table 2.

[實施例5] [Example 5]

以表2所示的調配比率且以與實施例1同樣的方式製備成形用組成物，且作為將組成物1(固化物1)作為主固化成分的熱固性組成物獲得。將進行其評價所得的結果示於表2。另外，在表2中，為了便於顯示，將利用實施例5所製造的熱固性組成物顯示為環氧樹脂組成物，但並不含有具有環氧基的成分。 The molding composition was prepared at the formulation ratio shown in Table 2 in the same manner as in Example 1, and was obtained as a thermosetting composition having Composition 1 (cured product 1) as the main curing component. Table 2 shows the results of the evaluation. In addition, in Table 2, for convenience of display, the thermosetting composition produced in Example 5 is shown as an epoxy resin composition, but does not contain a component having an epoxy group.

[比較例1] [Comparative Example 1]

將苯酚酚醛清漆改性三苯酚甲烷樹脂18.8g(愛沃特(Air Water)公司製造的「HE910C-10」，羥基當量為100g/eq)、2,7-二羥基萘9.6g(0.06莫耳)在150℃熔融混合30分鐘後，使液體溫度下降至120℃且添加4,4'-二苯基甲烷雙馬來醯亞胺71.6g(0.20莫耳)。將其在該溫度下攪拌30分鐘後進行常溫冷卻，由此獲得作為混合產物2的均質的 黑褐色的玻璃狀熔融物100.0g。 Phenol novolak modified triphenol methane resin 18.8g ("HE910C-10" manufactured by Air Water Corporation, hydroxyl equivalent of 100g/eq), 2,7-dihydroxynaphthalene 9.6g (0.06 mole ) After melt mixing at 150°C for 30 minutes, the liquid temperature was lowered to 120°C and 4,4'-diphenylmethane bismaleimide 71.6g (0.20 mole) was added. It was stirred at this temperature for 30 minutes and then cooled at room temperature, thereby obtaining a homogeneous product as the mixed product 2. 100.0 g of dark brown glassy melt.

利用ICI熔融黏度計測定出的150℃下的混合產物2的熔融黏度為80mPa‧s。而且，關於混合產物2的羥基當量，利用乙醯化返滴定法測定的結果為295g/eq。將本比較例1中所得的混合產物2設為固化劑2。 The melt viscosity of the mixed product 2 at 150°C measured by an ICI melt viscosity meter was 80 mPa‧s. Furthermore, the hydroxyl equivalent of the mixed product 2 was measured by the acetylation back titration method and found to be 295 g/eq. Let the mixed product 2 obtained in this comparative example 1 be the curing agent 2.

將利用實施例1所製作的固化劑1以及利用比較例1所製作的固化劑2的物性示於表1。 Table 1 shows the physical properties of the curing agent 1 produced in Example 1 and the curing agent 2 produced in Comparative Example 1.

Figure 105110535-A0305-02-0024-13
Figure 105110535-A0305-02-0024-13

[比較例2] [Comparative Example 2]

將該化學式(6)所表示的環氧樹脂、比較例1中所得的固化劑2、熔融二氧化矽、以及咪唑系固化促進劑(四國化成公司製造的「Curezol C11Z-A」)以表2所示的比率調配，以下，以與實施例2同樣的方式製備成形用組成物且作為環氧樹脂組成物獲得。將進行其評價所得的結果示於表2。 The epoxy resin represented by the chemical formula (6), the curing agent 2 obtained in Comparative Example 1, fused silica, and an imidazole curing accelerator ("Curezol C11Z-A" manufactured by Shikoku Chemicals Co., Ltd.) are shown in the table. The ratio formulation shown in 2 is prepared as follows and obtained as an epoxy resin composition in the same manner as in Example 2. Table 2 shows the results of the evaluation.

通過以下的方法測定利用實施例以及比較例所製作的環氧樹脂組成物以及熱固性組成物(以下，將它們統稱為「環氧樹脂組成物等」)的物性。 The physical properties of the epoxy resin composition and the thermosetting composition (hereinafter, these are collectively referred to as "epoxy resin composition etc.") prepared by Examples and Comparative Examples were measured by the following methods.

(1)組成物的熔融黏度 (1) Melt viscosity of the composition

將環氧樹脂組成物等2.5g製成片狀，利用高化式流動試驗儀(flow tester)(溫度為175℃，孔徑為1mm，長度為1mm)進行測定。 2.5 g of an epoxy resin composition etc. were made into a sheet shape, and it measured with the flow tester (temperature 175 degreeC, pore diameter 1mm, length 1mm).

(2)玻璃化轉變溫度 (2) Glass transition temperature

使用TMA(Thermomechanical Analyzer，熱機械分析裝置)，以升溫速度10℃/分鐘測定環氧樹脂組成物等的試片的線膨脹係數，將線膨脹係數的反曲點設為玻璃化轉變溫度。 Using a TMA (Thermomechanical Analyzer), the linear expansion coefficient of a test piece such as an epoxy resin composition was measured at a temperature increase rate of 10° C./min, and the inflection point of the linear expansion coefficient was defined as the glass transition temperature.

(3)350℃重量減少率(熱分解度測定) (3) 350℃ weight loss rate (measurement of thermal decomposition degree)

使用TGA(Thermogravimetric Analyzer，熱重量分析裝置)，以升溫速度10℃/分鐘加熱環氧樹脂組成物等的試片，測定到達350℃時的重量減少率。可以說該重量減少率越低高溫下低分解特性越優異。 Using a TGA (Thermogravimetric Analyzer, thermogravimetric analyzer), a test piece such as an epoxy resin composition was heated at a temperature increase rate of 10° C./minute, and the weight reduction rate at 350° C. was measured. It can be said that the lower the weight reduction rate, the better the low decomposition characteristics at high temperatures.

(4)阻燃性 (4) Flame retardancy

使用厚度1.6mm×寬度10mm×長度135mm的環氧樹脂組成物等的樣品(每一例為5片)，依照UL-94V測定續燃時間並進行評價。將對各樣品進行兩次接觸火焰所測定的續燃時間中的最長時間設為Fmax(單位：秒)，將對5片樣品進行試驗所得的續燃時間的合計設為Ftotal(單位：秒)。將它們的評價結果示於表2。 Using a sample of an epoxy resin composition or the like (thickness 1.6 mm×width 10 mm×length 135 mm) (5 pieces in each case), the after-flame time was measured and evaluated in accordance with UL-94V. Let Fmax (unit: seconds) the longest time of the after-flame time measured by each sample being exposed to flame twice, and let Ftotal (unit: seconds) the total of the after-flame time obtained by testing 5 samples. . Table 2 shows the evaluation results.

Figure 105110535-A0305-02-0026-15
Figure 105110535-A0305-02-0026-15

由表2瞭解到包含本發明的固化劑1的環氧樹脂組成物相比於使用公知的固化劑(固化劑2)的環氧樹脂組成物，玻璃化轉變溫度高，高溫下低分解特性也優異，能夠提供耐熱性優異的固化物，且該固化物的阻燃性也與由使用公知的固化劑(固化劑2)的環氧樹脂組成物所製作的固化物同等。而且，也能夠通過使用多種表中的固化促進劑，而在維持其他性能的狀況下使玻璃化轉變溫度特別地提升。此外，如實施例5所示，確認到本組成物即便在不含有具有環氧基的物質時，作為熱固性組成物也能夠獲得固 化物，且該固化物因為不含有源自具有環氧基的物質的成分，所以耐熱性以及阻燃性尤其優異。 It is understood from Table 2 that the epoxy resin composition containing the curing agent 1 of the present invention has a higher glass transition temperature and lower decomposition characteristics at high temperatures than the epoxy resin composition using a known curing agent (curing agent 2). It is excellent and can provide a cured product excellent in heat resistance, and the flame retardancy of this cured product is also equivalent to a cured product produced from an epoxy resin composition using a known curing agent (curing agent 2). Furthermore, it is also possible to raise the glass transition temperature particularly while maintaining other properties by using various curing accelerators in the table. In addition, as shown in Example 5, it was confirmed that the present composition can be obtained as a thermosetting composition even when it does not contain a substance having an epoxy group. Since the cured product does not contain a component derived from a substance having an epoxy group, it is particularly excellent in heat resistance and flame retardancy.

[產業利用性] [Industry availability]

由本發明提供的組成物可適於用作滿足高阻燃性、高耐熱性、以及高溫下低熱分解特性的環氧樹脂固化劑或熱固性組成物的固化性成分。 The composition provided by the present invention can be suitably used as a curable component of an epoxy resin curing agent or a thermosetting composition that satisfies high flame retardancy, high heat resistance, and low thermal decomposition characteristics at high temperatures.

而且，利用本發明，可提供使用滿足高阻燃性、高耐熱性、以及高溫下的低熱分解性的新穎的環氧樹脂固化劑的環氧樹脂組成物及其固化物、以及熱固性組成物及其固化物。 Furthermore, according to the present invention, it is possible to provide an epoxy resin composition and its cured product using a novel epoxy resin curing agent that satisfies high flame retardancy, high heat resistance, and low thermal decomposition at high temperatures, and a thermosetting composition and Its cured product.

利用本發明，可提供能夠形成環氧樹脂組成物的組成物及該環氧樹脂組成物、以及能夠形成熱固性組成物的組成物及該熱固性組成物，其尤其作為環氧樹脂固化劑有用，且尤其在用於半導體密封、用於功率元件密封、用作層間絕緣材料时，阻燃性、固化性、更高耐熱性優異。 The present invention can provide a composition capable of forming an epoxy resin composition and the epoxy resin composition, and a composition capable of forming a thermosetting composition and the thermosetting composition, which is particularly useful as an epoxy resin curing agent, and Especially when used in semiconductor sealing, power element sealing, and interlayer insulating materials, it has excellent flame retardancy, curability, and higher heat resistance.

Figure 105110535-A0305-02-0003-5
Figure 105110535-A0305-02-0003-5

Claims (20)

一種組成物，含有下述化學式(1)所表示的馬來醯亞胺化合物(A)、下述化學式(2)所表示的芳香族胺化合物(B)、以及下述化學式(3)所表示的酚化合物(C)：
Figure 105110535-A0305-02-0028-16
 化學式(1)中，Ar1為可存在取代基的碳數6~12的亞芳基，X1為直接鍵結、碳數1~6的二價烴基、O、S或SO2，p為0~2的整數；
Figure 105110535-A0305-02-0028-17
 化學式(2)中，Ar2為包含0個~2個的範圍的一級氨基且可存在烴的取代基的碳數6~12的亞芳基，X2為直接鍵結、碳數1~6的二價烴基、O、S或SO2，q為0~2的整數；
Figure 105110535-A0305-02-0028-18
 化學式(3)中，Ar3為以一分子內的烯丙基數成為2個~4個的範圍的方式包含烯丙基，並且包含0個~2個的範圍的羥基的碳數6~24的亞芳基，X3為直接鍵結、碳數1~6的二價烴基、O、S或SO2，r為0~2的整數；羥基當量為300g/eq以上至1500g/eq以下；基於源自前述馬來醯亞胺化合物(A)的馬來醯亞胺基的部分結構之總數為基於源自前述芳香族胺化合物(B)的一級氨基的部分結構與基於源自前述酚化合物(C)的烯丙基的部分結構之總數的1.5倍以上至2.5倍以下。 A composition containing a maleimide compound (A) represented by the following chemical formula (1), an aromatic amine compound (B) represented by the following chemical formula (2), and represented by the following chemical formula (3) Of phenol compounds (C):
Figure 105110535-A0305-02-0028-16
 In the chemical formula (1), Ar 1 is an arylene group having 6 to 12 carbon atoms in which substituents may be present, X 1 is a direct bond, a divalent hydrocarbon group having 1 to 6 carbon atoms, O, S or SO 2 , and p is Integer of 0~2;
Figure 105110535-A0305-02-0028-17
 In the chemical formula (2), Ar 2 is an arylene group having 6 to 12 carbon atoms, which contains a primary amino group in the range of 0 to 2, and a hydrocarbon substituent may be present, X 2 is a direct bond, and the carbon number is 1 to 6 Divalent hydrocarbon group, O, S or SO 2 , q is an integer of 0~2;
Figure 105110535-A0305-02-0028-18
 In the chemical formula (3), Ar 3 contains allyl groups so that the number of allyl groups in one molecule is in the range of 2 to 4 and contains 6 to 24 carbon atoms including hydroxyl groups in the range of 0 to 2 Arylene, X 3 is a direct bond, a C 1 to C 6 divalent hydrocarbon group, O, S or SO 2 , r is an integer of 0 to 2; hydroxyl equivalent is 300g/eq or more and 1500g/eq or less; based on The total number of partial structures of the maleimide group derived from the aforementioned maleimide compound (A) is based on the partial structure of the primary amino group derived from the aforementioned aromatic amine compound (B) and from the aforementioned phenol compound ( C) The total number of allyl partial structures is 1.5 times or more and 2.5 times or less. 如請求項1所記載之組成物，其中150℃熔融黏度為50mPa‧s以上至1000mPa‧s以下。 The composition as recited in claim 1, wherein the melt viscosity at 150°C is 50 mPa‧s or more to 1000 mPa‧s or less. 如請求項1或2所記載之組成物，其進一步含有該馬來醯亞胺化合物(A)與該芳香族胺化合物(B)的反應產物。 The composition according to claim 1 or 2, further containing a reaction product of the maleimide compound (A) and the aromatic amine compound (B). 如請求項3所記載之組成物，其中該反應產物為該馬來醯亞胺化合物(A)與該芳香族胺化合物(B)的邁克爾加成物。 The composition according to claim 3, wherein the reaction product is a Michael adduct of the maleimide compound (A) and the aromatic amine compound (B). 如請求項1或2所記載之組成物，其中該組成物為包含該馬來醯亞胺化合物(A)、該芳香族胺化合物(B)、以及該酚化合物(C)的組成物的熔融混合體。 The composition according to claim 1 or 2, wherein the composition is a melt of a composition containing the maleimide compound (A), the aromatic amine compound (B), and the phenol compound (C) Mixture. 如請求項1或2所記載之組成物，其中該酚化合物(C)包含下述化學式(4)所表示的雙酚化合物(C1)：[化學式(4)]
Figure 105110535-A0305-02-0030-19
 化學式(4)中，R4及R5分別獨立為碳數1~4的烴基，R6及R7分別獨立為氫原子、甲基、苯基，c及d分別獨立為0~3的整數。 The composition as described in claim 1 or 2, wherein the phenol compound (C) contains the bisphenol compound (C1) represented by the following chemical formula (4): [Chemical formula (4)]
Figure 105110535-A0305-02-0030-19
 In the chemical formula (4), R 4 and R 5 are independently C 1-4 hydrocarbon groups, R 6 and R 7 are independently hydrogen atoms, methyl groups, and phenyl groups, and c and d are independently integers of 0 to 3 . 如請求項1或2所記載之組成物，其中該馬來醯亞胺化合物(A)的該化學式(1)中的p為0或1。 The composition according to claim 1 or 2, wherein p in the chemical formula (1) of the maleimide compound (A) is 0 or 1. 如請求項1或2所記載之組成物，其中該芳香族胺化合物(B)為下述化學式(5)所表示的苯二胺化合物(B1)：
Figure 105110535-A0305-02-0030-20
 化學式(5)中，R2為碳數1~4的烴基，b為0~4的整數。 The composition according to claim 1 or 2, wherein the aromatic amine compound (B) is a phenylenediamine compound (B1) represented by the following chemical formula (5):
Figure 105110535-A0305-02-0030-20
 In the chemical formula (5), R 2 is a hydrocarbon group having 1 to 4 carbon atoms, and b is an integer of 0 to 4. 一種環氧樹脂固化劑，包含如請求項1至8中任一項所記載之組成物。 An epoxy resin curing agent comprising the composition described in any one of claims 1 to 8. 一種環氧樹脂組成物，包含如請求項9所記載之環氧樹脂固化劑與環氧樹脂。 An epoxy resin composition comprising the epoxy resin curing agent described in claim 9 and an epoxy resin. 如請求項10所記載之環氧樹脂組成物，其進一步包含固化促進劑。 The epoxy resin composition according to claim 10, which further contains a curing accelerator. 如請求項11所記載之環氧樹脂組成物，其中該固化促進劑包含選自咪唑系化合物、脲系化合物、以及鏻鹽 所組成的群中的一種或兩種以上。 The epoxy resin composition according to claim 11, wherein the curing accelerator comprises an imidazole-based compound, a urea-based compound, and a phosphonium salt One or more than two of the group formed. 如請求項12所記載之環氧樹脂組成物，其中該固化促進劑包含咪唑系化合物以及脲系化合物。 The epoxy resin composition according to claim 12, wherein the curing accelerator includes an imidazole-based compound and a urea-based compound. 如請求項10至13中任一項所記載之環氧樹脂組成物，其進一步包含無機填充材料。 The epoxy resin composition according to any one of claims 10 to 13, which further contains an inorganic filler. 一種固化物，其為如請求項10至14中任一項所記載之環氧樹脂組成物的固化物。 A cured product is a cured product of the epoxy resin composition according to any one of claims 10 to 14. 一種熱固性組成物，包含如請求項1至8中任一項所記載之組成物。 A thermosetting composition comprising the composition described in any one of claims 1 to 8. 如請求項16所記載之熱固性組成物，其進一步包含無機填充材料。 The thermosetting composition as described in claim 16, which further contains an inorganic filler. 一種固化物，其為如請求項16或17所記載之熱固性組成物的固化物。 A cured product which is a cured product of the thermosetting composition described in claim 16 or 17. 一種半導體裝置，其利用如請求項10至14中任一項所記載之環氧樹脂組成物或如請求項16或17所記載之熱固性組成物而密封。 A semiconductor device sealed with the epoxy resin composition described in any one of claims 10 to 14 or the thermosetting composition described in any one of claims 16 or 17. 一種層間絕緣材料，含有如請求項10至14中任一項所記載之環氧樹脂組成物或如請求項16或17所記載之熱固性組成物。 An interlayer insulating material containing the epoxy resin composition described in any one of claims 10 to 14 or the thermosetting composition described in any one of claims 16 or 17.
TW105110535A 2015-04-27 2016-04-01 Composition, epoxy resin curing agent, epoxy resin composition, thermosetting composition, cured product, semiconductor device, and interlayer insulating material TWI693250B (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2015-090428 2015-04-27
JP2015090428 2015-04-27
JP2015-255473 2015-12-26
JP2015255473A JP6546527B2 (en) 2015-04-27 2015-12-26 Composition, epoxy resin curing agent, epoxy resin composition, thermosetting composition, cured product, semiconductor device, and interlayer insulating material

Publications (2)

Publication Number Publication Date
TW201638175A TW201638175A (en) 2016-11-01
TWI693250B true TWI693250B (en) 2020-05-11

Family

ID=57488894

Family Applications (1)

Application Number Title Priority Date Filing Date
TW105110535A TWI693250B (en) 2015-04-27 2016-04-01 Composition, epoxy resin curing agent, epoxy resin composition, thermosetting composition, cured product, semiconductor device, and interlayer insulating material

Country Status (4)

Country Link
JP (1) JP6546527B2 (en)
KR (1) KR20160127665A (en)
CN (1) CN106084184B (en)
TW (1) TWI693250B (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101955754B1 (en) * 2016-02-16 2019-03-07 삼성에스디아이 주식회사 Epoxy resin composition for encapsulating semiconductor device and semiconductor device encapsulated by using the same
JP6724817B2 (en) * 2017-02-24 2020-07-15 信越化学工業株式会社 Thermosetting epoxy resin composition for optical semiconductor and semiconductor device
JP6867894B2 (en) * 2017-06-22 2021-05-12 エア・ウォーター株式会社 Compositions, epoxy resin curing agents, epoxy resin compositions, thermosetting compositions, cured products, semiconductor devices, and interlayer insulating materials
JP7272405B2 (en) * 2018-03-08 2023-05-12 味の素株式会社 Resin composition, sheet laminate material, printed wiring board and semiconductor device
JP6988588B2 (en) * 2018-03-08 2022-01-05 味の素株式会社 Resin composition, sheet-like laminated material, printed wiring board and semiconductor device
US11958940B2 (en) 2018-09-12 2024-04-16 Nippon Kayaku Kabushiki Kaisha Maleimide resin, curable resin composition, and cured product thereof
WO2024064047A1 (en) * 2022-09-19 2024-03-28 Henkel Ag & Co. Kgaa Resin composition for die attach film with excellent performance with large die applications

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102167825A (en) * 2011-03-11 2011-08-31 南京航空航天大学 Bismaleimide resin for microdiameter pultrusion process and preparation method thereof

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH647249A5 (en) * 1981-12-23 1985-01-15 Ciba Geigy Ag STORAGE-STABLE, HEAT-CURABLE, POLYIMIDE-BASED MIXTURES CONTAINING A POLYMERIZATION CATALYST.
US5037689A (en) * 1989-02-17 1991-08-06 Basf Aktiengesellschaft Toughened thermosetting structural materials
JPH0597965A (en) 1991-10-04 1993-04-20 Mitsui Toatsu Chem Inc Epoxy resin composition
JPH07268074A (en) * 1994-03-31 1995-10-17 Toagosei Co Ltd Thermosetting resin composition
JP3349963B2 (en) 1998-10-21 2002-11-25 日本電気株式会社 Flame-retardant epoxy resin composition and semiconductor device using the same
JP5030297B2 (en) * 2007-05-18 2012-09-19 日本化薬株式会社 Laminate resin composition, prepreg and laminate
JP6060541B2 (en) * 2012-02-23 2017-01-18 日立化成株式会社 Thermosetting resin composition for semiconductor encapsulation and semiconductor device using the same
JP6192523B2 (en) * 2013-03-05 2017-09-06 エア・ウォーター株式会社 Epoxy resin curing agent, production method, and use thereof
CN104530430B (en) * 2015-01-09 2017-02-01 西北工业大学 High-tenacity flame-retardant bismaleimide resin and preparation method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102167825A (en) * 2011-03-11 2011-08-31 南京航空航天大学 Bismaleimide resin for microdiameter pultrusion process and preparation method thereof

Also Published As

Publication number Publication date
JP2016204626A (en) 2016-12-08
KR20160127665A (en) 2016-11-04
CN106084184A (en) 2016-11-09
JP6546527B2 (en) 2019-07-17
CN106084184B (en) 2020-05-01
TW201638175A (en) 2016-11-01

Similar Documents

Publication Publication Date Title
TWI693250B (en) Composition, epoxy resin curing agent, epoxy resin composition, thermosetting composition, cured product, semiconductor device, and interlayer insulating material
EP3127933B1 (en) Heat-curable epoxy resin composition
JP6192523B2 (en) Epoxy resin curing agent, production method, and use thereof
JP5079721B2 (en) Epoxy resin composition and molded article
JP6052868B2 (en) Epoxy resin curing agent, production method, and use thereof
KR102353480B1 (en) Heat-curable epoxy resin composition
JP2010229260A (en) Epoxy resin composition and molded product
TW201636356A (en) Phosphonium compound, epoxy resin composition including the same and semiconductor device prepared using the same
JP5302147B2 (en) Epoxy resin composition for sealing and cured product
TWI826633B (en) Ester compounds, resin compositions, hardened materials and build-up films
JP6867894B2 (en) Compositions, epoxy resin curing agents, epoxy resin compositions, thermosetting compositions, cured products, semiconductor devices, and interlayer insulating materials
JP5946329B2 (en) Phenol oligomer, its production method and use
JP6374714B2 (en) Epoxy resin composition, adhesive, cured product, and electronic member
JP2006249139A (en) Epoxy resin composition for encapsulating semiconductor
JP2006117881A (en) Additive for epoxy resin, its composition and its use
JP2013142136A (en) Flame-retardant liquid epoxy resin composition for encapsulating semiconductor and semiconductor device
JP7295826B2 (en) epoxy resin composition
TWI835960B (en) Sealing composition and semiconductor device
TWI680974B (en) Thermosetting resin composition, insulating material containing the thermosetting resin composition, sealing material, conductive paste, hardened product obtained by hardening the thermosetting resin composition, substrate material having the thermosetting resin composition, impregnation of the thermosetting resin composition A prepreg formed from a base material, a structural material formed by curing a thermosetting resin composition of the prepreg, and a method for adjusting the thermal expansion rate
KR101724345B1 (en) Method for producing imide group-containing naphthol resin, thermosetting resin composition and cured product and use thereof
JPH04224859A (en) Resin composition
JP2003041118A (en) Resin composition for semiconductor-sealing material
JP2023066807A (en) Epoxy resin composition and cured product
TW201805322A (en) Polyvalent alkyne compound, method for producing the same and use thereof
JPH05255574A (en) Resin composition

Legal Events

Date Code Title Description
MM4A Annulment or lapse of patent due to non-payment of fees