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TW202305027A - Epoxy resin, curable resin composition, and cured products thereof - Google Patents

Epoxy resin, curable resin composition, and cured products thereof Download PDF

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TW202305027A
TW202305027A TW111126635A TW111126635A TW202305027A TW 202305027 A TW202305027 A TW 202305027A TW 111126635 A TW111126635 A TW 111126635A TW 111126635 A TW111126635 A TW 111126635A TW 202305027 A TW202305027 A TW 202305027A
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epoxy resin
resin composition
parts
curable resin
weight
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TW111126635A
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遠島隆行
中西政隆
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日商日本化藥股份有限公司
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates 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
    • C08G59/02Polycondensates containing more than one epoxy group per molecule
    • C08G59/04Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C08G59/06Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
    • C08G59/063Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates 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
    • C08G59/02Polycondensates containing more than one epoxy group per molecule
    • C08G59/04Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates 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
    • C08G59/18Macromolecules 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
    • C08G59/20Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32Epoxy compounds containing three or more epoxy groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00Compositions of epoxy resins; Compositions of derivatives of epoxy resins

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Abstract

The present invention provides an epoxy resin and a curable resin composition, a cured product thereof having excellent heat resistance, flame resistance, and tracking resistance. This epoxy resin is represented by formula (1). (In formula (1), n is the average number of repetitions and satisfies 1 < n < 20.).

Description

環氧樹脂、硬化性樹脂組成物、及硬化性樹脂組成物的硬化物Epoxy resin, curable resin composition, and cured product of curable resin composition

本發明是有關於一種具有特定結構的環氧樹脂、硬化性樹脂組成物、及硬化性樹脂組成物的硬化物。The present invention relates to an epoxy resin having a specific structure, a curable resin composition, and a cured product of the curable resin composition.

環氧樹脂由於電氣性質(介電常數/介電損耗角正切、絕緣性)、機械性質、接著性、熱性質(耐熱性等)等優異,因此廣泛用於澆鑄成型品、積層板、積體電路(integrated circuit,IC)密封材料等電氣/電子領域、結構用材料、接著劑、塗料等領域中。Epoxy resins are widely used in casting moldings, laminates, and integrated circuits due to their excellent electrical properties (dielectric constant/dielectric loss tangent, insulation), mechanical properties, adhesiveness, and thermal properties (heat resistance, etc.) Electrical/electronic fields such as integrated circuit (IC) sealing materials, structural materials, adhesives, coatings, etc.

近年來,於電氣/電子領域中,要求樹脂組成物的阻燃性、耐濕性、密接性、介電特性等性能提高、高純度化、用於使填料(無機填充劑或有機填充劑)高度填充的低黏度化、用於縮短成型週期的反應性提高等諸特性的進一步提高(專利文獻1)。另外,作為結構用材料,於航空宇宙材料、休閒/體育器具用途等中,要求輕量且機械物性優異的材料。特別是於半導體密封領域、基板(基板自身、或其周邊材料)中,隨著該半導體的變遷,因薄層化、堆疊化、系統化、三維化而變得複雜,要求非常高水準的耐熱性或高流動性等要求特性。In recent years, in the field of electrical/electronics, it is required to improve the flame retardancy, moisture resistance, adhesiveness, dielectric properties, etc. of the resin composition, to increase its purity, and to use it as a filler (inorganic filler or organic filler) Further improvement of various characteristics such as low viscosity for high filling and improved reactivity for shortening molding cycle (Patent Document 1). In addition, as structural materials, materials that are lightweight and have excellent mechanical properties are required for aerospace materials, leisure and sports equipment applications, and the like. Especially in the field of semiconductor sealing and substrate (substrate itself or its surrounding materials), as the semiconductor changes, it becomes complicated due to thinning, stacking, systemization, and three-dimensionalization, and a very high level of heat resistance is required. Requirements such as stability or high fluidity.

進而,隨著自動駕駛技術的發展或電動汽車的市場的擴大,對各種電源基板或逆變器基板要求對於FR-4基板而言迄今為止所不要求的耐漏電起痕性(CTI耐性:相對漏電起痕指數(Comparative Tracking Index)耐性)。Furthermore, with the development of autonomous driving technology and the expansion of the electric vehicle market, various power supply substrates and inverter substrates are required to have tracking resistance (CTI resistance: relative Tracking Index (Comparative Tracking Index) resistance).

一般而言,已知具有容易碳化的結構的環氧樹脂的耐漏電起痕性差,但另一方面而言阻燃性高。In general, epoxy resins having a structure that is easily carbonized are known to be poor in tracking resistance, but have high flame retardancy.

出於提高樹脂組成物的耐熱性的目的,有時導入芳香族交聯單元,但於此情況下,由於主骨架為芳香族,因此容易碳化,耐漏電起痕性下降。另外,於藉由高分子量化來提高耐熱性的情況下,藉由分子量變大,熱分解溫度上升,耐漏電起痕性下降。即,耐熱性以及耐漏電起痕性存在權衡的關係(非專利文獻1)。For the purpose of improving the heat resistance of the resin composition, an aromatic crosslinking unit may be introduced, but in this case, since the main skeleton is aromatic, it is easy to carbonize and the tracking resistance decreases. In addition, when the heat resistance is improved by increasing the molecular weight, the thermal decomposition temperature increases due to the increase in the molecular weight, and the tracking resistance decreases. That is, there is a trade-off relationship between heat resistance and tracking resistance (Non-Patent Document 1).

於此種背景下,期望開發出一種表現出高耐熱性,並且同時具有阻燃性以及耐漏電起痕性的材料。Against such a background, it is desired to develop a material that exhibits high heat resistance and simultaneously has flame retardancy and tracking resistance.

特別是於太陽能發電或風力發電、電動汽車(electric vehicle,EV)等用途中,耐漏電起痕特性受到重視,要求相對漏電起痕指數(CTI)超過600。 [現有技術文獻] [專利文獻] Especially in solar power generation or wind power generation, electric vehicle (electric vehicle, EV) and other applications, the tracking resistance property is emphasized, and the relative tracking index (CTI) is required to exceed 600. [Prior art literature] [Patent Document]

[專利文獻1]日本專利特開2015-147854號公報 [非專利文獻1]高可靠性環境應對多層材料的開發(住友電木(Sumitomo Bakelite)(股) 電路材料研究所 研究部 著) [Patent Document 1] Japanese Patent Laid-Open No. 2015-147854 [Non-Patent Document 1] Development of Multilayer Materials for High Reliability Environments (Sumitomo Bakelite Co., Ltd., Institute of Circuit Materials, Research Department)

[發明所欲解決之課題] 本發明鑒於所述課題,目的在於提供一種其硬化物的耐熱性、阻燃性、耐漏電起痕性優異的環氧樹脂、硬化性樹脂組成物。 [Problem to be Solved by the Invention] In view of the above problems, the present invention aims to provide an epoxy resin and a curable resin composition whose cured product is excellent in heat resistance, flame retardancy, and tracking resistance.

[解決課題之手段] 本發明者等人為解決所述課題進行了努力研究,結果完成了本發明。即,本發明是有關於以下的[1]~[6]。再者,於本申請案中,「(數值1)~(數值2)」表示包括上下限值。 [1] 一種環氧樹脂,由下述式(1)表示。 [Means to solve the problem] The inventors of the present invention have diligently studied to solve the above-mentioned problems, and as a result, completed the present invention. That is, the present invention relates to the following [1] to [6]. In addition, in this application, "(numerical value 1) - (numerical value 2)" means that upper and lower limits are included. [1] An epoxy resin represented by the following formula (1).

[化1]

Figure 02_image004
[chemical 1]
Figure 02_image004

(式(1)中,n是重覆數的平均值,1<n<20。) [2] 一種環氧樹脂,由下述式(2)表示。 (In formula (1), n is the average number of repetitions, 1<n<20.) [2] An epoxy resin represented by the following formula (2).

[化2]

Figure 02_image006
[Chem 2]
Figure 02_image006

(式(2)中,n是重覆數的平均值,1<n<20。) [3] 如前項[1]或[2]所述的環氧樹脂,其中,藉由凝膠滲透層析法(gel permeation chromatography,GPC)而得的重量平均分子量為400~3000。 [4] 一種硬化性樹脂組成物,含有如前項[1]至[3]中任一項所述的環氧樹脂。 [5] 如前項[4]所述的硬化性樹脂組成物,更含有硬化促進劑。 [6] 一種硬化物,為將如前項[4]或[5]所述的硬化性樹脂組成物硬化而成。 [發明的效果] (In formula (2), n is the average value of the number of repetitions, 1<n<20.) [3] The epoxy resin as described in [1] or [2] above, wherein the weight average molecular weight obtained by gel permeation chromatography (GPC) is 400-3000. [4] A curable resin composition containing the epoxy resin according to any one of [1] to [3]. [5] The curable resin composition as described in [4] above further contains a curing accelerator. [6] A cured product obtained by curing the curable resin composition as described in [4] or [5] above. [Effect of the invention]

本發明是有關於一種具有特定結構的環氧樹脂、硬化性樹脂組成物及其硬化物,該硬化物具有耐漏電起痕性、耐熱性、阻燃性。 因此,本發明可有效用於電氣電子零件用絕緣材料(高可靠性半導體密封材料等)及積層板(印刷配線板、增層基板等)或以碳纖維強化塑膠(carbon fiber reinforced plastic,CFRP)為代表的各種複合材料、接著劑、塗料等中。 The present invention relates to an epoxy resin with a specific structure, a curable resin composition and its cured product, the cured product has tracking resistance, heat resistance and flame retardancy. Therefore, the present invention can be effectively used for insulating materials for electric and electronic parts (high reliability semiconductor sealing materials, etc.), laminated boards (printed wiring boards, build-up substrates, etc.) or carbon fiber reinforced plastic (carbon fiber reinforced plastic, CFRP) Representative of various composite materials, adhesives, coatings, etc.

以下詳細地說明本發明。The present invention will be described in detail below.

本發明的環氧樹脂由下述式(1)表示。The epoxy resin of the present invention is represented by the following formula (1).

[化3]

Figure 02_image008
[Chem 3]
Figure 02_image008

(式(1)中,n是重覆數的平均值,1<n<20。)(In formula (1), n is the average number of repetitions, 1<n<20.)

所述式(1)所表示的化合物藉由採用導入了多個維持芳香環密度的同時不易碳化的亞異丙基結構的分子設計,而具有優異的耐漏電起痕性、耐熱性、阻燃性。The compound represented by the above formula (1) has excellent tracking resistance, heat resistance, flame retardancy, sex.

所述式(1)中,n的值可根據藉由凝膠滲透層析法(GPC,檢測器:RI(折射率(refractive index))的測定而求出的數量平均分子量、或者分離出的峰各自的面積比來計算。n的值進而佳為1<n<15,特佳為1<n<10。In the formula (1), the value of n can be determined according to the number average molecular weight obtained by the measurement of gel permeation chromatography (GPC, detector: RI (refractive index)), or the isolated The value of n is further preferably 1<n<15, particularly preferably 1<n<10.

藉由GPC測定而得的重量平均分子量較佳為400~4500,更佳為500~4000,進而佳為1000~3000。當重量平均分子量小於400時,不易獲得由分子量增加帶來的耐熱性提高效果。另外,當重量平均分子量大於4500時,難以藉由水洗等進行精製,除此之外,用於半導體密封材料等時黏度過高,無法確保流動性,從而配線間的充填變得困難,此外,於基板用途中亦難以確保預浸體的流動性,配線的埋入性受損。The weight average molecular weight measured by GPC becomes like this. Preferably it is 400-4500, More preferably, it is 500-4000, More preferably, it is 1000-3000. When the weight average molecular weight is less than 400, it is difficult to obtain the heat resistance improving effect by increasing the molecular weight. In addition, when the weight-average molecular weight exceeds 4500, it is difficult to purify by water washing, etc. In addition, when used for semiconductor sealing materials, etc., the viscosity is too high, fluidity cannot be ensured, and filling between wirings becomes difficult. In addition, Also in substrate applications, it is difficult to ensure the fluidity of the prepreg, and the embedding property of wiring is impaired.

所述式(1)所表示的環氧樹脂通常於常溫下為半固體~固體的樹脂狀,其軟化點較佳為100℃以下,進而佳為90℃以下。於軟化點高於100℃的情況下,黏度高,製成預浸體時纖維含浸性下降。另外,其環氧當量較佳為200 g/eq~1000 g/eq,進而佳為280 g/eq~800 g/eq,特佳為290 g/eq~700 g/eq,最佳為295 g/eq~600 g/eq。另外,其於150℃下的ICI黏度較佳為0.01 Pa·s~1.2 Pa·s,更佳為0.01 Pa·s~1.0 Pa·s,進而佳為0.01 Pa·s~0.8 Pa·s。若為所述範圍,則製成密封材料組成物時,可確保作為密封材料的適當的流動性。The epoxy resin represented by the above-mentioned formula (1) is usually a semi-solid to solid resin at normal temperature, and its softening point is preferably 100° C. or lower, more preferably 90° C. or lower. When the softening point is higher than 100°C, the viscosity is high, and the impregnation of fibers decreases when it is made into a prepreg. In addition, the epoxy equivalent is preferably 200 g/eq to 1000 g/eq, more preferably 280 g/eq to 800 g/eq, particularly preferably 290 g/eq to 700 g/eq, and most preferably 295 g /eq~600 g/eq. In addition, the ICI viscosity at 150° C. is preferably 0.01 Pa·s˜1.2 Pa·s, more preferably 0.01 Pa·s˜1.0 Pa·s, and still more preferably 0.01 Pa·s˜0.8 Pa·s. If it is the above-mentioned range, when it is made into a sealing material composition, the fluidity|fluidity suitable as a sealing material can be ensured.

作為所述式(1)所表示的環氧樹脂的較佳結構的一例,可列舉下述式(2)所表示的環氧樹脂。An example of a preferable structure of the epoxy resin represented by the above formula (1) includes an epoxy resin represented by the following formula (2).

[化4]

Figure 02_image010
[chemical 4]
Figure 02_image010

(式(2)中,n是重覆數的平均值,1<n<20。)(In formula (2), n is the average value of the number of repetitions, 1<n<20.)

所述式(2)中的n的較佳範圍與所述式(1)相同。The preferred range of n in the formula (2) is the same as that of the formula (1).

所述式(2)所表示的環氧樹脂的結晶性低,從而可降低溶劑溶解性或於溶劑中的結晶析出風險。The epoxy resin represented by the formula (2) has low crystallinity, so that the solubility in solvents or the risk of crystallization in solvents can be reduced.

本發明的環氧樹脂的製法並無特別限定,例如可藉由使下述式(3)所表示的酚樹脂與表鹵醇於溶劑、觸媒的存在下發生加成或閉環反應而獲得。相對於酚樹脂的酚性羥基1莫耳,表鹵醇的使用量通常為1.0莫耳~20.0莫耳,較佳為1.5莫耳~10.0莫耳。The production method of the epoxy resin of the present invention is not particularly limited, and can be obtained, for example, by adding or ring-closing a phenol resin represented by the following formula (3) and epihalohydrin in the presence of a solvent or a catalyst. The amount of epihalohydrin used is usually 1.0 mol to 20.0 mol, preferably 1.5 mol to 10.0 mol, per 1 mol of the phenolic hydroxyl group of the phenol resin.

[化5]

Figure 02_image012
[chemical 5]
Figure 02_image012

(式(3)中,n是重覆數的平均值,1<n<20。)(In formula (3), n is the average value of the number of repetitions, 1<n<20.)

所述式(3)中的n的較佳範圍與所述式(1)相同。The preferred range of n in the formula (3) is the same as that of the formula (1).

關於所述式(3)所表示的酚樹脂,藉由GPC測定而得的重量平均分子量較佳為400~4500,更佳為500~4000,進而佳為1000~3000。作為羥基當量的較佳範圍,為100 g/eq~300 g/eq,更佳為120 g/eq~250 g/eq,進而佳為120 g/eq~230 g/eq。作為150℃下的熔融黏度(ICI黏度)的較佳範圍,為0.01 Pa·s~3.0 Pa·s,更佳為0.02 Pa·s~2.0 Pa·s,進而佳為0.02 Pa·s~1.5 Pa·s。作為軟化點的較佳範圍,為40℃~180℃,更佳為50℃~150℃,進而佳為60℃~140℃。當軟化點小於40℃時,不易獲得由分子量增加帶來的耐熱性提高效果。另外,當軟化點高於180℃時,難以藉由水洗等進行精製,除此之外,用於半導體密封材料等的硬化劑時或製成環氧化物時,黏度過高,無法確保流動性,從而配線間的充填變得困難,此外,於基板用途中亦難以確保預浸體的流動性,配線的埋入性受損。As for the phenol resin represented by said formula (3), the weight average molecular weight measured by GPC is preferably 400-4500, More preferably, it is 500-4000, More preferably, it is 1000-3000. A preferable range of the hydroxyl equivalent is 100 g/eq to 300 g/eq, more preferably 120 g/eq to 250 g/eq, still more preferably 120 g/eq to 230 g/eq. The preferred range of melt viscosity (ICI viscosity) at 150°C is 0.01 Pa·s to 3.0 Pa·s, more preferably 0.02 Pa·s to 2.0 Pa·s, and still more preferably 0.02 Pa·s to 1.5 Pa ·s. The preferred range of the softening point is 40°C to 180°C, more preferably 50°C to 150°C, and still more preferably 60°C to 140°C. When the softening point is less than 40° C., the effect of improving heat resistance due to increase in molecular weight is not easily obtained. In addition, when the softening point is higher than 180°C, it is difficult to purify by washing with water. In addition, when used as a curing agent for semiconductor sealing materials or as an epoxy, the viscosity is too high and fluidity cannot be ensured. , it becomes difficult to fill between wirings, and it is also difficult to ensure the fluidity of the prepreg in substrate applications, and the embedding property of wirings is impaired.

作為環氧化反應中可使用的鹼金屬氫氧化物,可列舉氫氧化鈉、氫氧化鉀等。鹼金屬氫氧化物可為固體物質,亦可使用其水溶液。於使用水溶液的情況下,可為以下方法:將該鹼金屬氫氧化物的水溶液連續地添加至反應系統內,並且於減壓下或常壓下連續蒸餾出水及表鹵醇,進而進行分液以將水去除,使表鹵醇連續返回反應系統內。相對於酚樹脂的酚性羥基1莫耳,鹼金屬氫氧化物的使用量通常為0.9莫耳~2.5莫耳,較佳為0.95莫耳~1.5莫耳。若鹼金屬氫氧化物的使用量少,則反應不會充分進行。另一方面,相對於酚樹脂的酚性羥基1莫耳而過量使用超過2.5莫耳的鹼金屬氫氧化物的情況會導致副生成不必要的廢棄物。Sodium hydroxide, potassium hydroxide, etc. are mentioned as an alkali metal hydroxide which can be used for an epoxidation reaction. The alkali metal hydroxide may be a solid substance, and its aqueous solution may also be used. In the case of using an aqueous solution, the aqueous solution of the alkali metal hydroxide is continuously added to the reaction system, and water and epihalohydrin are continuously distilled off under reduced pressure or normal pressure, followed by liquid separation. In order to remove the water, the epihalohydrin is continuously returned to the reaction system. The amount of the alkali metal hydroxide used is usually 0.9 to 2.5 moles, preferably 0.95 to 1.5 moles per 1 mole of the phenolic hydroxyl group of the phenol resin. When the usage-amount of alkali metal hydroxide is small, reaction will not fully progress. On the other hand, excessive use of the alkali metal hydroxide exceeding 2.5 mol with respect to 1 mol of the phenolic hydroxyl group of the phenolic resin leads to unnecessary waste by-product.

為了促進所述反應,亦可添加四甲基氯化銨、四甲基溴化銨、三甲基苄基氯化銨等四級銨鹽作為觸媒。作為四級銨鹽的使用量,相對於酚樹脂的酚性羥基1莫耳,通常為0.1 g~15 g,較佳為0.2 g~10 g。若使用量過少,則無法獲得充分的反應促進效果,若使用量過多,則於環氧樹脂中殘存的四級銨鹽量增加,因此亦有可能成為使電可靠性劣化的原因。In order to promote the reaction, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzyl ammonium chloride may be added as a catalyst. The usage-amount of a quaternary ammonium salt is 0.1 g-15 g normally with respect to 1 mole of phenolic hydroxyl groups of a phenol resin, Preferably it is 0.2 g-10 g. If the amount used is too small, a sufficient reaction acceleration effect cannot be obtained. If the amount used is too large, the amount of quaternary ammonium salt remaining in the epoxy resin will increase, which may also cause deterioration of electrical reliability.

於環氧化反應時,就反應進行方面而言,較佳為添加甲醇、乙醇、異丙醇等醇類、二甲基碸、二甲基亞碸、四氫呋喃、二噁烷等非質子性極性溶媒等進行反應。於使用醇類的情況下,其使用量相對於表鹵醇的使用量通常為2重量%~50重量%,較佳為4重量%~20重量%。另外,於使用非質子性極性溶媒的情況下,其使用量相對於表鹵醇的使用量通常為5重量%~100重量%,較佳為10重量%~80重量%。反應溫度通常為30℃~90℃,較佳為35℃~80℃。反應時間通常為0.5小時~100小時,較佳為1小時~30小時。 於反應結束後,在對反應物進行水洗後、或者不進行水洗而於加熱減壓下將表鹵醇或溶媒等去除。另外,為了製成水解性鹵素更少的環氧樹脂,亦可將回收的環氧樹脂溶解於甲苯、甲基異丁基酮等溶劑中,並加入氫氧化鈉、氫氧化鉀等鹼金屬氫氧化物的水溶液進行反應,而使閉環可靠。於此情況下,相對於縮水甘油化中使用的酚樹脂的酚性羥基1莫耳,鹼金屬氫氧化物的使用量通常為0.01莫耳~0.3莫耳,較佳為0.05莫耳~0.2莫耳。反應溫度通常為50℃~120℃,反應時間通常為0.5小時~24小時。於反應結束後,將所生成的鹽藉由過濾、水洗等去除,進而於加熱減壓下將溶劑蒸餾去除,藉此獲得本發明的環氧樹脂。 In the epoxidation reaction, it is preferable to add alcohols such as methanol, ethanol, and isopropanol, and aprotic polar solvents such as dimethylsulfone, dimethylsulfoxide, tetrahydrofuran, and dioxane in terms of reaction progress. Wait for the reaction. When alcohols are used, the amount used is usually 2% by weight to 50% by weight, preferably 4% by weight to 20% by weight, based on the amount of epihalohydrin used. Moreover, when using an aprotic polar solvent, the usage-amount is 5 weight% - 100 weight% normally with respect to the usage-amount of epihalohydrin, Preferably it is 10 weight% - 80 weight%. The reaction temperature is usually 30°C to 90°C, preferably 35°C to 80°C. The reaction time is usually 0.5 hour to 100 hours, preferably 1 hour to 30 hours. After completion of the reaction, the reactant is washed with water or without washing with water, and the epihalohydrin, the solvent, and the like are removed under reduced pressure under heating. In addition, in order to make an epoxy resin with less hydrolyzable halogens, the recovered epoxy resin can also be dissolved in solvents such as toluene and methyl isobutyl ketone, and alkali metal hydrogen such as sodium hydroxide and potassium hydroxide can be added. Aqueous solutions of the oxides react to allow reliable ring closure. In this case, the amount of the alkali metal hydroxide used is usually 0.01 to 0.3 moles, preferably 0.05 to 0.2 moles per mole of the phenolic hydroxyl group of the phenolic resin used for glycidation. Ear. The reaction temperature is usually 50°C to 120°C, and the reaction time is usually 0.5 hour to 24 hours. After the reaction, the generated salt is removed by filtration, washing with water, etc., and the solvent is distilled off under heat and reduced pressure, thereby obtaining the epoxy resin of the present invention.

此處,對所述式(3)所表示的酚樹脂的製法進行說明。所述式(3)所表示的酚樹脂的製法並無特別限定,例如藉由使雙酚A及α,α,α',α'-四甲基苯二甲醇(或二異丙烯基苯、或者α,α,α',α'-四甲基苯二氟化物、α,α,α',α'-四甲基苯二氯化物、α,α,α',α'-四甲基苯二溴化物、α,α,α',α'-四甲基苯二碘化物等鹵素化合物)於酸觸媒下、於溶劑中發生反應,可獲得目標酚樹脂。此時,作為原料,較佳為使用於間位經取代的原料。具體而言,可列舉α,α,α',α'-四甲基-1,3-苯二甲醇、1,3-二異丙烯基苯,除此之外還可列舉α,α,α',α'-四甲基-1,3-苯二氟化物、α,α,α',α'-四甲基-1,3-苯二氯化物、α,α,α',α'-四甲基-1,3-苯二溴化物、α,α,α',α'-四甲基-1,3-苯二碘化物等鹵素化合物。藉由使用於間位上具有取代位置的原料,可使原料及合成後的化合物的結晶性下降,從而能夠降低溶劑溶解性或於溶劑中的結晶析出風險。於合成時,作為酸觸媒,除了使用鹽酸、磷酸、硫酸、甲酸、對甲苯磺酸、甲磺酸之外,還可使用氯化鋁、氯化鋅等路易斯酸、活性白土、酸性白土、白炭黑、沸石、二氧化矽氧化鋁等固體酸、酸性離子交換樹脂等。該些既可單獨使用亦可併用兩種以上。相對於作為反應基質的雙酚A與α,α,α',α'-四甲基苯二甲醇(或二異丙烯基苯、或者α,α,α',α'-四甲基苯二氟化物、α,α,α',α'-四甲基苯二氯化物、α,α,α',α'-四甲基苯二溴化物、α,α,α',α'-四甲基苯二碘化物等鹵素化合物)的重量總和,觸媒的使用量為0.01重量%~10重量%,較佳為0.1重量%~5重量%。若觸媒的使用量過多,則有雙酚A分解之虞,若觸媒的使用量過少,則有反應的進行變慢之虞。作為使用的溶劑,例如可列舉甲苯、二甲苯等芳香族溶劑、環己烷、正己烷等脂肪族溶劑,二乙基醚、二異丙基醚等醚類,乙酸乙酯、乙酸丁酯等酯系溶劑、甲基異丁基酮、環戊酮等酮系溶劑等的非水溶性溶劑,但並不限定於該些,亦可併用兩種以上。另外,除了併用所述非水溶性溶劑以外,亦可併用非質子性極性溶劑。例如可列舉二甲基碸、二甲基亞碸、二甲基甲醯胺、二甲基乙醯胺、1,3-二甲基-2-咪唑啶酮、N-甲基吡咯啶酮等,亦可併用兩種以上。於使用非質子性極性溶劑的情況下,較佳為使用沸點較所併用的非水溶性溶劑高的溶劑。反應溫度較佳為80℃~150℃,更佳為90℃~140℃,進而佳為100℃~130℃。若反應溫度過高,則有雙酚A分解之虞,若反應溫度過低,則有反應無法充分進行之虞。於使用醇系原料時會副生成水,因此於升溫時一面與溶劑共沸一面自系統內去除。反應結束後,利用鹼水溶液等將酸性觸媒中和後,向油層中加入非水溶性有機溶劑,反覆水洗直至廢水變為中性為止,之後於加熱減壓下去除溶劑。於使用活性白土或離子交換樹脂的情況下,反應結束後對反應液進行過濾,以去除觸媒。Here, the production method of the phenol resin represented by said formula (3) is demonstrated. The preparation method of the phenol resin represented by the formula (3) is not particularly limited, for example, by making bisphenol A and α, α, α', α'-tetramethylbenzenedimethanol (or diisopropenylbenzene, or α,α,α',α'-tetramethylbenzene difluoride, α,α,α',α'-tetramethylbenzene dichloride, α,α,α',α'-tetramethylbenzene Benzene dibromide, α, α, α', α'-tetramethylbenzene diiodide and other halogen compounds) react in a solvent under the presence of an acid catalyst to obtain the target phenolic resin. In this case, as a raw material, a meta-substituted raw material is preferably used. Specifically, α, α, α', α'-tetramethyl-1,3-benzenedimethanol, 1,3-diisopropenylbenzene, and α, α, α ',α'-Tetramethyl-1,3-benzenedifluoride, α,α,α',α'-Tetramethyl-1,3-benzenedichloride, α,α,α',α' -Tetramethyl-1,3-benzenedibromide, α,α,α',α'-tetramethyl-1,3-benzenediiodide and other halogen compounds. By using a raw material having a substitution position at the meta position, the crystallinity of the raw material and the synthesized compound can be reduced, thereby reducing the solubility in a solvent or the risk of crystallization in a solvent. In synthesis, as an acid catalyst, in addition to hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, p-toluenesulfonic acid, and methanesulfonic acid, Lewis acids such as aluminum chloride and zinc chloride, activated clay, acid clay, Silica, zeolite, silica alumina and other solid acids, acidic ion exchange resins, etc. These may be used alone or in combination of two or more. With respect to bisphenol A and α,α,α',α'-tetramethylbenzenedimethanol (or diisopropenylbenzene, or α,α,α',α'-tetramethylbenzenedimethanol as the reaction substrate Fluoride, α,α,α',α'-tetramethylbenzene dichloride, α,α,α',α'-tetramethylbenzene dibromide, α,α,α',α'-tetra The sum of the weights of halogen compounds such as methylbenzene diiodide) and the amount of the catalyst used are 0.01% by weight to 10% by weight, preferably 0.1% by weight to 5% by weight. When the usage-amount of a catalyst is too much, there exists a possibility that bisphenol A may decompose, and when the usage-amount of a catalyst is too little, there exists a possibility that progress of a reaction may become slow. Examples of solvents used include aromatic solvents such as toluene and xylene, aliphatic solvents such as cyclohexane and n-hexane, ethers such as diethyl ether and diisopropyl ether, ethyl acetate and butyl acetate, etc. Water-insoluble solvents such as ester-based solvents, ketone-based solvents such as methyl isobutyl ketone, and cyclopentanone are not limited to these, and two or more types may be used in combination. In addition, in addition to the above-mentioned water-insoluble solvent, an aprotic polar solvent may also be used in combination. For example, dimethylsulfide, dimethylsulfoxide, dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, N-methylpyrrolidone, etc. , and two or more types can also be used in combination. When using an aprotic polar solvent, it is preferable to use the solvent with a boiling point higher than the water-insoluble solvent used together. The reaction temperature is preferably from 80°C to 150°C, more preferably from 90°C to 140°C, still more preferably from 100°C to 130°C. When the reaction temperature is too high, bisphenol A may decompose, and when the reaction temperature is too low, the reaction may not sufficiently proceed. When alcohol-based raw materials are used, water is by-generated, so it is removed from the system while azeotropic with the solvent when the temperature rises. After the reaction, neutralize the acidic catalyst with an aqueous alkali solution, etc., add a non-water-soluble organic solvent to the oil layer, wash with water repeatedly until the waste water becomes neutral, and then remove the solvent under heating and reduced pressure. In the case of using activated clay or ion exchange resin, the reaction solution is filtered after the reaction to remove the catalyst.

作為所述式(3)所表示的酚樹脂的較佳結構的一例,可列舉下述式(4)所表示的酚樹脂。As an example of a preferable structure of the phenol resin represented by said formula (3), the phenol resin represented by following formula (4) is mentioned.

[化6]

Figure 02_image014
[chemical 6]
Figure 02_image014

(式(4)中,n是重覆數的平均值,1<n<20。)(In formula (4), n is the average value of the number of repetitions, 1<n<20.)

所述式(4)中的n的較佳範圍與所述式(1)相同。The preferred range of n in the formula (4) is the same as that of the formula (1).

以下,對本發明的硬化性樹脂組成物進行說明。 於本發明的硬化性樹脂組成物中,所述式(1)所表示的環氧樹脂可單獨使用、或與其他環氧樹脂併用。於併用的情況下,所述式(1)所表示的環氧樹脂於所有環氧樹脂中所佔的比例較佳為10重量%~98重量%,更佳為20重量%~95重量%,進而佳為30重量%~95重量%。藉由將添加量設為10重量%以上,可表現出耐漏電起痕性提高或高耐熱性、阻燃性。 Hereinafter, the curable resin composition of the present invention will be described. In the curable resin composition of the present invention, the epoxy resin represented by the formula (1) may be used alone or in combination with other epoxy resins. In the case of combined use, the proportion of the epoxy resin represented by the formula (1) in all epoxy resins is preferably 10% by weight to 98% by weight, more preferably 20% by weight to 95% by weight, More preferably, it is 30 weight% - 95 weight%. By making the addition amount 10 weight% or more, tracking resistance improvement, high heat resistance, and flame retardancy can be expressed.

作為可與本發明的環氧樹脂併用的其他環氧樹脂的具體例,可列舉:雙酚類(雙酚A、雙酚F、雙酚S、聯苯酚、雙酚AD等)或酚類(苯酚、烷基取代苯酚、芳香族取代苯酚、萘酚、烷基取代萘酚、二羥基苯、烷基取代二羥基苯、二羥基萘等)與各種醛(甲醛、乙醛、烷基醛、苯甲醛、烷基取代苯甲醛、羥基苯甲醛、萘醛、戊二醛、鄰苯二甲醛、巴豆醛、肉桂醛等)的縮聚物;所述酚類與各種二烯化合物(二環戊二烯、萜烯類、乙烯基環己烯、降冰片二烯、乙烯基降冰片烯、四氫茚、二乙烯基苯、二乙烯基聯苯、二異丙烯基聯苯、丁二烯、異戊二烯等)的聚合物;所述酚類與酮類(丙酮、甲基乙基酮、甲基異丁基酮、苯乙酮、二苯甲酮等)的縮聚物;所述酚類與芳香族二甲醇類(苯二甲醇、聯苯二甲醇等)的縮聚物;所述酚類與芳香族二氯甲基類(α,α'-二氯二甲苯、雙氯甲基聯苯等)的縮聚物;所述酚類與芳香族雙烷氧基甲基類(雙甲氧基甲基苯、雙甲氧基甲基聯苯、雙苯氧基甲基聯苯等)的縮聚物;所述雙酚類與各種醛的縮聚物或將醇類等加以縮水甘油化而得的縮水甘油醚系環氧樹脂、脂環式環氧樹脂、縮水甘油胺系環氧樹脂、縮水甘油酯系環氧樹脂等,只要為通常所使用的環氧樹脂則並不限定於該些。該些可單獨使用,亦可使用兩種以上。Specific examples of other epoxy resins that can be used in combination with the epoxy resin of the present invention include: bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.) or phenols ( Phenol, alkyl substituted phenol, aromatic substituted phenol, naphthol, alkyl substituted naphthol, dihydroxybenzene, alkyl substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.); said phenols with various diene compounds (dicyclopentadiene olefins, terpenes, vinyl cyclohexene, norbornadiene, vinyl norbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isopropene Pentadiene, etc.); polycondensates of said phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.); said phenols Condensation products with aromatic dimethanols (benzenedimethanol, biphenyldimethanol, etc.); said phenols and aromatic dichloromethyls (α,α'-dichloroxylene, dichloromethylbiphenyl etc.); polycondensation of said phenols with aromatic bis-alkoxymethyls (bismethoxymethylbenzene, bismethoxymethylbiphenyl, bisphenoxymethylbiphenyl, etc.) products; polycondensates of the bisphenols and various aldehydes or glycidyl ether epoxy resins, alicyclic epoxy resins, glycidylamine epoxy resins, glycidol The ester-based epoxy resin and the like are not limited to these as long as they are commonly used epoxy resins. These may be used alone, or two or more kinds may be used.

作為可於本發明的硬化性樹脂組成物中使用的硬化劑,可列舉:胺系硬化劑、酸酐系硬化劑、醯胺系硬化劑、酚系硬化劑等。作為可使用的硬化劑的具體例,例如可列舉鄰苯二胺、間苯二胺、對苯二胺、4,4'-二胺基二苯基碸、3,4'-二胺基二苯基碸、3,3'-二胺基二苯基碸、2,2'-二胺基二苯基碸、二乙基甲苯二胺、二甲基硫代甲苯二胺、二胺基二苯基甲烷、3,3'-二甲基-4,4'-二胺基二苯基甲烷、3,3'-二乙基-4,4'-二胺基二苯基甲烷、4,4'-二胺基-3,3'-二乙基-5,5'-二甲基二苯基甲烷、4,4'-二胺基-3,3',5,5'-四甲基二苯基甲烷、4,4'-二胺基-3,3',5,5'-四乙基二苯基甲烷、4,4'-二胺基-3,3',5,5'-四異丙基二苯基甲烷、4,4'-亞甲基雙(N-甲基苯胺)、雙(胺基苯基)芴、3,4'-二胺基二苯基醚、4,4'-二胺基二苯基醚、2,2'-雙[4-(4-胺基苯氧基)苯基]丙烷、雙[4-(4-胺基苯氧基)苯基]碸、1,3'-雙(4-胺基苯氧基)苯、1,4'-雙(4-胺基苯氧基)苯、1,4'-雙(4-胺基苯氧基)聯苯、4,4'-(1,3-伸苯基二亞異丙基)雙苯胺、4,4'-(1,4-伸苯基二亞異丙基)雙苯胺、萘二胺、聯苯胺、二甲基聯苯胺、國際公開第2017/170551號合成例1及合成例2中記載的芳香族胺化合物等芳香族胺化合物;1,3-雙(胺基甲基)環己烷、異佛爾酮二胺、4,4'-亞甲基雙(環己基胺)、降冰片烷二胺、乙二胺、丙二胺、四亞甲基二胺、五亞甲基二胺、六亞甲基二胺、二聚物二胺、三乙四胺等脂肪族胺等,但並不限定於此,可根據對組成物欲賦予的特性適宜地使用。為了確保適用期,較佳為使用芳香族胺,於欲賦予即時硬化性的情況下,較佳為使用脂肪族胺。藉由使用含有二官能成分作為主要成分的胺系化合物作為硬化劑,可於硬化反應時構築直線性高的網絡(network),從而可表現出特別優異的強韌性。另外,可列舉二氰二胺、由次亞麻油酸的二聚體及乙二胺合成的聚醯胺樹脂等醯胺系化合物;鄰苯二甲酸酐、偏苯三甲酸酐、均苯四甲酸酐、馬來酸酐、四氫鄰苯二甲酸酐、甲基四氫鄰苯二甲酸酐、甲基納迪克酸酐、六氫鄰苯二甲酸酐、甲基六氫鄰苯二甲酸酐等酸酐系化合物;雙酚類(雙酚A、雙酚F、雙酚S、聯苯酚、雙酚AD等)或酚類(苯酚、烷基取代苯酚、芳香族取代苯酚、萘酚、烷基取代萘酚、二羥基苯、烷基取代二羥基苯、二羥基萘等)與各種醛(甲醛、乙醛、烷基醛、苯甲醛、烷基取代苯甲醛、羥基苯甲醛、萘醛、戊二醛、鄰苯二甲醛、巴豆醛、肉桂醛等)的縮聚物,或者所述酚類與各種二烯化合物(二環戊二烯、萜烯類、乙烯基環己烯、降冰片二烯、乙烯基降冰片烯、四氫茚、二乙烯基苯、二乙烯基聯苯、二異丙烯基聯苯、丁二烯、異戊二烯等)的聚合物,或者所述酚類與酮類(丙酮、甲基乙基酮、甲基異丁基酮、苯乙酮、二苯甲酮等)的縮聚物,或者所述酚類與芳香族二甲醇類(苯二甲醇、聯苯二甲醇等)的縮聚物,或者所述酚類與芳香族二氯甲基類(α,α'-二氯二甲苯、雙氯甲基聯苯等)的縮聚物,或者所述酚類與芳香族雙烷氧基甲基類(雙甲氧基甲基苯、雙甲氧基甲基聯苯、雙苯氧基甲基聯苯等)的縮聚物,或者所述雙酚類與各種醛的縮聚物、及該些的改質物等酚系化合物;咪唑、三氟硼烷-胺錯合物、胍衍生物等,但並不限定於該些。Examples of the curing agent that can be used in the curable resin composition of the present invention include amine-based curing agents, acid anhydride-based curing agents, amide-based curing agents, and phenol-based curing agents. Specific examples of hardeners that can be used include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylene, 3,4'-diaminodiphenyl Phenylphenylene, 3,3'-diaminodiphenylene, 2,2'-diaminodiphenylene, diethyltoluenediamine, dimethylthiotoluenediamine, diaminodiphenyl Phenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 4, 4'-diamino-3,3'-diethyl-5,5'-dimethyldiphenylmethane, 4,4'-diamino-3,3',5,5'-tetramethyl diphenylmethane, 4,4'-diamino-3,3',5,5'-tetraethyldiphenylmethane, 4,4'-diamino-3,3',5,5 '-Tetraisopropyldiphenylmethane, 4,4'-methylenebis(N-methylaniline), bis(aminophenyl)fluorene, 3,4'-diaminodiphenylether, 4,4'-Diaminodiphenyl ether, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(4-aminophenoxy)benzene base] benzene, 1,3'-bis(4-aminophenoxy)benzene, 1,4'-bis(4-aminophenoxy)benzene, 1,4'-bis(4-aminophenoxy)benzene Oxy)biphenyl, 4,4'-(1,3-phenylenediisopropylidene)bisaniline, 4,4'-(1,4-phenylenediisopropylidene)bisaniline, Aromatic amine compounds such as naphthalene diamine, benzidine, dimethylbenzidine, aromatic amine compounds described in Synthesis Example 1 and Synthesis Example 2 of International Publication No. 2017/170551; 1,3-bis(aminomethyl ) cyclohexane, isophorone diamine, 4,4'-methylenebis(cyclohexylamine), norbornanediamine, ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylene Aliphatic amines such as methyldiamine, hexamethylenediamine, dimerdiamine, triethylenetetramine, etc. are not limited thereto, and can be used appropriately according to the properties to be imparted to the composition. In order to secure a pot life, it is preferable to use an aromatic amine, and it is preferable to use an aliphatic amine when immediate hardening property is to be imparted. By using an amine compound containing a difunctional component as a main component as a curing agent, a highly linear network can be constructed during the curing reaction, thereby exhibiting particularly excellent toughness. In addition, amide-based compounds such as dicyandiamine, polyamide resin synthesized from linolenic acid dimer and ethylenediamine; phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, etc. , maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride and other acid anhydride compounds ; bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.) or phenols (phenol, alkyl substituted phenol, aromatic substituted phenol, naphthol, alkyl substituted naphthol, Dihydroxybenzene, alkyl substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.), or said phenols with various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinyl norbornadiene, norbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.), or said phenols with ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.) polycondensate, or the polycondensate of the phenols and aromatic dichloromethyls (α, α'-dichloroxylene, dichloromethylbiphenyl, etc.), or the polycondensates of the phenols and aromatic bis-alkoxy Polycondensates of methyl groups (bismethoxymethylbenzene, bismethoxymethylbiphenyl, bisphenoxymethylbiphenyl, etc.), or polycondensates of the bisphenols and various aldehydes, and Phenolic compounds such as modified substances of these; imidazole, trifluoroborane-amine complexes, guanidine derivatives, etc., but are not limited to these.

於本發明的硬化性樹脂組成物中,相對於環氧樹脂的環氧基1當量,硬化劑的使用量較佳為0.5當量~1.5當量,特佳為0.6當量~1.2當量。藉由設為0.5當量~1.5當量,可獲得良好的硬化物性。In the curable resin composition of the present invention, the amount of the curing agent used is preferably 0.5 to 1.5 equivalents, particularly preferably 0.6 to 1.2 equivalents, relative to 1 equivalent of epoxy groups in the epoxy resin. Favorable cured physical properties can be obtained by setting it as 0.5 equivalent - 1.5 equivalent.

當使用所述硬化劑進行硬化反應時,亦可併用硬化促進劑。作為可使用的硬化促進劑,例如可列舉:2-甲基咪唑、2-乙基咪唑、2-苯基咪唑、2-乙基-4-甲基咪唑等咪唑類;2-(二甲基胺基甲基)苯酚、三乙二胺、三乙醇胺、1,8-二氮雜雙環(5,4,0)十一烯-7等三級胺類;三苯基膦、三(甲苯基)膦、四苯基溴化鏻、四苯基鏻四苯基硼酸鹽等膦類或鏻化合物;三丁基膦等有機膦類;辛酸錫等金屬化合物;四苯基鏻-四苯基硼酸鹽、四苯基鏻-乙基三苯基硼酸鹽等四取代鏻-四取代硼酸鹽;2-乙基-4-甲基咪唑-四苯基硼酸鹽、N-甲基嗎啉-四苯基硼酸鹽等四苯基硼鹽;苯甲酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸、萘甲酸、水楊酸等羧酸系化合物等。就促進胺系化合物與環氧樹脂的硬化反應的觀點而言,較佳為水楊酸等羧酸系化合物。相對於環氧樹脂100重量份,硬化促進劑可根據需要使用0.01重量份~15重量份。When the hardening reaction is performed using the hardening agent, a hardening accelerator may be used in combination. Examples of usable hardening accelerators include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, and 2-ethyl-4-methylimidazole; Aminomethyl)phenol, triethylenediamine, triethanolamine, 1,8-diazabicyclo(5,4,0)undecene-7 and other tertiary amines; triphenylphosphine, tri(tolyl ) phosphine, tetraphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate and other phosphines or phosphonium compounds; tributylphosphine and other organic phosphines; metal compounds such as tin octoate; tetraphenylphosphonium-tetraphenylboronic acid salt, tetraphenylphosphonium-ethyltriphenylborate and other tetrasubstituted phosphonium-tetrasubstituted borates; 2-ethyl-4-methylimidazole-tetraphenylborate, N-methylmorpholine-tetraphenyl Tetraphenylboron salts such as base borates; carboxylic acid compounds such as benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthoic acid, and salicylic acid, etc. From the viewpoint of accelerating the curing reaction between the amine compound and the epoxy resin, carboxylic acid compounds such as salicylic acid are preferred. The hardening accelerator can be used as needed in an amount of 0.01 to 15 parts by weight with respect to 100 parts by weight of the epoxy resin.

進而,於本發明的硬化性樹脂組成物中,根據需要可添加無機填充劑。作為無機填充劑,可列舉晶體二氧化矽、熔融二氧化矽、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(forsterite)、塊滑石(steatite)、尖晶石、二氧化鈦、滑石等的粉體或將該些球形化而成的珠粒等,但並不限定於該些。該些可單獨使用,亦可使用兩種以上。該些無機填充劑根據用途的不同而其使用量不同,但例如當用於半導體的密封劑用途時,就硬化性樹脂組成物的硬化物的耐熱性、耐濕性、力學性質、阻燃性等方面而言,較佳為以於硬化性樹脂組成物中佔20重量%以上的比例使用,更佳為30重量%以上,特別是為了提高相對於引線框架的線膨脹率,進而較佳為以佔70重量%~95重量%的比例使用。Furthermore, an inorganic filler can be added to the curable resin composition of this invention as needed. Examples of inorganic fillers include crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, forsterite , steatite, spinel, titanium dioxide, talc, and other powders, or beads obtained by spheroidizing these, but are not limited to these. These may be used alone, or two or more kinds may be used. The amount of these inorganic fillers differs depending on the application, but when used for sealing agents for semiconductors, for example, the heat resistance, moisture resistance, mechanical properties, and flame retardancy of the cured product of the curable resin composition In terms of other aspects, it is preferably used in a proportion of 20% by weight or more in the curable resin composition, more preferably 30% by weight or more, especially in order to increase the linear expansion rate relative to the lead frame, and more preferably It is used in a proportion of 70% to 95% by weight.

於本發明的硬化性樹脂組成物中,為了使成形時相對於模具的脫模良好,可調配脫模劑。作為脫模劑,可使用先前公知的任一者,例如可列舉:棕櫚蠟(carnauba wax)、褐煤蠟(montan wax)等酯系蠟;硬脂酸、棕櫚酸等脂肪酸及該些的金屬鹽;氧化聚乙烯、非氧化聚乙烯等聚烯烴系蠟等。該些可單獨使用,亦可併用兩種以上。該些脫模劑的調配量相對於所有有機成分較佳為0.5重量%~3重量%。若較此過少,則自模具的脫模變差,若較此過多,則與引線框架等的接著變差。In the curable resin composition of the present invention, a mold release agent may be blended in order to facilitate mold release from the mold during molding. As the release agent, any of the previously known ones can be used, for example, ester waxes such as carnauba wax and montan wax; fatty acids such as stearic acid and palmitic acid, and metal salts thereof ; Polyolefin-based waxes such as oxidized polyethylene and non-oxidized polyethylene. These may be used alone or in combination of two or more. It is preferable that the compounding quantity of these release agents is 0.5 weight% - 3 weight% with respect to all organic components. If the amount is too small, the release from the mold will deteriorate, and if the amount is too large, the adhesion to the lead frame and the like will deteriorate.

於本發明的硬化性樹脂組成物中,為了提高無機填充劑與樹脂成分的接著性,可調配偶合劑。作為偶合劑,可使用先前公知的任一者,例如可列舉:乙烯基烷氧基矽烷、環氧基烷氧基矽烷、苯乙烯基烷氧基矽烷、甲基丙烯醯氧基烷氧基矽烷、丙烯醯氧基烷氧基矽烷、胺基烷氧基矽烷、巰基烷氧基矽烷、異氰酸酯烷氧基矽烷等各種烷氧基矽烷化合物、烷氧基鈦化合物、鋁螯合物類等。該些可單獨使用,亦可併用兩種以上。關於偶合劑的添加方法,可於利用偶合劑預先對無機填充劑表面進行處理後與樹脂混練,亦可於在樹脂中混合偶合劑後再混練無機填充劑。In the curable resin composition of the present invention, a coupling agent may be formulated in order to improve the adhesion between the inorganic filler and the resin component. As the coupling agent, any of the previously known ones can be used, for example, vinyl alkoxy silane, epoxy alkoxy silane, styryl alkoxy silane, methacryl oxy alkoxy silane , acryloxyalkoxysilane, aminoalkoxysilane, mercaptoalkoxysilane, isocyanate alkoxysilane and other alkoxysilane compounds, alkoxytitanium compounds, aluminum chelates, etc. These may be used alone or in combination of two or more. Regarding the method of adding the coupling agent, the surface of the inorganic filler can be pre-treated with the coupling agent and then kneaded with the resin, or the inorganic filler can be kneaded after mixing the coupling agent in the resin.

進而,於本發明的硬化性樹脂組成物中,可根據需要而調配公知的添加劑。作為可使用的添加劑的具體例,可列舉:聚丁二烯及其改質物、丙烯腈共聚物的改質物、聚苯醚、聚苯乙烯、聚乙烯、聚醯亞胺、氟樹脂、馬來醯亞胺系化合物、氰酸酯系化合物、矽酮凝膠、矽油、以及碳黑、酞青藍、酞青綠等著色劑等。Furthermore, in the curable resin composition of this invention, a well-known additive can be mix|blended as needed. Specific examples of additives that can be used include: polybutadiene and its modified products, modified products of acrylonitrile copolymers, polyphenylene ether, polystyrene, polyethylene, polyimide, fluororesin, and Imide-based compounds, cyanate-based compounds, silicone gel, silicone oil, and colorants such as carbon black, phthalocyanine blue, and phthalocyanine green.

本發明的硬化性樹脂組成物藉由將上述各成分均勻地混合而獲得。本發明的硬化性樹脂組成物可藉由與先前已知的方法同樣的方法容易地製成其硬化物。例如,藉由根據需要使用擠出機、捏合機、輥等將環氧樹脂與硬化劑、以及視需要的硬化促進劑、無機填充劑、脫模劑、矽烷偶合劑及添加劑充分混合至均勻,獲得本發明的硬化性樹脂組成物,將其藉由熔融澆鑄法或轉注成型法、射出成型法、壓縮成型法等成型,進而於80℃~200℃下加熱2小時~10小時,藉此可獲得硬化物。The curable resin composition of the present invention is obtained by uniformly mixing the above-mentioned components. The curable resin composition of the present invention can be easily produced into its cured product by the same method as the conventionally known method. For example, by sufficiently mixing epoxy resin with hardener, and hardening accelerator, inorganic filler, release agent, silane coupling agent, and additives as needed to uniformity using extruder, kneader, roll, etc. as needed, The curable resin composition of the present invention is obtained, molded by melt casting, transfer molding, injection molding, compression molding, etc., and then heated at 80°C to 200°C for 2 hours to 10 hours, whereby Get hardened.

另外,本發明的硬化性樹脂組成物根據需要亦可包含溶劑。使包含溶劑的硬化性樹脂組成物(清漆)含浸於玻璃纖維、碳纖維、聚酯纖維、聚醯胺纖維、氧化鋁纖維、紙等纖維狀物質(基材)中並進行加熱乾燥而獲得預浸體,對所得的預浸體進行熱壓成形,藉此可製成本發明的硬化性樹脂組成物的硬化物。該硬化性樹脂組成物的溶劑含量以內部比例計通常為10重量%~70重量%,較佳為15重量%~70重量%左右。作為溶劑,例如可列舉:γ-丁內酯類;N-甲基吡咯啶酮、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N,N-二甲基咪唑啶酮等醯胺系溶劑;四亞甲基碸等碸類;二乙二醇二甲醚、二乙二醇二乙醚、丙二醇單甲醚、丙二醇單甲醚單乙酸酯、丙二醇單丁醚等醚系溶劑,較佳為低級(碳數1~3)烷二醇的單或二低級(碳數1~3)烷基醚;甲基乙基酮、甲基異丁基酮等酮系溶劑,更佳為兩個烷基可相同亦可不同的二低級(碳數1~3)烷基酮;甲苯、二甲苯等芳香族系溶劑等。該些可單獨使用,另外亦可為兩種以上的混合溶媒。Moreover, the curable resin composition of this invention may contain a solvent as needed. A prepreg is obtained by impregnating a curable resin composition (varnish) containing a solvent into a fibrous material (substrate) such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc., and heating and drying The obtained prepreg is hot press-molded to produce a cured product of the curable resin composition of the present invention. The solvent content of the curable resin composition is usually 10% by weight to 70% by weight, preferably about 15% by weight to 70% by weight, as an internal ratio. Examples of solvents include: γ-butyrolactones; N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethyl Amide-based solvents such as imidazolidinone; Tetramethylene glycol and other solvents; Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether monoacetate, propylene glycol monomethyl ether Ether-based solvents such as butyl ether, preferably mono- or di-lower (1-3 carbon number) alkyl ethers of lower (1-3 carbon number) alkanediols; methyl ethyl ketone, methyl isobutyl ketone, etc. The ketone-based solvent is more preferably a di-lower (1-3 carbon number) alkyl ketone whose two alkyl groups may be the same or different; aromatic solvents such as toluene and xylene, and the like. These may be used alone, or may be a mixed solvent of two or more.

另外,藉由於剝離膜上塗佈所述環氧樹脂清漆,並於加熱下將溶劑去除而進行B階段化,可獲得片狀的接著劑(亦簡稱為片)。該片狀接著劑可用作多層基板等中的層間絕緣層。In addition, a sheet-shaped adhesive agent (also simply referred to as a sheet) can be obtained by applying the above-mentioned epoxy resin varnish on a release film, removing the solvent under heating, and performing B-stage formation. This sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like.

本發明中所得的硬化物可用於各種用途。詳細而言,可列舉使用環氧樹脂等熱硬化性樹脂的一般用途,例如,可列舉:接著劑、塗料、塗敷劑、成形材料(包括片、膜、FRP等)、絕緣材料(包括印刷基板、電線包覆等)、密封劑、以及此外的向其他樹脂等中的添加劑等。The cured product obtained in the present invention can be used in various applications. Specifically, general applications using thermosetting resins such as epoxy resins are listed, for example, adhesives, paints, coating agents, molding materials (including sheets, films, FRP, etc.), insulating materials (including printing Substrates, wire coverings, etc.), sealants, and other additives to other resins, etc.

作為接著劑,可列舉:土木用、建築用、汽車用、一般事務用、醫療用的接著劑以及此外的電子材料用的接著劑。該些中,作為電子材料用的接著劑,可列舉:增層基板等多層基板的層間接著劑、晶粒接合劑、底部填充劑等半導體用接著劑;球柵陣列(ball grid array,BGA)增強用底部填充劑、異向性導電性膜(anisotropic conductive film,ACF)、異向性導電性膏(anisotropic conductive paste,ACP)等安裝用接著劑等。Examples of the adhesive include those for civil engineering, construction, automobiles, general office work, medical treatment, and other electronic materials. Among these, adhesives for electronic materials include: interlayer adhesives for multilayer substrates such as build-up substrates; adhesives for semiconductors such as die bonding agents and underfills; ball grid arrays (BGA) Underfill for reinforcement, anisotropic conductive film (ACF), anisotropic conductive paste (ACP) and other mounting adhesives.

作為密封劑,可列舉:用於電容器、電晶體、二極體、發光二極體、IC、大規模積體電路(large scale integration circuit,LSI)等的灌注密封、浸漬密封、轉移模具密封;用於IC、LSI類的板上晶片(chip on board,COB)、膜上晶片(chip on film,COF)、捲帶自動接合(tape automated bonding,TAB)等之類的灌注密封;用於覆晶的底部填充劑;四面扁平封裝(quad flat package,QFP)、球柵陣列(BGA)、晶片尺寸封裝(chip size package,CSP)等IC封裝類安裝時的密封(包括增強用底部填充劑)等。 [實施例] Examples of the sealant include potting, dipping, and transfer mold sealing for capacitors, transistors, diodes, light-emitting diodes, ICs, and large scale integration circuits (LSI); Used for potting and sealing of chip on board (COB), chip on film (COF), tape automated bonding (TAB), etc. of IC and LSI; Underfill for crystals; sealing for IC packages such as quad flat package (QFP), ball grid array (BGA), and chip size package (CSP) during installation (including underfill for reinforcement) wait. [Example]

接下來,藉由實施例對本發明更具體地進行說明,以下只要無特別說明,則份為重量份。再者,本發明並不限定於該些實施例。另外,於實施例中,環氧當量藉由依據日本工業標準(Japanese Industrial Standards,JIS)K-7236的方法測定,軟化點藉由依據JIS K-7234的方法測定。軟化點使用梅特勒-托利多(METTLER TOLEDO)公司的軟化點測定器FP90進行測定。羥基當量是將樣品於吡啶溶液中使用乙酸酐進行乙醯化,乙醯化完成後利用水將所殘存的酸酐分解,將其使用0.5 N的KOH乙醇溶液並藉由電位差滴定機進行滴定,藉此進行游離的乙酸量的測定,根據其結果求出羥基當量。Next, the present invention will be described more specifically by way of examples, and unless otherwise specified, parts are parts by weight. In addition, this invention is not limited to these Examples. In addition, in the examples, the epoxy equivalent was measured by a method based on Japanese Industrial Standards (Japanese Industrial Standards, JIS) K-7236, and the softening point was measured by a method based on JIS K-7234. The softening point was measured using a softening point measuring device FP90 from METTLER TOLEDO. The hydroxyl equivalent is to use acetic anhydride to acetylate the sample in a pyridine solution. After the acetylation is completed, use water to decompose the remaining anhydride, and use 0.5 N KOH ethanol solution to titrate it with a potentiometric titrator. Here, the amount of free acetic acid is measured, and the hydroxyl equivalent is determined from the result.

GPC(凝膠滲透層析法)分析 管柱:SHODEX GPC KF-601(兩根)、KF-602、KF-602.5、KF-603 流速:0.5 ml/min. 管柱溫度:40℃ 使用溶劑:四氫呋喃(tetra hydro furan,THF) 檢測器:RI(示差折射檢測器) GPC (Gel Permeation Chromatography) Analysis Column: SHODEX GPC KF-601 (two), KF-602, KF-602.5, KF-603 Flow rate: 0.5ml/min. Column temperature: 40°C Solvent used: tetrahydrofuran (tetra hydro furan, THF) Detector: RI (Differential Refractive Detector)

[合成例1] 加入甲苯250份、雙酚A 142.7份、α,α,α',α'-四甲基苯二甲醇97.1份、對甲苯磺酸2.5份,升溫至125℃並使其反應6小時。對有機層進行水洗直至廢液變為中性為止並加以濃縮後,獲得作為褐色固體樹脂的酚樹脂(P1)192份。數量平均分子量Mn:1279、重量平均分子量Mw:1774、羥基當量為203.8 g/eq、ICI黏度(150℃)為0.82 Pa·s、軟化點為98.0℃。將GPC圖示於圖1。 [Synthesis Example 1] 250 parts of toluene, 142.7 parts of bisphenol A, 97.1 parts of α,α,α',α'-tetramethylbenzenedimethanol, and 2.5 parts of p-toluenesulfonic acid were added, and the temperature was raised to 125° C. for 6 hours of reaction. The organic layer was washed with water until the waste liquid became neutral, and concentrated to obtain 192 parts of phenol resin (P1) as a brown solid resin. The number average molecular weight Mn: 1279, the weight average molecular weight Mw: 1774, the hydroxyl equivalent is 203.8 g/eq, the ICI viscosity (150°C) is 0.82 Pa·s, and the softening point is 98.0°C. The GPC profile is shown in FIG. 1 .

[合成例2] 一面對安裝有溫度計、冷卻管、分餾管、攪拌機的燒瓶實施氮吹掃,一面加入合成例1中所獲得的酚樹脂(P1)180份、表氯醇326.7份、二甲基亞碸163.3份、水3.6份,將內溫升溫至50℃。歷時1.5小時分批添加氫氧化鈉37.8份後,於55℃下反應2小時,於70℃下反應1小時。於加熱減壓下將未反應的表氯醇及溶劑蒸餾去除。加入甲基異丁基酮(methyl isobutyl ketone,MIBK)500份,利用水500份清洗一次有機層。將有機層放回反應容器中,加入30 wt%氫氧化鈉水溶液11.9份,於75℃下反應1小時。放置冷卻後,利用水100份清洗四次有機層,於加熱減壓下將溶劑蒸餾去除,獲得作為淺黃色固體樹脂的目標化合物(E1)201份。數量平均分子量Mn:1253,重量平均分子量Mw:1947,環氧當量為298.6 g/eq,ICI黏度(150℃)為0.44 Pa·s,軟化點為80.9℃。將GPC圖示於圖2。 [Synthesis Example 2] While purging the flask equipped with a thermometer, cooling tube, fractionating tube, and stirrer with nitrogen, add 180 parts of phenol resin (P1), 326.7 parts of epichlorohydrin, and 163.3 parts of dimethyl sulfide obtained in Synthesis Example 1. parts, 3.6 parts of water, and the internal temperature was raised to 50°C. After adding 37.8 parts of sodium hydroxide in batches over 1.5 hours, it was reacted at 55° C. for 2 hours, and then reacted at 70° C. for 1 hour. Unreacted epichlorohydrin and solvent were distilled off under reduced pressure. 500 parts of methyl isobutyl ketone (MIBK) was added, and the organic layer was washed once with 500 parts of water. The organic layer was put back into the reaction container, 11.9 parts of 30 wt % sodium hydroxide aqueous solution was added, and the reaction was carried out at 75° C. for 1 hour. After standing to cool, the organic layer was washed four times with 100 parts of water, and the solvent was distilled off under reduced pressure under heating to obtain 201 parts of the target compound (E1) as a pale yellow solid resin. The number average molecular weight Mn: 1253, the weight average molecular weight Mw: 1947, the epoxy equivalent is 298.6 g/eq, the ICI viscosity (150°C) is 0.44 Pa·s, and the softening point is 80.9°C. The GPC profile is shown in FIG. 2 .

[合成例3] 加入甲苯200份、苯酚235.3份、α,α,α',α'-四甲基苯二甲醇388.5份、對甲苯磺酸7.6份,升溫至125℃並使其反應5小時。加入甲苯200份,對有機層進行水洗直至廢液變為中性為止並加以濃縮後,獲得作為淺黃色固體樹脂的酚樹脂(P2)475份。數量平均分子量Mn:822、重量平均分子量Mw:1181、羥基當量為254.0 g/eq。將GPC圖示於圖3。 [Synthesis Example 3] 200 parts of toluene, 235.3 parts of phenol, 388.5 parts of α,α,α′,α′-tetramethylbenzenedimethanol, and 7.6 parts of p-toluenesulfonic acid were added, and the temperature was raised to 125° C. for 5 hours of reaction. After adding 200 parts of toluene, washing the organic layer with water until the waste liquid became neutral, and concentrating, 475 parts of phenol resin (P2) which is light yellow solid resin were obtained. The number average molecular weight Mn: 822, the weight average molecular weight Mw: 1181, and the hydroxyl equivalent are 254.0 g/eq. The GPC profile is shown in FIG. 3 .

[合成例4] 一面對安裝有溫度計、冷卻管、分餾管、攪拌機的燒瓶實施氮吹掃,一面加入合成例3中所獲得的酚樹脂(P2)400份、表氯醇582.7份、二甲基亞碸291.4份、水6.4份,將內溫升溫至50℃。歷時1.5小時分批添加氫氧化鈉67.3份後,於55℃下反應2小時,於70℃下反應1小時。於加熱減壓下將未反應的表氯醇及溶劑蒸餾去除。加入MIBK 900份,利用水400份清洗一次有機層。將有機層放回反應容器中,加入30 wt%氫氧化鈉水溶液21.1份,於75℃下反應1小時。放置冷卻後,利用水100份清洗六次有機層,於加熱減壓下將溶劑蒸餾去除,獲得作為淺黃色固體樹脂的目標化合物(E2)455份。數量平均分子量Mn:827,重量平均分子量Mw:1352,環氧當量為334.0 g/eq,ICI黏度(150℃)為0.17 Pa·s,軟化點為69.7℃。將GPC圖示於圖4。 [Synthesis Example 4] While purging the flask equipped with a thermometer, cooling tube, fractionating tube and stirrer with nitrogen, add 400 parts of phenol resin (P2), 582.7 parts of epichlorohydrin, and 291.4 parts of dimethyl sulfide obtained in Synthesis Example 3. parts, 6.4 parts of water, and the internal temperature was raised to 50°C. After adding 67.3 parts of sodium hydroxide in batches over 1.5 hours, it was reacted at 55° C. for 2 hours, and then reacted at 70° C. for 1 hour. Unreacted epichlorohydrin and solvent were distilled off under reduced pressure. 900 parts of MIBK was added, and the organic layer was washed once with 400 parts of water. Put the organic layer back into the reaction container, add 21.1 parts of 30 wt% sodium hydroxide aqueous solution, and react at 75° C. for 1 hour. After standing to cool, the organic layer was washed six times with 100 parts of water, and the solvent was distilled off under reduced pressure under heating to obtain 455 parts of the target compound (E2) as a pale yellow solid resin. The number average molecular weight Mn: 827, the weight average molecular weight Mw: 1352, the epoxy equivalent is 334.0 g/eq, the ICI viscosity (150°C) is 0.17 Pa·s, and the softening point is 69.7°C. The GPC profile is shown in FIG. 4 .

[合成例5] 一面對安裝有溫度計、冷卻管、分餾管、攪拌機的燒瓶實施氮吹掃,一面加入雙酚A酚醛清漆樹脂(以日本專利特開2014-198755號記載的比較例1為參考而合成的雙酚A與甲醛的縮合物,羥基當量:118 g/eq,ICI黏度(150℃)為檢測界限(6.8 Pa·s以上),軟化點為120.6℃,數量平均分子量Mn:1907,重量平均分子量Mw:4533,將GPC圖示於圖5。)100份、表氯醇415份、二甲基亞碸157份、水28.2份,將內溫升溫至35℃。歷時3小時分批添加氫氧化鈉36.1份後,於35℃下反應2小時,於70℃下反應0.5小時。於加熱減壓下將未反應的表氯醇及溶劑蒸餾去除。加入MIBK 440份,利用水170份清洗一次有機層。將有機層放回反應容器中,加入甲醇8份、水22.6份、30 wt%氫氧化鈉水溶液22.6份,於75℃下反應1小時。放置冷卻後,利用水100份清洗四次有機層,於加熱減壓下將溶劑蒸餾去除,獲得作為淺黃色固體樹脂的目標化合物(E3)147.5份。數量平均分子量Mn:2233,重量平均分子量Mw:39351,環氧當量為199.0 g/eq,ICI黏度(150℃)為1.22 Pa·s,軟化點為81.6℃。將GPC圖示於圖6。 [Synthesis Example 5] While carrying out nitrogen purging to the flask equipped with a thermometer, a cooling pipe, a fractionating pipe, and a stirrer, a bisphenol A novolac resin (bisphenol A novolak resin synthesized with reference to Comparative Example 1 described in Japanese Patent Application Laid-Open No. 2014-198755) was added. Condensate of phenol A and formaldehyde, hydroxyl equivalent: 118 g/eq, ICI viscosity (150°C) is the detection limit (above 6.8 Pa s), softening point is 120.6°C, number average molecular weight Mn: 1907, weight average molecular weight Mw : 4533, and the GPC chart is shown in FIG. 5.) 100 parts, 415 parts of epichlorohydrin, 157 parts of dimethylsulfoxide, 28.2 parts of water, and the internal temperature was raised to 35°C. After adding 36.1 parts of sodium hydroxide in batches over 3 hours, it was reacted at 35° C. for 2 hours, and then reacted at 70° C. for 0.5 hours. Unreacted epichlorohydrin and solvent were distilled off under reduced pressure. 440 parts of MIBK were added, and the organic layer was washed once with 170 parts of water. Put the organic layer back into the reaction vessel, add 8 parts of methanol, 22.6 parts of water, and 22.6 parts of 30 wt% sodium hydroxide aqueous solution, and react at 75°C for 1 hour. After standing to cool, the organic layer was washed four times with 100 parts of water, and the solvent was distilled off under reduced pressure under heating to obtain 147.5 parts of the target compound (E3) as a pale yellow solid resin. The number average molecular weight Mn: 2233, the weight average molecular weight Mw: 39351, the epoxy equivalent is 199.0 g/eq, the ICI viscosity (150°C) is 1.22 Pa·s, and the softening point is 81.6°C. The GPC profile is shown in FIG. 6 .

[實施例1、比較例1、比較例2] 相對於合成例2中所獲得的環氧樹脂(E1)、合成例4中所獲得的環氧樹脂(E2)及合成例5中所獲得的環氧樹脂(E3),分別將作為硬化劑的聯苯芳烷基型酚樹脂(日本化藥公司製造 GPH-65)、作為觸媒的三苯基膦(TPP、東京化成公司製造)、作為無機填充劑的矽膠(熔融二氧化矽 MSR-2212、龍森製造),以表1所示的比例進行調配,使用輥磨機均勻混合/混練,獲得硬化性樹脂組成物。 將該硬化性樹脂組成物粉碎後,利用壓片機加以片化。將經片化的硬化性樹脂組成物進行轉注成型(175℃ 60分鐘~15分鐘),進而脫模後,於160℃×2小時+180℃×6小時的條件下硬化,獲得評價用試驗片。 [Example 1, Comparative Example 1, Comparative Example 2] With respect to the epoxy resin (E1) obtained in Synthesis Example 2, the epoxy resin (E2) obtained in Synthesis Example 4, and the epoxy resin (E3) obtained in Synthesis Example 5, the Biphenyl aralkyl type phenol resin (GPH-65 manufactured by Nippon Kayaku Co., Ltd.), triphenylphosphine (TPP, manufactured by Tokyo Chemical Industry Co., Ltd.) as a catalyst, silica gel (fused silica MSR-2212) as an inorganic filler , manufactured by Ronsen), blended at the ratio shown in Table 1, and uniformly mixed/kneaded using a roller mill to obtain a curable resin composition. After pulverizing the curable resin composition, it was tableted with a tablet machine. The sheet-formed curable resin composition is subjected to transfer molding (175°C for 60 minutes to 15 minutes), and after demoulding, it is cured under the conditions of 160°C x 2 hours + 180°C x 6 hours to obtain a test piece for evaluation .

於下述條件下對評價用試驗片進行測定,將其結果示於表1。The test pieces for evaluation were measured under the following conditions, and the results are shown in Table 1.

<耐熱性試驗(Tg)> 使用動態黏彈性試驗機測定玻璃轉移溫度(tanδ為最大值時的溫度)。 ·動態黏彈性測定器:TA儀器(TA-instruments)製造的DMA-2980 ·升溫速度:2℃/分鐘 ·頻率:10 Hz <Heat resistance test (Tg)> The glass transition temperature (the temperature at which tan δ becomes the maximum value) was measured using a dynamic viscoelasticity testing machine. ・Dynamic viscoelasticity measuring device: DMA-2980 manufactured by TA-instruments ·Heating rate: 2°C/min ·Frequency: 10Hz

<耐漏電起痕性試驗(CTI)> 適用規格 IEC-Pub.60112-2003(第四版)及JIS-C2134-2007 對象試驗電壓400 V~600 V 試驗液 氯化銨0.1%水溶液 滴加數 50滴 或實施滴加直至試驗片破壞為止 試驗室的溫度以及濕度 21℃~23℃ 40%RH~45%RH 試驗裝置 亞馬洋(yamayo)試驗機有限公司製造 YST-112型 耐漏電起痕試驗機 試驗樣品形狀 直徑50 mm 厚度3 mm 每片測定1點 <Tracking Resistance Test (CTI)> Applicable standards IEC-Pub.60112-2003 (4th edition) and JIS-C2134-2007 Target test voltage 400 V~600 V Test solution Ammonium chloride 0.1% aqueous solution Add 50 drops or add until the test piece is broken The temperature and humidity of the test room 21℃~23℃ 40%RH~45%RH Test device YST-112 type tracking tester manufactured by Yamayo Testing Machine Co., Ltd. Test sample shape diameter 50 mm thickness 3 mm 1 point per slice

<阻燃性試驗> 將試驗片垂直地保持於夾具,將燃燒器的火焰調節為19 mm的藍色火焰,使試驗片的下端中央部與火焰的9.5 mm接觸10秒。與火焰接觸後,將燃燒器移開,測定燃燒持續時間。火焰熄滅後,立即與火焰接觸10秒,之后將燃燒器移開,測定燃燒持續時間。將各樣品10次的燃燒時間合計值示於表1。 <Flame Retardancy Test> The test piece was held vertically on the jig, the flame of the burner was adjusted to a 19 mm blue flame, and the center portion of the lower end of the test piece was brought into contact with 9.5 mm of the flame for 10 seconds. After contact with the flame, the burner is removed and the burning duration is measured. Immediately after the flame is extinguished, contact with the flame for 10 seconds, then remove the burner, and measure the duration of burning. Table 1 shows the total value of the burning time of 10 times of each sample.

[表1]   實施例1 比較例1 比較例2 環氧樹脂 E1 9.8     E2   10.8   E3     8.4 硬化劑 GPH-65 7 6 8.4 觸媒 TPP 0.2 0.2 0.2 填料 MSR-2212 83 83 83 評價結果 Tg(DMA tanδ Max) 165 150 188 耐漏電起痕性試驗 至破壞為止的滴加數 400 V - - >50(n2) 500 V >50(n1) >50(n1) 13(NG),>50 600 V >50(n3) >50(n3) - 阻燃性試驗 燃燒時間(秒) 22 24 36 判定 V-0 V-0 V-0 [Table 1] Example 1 Comparative example 1 Comparative example 2 epoxy resin E1 9.8 E2 10.8 E3 8.4 hardener GPH-65 7 6 8.4 catalyst TPP 0.2 0.2 0.2 filler MSR-2212 83 83 83 Evaluation results Tg (DMA tanδ Max) 165 150 188 The number of drops in the tracking resistance test until it is destroyed 400V - - >50(n2) 500V >50(n1) >50(n1) 13 (NG), >50 600V >50(n3) >50(n3) - Flame retardant test Burn time (seconds) twenty two twenty four 36 determination V-0 V-0 V-0

耐漏電起痕試驗的括號內的n之後的數值表示樣品數。比較例2的500 V的試驗表示第一次時藉由滴加13滴而試驗片發生破壞,第二次時即便滴加50滴試驗片亦未破壞。The number after n in parentheses in the tracking resistance test indicates the number of samples. The 500 V test of Comparative Example 2 shows that the test piece was destroyed by dropping 13 drops at the first time, but it was not broken even when 50 drops were dropped at the second time.

由表1的結果確認到,實施例1具有高耐熱性、高耐漏電起痕性、及高阻燃性。 [產業上之可利用性] From the results in Table 1, it was confirmed that Example 1 had high heat resistance, high tracking resistance, and high flame retardancy. [Industrial availability]

本發明的環氧樹脂可有效用於電氣電子零件用絕緣材料(高可靠性半導體密封材料等)及積層板(印刷配線板、BGA用基板、增層基板等)、接著劑(導電性接著劑等)或以CFRP為代表的各種複合材料用、塗料等用途中,特別是可有效用於要求耐漏電起痕性的電氣電子零件用絕緣材料(高可靠性半導體密封材料等)及積層板(印刷配線板、BGA用基板、增層基板等)用途中。The epoxy resin of the present invention can be effectively used as insulating materials for electrical and electronic parts (high reliability semiconductor sealing materials, etc.), laminated boards (printed wiring boards, substrates for BGA, build-up substrates, etc.), adhesives (conductive adhesives) etc.) or various composite materials represented by CFRP, coatings, etc., especially effective for insulating materials for electrical and electronic parts (high reliability semiconductor sealing materials, etc.) and laminates ( Printed wiring boards, BGA substrates, build-up substrates, etc.) applications.

none

圖1表示合成例1的GPC圖。 圖2表示合成例2的GPC圖。 圖3表示合成例3的GPC圖。 圖4表示合成例4的GPC圖。 圖5表示雙酚A酚醛清漆樹脂的GPC圖。 圖6表示合成例5的GPC圖。 FIG. 1 shows a GPC chart of Synthesis Example 1. FIG. 2 shows a GPC chart of Synthesis Example 2. FIG. 3 shows a GPC chart of Synthesis Example 3. FIG. 4 shows a GPC chart of Synthesis Example 4. Fig. 5 shows a GPC chart of bisphenol A novolac resin. FIG. 6 shows a GPC chart of Synthesis Example 5.

Figure 111126635-A0101-11-0002-2
Figure 111126635-A0101-11-0002-2

Claims (6)

一種環氧樹脂,由下述式(1)表示,
Figure 03_image016
式(1)中,n是重覆數的平均值,1<n<20。
An epoxy resin represented by the following formula (1),
Figure 03_image016
In the formula (1), n is the average value of the repetition number, 1<n<20.
一種環氧樹脂,由下述式(2)表示,
Figure 03_image018
式(2)中,n是重覆數的平均值,1<n<20。
An epoxy resin represented by the following formula (2),
Figure 03_image018
In formula (2), n is the average value of the number of repetitions, 1<n<20.
如請求項1或請求項2所述的環氧樹脂,其中,藉由凝膠滲透層析法而得的重量平均分子量為400~3000。The epoxy resin according to Claim 1 or Claim 2, wherein the weight average molecular weight obtained by gel permeation chromatography is 400-3000. 一種硬化性樹脂組成物,含有如請求項1至請求項3中任一項所述的環氧樹脂。A curable resin composition containing the epoxy resin according to any one of claim 1 to claim 3. 如請求項4所述的硬化性樹脂組成物,更含有硬化促進劑。The curable resin composition according to claim 4 further contains a curing accelerator. 一種硬化物,為將如請求項4或請求項5所述的硬化性樹脂組成物硬化而成。A cured product obtained by curing the curable resin composition according to Claim 4 or Claim 5.
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