TWI636071B - Hardener for epoxy resin and the preparing method thereof - Google Patents

Hardener for epoxy resin and the preparing method thereof Download PDF

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TWI636071B
TWI636071B TW106132696A TW106132696A TWI636071B TW I636071 B TWI636071 B TW I636071B TW 106132696 A TW106132696 A TW 106132696A TW 106132696 A TW106132696 A TW 106132696A TW I636071 B TWI636071 B TW I636071B
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curing agent
carbon atoms
epoxy resin
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TW201813989A (en
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李垠龍
李智愛
鄭榕洙
李貴恒
黃載錫
白美貞
鄭源浩
崔湖京
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新亞Ｔ＆Ｃ公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C08G59/625—Hydroxyacids
    • C08G59/628—Phenolcarboxylic acids
    • 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
    • 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
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4246—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof polymers with carboxylic terminal groups
    • C08G59/4269—Macromolecular compounds obtained by reactions other than those involving unsaturated carbon-to-carbon bindings
    • C08G59/4276—Polyesters
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/123—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/133—Hydroxy compounds containing aromatic rings
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/105—Esters; Ether-esters of monocarboxylic acids with phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)

Abstract

本發明涉及環氧樹脂用固化劑，更詳細地涉及環氧樹脂用固化劑，基於本發明的固化劑的固化物具有高玻璃轉移溫度、低吸濕力、優秀的黏結力、高剝離強度及低熱膨脹係數，同時顯著提高如介電常數、介電損耗等電特性，而能夠廣泛地利用於電氣電子領域。 The present invention relates to a curing agent for epoxy resin, and more particularly to a curing agent for epoxy resin. The cured product based on the curing agent of the present invention has high glass transition temperature, low hygroscopicity, excellent adhesion, high peel strength, and Low thermal expansion coefficient, while significantly improving electrical characteristics such as dielectric constant and dielectric loss, can be widely used in the field of electrical and electronics.

Description

環氧樹脂用固化劑及其製備方法    Curing agent for epoxy resin and preparation method thereof   

本發明涉及環氧樹脂用固化劑及其製備方法，更詳細地涉及環氧樹脂用固化劑，基於本發明的固化劑的固化物具有高玻璃轉移溫度、低吸濕力、優秀的黏結力、高剝離強度、低熱膨脹係數同時，可顯著提高介電常數、介電損耗等的電特性。 The present invention relates to a curing agent for epoxy resin and a preparation method thereof, and more specifically relates to a curing agent for epoxy resin. The cured product based on the curing agent of the present invention has a high glass transition temperature, low hygroscopicity, excellent adhesion, With high peel strength and low thermal expansion coefficient, electrical properties such as dielectric constant and dielectric loss can be significantly improved.

最近，隨著半導體產業高容量化、超高速化，已藉由異種金屬及部件整合化向小型化的趨勢發展。在這種整合複合化技術中，向裝置***異種材料及部件的包裝技術為核心，為此需要開發具有低熱膨脹係數(Low CTE)、低介電常數(Low Dk)、低介電損耗(Low Df)及耐熱性的核心原材料。 Recently, with the increase in the capacity and ultra-high speed of the semiconductor industry, the trend toward miniaturization has been achieved through the integration of dissimilar metals and components. In this integrated composite technology, packaging technology that inserts different materials and components into the device is the core. To this end, it is necessary to develop a low thermal expansion coefficient (Low CTE), low dielectric constant (Low Dk), and low dielectric loss (Low Df) and heat-resistant core raw materials.

在下一代積體電路(IC)基板(substrate)、印刷電路板(PCB)、撓性顯示器基板(Flexible display substrate)等中，作為用於高集成化、高微細化及高性能化的方法，通常使用於在短時間內處理多容量的半導體器件的集成度增加，此意味著器件配線寬度與寬度之間變窄，藉由上述增加電晶體的開關速度，可實現器件的高速化。 As a next-generation integrated circuit (IC) substrate, printed circuit board (PCB), flexible display substrate, etc., as a method for high integration, miniaturization, and high performance, Generally, the integration degree used to process a multi-capacity semiconductor device increases in a short time, which means that the width and width of the device wiring are narrowed. By increasing the switching speed of the transistor, the device can be made faster.

如上所述，最近揭露用於減少器件的配線寬度的多種方法，但是為了形成微細電路圖案，在現有的銅蝕刻的圖案形成方式中，減少電路圖案間隔有其侷限。由此，通過化學方法的銅(Copper)電路圖案形成可實現20/20μmm以下，但是因未形成圖案的表面光照度存在黏結力顯著降低的缺點。由此，為了實現高密度晶片上配線之間的狹窄線寬度，需要具有低介電常數及低介電損耗的優秀電絕緣特性，同時具有優秀黏結力的高分子物質。 As described above, various methods for reducing the wiring width of a device have recently been disclosed. However, in order to form a fine circuit pattern, in the conventional patterning method of copper etching, there is a limitation in reducing the circuit pattern interval. As a result, copper (Copper) circuit pattern formation by a chemical method can achieve 20/20 μm or less, but there is a disadvantage that the light intensity of the unpatterned surface is significantly reduced. Therefore, in order to achieve a narrow line width between wirings on a high-density wafer, a high-molecular substance having excellent electrical insulation characteristics with low dielectric constant and low dielectric loss and excellent adhesion is required.

具有上述效果的高分子物質且經常被使用的物質，包括廣泛被使用而具有優秀電特性、機械特性、黏結性的環氧(epoxy)樹脂，以及常作為固化劑使用的具有活性氫的如胺(amine)化合物、苯酚(phenol)化合物。 High-molecular substances with the above effects and frequently used substances include epoxy resins that are widely used and have excellent electrical, mechanical, and adhesive properties, and active hydrogens such as amines that are often used as curing agents. (amine) compound, phenol (phenol) compound.

但是，以上述具活性氫的固化劑對環氧樹脂進行固化時，環氧基和活性氫反應產生極性的高羥基，使最終固化物產生吸濕性變高，並且介電常數、介電損耗等電特性降低的問題，並且，因為固化物的玻璃轉移溫度低，使得耐熱性或剝離強度降低，因此降低了機械特性而具有無法同時滿足上述物性的問題。 However, when the epoxy resin is cured with the above-mentioned curing agent with active hydrogen, the epoxy group and the active hydrogen react to generate a polar high hydroxyl group, so that the final cured product has high hygroscopicity, and has a dielectric constant and a dielectric loss. Isoelectric properties are lowered, and because the glass transition temperature of the cured product is low, heat resistance or peel strength is lowered. Therefore, the mechanical properties are lowered and the physical properties cannot be satisfied at the same time.

並且，即使最終固化物有一個較佳地物性，但其他物性降低，尤其隨著介電常數、介電損耗等的電特性降低，將存在不能同時滿足低吸濕性、高耐熱性、優秀的機械特性以及優秀電特性的問題。 In addition, even if the final cured product has a better physical property, other physical properties decrease, especially as the electrical characteristics such as dielectric constant and dielectric loss decrease, there will be those that cannot simultaneously satisfy low hygroscopicity, high heat resistance, and excellent properties. Problems with mechanical properties and excellent electrical properties.

在韓國專利申請第2011-0105763號中，揭露了可用作電子器件的黏結及密封材料的環氧樹脂組合物，但其在包含上述組合物的固化劑的情況下，無法使用一般的胺類固化劑，將介電常數及介電損耗最小化，並且因為固化物的吸濕性高，無法使黏結力增加，從而存在無法用作高性能、高集成的電氣電子材料的問題。 Korean Patent Application No. 2011-0105763 discloses an epoxy resin composition that can be used as a bonding and sealing material for electronic devices. However, in the case of containing a curing agent for the above composition, general amines cannot be used. The curing agent minimizes the dielectric constant and the dielectric loss, and because the cured product has high hygroscopicity, it cannot increase the adhesive force, and thus it cannot be used as a high-performance, highly integrated electrical and electronic material.

《現有技術文獻》 "Existing Technology Literature"

專利文獻：韓國專利公報：第2011-0105763號。 Patent document: Korean Patent Gazette: No. 2011-0105763.

本發明為解決上述問題而提出，本發明所要解決的問題在於，提供一種環氧樹脂用固化劑，使固化物具有高玻璃轉移溫度、低吸濕力、優秀的黏結力、高剝離強度、低熱膨脹係數同時，可顯著提高介電常數、介電損耗等的電特性。 The present invention is made to solve the above problems, and the problem to be solved by the present invention is to provide a curing agent for epoxy resin, so that the cured product has a high glass transition temperature, low hygroscopicity, excellent adhesion, high peel strength, low At the same time, the thermal expansion coefficient can significantly improve electrical characteristics such as dielectric constant and dielectric loss.

本發明第二個所要解決的問題在於，藉由本發明固化劑可產生高玻璃轉移溫度、低吸濕力、優秀的黏結力、高剝離強度及低熱膨脹係數，同時顯著提高介電常數、介電損耗等的電特性，提供作為電氣、電子用密封材料或電氣、電子基板用層疊材料。 The second problem to be solved by the present invention is that the curing agent of the present invention can generate high glass transition temperature, low hygroscopicity, excellent adhesion, high peel strength and low thermal expansion coefficient, and at the same time significantly improve the dielectric constant and dielectric Electrical characteristics such as loss are provided as sealing materials for electrical and electronic applications or as laminated materials for electrical and electronic substrates.

本發明鑒於如上所述的問題而提出，提供包含重均分子量為1000~13000的由以下化學式1表示的化合物： The present invention has been made in view of the problems described above, and provides a compound represented by the following Chemical Formula 1 including a weight average molecular weight of 1,000 to 13,000:

在上述化學式1中，R1為碳數為6~24個的芳基或碳數為4個以下 的烷基，B為或或，A1、A2及A3分別獨立地為 氫原子、或，上 述A1、A2及A3中至少一個不是氫原子，n、m及k分別獨立地為0~8的有理數，l 為0.1~12的有理數，A4為氫原子、、 其中，R2為碳數為6~24個的芳基或碳數為4個以下的烷基，R3為碳數為6~24個的芳基或碳數為4個以下的烷基，i為0~8的有理數，j為0.1~8的有理數，R4為碳數為6~24個的芳基或碳數為4個以下的烷基，o為0~8的有理數，p為0.1~8的有理數，R5為碳數為6~24個的芳基或碳數為4個以下的烷基，若R7及R8均為氫原子或R7及R8中的一個為氫原子，則另一個為甲基。 In the above Chemical Formula 1, R 1 is an aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms, and B is or or , A 1 , A 2 and A 3 are each independently a hydrogen atom, or , At least one of the above A 1 , A 2 and A 3 is not a hydrogen atom, n, m and k are each independently a rational number from 0 to 8, l is a rational number from 0.1 to 12, and A 4 is a hydrogen atom, , Among them, R 2 is an aryl group having 6 to 24 carbons or an alkyl group having 4 or less carbons, R 3 is an aryl group having 6 to 24 carbons or an alkyl group having 4 or less carbons, i is a rational number from 0 to 8, j is a rational number from 0.1 to 8, R 4 is an aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms, o is a rational number from 0 to 8, and p is A rational number of 0.1 to 8, R 5 is an aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms. If R 7 and R 8 are both hydrogen atoms or one of R 7 and R 8 is Hydrogen atom, the other is methyl.

並且，根據本發明的一實施例，上述R1、R2、R3、R4及R5分別獨立地為碳數為4個以下的烷基或取代或非取代的芳基，上述芳基可包含選自由苯(phenyl)基、聯苯(biphenyl)基、萘(naphthyl)基、蒽(anthracene)基、菲(phenanthrene)基、芘(pyrene)基、苝(perylene)基、(chrysene)基、甲酚(cresol)基及芴(fluorene)基所組成的群組中的一種。 In addition, according to an embodiment of the present invention, the R 1 , R 2 , R 3 , R 4, and R 5 are each independently an alkyl group having 4 or less carbon atoms or a substituted or unsubstituted aryl group, and the aryl group It may include a group selected from the group consisting of a phenyl group, a biphenyl group, a naphthyl group, an anthracene group, a phenanthrene group, a pyrene group, a perylene group, (chrysene) group, cresol group and fluorene group.

並且，根據本發明的一實施例，上述R1、R2、R3、R4及R5可分別獨立地為非取代的苯基、萘基或聯苯基。 Moreover, according to an embodiment of the present invention, the R 1 , R 2 , R 3 , R 4, and R 5 may be each independently an unsubstituted phenyl group, a naphthyl group, or a biphenyl group.

並且，本發明提供包含由以下化學式2、化學式3及化學式4表示的單體進行共聚合的共聚物的環氧樹脂用固化劑，該共聚物的重均分子量(Mw(分子量))為1000~13000。 In addition, the present invention provides a curing agent for epoxy resin containing a copolymer copolymerized with monomers represented by the following Chemical Formula 2, Chemical Formula 3, and Chemical Formula 4, and the copolymer has a weight average molecular weight (Mw (molecular weight)) of 1,000 to 13000.

在上述化學式2中，a為0~8的有理數，若上述R7及R8均為氫原子或R7及R8中的一個為氫原子，則另一個為甲基。 In the above Chemical Formula 2, a is a rational number of 0 to 8; if R 7 and R 8 are both hydrogen atoms or one of R 7 and R 8 is a hydrogen atom, the other is a methyl group.

在上述化學式3中，B為或或，X1為鹵素 原子。 In the above Chemical Formula 3, B is or or X 1 is a halogen atom.

在上述化學式4中，X2為鹵素原子，R6為碳數為6~24個的芳基或碳數為4個以下的烷基。 In the above Chemical Formula 4, X 2 is a halogen atom, and R 6 is an aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms.

並且，根據本發明的一實施例，上述X1及X2分別獨立地為氟原子、氯原子、溴原子及碘原子中的一種，上述R6為取代或非取代的芳基，上述芳基可包含選自由苯基、聯苯基、萘基、蒽基、菲基、芘基、苝基、、甲酚基及芴基所組成的群組中的一種。 Furthermore, according to an embodiment of the present invention, the X 1 and X 2 are each independently one of a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, the R 6 is a substituted or unsubstituted aryl group, and the aryl group May include a member selected from the group consisting of phenyl, biphenyl, naphthyl, anthracenyl, phenanthryl, fluorenyl, fluorenyl, One of the group consisting of 2, cresol and fluorenyl.

並且，根據本發明的一實施例，上述R6可以為選自由非取代的苯基、萘基及聯苯基(biphenyl)所組成的群組中的一種。 In addition, according to an embodiment of the present invention, the R 6 may be one selected from the group consisting of an unsubstituted phenyl group, a naphthyl group, and a biphenyl group.

並且，根據本發明之環氧樹脂用固化劑的一實施例，可以為包含以1：0.1~1.5：0.1~3莫耳比的上述化學式2、化學式3及化學式4表示的單體進行共聚合的共聚物。 In addition, according to an embodiment of the curing agent for epoxy resin according to the present invention, a monomer including the above-mentioned chemical formula 2, chemical formula 3, and chemical formula 4 having a molar ratio of 1: 0.1 to 1.5: 0.1 to 3 may be copolymerized. Copolymer.

並且，本發明提供環氧樹脂用固化劑的製備方法，上述環氧樹脂用固化劑的製備方法包括：步驟1，向反應槽導入以1：0.1~1.5：0.1~3莫耳比的化學式2、化學式3及化學式4表示的單體；以及步驟2，將步驟1中所導入的單體進行反應，以製備由下述化學式1表示的共聚物。 In addition, the present invention provides a method for preparing a curing agent for epoxy resin. The method for preparing the curing agent for epoxy resin includes the following steps: 1. Introducing a chemical formula 2 with a molar ratio of 1: 0.1 to 1.5: 0.1 to 3 into a reaction tank. Monomers represented by Chemical Formula 3 and Chemical Formula 4; and Step 2, reacting the monomers introduced in Step 1 to prepare a copolymer represented by Chemical Formula 1 below.

在上述化學式2中，a為0~8的有理數，若上述R7及R8均為氫原子或R7及R8中的一個為氫原子，則另一個為甲基。 In the above Chemical Formula 2, a is a rational number of 0 to 8; if R 7 and R 8 are both hydrogen atoms or one of R 7 and R 8 is a hydrogen atom, the other is a methyl group.

在上述化學式3中，B為或或，X1為鹵素原 子。 In the above Chemical Formula 3, B is or or X 1 is a halogen atom.

在上述化學式4中，X2為鹵素原子，R6為碳數為6~24個的芳基或碳數為4個以下的烷基。 In the above Chemical Formula 4, X 2 is a halogen atom, and R 6 is an aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms.

在上述化學式1中，R1為碳數為6~24個的芳基或碳數為4個以下的烷基，B 為或、，A1、A2及A3分別獨立地為氫原子、 或，上述A1、 A2及A3中至少一個不是氫原子，n、m及k分別獨立地為0~8的有理數，l為0.1~ 12的有理數，A4為氫原子、、 上述R2為碳數為6~24個的芳基或碳數為4個以下的烷基，上述R3為碳數為6~24個的芳基或碳數為4個以下的烷基，i為0~8的有理數，j為0.1~8的有理數，上述R4為碳數為6~24個的芳基或碳數為4個以下的烷基，o為0~8的有理數，p為0.1~8的有理數，上述R5為碳數為6~24個的芳基或碳數為4個以下的烷基，若上述R7及R8均為氫原子或R7及R8中的一個為氫原子，則另一個為甲基。 In the above Chemical Formula 1, R 1 is an aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms, and B is or , , A 1 , A 2 and A 3 are each independently a hydrogen atom, or , At least one of the above A 1 , A 2 and A 3 is not a hydrogen atom, n, m and k are each independently a rational number of 0-8, l is a rational number of 0.1-12, and A4 is a hydrogen atom, , The R 2 is an aryl group having 6 to 24 carbons or an alkyl group having 4 or less carbons, the R 3 is an aryl group having 6 to 24 carbons or an alkyl group having 4 or less carbons, i is a rational number from 0 to 8, j is a rational number from 0.1 to 8, R 4 is an aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms, o is a rational number from 0 to 8, p It is a rational number of 0.1 to 8. The above R 5 is an aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms. If the above R 7 and R 8 are both hydrogen atoms or R 7 and R 8 One is a hydrogen atom, and the other is a methyl group.

並且，根據本發明的一實施例，還可包括如下步驟：在使上述單體進行反應之後，向上述反應槽導入水，來去除作為反應副產物生成的鹽之後，對所製備的環氧樹脂用固化劑進行分離的過程，進行一次以上。 In addition, according to an embodiment of the present invention, the method may further include the steps of: after reacting the monomers, introducing water into the reaction tank to remove salts generated as reaction by-products, and then preparing the prepared epoxy resin The process of separation with a curing agent is performed more than once.

並且，根據本發明的一實施例，在上述步驟2中，可使用三乙胺(triethylamine)、三甲胺(trimethylamine)、三丙胺(tripropylamine)、吡啶(pyridine)及N-甲基呱啶(N-methyl piperidine)所組成的群組中的一種以上的催化劑。 In addition, according to an embodiment of the present invention, in the above step 2, triethylamine, trimethylamine, tripropylamine, pyridine, and N-methylpyridine (N -methyl piperidine).

並且，本發明提供包含上述的環氧樹脂用固化劑及環氧樹脂的電氣電子用密封材料。 The present invention also provides an electrical and electronic sealing material containing the above-mentioned curing agent for epoxy resin and epoxy resin.

並且，本發明提供包含上述的環氧樹脂用固化劑及環氧樹脂的電氣電子用基板層疊材料。 The present invention also provides an electrical and electronic substrate laminate material including the above-mentioned curing agent for epoxy resin and epoxy resin.

並且，本發明提供包含上述的環氧樹脂用固化劑及環氧樹脂的環氧樹脂組合物。 The present invention also provides an epoxy resin composition containing the above-mentioned curing agent for epoxy resin and epoxy resin.

本發明的環氧樹脂用固化劑的固化物通過具有高玻璃轉移溫度來發揮優秀的熱穩定性，具有低吸濕力則可在半導體等中將水分的吸濕最小化，從而可防止在焊接製程中半導體內部剝離或裂紋等問題。並且，通過具有優秀的黏結力及高剝離強度，來顯著增加固化物的耐久性同時具有低熱膨脹係數，可防止封裝的彎曲現象。進而，藉由顯著提高的介電常數、介電損耗等，可實現基於電絕緣特性而顯著提高半導體的高密度集成，從而可廣泛地使用於電氣電子用密封材料、層疊材料等。 The cured product of the curing agent for epoxy resins of the present invention exhibits excellent thermal stability by having a high glass transition temperature, and having a low hygroscopic force can minimize moisture absorption in semiconductors and the like, thereby preventing the soldering during soldering. Problems such as peeling or cracking inside the semiconductor during the manufacturing process. In addition, by having excellent adhesive force and high peel strength, the durability of the cured product is significantly increased, and the coefficient of thermal expansion is low, which can prevent the bending phenomenon of the package. Furthermore, by significantly improving the dielectric constant, dielectric loss, and the like, it is possible to significantly improve the high-density integration of semiconductors based on electrical insulation characteristics, and thus it can be widely used for electrical and electronic sealing materials, laminated materials, and the like.

圖1係本發明一實施例的紅外線(IR)頻譜。 FIG. 1 is an infrared (IR) spectrum of an embodiment of the present invention.

圖2係本發明一實施例的凝膠滲透色譜法(GPC)曲線圖。 FIG. 2 is a gel permeation chromatography (GPC) curve diagram according to an embodiment of the present invention.

以下，參照圖式詳細說明本發明的實施例，以便本發明所屬技術領域聚通常知識的技術人員能夠容易實施。本發明能夠以多種不同的方式實現，並不侷限於在此說明的實施例。在圖式中，為了明確說明本發明，省略了與說明無關的部分，在說明書全文中，對於相同或類似的結構要素，標注了相同的圖式標記。 Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings so that those skilled in the art to which the present invention pertains can easily implement. The invention can be implemented in many different ways and is not limited to the embodiments described herein. In the drawings, in order to clearly explain the present invention, parts irrelevant to the description are omitted, and the same or similar structural elements are marked with the same drawing symbols throughout the specification.

如上所述，作為現有環氧樹脂用固化劑，包括常用而具有活性氫的如胺(amine)化合物、苯酚(phenol)化合物等固化劑，但是具有上述活性氫的固化劑，在固化環氧(epoxy)樹脂時，環氧基和活性氫的反應產生極性的高羥基，因此存在最終固化物的吸濕性變高，並且介電常數、介電損耗等電特性降低的問題。 As described above, the conventional curing agents for epoxy resins include commonly used curing agents such as amine compounds and phenol compounds having active hydrogen, but the curing agents having the above-mentioned active hydrogen are used to cure epoxy ( In the case of epoxy) resin, the reaction between the epoxy group and the active hydrogen generates a polar high hydroxyl group. Therefore, there is a problem that the hygroscopicity of the final cured product becomes high, and the electrical characteristics such as dielectric constant and dielectric loss are reduced.

對此，在本發明中，通過提供包含重均分子量(分子量)為1000~13000的由以下化學式1表示的化合物的環氧樹脂用固化劑，來解決上述問題。 In view of this, in the present invention, the above-mentioned problem is solved by providing a curing agent for an epoxy resin containing a compound represented by the following Chemical Formula 1 having a weight average molecular weight (molecular weight) of 1,000 to 13,000.

在上述化學式1中，R1為碳數為6~24個的芳基或碳數為4個以下 的烷基，B為或或，A1、A2及A3分別獨立地為 氫原子、或， 上述A1、A2及A3中至少一個不是氫原子，n、m及k分別獨立地為0~8的有理數， l為0.1~12的有理數，A4為氫原子、、 上述R2為碳數為6~24個的芳基或碳數為4個以下的烷基，上述R3為碳數為6~24個的芳基或碳數為4個以下的烷基，i為0~8的有理數，j為0.1~8的有理數，上述R4為碳數為6~24個的芳基或碳數為4個以下的烷基，o為0~8的有理數，p為0.1~8的有理數，上述R5為碳數為6~24個的芳基或碳數為4個以下的烷基，若上述R7及R8均為氫原子或R7及R8中的一個為氫原子，則另一個為甲基。 In the above Chemical Formula 1, R 1 is an aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms, and B is or or , A 1 , A 2 and A 3 are each independently a hydrogen atom, or , At least one of the above A 1 , A 2 and A 3 is not a hydrogen atom, n, m and k are each independently a rational number from 0 to 8, l is a rational number from 0.1 to 12, and A 4 is a hydrogen atom, , The R 2 is an aryl group having 6 to 24 carbons or an alkyl group having 4 or less carbons, the R 3 is an aryl group having 6 to 24 carbons or an alkyl group having 4 or less carbons, i is a rational number from 0 to 8, j is a rational number from 0.1 to 8, R 4 is an aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms, o is a rational number from 0 to 8, p It is a rational number of 0.1 to 8. The above R 5 is an aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms. If the above R 7 and R 8 are both hydrogen atoms or R 7 and R 8 One is a hydrogen atom, and the other is a methyl group.

通過上述，包含本發明的固化劑具有高玻璃轉移溫度，而耐熱性優秀，提高基於低吸濕力的固化物的可靠性、基於優秀的黏結力及高剝離強度的優秀的機械特性、基於低熱膨脹係數的固化物的產生不良的減少同時可實現基於提高電特性，如介電常數、介電損耗等的積體電路的實現。 As described above, the curing agent containing the present invention has a high glass transition temperature and excellent heat resistance. It improves the reliability of cured products based on low moisture absorption, excellent mechanical properties based on excellent adhesion and high peel strength, and low The reduction in the production of the cured product with a thermal expansion coefficient is reduced, and at the same time, the realization of the integrated circuit based on the improvement of the electrical characteristics, such as the dielectric constant and the dielectric loss, can be realized.

首先，對由化學式1表示的化合物進行說明。本發明的環氧樹脂用固化劑包含重均分子量(分子量)為1000~13000的由以下化學式1表示的化合物。 First, the compound represented by Chemical Formula 1 will be described. The curing agent for epoxy resins of the present invention includes a compound represented by the following Chemical Formula 1 having a weight average molecular weight (molecular weight) of 1,000 to 13,000.

在上述化學式1中，R1為碳數為6~24個的芳基或碳數為4個以下 的烷基，B為或或，A1、A2及A3分別獨立地為 氫原子、或 (以下，稱為化學式X)。 In the above Chemical Formula 1, R 1 is an aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms, and B is or or , A 1 , A 2 and A 3 are each independently a hydrogen atom, or (Hereinafter referred to as Chemical Formula X).

此時，不僅上述A1、A2及A3分別獨立，而且各個的選自由A1、A2及A3所組成的群組中的一種以上也獨立。例如，在上述化學式1中，在n為4、m為3、k為2的情況下，所包含的A1為4個、A2為3個、A3為2個，此時，在各個A1之間相互獨立，還在各個A2之間相互獨立，還在各個A3之間相互獨立。 At this time, not only the above-mentioned A 1 , A 2, and A 3 are independent, but also one or more selected from the group consisting of A 1 , A 2, and A 3 are also independent. For example, in the above Chemical Formula 1, n is 4, m is 3, k is 2, the included A 1 is 4, A 2 is 3, A 3 is 2, at this time, the respective A 1 is independent of each other, each A 2 is independent of each other, and each A 3 is also independent of each other.

並且，在上述A1、A2及A3中至少一個不是氫。若使上述A1、A2及A3均為氫的固化劑與環氧(epoxy)樹脂固化的情況下，根據環氧基和活性氫的反應產生極性的高羥基，因此可存在最終固化物的吸濕性變高、介電常數(Dk)、介電損耗(Df)等電特性降低的問題。 Further, in the above-mentioned A 1, A 2 and A 3 are not hydrogen. When the curing agent in which all of A 1 , A 2 and A 3 are hydrogen is cured with an epoxy resin, a polar high hydroxyl group is generated by a reaction between an epoxy group and an active hydrogen, so that a final cured product may exist. The problem is that the hygroscopicity becomes high, and the electrical characteristics such as the dielectric constant (Dk) and the dielectric loss (Df) decrease.

其次，上述n、m及k分別獨立地為0~8的有理數，在固化物的玻璃轉移溫度、耐熱性、電特性方面上，更佳地，n、m及k可分別獨立地為1.5~6的有理數。在選自由n、m及k所組成的群組中的一種以上大於8的情況下，當與環氧進行固化時，導致固化物的表面不均勻，並有可能在黏結力上產生問題，從而存在不適合用作層疊材料或密封材料的問題。 Secondly, the above-mentioned n, m, and k are each independently a rational number of 0 to 8. In terms of glass transition temperature, heat resistance, and electrical characteristics of the cured product, more preferably, n, m, and k can be independently 1.5 to 1.5. Rational number of 6. In the case where one or more members selected from the group consisting of n, m, and k is greater than 8, when cured with epoxy, the surface of the cured product is uneven, and there may be a problem in the adhesive force. There is a problem that it is not suitable for use as a laminated material or a sealing material.

並且，上述l為0.1~12的有理數。在上述l小於0.1的情況下，當與環氧進行固化時，存在固化物的耐熱性降低、玻璃轉移溫度降低的問題，固化物的耐熱性降低、玻璃轉移溫度降低的問題，還存在降低介電常數、介電損耗因數等難以實現所目的的物性的問題。並且，在l大於12的情況下，存在形成凝膠化物的可能性，當與環氧一同進行固化時，導致固化物的表面不均勻，並在黏結力上產生問題，從而存在不適合用作層疊材料及密封材料的問題。 In addition, the above-mentioned l is a rational number of 0.1-12. In the case where l is less than 0.1, when curing with epoxy, there is a problem that the heat resistance of the cured product is lowered and the glass transition temperature is lowered. The heat resistance of the cured product is lowered and the glass transition temperature is lowered. Problems such as permittivity and dielectric loss factor that make it difficult to achieve the desired physical properties. In addition, when l is greater than 12, there is a possibility of forming a gel. When curing with epoxy, the surface of the cured product is uneven and causes problems in adhesion, which is not suitable for lamination. Problems with materials and sealing materials.

並且，在上述化學式X中，A4為氫原子、、 此時，上述o為0~8的有理數，p為0.1~8的有理數。更佳地，在固化物的玻璃轉移溫度、耐熱性、電特性方面上，o、p可分別獨立地為2~6的有理數。在o和/或p大於8的情況下，當與環氧進行固化時，導致固化物的表面不均勻，並有可能在黏結力上產生問題，因此存在不適合用作層疊材料或密封材料的問題。 In the above chemical formula X, A 4 is a hydrogen atom, , In this case, o is a rational number from 0 to 8, and p is a rational number from 0.1 to 8. More preferably, in terms of the glass transition temperature, heat resistance, and electrical characteristics of the cured product, o and p may be independently a rational number of 2 to 6, respectively. In the case where o and / or p is greater than 8, when curing with epoxy, the surface of the cured product is uneven, and there may be problems in adhesion, so there is a problem that it is not suitable for use as a laminate or sealing material. .

在本發明的環氧樹脂用固化劑中，上述R1、R2、R3、R4及R5作為分別獨立地取代或者非取代的芳基，上述芳基可包含選自由苯基、聯苯基、萘基、蒽基、菲基、芘基、苝基、、甲酚基及芴基所組成的群組中的一種化 合物，更佳地，上述R1、R2、R3、R4及R5可分別獨立地為選自由非取代的苯基、萘基及聯苯基所組成的群組中的一種。在上述R1、R2、R3、R4及R5可分別獨立地為選自由非取代的苯基、萘基及聯苯基所組成的群組中的一種的情況下，在由上述化學式1表示的共聚物的物性中，與由包含R6為蒽基、菲基、芘基、苝基、及芴基的單體的共聚物固化而成的固化物相比，介電常數、介電損耗等顯著降低，從而可實現基於顯著提高電絕緣特性的半導體的高密度集成，從而可廣泛地利用於電氣電子用密封材料、層疊材料等。 In the curing agent for epoxy resins of the present invention, the R 1 , R 2 , R 3 , R 4, and R 5 are independently substituted or unsubstituted aryl groups, and the aryl group may include a group selected from phenyl, Phenyl, naphthyl, anthracenyl, phenanthryl, fluorenyl, fluorenyl, A compound in the group consisting of 1, cresol group and fluorenyl group, more preferably, the above R 1 , R 2 , R 3 , R 4 and R 5 may be each independently selected from unsubstituted phenyl and naphthalene One of the group consisting of phenyl and biphenyl. In the case where R 1 , R 2 , R 3 , R 4, and R 5 are each independently one selected from the group consisting of unsubstituted phenyl, naphthyl, and biphenyl, Among the physical properties of the copolymer represented by Chemical Formula 1, R 6 is anthracenyl, phenanthryl, fluorenyl, fluorenyl, Compared with cured products obtained by curing copolymers of fluorene-based monomers, the dielectric constant and dielectric loss are significantly reduced, enabling high-density integration based on semiconductors with significantly improved electrical insulation characteristics to be widely used. For electrical and electronic sealing materials, laminated materials, etc.

另一方面，由上述化學式1表示的化合物的重均分子量(分子量)只能為1000~13000，這是因為本發明的由化學式1表示的化合物可具有寬範圍的分子量。由此，並不是被稱為由化學式1表示的化合物，就可表達本發明目的的效果。 On the other hand, the weight average molecular weight (molecular weight) of the compound represented by the above Chemical Formula 1 can only be 1000 to 13,000, because the compound represented by the Chemical Formula 1 of the present invention can have a wide range of molecular weights. Therefore, the effect of the object of the present invention can be expressed without being called a compound represented by Chemical Formula 1.

對由本發明的化學式1表示的化合物可具有寬範圍的分子量分佈的理由進行具體觀察，是因為在共聚物中包含在分子量中可隨機確定的聚合物(由化學式X表示的A1、A2及A3)接枝的重複單位。即，在A1為上述化學式X的情況下，在由化學式X表示的聚合物內還包含可由化學式X表示之選自由A1、A2及A3所組成的群組中的一種以上。這是在以下進行說明的由化學式3表示的單體和由化學式2表示的單體進行共聚合中，可根據聚合物的聚合度由化學式2表示的聚合物的分子量可以非常隨機，除此之外，由化學式2表示的聚合物的聚合度越大，可與由化學式3表示的單體進行反應的反應位點，即，包含於由化學式2表示的聚合物的羥基增加，按各個羥基再次與化學式3的單體隨機進行反應來實現聚合，因此分子量非常隨機同時可具有非常寬的分子量分佈。 The reason why the compound represented by Chemical Formula 1 of the present invention can have a wide range of molecular weight distribution is specifically observed because the copolymer includes polymers whose molecular weight can be randomly determined (A 1 , A 2, and A 3 ) Grafted repeating unit. That is, when A 1 is the above-mentioned chemical formula X, the polymer represented by the chemical formula X further includes one or more selected from the group consisting of A 1 , A 2, and A 3 , which can be represented by the chemical formula X. This is described below in the copolymerization of the monomer represented by Chemical Formula 3 and the monomer represented by Chemical Formula 2. The molecular weight of the polymer represented by Chemical Formula 2 can be very random according to the degree of polymerization of the polymer, except that In addition, the greater the degree of polymerization of the polymer represented by Chemical Formula 2, the more reaction sites that can react with the monomer represented by Chemical Formula 3, that is, the hydroxyl groups contained in the polymer represented by Chemical Formula 2 increase, and again for each hydroxyl group. Polymerization is performed by randomly reacting with the monomer of Chemical Formula 3, so the molecular weight is very random and it can have a very wide molecular weight distribution.

對此進行整理，由本發明的化學式1表示的化合物可包含非常隨機地確定分子量的A1(A1a、A1b、A1c、......)和/或、A2(A2a、A2b、A2c、......”)和/或A3(A3a、A3b、A3c、......)，隨著還在上述A1a(和/或A1b、A1c、......)和/或、A2a(和/或、A2b、A2c、......)和/或A3a(和/或A3b、A3c、......)中以層層接枝的方式可包含非常隨機地確定分子量的A1a(A1a、A1b、A1c、......)、A2a(A2a、A2b、A2c、......)及A3a(A3a、A3b、A3c、......)化學式1的化合物可具有寬範圍的分子量分佈。但是，即使是簡單地由上述化學式1表示的化合物，也並 不是可表達本發明所目的的物性，具有上述化學式1的結構式的同時需要滿足特定的分子量，才能表達所目的的物性。 To sort this out, the compound represented by Chemical Formula 1 of the present invention may include A 1 (A 1a , A 1b , A 1c , ...) and / or A 2 (A 2a , A 2b , A 2c , ... ") and / or A 3 (A 3a , A 3b , A 3c , ...), along with A 1a (and / or A 1b) , A 1c , ...) and / or, A 2a (and / or, A 2b , A 2c , ...) and / or A 3a (and / or A 3b , A 3c , The layer-by-layer grafting method can include A 1a (A 1a , A 1b , A 1c , ...), A 2a (A 2a , A 2b , A2c , ...) and A3a ( A3a , A3b , A3c , ...) The compounds of Chemical Formula 1 may have a wide range of molecular weight distributions. However, even if it is simply The compound represented by the above Chemical Formula 1 does not express the desired physical properties of the present invention, and has the structural formula of the aforementioned Chemical Formula 1 and needs to satisfy a specific molecular weight in order to express the desired physical properties.

由此，本發明的由上述化學式1表示的化合物的重均分子量滿足1000~13000，從而通過包含本發明的環氧樹脂用固化劑來固化而成的固化物可同時具有優秀的耐熱性、高機械強度、優秀的內吸濕性及顯著提高的電特性。在由化學式1表示的化合物的重均分子量(分子量)小於1000的情況下，當與環氧進行固化時，存在降低固化物的耐熱性，並且玻璃轉移溫度的問題，存在介電常數、介電損耗因數的電特性也降低的問題，在重均分子量大於13000的情況下，存在形成凝膠化物的可能性，當與環氧一同進行固化時，導致剝離強度降低，並且固化物的表面不均勻，來在黏結力上產生問題，因此可存在不適合用作層疊材料及密封材料的問題。根據本發明的一較佳實施例，為了實現更提高得物性，由化學式1表示的化合物的重均分子量可以為5000~9000。 Therefore, the weight average molecular weight of the compound represented by the above-mentioned chemical formula 1 of the present invention satisfies 1,000 to 13,000, and thus a cured product cured by containing the curing agent for an epoxy resin of the present invention can have both excellent heat resistance and high heat resistance. Mechanical strength, excellent hygroscopicity and significantly improved electrical characteristics. In the case where the weight average molecular weight (molecular weight) of the compound represented by Chemical Formula 1 is less than 1,000, when curing with epoxy, there is a problem that the heat resistance of the cured product is lowered and the glass transition temperature is lowered, and there is a dielectric constant and a dielectric The electrical characteristics of the loss factor are also reduced. When the weight average molecular weight is greater than 13,000, there is a possibility of forming a gel. When curing with epoxy, the peel strength is reduced, and the surface of the cured product is uneven. In order to cause a problem in adhesion, there may be a problem that it is not suitable for use as a laminated material and a sealing material. According to a preferred embodiment of the present invention, in order to achieve more improved physical properties, the weight average molecular weight of the compound represented by Chemical Formula 1 may be 5,000 to 9,000.

並且，本發明作為對由以下化學式2、化學式3及化學式4表示的單體進行共聚合的共聚物，提供包含重均分子量(分子量)為1000~13000的共聚物的環氧樹脂用固化劑。 In addition, the present invention provides a curing agent for an epoxy resin as a copolymer that copolymerizes monomers represented by the following Chemical Formula 2, Chemical Formula 3, and Chemical Formula 4 including a copolymer having a weight average molecular weight (molecular weight) of 1,000 to 13,000.

在上述化學式2中，a為0~8的有理數，若上述R7及R8均為氫原子或R7及R8中的一個為氫原子，則另一個為甲基。 In the above Chemical Formula 2, a is a rational number of 0 to 8; if R 7 and R 8 are both hydrogen atoms or one of R 7 and R 8 is a hydrogen atom, the other is a methyl group.

在上述化學式3中，B為或或，X1為鹵素原 子。 In the above Chemical Formula 3, B is or or X 1 is a halogen atom.

在上述化學式4中，X2為鹵素原子，R6為碳數為5~24個的芳基或碳數為4個以下的烷基。 In the above Chemical Formula 4, X 2 is a halogen atom, and R 6 is an aryl group having 5 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms.

首先，對上述化學式2進行說明。由上述化學式2表示的單體與由上述化學式3表示的單體形成共聚合，a為0~8的有理數，考慮固化物的耐熱性、玻璃轉移溫度，較佳地，平均值可以不是0。在a的平均值大於8的情況下，當與環氧進行固化時，導致固化物的表面不均勻來在黏結力上產生問題，因此存在不適合用作層疊材料及密封材料的問題。 First, the above-mentioned chemical formula 2 will be described. The monomer represented by the above Chemical Formula 2 and the monomer represented by the above Chemical Formula 3 form a copolymer, and a is a rational number of 0 to 8. Considering the heat resistance of the cured product and the glass transition temperature, the average value may not be zero. When the average value of a is larger than 8, curing of the epoxy resin causes unevenness in the surface of the cured product, which causes problems in adhesion. Therefore, it is not suitable for use as a laminated material and a sealing material.

根據本發明，由上述化學式2及化學式3表示的單體分別能夠以1：0.1~1.5的莫耳比共聚合，較佳地是1：0.5~1.2。使用本發明的固化劑的固化物滿足上述範圍，從而提高基於高玻璃轉移溫度的耐熱性，在介電常數、介電損耗因數等電特性上優秀，並且剝離強度變高，從而存在機械物性上得到提高得優點。 According to the present invention, the monomers represented by the above Chemical Formula 2 and Chemical Formula 3 can be copolymerized at a molar ratio of 1: 0.1 to 1.5, and preferably 1: 0.5 to 1.2. The cured product using the curing agent of the present invention satisfies the above-mentioned range, thereby improving the heat resistance based on a high glass transition temperature, being excellent in electrical characteristics such as a dielectric constant, a dielectric loss factor, and having a high peel strength, so that there are mechanical properties. The advantages are improved.

在由上述化學式2及化學式3表示的單體以小於1：0.1的莫耳比共聚合的情況下，可存在形成凝膠化物的可能性，當與環氧一同進行固化時，導致剝離強度降低，並且固化物的表面不均勻，來在黏結力上產生問題，因此可存在不適合用作層疊材料及密封材料的問題。 When the monomers represented by the above Chemical Formulas 2 and 3 are copolymerized at a molar ratio of less than 1: 0.1, there is a possibility that a gel may be formed, and when cured together with epoxy, the peel strength is reduced. In addition, the surface of the cured product is not uniform, which causes problems in adhesion. Therefore, it may be unsuitable for use as a laminated material and a sealing material.

接著，對上述化學式3進行說明。在由上述化學式3表示的單體中，X1為鹵素原子可包含選自由氟原子、氯原子、溴原子及碘原子所組成的群組中的一種，較佳地，可以為氯原子。 Next, the above-mentioned chemical formula 3 will be described. In the monomer represented by the above Chemical Formula 3, X1 is a halogen atom and may include one selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and may preferably be a chlorine atom.

由上述化學式3表示的單體作為與由上述化學式2及化學式4表示的單體形成共聚合的單體，更佳地，由上述化學式3表示的單體可以為由以下化學式3-1表示的單體。 The monomer represented by the above Chemical Formula 3 is a monomer that forms a copolymer with the monomers represented by the aforementioned Chemical Formulas 2 and 4, and more preferably, the monomer represented by the aforementioned Chemical Formula 3 may be represented by the following Chemical Formula 3-1 monomer.

上述化學式3-1中X1為鹵素原子。 In the above Chemical Formula 3-1, X 1 is a halogen atom.

在上述化學式3-1中，與苯環相結合的兩個官能團(-COX1)具有間位(meta)配向，從而與兩個上述官能團為鄰位(ortho)或對位(para)配向的情況相比，可同時實現提高的耐熱性和優秀的電特性，並且可實現內吸濕性及低熱膨脹系數值。具體地，在基於以下實施例的固化物的情況下，可確認玻璃轉移溫度高，並且介電常數、介電損耗因數吸濕率、熱膨脹係數(CTE)(a1，ppm)、熱膨脹係數(a2，ppm)值降低。 In the above Chemical Formula 3-1, the two functional groups (-COX 1 ) combined with the benzene ring have a meta orientation, so that the two functional groups are ortho or para aligned with the two functional groups. Compared to the case, it is possible to achieve both improved heat resistance and excellent electrical characteristics, and it is possible to achieve internal hygroscopicity and a low coefficient of thermal expansion. Specifically, in the case of the cured product based on the following examples, it can be confirmed that the glass transition temperature is high, and the dielectric constant, the dielectric loss factor, the moisture absorption rate, the coefficient of thermal expansion (CTE) (a1, ppm), and the coefficient of thermal expansion (a2) (Ppm) value decreases.

並且，較佳地，在由上述化學式3表示的單體中僅包含由化學式3-1表示的單體，包含一部分由化學式3-1表示的單體，在鄰位或對位元配向的情況的單體，作為剩餘的包含的共聚物存在玻璃轉移溫度低，並且介電常數和介電損耗高的問題。 In addition, it is preferable that the monomer represented by the chemical formula 3 includes only the monomer represented by the chemical formula 3-1, and includes a part of the monomer represented by the chemical formula 3-1, and is aligned in the ortho or para position. The remaining monomers have the problems of low glass transition temperature and high dielectric constant and dielectric loss.

並且，在上述化學式3-1的情況下，包含作為鹵素原子的X1。在上述X1為鹵素原子的情況下，在低溫下(例如，60℃以下)，還通過催化劑，來容易地利用HX氣體去除上述鹵素原子，並且可顯著地降低反應時間，從而隨著反應在低溫條件下，短時間內容易地進行，步驟進行的危險性減少，並且可提高生產率。 Further, in the case of the aforementioned Chemical Formula 3-1, X 1 as a halogen atom is included. In the case where X 1 is a halogen atom, at a low temperature (for example, 60 ° C. or lower), the halogen atom can be easily removed by HX gas through a catalyst, and the reaction time can be significantly reduced. Under low temperature conditions, it is easy to perform in a short time, the risk of performing the steps is reduced, and productivity can be improved.

接著，對上述化學式4進行說明。由上述化學式4表示的單體為在由上述化學式2及化學式3表示的單體的共聚合反應中作為末端螯合劑包含的單體。 Next, the above-mentioned chemical formula 4 will be described. The monomer represented by the aforementioned Chemical Formula 4 is a monomer contained as a terminal chelating agent in the copolymerization reaction of the monomers represented by the aforementioned Chemical Formulas 2 and 3.

根據由上述化學式4表示的單體的X2及R6的種類，由包含其共聚合而成的共聚物固化的固化物的物性可不同。 The physical properties of the cured product cured by the copolymer including the copolymer may vary depending on the types of X 2 and R 6 of the monomer represented by the aforementioned Chemical Formula 4.

根據本發明，上述X2包含選自氟原子、氯原子、溴原子及碘原子所組成的群組中的一種，上述R6作為取代或非取代的芳基或取代或非取代的C1~C4的烷基，上述芳基可包含選自由苯基、聯苯基、萘基、蒽基、菲基、芘基、苝基、、甲酚基及芴基所組成的群組中的一種。更佳地，上述R6可以為非取代的苯基、聯苯基或萘基。 According to the present invention, the X 2 contains one selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and the R 6 is a substituted or unsubstituted aryl group or a substituted or unsubstituted C 1 ~ C 4 alkyl, the aryl may include a group selected from phenyl, biphenyl, naphthyl, anthracenyl, phenanthryl, fluorenyl, fluorenyl, One of the group consisting of 2, cresol and fluorenyl. More preferably, the aforementioned R 6 may be an unsubstituted phenyl group, a biphenyl group, or a naphthyl group.

在上述R6為非取代的苯基、聯苯基或萘基的情況下，在由上述化學式1表示的共聚物的物性中，與由在R6中包含選自由蒽基、菲基、芘基、苝基、、甲酚基及芴基所組成的群組中的一種單體的共聚物固化而成的固化物相比，介電常數、介電損耗數值降低，從而可取得電特性顯著提高的固化物。 In the case where R 6 is an unsubstituted phenyl, biphenyl, or naphthyl group, the physical properties of the copolymer represented by the above Chemical Formula 1 are different from those in which R 6 is selected from anthracenyl, phenanthryl, and fluorene. Base, base, Compared with a cured product in which a copolymer of one monomer in the group consisting of cresol group and fluorenyl group is cured, the dielectric constant and the dielectric loss value are reduced, so that a cured product having significantly improved electrical characteristics can be obtained.

根據本發明的一較佳實施例，可以是以1：0.1~1.5：0.1~3的莫耳比對由上述化學式2、化學式3及化學式4表示的單體進行共聚合的，較佳地是1：0.5~1.2：1.6~2.8。 According to a preferred embodiment of the present invention, the monomers represented by the above Chemical Formula 2, Chemical Formula 3, and Chemical Formula 4 may be copolymerized with a molar ratio of 1: 0.1 to 1.5: 0.1 to 3, preferably 1: 0.5 ~ 1.2: 1.6 ~ 2.8.

分別能夠以1：0.1~1.5：0.1~3的莫耳比對由上述化學式2、化學式3及化學式4表示的單體進行共聚合，通過滿足上述範圍，來提高耐熱性，並且在介電常數、介電損耗因數等電特性中優秀，使剝離強度便大來存在在機械物性中得到提高的優點。 The monomers represented by the above Chemical Formula 2, Chemical Formula 3, and Chemical Formula 4 can be copolymerized at a Mohr ratio of 1: 0.1 to 1.5: 0.1 to 3, respectively. By satisfying the above range, heat resistance can be improved, and the dielectric constant can be improved. It is excellent in electrical characteristics such as dielectric loss factor, and it has the advantage that the peel strength is increased to improve mechanical properties.

在由化學式2及化學式3表示的單體以小於1：0.1的莫耳比共聚合的情況下，可存在固化物的玻璃轉移溫度低，介電常數、介電損耗因數等電特性降低的問題，在以大於1：1.5的莫耳比進行共聚合的情況下，存在形成凝膠化物的可能性，當與環氧進行固化時，導致剝離強度降低，並且固化物的表面不均勻，來在黏結力上產生問題，因此可存在不適合用作層疊材料及密封材料的問題。 When the monomers represented by Chemical Formula 2 and Chemical Formula 3 are copolymerized at a molar ratio of less than 1: 0.1, there may be problems that the glass transition temperature of the cured product is low, and the electrical characteristics such as the dielectric constant and the dielectric loss factor are reduced. In the case of copolymerization at a molar ratio of more than 1: 1.5, there is a possibility of forming a gel. When curing with epoxy, the peel strength is reduced, and the surface of the cured product is uneven. Since a problem arises in the adhesive force, there is a problem that it is not suitable for use as a laminated material and a sealing material.

接著，本發明提供環氧樹脂用固化劑的製備方法，上述環氧樹脂用固化劑的製備方法包括：步驟1，以1：0.1~1.5：0.1~3的莫耳比向反應槽導入由以下化學式2、化學式3及化學式4表示的單體；以及步驟2，通過使在上述步驟1中導入的單體進行反應，來製備由以下化學式1表示的共聚物。 Next, the present invention provides a method for preparing a curing agent for epoxy resin. The method for preparing the above-mentioned curing agent for epoxy resin includes the following steps: Step 1. Introduce a molar ratio of 1: 0.1 to 1.5: 0.1 to 3 into the reaction tank from the following: Monomers represented by Chemical Formula 2, Chemical Formula 3, and Chemical Formula 4; and Step 2, a copolymer represented by the following Chemical Formula 1 is prepared by reacting the monomer introduced in Step 1 described above.

在上述化學式2中，a為0~8的有理數，若上述R7及R8均為氫原子或R7及R8中的一個為氫原子，則另一個為甲基。 In the above Chemical Formula 2, a is a rational number of 0 to 8; if R 7 and R 8 are both hydrogen atoms or one of R 7 and R 8 is a hydrogen atom, the other is a methyl group.

在上述化學式3中，B為或或，X1為鹵素原 子。 In the above Chemical Formula 3, B is or or X 1 is a halogen atom.

在上述化學式4中，X2為鹵素原子，R6為碳數為6~24個的芳基或碳數為4個以下的烷基。 In the above Chemical Formula 4, X 2 is a halogen atom, and R 6 is an aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms.

在上述化學式1中，R1為碳數為6~24個的芳基或碳數為4個以下的烷基，B 為或或，A1、A2及A3分別獨立地為氫原子、 或，上述A1、 A2及A3中至少一個不是氫原子，n、m及k分別獨立地為0~8的有理數，l為0.1~ 12的有理數，A4為氫原子、、 上述R2為碳數為6~24個的芳基或碳數為4個以下的烷基，上述R3為碳數為6~24個的芳基或碳數為4個以下的烷基，i為0~8的有理數，j為0.1~8的有理數，上述R4為碳數為6~24個的芳基或碳數為4個以下的烷基，o為0~8的有理數，p為0.1~8的有理數，上述R5為碳數為6~24個的芳基或碳數為4個以下的烷基，若上述R7及R8均為氫原子或R7及R8中的一個為氫原子，則另一個為甲基。 In the above Chemical Formula 1, R 1 is an aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms, and B is or or , A 1 , A 2 and A 3 are each independently a hydrogen atom, or , At least one of the above A 1 , A 2 and A 3 is not a hydrogen atom, n, m and k are each independently a rational number from 0 to 8, l is a rational number from 0.1 to 12, and A 4 is a hydrogen atom, , The R 2 is an aryl group having 6 to 24 carbons or an alkyl group having 4 or less carbons, the R 3 is an aryl group having 6 to 24 carbons or an alkyl group having 4 or less carbons, i is a rational number from 0 to 8, j is a rational number from 0.1 to 8, R 4 is an aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms, o is a rational number from 0 to 8, p It is a rational number of 0.1 to 8. The above R 5 is an aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms. If the above R 7 and R 8 are both hydrogen atoms or R 7 and R 8 One is a hydrogen atom, and the other is a methyl group.

以下，按步驟對本發明的製備方法進行詳細說明。 Hereinafter, the preparation method of the present invention will be described in detail according to the steps.

在本發明的環氧樹脂用固化劑的製備方法中，在上述步驟1中，向附著有氮投入管、溫度計、環流冷卻器的反應槽投入有機溶劑後，以1：0.1~1.5：0.1~3的莫耳比導入由上述化學式2、化學式3及化學式4表示的單體，更較佳地，以1：0.5~1.2：1.6~2.8的莫耳比導入並溶解，從而在後面的步驟中，可製備由上述化學式2、化學式3及化學式4表示的單體反復共聚合而成的結構的化學式1。 In the method for preparing a curing agent for epoxy resins of the present invention, in step 1 above, an organic solvent is charged into a reaction tank to which a nitrogen input pipe, a thermometer, and a circulation cooler are attached, and the ratio is 1: 0.1 to 1.5: 0.1 to A monomer represented by the above Chemical Formula 2, Chemical Formula 3, and Chemical Formula 4 is introduced at 3, and more preferably, it is introduced and dissolved at a molar ratio of 1: 0.5 to 1.2: 1.6 to 2.8, so that it is dissolved in a later step. The chemical formula 1 having a structure in which the monomers represented by the chemical formula 2, chemical formula 3, and chemical formula 4 are repeatedly copolymerized can be prepared.

在由化學式2及化學式3表示的單體以小於1：0.1的莫耳比共聚合的情況下，可存在固化物的玻璃轉移溫度低、介電常數、介電損耗因數等電特性降低的問題，在以大於1：1.5的莫耳比進行共聚合的情況下，存在形成凝膠化物的可能性，當與環氧進行固化時，導致固化物的剝離強度降低，固化物的表面不均勻，來在黏結力上產生問題，從而可存在不適合用作層疊材料及密封材料的問題。 When the monomers represented by Chemical Formula 2 and Chemical Formula 3 are copolymerized at a molar ratio of less than 1: 0.1, there may be problems that the glass transition temperature of the cured product is low, and the electrical characteristics such as dielectric constant and dielectric loss factor are reduced. In the case of copolymerization at a molar ratio of more than 1: 1.5, there is a possibility of forming a gel. When curing with epoxy, the peeling strength of the cured product is reduced, and the surface of the cured product is uneven. In order to cause a problem in adhesion, there may be a problem that it is not suitable for use as a laminated material and a sealing material.

此時，在上述有機溶劑為製備環氧樹脂用固化劑時包含的有機溶劑的情況下，可無限制地使用，作為對此的非限制性例，可獨立或並用兩種以上使用選自由甲苯、甲基乙基酮及甲基異丁基酮所組成的群組中的一種以上等的有機溶劑。 At this time, when the above-mentioned organic solvent is an organic solvent contained in the preparation of the curing agent for epoxy resin, it can be used without limitation. As a non-limiting example, two or more kinds can be used independently or in combination. Organic solvents including one or more of the group consisting of methyl ethyl ketone and methyl isobutyl ketone.

在本發明的環氧樹脂用固化劑的製備方法中，在上述步驟2中，在20~40℃且氮氛下，完全溶解在上述步驟1中導入的單體，並且將催化劑均等地滴入1~3小時後，進行1~3小時的熟成步驟來可製備由上述化學式1表示的共聚物。此時在滴入及熟成步驟中存在發熱現象，因此需要在50℃以下的反應溫度下進行。 In the method for preparing a curing agent for an epoxy resin of the present invention, in the above step 2, the monomer introduced in the above step 1 is completely dissolved at 20 to 40 ° C. under a nitrogen atmosphere, and the catalyst is dropped uniformly. After 1 to 3 hours, a maturation step of 1 to 3 hours is performed to prepare a copolymer represented by the above Chemical Formula 1. At this time, heat generation occurs during the dropping and aging steps, and therefore it is necessary to perform the reaction at a reaction temperature of 50 ° C or lower.

上述催化劑起到在反應的催化劑及酯過程中產生的HCl氣體的作用，可使用在通常的固化劑的共聚合步驟中可使用的催化劑及酸捕集劑，較佳地，可以為選自三乙胺(triethylamine)、三甲胺(trimethylamine)、三丙胺(tripropylamine)、吡啶(pyridine)及N-甲基呱啶(N-methyl piperidine)所組成的群組中的一種以上，更佳地，使用三乙胺。作為上述催化劑可獨立或和一種以上的催化劑並用而使用。 The above-mentioned catalyst functions as a catalyst for the reaction and an HCl gas generated in the ester process. A catalyst and an acid trapping agent that can be used in the copolymerization step of a general curing agent can be used. One or more of the group consisting of triethylamine, trimethylamine, tripropylamine, pyridine, and N-methyl piperidine, more preferably, use Triethylamine. These catalysts can be used alone or in combination with one or more catalysts.

在本發明的環氧樹脂用固化劑的製備方法中，還包括如下步驟：在使上述單體進行反應之後，向上述反應槽導入水，來去除作為反應副產物生成的鹽之後，將對所製備的環氧樹脂用固化劑進行分離的過程，較佳地，進行一次以上的上述步驟。 The method for preparing a curing agent for epoxy resins of the present invention further includes the steps of: after reacting the monomers, introducing water into the reaction tank to remove salts generated as reaction by-products, and then The separation process of the prepared epoxy resin curing agent is preferably performed the above steps more than once.

通過上述步驟2的反應，來析出共聚物和作為附加物生成的鹽，為了去除作為附加物生成的鹽，可通過投入水等溶劑來進行脫鹽。在上述脫鹽步驟中，具體地，溶解作為附加反應生成的鹽之後，可進行分液來分離共聚合的化合物之後，在150~200℃的溫度下，對已分離的共聚合化合物進行真空脫氣。 The copolymer and the salt produced as an additive are precipitated by the reaction in Step 2 described above. In order to remove the salt produced as an additive, a solvent such as water can be added to carry out desalting. In the above desalting step, specifically, after dissolving the salt formed as an additional reaction, liquid separation can be performed to separate the copolymerized compound, and then the separated copolymerized compound is vacuum degassed at a temperature of 150 to 200 ° C. .

進而，本發明提供電氣電子用密封材料(Encapsulant)，其特徵在於，包含本發明的環氧樹脂用固化劑及環氧樹脂。 Furthermore, the present invention provides an encapsulant for electric and electronics, which comprises the curing agent for epoxy resin and epoxy resin of the present invention.

並且，本發明提供電氣電子用基板用層疊材料，其特徵在於，包含本發明的環氧樹脂用固化劑及環氧樹脂。 In addition, the present invention provides a laminated material for a substrate for electric and electronics, which comprises the curing agent for epoxy resin and epoxy resin according to the present invention.

並且，本發明提供環氧樹脂組合物，其特徵在於，包含本發明的環氧樹脂用固化劑及環氧樹脂。 The present invention also provides an epoxy resin composition comprising the curing agent for an epoxy resin of the present invention and an epoxy resin.

作為上述環氧樹脂，在不損傷本發明的效果的範圍下，可使用公知的環氧樹脂，作為對此的非限制性例，可獨立或並用兩種以上使用2價的苯酚類的環氧化物，如，雙酚A、雙酚F、雙酚S、雙酚芴、2,2’-聯苯酚、3、3’、5、5’-四甲基-4、4’-二羥基聯苯酚、間苯二酚、萘二醇類等；3價以上的苯酚類的環氧化物，如三-(4-羥基苯基)甲烷、1、1、2、2-四(4-羥基苯基)乙烷、酚醛、鄰甲酚醛等；二環戊二烯和苯酚類的共聚合樹脂的環氧化物、由苯酚類和二氯甲基聯苯等合成的聯苯芳烷基型苯酚樹脂的環氧化物、由萘酚類和對二甲苯二氯化物等合成的萘酚芳烷基樹脂累的環氧化物等。 As the above-mentioned epoxy resin, a known epoxy resin may be used within a range that does not impair the effects of the present invention. As a non-limiting example, two or more types of divalent phenol-based epoxy resins may be used independently or in combination. Compounds such as bisphenol A, bisphenol F, bisphenol S, bisphenol hydrazone, 2,2'-biphenol, 3, 3 ', 5, 5'-tetramethyl-4, 4'-dihydroxyl Phenol, resorcinol, naphthalene glycols, etc .; epoxides of phenols above 3, such as tri- (4-hydroxyphenyl) methane, 1, 1, 2, 2-tetrakis (4-hydroxybenzene) Group) ethane, phenolic, o-cresol, etc .; epoxides of copolymerized resins of dicyclopentadiene and phenols; biphenylaralkyl phenol resins synthesized from phenols and dichloromethylbiphenyl Epoxides, naphthol aralkyl resins synthesized from naphthols and p-xylene dichloride, etc.

只是，根據本發明的一較佳實施例，為了表達優秀的電特性、內吸濕性、提高的剝離強度、耐熱性，上述環氧樹脂可包含選自由鄰苯基苯酚酚醛環氧型(Ortho Phenylphenol Novolac Epoxy)、二環戊二烯和苯酚類的共聚合樹脂的環氧化物型、由二氯甲基聯苯等合成的聯苯基芳烷基型苯酚樹脂的氧化物型所組成的群組中的一種以上，此時固化的密封材料或層疊材料可以在1GHz的頻率下，介電常數(Dk)為3.0以下，介電損耗為0.01以下，這種提高的電絕緣特性具有在積體電路基板、印製電路板等中可實現通過半導體的高集成化的器件的高速化的優點。 However, according to a preferred embodiment of the present invention, in order to express excellent electrical characteristics, internal hygroscopicity, improved peel strength, and heat resistance, the epoxy resin may include a material selected from the group consisting of o-phenylphenol novolac epoxy (Ortho Phenylphenol Novolac Epoxy), epoxy resin type of copolymer resin of dicyclopentadiene and phenols, and oxide type of biphenylaralkyl phenol resin synthesized from dichloromethyl biphenyl More than one of the group, the sealing material or laminated material cured at this time can have a dielectric constant (Dk) of 3.0 or less and a dielectric loss of 0.01 or less at a frequency of 1 GHz. In circuit boards, printed circuit boards, etc., it is possible to realize the advantage of high speed of a device that is highly integrated through semiconductors.

並且，為了提高固化物的物性，除了環氧樹脂及本發明的固化劑之外，還可配合無機填充材料。在配合無機填充材料的情況下，可提高內吸濕性等的物性，在包含無機填充材料的情況下，可作為密封用適合。作為上述無機填充材料可無限制地使用通常的電氣電子用密封材料或使用於電氣電子基板用層疊材料的無機充電材料，作為對此的非限制性例，可使用二氧化矽、氧化鋁、鋯石、矽酸鈣、碳酸鈣、碳化矽、氮化矽、氮化硼、氧化鋯、鎂橄欖石、硬脂酸鹽、尖晶石、莫來石、二氧化鈦等，並且可以獨立或組合兩種以上，較佳地，將熔融二氧化矽作為主成分，作為其形態可例舉破碎狀、或球形狀。通常，作為二氧化矽，組合具有幾種粒子直徑分佈的二氧化矽來使用。較佳地，可進行組合的二氧化矽的平均粒子直徑的範圍為0.5~100μmm。較佳地，在配合無機填充材料的情況下，含有率為83重量百分比以上，更佳地，可以為83~90重量百分比。若小於83重量百分比，則導致有機成分的含有率變高並有可能為未充分地發揮耐濕性、低線膨脹性。 In addition, in order to improve the physical properties of the cured product, an inorganic filler may be blended in addition to the epoxy resin and the curing agent of the present invention. When an inorganic filler is blended, physical properties such as internal hygroscopicity can be improved, and when an inorganic filler is included, it can be suitably used for sealing. As the above-mentioned inorganic filler, an ordinary sealing material for electrics and electronics or an inorganic charging material for laminated materials for electric and electronic substrates can be used without limitation. As a non-limiting example, silicon dioxide, alumina, and zirconium can be used. Stone, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, forsterite, stearate, spinel, mullite, titanium dioxide, etc. In the above, it is preferable to use fused silicon dioxide as a main component, and the shape thereof may be, for example, a crushed shape or a spherical shape. Generally, as the silica, a combination of silicas having several particle diameter distributions is used. Preferably, the average particle diameter of the silicon dioxide that can be combined ranges from 0.5 to 100 μmm. In the case of blending an inorganic filler, the content rate is preferably 83% by weight or more, and more preferably, it may be 83 to 90% by weight. If it is less than 83% by weight, the content rate of the organic component will be high, and the moisture resistance and low linear expansion property may not be sufficiently exhibited.

並且，可根據需要適當的配合聚酯、聚醯胺、聚醯亞胺、聚醚、聚氨酯、石油樹脂、茚代內樹脂、苯氧基樹脂等的低聚物或高分子化合物，可配合顏料、阻燃劑、觸變性賦予劑、偶聯劑、流動性提高劑等的添加劑。 In addition, oligomers or polymer compounds such as polyester, polyamide, polyimide, polyether, polyurethane, petroleum resin, indene resin, and phenoxy resin can be appropriately blended as required, and pigments can be blended. , Flame retardant, thixotropy imparting agent, coupling agent, fluidity improving agent and other additives.

作為上述顏料有有機類或無機類的體質顏料、鱗片狀顏料等。作為觸變性賦予劑有矽酮類、蓖麻油類、脂肪醯胺蠟、氧化聚乙烯蠟、有機膨潤土類等。並且可根據需要還可配合胺類、咪唑類、有機膦類、路易士酸等的固化促進劑。作為固化促進劑的配合量，通常相對於100重量份的環氧樹脂，較佳地是0.2~5重量份。 Examples of the pigment include organic or inorganic extender pigments and scaly pigments. Examples of the thixotropic agent include silicones, castor oils, fatty ammonium waxes, oxidized polyethylene waxes, and organic bentonite. In addition, curing accelerators such as amines, imidazoles, organic phosphines, and Lewis acids can also be added as required. The compounding amount of the curing accelerator is usually preferably 0.2 to 5 parts by weight based on 100 parts by weight of the epoxy resin.

並且，可根據需要配合離型劑，如巴西棕櫚蠟、OP蠟等；偶聯劑，如γ-環氧丙氧基丙基三甲氧基矽烷等；著色劑，如碳黑等；阻燃劑，如三氧化銻等；低應力劑，如石油等，潤滑劑，如硬脂酸鈣等。 In addition, release agents such as carnauba wax, OP wax, etc .; coupling agents, such as γ-glycidoxypropyltrimethoxysilane, etc .; colorants, such as carbon black, etc .; , Such as antimony trioxide; low stress agents, such as petroleum, lubricants, such as calcium stearate.

可通過注型、壓縮成型、轉移成型等的成型方法，來對本發明的環氧樹脂用固化劑的密封材料組合物進行固化，從而取得基於本發明的優選一實施例的密封材料。較佳地，可通過轉移成型取得，通常生成固化物時的溫度可以為120~220℃。 The sealing material composition of the curing agent for epoxy resins of the present invention can be cured by molding methods such as injection molding, compression molding, and transfer molding to obtain a sealing material based on a preferred embodiment of the present invention. Preferably, it can be obtained by transfer molding. Generally, the temperature at which a cured product is generated may be 120 to 220 ° C.

以下，通過以下實施例更具體地說明本發明。此時，以下實施例只是為了便於理解而提出，並不是限制本發明的範圍。 Hereinafter, the present invention will be described more specifically with reference to the following examples. At this time, the following embodiments are only provided for easy understanding, and do not limit the scope of the present invention.

《實施例》"Example" 實施例1．環氧樹脂用固化劑的製備     Example 1. Preparation of curing agent for epoxy resin    

步驟1：向附著有氮投入管、溫度計、環流冷卻器的反應槽導入作為有機溶劑之1450g的甲苯、306g之由以下化學式2-1表示的單體(0.45莫耳)、81.2g之由以下化學式3-2表示的單體(0.4莫耳)、168.68g之由以下化學式4-1表示的單體(1.2莫耳)。 Step 1: Introduce 1,450 g of toluene as an organic solvent, 306 g of a monomer (0.45 mol) represented by the following chemical formula 2-1, and 81.2 g of the following into a reaction tank to which a nitrogen input pipe, a thermometer, and a circulation cooler are attached. A monomer (0.4 mole) represented by Chemical Formula 3-2 and 168.68 g of a monomer (1.2 mole) represented by the following Chemical Formula 4-1.

步驟2：在投入氮氣且30℃溫度條件下，完全溶解在上述步驟1中導入之由以下化學式2-1、化學式3-2及化學式4-1表示的單體，並且將202.38g的三乙胺(2莫耳)均等地滴入2小時之後，進行2小時的熟成步驟，當進行滴入及熟成步驟時，反應溫度不超過50℃。 Step 2: Under the conditions of introducing nitrogen and 30 ° C temperature, completely dissolve the monomers represented by the following Chemical Formula 2-1, Chemical Formula 3-2, and Chemical Formula 4-1 introduced in the above Step 1, and 202.38 g of triethyl After the amine (2 moles) was added dropwise for 2 hours, a ripening step was performed for 2 hours. When the dropping and ripening steps were performed, the reaction temperature did not exceed 50 ° C.

此時，為了去除作為附加物生成的鹽，通過投入350g的水來進行脫鹽之後，為了去除進行分離固化劑化合物並可剩下的鹽，以如上所述的方法再次進行脫鹽步驟之後，進行了分液。然後，在180℃溫度下，對分離的固化劑化合物進行真空脫氣，來獲取435g之重均分子量(分子量)為5450的褐色固態之如下表1的環氧樹脂用固化劑。 At this time, in order to remove the salt produced as an additive, 350 g of water was added to carry out desalting, and in order to remove the remaining salt that separated the curing agent compound, the desalting step was performed again as described above, and then Liquid separation. Then, the separated curing agent compound was vacuum degassed at a temperature of 180 ° C. to obtain 435 g of a brown solid having a weight average molecular weight (molecular weight) of 5450 as the curing agent for epoxy resin as shown in Table 1 below.

上述b為2。 The above b is 2.

實施例2．環氧樹脂用固化劑的製備     Example 2. Preparation of curing agent for epoxy resin    

與實施例1相同地進行而製備，分別投入306g(0.45莫耳)、97.45g(0.48莫耳)、146.19g(1.04莫耳)之由上述化學式2-1、化學式3-2及化學式4-1表示的單體，來獲取440g之重均分子量(分子量)為7180的褐色固態之如下表1的環氧樹脂用固化劑。 It was prepared in the same manner as in Example 1. 306 g (0.45 mol), 97.45 g (0.48 mol), and 146.19 g (1.04 mol) were respectively prepared from the above chemical formula 2-1, chemical formula 3-2, and chemical formula 4- The monomer represented by 1 was used to obtain 440 g of a brown solid solid having a weight average molecular weight (molecular weight) of 7180 as the curing agent for epoxy resins shown in Table 1 below.

實施例3．環氧樹脂用固化劑的製備     Example 3. Preparation of curing agent for epoxy resin    

與實施例1相同地進行而製備，分別投入306g(0.45莫耳)、107.6g(0.53莫耳)及132.13g(0.94莫耳)之由上述化學式2-1、化學式3-2及化學式4-1表示的單體，來獲取438g之重均分子量(分子量)為8737的褐色固態之如下表1的環氧樹脂用固化劑。 Preparation was carried out in the same manner as in Example 1. 306 g (0.45 mol), 107.6 g (0.53 mol), and 132.13 g (0.94 mol) were prepared from the above chemical formulas 2-1, 3-2, and 4- The monomer represented by 1 was used to obtain 438 g of a brown solid solid having a weight average molecular weight (molecular weight) of 8737 as the curing agent for epoxy resins shown in Table 1 below.

實施例4．環氧樹脂用固化劑的製備     Example 4. Preparation of curing agent for epoxy resin    

與實施例1相同地進行而製備，替代由上述化學式3-2表示的單體投入由以下化學式3-3表示的單體，來獲取428g之重均分子量(分子量)為5670的褐色固態之如下表1的環氧樹脂用固化劑。 The preparation was carried out in the same manner as in Example 1, and instead of the monomer represented by the above Chemical Formula 3-2, a monomer represented by the following Chemical Formula 3-3 was added to obtain 428 g of a brown solid having a weight average molecular weight (molecular weight) of 5670 as follows Table 1 is a curing agent for epoxy resin.

實施例5．環氧樹脂用固化劑的製備     Example 5. Preparation of curing agent for epoxy resin    

與實施例1相同地進行而製備，替代由上述化學式3-2表示的單體投入由以下化學式3-4表示的單體，來獲取420g之重均分子量(分子量)為5530的褐色固態之如下表1的環氧樹脂用固化劑。 It was prepared in the same manner as in Example 1. Instead of the monomer represented by the above Chemical Formula 3-2, a monomer represented by the following Chemical Formula 3-4 was added to obtain 420 g of a brown solid having a weight average molecular weight (molecular weight) of 5530 as follows Table 1 is a curing agent for epoxy resin.

實施例6．環氧樹脂用固化劑的製備     Example 6. Preparation of curing agent for epoxy resin    

與實施例1相同地進行而製備，替代81.2g(0.4莫耳)之由上述化學式3-2表示的單體投入40.6g(0.2莫耳)之由以下化學式3-2表示的單體及40.6g (0.2莫耳)之由以下化學式3-4表示的單體，來獲取410g之重均分子量(分子量)為5510的褐色固態之如下表1的環氧樹脂用固化劑。 It was prepared in the same manner as in Example 1. Instead of 81.2 g (0.4 mole) of the monomer represented by the above chemical formula 3-2, 40.6 g (0.2 mole) of the monomer represented by the following chemical formula 3-2 and 40.6 were prepared. g (0.2 mol) of the monomer represented by the following Chemical Formula 3-4 to obtain 410 g of a brown solid having a weight average molecular weight (molecular weight) of 5510 as a curing agent for an epoxy resin as shown in Table 1 below.

實施例7．環氧樹脂用固化劑的製備     Example 7. Preparation of curing agent for epoxy resin    

與實施例1相同地進行而製備，替代168.68g(1.2莫耳)之由上述化學式4-1表示的單體投入228.756g(1.2莫耳)之由以下化學式6表示的單體，來獲取455g之重均分子量(分子量)為7557的褐色固態之如下表1的環氧樹脂用固化劑。 It was prepared in the same manner as in Example 1. Instead of 168.68 g (1.2 mole) of the monomer represented by the above chemical formula 4-1, 228.756 g (1.2 mole) of the monomer represented by the following chemical formula 6 was added to obtain 455 g. The brown solid solid having a weight average molecular weight (molecular weight) of 7557 is a curing agent for epoxy resins as shown in Table 1 below.

實施例8．環氧樹脂用固化劑的製備     Example 8. Preparation of curing agent for epoxy resin    

與實施例1相同地進行而製備，替代168.68g(1.2莫耳)之由上述化學式4-1表示的單體投入228.756g(1.2莫耳)之由以下化學式6-1表示的單體，來獲取467g之重均分子量(分子量)為7323的褐色固態之如下表1的環氧樹脂用固化劑。 It was prepared in the same manner as in Example 1. Instead of 168.68 g (1.2 mol) of the monomer represented by the above chemical formula 4-1, 228.756 g (1.2 mol) of the monomer represented by the following chemical formula 6-1 was used. 467 g of a brown solid having a weight average molecular weight (molecular weight) of 7323 was obtained as the curing agent for epoxy resins in Table 1 below.

實施例9．環氧樹脂用固化劑的製備     Example 9. Preparation of curing agent for epoxy resin    

與實施例1相同地進行而製備，替代168.68g(1.2莫耳)之由上述化學式4-1表示的單體投入94.188g(1.2莫耳)之由以下化學式8表示的單體，來獲取360g之重均分子量(分子量)為4395的褐色固態之如下表1的環氧樹脂用固化劑。 It was prepared in the same manner as in Example 1. Instead of 168.68 g (1.2 mol) of the monomer represented by the above chemical formula 4-1, 94.188 g (1.2 mol) of the monomer represented by the following chemical formula 8 was added to obtain 360 g. The brown solid solid having a weight average molecular weight (molecular weight) of 4395 is a curing agent for epoxy resins as shown in Table 1 below.

實施例10．環氧樹脂用固化劑的製備     Example 10. Preparation of curing agent for epoxy resin    

與實施例1相同地進行而製備，替代168.68g(1.2莫耳)之由上述化學式4-1表示的單體投入111.024g(1.2莫耳)之由以下化學式8-1表示的單體，來獲取378g之重均分子量(分子量)為4620的褐色固態之如下表1的環氧樹脂用固化劑。 It was prepared in the same manner as in Example 1. Instead of 168.68 g (1.2 mol) of the monomer represented by the above chemical formula 4-1, 111.024 g (1.2 mol) of the monomer represented by the following chemical formula 8-1 was used. 378 g of a brown solid having a weight average molecular weight (molecular weight) of 4620 was obtained as the curing agent for epoxy resins in Table 1 below.

實施例11．環氧樹脂用固化劑的製備     Example 11. Preparation of curing agent for epoxy resin    

與實施例1相同地進行而製備，替代由上述化學式3-2表示的單體投入111.648g(0.4莫耳)之由以下化學式3-5表示的單體，來獲取451g之重均分子量(分子量)為7710的褐色固態之如下表1的環氧樹脂用固化劑。 The preparation was carried out in the same manner as in Example 1. Instead of the monomer represented by the above Chemical Formula 3-2, 111.648 g (0.4 mol) of the monomer represented by the following Chemical Formula 3-5 was added to obtain a weight average molecular weight (molecular weight) of 451 g. ) Is a brown solid of 7710 which is the curing agent for epoxy resins shown in Table 1 below.

比較例1．環氧樹脂用固化劑的製備     Comparative Example 1. Preparation of curing agent for epoxy resin    

與實施例1相同地進行而製備，分別投入306g(0.45莫耳)、4.06g(0.02莫耳)、275.517g(1.96莫耳)之由上述化學式2-1、化學式3-2及化學式4-1表示的單體，來獲取467g之重均分子量(分子量)為750的褐色固態之如下表1的環氧樹脂用固化劑。 It was prepared in the same manner as in Example 1, and 306 g (0.45 mole), 4.06 g (0.02 mole), and 275.517 g (1.96 mole) of the above-mentioned chemical formula 2-1, chemical formula 3-2, and chemical formula 4- The monomer represented by 1 was used to obtain 467 g of a brown solid solid having a weight average molecular weight (molecular weight) of 750 as the curing agent for epoxy resins shown in Table 1 below.

比較例2．環氧樹脂用固化劑的製備     Comparative Example 2. Preparation of curing agent for epoxy resin    

與實施例1相同地進行而製備，分別投入306g(0.45莫耳)、182.718g(0.9莫耳)及28.114g(0.2莫耳)之由上述化學式2-1、化學式3-2及化學式4-1表示的單體，來獲取402g之重均分子量(分子量)為15951的褐色固態之如下表1的環氧樹脂用固化劑。 It was prepared in the same manner as in Example 1. 306 g (0.45 mole), 182.718 g (0.9 mole), and 28.114 g (0.2 mole) were prepared from the above chemical formula 2-1, chemical formula 3-2, and chemical formula 4-. The monomer represented by 1 was used to obtain 402 g of a brown solid with a weight average molecular weight (molecular weight) of 15951 as the curing agent for epoxy resins in Table 1 below.

比較例3．環氧樹脂用固化劑的製備     Comparative Example 3. Preparation of curing agent for epoxy resin    

與實施例1相同地製備，替代由上述化學式2-1表示的單體投入206g(0.677莫耳)之由以下化學式9表示的單體，來獲取339g之重均分子量(分子量)為2057的褐色固態之如下表1的環氧樹脂用固化劑。 It was prepared in the same manner as in Example 1. Instead of the monomer represented by the above Chemical Formula 2-1, 206 g (0.677 mol) of the monomer represented by the following Chemical Formula 9 was added to obtain 339 g of a brown having a weight average molecular weight (molecular weight) of 2057. The solid state is as shown in Table 1 below.

，此時，上述n為1。 At this time, the above-mentioned n is 1.

比較例4．環氧樹脂用固化劑的製備     Comparative Example 4. Preparation of curing agent for epoxy resin    

與實施例1相同地製備，替代由上述化學式2-1表示的單體投入228.29g(1.0莫耳)之由以下化學式10表示的單體，來獲取347g之重均分子量(分子量)為1035的褐色固態之如下表1的環氧樹脂用固化劑。 It was prepared in the same manner as in Example 1. Instead of the monomer represented by the above Chemical Formula 2-1, 228.29 g (1.0 mole) of the monomer represented by the following Chemical Formula 10 was added to obtain 347 g of a weight average molecular weight (molecular weight) of 1035. The brown solid is the curing agent for epoxy resin shown in Table 1 below.

實驗例     Experimental example    

分別以當量比混合環氧樹脂(鄰苯基苯酚酚醛環氧樹脂(Ortho Phenylphenol-Novolac Epoxy Resin)、SE-5000、每環氧250g/eq、新亞T&C)和上述實施例1~實施例11、比較例1~比較例4的固化劑及基於以下表2的固化劑之後，如以下表3~表5和C11Z(固化促進劑，2-十一烷基咪唑(2-undecylimidazole))進行配合來製作清漆。之後利用標樂(BUEHLER)公司的衝壓設備(SimpliMet1000的自動鑲樣機(Automatic MountingPress)設備)劑型成型作業，來製作固化物，對此測定如下物性以在表3~表5中顯示其結果。 Epoxy resin (Ortho Phenylphenol-Novolac Epoxy Resin), SE-5000, 250g / eq per epoxy, Xinya T & C, and the above-mentioned Examples 1 to 11 were respectively mixed in an equivalent ratio. 1. After the curing agent of Comparative Examples 1 to 4 and the curing agent based on Table 2 below, compound them as shown in Tables 3 to 5 and C11Z (curing accelerator, 2-undecylimidazole). To make varnish. Thereafter, a solidified product was produced by using BUEHLER's stamping equipment (SimpliMet1000 Automatic Mounting Press equipment) dosage form molding operation, and the following physical properties were measured to show the results in Tables 3 to 5.

作為上述成型作業，在180℃且80bar的壓力下進行20分鐘的固化，並利用水進行10分鐘的冷卻之後，在180℃溫度下進行2小時的後固化。 As the above-mentioned molding operation, curing was performed at 180 ° C. and a pressure of 80 bar for 20 minutes, and after cooling with water for 10 minutes, post-curing was performed at 180 ° C. for 2 hours.

《物性評價》     "Physical Evaluation"     1．介電常數(Dielectric Constant)及消耗因數(Dissipation Factor)     1. Dielectric Constant and Dissipation Factor    

通過JIS-C-6481方法，利用安捷倫E4991A射頻阻抗/材料分析儀(Agilent E4991A RF Impedance/Material analyzer)進行測定，若上述樹脂越低，固化物的電特性越優秀。 Measured by the JIS-C-6481 method using an Agilent E4991A RF Impedance / Material analyzer. The lower the resin, the better the electrical characteristics of the cured product.

2．玻璃轉移溫度(Tg)及品質減少溫度(5% Weight Loss Temperature，Td)     2. Glass transition temperature (Tg) and quality reduction temperature (5% Weight Loss Temperature, Td)    

利用差示掃描量熱儀(DSC)測定玻璃轉移溫度及固化物之5%的品質減少溫度(Td)，作為固化物的5%的品質減少溫度，利用熱重分析儀(TGA)每分鐘升溫10度後測定了固化物的重量減量為5%時的溫度。 A differential scanning calorimeter (DSC) was used to measure the glass transition temperature and the 5% mass reduction temperature (Td) of the cured product. As a 5% mass reduction temperature of the cured product, the temperature was increased by a thermogravimetric analyzer (TGA) every minute. After 10 degrees, the temperature at which the weight loss of the cured product was 5% was measured.

3．吸濕率(Water Absorption，重量百分比)     3． Moisture absorption (Water Absorption, weight percentage)    

作為吸濕率在100℃的沸水中將固化物放置2小時之後，以重量增加率(重量百分比)進行測定。吸濕率越低，固化物的物性越優秀。 The cured product was left as a moisture absorption rate in boiling water at 100 ° C. for 2 hours, and then measured at a weight increase rate (weight percentage). The lower the moisture absorption, the better the physical properties of the cured product.

4．剝離強度(1/2盎司銅玻璃強度(1/2 oz copper Peel Strength))     4． Peel Strength (1/2 oz copper Peel Strength)    

通過gIS C-6417方法測定了剝離強度。剝離強度越大，機械強度越優秀。 The peel strength was measured by the gIS C-6417 method. The greater the peel strength, the better the mechanical strength.

5．熱膨脹係數(CTE，ppm/℃)     5． Coefficient of Thermal Expansion (CTE, ppm / ℃)    

作為熱膨脹係數(CTE，ppm/℃)，根據ASTM E831方法利用TMA(梅特勒-托利多(Mettler Toredo))設備測定玻璃轉移溫度前後的熱膨脹係數，來分別以a1和、a2顯示。熱膨脹系數值越小，半導體包裝的彎曲現象(Warpage)發生得少。 As the coefficient of thermal expansion (CTE, ppm / ° C), the coefficients of thermal expansion before and after the glass transition temperature were measured using a TMA (Mettler Toredo) device in accordance with the ASTM E831 method, and are shown as a1 and a2, respectively. The smaller the thermal expansion coefficient value, the less warpage of the semiconductor package occurs.

具體地，如在上述表3中可確認，可確認在基於實施例1~實施例3的固化物(固化物1~固化物3)的情況下，與基於實施例4~實施例5的固化物(固化物4~固化物5)相比，玻璃轉移溫度高，介電常數、介電損耗因數、吸濕率、熱膨脹係數(a1，ppm)、熱膨脹係數(a2，ppm)值顯著低。 Specifically, as can be confirmed in the above Table 3, it can be confirmed that in the case of the cured product (cured product 1 to cured product 3) of Example 1 to Example 3, and the cured product of Example 4 to Example 5 (Cured product 4 to cured product 5), the glass transition temperature is higher, the dielectric constant, dielectric loss factor, moisture absorption, thermal expansion coefficient (a1, ppm), thermal expansion coefficient (a2, ppm) values are significantly lower.

並且，可確認與基於實施例6的固化物6相比，基於實施例1~實施例3的固化物1~固化物3的介電常數和介電損耗低，吸濕率、熱膨脹係數(a1，ppm)、熱膨脹係數(a2，ppm)值低。並且，可確認玻璃轉移溫度高。 In addition, it was confirmed that, compared with the cured product 6 based on Example 6, the cured products 1 to 3 based on Examples 1 to 3 had lower dielectric constants and dielectric losses, and a higher moisture absorption rate and thermal expansion coefficient (a1). , Ppm) and low coefficient of thermal expansion (a2, ppm). In addition, it was confirmed that the glass transition temperature was high.

並且，可確認與基於實施例7~實施例8的固化物相比，基於實施例1~實施例3的固化物的介電常數和介電損耗低。相反地，可確認基於實施例1~實施例3的固化物的玻璃轉移溫度低，並且熱膨脹係數(a1，ppm)、熱膨脹係數(a2，ppm)值高。 In addition, it was confirmed that the cured products based on Examples 1 to 3 have lower dielectric constants and dielectric losses than the cured products based on Examples 7 to 8. On the contrary, it was confirmed that the glass transition temperature of the cured products based on Examples 1 to 3 was low, and the values of the coefficient of thermal expansion (a1, ppm) and the coefficient of thermal expansion (a2, ppm) were high.

並且，可確認與基於實施例1~實施例3的固化物相比，基於實施例9~實施例10的固化物的介電常數和介電損耗等同，但是玻璃轉移溫度低、熱膨脹係數(a1，ppm)、熱膨脹係數(a2，ppm)值高。 In addition, it was confirmed that the cured products based on Examples 9 to 10 have the same dielectric constant and dielectric loss as the cured products based on Examples 1 to 3, but the glass transition temperature is low and the thermal expansion coefficient (a1 , Ppm) and the coefficient of thermal expansion (a2, ppm) are high.

並且，可確認與基於實施例1~實施例3的固化物相比，基於實施例11的固化物的介電損耗損耗低，但是介電常數高。 In addition, it was confirmed that the cured product according to Example 11 has a lower dielectric loss loss than the cured product according to Examples 1 to 3, but has a higher dielectric constant.

並且，如上述表3~表5中可確認，可確認通過使用苯酚酚醛(固化劑1)等的固化劑1~7及比較例1、比較例2、比較例3及比較例4的固化劑，來固化的固化物與利用基於實施例的固化劑固化的固化物相比，介電常數、介電損耗及吸濕率顯著高，一部分比較化合物(比較固化物4、比較固化物5、比較固化物8)的玻璃轉移溫度也顯著低。 In addition, as can be confirmed in the above Tables 3 to 5, it was confirmed that by using curing agents 1 to 7 such as phenol novolac (curing agent 1) and curing agents of Comparative Example 1, Comparative Example 2, Comparative Example 3, and Comparative Example 4 Compared with the cured product cured by the curing agent based on the embodiment, the cured product to be cured has a significantly higher dielectric constant, dielectric loss, and moisture absorption rate, and some of the comparative compounds (comparative cured product 4, comparative cured product 5, comparative The glass transition temperature of the cured product 8) was also significantly low.

並且，在比較固化物4、固化物5、固化物9的情況下，剝離強度也顯著低，從而可確認機械物性不佳。 In addition, when the cured product 4, cured product 5, and cured product 9 were compared, the peel strength was also significantly low, and it was confirmed that the mechanical properties were not good.

Claims (13)

一種環氧樹脂用固化劑，包含由以下化學式1表示的化合物，該化合物的重均分子量為1000~13000：
Figure TWI636071B_C0001
在化學式1中，R1為碳數為6~24個的取代或非取代的芳基或碳數為4個以下的烷基，B為
Figure TWI636071B_C0002
或
Figure TWI636071B_C0003
或
Figure TWI636071B_C0004
，A1、A2及A3分別獨立地為氫原子、
Figure TWI636071B_C0005
或
Figure TWI636071B_C0006
所述A1、A2及A3中至少一個不是氫原子，n、m及k分別獨立地為0~8的有理數，l為0.1~12的有理數，A4為氫原子、
Figure TWI636071B_C0007
、
Figure TWI636071B_C0008
R2為碳數為6~24個的取代或非取代的芳基或碳數為4個以下的烷基，R3為碳數為6~24個的取代或非取代的芳基或碳數為4個以下的烷基，i為0~8的有理數，j為0.1~8的有理數，R4為碳數為6~24個的取代或非取代的芳基或碳數為4個以下的烷基，o為0~8的有理數，p為0.1~8的有理數，R5為碳數為6~24個的取代或非取代的芳基或碳數為4個以下的烷基，以及若R7及R8均為氫原子或R7及R8中的一個為氫原子，則另一個為甲基。A curing agent for epoxy resin, which includes a compound represented by the following Chemical Formula 1, and the compound has a weight average molecular weight of 1,000 to 13,000:
Figure TWI636071B_C0001
In Chemical Formula 1, R 1 is a substituted or unsubstituted aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms, and B is
Figure TWI636071B_C0002
or
Figure TWI636071B_C0003
or
Figure TWI636071B_C0004
, A 1 , A 2 and A 3 are each independently a hydrogen atom,
Figure TWI636071B_C0005
or
Figure TWI636071B_C0006
At least one of A 1 , A 2 and A 3 is not a hydrogen atom, n, m and k are each independently a rational number from 0 to 8, l is a rational number from 0.1 to 12, and A 4 is a hydrogen atom,
Figure TWI636071B_C0007
,
Figure TWI636071B_C0008
R 2 is a substituted or unsubstituted aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms; R 3 is a substituted or unsubstituted aryl group or carbon number having 6 to 24 carbon atoms Is 4 or less alkyl groups, i is a rational number of 0 to 8, j is a rational number of 0.1 to 8, R 4 is a substituted or unsubstituted aryl group having 6 to 24 carbon atoms or having 4 or less carbon atoms Alkyl, o is a rational number from 0 to 8, p is a rational number from 0.1 to 8, R 5 is a substituted or unsubstituted aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms, and if R 7 and R 8 are each a hydrogen atom or one of R 7 and R 8 is a hydrogen atom, and the other is a methyl group. 如申請專利範圍第1項所述之環氧樹脂用固化劑，其中，所述R1、R2、R3、R4及R5分別獨立地為碳數為4個以下的烷基或取代或非取代的芳基，所述芳基選自由苯基、聯苯基、萘基、蒽基、菲基、芘基、苝基、
Figure TWI636071B_C0009
基、甲酚基及芴基所組成的群組中的一種。The curing agent for epoxy resins according to item 1 of the scope of patent application, wherein the R 1 , R 2 , R 3 , R 4, and R 5 are each independently an alkyl group having 4 or less carbon atoms or substituted. Or an unsubstituted aryl group selected from the group consisting of phenyl, biphenyl, naphthyl, anthracenyl, phenanthryl, fluorenyl, fluorenyl,
Figure TWI636071B_C0009
One of the group consisting of a methyl group, a cresol group and a fluorenyl group. 如申請專利範圍第2項所述之環氧樹脂用固化劑，其中，所述R1、R2、R3、R4及R5分別獨立地為非取代的苯基、萘基或聯苯基。The curing agent for epoxy resins according to item 2 of the scope of patent application, wherein the R 1 , R 2 , R 3 , R 4, and R 5 are each independently an unsubstituted phenyl, naphthyl, or biphenyl base. 一種環氧樹脂用固化劑，包含由以下化學式2、化學式3及化學式4表示的單體進行共聚合的共聚物，該共聚物之重均分子量為1000~13000：
Figure TWI636071B_C0010
在化學式2中，a為0~8的有理數，若R7及R8均為氫原子或R7及R8中的一個為氫原子，則另一個為甲基；
Figure TWI636071B_C0011
在化學式3中，B為
Figure TWI636071B_C0012
或
Figure TWI636071B_C0013
或
Figure TWI636071B_C0014
，X1為鹵素原子；以及
Figure TWI636071B_C0015
在化學式4中，X2為鹵素原子，R6為碳數為6~24個的芳基或碳數為4個以下的烷基。A curing agent for epoxy resin, comprising a copolymer copolymerized by the monomers represented by the following Chemical Formula 2, Chemical Formula 3, and Chemical Formula 4, and the weight average molecular weight of the copolymer is 1000-13000:
Figure TWI636071B_C0010
In Chemical Formula 2, a is a rational number from 0 to 8, if R 7 and R 8 are both hydrogen atoms or one of R 7 and R 8 is a hydrogen atom, the other is methyl;
Figure TWI636071B_C0011
In Chemical Formula 3, B is
Figure TWI636071B_C0012
or
Figure TWI636071B_C0013
or
Figure TWI636071B_C0014
X 1 is a halogen atom;
Figure TWI636071B_C0015
In Chemical Formula 4, X 2 is a halogen atom, and R 6 is an aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms. 如申請專利範圍第4項所述之環氧樹脂用固化劑，其中，所述X1及X2分別獨立地為氟原子、氯原子、溴原子或碘原子，以及所述R6為芳基，該芳基選自由苯基、聯苯基、萘基、蒽基、菲基、芘基、苝基、
Figure TWI636071B_C0016
基、甲酚基及芴基所組成的群組中的一種。The curing agent for epoxy resins according to item 4 of the scope of the patent application, wherein X 1 and X 2 are each independently a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and the R 6 is an aryl group The aryl group is selected from the group consisting of phenyl, biphenyl, naphthyl, anthracenyl, phenanthryl, fluorenyl, fluorenyl,
Figure TWI636071B_C0016
One of the group consisting of a methyl group, a cresol group and a fluorenyl group. 如申請專利範圍第5項所述之環氧樹脂用固化劑，其中，所述R6為非取代的苯基、萘基或聯苯基中的一種。The curing agent for epoxy resins according to item 5 of the scope of patent application, wherein R 6 is one of an unsubstituted phenyl group, a naphthyl group, or a biphenyl group. 如申請專利範圍第4項所述之環氧樹脂用固化劑，其中，化學式2、化學式3及化學式4表示的單體係以1：0.1~1.5：0.1~3的莫耳比進行共聚合。The curing agent for epoxy resins as described in item 4 of the scope of patent application, wherein the single system represented by Chemical Formula 2, Chemical Formula 3, and Chemical Formula 4 is copolymerized at a molar ratio of 1: 0.1 to 1.5: 0.1 to 3. 一種環氧樹脂用固化劑的製備方法，包括：步驟1，向反應槽導入由以下化學式2、化學式3及化學式4表示的單體，其莫耳比係1：0.1~1.5：0.1~3；以及步驟2，將步驟1中所導入的單體進行反應，以製備由以下化學式1表示的共聚物：
Figure TWI636071B_C0017
在化學式2中，a為0~8的有理數，若上述R7及R8均為氫原子或R7及R8中的一個為氫原子，則另一個為甲基；
Figure TWI636071B_C0018
在化學式3中，B為
Figure TWI636071B_C0019
或
Figure TWI636071B_C0020
或
Figure TWI636071B_C0021
，X1為鹵素原子；
Figure TWI636071B_C0022
在化學式4中，X2為鹵素原子，R6為碳數為6~24個的芳基或碳數為4個以下的烷基；以及
Figure TWI636071B_C0023
在化學式1中，R1為碳數為6~24個的芳基或碳數為4個以下的烷基，B為
Figure TWI636071B_C0024
或
Figure TWI636071B_C0025
或
Figure TWI636071B_C0026
，A1、A2及A3分別獨立地為氫原子、
Figure TWI636071B_C0027
或
Figure TWI636071B_C0028
所述A1、A2及A3中至少一個不是氫原子，n、m及k分別獨立地為0~8的有理數，l為0.1~12的有理數，A4為氫原子、
Figure TWI636071B_C0029
、
Figure TWI636071B_C0030
Figure TWI636071B_C0031
R2為碳數為6~24個的芳基或碳數為4個以下的烷基，R3為碳數為6~24個的芳基或碳數為4個以下的烷基，i為0~8的有理數，j為0.1~8的有理數，R4為碳數為6~24個的芳基或碳數為4個以下的烷基，o為0~8的有理數，p為0.1~8的有理數，R5為碳數為6~24個的芳基或碳數為4個以下的烷基，以及若R7及R8均為氫原子或R7及R8中的一個為氫原子，則另一個為甲基。A method for preparing a curing agent for epoxy resin, comprising: step 1, introducing a monomer represented by the following Chemical Formula 2, Chemical Formula 3, and Chemical Formula 4 into a reaction tank, and having a molar ratio of 1: 0.1 to 1.5: 0.1 to 3; And step 2, the monomer introduced in step 1 is reacted to prepare a copolymer represented by the following chemical formula 1:
Figure TWI636071B_C0017
In Chemical Formula 2, a is a rational number from 0 to 8, if R 7 and R 8 are both hydrogen atoms or one of R 7 and R 8 is a hydrogen atom, the other is methyl;
Figure TWI636071B_C0018
In Chemical Formula 3, B is
Figure TWI636071B_C0019
or
Figure TWI636071B_C0020
or
Figure TWI636071B_C0021
X 1 is a halogen atom;
Figure TWI636071B_C0022
In Chemical Formula 4, X 2 is a halogen atom, and R 6 is an aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms; and
Figure TWI636071B_C0023
In Chemical Formula 1, R 1 is an aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms, and B is
Figure TWI636071B_C0024
or
Figure TWI636071B_C0025
or
Figure TWI636071B_C0026
, A 1 , A 2 and A 3 are each independently a hydrogen atom,
Figure TWI636071B_C0027
or
Figure TWI636071B_C0028
At least one of A 1 , A 2 and A 3 is not a hydrogen atom, n, m and k are each independently a rational number from 0 to 8, l is a rational number from 0.1 to 12, and A 4 is a hydrogen atom,
Figure TWI636071B_C0029
,
Figure TWI636071B_C0030
Figure TWI636071B_C0031
R 2 is an aryl group having 6 to 24 carbons or an alkyl group having 4 or less carbons, R 3 is an aryl group having 6 to 24 carbons or an alkyl group having 4 or less carbons, and i is Rational number from 0 to 8, j is a rational number from 0.1 to 8, R 4 is an aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms, o is a rational number from 0 to 8, and p is 0.1 to A rational number of 8, R 5 is an aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms, and if R 7 and R 8 are both hydrogen atoms or one of R 7 and R 8 is hydrogen Atom, the other is methyl. 如申請專利範圍第8項所述之環氧樹脂用固化劑的製備方法，進一步包括：在使所述單體進行反應之後，向該反應槽導入水以去除作為反應副產物生成的鹽之後，對所製備的環氧樹脂用固化劑進行分離，該分離的過程進行一次以上。The method for preparing a curing agent for epoxy resins according to item 8 of the scope of patent application, further comprising: after reacting the monomers, introducing water into the reaction tank to remove salts generated as reaction by-products, The prepared curing agent for epoxy resin is separated, and the separation process is performed more than once. 如申請專利範圍第8項所述之環氧樹脂用固化劑的製備方法，其中，在該步驟2中，使用選自由三乙胺、三甲胺、三丙胺、吡啶及N-甲基呱啶所組成的群組中的一種以上的催化劑。The method for preparing a curing agent for epoxy resins according to item 8 of the scope of patent application, wherein, in step 2, a material selected from the group consisting of triethylamine, trimethylamine, tripropylamine, pyridine and N-methylpyridine A group of more than one catalyst. 一種電氣電子用密封材料，包括：如申請專利範圍第1項至第7項中任一項所述之環氧樹脂用固化劑；以及環氧樹脂。An electrical and electronic sealing material, comprising: the curing agent for epoxy resin as described in any one of claims 1 to 7 of the scope of patent application; and epoxy resin. 一種電氣電子用基板層疊材料，包括：如申請專利範圍第1項至第7項中任一項所述之環氧樹脂用固化劑；以及環氧樹脂。A laminate material for electric and electronic substrates, comprising: the curing agent for epoxy resins as described in any one of items 1 to 7 of the scope of patent application; and epoxy resins. 一種環氧樹脂組合物，包括：如申請專利範圍第1項至第7項中任一項所述之環氧樹脂用固化劑；以及環氧樹脂。An epoxy resin composition, comprising: the curing agent for epoxy resin as described in any one of items 1 to 7 of the scope of patent application; and epoxy resin.
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