TWI618744B - Epoxy resin mixture, epoxy resin composition, hardened material, and semiconductor device - Google Patents
Epoxy resin mixture, epoxy resin composition, hardened material, and semiconductor device Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/38—Epoxy compounds containing three or more epoxy groups together with di-epoxy compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
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- H01—ELECTRIC ELEMENTS
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Abstract
本發明提供一種環氧樹脂混合物,其具有優異之硬化物之耐熱性,並且可同時滿足與該耐熱性相反之特性、即硬化物之機械強度、難燃性、高溫下之彈性模數優異,且硬化前黏度低等特性。本發明之環氧樹脂混合物係藉由使下述式(1)表示之酚樹脂(A)及聯苯酚(B)同時與表鹵醇(epihalohydrin)進行反應而獲得。 The present invention provides an epoxy resin mixture, which has excellent heat resistance of a hardened material, and can simultaneously satisfy the properties opposite to the heat resistance, that is, the mechanical strength of the hardened material, flame resistance, and excellent elastic modulus at high temperature. And low viscosity before hardening and other characteristics. The epoxy resin mixture of the present invention is obtained by simultaneously reacting a phenol resin (A) and biphenol (B) represented by the following formula (1) with an epihalohydrin.
(式中,(a)(b)之比率(莫耳比)為(a)/(b)=1~3,n表示重複數)。 (In the formula, the ratio (molar ratio) of (a) (b) is (a) / (b) = 1 to 3, and n represents the number of repetitions).
Description
本發明係關於一種適於要求耐熱性之電氣電子材料用途之環氧樹脂混合物、環氧樹脂組成物、其硬化物及半導體裝置。 The present invention relates to an epoxy resin mixture, an epoxy resin composition, a cured product thereof, and a semiconductor device suitable for use in electrical and electronic materials that require heat resistance.
環氧樹脂組成物因作業性及其硬化物之優異之電特性、耐熱性、接著性、耐濕性(耐水性)等而廣泛用於電氣、電子零件、構造用材料、接著劑、塗料等領域。 Epoxy resin compositions are widely used in electrical, electronic parts, structural materials, adhesives, coatings, etc. due to their excellent electrical properties, heat resistance, adhesion, and moisture resistance (water resistance), etc. field.
然而,近年來,於電氣、電子領域中,伴隨其發展,謀求以樹脂組成物之高純度化為首之耐濕性、密接性、介電特性、用於使填料(無機或有機填充劑)高填充之低黏度化、用於縮短成型週期之反應性之提高等各特性之更進一步的提昇。又,作為構造材料,於航空太空材料、休閒、運動器具用途等中謀求輕量且機械物性優異之材料。尤其於半導體密封領域、基板(基板本身或其周邊材料),伴隨其半導體之變遷而造成薄層化、堆疊化、系統化、三維化變得複雜,要求非常高水準之耐熱性或高流動性等要求特性。再者,尤其伴隨塑膠封裝擴大至車輛用途,耐熱性之提昇要求更加嚴格。具體而言,因半導體之驅動溫度之上升,而要求150℃以上之耐熱性。一般而言,環氧樹脂有軟化點高之環氧樹脂具有高耐熱性之傾向,但另一方面,有黏度上升之傾向,故而難以用於密封材料。又,熱分解溫度之降低、難燃性之降低成為課題。 However, in recent years, in the electrical and electronic fields, along with its development, we have sought to improve the moisture resistance, adhesion, and dielectric properties of resin compositions, including high-purity resins, and to increase fillers (inorganic or organic fillers). Further improvement of various characteristics such as low viscosity of the filling and improvement of reactivity for shortening the molding cycle. In addition, as a structural material, materials that are lightweight and excellent in mechanical properties are used in aerospace materials, leisure, and sports equipment applications. Especially in the field of semiconductor sealing, substrates (the substrate itself or its surrounding materials), the thinning, stacking, systemization, and three-dimensionality have become complicated with the changes in its semiconductors, which require very high levels of heat resistance or high fluidity. And other required characteristics. Furthermore, especially with the expansion of plastic packaging to vehicle applications, the requirements for improving heat resistance have become more stringent. Specifically, heat resistance of 150 ° C. or higher is required due to an increase in driving temperature of a semiconductor. In general, epoxy resins tend to have high heat resistance, but on the other hand, they tend to increase viscosity, making them difficult to use as sealing materials. In addition, a reduction in thermal decomposition temperature and a reduction in flame resistance have become problems.
非專利文獻1:“2008年STRJ報告 半導體技術藍圖專門委員會平成20年度報告”、第8章、p1-1、[online]、平成21年3月、JEITA(公司)電子資訊技術產業協會、半導體技術藍圖專門委員會、[平成24年5月30日檢索]、<http://strj-jeita.elisasp.net/strj/nenjihoukoku-2008.cfm> Non-Patent Document 1: "2008 Annual Report of the Special Committee on Semiconductor Technology Blueprints of the 2008 STRJ Report", Chapter 8, p1-1, [online], March, 2011, JEITA (Company) Electronic Information Technology Industry Association, Semiconductors Technical Blueprint Special Committee, [Retrieved on May 30, 2012], <http://strj-jeita.elisasp.net/strj/nenjihoukoku-2008.cfm>
非專利文獻2:高倉信之等、松下電工技報 車相關設備技術 車輛用高溫動作IC、74號、日本、2001年5月31日、35-40頁 Non-Patent Literature 2: Takakura Nobuyuki, Matsushita Electric Works Bulletin Vehicle-Related Equipment Technology Vehicle High-Temperature Action IC, No. 74, Japan, May 31, 2001, pages 35-40
若將環氧樹脂一般性地高Tg化,則難燃性降低。其係由交聯密度提昇所產生之影響。然而,於要求對需要難燃性之半導體周邊材料之高Tg化時,當務之急為開發具有其相反之特性之樹脂。 When the Tg of an epoxy resin is generally increased, the flame retardancy is reduced. It is caused by the increase in crosslinking density. However, when high Tg is required for a semiconductor peripheral material that requires flame retardancy, it is urgent to develop a resin having the opposite characteristics.
又,日本特開2013-43958號公報、國際公開第2007/007827號中,作為解決本課題之手法,介紹有利用二羥基苯類之伸聯苯基芳烷基型之樹脂。 In addition, in Japanese Patent Application Laid-Open No. 2013-43958 and International Publication No. 2007/007827, as a method for solving this problem, a diphenylphenyl aralkyl type resin using dihydroxybenzenes is introduced.
然而,上述環氧樹脂兼具較高之耐熱性及難燃性,但另一方面,機械特性降低。又,由於環氧樹脂本身之黏度過高,故實際上難以用作密封材料。 However, the above-mentioned epoxy resin has both high heat resistance and flame resistance, but on the other hand, the mechanical properties are reduced. In addition, since the viscosity of the epoxy resin itself is too high, it is actually difficult to use it as a sealing material.
即,本發明之目的在於提供一種環氧樹脂混合物,其具有優異之硬化物之耐熱性並且可同時滿足與該耐熱性相反之特性、即硬化物之機械強度、難燃性、高溫下之彈性模數優異,且硬化前黏度低等特性,進而,本發明之目的在於提供一種使用有該環氧樹脂混合物之環氧樹脂組成物、硬化物及半導體裝置。 That is, an object of the present invention is to provide an epoxy resin mixture which has excellent heat resistance of a hardened material and can simultaneously satisfy the characteristics opposite to the heat resistance, namely, mechanical strength, flame resistance, and elasticity at high temperature of the hardened material. The modulus is excellent, and the viscosity before curing is low. Furthermore, an object of the present invention is to provide an epoxy resin composition, a cured product, and a semiconductor device using the epoxy resin mixture.
本發明人等係鑒於如上所述之實際情況而努力研究,結果完成本發明。 The present inventors have made intensive studies in view of the actual situation as described above, and as a result, have completed the present invention.
即,本發明係關於如下者:
(1)一種環氧樹脂混合物,其係藉由使下述式(1)表示之酚樹脂(A)及聯苯酚同時與表鹵醇(epihalohydrin)(B)進行反應而獲得;
(式中,(a)(b)之比率(莫耳比)為(a)/(b)=1~3,n表示重複數);(2)如前項(1)之環氧樹脂混合物,其中,酚樹脂(A)與聯苯酚(B)之比,相對於(A)之羥基當量1莫耳當量,(B)之羥基為0.08~0.33倍莫耳;(3)如前項(1)或(2)之環氧樹脂混合物,其軟化點為80~100℃;(4)如前項(1)至(3)中任一項之環氧樹脂混合物,其於150℃之ICI熔融黏度(錐板(cone plate)法)為0.05~0.30Pa.s;(5)一種硬化性樹脂組成物,其係以前項(1)至(4)中任一項之環氧樹脂混合物及硬化劑作為必需成分;(6)一種環氧樹脂組成物,其係以前項(1)至(4)中任一項之環氧樹脂混合物及硬化觸媒作為必需成分;(7)一種硬化物,其係使前項(5)或(6)之硬化性樹脂組成物硬化而成;(8)一種半導體裝置,其係使用前項(5)或(6)之硬化性樹脂組成物密封半導體晶片而獲得。 (In the formula, the ratio (molar ratio) of (a) (b) is (a) / (b) = 1 ~ 3, n represents the repeating number); (2) the epoxy resin mixture as described in (1) above, Among them, the ratio of the phenol resin (A) to the biphenol (B) is 1 mole equivalent to the hydroxyl equivalent of (A), and the hydroxyl group of (B) is 0.08 to 0.33 times mole; (3) As described in the above item (1) Or (2) the epoxy resin mixture having a softening point of 80 to 100 ° C; (4) the epoxy resin mixture according to any one of the items (1) to (3) above, whose ICI melt viscosity at 150 ° C ( Cone plate method) is 0.05 ~ 0.30Pa. s; (5) a curable resin composition, which is an epoxy resin mixture and a hardener of any one of the foregoing items (1) to (4) as essential components; (6) an epoxy resin composition, which The epoxy resin mixture and hardening catalyst according to any one of the preceding items (1) to (4) as essential components; (7) a hardened product comprising the hardening resin of the preceding item (5) or (6) (8) A semiconductor device obtained by sealing a semiconductor wafer with a curable resin composition according to the item (5) or (6) above.
本發明之環氧樹脂混合物由於其硬化物具有耐熱性、吸水特 性及機械特性優異之特性,故對電氣電子零件用絕緣材料及積層板(印刷配線板、增層(buildup)基板等)或以CFRP為首之各種複合材料、接著劑、塗料等是有用的。 The epoxy resin mixture of the present invention has heat resistance and water absorption properties due to its hardened material. Because of its excellent properties and mechanical properties, it is useful for insulating materials for electrical and electronic parts, multilayer boards (printed wiring boards, buildup substrates, etc.) or various composite materials such as CFRP, adhesives, and coatings.
本發明之環氧樹脂混合物係下述式(1)表示之酚樹脂(A)之環氧化物與聯苯酚(B)之環氧丙基化物之混合物。 The epoxy resin mixture of the present invention is a mixture of an epoxide of a phenol resin (A) and an epoxypropylate of biphenol (B) represented by the following formula (1).
(式中,(a)(b)之比率(莫耳比)為(a)/(b)=1~3,n表示重複數)。 (In the formula, the ratio (molar ratio) of (a) (b) is (a) / (b) = 1 to 3, and n represents the number of repetitions).
此處,本發明之環氧樹脂混合物中,於上述式(1)表示之酚樹脂之環氧化合物中,於凝膠滲透層析法(GPC)測定之面積%中,n=0之環氧化合物較佳為5~59面積%,更佳為10~49面積%,又,n=1之環氧化合物較佳為5~35面積%,更佳為5~29面積%。 Here, in the epoxy resin mixture of the present invention, among the epoxy compounds of the phenol resin represented by the above formula (1), in the area% measured by gel permeation chromatography (GPC), epoxy with n = 0 The compound is preferably 5 to 59 area%, more preferably 10 to 49 area%, and the epoxy compound of n = 1 is preferably 5 to 35 area%, and more preferably 5 to 29 area%.
另一方面,聯苯酚之環氧化物係於本發明之環氧樹脂混合物中,於GPC測定之面積%中,較佳為5~25面積%,更佳為5~19面積%。 On the other hand, the epoxide of biphenol is in the epoxy resin mixture of the present invention, and it is preferably 5 to 25 area%, and more preferably 5 to 19 area% in the area% determined by GPC.
又,本發明之環氧樹脂混合物較佳為熔融黏度為0.05~0.30Pa.s(ICI 熔融黏度150℃錐板法)。 In addition, the epoxy resin mixture of the present invention preferably has a melt viscosity of 0.05 to 0.30 Pa. s (ICI Melt viscosity 150 ° C cone plate method).
本發明中使用之酚樹脂係下述式(1)表示之酚樹脂。 The phenol resin used in the present invention is a phenol resin represented by the following formula (1).
(式中,(a)(b)之比率(莫耳比)為(a)/(b)=1~3,n表示重複數)。 (In the formula, the ratio (molar ratio) of (a) (b) is (a) / (b) = 1 to 3, and n represents the number of repetitions).
上述式(1)表示之酚樹脂之軟化點較佳為55~100℃,更佳為55℃~80℃,更佳為60~80℃。 The softening point of the phenol resin represented by the above formula (1) is preferably 55 to 100 ° C, more preferably 55 to 80 ° C, and even more preferably 60 to 80 ° C.
又,作為重複數之n較佳為1.05~3.0,更佳為1.05~2.0。 Further, n as the number of repetitions is preferably 1.05 to 3.0, and more preferably 1.05 to 2.0.
進而,(a)(b)之比率(莫耳比)通常為(a)/(b)=1~3,更佳為1~2.5。其原因在於:若(a)之比率過大則有導致凝膠化之虞。再者,該比率可於凝膠滲透層析法(GPC)中,基於n=1時之由(a)(b)產生之波峰之面積比而算出。 Furthermore, the ratio (molar ratio) of (a) (b) is usually (a) / (b) = 1 to 3, more preferably 1 to 2.5. The reason is that if the ratio of (a) is too large, gelation may occur. The ratio can be calculated in a gel permeation chromatography (GPC) based on the area ratio of the peaks generated by (a) and (b) when n = 1.
此處,酚樹脂中之n=1之化合物於(i)(間苯二酚)-(聯伸苯)-(間苯二酚)結構之RR結構、(ii)(間苯二酚)-(聯伸苯)-(苯酚)結構之RP結構、(iii)(苯酚)-(聯伸苯)-(苯酚)結構之PP結構之比率中,較佳為4>(RP結構)/(RR結構)>0.5。其原因在於:藉由使之處於該範圍內,可確保高耐熱性。又,較佳為4>(RP結構)/(PP結構)>0.5。其原因在於:藉由使之處於該範圍內,可確保高難燃性。 Here, the compound of n = 1 in the phenol resin is the RR structure of (i) (resorcinol)-(biphenylene)-(resorcinol) structure, (ii) (resorcinol)- Among the ratios of the RP structure of the (biphenylene)-(phenol) structure and the PP structure of (iii) (phenol)-(biphenylene)-(phenol) structure, the ratio is preferably 4> (RP structure) / (RR Structure)> 0.5. The reason for this is that by setting it within this range, high heat resistance can be secured. In addition, 4> (RP structure) / (PP structure)> 0.5 is preferable. The reason for this is that by keeping it within this range, high flame resistance can be ensured.
本案發明中使用之聯苯酚具有下述結構。 The biphenol used in the present invention has the following structure.
(上述式中,複數個存在之R1分別獨立存在,表示氫原子或碳數1~3之烷基,k表示1~4之整數) (In the above formula, a plurality of R 1 exist independently, respectively, representing a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and k represents an integer of 1 to 4)
上述結構之聯苯酚存在例如2,2'體、2,4'體、4,4'體等,其中較佳為4,4'體之聯苯酚。 The biphenol having the above structure includes, for example, a 2,2 'body, a 2,4' body, a 4,4 'body, and the like, and among them, a 4,4' body is preferred.
又,可較佳地使用純度為95%以上者。 In addition, those having a purity of 95% or more can be preferably used.
於本發明中,藉由利用表鹵醇使上述式(1)表示之酚樹脂與聯苯酚之混合物同時環氧化而獲得目標環氧樹脂混合物。 In the present invention, a target epoxy resin mixture is obtained by simultaneously epoxidizing a mixture of a phenol resin and biphenol represented by the above formula (1) with epihalohydrin.
此處,上述式(1)表示之酚樹脂(A)與聯苯酚(B)之比率,相對於酚樹脂(A)之羥基當量1莫耳當量,聯苯酚(B)之羥基較佳為0.08~0.43倍莫耳,更佳為0.08~0.33倍莫耳。 Here, the ratio of the phenol resin (A) and the biphenol (B) represented by the above formula (1) is preferably 0.08 with respect to the hydroxyl equivalent of the phenol resin (A), and the hydroxyl group of the biphenol (B) is preferably 0.08 ~ 0.43 times mole, more preferably 0.08 ~ 0.33 times mole.
若為0.08倍莫耳以上,則低黏度化、機械特性得到進一步改善,若為0.43倍莫耳以下,則製造時結晶之析出更少,而產率進一步提昇,又,耐熱性亦進一步提昇。 If it is 0.08 times mole or more, the viscosity is lowered and the mechanical properties are further improved. If it is less than 0.43 times mole, the precipitation of crystals during production is less, the yield is further improved, and the heat resistance is further improved.
以下,記載具體之環氧樹脂混合物之製造方法。 Hereinafter, the specific manufacturing method of an epoxy resin mixture is described.
本發明之環氧樹脂混合物係藉由使上述式(1)表示之酚樹脂(A)與聯苯酚(B)之混合物與表鹵醇進行反應而獲得。此後之下文中,將酚樹脂(A)與聯苯酚(B)之混合物記作本發明之酚樹脂混合物。 The epoxy resin mixture of the present invention is obtained by reacting a mixture of the phenol resin (A) and biphenol (B) represented by the formula (1) with epihalohydrin. Hereinafter, the mixture of phenol resin (A) and biphenol (B) is referred to as the phenol resin mixture of the present invention.
本發明之環氧樹脂混合物之環氧當量相對於作為原料的酚樹脂混合物之理論環氧當量為1.02倍~1.13倍。更佳為1.03~1.10倍。於低於1.02倍之情形時,有環氧之合成、純化花費大量之費用之情況,又,於超過1.11倍之情形時,有產生由上述相同氯量所致之問題之情況。 The epoxy equivalent of the epoxy resin mixture of the present invention is 1.02 times to 1.13 times the theoretical epoxy equivalent of the phenol resin mixture as a raw material. It is more preferably 1.03 to 1.10 times. When it is less than 1.02 times, it may cost a lot of money to synthesize and purify epoxy, and when it is more than 1.11 times, it may cause problems caused by the same amount of chlorine as described above.
又,作為藉由反應所獲得之環氧樹脂混合物中殘留之總氯,較佳為5000ppm以下,更佳為3000ppm以下,尤佳為1000ppm以下。由氯量造成之不良影響與上述相同。再者,關於氯離子、鈉離子,分別較佳為5ppm以下,更佳為3ppm以下。氯離子於上文中有所記載而自不用說,但鈉離子等陽離子亦尤其於功率裝置用途中為非常重要之因素,成為施加高電壓時之不良模式之一原因。 The total chlorine remaining in the epoxy resin mixture obtained by the reaction is preferably 5000 ppm or less, more preferably 3000 ppm or less, and even more preferably 1000 ppm or less. The adverse effects caused by the amount of chlorine are the same as described above. The chloride ion and sodium ion are each preferably 5 ppm or less, and more preferably 3 ppm or less. Chloride ions are described above and needless to say, but cations such as sodium ions are also very important factors especially in power device applications, and become one of the reasons for the poor mode when high voltage is applied.
此處,所謂理論環氧當量,係表示於本發明之酚樹脂混合物之酚性羥基不多不少地環氧丙基化時算出之環氧當量。藉由使環氧當量處於上述範圍內,可獲得硬化物之耐熱性、電氣可靠性優異之環氧樹脂。 Here, the theoretical epoxy equivalent is an epoxy equivalent calculated when the phenolic hydroxyl group of the phenol resin mixture of the present invention is not epoxidized in a large amount. When the epoxy equivalent is within the above range, an epoxy resin having excellent heat resistance and electrical reliability can be obtained.
本發明之環氧樹脂混合物擁有具有軟化點之樹脂狀之形態。此處,軟化點較佳為70~110℃,更佳為80~100℃。若軟化點過低則保管時之黏連(blocking)成為問題,而必須於低溫下進行操作等問題較多。反之,於軟化點過高之情形時,在與其他樹脂(例如硬化劑)混練時,有產生操作性變差等問題之情況。又,熔融黏度較佳為0.05~0.30Pa.s(ICI熔融黏度150℃錐板法),更佳為0.07~0.20Pa.s。於混合無機材料(填料等)而使用之情形時,產生流動性差等問題。 The epoxy resin mixture of the present invention has a resinous form having a softening point. Here, the softening point is preferably 70 to 110 ° C, and more preferably 80 to 100 ° C. If the softening point is too low, blocking during storage becomes a problem, and there are many problems such as having to operate at a low temperature. Conversely, when the softening point is too high, problems such as poor workability may occur when kneaded with other resins (for example, hardeners). The melt viscosity is preferably 0.05 to 0.30 Pa. s (ICI 150 ° C cone-plate method), more preferably 0.07 ~ 0.20Pa. s. When an inorganic material (a filler, etc.) is mixed and used, problems such as poor fluidity arise.
作為本發明之環氧樹脂混合物之合成法中使用之表鹵醇,較佳為工業上容易取得之表氯醇。表鹵醇之使用量相對於本發明之酚樹脂混合物之羥基1莫耳,通常為3.0~15莫耳,較佳為3.0~10莫耳,更佳為3.5~8.5莫耳,尤佳為4.5~8.5莫耳。 As the epihalohydrin used in the method for synthesizing the epoxy resin mixture of the present invention, epichlorohydrin which is easily available industrially is preferred. The amount of epihalohydrin used is 1 mole relative to the hydroxyl group of the phenol resin mixture of the present invention, which is generally 3.0 to 15 moles, preferably 3.0 to 10 moles, more preferably 3.5 to 8.5 moles, and even more preferably 4.5. ~ 8.5 Mol.
若低於3.0莫耳,則有獲得之環氧樹脂混合物之環氧當量變大之情況,又,獲得之環氧樹脂混合物之操作作業性有可能變差。若超過15莫耳則溶劑量變多。 If it is less than 3.0 mol, the epoxy equivalent of the obtained epoxy resin mixture may become large, and the workability of the obtained epoxy resin mixture may be deteriorated. If it exceeds 15 mol, the amount of the solvent increases.
可於上述反應中使用鹼金屬氫氧化物。作為可用於上述反應之鹼金屬氫氧化物,可列舉氫氧化鈉、氫氧化鉀等,可利用固形物,亦可 使用其水溶液,於本發明中,就溶解性、處理之方面而言,尤佳為使用成型為薄片狀之固形物。 An alkali metal hydroxide can be used in the above reaction. Examples of the alkali metal hydroxide that can be used in the above reaction include sodium hydroxide, potassium hydroxide, and the like. A solid substance may be used, or The aqueous solution is used. In the present invention, in terms of solubility and handling, it is particularly preferable to use a solid formed into a sheet shape.
鹼金屬氫氧化物之使用量相對於原料之本發明之酚樹脂混合物之羥基1莫耳,通常為0.90~1.5莫耳,較佳為0.95~1.25莫耳,更佳為0.99~1.15莫耳。 The amount of the alkali metal hydroxide used is 1 mole relative to the hydroxyl group of the phenol resin mixture of the present invention, which is usually 0.90 to 1.5 moles, preferably 0.95 to 1.25 moles, and more preferably 0.99 to 1.15 moles.
為促進反應,亦可添加氯化四甲基銨、溴化四甲基銨、氯化三甲基苄基銨等四級銨鹽作為觸媒。作為四級銨鹽之使用量,相對於原料酚混合物之羥基1莫耳,通常為0.1~15g,較佳為0.2~10g。 To promote the reaction, quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide, and trimethylbenzylammonium chloride can be added as catalysts. The used amount of the quaternary ammonium salt is generally 0.1 to 15 g, preferably 0.2 to 10 g, relative to 1 mole of the hydroxyl group of the raw material phenol mixture.
於本反應中除上述表鹵醇以外,較佳為併用非極性質子溶劑(二甲基亞碸、二烷、二甲基咪唑啶酮等)或碳數1~5之醇。作為碳數1~5之醇,為甲醇、乙醇、異丙醇等醇類。非極性質子溶劑或碳數1~5之醇之使用量相對於表鹵醇之使用量,通常為2~50重量%,較佳為4~25重量%。又,亦可一面藉由共沸脫水等方法控制體系內之水分一面進行環氧化。 In this reaction, in addition to the above epihalohydrin, it is preferred to use a non-polar protic solvent Alkanes, dimethyl imidazolidone, etc.) or alcohols having 1 to 5 carbon atoms. Examples of the alcohol having 1 to 5 carbon atoms include alcohols such as methanol, ethanol, and isopropanol. The amount of the non-polar protic solvent or the alcohol having 1 to 5 carbons is usually 2 to 50% by weight, preferably 4 to 25% by weight, relative to the amount of epihalohydrin. In addition, the epoxidation can also be performed while controlling the moisture in the system by methods such as azeotropic dehydration.
於體系中之水分較多之情形時,有所獲得之環氧樹脂混合物之硬化物之電氣可靠性變差之情況,較佳為將水分控制為5%以下而合成。又,於使用非極性質子溶劑獲得環氧樹脂時可獲得電氣可靠性優異之環氧樹脂混合物之硬化物,故而可較佳地使用非極性質子溶劑。 When there is a large amount of water in the system, the electrical reliability of the hardened product of the epoxy resin mixture obtained may be deteriorated, and it is preferable to synthesize by controlling the water content to 5% or less. In addition, when an epoxy resin is obtained using a non-polar proton solvent, a cured product of an epoxy resin mixture having excellent electrical reliability can be obtained. Therefore, a non-polar proton solvent can be preferably used.
反應溫度通常為30~90℃,較佳為35~80℃。尤其是於本發明中,為進行更高純度之環氧化,較佳為60℃以上,尤佳為於接近回流條件之條件下進行反應。反應時間通常為0.5~10小時,較佳為1~8小時,尤佳為1~3小時。若反應時間短則不完全進行反應,若反應時間變長則產生副產物,故而欠佳。 The reaction temperature is usually 30 to 90 ° C, preferably 35 to 80 ° C. In particular, in the present invention, in order to perform epoxidation with higher purity, it is preferably 60 ° C or higher, and it is particularly preferable to perform the reaction under conditions close to reflux conditions. The reaction time is usually 0.5 to 10 hours, preferably 1 to 8 hours, and particularly preferably 1 to 3 hours. If the reaction time is short, the reaction is not completed, and if the reaction time is long, by-products are generated, which is not preferable.
將該等環氧化反應之反應物水洗後,或不水洗而於加熱減壓下去除表鹵醇或溶劑等。又,為進一步製成水解性鹵素較少之環氧樹脂混合物,亦可以碳數4~7之酮化合物(例如可列舉:甲基異丁基酮、甲基乙基酮、環 戊酮、環己酮等)作為溶劑而溶解所回收之環氧化物,並加入氫氧化鈉、氫氧化鉀等鹼金屬氫氧化物之水溶液進行反應,使之確實地閉環。於此情形時,鹼金屬氫氧化物之使用量相對於環氧化中所使用之酚樹脂混合物之羥基1莫耳,通常為0.01~0.3莫耳,較佳為0.05~0.2莫耳。反應溫度通常為50~120℃,反應時間通常為0.5~2小時。 After washing the reactants of the epoxidation reaction with water, or without washing, the epihalohydrin or the solvent is removed under heating and reduced pressure. In addition, in order to further prepare an epoxy resin mixture with less hydrolyzable halogen, a ketone compound having 4 to 7 carbon atoms (for example, methyl isobutyl ketone, methyl ethyl ketone, and cyclic Pentanone, cyclohexanone, etc.) are dissolved as a solvent to dissolve the recovered epoxide, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to react to make the ring closed reliably. In this case, the amount of the alkali metal hydroxide used is 0.01 to 0.3 mol, preferably 0.05 to 0.2 mol, relative to 1 mol of the hydroxyl group of the phenol resin mixture used in the epoxidation. The reaction temperature is usually 50 to 120 ° C, and the reaction time is usually 0.5 to 2 hours.
反應結束後,藉由過濾、水洗等去除生成之鹽,進而於加熱減壓下蒸餾去除溶劑,藉此獲得本發明之環氧樹脂混合物。 After the reaction is completed, the produced salt is removed by filtration, water washing, etc., and the solvent is distilled off under heating and reduced pressure, thereby obtaining the epoxy resin mixture of the present invention.
本發明之環氧樹脂混合物呈現半晶狀之樹脂狀。 The epoxy resin mixture of the present invention exhibits a semi-crystalline resinous shape.
通常之環氧樹脂混合物為不配向而透明之非晶質狀態之樹脂。於本發明中,該樹脂混合物具有結晶性,成為白濁之不透明之狀態。所謂半晶狀,係表示該狀態,且藉由使之為半晶狀而產生之樹脂之硬度變硬,混練、粉碎時容易粉碎,成為生產性佳之樹脂。此處,半晶狀不僅表示如上所述之白濁之狀態之樹脂,且亦包含即便為非晶質狀態之透明樹脂,於100℃±30℃之範圍反應後放置10分鐘以上,其後慢慢冷卻,藉此白濁者。此種樹脂亦藉由製成樹脂組成物時之混練等,同樣地促進結晶化,有助於生產性。 Common epoxy resin mixtures are non-aligned and transparent amorphous resins. In the present invention, the resin mixture has crystallinity and is in a cloudy and opaque state. The so-called semi-crystalline state means this state, and the hardness of the resin produced by making it semi-crystalline is hardened, and it is easy to pulverize during kneading and pulverization, and it becomes a resin with good productivity. Here, the semi-crystalline state means not only the resin in a state of white turbidity as described above, but also a transparent resin in an amorphous state, which is left to stand for more than 10 minutes after reacting in a range of 100 ° C ± 30 ° C, and then slowly Cool, so that those who are cloudy. Such a resin also promotes crystallization by kneading and the like when making a resin composition, and contributes to productivity.
於本發明之環氧樹脂混合物中,會同時存在上述式(1)表示之酚樹脂之環氧化物及二環氧丙氧基聯苯(其中,於該芳香環具有取代基之情形時,取代基之數為4以下,碳數為4以下),但於如上所述之較佳之條件下之反應中,亦存在上述式(1)表示之酚樹脂結構及聯苯酚結構因表鹵醇而連接之結構。因此,藉由同時使本發明之酚樹脂混合物環氧化,而產生該結構,相對黏度容易變低,就本發明之目標流動性之提昇而言較佳。又,強韌性等機械特性亦提昇。 In the epoxy resin mixture of the present invention, both the epoxide of the phenol resin represented by the above formula (1) and diglycidoxybiphenyl (where the aromatic ring has a substituent, the substitution The number of groups is 4 or less and the number of carbons is 4 or less), but in the reaction under the preferable conditions as described above, the phenol resin structure and the biphenol structure represented by the above formula (1) also exist due to epihalohydrin. The structure. Therefore, by simultaneously epoxidizing the phenol resin mixture of the present invention to produce the structure, the relative viscosity tends to be low, which is better in terms of improving the target fluidity of the present invention. In addition, mechanical properties such as toughness are also improved.
又,與僅使聯苯酚環氧化之情形相比,利用此種製法所獲得之環氧樹脂混合物由於結晶性低,故可容易地進行純化,因此容易地獲得殘留氯量少之環氧樹脂混合物。 In addition, compared with the case where only biphenol is epoxidized, the epoxy resin mixture obtained by this method has low crystallinity and can be easily purified. Therefore, an epoxy resin mixture having a small amount of residual chlorine can be easily obtained. .
於本發明中,具有上述式(1)表示之酚樹脂結構及聯苯酚結構因表鹵醇連接之結構的環氧樹脂於GPC測定之面積%中,較佳為0.01~10面積%,尤佳為0.1~10面積%。 In the present invention, an epoxy resin having a structure in which the phenol resin structure and the biphenol structure represented by the above formula (1) are connected by epihalohydrin is determined by GPC, and is preferably 0.01 to 10 area%, and particularly preferably It is 0.1 to 10 area%.
本發明之環氧樹脂組成物含有本發明之環氧樹脂混合物、硬化觸媒及/或硬化劑。又,較佳為含有其他環氧樹脂作為任意成分。 The epoxy resin composition of this invention contains the epoxy resin mixture of this invention, a hardening catalyst, and / or a hardener. Moreover, it is preferable to contain another epoxy resin as an arbitrary component.
於本發明之環氧樹脂組成物中,除本發明之環氧樹脂混合物以外,亦可含有其他種類之環氧樹脂。於總環氧樹脂中,本發明之環氧樹脂混合物之比例較佳為20重量%以上,更佳為30重量%以上,尤佳為40重量%以上。 The epoxy resin composition of the present invention may contain other types of epoxy resins in addition to the epoxy resin mixture of the present invention. In the total epoxy resin, the proportion of the epoxy resin mixture of the present invention is preferably 20% by weight or more, more preferably 30% by weight or more, and even more preferably 40% by weight or more.
作為可與本發明之環氧樹脂混合物併用之其他環氧樹脂,可列舉:酚醛清漆型環氧樹脂、雙酚型環氧樹脂、聯苯型環氧樹脂、三苯甲烷型環氧樹脂、苯酚芳烷基型環氧樹脂等。具體而言,可列舉:雙酚A、雙酚S、硫代聯苯酚、雙酚茀、萜二酚、4,4'-聯苯酚、2,2'-聯苯酚、3,3',5,5'-四甲基-[1,1'-聯苯]-4,4'-二醇、對苯二酚、間苯二酚、萘二醇、三-(4-羥基苯基)甲烷、1,1,2,2-四(4-羥基苯基)乙烷、酚類(苯酚、烷基取代苯酚、萘酚、烷基取代萘酚、二羥基苯、二羥基萘等)與甲醛、乙醛、苯甲醛、對羥基苯甲醛、鄰羥基苯甲醛、對羥基苯乙酮、鄰羥基苯乙酮、二環戊二烯、糠醛、4,4'-雙(氯甲基)-1,1'-聯苯、4,4'-雙(甲氧基甲基)-1,1'-聯苯、1,4-雙(氯甲基)苯或1,4-雙(甲氧基甲基)苯等之聚縮合物及該等之改質物、四溴雙酚A等鹵代雙酚類以及由醇類衍生之環氧丙基醚化物、脂環式環氧樹脂、環氧丙基胺系環氧樹脂、環氧丙基酯系環氧樹脂、倍半矽氧烷系環氧樹脂(鏈狀、環狀、階梯狀或者該等至少2種以上之混合結構之矽氧烷結構具有環氧丙基及/或環氧環己烷結構之環氧樹脂)等固體或液狀環氧樹脂,但並不限定於該等。 Examples of other epoxy resins that can be used in combination with the epoxy resin mixture of the present invention include novolac epoxy resin, bisphenol epoxy resin, biphenyl epoxy resin, triphenylmethane epoxy resin, and phenol. Aralkyl-type epoxy resin and the like. Specific examples include bisphenol A, bisphenol S, thiobiphenol, bisphenol hydrazone, terpene diphenol, 4,4'-biphenol, 2,2'-biphenol, 3,3 ', 5 , 5'-tetramethyl- [1,1'-biphenyl] -4,4'-diol, hydroquinone, resorcinol, naphthalene glycol, tri- (4-hydroxyphenyl) methane , 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde , Acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4'-bis (chloromethyl) -1 1,1'-biphenyl, 4,4'-bis (methoxymethyl) -1,1'-biphenyl, 1,4-bis (chloromethyl) benzene or 1,4-bis (methoxy) Polycondensates of methyl) benzene, etc., and their modifications, halogenated bisphenols such as tetrabromobisphenol A, and epoxypropyl etherate, alicyclic epoxy resin, and propylene oxide derived from alcohols Based amine epoxy resin, epoxy propyl ester epoxy resin, silsesquioxane epoxy resin (chain, cyclic, stepped, or a mixed structure of at least two or more of these siloxane structures) With epoxy and / or Epoxy cyclohexane structure epoxy resin) and other solid or liquid epoxy resins are not limited to these.
作為本發明中可使用之硬化觸媒(硬化促進劑)之具體例, 可列舉:三乙胺、三丙胺、三丁胺等胺化合物;吡啶、二甲基胺基吡啶、1,8-二氮雜雙環[5.4.0]-7-十一烯、咪唑、三唑、四唑、2-甲基咪唑、2-苯基咪唑、2-十一烷基咪唑、2-十七烷基咪唑、2-苯基-4-甲基咪唑、1-苄基-2-苯基咪唑、1-苄基-2-甲基咪唑、1-氰乙基-2-甲基咪唑、1-氰乙基-2-苯基咪唑、1-氰乙基-2-十一烷基咪唑、2,4-二胺基-6(2'-甲基咪唑(1'))乙基-對稱三、2,4-二胺基-6(2'-十一烷基咪唑(1'))乙基-對稱三、2,4-二胺基-6(2'-乙基,4-甲基咪唑(1'))乙基-對稱三、2,4-二胺基-6(2'-甲基咪唑(1'))乙基-對稱三-異三聚氰酸加成物、2-甲基咪唑異三聚氰酸之2:3加成物、2-苯基咪唑異三聚氰酸加成物、2-苯基-3,5-二羥基甲基咪唑、2-苯基-4-羥基甲基-5-甲基咪唑、1-氰乙基-2-苯基-3,5-二氰基乙氧基甲基咪唑等各種雜環式化合物類;及該等雜環式化合物類與鄰苯二甲酸、間苯二甲酸、對苯二甲酸、1,2,4-苯三甲酸、焦蜜石酸、萘二甲酸、馬來酸、草酸等多元羧酸之鹽類;雙氰胺等醯胺類;1,8-二氮雜雙環(5.4.0)十一烯-7等二氮雜化合物及該等之四苯基硼酸鹽、酚系酚醛清漆等鹽類;與上述多元羧酸類或膦酸類之鹽類;氫氧化四甲基銨、氫氧化四乙基銨、氫氧化四丙基銨、氫氧化四丁基銨、氫氧化三甲基乙基銨、氫氧化三甲基丙基銨、氫氧化三甲基丁基銨、氫氧化三甲基十六烷基銨、氫氧化三辛基甲基銨、氯化四甲基銨、溴化四甲基銨、碘化四甲基銨、乙酸四甲基銨、乙酸三辛基甲基銨等銨鹽;三苯基膦、三(甲苯甲醯基)膦、溴化四苯基鏻、四苯基硼酸四苯基鏻等膦類或鏻化合物;2,4,6-三胺基甲基苯酚等酚類;胺加成物;羧酸金屬鹽(2-乙基己酸、硬脂酸、蘿酸、肉豆蔻酸等之鋅鹽、錫鹽、鋯鹽)或磷酸酯金屬(磷酸辛酯、磷酸硬脂酯等之鋅鹽)、烷氧基金屬鹽(三丁基鋁、四丙基鋯等)、乙醯丙酮鹽(乙醯丙酮鋯螯合物、乙醯丙酮鈦螯合物等)等金屬化合物等。於本發明中,尤其於硬化時之著色或其變化之方面而言, 較佳為鏻鹽或銨鹽、金屬化合物類。又,於使用四級鹽之情形時,有於與鹵素之鹽之硬化物中殘留鹵素之情況。 Specific examples of the hardening catalyst (hardening accelerator) usable in the present invention include amine compounds such as triethylamine, tripropylamine, and tributylamine; pyridine, dimethylaminopyridine, and 1,8-diamine. Azabicyclo [5.4.0] -7-undecene, imidazole, triazole, tetrazole, 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole , 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl 2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,4-diamino-6 (2'-methylimidazole (1 ')) ethyl-symmetric tris , 2,4-diamino-6 (2'-undecylimidazole (1 ')) ethyl-symmetric tris , 2,4-diamino-6 (2'-ethyl, 4-methylimidazole (1 ')) ethyl-symmetric tris , 2,4-diamino-6 (2'-methylimidazole (1 ')) ethyl-symmetric tris -Isotricyanic acid adduct, 2-methylimidazole isotricyanic acid 2: 3 adduct, 2-phenylimidazole isotricyanic acid adduct, 2-phenyl-3,5 -Dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole, etc. Heterocyclic compounds; and these heterocyclic compounds with phthalic acid, isophthalic acid, terephthalic acid, 1,2,4-benzenetricarboxylic acid, pyromelic acid, naphthalenedicarboxylic acid, horse Salts of polycarboxylic acids such as maleic acid and oxalic acid; ammoniums such as dicyandiamide; diaza compounds such as 1,8-diazabicyclo (5.4.0) undecene-7; and tetraphenyl Borates, phenolic novolacs and other salts; salts with the above polycarboxylic acids or phosphonic acids; tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide , Trimethylethylammonium hydroxide, trimethylpropylammonium hydroxide, trimethylbutylammonium hydroxide, trimethylhexadecylammonium hydroxide, trioctylmethylammonium hydroxide, chloride Tetramethylammonium, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium acetate, ethyl Ammonium salts such as trioctylmethylammonium; phosphines or phosphonium compounds such as triphenylphosphine, tris (tolylmethyl) phosphine, tetraphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate; 2,4, 6-triaminomethylphenol and other phenols; amine adducts; carboxylic acid metal salts (zinc, tin and zirconium salts of 2-ethylhexanoic acid, stearic acid, rosic acid, myristic acid, etc.) Or phosphate metal (zinc salt of octyl phosphate, stearyl phosphate, etc.), metal alkoxy salt (tributylaluminum, tetrapropylzirconium, etc.), acetamidine acetone (acetamidine zirconium chelate, Metal compounds such as acetoacetone titanium chelate and the like). In the present invention, sulfonium salts, ammonium salts, and metal compounds are particularly preferred in terms of coloring or changes during curing. In the case where a quaternary salt is used, halogen may remain in a hardened substance with a salt of halogen.
硬化促進劑相對於環氧樹脂100,視需要使用0.01~5.0重量份。 The hardening accelerator is used in an amount of 0.01 to 5.0 parts by weight with respect to the epoxy resin 100 as necessary.
較佳為本發明之環氧樹脂組成物中含有硬化劑。例如可列舉:胺系化合物、酸酐系化合物、醯胺系化合物、酚樹脂、羧酸系化合物等。作為可使用之硬化劑之具體例,可列舉:二胺基二苯基甲烷、二伸乙基三胺、三伸乙基四胺、二胺基二苯基碸、異佛爾酮二胺、雙氰胺、由次亞麻油酸之二聚物及伸乙基二胺合成之聚醯胺樹脂等含氮化合物(胺、醯胺化合物);鄰苯二甲酸酐、1,2,4-苯三甲酸酐、1,2,4-苯三甲酸二酐、馬來酸酐、四氫鄰苯二甲酸酐、甲基四氫鄰苯二甲酸酐、甲基耐地酸酐、耐地酸酐、六氫鄰苯二甲酸酐、甲基六氫鄰苯二甲酸酐、丁烷四羧酸二酐、雙環[2,2,1]庚烷-2,3-二羧酸酐、甲基雙環[2,2,1]庚烷-2,3-二羧酸酐、環己烷-1,3,4-三羧酸-3,4-酐等酸酐;藉由各種醇、甲醇改質聚矽氧與上述酸酐之加成反應而獲得之羧酸樹脂;雙酚A、雙酚F、雙酚S、雙酚茀、萜二酚、4,4'-聯苯酚、2,2'-聯苯酚、3,3',5,5'-四甲基-[1,1'-聯苯]-4,4'-二醇、對苯二酚、間苯二酚、萘二醇、三-(4-羥基苯基)甲烷、1,1,2,2-四(4-羥基苯基)乙烷、酚類(苯酚、烷基取代苯酚、萘酚、烷基取代萘酚、二羥基苯、二羥基萘等)與甲醛、乙醛、苯甲醛、對羥基苯甲醛、鄰羥基苯甲醛、對羥基苯乙酮、鄰羥基苯乙酮、二環戊二烯、糠醛、4,4'-雙(氯甲基)-1,1'-聯苯、4,4'-雙(甲氧基甲基)-1,1'-聯苯、1,4'-雙(氯甲基)苯或1,4'-雙(甲氧基甲基)苯等之聚縮合物及該等之改質物、四溴雙酚A等鹵代雙酚類、萜烯與酚類之縮合物等酚樹脂;咪唑、三氟硼烷-胺錯合物、胍衍生物之化合物等,但並不限定於該等。該等可單獨使用,亦可使用2種以上。 The epoxy resin composition of the present invention preferably contains a hardener. Examples include amine-based compounds, acid anhydride-based compounds, amidine-based compounds, phenol resins, and carboxylic acid-based compounds. Specific examples of usable hardeners include diaminodiphenylmethane, diethylenetriamine, triethylenetriamine, diaminodiphenylphosphonium, isophoronediamine, Nitrogen compounds (amines, amidine compounds) such as dicyandiamide, polyamine resins synthesized from the dimer of linolenic acid and ethylenediamine; phthalic anhydride, 1,2,4-benzene Tricarboxylic anhydride, 1,2,4-benzenetricarboxylic dianhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl dianhydride, phthalic anhydride, hexahydrophthalic anhydride Phthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic dianhydride, bicyclic [2,2,1] heptane-2,3-dicarboxylic anhydride, methylbicyclic [2,2, 1] Acid anhydrides such as heptane-2,3-dicarboxylic anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride; modification of polysiloxane with various alcohols and methanol Carboxylic acid resin obtained by addition reaction; bisphenol A, bisphenol F, bisphenol S, bisphenol hydrazone, terpene diphenol, 4,4'-biphenol, 2,2'-biphenol, 3,3 ' , 5,5'-tetramethyl- [1,1'-biphenyl] -4,4'-diol, hydroquinone, resorcinol, naphthalene glycol, tri- (4-hydroxyphenyl Methane, 1,1,2 , 2-tetrakis (4-hydroxyphenyl) ethane, phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde , P-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4'-bis (chloromethyl) -1,1'-biphenyl , 4,4'-bis (methoxymethyl) -1,1'-biphenyl, 1,4'-bis (chloromethyl) benzene, or 1,4'-bis (methoxymethyl) benzene Polycondensates and their modified products, halogenated bisphenols such as tetrabromobisphenol A, phenol resins such as condensates of terpenes and phenols; imidazole, trifluoroborane-amine complexes, guanidine derivatives But not limited to these. These can be used alone or in combination of two or more.
於本發明中,為了尤其用於電子材料用途,較佳為上述酚樹脂。 In the present invention, in order to be used especially for electronic material applications, the aforementioned phenol resin is preferred.
本發明之環氧樹脂組成物(以下,亦稱為硬化性樹脂組成物)中之硬化劑之使用量相對於環氧樹脂之環氧基1當量,較佳為0.7~1.2當量。於相對於環氧基1當量未達0.7當量、或者超過1.2當量之情形時,均有硬化不完全而無法獲得良好之硬化物性之情況。 The usage-amount of the hardening | curing agent in the epoxy resin composition (henceforth a curable resin composition) of this invention is 0.7-1.2 equivalent with respect to 1 equivalent of epoxy groups of an epoxy resin. When the equivalent of epoxy equivalent is less than 0.7 equivalent or exceeds 1.2 equivalent, there are cases where the hardening is incomplete and good hardened physical properties cannot be obtained.
再者,作為其他成分,較佳為使用氰酸酯化合物。氰酸酯化合物除單獨進行硬化反應以外,可藉由與環氧樹脂之反應,而製成交聯密度更高之耐熱性之硬化物。作為氰酸酯樹脂,例如可列舉:2,2-雙(4-氰酸酯基苯基)丙烷、雙(3,5-二甲基-4-氰酸酯基苯基)甲烷、2,2-雙(4-氰酸酯基苯基)乙烷、該等之衍生物、芳香族氰酸酯化合物等。又,例如亦可藉由如上述硬化材料中記載之各種酚樹脂與氰酸或其鹽類之反應而合成。於本發明中尤佳為如2,2-雙(4-氰酸酯基苯基)丙烷或其衍生物(部分聚合物等)般分子內不具有苄基位之亞甲基結構之結構者,該等可單獨使用1種,亦可併用2種以上。 Moreover, it is preferable to use a cyanate ester compound as another component. In addition to the cyanate ester compound undergoing a hardening reaction alone, it can be made into a heat-resistant hardened material with a higher crosslink density by reaction with an epoxy resin. Examples of the cyanate resin include 2,2-bis (4-cyanatephenyl) propane, bis (3,5-dimethyl-4-cyanatephenyl) methane, and 2, 2-bis (4-cyanatophenyl) ethane, derivatives thereof, aromatic cyanate compounds, and the like. Moreover, it can synthesize | combine by reaction of various phenol resin as described in the said hardening material with cyanic acid or its salt, for example. Particularly preferred in the present invention is a structure that does not have a methylene structure in the molecule like a 2,2-bis (4-cyanatephenyl) propane or a derivative thereof (partial polymer, etc.). These can be used alone or in combination of two or more.
本發明之環氧樹脂組成物中亦可含有含磷化合物作為難燃性賦予成分。含磷化合物可為反應型者亦可為添加型者。作為含磷化合物之具體例,可列舉:磷酸三甲酯、磷酸三乙酯、磷酸三甲酚酯、磷酸三(二甲苯)酯、磷酸甲酚基二苯酯、磷酸甲酚基-2,6-二(二甲苯)酯、1,3-伸苯基雙(磷酸二(二甲苯)酯)、1,4-伸苯基雙(磷酸二(二甲苯)酯)、4,4'-聯苯基(磷酸二(二甲苯)酯)等磷酸酯類;9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物、10(2,5-二羥基苯基)-10H-9-氧雜-10-磷雜菲-10-氧化物等膦類;使環氧樹脂與上述膦類活性氫反應而獲得之含磷環氧化合物、紅磷等,較佳為磷酸酯類、膦類或含磷環氧化合物,尤佳為1,3-伸苯基雙(磷酸二(二甲苯)酯)、1,4-伸苯基雙(磷酸二(二甲苯)酯)、4,4'-聯苯基(磷酸二(二甲苯)酯)或含磷環氧化合物。含磷化合物之含量較佳為含磷化合物/總環氧樹脂=0.1~0.6(重量比)。若未達 0.1則有難燃性不充分之情況,若超過0.6則有對硬化物之吸濕性、介電特性造成不良影響之情況。 The epoxy resin composition of the present invention may contain a phosphorus-containing compound as a flame retardancy-imparting component. The phosphorus-containing compound may be a reactive type or an additive type. Specific examples of the phosphorus-containing compound include trimethyl phosphate, triethyl phosphate, tricresol phosphate, tricresyl phosphate, cresol phosphate diphenyl ester, and cresol phosphate-2,6. -Di (xylene) ester, 1,3-phenylene bis (di (xylyl) phosphate), 1,4-phenylene bis (di (xyl) phosphate), 4,4'-diphenyl Phosphoric acid esters such as phenyl (bis (xylyl phosphate)); 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10 (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide and other phosphines; phosphorus-containing epoxy compounds, red phosphorus, etc. obtained by reacting epoxy resin with the above-mentioned phosphine active hydrogen, preferably phosphoric acid Esters, phosphines or phosphorus-containing epoxy compounds, particularly preferably 1,3-phenylene bis (dimethyl (xyl) phosphate), 1,4-phenylene bis (dimethyl (xyl) phosphate) , 4,4'-biphenyl (di (xylyl phosphate)) or a phosphorus-containing epoxy compound. The content of the phosphorus-containing compound is preferably phosphorus-containing compound / total epoxy resin = 0.1 to 0.6 (weight ratio). If not reached If 0.1, the flame retardance may be insufficient. If it exceeds 0.6, the moisture absorption and dielectric properties of the cured product may be adversely affected.
進而,本發明之環氧樹脂組成物中亦可視需要摻合黏合劑樹脂。作為黏合劑樹脂,可列舉:丁醛系樹脂、縮醛系樹脂、丙烯酸系樹脂、環氧-尼龍系樹脂、NBR-酚系樹脂、環氧-NBR系樹脂、聚醯胺系樹脂、聚醯亞胺系樹脂、聚矽氧系樹脂等,但並不限定於該等。黏合劑樹脂之摻合量較佳為無損硬化物之難燃性、耐熱性之範圍,相對於環氧樹脂與硬化劑之合計100重量份,通常視需要使用0.05~50重量份,較佳為0.05~20重量份。 Further, an adhesive resin may be blended into the epoxy resin composition of the present invention as necessary. Examples of the binder resin include a butyral resin, an acetal resin, an acrylic resin, an epoxy-nylon resin, an NBR-phenol resin, an epoxy-NBR resin, a polyamide resin, and a polyfluorene resin. The imine-based resin, the polysiloxane-based resin, and the like are not limited thereto. The blending amount of the binder resin is preferably in a range that does not damage the flame retardancy and heat resistance of the hardened material. It is generally used in an amount of 0.05 to 50 parts by weight based on 100 parts by weight of the total amount of the epoxy resin and the hardener. 0.05 ~ 20 parts by weight.
本發明之環氧樹脂組成物中,可視需要添加無機填充劑。作為無機填充劑,可列舉:結晶矽石、熔融矽石、氧化鋁、鋯英石、矽酸鈣、碳酸鈣、碳化矽、氮化矽、氮化硼、氧化鋯、鎂橄欖石、塊滑石、尖晶石、二氧化鈦、滑石等粉體或使該等球形化而成之珠粒等,但並不限定於該等。該等填充材料可單獨使用,亦可使用2種以上。該等無機填充劑之含量雖亦取決於用途,但於本發明之環氧樹脂組成物中一般使用占0~95重量%之量,尤其於密封材料之用途中使用之情形時,較佳為根據封裝之形狀於較佳為50~95重量%、尤佳為65~95重量%之範圍而區別使用。進而,於本發明之環氧樹脂組成物中,可添加抗氧化劑、光穩定劑、矽烷偶合劑、硬脂酸、棕櫚酸、硬脂酸鋅、硬脂酸鈣等脫模劑、顏料等各種複合劑、各種熱硬化性樹脂。關於偶合材料,尤佳為添加具有環氧基之偶合材料、或具有硫醇基之偶合材料。 In the epoxy resin composition of the present invention, an inorganic filler may be added as necessary. Examples of the inorganic filler include crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, forsterite, and talc , Spinel, titanium dioxide, talc and other powders or beads made of these spheres, but it is not limited to these. These fillers can be used alone or in combination of two or more. Although the content of these inorganic fillers also depends on the application, it is generally used in an amount of 0 to 95% by weight in the epoxy resin composition of the present invention, especially when it is used in the application of a sealing material. According to the shape of the package, it is preferably used in a range of preferably 50 to 95% by weight, particularly preferably 65 to 95% by weight. Furthermore, to the epoxy resin composition of the present invention, various additives such as antioxidants, light stabilizers, silane coupling agents, stearic acid, palmitic acid, zinc stearate, calcium stearate, and pigments can be added. Compounding agents and various thermosetting resins. The coupling material is particularly preferably a coupling material having an epoxy group or a coupling material having a thiol group.
本發明之環氧樹脂組成物係藉由將各成分均勻地混合而獲得。本發明之環氧樹脂組成物可利用與先前已知之方法相同之方法而容易地製成其硬化物。例如視需要使用擠出機、捏合機、輥、行星混合機等而將環氧樹脂成分及硬化劑成分以及視需要之硬化促進劑、含磷化合物、黏 合劑樹脂、無機填充材料及摻合劑等充分地混合直至均勻而獲得環氧樹脂組成物,於所獲得之環氧樹脂組成物為液狀之情形時,藉由灌注或澆鑄,將該組成物含浸於基材,或流入至模具中進行澆鑄成型,藉由加熱使之硬化。又,於所獲得之環氧樹脂組成物為固體之情形時,熔融後澆鑄成型,或者使用轉移成型機等使之成型,進而藉由加熱使之硬化。硬化溫度、時間為80~200℃及2~10小時。作為硬化方法,亦可於高溫下使之瞬間硬化,但較佳為逐步升溫,而推進硬化反應。具體而言,於80~150℃之間進行初期硬化,於100℃~200℃之間進行後硬化。作為硬化之階段,較佳為分為2~8個階段升溫,更佳為2~4個階段。 The epoxy resin composition of this invention is obtained by mixing each component uniformly. The epoxy resin composition of the present invention can be easily made into a cured product by the same method as the conventionally known method. For example, if necessary, an extruder, a kneader, a roller, a planetary mixer, etc. are used to combine the epoxy resin component and the hardener component, and the hardening accelerator, phosphorus compound, The mixture resin, the inorganic filler, and the admixture are sufficiently mixed until uniform to obtain an epoxy resin composition. When the obtained epoxy resin composition is liquid, the composition is impregnated by pouring or casting. It is cast on a substrate or poured into a mold, and is hardened by heating. In the case where the obtained epoxy resin composition is solid, it is casted after being melted, or molded using a transfer molding machine or the like, and then hardened by heating. The hardening temperature and time are 80 ~ 200 ℃ and 2 ~ 10 hours. As a hardening method, it may be hardened instantaneously at a high temperature, but it is preferable to gradually increase the temperature and advance the hardening reaction. Specifically, initial hardening is performed at 80 to 150 ° C, and post-hardening is performed at 100 to 200 ° C. The hardening stage is preferably divided into 2 to 8 stages, and more preferably 2 to 4 stages.
又,使本發明之環氧樹脂組成物溶解於甲苯、二甲苯、丙酮、甲基乙基酮、甲基異丁基酮、二甲基甲醯胺、二甲基乙醯胺、N-甲基吡咯啶酮等溶劑,製成硬化性樹脂組成物清漆,並使其含浸於玻璃纖維、碳纖維、聚酯纖維、聚醯胺纖維、氧化鋁纖維、紙等基材並進行加熱乾燥而獲得預浸體,對所得之預浸體進行熱壓成形,藉此可製成本發明之環氧樹脂組成物之硬化物。此時之溶劑使用於本發明之環氧樹脂組成物與該溶劑之混合物中通常占10~70重量%、較佳為占15~70重量%之量。 The epoxy resin composition of the present invention is dissolved in toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, and N-formaldehyde. A solvent such as pyrrolidone is used to prepare a hardening resin composition varnish, which is impregnated with glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, and other substrates, and dried by heating to obtain a preliminary The hardened body of the epoxy resin composition of the present invention can be prepared by hot pressing forming the obtained prepreg. The solvent used at this time in the mixture of the epoxy resin composition of the present invention and the solvent usually accounts for 10 to 70% by weight, preferably 15 to 70% by weight.
作為該等組成物之具體用途,可列舉:接著劑、塗料、塗佈劑、成形材料(包含片材、膜、FRP等)、絕緣材料(包含印刷基板、電線被覆等之除密封材料以外、及密封材料、基板用氰酸酯樹脂組成物)、或對作為抗蝕劑用硬化劑之丙烯酸酯系樹脂等其他樹脂等之添加劑等。於本發明中,尤佳為用於電子材料用之絕緣材料(包含印刷基板、電線被覆等之除密封材料以外、及密封材料、基板用之氰酸酯樹脂組成物)。 Specific applications of these compositions include adhesives, coatings, coating agents, molding materials (including sheets, films, FRP, etc.), insulating materials (including printed circuit boards, wire coatings, etc., in addition to sealing materials, And sealing materials, cyanate resin compositions for substrates), additives to other resins such as acrylate resins as hardeners for resists, and the like. In the present invention, it is particularly preferred that it is an insulating material for electronic materials (including printed circuit boards, wire coatings, etc., in addition to sealing materials, and sealing materials, and cyanate resin compositions for substrates).
作為接著劑,除土木用、建築用、汽車用、一般事務用、醫療用之接著劑以外,可列舉電子材料用之接著劑。作為該等中電子材料用之接著劑,可列舉:增層基板等多層基板之層間接著劑、黏晶(die bonding) 劑、底膠(underfill)等半導體用接著劑、BGA加強用底膠、各向異性導電膜(ACF)、各向異性導電膏(ACP)等安裝用接著劑等。 Examples of the adhesive include adhesives for civil engineering, construction, automotive, general office, and medical use, and adhesives for electronic materials. Examples of such adhesives for electronic materials include indirect coating of layers of multilayer substrates such as build-up substrates, and die bonding. Adhesives, semiconductor adhesives such as underfills, BGA reinforcement primers, anisotropic conductive films (ACF), anisotropic conductive pastes (ACP), and other mounting adhesives.
作為密封劑、基板,可列舉:電容器、電晶體、二極體、發光二極體、IC、LSI等用之灌注、浸漬、轉注成型密封、IC、LSI類之COB、COF、TAB等用之灌注密封、倒裝晶片等用之底膠、QFP、BGA、CSP等IC封裝類安裝時之密封(包含加強用底膠)及封裝基板等。又,亦適於網路基板或模組基板之要求功能性之基板用途。 Examples of the sealant and substrate include capacitors, transistors, diodes, light-emitting diodes, ICs, LSIs, etc. used for potting, dipping, injection molding, and IC, LSI-based COB, COF, and TAB. Primers for potting and sealing, flip-chips, etc., IC packaging such as QFP, BGA, CSP, etc. (including primers for reinforcement) and package substrates for mounting. In addition, it is also suitable for network substrates or module substrates that require functionality.
本發明之環氧樹脂組成物尤佳為用於半導體裝置。 The epoxy resin composition of the present invention is particularly preferably used in a semiconductor device.
半導體裝置成為上述列舉之IC封裝群。 The semiconductor device becomes the IC package group listed above.
本發明之半導體裝置係藉由利用本發明之環氧樹脂組成物將設置於封裝基板或模具等支持體之矽晶片密封而獲得。成型溫度、成型方法係如上所述。 The semiconductor device of the present invention is obtained by sealing a silicon wafer provided on a support such as a package substrate or a mold with the epoxy resin composition of the present invention. The molding temperature and molding method are as described above.
[實施例] [Example]
其次,藉由實施例進一步具體地說明本發明,以下內容中,份只要未特別事先說明即為重量份。再者,本發明並不限定於該等實施例。 Next, the present invention will be described more specifically by way of examples. In the following description, parts are parts by weight unless otherwise specified. The present invention is not limited to these examples.
以下記載實施例中所使用之各種分析方法。 Various analysis methods used in the examples are described below.
環氧當量:依據JIS K 7236(ISO 3001) Epoxy equivalent: according to JIS K 7236 (ISO 3001)
ICI熔融黏度:依據JIS K 7117-2(ISO 3219) ICI melt viscosity: according to JIS K 7117-2 (ISO 3219)
軟化點:依據JIS K 7234 Softening point: According to JIS K 7234
總氯:依據JIS K 7243-3(ISO 21672-3) Total chlorine: according to JIS K 7243-3 (ISO 21672-3)
氯離子:依據JIS K 7243-1(ISO 21672-1) Chloride: in accordance with JIS K 7243-1 (ISO 21672-1)
GPC: GPC:
管柱(Shodex KF-603、KF-602.5、KF-602、KF-601×2) Columns (Shodex KF-603, KF-602.5, KF-602, KF-601 × 2)
連結溶離液為四氫呋喃 Tetrahydrofuran
流速為0.5ml/min Flow rate is 0.5ml / min
管柱溫度為40℃ 40 ° C column temperature
檢測:RI(示差折射率檢測器) Detection: RI (differential refractive index detector)
(實施例1) (Example 1)
於具備攪拌機、回流冷卻管、攪拌裝置之燒瓶,一面實施氮氣沖洗一面加入依據國際公開第2007/007827號所製造之酚樹脂((a)/(b)=1.3、n=1.5、(RP結構)/(RR結構)=2.15、(RP結構)/(PP結構)=2.1(GPC測定)、羥基當量134g/eq.、軟化點93℃)132份、4,4'-聯苯酚29.3份(相對於酚樹脂(A)之羥基當量1莫耳當量,聯苯酚(B)之羥基為0.32倍莫耳)、表氯醇541份(相對於酚樹脂為4.5莫耳當量)、二甲基亞碸124份,於攪拌下將其等溶解,升溫至40~45℃。繼而,歷時90分鐘分批添加薄片狀之氫氧化鈉54.6份後,進而於40℃反應1小時,於60℃反應1小時,於70℃反應1小時。反應結束後,使用旋轉蒸發器於減壓下蒸餾去除過量之表氯醇等溶劑類。於殘留物中加入甲基異丁基酮500份並將其溶解,利用水300份進行水洗後,升溫至70℃。於攪拌下加入30重量%之氫氧化鈉水溶液17份,進行反應1小時,其後進行水洗直至油層之清洗液變為中性,使用旋轉蒸發器於減壓下自所獲得之溶液蒸餾去除甲基異丁基酮等,藉此獲得本發明之環氧樹脂混合物(EP1)201份。所獲得之環氧樹脂混合物(EP1)之環氧當量為192g/eq.,於軟化點95℃、150℃之熔融黏度(ICI熔融黏度錐板#1)為0.11Pa.s。又,利用凝膠滲透層析法測定所獲得之環氧樹脂混合物(EP1),結果確認出含有聯苯酚之環氧樹脂15.3面積%,並確認出含有上述式(1)中n=0之環氧化物28.8面積%、n=1之環氧化物17.6面積%。 Add a phenol resin ((a) / (b) = 1.3, n = 1.5, (RP structure) manufactured according to International Publication No. 2007/007827 to a flask equipped with a stirrer, a reflux cooling tube, and a stirring device while purging with nitrogen. ) / (RR structure) = 2.15, (RP structure) / (PP structure) = 2.1 (determined by GPC), hydroxyl equivalent 134g / eq., Softening point 93 ° C) 132 parts, 4,4'-biphenol 29.3 parts ( 1 mol equivalent with respect to the hydroxy equivalent of phenol resin (A), 0.32 times mol equivalent with biphenol (B)), 541 parts of epichlorohydrin (4.5 mol equivalent with respect to phenol resin), dimethylene碸 124 parts, dissolve them with stirring, and raise the temperature to 40 ~ 45 ° C. Then, 54.6 parts of flake-shaped sodium hydroxide was added in portions over 90 minutes, and then reacted at 40 ° C for 1 hour, 60 ° C for 1 hour, and 70 ° C for 1 hour. After completion of the reaction, excess solvents such as epichlorohydrin were distilled off under reduced pressure using a rotary evaporator. To the residue, 500 parts of methyl isobutyl ketone was added and dissolved, and after washing with 300 parts of water, the temperature was raised to 70 ° C. 17 parts of a 30% by weight sodium hydroxide aqueous solution was added under stirring, and the reaction was performed for 1 hour, followed by water washing until the cleaning solution of the oil layer became neutral, and the formazan was distilled off from the obtained solution under reduced pressure using a rotary evaporator. Based on isobutyl ketone, etc., thereby obtaining 201 parts of the epoxy resin mixture (EP1) of the present invention. The epoxy equivalent of the obtained epoxy resin mixture (EP1) was 192 g / eq., And the melt viscosity (ICI melt viscosity cone plate # 1) at a softening point of 95 ° C and 150 ° C was 0.11 Pa. s. The obtained epoxy resin mixture (EP1) was measured by gel permeation chromatography. As a result, it was confirmed that the epoxy resin containing biphenol contained 15.3 area%, and it was confirmed that the ring containing n = 0 in the formula (1) was contained. 28.8 area% of oxide, 17.6 area% of epoxide with n = 1.
(實施例2及比較例1) (Example 2 and Comparative Example 1)
使用上述所獲得之環氧樹脂混合物(EP1)或者比較用環氧樹脂(EP2:於實施例1中將酚樹脂變更為172份,且不添加聯苯酚者),以等當量摻合 環氧樹脂及硬化劑(P-1:苯酚芳烷基樹脂(日本化藥(股)製造KAYAHARD GPH-65)、P-2:苯酚芳烷基樹脂(三井化學(股)製造Milex XLC-3L)),並摻合硬化觸媒(硬化促進劑:三苯基膦(北興化學(股)製造TPP))與視需要之填料(熔融矽石瀧森製造MSR-2122表中之填料量%係占整個環氧樹脂組成物之比例),使用混合輥均勻地混合、混練,而獲得硬化性樹脂組成物。利用混合機將該硬化性樹脂組成物粉碎,進而利用壓片機進行壓片化。將該壓片化後之硬化性樹脂組成物轉移成型(175℃×60秒)並進而脫模,其後於160℃×2小時+180℃×6小時之條件下進行硬化,獲得評價用試片。 Using the epoxy resin mixture (EP1) obtained above or the comparative epoxy resin (EP2: the phenol resin was changed to 172 parts in Example 1 without adding biphenol), and blended in equivalent amounts Epoxy resin and hardener (P-1: phenol aralkyl resin (KAYAHARD GPH-65 manufactured by Nippon Kayaku Co., Ltd.), P-2: phenol aralkyl resin (Milex XLC-3L manufactured by Mitsui Chemicals Co., Ltd.) )), And blending hardening catalyst (hardening accelerator: triphenylphosphine (TPP manufactured by Beixing Chemical Co., Ltd.)) and fillers as needed (filler content in the table of MSR-2122 manufactured by Fused Silica Mori The proportion of the entire epoxy resin composition) is uniformly mixed and kneaded using a mixing roller to obtain a curable resin composition. This curable resin composition was pulverized by a mixer, and further tabletted by a tableting machine. The tablet-shaped curable resin composition was transferred to a mold (175 ° C × 60 seconds) and further demolded, and then cured at 160 ° C × 2 hours + 180 ° C × 6 hours to obtain an evaluation test. sheet.
使用該評價用試片,按照以下之要點測定硬化物之物性。再者,根據硬化物之物性之評價項目,使用之硬化劑種類係如下述表1所示,關於硬化促進劑之使用量,耐熱性及收縮率之評價中使用之試樣中,相對於環氧樹脂重量為1%,難燃性之評價中使用之試樣中,相對於環氧樹脂重量為2%。試驗結果亦示於下述表1。 Using this test piece for evaluation, the physical properties of the cured product were measured in accordance with the following points. In addition, according to the evaluation items of the physical properties of the hardened material, the types of hardener used are as shown in Table 1 below. Among the samples used in the evaluation of the amount of hardening accelerator, heat resistance, and shrinkage, The weight of the oxygen resin was 1%, and the sample used for the evaluation of the flame retardancy was 2% relative to the weight of the epoxy resin. The test results are also shown in Table 1 below.
<TMA測定條件> <TMA measurement conditions>
熱機械測定裝置TA-instruments製造、Q400EM Manufacture of thermo-mechanical measuring device TA-instruments, Q400EM
測定溫度範圍:40℃~280℃ Measuring temperature range: 40 ℃ ~ 280 ℃
升溫速度:2℃/分鐘 Heating rate: 2 ° C / min
<難燃性試驗> <Flammability test>
.難燃性之判定:依據UL94進行。其中,以樣品尺寸為寬度12.5mm×長度150mm,厚度為0.8mm之條件進行試驗。 . Judgment of flame retardancy: According to UL94. The test was performed under the conditions that the sample size was 12.5 mm in width × 150 mm in length and 0.8 mm in thickness.
.殘焰時間:使5個為1組之樣品接觸火焰10次後之殘焰時間之合計 . Residual flame time: The total amount of residual flame time after 5 samples of a group are exposed to the flame 10 times
<硬化收縮> <Hardening shrinkage>
依據JISK-6911(成型收縮率) According to JISK-6911 (molding shrinkage)
相對於比較例1,不論是否含有聯苯酚之環氧化物,均可保持耐熱性,改善收縮率,又,於難燃性試驗中即便改變硬化劑,燃燒時間亦縮短,因此本發明之環氧樹脂組成物可兼具較高之耐熱性及難燃性。 Compared with Comparative Example 1, epoxide containing or without biphenol can maintain heat resistance and improve shrinkage. In addition, even if the hardener is changed in the flame retardancy test, the burning time is shortened. Therefore, the epoxy resin of the present invention The resin composition can have both high heat resistance and flame resistance.
(實施例3) (Example 3)
於具備攪拌機、回流冷卻管、攪拌裝置之燒瓶,一面實施氮氣沖洗一面加入依據國際公開第2007/007827號所製造之酚樹脂((a)/(b)=1.3、n=1.5、(RP結構)/(RR結構)=2.15、(RP結構)/(PP結構)=2.1(GPC測定)、羥基當量134g/eq.、軟化點93℃)97.8份、4,4'-聯苯酚25.1份(相對於酚樹脂(A)之羥基當量1莫耳當量,聯苯酚(B)之羥基為0.37倍莫耳)、表氯醇555份(相對於酚樹脂為6莫耳當量)、甲醇55.5份,於攪拌下將其等溶解,升溫至70℃。繼而,歷時90分鐘分批添加薄片狀之氫氧化鈉42份後,於70℃反應1小時。反應結束後進行水洗,然後使用旋轉蒸發器於減壓下,將所獲得之有機層之過量之表氯醇等溶劑類蒸餾去除。於殘留物中加入甲基異丁基酮500份將其溶解,升溫至70℃。於攪拌下加入30重量%之氫氧化鈉水溶液10份,進行反應1小時,其後進行水洗直至油層之清洗液變為中性,使用旋轉蒸發器於減壓下自所獲得之溶液蒸餾去 除甲基異丁基酮等,藉此獲得本發明之環氧樹脂混合物(EP3)161份。所獲得之環氧樹脂混合物(EP3)之環氧當量為192g/eq.,於軟化點82℃、150℃之熔融黏度(ICI熔融黏度錐板#1)為0.07Pa.s。又,利用凝膠滲透層析法測定所獲得之環氧樹脂混合物(EP3),結果確認出含有聯苯酚之環氧樹脂12.0面積%,並確認出含有上述式(1)中n=0之環氧化物24.4面積%、n=1之環氧化物16.5面積%。 Add a phenol resin ((a) / (b) = 1.3, n = 1.5, (RP structure) manufactured according to International Publication No. 2007/007827 to a flask equipped with a stirrer, a reflux cooling tube, and a stirring device while purging with nitrogen. ) / (RR structure) = 2.15, (RP structure) / (PP structure) = 2.1 (determined by GPC), hydroxyl equivalent 134g / eq., Softening point 93 ° C) 97.8 parts, 2,4'-biphenol 25.1 parts ( The hydroxyl equivalent of phenol resin (A) is 1 mole equivalent, the hydroxyl group of biphenol (B) is 0.37 moles), 555 parts of epichlorohydrin (6 mole equivalents to phenol resin), and 55.5 parts of methanol. These were dissolved under stirring, and the temperature was raised to 70 ° C. Then, 42 parts of flake-shaped sodium hydroxide was added in portions over 90 minutes, and then reacted at 70 ° C for 1 hour. After completion of the reaction, the resultant was washed with water, and then the excess organic solvent such as epichlorohydrin was distilled off under reduced pressure using a rotary evaporator. 500 parts of methyl isobutyl ketone was added to the residue to dissolve it, and the temperature was raised to 70 ° C. 10 parts of a 30% by weight aqueous solution of sodium hydroxide was added under stirring, and the reaction was performed for 1 hour, followed by washing with water until the cleaning solution of the oil layer became neutral, and the resulting solution was distilled off under reduced pressure using a rotary evaporator. By removing methyl isobutyl ketone and the like, 161 parts of the epoxy resin mixture (EP3) of the present invention was obtained. The epoxy equivalent of the obtained epoxy resin mixture (EP3) was 192 g / eq., And the melt viscosity (ICI melt viscosity cone plate # 1) at a softening point of 82 ° C and 150 ° C was 0.07 Pa. s. The obtained epoxy resin mixture (EP3) was measured by gel permeation chromatography. As a result, it was confirmed that the epoxy resin containing biphenol contained 12.0 area%, and it was confirmed that the ring containing n = 0 in the above formula (1) was contained. 24.4 area% of oxide, 16.5 area% of epoxide with n = 1.
(實施例4) (Example 4)
於具備攪拌機、回流冷卻管、攪拌裝置之燒瓶,一面實施氮氣沖洗一面加入依據國際公開第2007/007827號所製造之酚樹脂((a)/(b)=1.3、n=1.5、(RP結構)/(RR結構)=2.15、(RP結構)/(PP結構)=2.1(GPC測定)、羥基當量134g/eq.、軟化點93℃)101.8份、4,4'-聯苯酚22.3份(相對於酚樹脂(A)之羥基當量1莫耳當量,聯苯酚(B)之羥基為0.316倍莫耳)、表氯醇555份(相對於酚樹脂為6莫耳當量)、二甲基亞碸125份,於攪拌下將其等溶解,升溫至40~45℃。繼而,歷時90分鐘分批添加薄片狀之氫氧化鈉42份後,進而於40℃反應1小時,於60℃反應1小時,於70℃反應1小時。反應結束後,使用旋轉蒸發器於減壓下,蒸餾去除過量之表氯醇等溶劑類。於殘留物中加入甲基異丁基酮500份將其溶解,利用水300份進行水洗後,升溫至70℃。於攪拌下加入30重量%之氫氧化鈉水溶液10份,進行反應1小時,其後進行水洗直至油層之清洗液變為中性,使用旋轉蒸發器於減壓下自所獲得之溶液蒸餾去除甲基異丁基酮等,藉此獲得本發明之環氧樹脂混合物(EP4)159份。所獲得之環氧樹脂混合物(EP4)之環氧當量為189g/eq.,於軟化點98℃、150℃之熔融黏度(ICI熔融黏度錐板#1)為0.08Pa.s。又,利用凝膠滲透層析法測定所獲得之環氧樹脂混合物(EP4),結果確認出含有聯苯酚之環氧樹脂14.9面積%,並確認出含有上述式(1)中n=0之環氧化物29.3面積%、n=1之環氧化物18.6面積 %。 Add a phenol resin ((a) / (b) = 1.3, n = 1.5, (RP structure) manufactured according to International Publication No. 2007/007827 to a flask equipped with a stirrer, a reflux cooling tube, and a stirring device while purging with nitrogen. ) / (RR structure) = 2.15, (RP structure) / (PP structure) = 2.1 (determined by GPC), hydroxyl equivalent 134g / eq., Softening point 93 ° C) 101.8 parts, 4,4'-biphenol 22.3 parts ( 1 mol equivalent with respect to the hydroxyl equivalent of phenol resin (A), 0.316 times mol equivalent with biphenol (B)), 555 parts of epichlorohydrin (6 mol equivalent with respect to phenol resin), dimethylene碸 125 parts, dissolve them under stirring, and raise the temperature to 40 ~ 45 ° C. Then, 42 parts of flake-shaped sodium hydroxide was added in portions over 90 minutes, and then reacted at 40 ° C for 1 hour, 60 ° C for 1 hour, and 70 ° C for 1 hour. After the reaction was completed, excess solvent such as epichlorohydrin was distilled off under reduced pressure using a rotary evaporator. 500 parts of methyl isobutyl ketone was added to the residue to dissolve it, and after washing with 300 parts of water, the temperature was raised to 70 ° C. 10 parts of a 30% by weight sodium hydroxide aqueous solution was added under stirring, and the reaction was performed for 1 hour, followed by water washing until the cleaning solution of the oil layer became neutral, and the formazan was distilled off from the obtained solution using a rotary evaporator under reduced pressure. Butyl isobutyl ketone, etc., thereby obtaining 159 parts of the epoxy resin mixture (EP4) of the present invention. The epoxy equivalent of the obtained epoxy resin mixture (EP4) was 189 g / eq., And its melt viscosity (ICI melt viscosity cone plate # 1) at a softening point of 98 ° C and 150 ° C was 0.08 Pa. s. The obtained epoxy resin mixture (EP4) was measured by gel permeation chromatography. As a result, it was confirmed that the epoxy resin containing biphenol contained 14.9 area%, and it was confirmed that the ring containing n = 0 in the formula (1) was contained. 29.3 area% of oxide, n = 18.6 area of epoxide %.
(實施例5、6) (Examples 5 and 6)
以表2之比例(當量)摻合硬化劑(P-3:酚系酚醛清漆(明和化成工業(股)製造H-1))、硬化觸媒(硬化促進劑:三苯基膦(北興化學(股)製造TPP)),使用混合輥均勻地混合、混練上述所獲得之環氧樹脂混合物(EP3、EP4)或者比較用環氧樹脂(EP2),而獲得硬化性樹脂組成物。利用混合機將該硬化性樹脂組成物粉碎,進而利用壓片機進行壓片化。將該壓片化後之硬化性樹脂組成物轉移成型(175℃×60秒)並進而脫模,其後於160℃×2小時+180℃×6小時之條件下進行硬化,獲得評價用試片。使用該評價用試片,按照以下之要點測定硬化物之物性。試驗結果亦示於表2。 The hardener (P-3: phenolic novolac (H-1 manufactured by Meiwa Chemical Industry Co., Ltd.)) and hardening catalyst (hardening accelerator: triphenylphosphine (Beixing Chemicals) (Production of TPP))), the epoxy resin mixture (EP3, EP4) or comparative epoxy resin (EP2) obtained as described above was uniformly mixed and kneaded using a mixing roller to obtain a curable resin composition. This curable resin composition was pulverized by a mixer, and further tabletted by a tableting machine. The tablet-shaped curable resin composition was transferred to a mold (175 ° C × 60 seconds) and further demolded, and then cured at 160 ° C × 2 hours + 180 ° C × 6 hours to obtain an evaluation test. sheet. Using this test piece for evaluation, the physical properties of the cured product were measured in accordance with the following points. The test results are also shown in Table 2.
<TMA測定條件> <TMA measurement conditions>
熱機械測定裝置TA-instruments製造、Q400EM Manufacture of thermo-mechanical measuring device TA-instruments, Q400EM
測定溫度範圍:40℃~280℃ Measuring temperature range: 40 ℃ ~ 280 ℃
升溫速度:2℃/分鐘 Heating rate: 2 ° C / min
<剝離強度> <Peel strength>
.180℃剝離試驗依據JIS K-6854-2使用壓延銅箔 . 180 ° C peel test using rolled copper foil in accordance with JIS K-6854-2
由以上之結果可知,本發明之環氧樹脂組成物之硬化物可於 維持較高之耐熱性之狀態下改良強韌性。即,本發明之環氧樹脂組成物可兼具硬化物之較高之耐熱性及強韌性。 From the above results, it can be seen that the cured product of the epoxy resin composition of the present invention can be used in Improved toughness while maintaining high heat resistance. That is, the epoxy resin composition of the present invention can have both high heat resistance and toughness of a cured product.
(實施例7) (Example 7)
於具備攪拌機、回流冷卻管、攪拌裝置之燒瓶,一面實施氮氣沖洗一面加入依據國際公開第2007/007827號所製造之酚樹脂((a)/(b)=1.3、n=1.5、(RP結構)/(RR結構)=2.15、(RP結構)/(PP結構)=2.1(GPC測定)、羥基當量134g/eq.、軟化點93℃)109.9份、4,4'-聯苯酚16.8份(相對於酚樹脂(A)之羥基當量1莫耳當量,聯苯酚(B)之羥基為0.22倍莫耳)、表氯醇463份(相對於酚樹脂為5莫耳當量)、二甲基亞碸100份,於攪拌下將其等溶解,升溫至40~45℃。繼而,歷時90分鐘分批添加薄片狀之氫氧化鈉42份後,進而於40℃反應1小時,於60℃反應1小時,於70℃反應1小時。反應結束後,使用旋轉蒸發器於減壓下,蒸餾去除過量之表氯醇等溶劑類。於殘留物中加入甲基異丁基酮500份將其溶解,利用水300份進行水洗後,升溫至70℃。於攪拌下加入30重量%之氫氧化鈉水溶液10份,進行反應1小時,其後進行水洗直至油層之清洗液變為中性,使用旋轉蒸發器於減壓下自所獲得之溶液蒸餾去除甲基異丁基酮等,藉此獲得本發明之環氧樹脂混合物(EP5)169份。所獲得之環氧樹脂混合物(EP5)之環氧當量為189g/eq.,於軟化點83℃、150℃之熔融黏度(ICI熔融黏度錐板#1)為0.07Pa.s。又,利用凝膠滲透層析法測定所獲得之環氧樹脂混合物(EP5),結果確認出含有聯苯酚之環氧樹脂11.0面積%,並確認出含有上述式(1)中n=0之環氧化物29.1面積%、n=1之環氧化物17.7面積%。 Add a phenol resin ((a) / (b) = 1.3, n = 1.5, (RP structure) manufactured according to International Publication No. 2007/007827 to a flask equipped with a stirrer, a reflux cooling tube, and a stirring device while purging with nitrogen. ) / (RR structure) = 2.15, (RP structure) / (PP structure) = 2.1 (determined by GPC), hydroxyl equivalent 134g / eq., Softening point 93 ° C) 109.9 parts, 4,4'-biphenol 16.8 parts ( 1 mol equivalent with respect to the hydroxy equivalent of phenol resin (A), 0.22 times mol equivalent with biphenol (B)), 463 parts of epichlorohydrin (5 mol equivalent with respect to phenol resin), dimethylene碸 100 parts, dissolve them under stirring, and raise the temperature to 40 ~ 45 ° C. Then, 42 parts of flake-shaped sodium hydroxide was added in portions over 90 minutes, and then reacted at 40 ° C for 1 hour, 60 ° C for 1 hour, and 70 ° C for 1 hour. After the reaction was completed, excess solvent such as epichlorohydrin was distilled off under reduced pressure using a rotary evaporator. 500 parts of methyl isobutyl ketone was added to the residue to dissolve it, and after washing with 300 parts of water, the temperature was raised to 70 ° C. 10 parts of a 30% by weight sodium hydroxide aqueous solution was added under stirring, and the reaction was performed for 1 hour, followed by water washing until the cleaning solution of the oil layer became neutral, and the formazan was distilled off from the obtained solution using a rotary evaporator under reduced pressure. Butyl isobutyl ketone, etc., thereby obtaining 169 parts of the epoxy resin mixture (EP5) of the present invention. The epoxy equivalent of the obtained epoxy resin mixture (EP5) was 189 g / eq., And the melt viscosity (ICI melt viscosity cone plate # 1) at a softening point of 83 ° C and 150 ° C was 0.07 Pa. s. Further, the obtained epoxy resin mixture (EP5) was measured by gel permeation chromatography. As a result, it was confirmed that the epoxy resin containing biphenol contained 11.0 area%, and it was confirmed that the ring containing n = 0 in the formula (1) was contained. 29.1 area% of oxide, 17.7 area% of epoxide with n = 1.
(實施例8) (Example 8)
以表3之比例(當量)摻合硬化劑(P-4:實施例1中使用之酚樹脂依據國際公開第2007/007827號所製造之酚樹脂((a)/(b)=1.3、n=1.5、 (RP結構)/(RR結構)=2.15、(RP結構)/(PP結構)=2.1(GPC測定)、羥基當量134g/eq.、軟化點93℃))、硬化觸媒(硬化促進劑:三苯基膦(北興化學(股)製造TPP)),使用混合輥均勻地混合、混練上述所獲得之環氧樹脂混合物(EP5)或者比較用環氧樹脂(EP2),而獲得硬化性樹脂組成物。利用混合機將該硬化性樹脂組成物粉碎,進而利用壓片機進行壓片化。將該壓片化後之硬化性樹脂組成物轉移成型(175℃×60秒)並進而脫模,其後於160℃×2小時+180℃×6小時之條件下進行硬化,獲得評價用試片。 The hardener (P-4: phenol resin used in Example 1 was produced in accordance with the ratio (equivalent) in Table 3 according to International Publication No. 2007/007827 ((a) / (b) = 1.3, n = 1.5, (RP structure) / (RR structure) = 2.15, (RP structure) / (PP structure) = 2.1 (GPC measurement), hydroxyl equivalent 134g / eq., Softening point 93 ° C)), hardening catalyst (hardening accelerator: Triphenylphosphine (TPP manufactured by Beixing Chemical Co., Ltd.)), and the epoxy resin mixture (EP5) or comparative epoxy resin (EP2) obtained as described above are uniformly mixed and kneaded with a mixing roller to obtain a hardenable resin composition. Thing. This curable resin composition was pulverized by a mixer, and further tabletted by a tableting machine. The tablet-shaped curable resin composition was transferred to a mold (175 ° C × 60 seconds) and further demolded, and then cured at 160 ° C × 2 hours + 180 ° C × 6 hours to obtain an evaluation test. sheet.
使用該評價用試片,按照以下之要點測定硬化物之物性。試驗結果亦示於表2。 Using this test piece for evaluation, the physical properties of the cured product were measured in accordance with the following points. The test results are also shown in Table 2.
<TMA測定條件> <TMA measurement conditions>
熱機械測定裝置TA-instruments製造、Q400EM Manufacture of thermo-mechanical measuring device TA-instruments, Q400EM
測定溫度範圍:40℃~280℃ Measuring temperature range: 40 ℃ ~ 280 ℃
升溫速度:2℃/分鐘 Heating rate: 2 ° C / min
<吸濕性> <Hygroscopicity>
根據利用85℃、85%之高溫高濕槽放置24小時後之重量增加%進行評價 Evaluation based on% weight increase after leaving the tank at 85 ° C and 85% for 24 hours
<耐熱分解特性測定條件> <Measurement conditions for thermal decomposition resistance>
利用循環式研磨機將所獲得之試片之一部分粉碎,製成粉狀,使其等通過100μm篩孔進行篩選而使粒徑一致為留在75μm篩孔上者,取5-10mg之樣品,利用TG-DTA確認熱重量減少溫度。以5%之重量減少溫度作為指標。 A part of the obtained test pieces was pulverized with a circular mill to make a powder, and the particles were screened through a 100 μm sieve to make the particle size uniformly remain on the 75 μm sieve. Take a 5-10 mg sample. The thermal weight reduction temperature was confirmed by TG-DTA. Take 5% weight reduction temperature as an indicator.
利用TG-DTA進行測定(Td5) Measurement by TG-DTA (Td5)
測定樣品:粉狀(通過100μm篩孔、留在75μm篩孔)5-10mg Measurement sample: powdery (pass through 100μm sieve hole, leave on 75μm sieve hole) 5-10mg
測定條件:升溫速度10℃/min空氣流速200ml/min測定5%重量減 少溫度。 Measurement conditions: heating rate 10 ℃ / min air flow rate 200ml / min determination 5% weight loss Less temperature.
由以上之結果可知,即便本發明之環氧樹脂經一半以下之大幅低黏度化,而亦可維持較高之耐熱性且於其他特性方面亦維持較高之特性。即,本發明之環氧樹脂成為可改善難以與耐熱兼具之各特性之樹脂。 From the above results, it can be seen that even if the epoxy resin of the present invention is substantially reduced in viscosity by less than half, it can maintain high heat resistance and also maintain high characteristics in other characteristics. That is, the epoxy resin of the present invention is a resin that can improve various characteristics that are difficult to have both heat resistance and heat resistance.
參照特定之態樣詳細地說明本發明,但業者應理解可於不脫離本發明之精神與範圍之情況下進行各種變更及修正。 The present invention will be described in detail with reference to specific aspects, but it should be understood that various changes and modifications can be made without departing from the spirit and scope of the present invention.
再者,本申請案係基於2013年9月12日提出申請之日本專利申請案(特願2013-189035),其全部內容係以引用之形式援用。又,此處引用之所有參照係以整體之形式併入本文中。 Furthermore, this application is based on a Japanese patent application filed on September 12, 2013 (Japanese Patent Application No. 2013-189035), the entire contents of which are incorporated by reference. Also, all references cited herein are incorporated herein in their entirety.
[產業上之可利用性] [Industrial availability]
本發明之環氧樹脂混合物由於其硬化物具有耐熱性、吸水特性及難燃性優異之特性,故對電氣電子零件用絕緣材料及積層板(印刷配線板、增層基板等)或以CFRP為首之各種複合材料、接著劑、塗料等是有用的。 The epoxy resin mixture of the present invention is excellent in heat resistance, water absorption properties, and flame retardancy, so it is suitable for insulating materials for electrical and electronic parts and laminated boards (printed wiring boards, build-up substrates, etc.) or CFRP. A variety of composite materials, adhesives, coatings, etc. are useful.
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JP7024227B2 (en) * | 2017-06-29 | 2022-02-24 | Dic株式会社 | Epoxy resin manufacturing method, epoxy resin, epoxy resin composition and cured product thereof |
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2000191885A (en) * | 1998-10-20 | 2000-07-11 | Nitto Denko Corp | Resin composition for sealing semiconductor and semiconductor device made by using it |
JP2013043958A (en) * | 2011-08-25 | 2013-03-04 | Meiwa Kasei Kk | Epoxy resin, method of producing the same, and use of the same |
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JPH0940751A (en) * | 1995-07-27 | 1997-02-10 | Taiyo Ink Mfg Ltd | Impact-resistant insulating resin composition |
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JP2000191885A (en) * | 1998-10-20 | 2000-07-11 | Nitto Denko Corp | Resin composition for sealing semiconductor and semiconductor device made by using it |
JP2013043958A (en) * | 2011-08-25 | 2013-03-04 | Meiwa Kasei Kk | Epoxy resin, method of producing the same, and use of the same |
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KR20210031539A (en) | 2021-03-19 |
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