TW201412804A - Epoxy resin composition, cured product thereof, and curable resin composition - Google Patents

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

Info

Publication number
TW201412804A
TW201412804A TW102120279A TW102120279A TW201412804A TW 201412804 A TW201412804 A TW 201412804A TW 102120279 A TW102120279 A TW 102120279A TW 102120279 A TW102120279 A TW 102120279A TW 201412804 A TW201412804 A TW 201412804A
Authority
TW
Taiwan
Prior art keywords
resin composition
epoxy resin
curable resin
epoxy
present
Prior art date
Application number
TW102120279A
Other languages
Chinese (zh)
Inventor
Masataka Nakanishi
Seiji Ebara
Kazuma Inoue
Kazumi Obuchi
Original Assignee
Nippon Kayaku Kk
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Kayaku Kk filed Critical Nippon Kayaku Kk
Publication of TW201412804A publication Critical patent/TW201412804A/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/26—Di-epoxy compounds heterocyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4215—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof cycloaliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/681—Metal alcoholates, phenolates or carboxylates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterized by the type of post-polymerisation functionalisation
    • C08G2650/20—Cross-linking

Landscapes

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

Abstract

This epoxy resin composition contains an epoxy resin represented by formula (2) and a carboxylic acid and/or a cationic polymerization catalyst, and has two or fewer hues in the Gardner colorimetric method (40% MEK solution); this curable resin composition contains an epoxy resin represented by formula (2) and a phenolic resin and/or a polymerization catalyst (in the formula, the R's each independently represent a hydrogen atom, an alkyl group of 1-6 carbon atoms, or an alkoxy group of 1-6 carbon atoms.).

Description

環氧樹脂組成物、及其之硬化物、以及、硬化性樹脂組成物 Epoxy resin composition, cured product thereof, and curable resin composition

本發明係關於一種適合於電氣電子材料用途、尤其是光學材料用途之環氧樹脂組成物、及其之硬化物。進而，本發明亦關於一種適合於要求耐熱性、阻燃性之電氣電子材料用途之硬化性樹脂組成物。 The present invention relates to an epoxy resin composition suitable for use in electrical and electronic materials, particularly optical materials, and cured products thereof. Furthermore, the present invention also relates to a curable resin composition suitable for use in electrical and electronic materials requiring heat resistance and flame retardancy.

先前以來，於LED製品、透明基板材料等用途中，就性能與經濟性之平衡之方面而言，一直採用環氧樹脂組成物。尤其使用有耐熱性、透明性、機械特性之平衡性優異之雙酚A型環氧樹脂的環氧樹脂組成物一直獲得廣泛使用(專利文獻1~3)。 Previously, in applications such as LED products and transparent substrate materials, epoxy resin compositions have been used in terms of balance between performance and economy. In particular, an epoxy resin composition of a bisphenol A type epoxy resin having excellent heat resistance, transparency, and balance of mechanical properties has been widely used (Patent Documents 1 to 3).

如上所述，雙酚A型環氧樹脂作為光學用樹脂具有通用性，但該等通常為液狀，存在於片材化或預浸體化時產生褶皺等問題，又，亦有增大分子量而固形化者，但其僅直線延伸，因而硬化物過於柔軟，難以表現出耐熱性。 As described above, the bisphenol A type epoxy resin has versatility as an optical resin, but these are usually liquid, and there are problems such as wrinkles occurring during sheet formation or prepreg, and also an increase in molecular weight. On the other hand, the solidified person extends only in a straight line, so that the hardened material is too soft and it is difficult to exhibit heat resistance.

另一方面，藉由含浸於作為透明材料之一的玻璃布中之後使之硬化，而製作玻璃之代替品之技術的開發獲得推進。作為此種玻璃代替用途，已知可使用各種環氧樹脂組成物，對於習知之環氧樹脂，於與玻璃布之折射率之差較大之情形、或雙折射率較高之情形時，會因漫反射等使視認性降低，難以作為LCD或偏向光而使用。又，尤其對於朝利用偏向之LCD的玻璃代替環氧樹脂等透明基材，強烈要求為低雙折射率。 On the other hand, development of a technique for producing a substitute for glass by impregnating it with a glass cloth as one of transparent materials has been advanced. As such a glass substitute use, it is known that various epoxy resin compositions can be used. In the case of a conventional epoxy resin, when the difference in refractive index from the glass cloth is large or when the birefringence is high, The visibility is lowered by diffuse reflection or the like, and it is difficult to use it as an LCD or a deflected light. Further, in particular, in order to replace a transparent substrate such as an epoxy resin with a glass using a biased LCD, a low birefringence is strongly required.

因此，強烈期待開發出滿足上述要求特性之光學材料用之環氧樹脂。 Therefore, it is strongly desired to develop an epoxy resin for an optical material that satisfies the above-mentioned required characteristics.

又，除上述以外，硬化性樹脂組成物由於作業性及其之硬化物之優異之電氣特性、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。 In addition, the curable resin composition is widely used for electrical and electronic parts and structural materials due to excellent electrical properties, heat resistance, adhesion, moisture resistance (water resistance) of the workability and the cured product thereof. , adhesives, coatings and other fields.

但近年來，於電氣電子領域中隨著其發展，要求進一步提高樹脂組成物之高純度化以及耐濕性、密接性、介電特性、用以使填料(無機或有機填充劑)高填充之低黏度化、用以縮短成型週期之反應性之上升等各特性。又，作為構造材，關於航太材料、娛樂運動器具用途等，要求輕量且機械物性優異之材料。尤其關於半導體密封領域、基板(基板本身、或其周邊材料)，隨著半導體之變遷，變得薄層化、堆疊化、系統化、立體化，變得複雜，而謀求非常高水準之耐熱性或高流動性等要求特性。再者，尤其隨著擴展至塑膠封裝之車載用途，耐熱性之提高要求進一步變嚴格，需要為高Tg且低線膨脹率之樹脂，且當然需要對回流焊之應對，同時要求吸水率之降低或維持。進而就環境問題而言，近年來，作為阻燃劑之鹵素系環氧樹脂與三氧化二銻尤其多用作電氣電子零件之阻燃劑，但業界指出使用有該等之製品會因廢棄其之後之不適當處理，而助長戴奧辛等有毒物質之產生。 However, in recent years, in the field of electrical and electronic fields, it is required to further improve the high purity of the resin composition, moisture resistance, adhesion, dielectric properties, and high filling of fillers (inorganic or organic fillers). Low viscosity, various characteristics such as an increase in reactivity during the molding cycle. In addition, as a structural material, materials which are lightweight and excellent in mechanical properties are required for aerospace materials and recreational sports equipment applications. In particular, in the field of semiconductor sealing, the substrate (the substrate itself, or its surrounding materials) becomes thinner, stacked, systemized, and three-dimensional as the semiconductor changes, and a very high level of heat resistance is sought. Or high fluidity and other required characteristics. Furthermore, in particular, with the expansion to the automotive use of plastic packaging, the improvement of heat resistance is further severed, and a resin having a high Tg and a low linear expansion ratio is required, and of course, it is necessary to cope with reflow soldering, and at the same time, a reduction in water absorption rate is required. Or maintain. Further, in terms of environmental problems, in recent years, halogen-based epoxy resins and antimony trioxides, which are flame retardants, are particularly useful as flame retardants for electric and electronic parts, but the industry has pointed out that the use of such products may be discarded after disposal. Inappropriate treatment, and promote the production of toxic substances such as Dioxin.

專利文獻1：日本特開平07-157536號公報 Patent Document 1: Japanese Laid-Open Patent Publication No. 07-157536

專利文獻2：日本特開2005-082798號公報 Patent Document 2: Japanese Laid-Open Patent Publication No. 2005-082798

專利文獻3：日本特開2007-284680號公報 Patent Document 3: Japanese Laid-Open Patent Publication No. 2007-284680

非專利文獻1：“2008年STRJ報告半導體藍圖專業委員會2008年度報告”，第8章，p1-17，[online]，2009年3月，JEITA(公司)電子資訊技術產業協會半導體技術藍圖專業委員會，[2012年5月30日檢索]，<http：//strj-jeita.elisasp.net/strj/nenjihoukoku-2008.cfm> Non-Patent Document 1: "2008 STRJ Report Semiconductor Blueprint Professional Committee 2008 Annual Report", Chapter 8, p1-17, [online], March 2009, JEITA (Company) Electronic Information Technology Industry Association Semiconductor Technology Blueprint Professional Committee , [Searched on May 30, 2012], <http://strj-jeita.elisasp.net/strj/nenjihoukoku-2008.cfm>

非專利文獻2：高倉信及其他，松下電工技報與車輛相關之裝置技術車載用高溫動作IC，74號，日本，2001年5月31日，35-40頁 Non-Patent Document 2: Takakura and others, Matsushita Electric Technology and Vehicle-related Device Technology High-temperature Action IC for Vehicles, No. 74, Japan, May 31, 2001, 35-40

針對如上所述之光學材料用途之問題，使用與雙酚A型環氧樹脂同樣具有不具苄基亞甲基鍵之結構的作為三酚體環氧樹脂之Printec製造之VG3105等。然而，該等有初期之著色，為了用作光學材料，要求進一步之透明性。 For the use of the optical material as described above, VG3105 manufactured by Printec, which is a trisphenol epoxy resin having a structure other than the bisphenol A type epoxy resin, and the like, is used. However, these have early coloring and require further transparency in order to be used as an optical material.

作為解決此種問題之方法，亦對倍半矽氧烷(silsesquioxane)結構之環氧樹脂或脂環式環氧樹脂之應用進行了研究，倍半矽氧烷結構之環氧樹脂雖然於耐熱性方面較高，但脆性明顯，亦有線膨脹率變高之傾向，此外折射率降低。又，脂環式環氧樹脂亦提高玻璃轉移點之意義上之耐熱性，但脆性或其低折射率成為課題，業界期待光學特性良好進而強韌性高之芳香族環氧丙醚化合物。 As a method for solving such a problem, the application of an epoxy resin or an alicyclic epoxy resin having a silsesquioxane structure has been studied, and an epoxy resin having a sesquiterpene oxide structure is used for heat resistance. The aspect is high, but the brittleness is obvious, and the linear expansion ratio tends to be high, and the refractive index is lowered. Further, the alicyclic epoxy resin also has heat resistance in the sense of a glass transition point, but brittleness or a low refractive index thereof is a problem, and an aromatic epoxidized propylene ether compound having excellent optical properties and high toughness is expected in the industry.

又，作為解決上述電氣電子領域之用途之問題的方法之一，提出有骨架中具有磷原子之環氧樹脂。尤其是通常之磷酸酯型化合物由於穩定性較低，故而使用穩定性良好之環狀磷酸酯化合物。又，開發出即便不使用磷酸酯化合物，藉由選擇樹脂骨架，阻燃性亦優於習知之環氧樹脂 者。然而，目前尤其於半導體密封材之領域中，對不使用磷系阻燃劑亦可阻燃化之系統之開發進行了研究，一般而言要求稱為無鹵素、無銻、無磷之阻燃性。 Further, as one of the methods for solving the problems in the above-mentioned electric and electronic field, an epoxy resin having a phosphorus atom in a skeleton has been proposed. In particular, since a usual phosphate ester type compound has low stability, a cyclic phosphate compound having good stability is used. Moreover, it has been developed that the flame retardancy is superior to the conventional epoxy resin by selecting a resin skeleton even without using a phosphate compound. By. However, in the field of semiconductor sealing materials, the development of a system that can also be flame-retarded without using a phosphorus-based flame retardant has been studied. Generally, it is called a halogen-free, flawless, phosphorus-free flame retardant. Sex.

因此，本發明之第1發明之目的在於提供一種環氧樹脂組成物，其於透明性、耐熱性方面優異，且折射率較高，雙折射率較低，又，延遲(retardation)較低，因此可應用於要求高度之光學特性之光學構件。 Therefore, an object of the first invention of the present invention is to provide an epoxy resin composition which is excellent in transparency and heat resistance, has a high refractive index, a low birefringence, and a low retardation. Therefore, it can be applied to an optical member requiring a high degree of optical characteristics.

又，本發明之第2發明之目的在於提供一種硬化性樹脂組成物，其可同時實現較高之耐熱性與阻燃性，且有利於電氣電子領域之用途。 Further, an object of the second invention of the present invention is to provide a curable resin composition which can simultaneously achieve high heat resistance and flame retardancy, and is advantageous for use in the field of electrical electronics.

本發明者等人鑒於如上所述之實際情況進行努力研究，結果完成本發明。 The present inventors conducted an effort to study in view of the actual situation as described above, and as a result, completed the present invention.

即，本發明係關於下述(1)至(11)。 That is, the present invention relates to the following (1) to (11).

(1)一種環氧樹脂組成物，其係含有藉由下述式(1)所表示之酚系樹脂與表鹵醇(epihalohydrin)之反應而獲得之環氧樹脂、與羧酸類及/或陽離子聚合觸媒者，並且上述環氧樹脂於加德納比色法(40%甲基乙基酮溶液)中之色相為2以下。 (1) An epoxy resin composition comprising an epoxy resin obtained by a reaction of a phenolic resin represented by the following formula (1) and an epihalohydrin, and a carboxylic acid and/or a cation The catalyst was polymerized, and the hue of the above epoxy resin in the Gardner colorimetric method (40% methyl ethyl ketone solution) was 2 or less.

(式中，存在複數個之R分別獨立地表示氫原子、碳數1~6之烷基或碳數1~6之烷氧基) (wherein a plurality of R independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms)

(2)如前項(1)之環氧樹脂組成物，其中與表鹵醇反應之酚系樹脂中之殘留酚酞衍生物之量為2%以下。 (2) The epoxy resin composition according to the above (1), wherein the amount of the residual phenolphthalein derivative in the phenolic resin reacted with the epihalohydrin is 2% or less.

(3)如前項(1)之環氧樹脂組成物，其中與表鹵醇反應之酚系樹脂中之殘留鐵成分為50ppm以下。 (3) The epoxy resin composition according to the above item (1), wherein the residual iron component in the phenol resin reacted with the epihalohydrin is 50 ppm or less.

(4)如前項(3)之環氧樹脂組成物，其含有過渡金屬鹽。 (4) The epoxy resin composition according to the above item (3), which contains a transition metal salt.

(5)如前項(3)之環氧樹脂組成物，其含有四級鏻鹽。 (5) The epoxy resin composition according to the above item (3), which contains a quaternary phosphonium salt.

(6)如前項(3)之環氧樹脂組成物，其含有陽離子聚合起始劑。 (6) The epoxy resin composition according to the above item (3), which contains a cationic polymerization initiator.

(7)一種環氧樹脂硬化物，其係使前項(4)至(6)中任一項之環氧樹脂組成物硬化而成者。 (7) A cured epoxy resin obtained by curing the epoxy resin composition according to any one of the above items (4) to (6).

(8)如前項(1)至(6)中任一項之環氧樹脂組成物，其係玻璃代替用環氧樹脂組成物。 (8) The epoxy resin composition according to any one of the above items (1) to (6), which is a glass substitute for the epoxy resin composition.

(9)一種硬化性樹脂組成物，其含有下述式(2)所表示之環氧樹脂、與酚系樹脂及/或聚合觸媒。 (9) A curable resin composition comprising an epoxy resin represented by the following formula (2), a phenol resin, and/or a polymerization catalyst.

(式中，存在複數個之R分別獨立地表示氫原子、碳數1~6之烷基、或碳數1~6之烷氧基) (wherein a plurality of R independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms)

(10)如前項(9)之硬化性樹脂組成物，其中酚系樹脂為酚芳烷基樹脂(具有芳香族伸烷基結構之樹脂)。 (10) The curable resin composition according to the above item (9), wherein the phenol resin is a phenol aralkyl resin (a resin having an aromatic alkylene structure).

(11)如前項(9)之硬化性樹脂組成物，其中聚合觸媒為陽離子聚合觸媒。 (11) A curable resin composition according to the above item (9), wherein the polymerization catalyst is a cationic polymerization catalyst.

作為本發明之第1發明的環氧樹脂組成物於透明性、耐熱性優異，且折射率較高，又，雙折射較低，因此可應用於要求高度之光學特性之光學構件。 The epoxy resin composition of the first invention of the present invention is excellent in transparency and heat resistance, has a high refractive index, and has low birefringence. Therefore, it can be applied to an optical member requiring high optical characteristics.

又，作為本發明之第2發明的硬化性樹脂組成物係確保充分之硬化性，並且不使用阻燃劑、磷系化合物亦表現出阻燃性，有助於組成物中之阻燃劑、磷系化合物之減少的環氧樹脂，並且對於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(carbonfiber reinforced plastics，碳纖維強化塑膠)為首之各種複合材料、接著劑、塗料等有用。尤其於保護半導體元件之半導體密封材料或基板材料極有用。 In addition, the curable resin composition of the second aspect of the present invention ensures sufficient curability, and exhibits flame retardancy without using a flame retardant or a phosphorus-based compound, and contributes to a flame retardant in the composition. An epoxy resin having a reduced phosphorus compound, and an insulating material for electric and electronic parts, a laminate (printed wiring board, a build-up substrate, etc.), or various composite materials including CFRP (carbon fiber reinforced plastics), followed by various composite materials. Agents, coatings, etc. are useful. It is particularly useful for protecting a semiconductor sealing material or a substrate material of a semiconductor element.

本發明之第1發明(以下亦稱為「第1發明」)係一種環氧樹脂組成物，其係含有藉由下述式(1)所表示之酚系樹脂與表鹵醇之反應而獲得之環氧樹脂、與羧酸類及/或陽離子聚合觸媒者，並且上述環氧樹脂於加德納比色法(40%甲基乙基酮溶液)中之色相為2以下。 The first invention of the present invention (hereinafter also referred to as "the first invention") is an epoxy resin composition which is obtained by a reaction of a phenolic resin represented by the following formula (1) with an epihalohydrin. The epoxy resin, the carboxylic acid and/or the cationic polymerization catalyst, and the hue of the above epoxy resin in the Gardner colorimetric method (40% methyl ethyl ketone solution) is 2 or less.

(式中，存在複數個之R分別獨立地表示氫原子、碳數1~6之烷基或碳數1~6之烷氧基) (wherein a plurality of R independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms)

又，本發明之第2發明(以下亦稱為「第2發明」)係一種硬化性樹脂組成物，其含有下述式(2)所表示之環氧樹脂、與酚系樹脂及/或聚合觸媒。 In addition, the second invention of the present invention (hereinafter also referred to as "the second invention") is a curable resin composition containing an epoxy resin represented by the following formula (2), a phenol resin, and/or polymerization. catalyst.

(式中，存在複數個之R分別獨立地表示氫原子、碳數1~6之烷基、或碳數1~6之烷氧基) (wherein a plurality of R independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms)

作為第1及第2之各發明之樹脂組成物所含有之環氧樹脂係具有苯酚鄰苯二甲醯亞胺骨架之環氧樹脂。該環氧樹脂之基礎骨架係揭示於英國專利1158606號公報(專利文獻4)。根據專利文獻4，揭示有環氧當量每千克3.4(若換算成目前之環氧當量則為294g/eq.)，色相為加德納8(於甲基二醇中為40%)，軟化點66℃(kolfer加熱器)，氯含量2.2%之結果。又，揭示有與DDS(二胺基二苯基碸)之硬化物性。 The epoxy resin contained in the resin composition of each of the first and second inventions is an epoxy resin having a phenol phthalimide skeleton. The base skeleton of the epoxy resin is disclosed in British Patent No. 1,158,606 (Patent Document 4). According to Patent Document 4, it is disclosed that an epoxy equivalent of 3.4 per kilogram (or 294 g/eq. if converted to the current epoxy equivalent), and a hue of Gardner 8 (40% in methyl glycol), softening point 66 ° C (kolfer heater), the result of a chlorine content of 2.2%. Further, it has been revealed that it has a cured property with DDS (diaminodiphenylphosphonium).

若如此則難以拓展至光學材料，要求透明性更高之樹脂。 If this is the case, it is difficult to expand to an optical material, and a resin having higher transparency is required.

又，根據上述專利文獻4之資料，提示該樹脂之氯量非常多，不適合於電子材料用途，又，著色非常嚴重，因此難以用於需要色調之用途中。又，提示若環氧當量為294g/eq.，則與理論值(252.7g/eq.)相比較大，又，較多地含有因氯量導致環氧化合物不閉環而殘留之表鹵醇結構，無論是否為二官能，只要為此種未完成環氧環之結構，則以下情形較多：交聯不會順利進行，於進行由酚系樹脂引起之硬化、或由咪唑等鹼性觸媒引起之陰離子聚合、由鎓鹽等引起之陽離子聚合時，於其機械特性或吸水性等特性方面產生課題。尤其於電子材料用途中，不僅於該等硬化中，於胺系之硬 化中亦可預料到硬化時之氯之游離引起的配線之腐蝕等，成為電氣可靠性降低之因素。 Moreover, according to the information of the above-mentioned Patent Document 4, it is suggested that the resin has a large amount of chlorine, is not suitable for use in electronic materials, and is highly colored, so that it is difficult to use it in applications requiring color tone. Further, when the epoxy equivalent is 294 g/eq., it is larger than the theoretical value (252.7 g/eq.), and the epihalohydrin structure remaining in the epoxy compound without ring closure due to the amount of chlorine is often contained. Regardless of whether it is a difunctional or not, as long as it is a structure of such an unfinished epoxy ring, there are many cases in which crosslinking is not progressed smoothly, and hardening by a phenol resin or alkaline catalyst such as imidazole is performed. When the anionic polymerization or the cationic polymerization caused by a phosphonium salt or the like is caused, problems occur in properties such as mechanical properties and water absorbability. Especially in the use of electronic materials, not only in these hardenings, but also in the hardening of amines. In the middle of the chemical process, corrosion of the wiring due to the release of chlorine during hardening can be expected, and the electrical reliability is lowered.

近年來，尤其於半導體之晶片與基板之接合中，使用銅線之情況增多，此種電氣腐蝕之課題變得更加重要，成為應解決之課題點。 In recent years, in particular, in the bonding of semiconductor wafers and substrates, the use of copper wires has increased, and the problem of such electrical corrosion has become more important, and this has become a problem to be solved.

又，本專利文獻4中並無關於阻燃性之記載。 Further, in Patent Document 4, there is no description about the flame retardancy.

作為第1發明之環氧樹脂組成物中所使用之環氧樹脂係藉由下述式(1) The epoxy resin used in the epoxy resin composition of the first invention is represented by the following formula (1)

(式中，存在複數個之R分別獨立地表示氫原子、碳數1~6之烷基或碳數1~6之烷氧基)所表示之酚系樹脂與表鹵醇之反應而獲得之環氧樹脂，具體而言為下述式(2) (wherein a plurality of Rs independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms) and a reaction of a phenolic resin with an epihalohydrin Epoxy resin, specifically, the following formula (2)

(式中，存在複數個之R分別獨立地表示氫原子、碳數1~6之烷基、或碳數1~6之烷氧基)所表示之環氧樹脂。 (In the formula, there are an epoxy resin represented by a plurality of R independently representing a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms).

此處，作為第1發明之環氧樹脂組成物所使用之環氧樹脂係較佳為含有上述環氧化合物70~95%(凝膠滲透層析法面積%)，更佳為70~93%之環氧樹脂。此處，於合成上述環氧化合物之含量超過95%之純度之環氧樹脂時，有時具有極大之能量，又，於純度過高之情形時，有時確認到結晶性變高之可能性、或強韌性之降低。若低於70%，則有時環氧之環不會完全閉環，大量包含不具有官能基之化合物。又，該等未完全閉環之化合物之多數含有氯之情形較多，作為電子材料用途，有時有高溫多濕條件下之氯離子之游離、及由此引起之配線之腐蝕之擔憂。 Here, the epoxy resin used as the epoxy resin composition of the first invention preferably contains 70 to 95% of the epoxy compound (% by area of gel permeation chromatography), more preferably 70 to 93%. Epoxy resin. Here, when an epoxy resin having a purity of more than 95% of the epoxy compound is synthesized, there is a case where the energy is extremely high, and when the purity is too high, the possibility of high crystallinity may be confirmed. , or the reduction of strength and toughness. If it is less than 70%, the epoxy ring may not be completely closed, and a large amount of a compound having no functional group may be contained. Further, many of the compounds which are not completely closed are contained in the case of chlorine, and as an electronic material, there is a concern that chlorine ions are released under high-temperature and high-humidity conditions, and corrosion of wiring caused thereby.

又，於本環氧樹脂內殘留具有酚酞結構之環氧樹脂之情形時，會成為電氣可靠性之降低、較大著色之原因，故不宜殘留具有酚酞結構之環氧樹脂，較佳為2%以下，尤佳為1%以下。該具有酚酞結構之環氧樹脂之來自原料之雜質之影響較大。若超過2%，則尤其著色變強，故而欠佳。 Further, when an epoxy resin having a phenolphthalein structure remains in the epoxy resin, the electrical reliability is lowered and the coloring is caused, so that it is not preferable to leave an epoxy resin having a phenolphthalein structure, preferably 2%. The following is particularly preferably 1% or less. The epoxy resin having a phenolphthalein structure has a large influence on impurities derived from raw materials. If it exceeds 2%, especially the coloring becomes strong, and it is unpreferable.

於上述式(1)及(2)中，R最佳為氫原子。作為R所表示之上述碳數1~6之烷基，例如可列舉：甲基、乙基、丙基、丁基、戊基、 己基等具有直鏈、支鏈或環狀結構之烷基。此處，R較佳為甲基、乙基，尤佳為甲基。 In the above formulas (1) and (2), R is most preferably a hydrogen atom. Examples of the alkyl group having 1 to 6 carbon atoms represented by R include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. An alkyl group having a linear, branched or cyclic structure such as a hexyl group. Here, R is preferably a methyl group or an ethyl group, and particularly preferably a methyl group.

作為R所表示之碳數1~6之烷氧基，例如可列舉：甲氧基、乙氧基、丙氧基、丁氧基等具有直鏈、支鏈或環狀結構之烷氧基。此處，R較佳為甲氧基、乙氧基、丙氧基，尤佳為甲氧基。 Examples of the alkoxy group having 1 to 6 carbon atoms represented by R include alkoxy groups having a linear, branched or cyclic structure such as a methoxy group, an ethoxy group, a propoxy group or a butoxy group. Here, R is preferably a methoxy group, an ethoxy group or a propoxy group, and particularly preferably a methoxy group.

作為上述式(2)之環氧樹脂之較佳樹脂特性，環氧當量相對於理論環氧當量(252.7g/eq.)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，環氧之合成、純化耗費大量費用，故而於產業上欠佳，又，於超過1.13倍之情形時，與上述同樣地有由氯量引起之課題之擔憂。 As a preferable resin characteristic of the epoxy resin of the above formula (2), the epoxy equivalent is 1.02 to 1.13 times the theoretical epoxy equivalent (252.7 g/eq.). More preferably 1.03 to 1.10 times. When it is less than 1.02 times, the synthesis and purification of the epoxy are expensive, and it is industrially unsatisfactory. When the ratio is more than 1.13 times, there is a concern that the amount of chlorine is caused by the same amount as described above.

又，作為殘留於所獲得之環氧樹脂中之總氯，較佳為5000ppm以下，更佳為3000ppm以下，尤佳為2000ppm以下。關於由氯量引起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。氯離子上文已有記載，無需贅言，鈉離子等陽離子尤其於功率裝置用途中亦成為非常重要之因素，成為施加高電壓時之不良模式之一原因。 Further, the total chlorine remaining in the obtained epoxy resin is preferably 5,000 ppm or less, more preferably 3,000 ppm or less, and still more preferably 2,000 ppm or less. The adverse effects caused by the amount of chlorine are the same as described above. Further, the chloride ion and the sodium ion are each preferably 5 ppm or less, more preferably 3 ppm or less. Chloride ions have been described above, and it is needless to say that cations such as sodium ions are also a very important factor especially in power device applications, and are one of the bad modes when high voltage is applied.

此處，所謂理論環氧當量，表示上述式(1)之酚系化合物之酚性羥基無過多或不足而環氧丙化時所算出之環氧當量。 Here, the theoretical epoxy equivalent means an epoxy equivalent calculated when the phenolic hydroxyl group of the phenol compound of the above formula (1) is not excessively or insufficiently and is epoxidized.

又，作為具體之環氧當量之值，於R均為氫原子之情形時，較佳為257.8g/eq.~285.6g/eq.，尤佳為260.3g/eq.~278.0g/eq.。藉由使環氧當量於上述範圍內，可獲得硬化物之耐熱性、電氣可靠性優異之環氧樹脂。 Further, as a specific epoxy equivalent value, when R is a hydrogen atom, it is preferably 257.8 g/eq. to 285.6 g/eq., particularly preferably 260.3 g/eq. to 278.0 g/eq. . When the epoxy equivalent is within the above range, an epoxy resin excellent in heat resistance and electrical reliability of the cured product can be obtained.

本發明之樹脂組成物所使用之環氧樹脂(亦僅稱為「本發明 之環氧樹脂」)含有具有軟化點之樹脂狀之形態。此處，作為軟化點，較佳為70~130℃，更佳為80~120℃。於取代基R均為氫原子之情形時，尤佳為70~120℃，更佳為80~110℃。若軟化點過低，則保管時之黏連成為問題，不得不於低溫下操作等，課題較多。反之，於軟化點過高之情形時，與其他樹脂混練時，會產生操作惡化等問題。又，熔融黏度較佳為1Pa‧s(ICI(高剪切)熔融黏度150℃錐板法)以下。於混合無機材料(填料等)而使用之情形時，有時流動性會惡化，又，玻璃布等之網眼亦變得更微細，有時含浸性較差。 Epoxy resin used in the resin composition of the present invention (also referred to as "the present invention" The epoxy resin") has a resin-like form having a softening point. Here, as the softening point, it is preferably 70 to 130 ° C, more preferably 80 to 120 ° C. When the substituent R is a hydrogen atom, it is preferably 70 to 120 ° C, more preferably 80 to 110 ° C. If the softening point is too low, the adhesion at the time of storage becomes a problem, and it is necessary to operate at a low temperature, and there are many problems. On the other hand, when the softening point is too high, when it is kneaded with other resins, problems such as deterioration of operation may occur. Further, the melt viscosity is preferably 1 Pa ‧ or less (ICI (high shear) melt viscosity 150 ° C cone and plate method). When it is used in the case of mixing an inorganic material (filler or the like), the fluidity may be deteriorated, and the mesh of the glass cloth or the like may become finer, and the impregnation property may be inferior.

第1發明所使用之環氧樹脂於透明性(色相)方面優異。於加德納比色法(目測40%甲基乙基酮溶液)中為2以下，較佳為1.5以下。尤其於拓展至光學材料之情況不言而喻，於通常之PCB基板等中亦對基板之顏色造成影響，故而要求著色較少者。 The epoxy resin used in the first invention is excellent in transparency (hue). In the Gardner colorimetric method (visual inspection of a 40% methyl ethyl ketone solution), it is 2 or less, preferably 1.5 or less. In particular, the case of expanding to an optical material is self-evident, and it affects the color of the substrate in a normal PCB substrate or the like, and therefore requires less coloring.

第2發明所使用之環氧樹脂如上所述無須為透明性(色相)優異者，但較佳為同樣優異。 The epoxy resin used in the second invention does not need to be excellent in transparency (hue) as described above, but is preferably excellent in the same manner.

又，本發明之環氧樹脂具有高折射率。較佳為1.61以上，更佳為1.62以上，尤佳為1.62~1.65。尤其於必須調整折射率之領域中，若折射率較高，則可減少所使用之組成物之芳香環量，可有助於耐光特性之提高。又，於透鏡等用途中，越高折射率越能製作應變更小之透鏡，故而較佳。 Further, the epoxy resin of the present invention has a high refractive index. It is preferably 1.61 or more, more preferably 1.62 or more, and particularly preferably 1.62 to 1.65. In particular, in the field where the refractive index must be adjusted, if the refractive index is high, the amount of the aromatic ring of the composition to be used can be reduced, which contributes to an improvement in light resistance. Further, in applications such as lenses, it is preferable to use a lens having a smaller refractive index as the lens can be changed.

以下，對本發明之環氧樹脂之製造法進行說明。 Hereinafter, a method for producing an epoxy resin of the present invention will be described.

上述式(2)之化合物係以由酚酞衍生物及胺基苯衍生物所合成(例如，日本特開2005-290378號公報所列舉)之酚系化合物(DPPI)與表鹵醇之反應而獲得。將本發明之環氧樹脂之具體製造方法例示於以下。 The compound of the above formula (2) is obtained by a reaction of a phenolic compound (DPPI) synthesized from a phenolphthalein derivative and an aminobenzene derivative (for example, as exemplified in JP-A-2005-290378) with an epihalohydrin. . A specific production method of the epoxy resin of the present invention is exemplified below.

作為酚酞衍生物，公知的是可以苯二甲酸(phthalic acid)與該各種酚類進行合成，且若所使用之酚類為苯酚，則可獲得酚酞，若為甲酚，則可獲得甲酚酞。 As the phenolphthalein derivative, it is known that phthalic acid can be synthesized with the various phenols, and if the phenol used is phenol, phenolphthalein can be obtained, and if it is cresol, cresol can be obtained.

此處，作為上述各種酚類，例如可列舉：苯酚、甲酚、乙酚、丙酚、二甲苯酚、甲基丁基苯酚等。 Here, examples of the various phenols include phenol, cresol, ethylphenol, propofol, xylenol, and methylbutylphenol.

又，作為藉由上述反應而獲得之酚酞衍生物，例如可列舉下述結構。 In addition, examples of the phenolphthalein derivative obtained by the above reaction include the following structures.

(式中，R表示與上述相同之含義，n表示1~2之整數) (wherein R represents the same meaning as above, and n represents an integer of 1 to 2)

作為胺基苯衍生物，可列舉下述結構者。 Examples of the aminobenzene derivative include the following structures.

(式中，R表示與上述相同之含義，m表示1~2之整數) (wherein R represents the same meaning as above, and m represents an integer of 1 to 2)

酚系化合物(DPPI)中之殘留酚酞衍生物之量較佳為2%以下，更佳為1%以下，進而較佳為0.5%以下，尤佳為0.1%以下(以高速液相層析法測定)。於殘留該酚酞衍生物之情形時，有反應時著色變大之傾向。胺基苯衍生物亦相同。又，殘留之鐵成分(ICP發光分析)量亦為引起著色之因素之一。殘留鐵成分較佳為100ppm以下，更佳為50ppm以下，尤佳為10ppm以下。又，作為主體之酚系化合物(DPPI)期待98%以上之純度。 The amount of the residual phenolphthalein derivative in the phenolic compound (DPPI) is preferably 2% or less, more preferably 1% or less, further preferably 0.5% or less, and particularly preferably 0.1% or less (by high-speed liquid chromatography). Determination). When the phenolphthalein derivative is left, the coloration tends to increase upon reaction. The aminobenzene derivatives are also the same. Further, the amount of residual iron component (ICP luminescence analysis) is also one of the factors causing coloration. The residual iron component is preferably 100 ppm or less, more preferably 50 ppm or less, and still more preferably 10 ppm or less. Further, the main phenolic compound (DPPI) is expected to have a purity of 98% or more.

殘留酚酞衍生物之量可藉由DPPI之純化(洗淨、再結晶、再沈澱等)進行調整。 The amount of the residual phenolphthalein derivative can be adjusted by purification of DPPI (washing, recrystallization, reprecipitation, etc.).

於獲得本發明之環氧樹脂之反應中，作為表鹵醇，較佳為工業上容易獲取之表氯醇。表鹵醇之使用量相對於酚系化合物(DPPI)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5.5~8.5莫耳。 In the reaction for obtaining the epoxy resin of the present invention, as the epihalohydrin, epichlorohydrin which is industrially easily available is preferable. The amount of the epihalohydrin used is usually 3.0 to 15 moles, preferably 3.0 to 10 moles, more preferably 3.5 to 8.5 moles, and more preferably 5.5 to hydroxyl moles of the phenolic compound (DPPI). 8.5 m.

若低於3.0莫耳，則有時環氧當量變大，又，有時所獲得之環氧樹脂之作業性變差。若超過15莫耳，則溶劑量變多。 When it is less than 3.0 mol, the epoxy equivalent may become large, and the workability of the obtained epoxy resin may worsen. If it exceeds 15 moles, the amount of solvent will increase.

於上述酚系樹脂與表鹵醇之反應中，可使用鹼金屬氫氧化物，作為可使用之鹼金屬氫氧化物，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，但於本發明中，尤其就溶解性、操作之方面而言，較佳為使用成型為薄片狀之固形物。 In the reaction between the phenolic resin and the epihalohydrin, an alkali metal hydroxide can be used, and as the alkali metal hydroxide which can be used, sodium hydroxide, potassium hydroxide or the like can be used, and a solid matter can be used. Although it is an aqueous solution, in the present invention, in particular, in terms of solubility and handling, it is preferred 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酚系混合物之羥基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 to be used is usually 0.90 to 1.5 moles, preferably 0.95 to 1.25 moles, more preferably 0.99 to 1.15 moles, per mole of the hydroxyl group of the raw material phenol-based mixture.

為了促進反應，亦可添加四甲基氯化銨、四甲基溴化銨、三 甲基氯化苄基銨等四級銨鹽作為觸媒。作為四級銨鹽之使用量，相對於原料酚系混合物之羥基1莫耳通常為0.1~15g，較佳為0.2~10g。 In order to promote the reaction, tetramethylammonium chloride, tetramethylammonium bromide, and the like may also be added. A quaternary ammonium salt such as methylbenzylammonium chloride is used as a catalyst. The amount of the quaternary ammonium salt used is usually 0.1 to 15 g, preferably 0.2 to 10 g, based on the hydroxyl group of the raw material phenol-based mixture.

於本反應中，較佳為除上述表鹵醇以外，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，有甲醇、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手法控制系統內之水分一面進行環氧化。 In the present reaction, it is preferred to use a nonpolar protic solvent (dimethyl sulfoxide, two in addition to the above epihalohydrin). An alkane, dimethylimidazolidinone, etc., or an alcohol 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 nonpolar protic solvent or the alcohol having 1 to 5 carbon atoms is usually 2 to 50% by weight, preferably 4 to 25% by weight based on the amount of the epihalohydrin. Further, the epoxidation may be carried out while controlling the moisture in the system by a method such as azeotropic dehydration.

於系統中之水分較多之情形時，關於所獲得之環氧樹脂，電氣可靠性變差，故而欠佳，較佳為將水分控制於5%以下而進行合成。又，於使用非極性質子溶劑而獲得環氧樹脂時，可獲得電氣可靠性優異之環氧樹脂，故而可適宜地使用非極性質子溶劑。 When the amount of moisture in the system is large, the electrical reliability of the obtained epoxy resin is deteriorated, which is not preferable, and it is preferred to carry out the synthesis by controlling the moisture to 5% or less. Further, when an epoxy resin is obtained by using a nonpolar protic solvent, an epoxy resin having excellent electrical reliability can be obtained, and therefore, a nonpolar protic solvent can be suitably used.

反應溫度通常為30~90℃，較佳為35~80℃。尤其於本發明中，為了更高純度之環氧化，較佳為60℃以上，尤佳為接近於回流條件之條件之反應。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，則有時反應未完全進行，若反應時間變長，則有時會產生副產物。 The reaction temperature is usually from 30 to 90 ° C, preferably from 35 to 80 ° C. In particular, in the present invention, for higher purity epoxidation, it is preferably 60 ° C or higher, and particularly preferably a reaction which is close to the conditions of reflux conditions. The reaction time is usually from 0.5 to 10 hours, preferably from 1 to 8 hours, and particularly preferably from 1 to 3 hours. When the reaction time is short, the reaction may not proceed completely, and if the reaction time is long, by-products may be generated.

將該等環氧化反應之反應物水洗後，或不經水洗而於加熱減壓下去除表鹵醇或溶劑等。又，為了進而製作水解性鹵素較少之環氧樹脂，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)作為溶劑而使所回收之環氧樹脂溶解，並添加氫氧化鈉、氫氧化鉀等鹼金屬氫氧化物之水溶液而進行反應，從而確實地進行閉環。於此 情形時，鹼金屬氫氧化物之使用量相對於環氧化時所使用之原料酚系混合物之羥基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 the reactants of the epoxidation reaction are washed with water or without heating, the epihalohydrin or the solvent is removed under heating and reduced pressure. Further, in order to further produce an epoxy resin having less hydrolyzable halogen, a ketone compound having 4 to 7 carbon atoms may be used (for example, methyl isobutyl ketone, methyl ethyl ketone, cyclopentanone, cyclohexanone) The epoxy resin thus recovered is dissolved as a solvent, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to carry out a reaction, whereby the ring closure is surely carried out. herein In the case, the amount of the alkali metal hydroxide to be used is usually 0.01 to 0.3 mol, preferably 0.05 to 0.2 mol, based on the hydroxyl group of the raw material phenol-based 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.

又，於與表鹵醇之反應中，較佳為自反應初始以氮氣等不活性氣體進行置換，空腔內之氧濃度較佳為10%以下。氧之殘留對著色產生影響。作為手法，可列舉於裝入酚系化合物(DPPI)前吹入(氣體中、或液體中)氮氣等不活性氣體，或暫時以減壓抽真空後，以不活性氣體進行置換之方法。於未以不活性氣體置換之情形時，有時會於所獲得之樹脂中產生著色。於吹入不活性氣體之情形時，其量視該加熱器之容積而有所不同，較佳為吹入可以0.5~10小時置換該加熱器之容積之1~3倍量之量的不活性氣體。 Further, in the reaction with the epihalohydrin, it is preferred to replace it with an inert gas such as nitrogen gas from the initial stage of the reaction, and the oxygen concentration in the cavity is preferably 10% or less. The residual oxygen has an effect on the coloration. Examples of the method include a method of injecting an inert gas such as nitrogen gas (in a gas or a liquid) before charging a phenolic compound (DPPI), or temporarily evacuating it under reduced pressure, and then replacing it with an inert gas. When it is not replaced with an inert gas, coloring may occur in the obtained resin. When the inactive gas is blown, the amount varies depending on the volume of the heater, and it is preferable that the amount of inactivation of the heater may be replaced by an amount of 1 to 3 times the volume of the heater for 0.5 to 10 hours. gas.

反應結束後，藉由過濾、水洗等去除所生成之鹽，進而於加熱減壓下將溶劑蒸餾去除，藉此獲得本發明之環氧樹脂。 After completion of the reaction, the salt formed is removed by filtration, washing with water, or the like, and the solvent is distilled off under heating and reduced pressure to obtain an epoxy resin of the present invention.

以下，記載包含本發明之環氧樹脂之第1發明與第2發明之硬化性樹脂組成物。 Hereinafter, the curable resin composition of the first invention and the second invention comprising the epoxy resin of the present invention will be described.

第1發明之環氧樹脂組成物(以下亦稱為「硬化性樹脂組成物」)含有本發明之環氧樹脂作為必須成分。 The epoxy resin composition of the first invention (hereinafter also referred to as "curable resin composition") contains the epoxy resin of the present invention as an essential component.

對於第1發明之硬化性樹脂組成物，可應用由以羧酸類作為必須成分之硬化劑引起之熱硬化(硬化性樹脂組成物A)與以酸等陽離子聚合觸媒作為硬化觸媒之陽離子硬化(硬化性樹脂組成物B)兩種方法。 In the curable resin composition of the first aspect of the invention, thermosetting (curable resin composition A) by a curing agent containing a carboxylic acid as an essential component and cationic hardening by using a cationic polymerization catalyst such as an acid as a curing catalyst can be applied. (Curable resin composition B) Two methods.

於硬化性樹脂組成物A及硬化性樹脂組成物B，本發明之環氧樹脂可單獨地或與其他環氧樹脂併用而使用。於併用之情形時，本發明之環氧樹脂於全部環氧樹脂中所占之比率較佳為30質量%以上，尤佳為 40質量%以上。其中，於將本發明之環氧樹脂用作硬化性樹脂組成物之改質劑之情形時，亦可以1~30質量%之比率添加。 In the curable resin composition A and the curable resin composition B, the epoxy resin of the present invention can be used singly or in combination with other epoxy resins. When used in combination, the ratio of the epoxy resin of the present invention to all epoxy resins is preferably 30% by mass or more, and particularly preferably 40% by mass or more. In the case where the epoxy resin of the present invention is used as a modifier of a curable resin composition, it may be added in a ratio of 1 to 30% by mass.

作為可與本發明之環氧樹脂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、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、茀雙酚、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、萘二酚、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)苯等之縮聚物及該等之改質物、由四溴雙酚A等鹵化雙酚類以及醇類衍生之環氧丙醚化物、脂環式環氧樹脂、環氧丙基胺系環氧樹脂、環氧丙酯系環氧樹脂、倍半矽氧烷系之環氧樹脂(於鏈狀、環狀、梯狀、或該等至少2種以上之混合結構之矽氧烷結構中具有環氧丙基及/或環氧環己烷結構的環氧樹脂)等固形或液狀環氧樹脂，但並不限定於該等。 Examples of other epoxy resins which can be used in combination with the epoxy resin of the present invention include novolak type epoxy resin, bisphenol type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, and phenolic phenol. An alkyl type epoxy resin or the like. Specific examples thereof include bisphenol A, bisphenol S, thiobiphenol, quinone bisphenol, nonylphenol, 4,4′-biphenol, 2,2′-biphenol, 3,3′, 5 , 5'-tetramethyl-[1,1'-biphenyl]-4,4'-diol, hydroquinone, resorcinol, naphthalenediol, tris(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(methoxy a polycondensate of benzene or the like, a modified substance thereof, a halogenated bisphenol such as tetrabromobisphenol A or an alcohol-derived glycidyl etherate, an alicyclic epoxy resin, or a glycidylamine ring An epoxy resin, a glycidyl ester epoxy resin, or a sesquioxane-based epoxy resin (having a chain structure, a ring shape, a ladder shape, or a mixture structure of at least two or more kinds of the above structures) Epoxypropyl and/or ring Epoxy cyclohexane structure) solid or liquid epoxy resin and the like, but is not limited to such.

尤其將本發明之硬化性樹脂組成物用於光學用途之情形時，較佳為併用本發明之環氧樹脂與脂環式環氧樹脂或倍半矽氧烷結構之環氧樹脂而使用。尤其於脂環式環氧樹脂之情形時，較佳為骨架中具有環氧環己烷結構之化合物，尤佳為藉由具有環己烯結構之化合物之氧化反應而獲得之環氧樹脂。 In particular, when the curable resin composition of the present invention is used for optical applications, it is preferred to use the epoxy resin of the present invention in combination with an alicyclic epoxy resin or an epoxy resin having a sesquiterpene oxide structure. Particularly in the case of the alicyclic epoxy resin, a compound having an epoxycyclohexane structure in the skeleton is preferable, and an epoxy resin obtained by an oxidation reaction of a compound having a cyclohexene structure is particularly preferable.

作為具有環己烯結構之化合物，可列舉可藉由環己烯羧酸與醇類之酯 化反應或環己烯甲醇與羧酸類之酯化反應(Tetrahedron vol.36 p.2409(1980),Tetrahedron Letter p.4475(1980)等中所記載之手法)、或環己烯醛之季先科反應(tishchenko reaction，日本特開2003-170059號公報、日本特開2004-262871號公報等中所記載之手法)、以及環己烯羧酸酯之酯交換反應(日本特開2006-052187號公報等中所記載之手法)而製造之化合物。 As a compound having a cyclohexene structure, an ester which can be obtained by a cyclohexene carboxylic acid and an alcohol The reaction or the esterification reaction of cyclohexene methanol with a carboxylic acid (Tetrahedron vol. 36 p. 2409 (1980), Tetrahedron Letter p. 4475 (1980), etc.), or the predatory reaction of cyclohexenal (the method described in Japanese Patent Laid-Open Publication No. 2003-170871, and the like), and the transesterification reaction of cyclohexene carboxylate (JP-A-2006-052187, etc.) A compound produced by the method described in the above.

作為醇類，只要為具有醇性羥基之化合物則無特別限定，可列舉：乙二醇、1,2-丙二醇、1,3-丙二醇、1,2-丁二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、環己烷二甲醇等二醇類，甘油、三羥甲基乙烷、三羥甲基丙烷、三羥甲基丁烷、2-羥基甲基-1,4-丁二醇等三醇類，新戊四醇等四醇類等。又，作為羧酸類，可列舉：草酸、順丁烯二酸、反丁烯二酸、鄰苯二甲酸、間苯二甲酸、己二酸、環己烷二羧酸等，但不限於此。 The alcohol is not particularly limited as long as it is a compound having an alcoholic hydroxyl group, and examples thereof include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,2-butanediol, and 1,4-butane. a glycol such as an alcohol, 1,5-pentanediol, 1,6-hexanediol or cyclohexanedimethanol, glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, Triols such as 2-hydroxymethyl-1,4-butanediol, tetraols such as pentaerythritol, and the like. Further, examples of the carboxylic acid include oxalic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, adipic acid, and cyclohexanedicarboxylic acid, but are not limited thereto.

進而，作為上述以外之具有環己烯結構之化合物，可列舉由環己烯醛衍生物與醇體之縮醛反應產生之縮醛化合物。作為反應手法，只要應用通常之縮醛化反應即可製造，例如揭示有：一面使用甲苯、二甲苯等溶劑作為反應介質而進行共沸脫水一面進行反應之方法(美國專利第2945008號說明書)；使多元醇溶解於濃鹽酸後一面緩慢添加醛類一面進行反應之方法(日本特開昭48-96590號公報)；使用水作為反應介質之方法(美國專利第3092640號說明書)；使用有機溶劑作為反應介質之方法(日本特開平7-215979號公報)；使用固體酸觸媒之方法(日本特開2007-230992號公報)等。就結構之穩定性而言較佳為環狀縮醛結構。 Further, examples of the compound having a cyclohexene structure other than the above include an acetal compound produced by a reaction of a cyclohexenal derivative with an acetal of an alcohol. The reaction method can be produced by applying a usual acetalization reaction. For example, a method of performing azeotropic dehydration using a solvent such as toluene or xylene as a reaction medium is disclosed (U.S. Patent No. 2945008); A method in which a polyol is slowly dissolved in concentrated hydrochloric acid and a reaction is carried out while slowly adding an aldehyde (JP-A-48-96590); a method using water as a reaction medium (U.S. Patent No. 3092640); using an organic solvent as a solvent A method of using a reaction medium (Japanese Patent Laid-Open Publication No. Hei 7-215979); a method using a solid acid catalyst (JP-A-2007-230992). A cyclic acetal structure is preferred in terms of structural stability.

作為該等環氧樹脂之具體例，可列舉：ERL-4221、UVR-6105、ERL-4299(均為商品名，均為Dow Chemical製造)、Celloxide 2021P，Epolead GT401、 EHPE3150、EHPE3150CE(均為商品名，均為Daicel化學工業製造)及二環戊二烯二環氧化物等，但不限定於該等(參考文獻：環氧樹脂綜述 基礎篇I p76-85)。 Specific examples of the epoxy resin include ERL-4221, UVR-6105, and ERL-4299 (all of which are trade names, all manufactured by Dow Chemical), Celloxide 2021P, and Epolead GT401. EHPE3150, EHPE3150CE (all trade names, all manufactured by Daicel Chemical Industry) and dicyclopentadiene diepoxide, etc., but are not limited to these (Reference: Epoxy Resin General Fundamentals I p76-85).

該等可單獨使用，亦可併用2種以上。 These may be used alone or in combination of two or more.

以下，對各硬化性樹脂組成物進行說明。 Hereinafter, each curable resin composition will be described.

硬化性樹脂組成物A(由硬化劑引起之熱硬化) Curable resin composition A (thermal hardening caused by hardener)

作為本發明之硬化性樹脂組成物A所含有之硬化劑，以具有羧酸結構之樹脂(以下稱為羧酸類)作為必須成分。作為羧酸類，尤佳為2~4官能之羧酸，進而較佳為藉由使2~4官能之多元醇與酸酐進行加成反應而獲得之多羧酸。又，環己烷-1,3,4-三羧酸-3,4-酐等具有酸酐與羧酸之結構亦較佳。通常於光學材料用途中使用酸酐，但於本發明之硬化性組成物A中，就抑制揮發性之方面而言，亦將羧酸作為必須成分。 The curing agent contained in the curable resin composition A of the present invention contains a resin having a carboxylic acid structure (hereinafter referred to as a carboxylic acid) as an essential component. The carboxylic acid is preferably a 2-4 carboxylic acid, and more preferably a polycarboxylic acid obtained by subjecting a 2-4 functional polyol to an acid anhydride. Further, a structure having an acid anhydride and a carboxylic acid such as cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride is also preferable. An acid anhydride is usually used in the use of an optical material, but in the curable composition A of the present invention, a carboxylic acid is also an essential component in terms of suppressing volatility.

作為2~4官能之多元醇，只要為具有醇性羥基之化合物則無特別限定，可列舉：乙二醇、1,2-丙二醇、1,3-丙二醇、1,2-丁二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、環己烷二甲醇、2,4-二乙基戊二醇、2-乙基-2-丁基-1,3-丙二醇、新戊二醇、三環癸烷二甲醇、降莰烯二醇等二醇類；甘油、三羥甲基乙烷、三羥甲基丙烷、三羥甲基丁烷、2-羥基甲基-1,4-丁二醇等三醇類；新戊四醇、二(三羥甲基丙烷)等四醇類等。 The 2~4-functional polyol is not particularly limited as long as it is a compound having an alcoholic hydroxyl group, and examples thereof include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, and 1,2-butanediol. , 4-butanediol, 1,5-pentanediol, 1,6-hexanediol, cyclohexanedimethanol, 2,4-diethylpentanediol, 2-ethyl-2-butyl- a diol such as 1,3-propanediol, neopentyl glycol, tricyclodecane dimethanol or norbornene diol; glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, Triols such as 2-hydroxymethyl-1,4-butanediol; tetraols such as pentaerythritol and di(trimethylolpropane).

尤佳為環己烷二甲醇、2,4-二乙基戊二醇、2-乙基-2-丁基-1,3-丙二醇、新戊二醇、三環癸烷二甲醇、降莰烯二醇等支鏈狀或環狀之多元醇。 Particularly preferred are cyclohexanedimethanol, 2,4-diethylpentanediol, 2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol, tricyclodecane dimethanol, and hydrazine A branched or cyclic polyol such as an ene glycol.

作為酸酐，尤佳為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-酸酐等。 As the acid anhydride, methyl tetrahydrophthalic anhydride, methyl acid anhydride, ceric acid anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butane tetracarboxylic anhydride, and the like are preferable. Bicyclo[2,2,1]heptane-2,3-dicarboxylic anhydride, methylbicyclo[2,2,1]heptane-2,3-dicarboxylic anhydride, cyclohexane-1,3,4- Tricarboxylic acid-3,4-anhydride, and the like.

尤佳為下述式(5) Yu Jia is the following formula (5)

(式中，Q表示氫原子、甲基、羧基中之至少1種)所表示之六氫鄰苯二甲酸酐、甲基六氫鄰苯二甲酸酐、環己烷-1,3,4-三羧酸-3,4-酸酐。 (wherein, Q represents at least one of a hydrogen atom, a methyl group and a carboxyl group), hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, cyclohexane-1,3,4- Tricarboxylic acid-3,4-anhydride.

作為可與該等羧酸類併用之硬化劑，例如可列舉胺系化合物、酸酐系化合物、醯胺系化合物、酚系化合物等。作為可使用之硬化劑之具體例，可列舉：由二胺基二苯甲烷、二乙三胺、三乙四胺、二胺基二苯基碸、異佛酮二胺(isophoronediamine)、雙氰胺、次亞麻油酸之二聚物與乙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、偏苯三甲酸酐、均苯四甲酸二酐(pyromellitic dianhydride)、順丁烯二酸酐、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、茀雙酚、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、萘二酚、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)苯等之縮聚物及該等之改質物、四溴雙酚A等鹵化雙酚類、萜與酚類之縮合物等多酚類；咪唑、三氟化硼-胺錯合物、胍衍生物之化合物等，但不限定於該等。該等可單獨使用，亦可使用2種以上。 Examples of the curing agent which can be used in combination with the carboxylic acid include an amine compound, an acid anhydride compound, a guanamine compound, and a phenol compound. Specific examples of the hardener which can be used include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylphosphonium, isophoronediamine, and dicyandiamide. Nitrogen-containing compounds (amines, guanamine compounds) such as polyamines synthesized from amines and linolenic acid dimers and ethylenediamine; phthalic anhydride, trimellitic anhydride, and pyromellitic dianhydride ( Pyromellitic dianhydride), maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylic acid anhydride, ceric anhydride, hexahydrophthalic anhydride, methyl hexahydrogen Phthalic anhydride, butane tetracarboxylic anhydride, bicyclo[2,2,1]heptane-2,3-dicarboxylic anhydride, methylbicyclo[2,2,1]heptane-2,3-dicarboxylate Anhydride, cyclohexane-1,3,4-tricarboxylic acid An acid anhydride such as 3,4-anhydride; a carboxylic acid resin obtained by an addition reaction of various alcohols and methanol modified polyfluorene oxide with the above acid anhydride; bisphenol A, bisphenol F, bisphenol S, bismuth bisphenol, Cinhydrin, 4,4'-biphenol, 2,2'-biphenol, 3,3',5,5'-tetramethyl-[1,1'-biphenyl]-4,4'- Alcohol, hydroquinone, resorcinol, naphthalenediol, tris(4-hydroxyphenyl)methane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, phenols (phenol, Alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) with formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyl Acetophenone, dicyclopentadiene, furfural, 4,4'-bis(chloromethyl)-1,1'-biphenyl, 4,4'-bis(methoxymethyl)-1,1' a polycondensate of biphenyl, 1,4'-bis(chloromethyl)benzene or 1,4'-bis(methoxymethyl)benzene, and the like, and a halogenated double such as tetrabromobisphenol A Polyphenols such as phenols, condensates of hydrazines and phenols; compounds of imidazole, boron trifluoride-amine complexes, and anthracene derivatives, but are not limited thereto. These may be used alone or in combination of two or more.

本發明之硬化性樹脂組成物A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當量之情形、或超過1.2當量之情形時，均存在硬化不完全而無法獲得良好之硬化物性之情況。 The amount of the curing agent used in the curable resin composition A of the present invention is preferably from 0.7 to 1.2 equivalents per equivalent of the epoxy group of the epoxy resin. When the amount is less than 0.7 equivalents per equivalent of the epoxy group or exceeds 1.2 equivalents, the hardening is incomplete and good cured physical properties are not obtained.

於本發明之硬化性樹脂組成物A，亦可與硬化劑一併使用硬化促進劑(硬化觸媒)。作為可使用之硬化促進劑之具體例，可列舉：2-甲基咪唑、2-乙基咪唑及2-乙基-4-甲基咪唑等咪唑類，2-(二甲胺甲基)苯酚或1,8-二氮雜雙環(5,4,0)十一烯-7等三級胺類，三苯基膦等膦類，四丁基銨鹽、三異丙基甲基銨鹽、三甲基癸基銨鹽、鯨蠟基三甲基銨鹽、鯨蠟基三甲基氫氧化銨等四級銨鹽，三苯基苄基鏻鹽、三苯基乙基鏻鹽、四丁基鏻鹽等四級鏻鹽(四級鹽之相對離子為鹵素、有機酸根離子、氫氧化物離子等， 雖然無特別指定，但尤佳為有機酸根離子、氫氧化物離子)，辛酸錫、羧酸鋅(2-乙基己酸鋅、硬脂酸鋅、二十二酸鋅、肉豆蔻酸鋅)或磷酸酯鋅(磷酸辛酯鋅、磷酸硬脂酯鋅等)等鋅化合物等過渡金屬化合物(過渡金屬鹽)等。硬化促進劑相對於環氧樹脂100可視需要使用0.01~5.0重量份。 In the curable resin composition A of the present invention, a curing accelerator (curing catalyst) may be used together with the curing agent. Specific examples of the hardening accelerator which can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole and 2-ethyl-4-methylimidazole, and 2-(dimethylaminomethyl)phenol. Or a tertiary amine such as 1,8-diazabicyclo(5,4,0)undecene-7, a phosphine such as triphenylphosphine, a tetrabutylammonium salt or a triisopropylmethylammonium salt, Tetramethylammonium salt, cetyltrimethylammonium salt, cetyltrimethylammonium hydroxide and other quaternary ammonium salts, triphenylbenzylphosphonium salt, triphenylethylphosphonium salt, tetrabutyl a quaternary phosphonium salt such as a sulfonium salt (the relative ions of the quaternary salt are halogen, organic acid ion, hydroxide ion, etc. Although not specified, it is especially organic acid ion, hydroxide ion), tin octoate, zinc carboxylate (zinc 2-ethylhexanoate, zinc stearate, zinc behenate, zinc myristate) A transition metal compound (transition metal salt) such as a zinc compound such as zinc phosphate (zinc phosphate phosphate or zinc stearyl phosphate). The hardening accelerator may be used in an amount of 0.01 to 5.0 parts by weight based on the epoxy resin 100.

於本發明中，尤其為了保持光學特性，較佳為使用四級鏻鹽或過渡金屬化合物(過渡金屬鹽)。 In the present invention, in particular, in order to maintain optical characteristics, a quaternary phosphonium salt or a transition metal compound (transition metal salt) is preferably used.

本發明之硬化性樹脂組成物A亦可含有含磷之化合物作為阻燃性賦予成分。作為含磷之化合物，可為反應型，亦可為添加型。作為含磷之化合物之具體例，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)(trixylenyl phosphate)、磷酸甲酚二苯酯、磷酸甲苯基2,6-二(二甲苯)酯、1,3-伸苯基雙(二(二甲苯基)磷酸酯)、1,4-伸苯基雙(二(二甲苯基)磷酸酯)及4,4'-聯苯(二(二甲苯基)磷酸酯)等磷酸酯類；9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物或10-(2,5-二羥基苯基)-10H-9-氧雜-10-磷雜菲-10-氧化物(9,10-Dihydro-9-oxa-10-phosphaphenanthrene 10-oxide)等膦類；使環氧樹脂與上述膦類之活性氫進行反應而獲得之含磷之環氧樹脂、紅磷等，較佳為磷酸酯類、膦類或含磷之環氧樹脂，尤佳為1,3-伸苯基雙(二(二甲苯基)磷酸酯)、1,4-伸苯基雙(二(二甲苯基)磷酸酯)、4,4'-聯苯(二(二甲苯基)磷酸酯)或含磷之環氧樹脂。含磷之化合物之含量相對於本發明之硬化性樹脂組成物A中之環氧樹脂成分之總量較佳為0.6倍以下。於超過0.6倍之情形時，有時會對硬化物之吸濕性、介電特性造成不良影響。 The curable resin composition A of the present invention may further contain a phosphorus-containing compound as a flame retardancy imparting component. As the phosphorus-containing compound, it may be a reaction type or an addition type. Specific examples of the phosphorus-containing compound include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, and toluene phosphate 2 , 6-bis(xylene) ester, 1,3-phenylene bis(di(xylenyl) phosphate), 1,4-phenylphenylbis(diphenyl)phosphate, and 4, Phosphate such as 4'-biphenyl (di(xylenyl) phosphate); 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide or 10-(2,5- Phosphines such as dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide; The phosphorus-containing epoxy resin, red phosphorus or the like obtained by reacting the active hydrogen of the phosphine is preferably a phosphate ester, a phosphine or a phosphorus-containing epoxy resin, and particularly preferably a 1,3-phenylene double (di(xylyl)phosphate), 1,4-phenylene bis(diphenylphosphine), 4,4'-biphenyl (di(xylenyl) phosphate) or phosphorus Epoxy resin. The content of the phosphorus-containing compound is preferably 0.6 times or less the total amount of the epoxy resin component in the curable resin composition A of the present invention. When it exceeds 0.6 times, it may adversely affect the hygroscopicity and dielectric properties of a hardened material.

進而，於本發明之硬化性樹脂組成物A，亦可視需要添加抗氧化劑。作為可使用之抗氧化劑，可列舉酚系、硫系、磷系抗氧化劑。抗 氧化劑可單獨使用或組合2種以上而使用。抗氧化劑之使用量相對於本發明之硬化性樹脂組成物中A之樹脂成分100重量份通常為0.008~1重量份，較佳為0.01~0.5重量份。 Further, in the curable resin composition A of the present invention, an antioxidant may be added as needed. Examples of the antioxidant that can be used include a phenol-based, sulfur-based, and phosphorus-based antioxidant. anti- The oxidizing agents may be used singly or in combination of two or more. The amount of the antioxidant to be used is usually from 0.008 to 1 part by weight, preferably from 0.01 to 0.5 part by weight, per 100 parts by weight of the resin component of the curable resin composition of the present invention.

作為酚系抗氧化劑之具體例，可例示：2,6-二第三丁基對甲酚、丁基化羥基苯甲醚、2,6-二第三丁基對乙酚、β-(3,5-二第三丁基-4-羥基苯基)丙酸硬脂酯、3-(3,5-二第三丁基-4-羥基苯基)丙酸異辛酯、2,4-雙(正辛硫基)-6-(4-羥基-3,5-二第三丁基苯胺基)-1,3,5-三、2,4-雙[(辛硫基)甲基]鄰甲酚等單酚類；2,2'-亞甲基雙(4-甲基-6-第三丁基苯酚)、2,2'-亞甲基雙(4-乙基-6-第三丁基苯酚)、4,4'-硫代雙(3-甲基-6-第三丁基苯酚)、4,4'-亞丁基雙(3-甲基-6-第三丁基苯酚)、三乙二醇雙[3-(3-第三丁基-5-甲基-4-羥基苯基)丙酸酯]、1,6-己二醇雙[3-(3,5-二第三丁基-4-羥基苯基)丙酸酯]、N,N'-六亞甲基雙(3,5-二第三丁基-4-羥基-苯丙醯胺)、2,2-硫代-二伸乙基雙[3-(3,5-二第三丁基-4-羥基苯基)丙酸酯]、3,5-二第三丁基-4-羥基苄基膦酸二乙酯、3,9-雙[1,1-二甲基-2-{β-(3-第三丁基-4-羥基-5-甲基苯基)丙醯氧基}乙基]2,4,8,10-四氧雜螺[5,5]十一烷、雙(3,5-二第三丁基-4-羥基苄基磺酸乙酯)鈣等雙酚類；1,1,3-三(2-甲基-4-羥基-5-第三丁基苯基)丁烷、1,3,5-三甲基-2,4,6-三(3,5-二第三丁基-4-羥基苄基)苯、四[亞甲基-3-(3',5'-二第三丁基-4'-羥基苯基)丙酸酯]甲烷、雙[3,3'-雙(4'-羥基-3'-第三丁基苯基)丁酸]乙二醇酯、三(3,5-二第三丁基-4-羥基苄基)異三聚氰酸酯、1,3,5-三(3',5'-二第三丁基-4'-羥基苄基)均三-2,4,6-(1H,3H,5H)三酮、生育酚等高分子型酚類。 Specific examples of the phenolic antioxidant include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, and β-(3) ,5-di-t-butyl-4-hydroxyphenyl)propionic acid stearyl ester, 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid isooctyl ester, 2,4- Bis(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-three Monophenols such as 2,4-bis[(octylthio)methyl]o-cresol; 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2 '-Methylene bis(4-ethyl-6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 4,4'-Adenine Bis(3-methyl-6-tert-butylphenol), triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1 ,6-hexanediol bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylene bis (3,5-di third Butyl-4-hydroxy-phenylpropanamide), 2,2-thio-di-extension ethyl bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], Diethyl 3,5-di-t-butyl-4-hydroxybenzylphosphonate, 3,9-bis[1,1-dimethyl-2-{β-(3-tert-butyl-4- Hydroxy-5-methylphenyl)propoxycarbonyl}ethyl]2,4,8,10-tetraoxaspiro[5,5]undecane, bis(3,5-di-t-butyl- Ethyl 4-hydroxybenzylsulfonate) bisphenols such as calcium; 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5 -trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tetrakis[methylene-3-(3',5'-di-3rd Methyl-4'-hydroxyphenyl)propionate]methane, bis[3,3'-bis(4'- Glycol-3'-tert-butylphenyl)butyrate]ethylene glycol, tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanate, 1,3,5 -Tris(3',5'-di-t-butyl-4'-hydroxybenzyl) is three -2,4,6-(1H,3H,5H) triols, polymer phenols such as tocopherols.

作為硫系抗氧化劑之具體例，可例示：3,3'-硫代二丙酸二月桂酯、3,3'-硫代二丙酸二肉豆蔻酯、3,3'-硫代二丙酸二硬脂酯等。 Specific examples of the sulfur-based antioxidant include dilauryl 3,3'-thiodipropionate, 3,3'-thiodipropionate dimyristate, and 3,3'-thiodipropane. Distearyl ester and the like.

作為磷系抗氧化劑之具體例，可例示：亞磷酸三苯酯、亞磷酸二苯基異癸酯、亞磷酸苯基二異癸酯、亞磷酸三(壬基苯基)酯、二異癸基新戊四醇亞磷酸酯、三(2,4-二第三丁基苯基)亞磷酸酯、環狀新戊烷四基雙(十八烷基)亞磷酸酯、環狀新戊烷四基二(2,4-二第三丁基苯基)亞磷酸酯、環狀新戊烷四基二(2,4-二第三丁基-4-甲基苯基)亞磷酸酯、雙[2-第三丁基-6-甲基-4-{2-(十八烷基氧羰基)乙基}苯基]氫亞磷酸酯等亞磷酸酯類；9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物、10-(3,5-二第三丁基-4-羥基苄基)-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物、10-癸氧基-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物等氧雜磷雜菲氧化物類等。 Specific examples of the phosphorus-based antioxidant include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisononyl phosphite, tris(nonylphenyl) phosphite, and diisoindole. Neopentyl pentaerythritol phosphite, tris(2,4-di-t-butylphenyl)phosphite, cyclic neopentyltetrakis(bis-octadecyl)phosphite, cyclic neopentane Tetrakis(2,4-di-t-butylphenyl)phosphite, cyclic neopentyltetrakis(2,4-di-t-butyl-4-methylphenyl)phosphite, Phosphites such as bis[2-t-butyl-6-methyl-4-{2-(octadecyloxycarbonyl)ethyl}phenyl]hydrogen phosphite; 9,10-dihydro- 9-oxa-10-phosphaphenanthrene-10-oxide, 10-(3,5-di-t-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10- Oxyphosphorus phenanthrene oxides such as phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.

該等抗氧化劑可分別單獨使用，亦可組合2種以上而併用。尤其於本發明中較佳為磷系之抗氧化劑。 These antioxidants may be used alone or in combination of two or more. Particularly preferred in the present invention are phosphorus-based antioxidants.

進而，於本發明之硬化性樹脂組成物A，亦可視需要添加光穩定劑。 Further, in the curable resin composition A of the present invention, a light stabilizer may be added as needed.

作為光穩定劑，較佳為受阻胺系之光穩定劑，尤佳為HALS等。作為HALS並無特別限定，但作為代表性者，可列舉：二丁基胺-1,3,5-三-N,N'-雙(2,2,6,6-四甲基-4-哌啶基-1,6-六亞甲基二胺與N-(2,2,6,6-四甲基-4-哌啶基)丁基胺之縮聚物、琥珀酸二甲酯-1-(2-羥基乙基)-4-羥基-2,2,6,6-四甲基哌啶縮聚物、聚[{6-(1,1,3,3-四甲基丁基)胺基-1,3,5-三-2,4-二基}{(2,2,6,6-四甲基-4-哌啶基)亞胺基}六亞甲基{(2,2,6,6-四甲基-4-哌啶基)亞胺基}]、丙二酸雙(1,2,2,6,6-五甲基-4-哌啶基)[[3,5-雙(1,1-二甲基乙基)-4-羥基苯基]甲基]丁酯、癸二酸雙(2,2,6,6-四甲基-4-哌啶基)酯、癸二酸雙(1,2,2,6,6-五甲基-4-哌啶基)酯、癸二酸雙(1-辛氧基-2,2,6,6-四甲基-4-哌啶基)酯、2-(3,5-二第三丁基-4-羥 基苄基)-2-正丁基丙二酸雙(1,2,2,6,6-五甲基-4-哌啶基)酯等。HALS可僅使用1種，亦可併用2種以上。 As the light stabilizer, a hindered amine light stabilizer is preferred, and HALS or the like is particularly preferred. The HALS is not particularly limited, but as a representative, dibutylamine-1,3,5-three may be mentioned. -N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl-1,6-hexamethylenediamine and N-(2,2,6,6-tetramethyl) Polycondensate of phenyl-4-piperidinyl)butylamine, dimethyl succinate-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate , poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-three -2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidinyl)imido}hexamethylene {(2,2,6,6-tetramethyl-) 4-piperidinyl)imido}], malonic acid bis(1,2,2,6,6-pentamethyl-4-piperidinyl)[[3,5-bis(1,1-di) Methyl ethyl)-4-hydroxyphenyl]methyl]butyl ester, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, sebacic acid bis(1, 2,2,6,6-pentamethyl-4-piperidinyl) bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate , 2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butylmalonic acid bis(1,2,2,6,6-pentamethyl-4-piperidinyl ) esters, etc. HALS may be used alone or in combination of two or more.

進而，於本發明之硬化性樹脂組成物A，可視需要添加黏合劑樹脂。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，但不限定於該等。黏合劑樹脂之調配量較佳為無損硬化物之阻燃性、耐熱性之範圍，相對於本發明之硬化性樹脂組成物A中之樹脂成分(環氧樹脂與黏合劑樹脂之總量)100重量份通常視需要使用0.05~50重量份，較佳為0.05~20質量份。 Further, in the curable resin composition A of the present invention, a binder resin may be added as needed. 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 polyamine resin, and a polyfluorene. The imide resin, the polyoxynene resin, etc. are not limited to these. The blending amount of the binder resin is preferably in the range of flame retardancy and heat resistance of the hardened cured product, and the resin component (the total amount of the epoxy resin and the binder resin) in the curable resin composition A of the present invention is 100. The parts by weight are usually used in an amount of 0.05 to 50 parts by weight, preferably 0.05 to 20 parts by mass.

於本發明之硬化性樹脂組成物A，可視需要添加無機填充材。作為無機填充材，可列舉：晶體二氧化矽、熔融二氧化矽、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、氧化鈦、滑石等之粉體或使該等球形化而成之顆粒等，但不限定於該等。該等可單獨使用，亦可使用2種以上。該等無機填充材之含量係使用在本發明之硬化性樹脂組成物A中占95質量%以下之量。進而，於本發明之硬化性樹脂組成物A，可添加矽烷偶合劑、硬脂酸、棕櫚酸、硬脂酸鈣、羧酸鋅(2-乙基己酸鋅、硬脂酸鋅、二十二酸鋅、肉豆蔻酸鋅)或磷酸酯鋅(磷酸辛酯鋅、磷酸硬脂酯鋅等)等鋅化合物、界面活性劑、染料、顏料、紫外線吸收劑等各種調配劑、各種熱硬化性樹脂。 In the curable resin composition A of the present invention, an inorganic filler may be added as needed. Examples of the inorganic filler include crystalline cerium oxide, molten cerium oxide, aluminum oxide, zircon, calcium silicate, calcium carbonate, cerium carbide, tantalum nitride, boron nitride, zirconium oxide, forsterite, and the like. A powder such as talc, spinel, titanium oxide or talc, or particles obtained by spheroidizing the particles, etc., but is not limited thereto. These may be used alone or in combination of two or more. The content of the inorganic filler is 95% by mass or less based on the curable resin composition A of the present invention. Further, in the curable resin composition A of the present invention, a decane coupling agent, stearic acid, palmitic acid, calcium stearate, zinc carboxylate (zinc 2-ethylhexanoate, zinc stearate, and twentieth may be added). Zinc compound such as zinc diacid or zinc myristate or zinc phosphate (zinc phosphate phosphite, zinc stearyl phosphate, etc.), various preparation agents such as a dye, a pigment, a UV absorber, and various thermosetting properties Resin.

於將本發明之硬化性樹脂組成物A用於光半導體密封劑之情形時，可視需要添加螢光體。螢光體係例如具有如下作用者：吸收自藍色LED元件發出之藍色光之一部分，並發出經波長轉換而成之黃色光，藉 此形成白色光。使螢光體預先分散於硬化性樹脂組成物中，然後密封光半導體。作為螢光體並無特別限制，可使用先前公知之螢光體，例如可例示稀土元素之鋁酸鹽、硫代沒食子酸鹽、原矽酸鹽等。更具體而言，可列舉：YAG螢光體、TAG螢光體、原矽酸酯螢光體、硫代五倍子酸鹽(thiogallate)螢光體、硫化物螢光體等螢光體，且可例示YAlO3：Ce、Y3Al5O12：Ce、Y4Al2O9：Ce、Y2O2S：Eu、Sr5(PO4)3Cl：Eu、(SrEu)O‧Al2O3等。作為該螢光體之粒徑，係使用該領域中公知之粒徑，但作為平均粒徑，較佳為1~250μm，尤佳為2~50μm。於使用該等螢光體之情形時，其添加量相對於樹脂成分100重量份較佳為1~80重量份，尤佳為5~60重量份。 When the curable resin composition A of the present invention is used for a photo-semiconductor encapsulant, a phosphor may be added as needed. The fluorescent system has, for example, a function of absorbing a portion of the blue light emitted from the blue LED element and emitting wavelength-converted yellow light, thereby forming white light. The phosphor is previously dispersed in the curable resin composition, and then the photo-semiconductor is sealed. The phosphor is not particularly limited, and a conventionally known phosphor can be used, and examples thereof include an aluminate of a rare earth element, a thiogallate, a protopinate, and the like. More specifically, a phosphor such as a YAG phosphor, a TAG phosphor, a prophthalate phosphor, a thiogallate phosphor, or a sulfide phosphor can be used. Illustrative YAlO 3 :Ce, Y 3 Al 5 O 12 :Ce, Y 4 Al 2 O 9 :Ce, Y 2 O 2 S:Eu, Sr 5 (PO 4 ) 3 Cl:Eu, (SrEu)O‧Al 2 O 3 and so on. As the particle diameter of the phosphor, a particle diameter known in the art is used, but the average particle diameter is preferably from 1 to 250 μm, particularly preferably from 2 to 50 μm. In the case of using such a phosphor, the amount thereof is preferably from 1 to 80 parts by weight, particularly preferably from 5 to 60 parts by weight, per 100 parts by weight of the resin component.

本發明之硬化性樹脂組成物A可藉由將上述各成分均勻混合而獲得。本發明之硬化性樹脂組成物A可藉由與習知之方法相同之方法容易地製作其之硬化物。例如可藉由如下方式獲得本發明之硬化物：將本發明之環氧樹脂、硬化劑以及視需要之硬化促進劑、含磷之化合物、黏合劑樹脂、無機填充材及調配劑，視需要使用擠出機、捏合機、輥等充分混合直至均勻而獲得硬化性樹脂組成物，灌注該硬化性樹脂組成物並熔融後(液狀之情形不熔融)澆鑄成型或使用轉注成型機等進行成型，進而以80~200℃加熱2~10小時。 The curable resin composition A of the present invention can be obtained by uniformly mixing the above components. The curable resin composition A of the present invention can be easily produced into a cured product by the same method as a conventional method. For example, the cured product of the present invention can be obtained by using the epoxy resin, the hardener, and optionally the hardening accelerator, the phosphorus-containing compound, the binder resin, the inorganic filler, and the compounding agent of the present invention, as needed. The extruder, the kneader, the roll, and the like are sufficiently mixed until uniform to obtain a curable resin composition, and after the curable resin composition is poured and melted (in the case of liquid, it is not melted), it is molded or molded by using a transfer molding machine or the like. Further, it is heated at 80 to 200 ° C for 2 to 10 hours.

又，可藉由如下方式製作本發明之硬化性樹脂組成物A之硬化物：視需要將本發明之硬化性樹脂組成物A溶解於甲苯、二甲苯、丙酮、甲基乙基酮、甲基異丁基酮、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺及N-甲基吡咯啶酮等溶劑，製成硬化性樹脂組成物清漆，使之含浸於玻璃纖維、碳纖維、聚酯纖維、聚醯胺纖維、氧化鋁纖維及紙等基材並進行加熱 乾燥，對所獲得之預浸體進行熱壓成形。此時之溶劑係使用在本發明之硬化性樹脂組成物A與該溶劑之混合物中通常占10~70質量%、較佳為占15~70質量%之量。又，若為液狀組成物，亦可直接以例如RTM(resin transfer molding，樹脂轉注成型)方式獲得含有碳纖維之環氧樹脂硬化物。 Further, the cured product of the curable resin composition A of the present invention can be produced by dissolving the curable resin composition A of the present invention in toluene, xylene, acetone, methyl ethyl ketone or methyl group as necessary. A solvent such as isobutyl ketone, N,N-dimethylformamide, N,N-dimethylacetamide or N-methylpyrrolidone is used to form a varnish of a curable resin composition, which is impregnated with Substrate and heating of glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber and paper Drying, the obtained prepreg is subjected to hot press forming. The solvent in this case is usually used in an amount of 10 to 70% by mass, preferably 15 to 70% by mass, based on the mixture of the curable resin composition A of the present invention and the solvent. Further, in the case of a liquid composition, an epoxy resin-containing cured product containing carbon fibers can be directly obtained by, for example, RTM (resin transfer molding).

又，於以膜或片材形狀使用本發明之硬化性樹脂組成物A之情形時，具有B階之柔韌性特性等優異之特性。此種膜或片材形狀之樹脂組成物係藉由如下方式獲得：將本發明之硬化性樹脂組成物A作為上述硬化性樹脂組成物清漆而塗佈於剝離膜上，於加熱下去除溶劑後，進行B階化。該膜或片材狀之樹脂組成物可用作多層基板等之接著劑(層間絕緣層)。 In the case where the curable resin composition A of the present invention is used in the form of a film or a sheet, it has excellent properties such as flexibility properties of the B-stage. The resin composition of the film or sheet shape is obtained by applying the curable resin composition A of the present invention as a curable resin composition varnish to a release film, and removing the solvent after heating. , B-staged. The film or sheet-like resin composition can be used as an adhesive (interlayer insulating layer) of a multilayer substrate or the like.

硬化性樹脂組成物B(由酸性硬化觸媒引起之陽離子硬化)使用酸性硬化觸媒(陽離子聚合觸媒)而進行硬化的本發明之硬化性樹脂組成物B含有光聚合起始劑或熱聚合起始劑作為酸性硬化觸媒。亦可進而含有稀釋劑、聚合性單體、聚合性低聚物、聚合起始輔助劑、光敏劑等各種公知之化合物、材料等。又，亦可視需要含有無機填充材、著色顏料、紫外線吸收劑、抗氧化劑、穩定劑等各種公知之添加劑。 The curable resin composition B (cation hardening by an acid hardening catalyst) and the hardening resin composition B of the present invention hardened using an acidic curing catalyst (cationic polymerization catalyst) contains a photopolymerization initiator or thermal polymerization. The starter acts as an acidic hardening catalyst. Further, various known compounds, materials, and the like may be contained, such as a diluent, a polymerizable monomer, a polymerizable oligomer, a polymerization initiation aid, and a photosensitizer. Further, various known additives such as an inorganic filler, a coloring pigment, an ultraviolet absorber, an antioxidant, and a stabilizer may be contained as needed.

作為酸性硬化觸媒，較佳為陽離子聚合起始劑，尤佳為光或熱陽離子聚合起始劑。藉由調配利用活性能量射線而活化之陽離子聚合起始劑及/或利用熱而活化之陽離子聚合起始劑，可用作硬化性樹脂組成物B。 As the acid curing catalyst, a cationic polymerization initiator is preferred, and a photo or thermal cationic polymerization initiator is preferred. The cationic polymerization initiator activated by the active energy ray and/or the cationic polymerization initiator activated by heat can be used as the curable resin composition B.

作為利用活性能量射線之照射而使本發明之硬化性樹脂組成物B之陽離子聚合開始的陽離子聚合起始劑，可列舉：重氮鎓鹽、錪鹽、鋶鹽、硒鹽、吡啶鎓鹽、二茂鐵鹽、鏻鹽、及硫代吡啶鹽等，較佳為錪鹽 及鋶鹽，進而較佳為二芳基錪鹽及二烷基苯甲醯甲基鋶鹽，尤其可較佳地使用二芳基錪鹽。 The cationic polymerization initiator which starts the cationic polymerization of the curable resin composition B of the present invention by irradiation with an active energy ray may, for example, be a diazonium salt, a phosphonium salt, a phosphonium salt, a selenium salt or a pyridinium salt. a ferrocene salt, a cerium salt, a thiopyridinium salt or the like, preferably a cerium salt And a phosphonium salt, further preferably a diarylsulfonium salt and a dialkyl benzamidine methyl phosphonium salt, and particularly preferably a diarylsulfonium salt.

於將錪鹽及鋶鹽等光陽離子聚合起始劑用於本發明之陽離子硬化性樹脂組成物B之情形時，作為陰離子，可列舉：BF4 -、AsF6 -，SbF6 -、PF6 -、及B(C6F5)4 -等，較佳為SbF6 -、PF6 -、或B(C6F5)4 -，尤較佳為SbF6 -或B(C6F5)4 -。 When a photocationic polymerization initiator such as a phosphonium salt or a phosphonium salt is used in the cationically curable resin composition B of the present invention, examples of the anion include BF 4 - , AsF 6 - , SbF 6 - , and PF 6 . - and B(C 6 F 5 ) 4 - and the like, preferably SbF 6 - , PF 6 - , or B(C 6 F 5 ) 4 - , more preferably SbF 6 - or B (C 6 F 5 ) 4 - .

若列舉光陽離子聚合起始劑之具體例，則可列舉：雙(十二烷基苯基)錪六氯銻酸鹽(GE東芝聚矽氧公司製造，UV-9380C之主要成分)、甲苯基異丙苯基錪四(五氯苯基)硼酸鹽(Rhodia公司製造，PHOTOINITIATOR2074)、雙(烷基(C=10~14)苯基錪)六氯銻酸鹽(和光純藥製造之光陽離子聚合起始劑WPI-016)等。 Specific examples of the photocationic polymerization initiator include bis(dodecylphenyl)phosphonium hexachlorophosphonate (manufactured by GE Toshiba Polyoxane Co., Ltd., a main component of UV-9380C), and tolyl group. Propyl phenyltetrakis(pentachlorophenyl)borate (manufactured by Rhodia Co., Ltd., PHOTOINITIATOR 2074), bis(alkyl (C=10-14) phenylhydrazine) hexachloroantimonate (photochemical cation manufactured by Wako Pure Chemical Industries, Ltd.) Polymerization initiator WPI-016) and the like.

作為使本發明之硬化性樹脂組成物B硬化時之活性能量射線，亦可使用X射線、電子束、紫外線及可見光等，較佳為紫外線或可見光，尤佳為紫外線。於使用紫外線之情形時，其波長範圍並無特別限定，較佳為150~400nm，進而較佳為200~380nm。於使用紫外線之情形時，可效率良好地開始陽離子聚合。 As the active energy ray when the curable resin composition B of the present invention is cured, X-rays, electron beams, ultraviolet rays, visible light or the like may be used, and ultraviolet rays or visible rays are preferable, and ultraviolet rays are particularly preferable. In the case of using ultraviolet rays, the wavelength range thereof is not particularly limited, and is preferably 150 to 400 nm, and more preferably 200 to 380 nm. In the case of using ultraviolet rays, cationic polymerization can be started efficiently.

又，於本發明之硬化性樹脂組成物B，亦可視需要併用增感劑以進一步提高光陽離子聚合起始劑之活性。作為可用於本發明之增感劑，例如可使用Crivello於《聚合物科學進展》(Adv.in Plymer Sci.,62,1(1984))中所揭示之化合物。具體而言，有芘、苝、吖啶橙、9-氧硫、2-氯-9-氧硫及苯并黃素等。又，亦可使用作為光自由基聚合起始劑而廣泛使用之化合物，具體而言，可列舉二苯基酮、2,4-二乙基-9-氧硫、2-異丙基-9-氧硫、2,4-二氯-9-氧硫等9-氧硫類，安息香甲醚、安息香***、安息香 異丙醚等安息香醚類，2,2-二甲氧基-1,2-二苯基乙烷-1-酮等苯偶醯二甲基縮酮類，2-羥基-2-甲基-1-苯基丙烷-1-酮、1-(4-異丙基苯基)-2-羥基-2-甲基丙烷-1-酮、1-羥基環己基苯基酮等α-羥基烷基苯酮類，樟腦醌等α-二羰基化合物等。於本發明中，可尤佳地使用9-氧硫類或α-羥基烷基苯酮類。 Further, in the curable resin composition B of the present invention, a sensitizer may be used in combination as needed to further increase the activity of the photocationic polymerization initiator. As the sensitizer which can be used in the present invention, for example, a compound disclosed by Crivello in Adv. in Plymer Sci., 62, 1 (1984) can be used. Specifically, there are strontium, barium, acridine orange, 9-oxosulfur 2-chloro-9-oxosulfur And benzoflavin and the like. Further, a compound which is widely used as a photoradical polymerization initiator can be used, and specific examples thereof include diphenyl ketone and 2,4-diethyl-9-oxygen sulphide. 2-isopropyl-9-oxosulfur 2,4-dichloro-9-oxosulfur 9-oxosulfur Benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin dimethyl ketal such as 2,2-dimethoxy-1,2-diphenylethane-1-one , 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxyl ring An α-hydroxyalkylphenone such as hexyl phenyl ketone or an α-dicarbonyl compound such as camphorquinone. In the present invention, 9-oxygen sulfur can be preferably used. Or an alpha-hydroxyalkyl phenone.

光陽離子聚合起始劑於本發明之硬化性樹脂組成物B中之調配量可根據活性能量射線之種類或照射量而適當調整。例如於紫外線之情形時，相對於陽離子硬化性樹脂組成物B之合計100質量份較佳為設為0.1~10質量份，更佳為0.5~5份，進而較佳為1~3份。於陽離子聚合起始劑之調配量少於0.1份之情形時，有時硬化性較差，反之，於多於10質量份之情形時，有時會使硬化物中真正必須之成分減少而降低硬化物之物性，或使硬化物之著色加劇。 The amount of the photocationic polymerization initiator to be used in the curable resin composition B of the present invention can be appropriately adjusted depending on the type of the active energy ray or the amount of irradiation. For example, in the case of ultraviolet rays, the total amount of the cationically curable resin composition B is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts, still more preferably 1 to 3 parts. When the compounding amount of the cationic polymerization initiator is less than 0.1 part, the hardenability may be inferior. On the other hand, in the case of more than 10 parts by mass, the actually necessary component in the hardened material may be reduced to reduce hardening. The physical properties of the object, or the coloration of the hardened material is intensified.

於本發明之硬化性樹脂組成物B添加增感劑之情形時之調配量可根據活性能量射線之種類或照射量而適當調整。例如於紫外線之情形時，相對於硬化性樹脂組成物B之合計100質量份較佳為設為5質量份以下，進而較佳為0.2~2份。於增感劑之調配量多於5質量份之情形時，有時會使硬化物中真正必須之成分減少而降低硬化物之物性，或使硬化物之著色加劇。 When the sensitizer is added to the curable resin composition B of the present invention, the amount of the sensitizer can be appropriately adjusted depending on the type of the active energy ray or the amount of irradiation. For example, in the case of ultraviolet rays, the total mass of the curable resin composition B is preferably 5 parts by mass or less, more preferably 0.2 to 2 parts. When the amount of the sensitizer is more than 5 parts by mass, the components which are really necessary in the hardened material may be reduced to lower the physical properties of the cured product or to increase the color of the cured product.

於活性能量射線為紫外線或可見光之情形時，陽離子硬化性樹脂組成物曝露於空氣中，較佳為此時氛圍之濕度較低，較佳為濕度80%R.H.以下，進而較佳為70%R.H.以下。此處，於將紫外線或可見光設置於生產線中之情形時，亦可採用向光照射裝置之近前吹送乾燥空氣之方法、或安裝加熱裝置而降低濕度之方法。 When the active energy ray is ultraviolet or visible light, the cationically curable resin composition is exposed to the air, and preferably the humidity of the atmosphere is low at this time, preferably 80% RH or less, and further preferably 70% RH. the following. Here, in the case where ultraviolet rays or visible light are provided in the production line, a method of blowing dry air to the vicinity of the light irradiation device or a method of installing the heating device to reduce the humidity may be employed.

亦可將藉由熱進行活化而使陽離子聚合開始之化合物、即熱陽離子聚合起始劑用於本發明之硬化性樹脂組成物B中。作為該化合物，可例示：四級銨鹽、鏻鹽及鋶鹽等各種鎓鹽類、或烷氧基矽烷與鋁錯合物之組合等。作為可獲得之製品，可列舉：Adekaopton CP-66及Adekaopton CP-77(均為商品名，旭電化工業(股)製造)、San-Aid SI-60L、San-Aid SI-80L及San-Aid SI-100L(均為商品名，三新化學工業(股)製造)、及CI系列(日本曹達(股)製造)等。 A compound which initiates cationic polymerization by activation by heat, that is, a thermal cationic polymerization initiator, can also be used in the curable resin composition B of the present invention. The compound may, for example, be a combination of various sulfonium salts such as a quaternary ammonium salt, a phosphonium salt or a phosphonium salt, or a combination of an alkoxysilane and an aluminum complex. As the available products, Adekaopton CP-66 and Adekaopton CP-77 (all trade names, manufactured by Asahi Kasei Co., Ltd.), San-Aid SI-60L, San-Aid SI-80L, and San-Aid are exemplified. SI-100L (all trade names, manufactured by Sanshin Chemical Industry Co., Ltd.), and CI series (made by Japan Soda Co., Ltd.).

熱陽離子聚合起始劑於本發明之硬化性樹脂組成物B中之調配比率相對於陽離子硬化性樹脂組成物100質量份較佳為設為0.01~10質量份之範圍，更佳為0.1~5份，進而較佳為0.5~3份。於該調配比率未達0.01質量份之情形時，即便其藉由熱之作用而活化，有時亦無法使開環聚合性基之開環反應充分進行。又，即便調配超過10質量份之該聚合起始劑，使聚合進行之作用亦不會進一步提高，且有時會降低硬化物之物性，故而欠佳。 The blending ratio of the thermal cationic polymerization initiator in the curable resin composition B of the present invention is preferably in the range of 0.01 to 10 parts by mass, more preferably 0.1 to 5, based on 100 parts by mass of the cationically curable resin composition. The fraction is further preferably 0.5 to 3 parts. When the compounding ratio is less than 0.01 parts by mass, even if it is activated by the action of heat, the ring-opening reaction of the ring-opening polymerizable group may not proceed sufficiently. Further, even if more than 10 parts by mass of the polymerization initiator is blended, the effect of the polymerization is not further improved, and the physical properties of the cured product may be lowered, which is not preferable.

進而，於本發明之硬化性樹脂組成物B，可視需要添加無機填充材或矽烷偶合劑、脫模劑、顏料等各種調配劑、各種熱硬化性樹脂之各種調配劑。作為具體例如上所述。 Further, in the curable resin composition B of the present invention, various preparation agents such as an inorganic filler, a decane coupling agent, a release agent, and a pigment, and various thermosetting resins may be added as needed. As a specific example, it is described above.

本發明之硬化性樹脂組成物B可藉由均勻地混合各成分而獲得。又，亦可於使本發明之硬化性樹脂組成物B均勻地溶解於聚乙二醇單***或環己酮、γ-丁內酯等有機溶劑之後，藉由乾燥去除溶劑而使用。此時之溶劑於本發明之硬化性樹脂組成物B與該溶劑之混合物中通常為10~70質量%，較佳為15~70質量%。 The curable resin composition B of the present invention can be obtained by uniformly mixing the components. In addition, the curable resin composition B of the present invention may be uniformly dissolved in an organic solvent such as polyethylene glycol monoethyl ether or cyclohexanone or γ-butyrolactone, and then used by drying to remove the solvent. The solvent at this time is usually 10 to 70% by mass, preferably 15 to 70% by mass, based on the mixture of the curable resin composition B of the present invention and the solvent.

本發明之硬化性樹脂組成物B可藉由加熱及/或紫外線照射而硬化(例如參考文獻：環氧樹脂綜述 第1卷 基礎篇I p82-84)，此時之熱量及/或紫外線照射量依存於硬化性樹脂組成物B之組成而有所不同，故而根據各自之組成決定硬化條件。基本上，只要為硬化物可表現出使用目的所需之強度之硬化條件即可。通常，該等硬化性樹脂組成物難以僅憑光照射而完全硬化，故而於要求耐熱性之用途中，必須於光照射後藉由加熱使反應完全結束。又，由於必須使光硬化時之照射光透射至細微部分，故而對於本發明之環氧樹脂及硬化性樹脂組成物B，期待透明性高之化合物及組成物。 The curable resin composition B of the present invention can be hardened by heating and/or ultraviolet irradiation (for example, Reference: Epoxy Resin Review Volume 1 Basics I p82-84), and heat and/or ultraviolet irradiation amount at this time Depending on the composition of the curable resin composition B, the curing conditions are determined according to the respective compositions. Basically, it is sufficient that the hardened material exhibits the hardening conditions required for the purpose of use. In general, it is difficult for these curable resin compositions to be completely cured by light irradiation. Therefore, in applications requiring heat resistance, it is necessary to completely terminate the reaction by heating after light irradiation. In addition, since the irradiation light at the time of photohardening must be transmitted to the fine portion, the epoxy resin and the curable resin composition B of the present invention are expected to have a compound and a composition having high transparency.

於光照射後進行加熱之情形時，可於通常之硬化性樹脂組成物B之硬化溫度區域進行。例如較佳為於常溫~150℃進行30分鐘~7天之範圍。根據硬化性樹脂組成物B之調配而變化，尤其是越為高溫度區域，對光照射後之硬化促進越具效果，越可憑藉短時間之熱處理而產生效果。又，越為低溫越需要長時間之熱處理。藉由此種熱後硬化，亦產生成為老化處理之效果。 When heating is performed after light irradiation, it can be carried out in the hardening temperature region of the usual curable resin composition B. For example, it is preferably carried out at a temperature of from -150 ° C for a period of from 30 minutes to 7 days. It changes depending on the blending of the curable resin composition B, and in particular, the higher the temperature region, the more effective the hardening promotion after light irradiation, and the effect can be obtained by heat treatment for a short period of time. Moreover, the lower the temperature, the longer the heat treatment is required. By such post-heat hardening, the effect of aging treatment also occurs.

又，使該等硬化性樹脂組成物B硬化而獲得之硬化物之形狀亦可視用途而採用各種形狀，因此並無特別限定，例如可設為膜狀、片材狀、塊狀等形狀。成形之方法根據應用之部位、構件而有所不同，例如可列舉：鑄型法、澆鑄成型法、絲網印刷法、旋轉塗佈法、噴霧法、轉印法、滴塗方式等，但不限定於該等，只要為了獲得所期待之形狀而採用適當之方法即可。成形模具可使用研磨玻璃、硬質不鏽鋼研磨板、聚碳酸酯板、聚對苯二甲酸乙二酯板、聚甲基丙烯酸甲酯板等。又，為了提高成形模具與硬化性樹脂組成物B之脫模性，可使用聚對苯二甲酸乙二酯膜、聚 碳酸酯膜、聚氯乙烯膜、聚乙烯膜、聚四氯乙烯膜、聚丙烯膜、聚醯亞胺膜等。 In addition, the shape of the cured product obtained by curing the curable resin composition B can be various shapes depending on the application, and is not particularly limited. For example, it may be in the form of a film, a sheet, or a block. The method of molding varies depending on the location and the member to be applied, and examples thereof include a mold method, a casting method, a screen printing method, a spin coating method, a spray method, a transfer method, and a dispensing method, but It is limited to these, and an appropriate method may be employed in order to obtain a desired shape. As the forming mold, a ground glass, a hard stainless steel grinding plate, a polycarbonate plate, a polyethylene terephthalate plate, a polymethyl methacrylate plate or the like can be used. Further, in order to improve the mold release property of the mold and the curable resin composition B, a polyethylene terephthalate film or a poly A carbonate film, a polyvinyl chloride film, a polyethylene film, a polytetrachloroethylene film, a polypropylene film, a polyimide film, or the like.

例如用於陽離子硬化性之抗蝕劑時，首先將溶解於聚乙二醇單***或環己酮、γ-丁內酯等有機溶劑之硬化性樹脂組成物B藉由絲網印刷、旋轉塗佈法等手法以5~160μm之膜厚塗佈於覆銅積層板或陶瓷基板、玻璃基板等基板上，並以60~110℃對塗膜進行預乾燥。對所獲得之基板上之硬化性樹脂組成物B通過描繪有所需圖案之負型膜而照射紫外線(例如低壓水銀燈、高壓水銀燈、超高壓水銀燈、氙氣燈、雷射光等)，繼而以70~120℃進行曝光後烘烤處理。其後，以聚乙二醇單***等溶劑將未曝光部分溶解去除(顯影)，進而若有必要，則藉由紫外線之照射及/或加熱(例如以100~200℃進行0.5~3小時)而進行充分之硬化，藉此獲得硬化物。以此方式亦可獲得印刷配線板。再者，上述方法為負型抗蝕劑之情形，但本發明之硬化性樹脂組成物B亦可作為正型抗蝕劑使用。 For example, in the case of a cationically curable resist, first, a curable resin composition B dissolved in an organic solvent such as polyethylene glycol monoethyl ether or cyclohexanone or γ-butyrolactone is screen-printed or spin-coated. The coating method is applied to a copper clad laminate, a ceramic substrate, a glass substrate or the like with a film thickness of 5 to 160 μm, and the coating film is pre-dried at 60 to 110 °C. The curable resin composition B on the obtained substrate is irradiated with ultraviolet rays (for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, a laser beam, etc.) by a negative film in which a desired pattern is drawn, and then 70~ The post-exposure baking treatment was carried out at 120 °C. Thereafter, the unexposed portion is dissolved (developed) in a solvent such as polyethylene glycol monoethyl ether, and further, if necessary, irradiated with ultraviolet rays and/or heated (for example, at 100 to 200 ° C for 0.5 to 3 hours) Further hardening is performed to obtain a cured product. A printed wiring board can also be obtained in this way. Further, the above method is a case of a negative resist, but the curable resin composition B of the present invention can also be used as a positive resist.

使本發明之硬化性樹脂組成物A及硬化性樹脂組成物B硬化而成之硬化物可用於以光學零件材料為首之各種用途。所謂光學用材料，一般表示用於使可見光、紅外線、紫外線、X射線及雷射等光通過該材料中之用途的材料。更具體而言，除燈型、SMD型等LED用密封材以外，於與顯示體相關之領域中，可列舉：液晶顯示器之基板材料、導光板、稜鏡片材、偏向板、相位差板、視野角修正膜、接著劑及以偏光元件保護膜為首之液晶用膜等，作為下一代平板顯示器而受期待之彩色PDP(電漿顯示器)之密封材、抗反射膜、光學修正膜、外罩材、前表面玻璃之保護膜、前表面玻璃代替材料及接著劑等，LED顯示裝置所使用之LED之模具材、 LED之密封材、前表面玻璃之保護膜、前表面玻璃代替材料及接著劑等，電漿定址液晶(PALC)顯示器中之基板材料、導光板、稜鏡片材、偏向板、相位差板、視野角修正膜、接著劑及偏光元件保護膜等，有機EL(電致發光)顯示器中之前表面玻璃之保護膜、前表面玻璃代替材料及接著劑等，場發射顯示器(FED)中之各種膜基板、前表面玻璃之保護膜、前表面玻璃代替材料及接著劑等。於光記錄領域中，可列舉：VD(視訊碟片)、CD/CD-ROM、CD-R/RW、DVD-R/DVD-RAM、MO/MD、PD(相變化碟片)及光學卡用之碟片基板材料、拾取透鏡、保護膜、密封材及接著劑等。 The cured product obtained by curing the curable resin composition A and the curable resin composition B of the present invention can be used for various applications including optical component materials. The material for optics generally means a material for use in light, such as visible light, infrared rays, ultraviolet rays, X-rays, and laser light. More specifically, in addition to the sealing material for LEDs such as a lamp type and an SMD type, in the field of the display body, a substrate material of a liquid crystal display, a light guide plate, a enamel sheet, a deflecting plate, a phase difference plate, and A sealing material, an anti-reflection film, an optical correction film, and an outer cover material of a color PDP (plasma display) which is expected as a next-generation flat panel display, such as a viewing angle correction film, an adhesive, and a liquid crystal film including a polarizing element protective film. , a protective film for the front surface glass, a front surface glass substitute material, an adhesive, etc., an LED mold material used for the LED display device, LED sealing material, front surface glass protective film, front surface glass replacement material and adhesive, etc., substrate material, light guide plate, enamel sheet, deflecting plate, phase difference plate, field of view in plasma-addressed liquid crystal (PALC) display An angle correction film, an adhesive, a polarizing element protective film, etc., a protective film for a front surface glass, a front surface glass substitute material, an adhesive, etc. in an organic EL (electroluminescence) display, and various film substrates in a field emission display (FED) , a protective film for the front surface glass, a front surface glass substitute material, an adhesive, and the like. In the field of optical recording, there are VD (Video Disc), CD/CD-ROM, CD-R/RW, DVD-R/DVD-RAM, MO/MD, PD (phase change disc) and optical card. A disc substrate material, a pickup lens, a protective film, a sealing material, an adhesive, and the like.

於光學機器領域中，可列舉：靜態相機之透鏡用材料、取景器稜鏡、目標稜鏡、取景器蓋及受光感測器部等，攝影機之攝影透鏡、及取景器等，投影電視之投射透鏡、保護膜、密封材、及接著劑等，光感測機器之透鏡用材料、密封材、接著劑及膜等。於光零件領域中，可列舉：光通訊系統中之光開關周邊之光纖材料、透鏡、波導、元件之密封材及接著劑等，光連接器周邊之光纖材料、套圈、密封材及接著劑等，光被動零件或光電路零件中之透鏡、波導、LED之密封材、CCD之密封材及接著劑等，光電子積體電路(OEIC)周邊之基板材料、光纖材料、元件之密封材及接著劑等。於光纖領域中，可列舉：裝飾顯示器用照明、光導等工業用途之感測器類及顯示、標記類等，通訊基礎建設用及家庭內之數位機器連接用之光纖等。於半導體積體電路周邊材料中，可列舉：LSI(大規模積體電路)或超LSI(超大規模積體電路)材料用之微影蝕刻用之抗蝕劑材料等。於汽車、運輸機領域中，可列舉：汽車用之反光燈、軸承護圈、齒輪部分、耐蝕塗層、開關部分、前照燈、引擎內零件、電裝零件、各種內飾外飾品、 驅動引擎、制動油箱、汽車用防鏽鋼板、內部儀錶板、內飾材、保護/捆束用導線、燃料軟管、汽車燈及玻璃代替品等，列車用之雙層玻璃等，飛機之構造材之韌性賦予劑、引擎周邊零件、保護/捆束用導線及耐蝕塗層等。於建築領域中，可列舉：內飾/加工用材料、電罩、片材、玻璃中間膜、玻璃代替品及太陽電池周邊材料等。於農業用中，可列舉暖房被覆用膜等。作為下一代之光/電子功能有機材料，可列舉：有機EL元件周邊材料、有機光折射元件、作為光-光轉換裝置之光放大元件、光運算元件、有機太陽電池周邊之基板材料、光纖材料、元件之密封材及接著劑等。 In the field of optical equipment, the lens material for a static camera, the viewfinder 稜鏡, the target 稜鏡, the viewfinder cover, and the light-receiving sensor unit, the photographic lens of the camera, the viewfinder, etc., and the projection of the projection television A lens, a protective film, a sealing material, an adhesive, and the like, a lens material for a light sensing device, a sealing material, an adhesive, a film, and the like. In the field of optical components, there are mentioned optical fiber materials, lenses, waveguides, component sealing materials and adhesives in the optical communication system, optical fiber materials, ferrules, sealing materials and adhesives around the optical connectors. For example, lenses, waveguides, LED sealing materials, CCD sealing materials and adhesives in optical passive components or optical circuit components, substrate materials around optical organic integrated circuits (OEIC), optical fiber materials, component sealing materials, and the like Agents, etc. In the field of optical fibers, there are various types of sensors for industrial use such as lighting for decorative displays, light guides, displays, markings, and the like, and optical fibers for communication infrastructure construction and digital connection in homes. In the material of the semiconductor integrated circuit, a resist material for lithography for LSI (large-scale integrated circuit) or super LSI (very large-scale integrated circuit) material can be used. In the field of automobiles and transportation machines, there are listed: reflector lamps for automobiles, bearing retainers, gear parts, corrosion-resistant coatings, switch parts, headlights, engine parts, electric parts, various interior accessories, Drive engine, brake oil tank, anti-rust steel plate for automobile, interior instrument panel, interior material, wire for protection/bundling, fuel hose, automobile lamp and glass substitute, double-glazing for train, etc. Reinforcing agent for materials, peripheral parts for engines, wires for protection/bundling, and corrosion-resistant coatings. In the field of construction, there are listed materials such as interior/processing materials, electric covers, sheets, glass interlayer films, glass substitutes, and solar cell peripheral materials. In the agricultural use, a film for warm room coating or the like can be cited. Examples of the next-generation optical/electronic functional organic material include organic EL element peripheral materials, organic light refractive elements, optical amplifying elements as optical-optical conversion devices, optical arithmetic elements, substrate materials around organic solar cells, and optical fiber materials. , components of sealing materials and adhesives.

作為密封劑，可列舉：電容器、電晶體、二極體、發光二極體、IC(Integrated Circuit，積體電路)及LSI等所使用之灌注、浸漬及轉注成型密封，IC或LSI類之COB(Chip on Board，板上晶片封裝)、COF(Chip On Film，薄膜覆晶)及TAB(Tape Automated Bonding，捲帶式自動接合)等所使用之灌注密封，倒裝晶片等所使用之底膠、BGA(Ball Grid Array，球柵陣列)或CSP(Chip Scale Package，晶片尺寸封裝)等IC封裝類安裝時之密封(加強用底膠)等。 Examples of the sealant include a capacitor, a transistor, a diode, a light-emitting diode, an IC (Integrated Circuit), an LSI, etc., a potting, dipping, and transfer molding seal, and an IC or LSI COB. (Chip on Board, on-chip package), COF (Chip On Film), TAB (Tape Automated Bonding), etc. Sealing (strengthening primer) for mounting IC packages such as BGA (Ball Grid Array) or CSP (Chip Scale Package).

作為光學用材料之其他用途，可列舉使用有硬化性樹脂組成物A或硬化性樹脂組成物B之一般用途，例如可列舉：接著劑、塗料、塗佈劑、成形材料(包括片材、膜、FRP(Fiber Reinforced Plastics，纖維強化塑膠)等)、絕緣材料(包括印刷基板、電線覆層等)、密封劑及對其他樹脂等之添加劑等。於將本發明之硬化性樹脂組成物A或硬化性樹脂組成物B用作對其他樹脂之添加劑之情形時，例如可列舉於密封材或基板用之氰酸酯樹脂組成物中用作硬化劑之情形，或作為抗蝕劑用硬化劑而用於丙烯酸 酯系樹脂等之情形。作為接著劑，可列舉：土木用、建築用、汽車用、一般事務用、醫療用及電子材料用。該等之中作為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、固晶劑及底膠等半導體用接著劑、BGA加強用底膠，各向異性導電膜(ACF)及各向異性導電膏(ACP)等安裝用接著劑等。 The other use of the material for optical use is a general use using the curable resin composition A or the curable resin composition B, and examples thereof include an adhesive, a coating material, a coating agent, and a molding material (including a sheet and a film). , FRP (Fiber Reinforced Plastics, etc.), insulating materials (including printed boards, wire coatings, etc.), sealants, additives to other resins, etc. When the curable resin composition A or the curable resin composition B of the present invention is used as an additive to other resins, for example, it can be used as a hardener in a sealant or a cyanate resin composition for a substrate. In the case, or as a hardener for resist, used in acrylic acid The case of an ester resin or the like. Examples of the adhesive include civil engineering, construction, automotive, general affairs, medical, and electronic materials. Examples of the adhesive used for the electronic material include an interlayer adhesive for a multilayer substrate such as a build-up substrate, a semiconductor adhesive such as a die bond and a primer, a BGA reinforcing primer, and an anisotropic conductive film ( ACF) and an adhesive for mounting such as an anisotropic conductive paste (ACP).

以下對第2發明之硬化性樹脂組成物進行說明。 The curable resin composition of the second invention will be described below.

於第2發明之硬化性樹脂組成物中，將酚系樹脂或聚合觸媒作為必須成分而使用。 In the curable resin composition of the second aspect of the invention, a phenol resin or a polymerization catalyst is used as an essential component.

作為第2發明所含有之酚系樹脂，可列舉：雙酚A、雙酚F、雙酚S、茀雙酚、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、萘二酚、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、1,4'-雙(甲氧基甲基)苯等之縮聚物及該等之改質物、四溴雙酚A等鹵化雙酚類、萜與酚類之縮合物等多酚類，但不限定於該等。該等可單獨使用，亦可使用2種以上。 Examples of the phenolic resin contained in the second invention include bisphenol A, bisphenol F, bisphenol S, bisphenol, stilbene, 4,4'-biphenol, 2,2'-biphenol, and 3,3',5,5'-tetramethyl-[1,1'-biphenyl]-4,4'-diol, hydroquinone, resorcinol, naphthalenediol, tris(4- Hydroxyphenyl)methane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxyl Naphthalene, etc. with formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4'-bis(chlorine) Methyl)-1,1'-biphenyl, 4,4'-bis(methoxymethyl)-1,1'-biphenyl, 1,4'-bis(chloromethyl)benzene, 1,4 a polycondensate such as a polycondensate such as bis(methoxymethyl)benzene or the like, a modified product thereof, a halogenated bisphenol such as tetrabromobisphenol A or a condensate of hydrazine or a phenol, but is not limited thereto. Wait. These may be used alone or in combination of two or more.

作為較佳之酚系樹脂，可列舉酚芳烷基樹脂(具有芳香族伸烷基結構之樹脂)，尤佳為其特徵在於：其係具有選自苯酚、萘酚、甲酚中之至少一種之結構，且成為其鍵結部之伸烷基部為選自苯結構、聯苯結構、萘結構中之至少一種的樹脂(具體而言可列舉：賽洛克(Xylok)樹脂、萘酚賽洛 克樹脂(Naphthol Xylok)、苯酚聯伸苯基酚醛清漆樹脂、甲酚-聯伸苯基酚醛清漆樹脂、苯酚-萘酚醛清漆樹脂等)。 Preferred examples of the phenolic resin include a phenol aralkyl resin (a resin having an aromatic alkylene structure), and particularly preferably at least one selected from the group consisting of phenol, naphthol and cresol. The resin having a structure in which the alkyl group portion of the bonding portion is at least one selected from the group consisting of a benzene structure, a biphenyl structure, and a naphthalene structure (specifically, Xylok resin, naphthol celelo) Naphthol Xylok, phenol-linked phenyl novolac resin, cresol-linked phenyl novolac resin, phenol-naphthol novolak resin, etc.).

於第2發明之硬化性樹脂組成物中，含有酚系樹脂之硬化劑之使用量相對於全部環氧樹脂之環氧基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當量之情形、或超過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虞。 In the curable resin composition of the second aspect of the invention, the amount of the curing agent containing the phenol resin is preferably 0.7 to 1.2 equivalents per equivalent of the epoxy group of the entire epoxy resin. When the amount is less than 0.7 equivalents per equivalent of the epoxy group or exceeds 1.2 equivalents, the hardening is incomplete and good hardening properties are not obtained.

作為第2發明之硬化性樹脂組成物所含有之聚合觸媒，只要為藉由熱或光而使聚合開始之觸媒則可無限定地使用，具體而言，可使用硬化促進劑或酸性硬化觸媒。 The polymerization catalyst contained in the curable resin composition of the second invention can be used without limitation as long as it is a catalyst for starting polymerization by heat or light. Specifically, a curing accelerator or an acid hardening can be used. catalyst.

作為可使用之硬化促進劑之具體例，可列舉與可用於上述第1發明之硬化性樹脂組成物A者相同之硬化促進劑。於使用硬化促進劑之情形時，關於其使用量，亦與上述第1發明之硬化性樹脂組成物A相同。 Specific examples of the hardening accelerator which can be used include the same curing accelerators as those used in the curable resin composition A of the first invention. When the curing accelerator is used, the amount of the curing accelerator is the same as that of the curable resin composition A of the first invention.

作為酸性硬化觸媒，較佳為陽離子聚合起始劑，尤佳為光或熱陽離子聚合起始劑。藉由調配利用活性能量射線而活化之陽離子聚合起始劑及/或利用熱而活化之陽離子聚合起始劑，可作為下述硬化性樹脂組成物2B而使用。 As the acid curing catalyst, a cationic polymerization initiator is preferred, and a photo or thermal cationic polymerization initiator is preferred. The cationic polymerization initiator activated by the active energy ray and/or the cationic polymerization initiator activated by heat can be used as the curable resin composition 2B described below.

作為利用活性能量射線之照射而使下述本發明之硬化性樹脂組成物2B之陽離子聚合開始的陽離子聚合起始劑，可列舉與可用於上述第1發明之硬化性樹脂組成物B者相同之陽離子聚合起始劑。 The cationic polymerization initiator which starts cationic polymerization of the curable resin composition 2B of the present invention by the irradiation of the active energy ray is the same as the curable resin composition B which can be used in the first invention. Cationic polymerization initiator.

亦可將利用熱而活化而使陽離子聚合開始之化合物、即熱陽離子聚合起始劑用於本發明之硬化性樹脂組成物2B。作為該化合物，亦可列舉與可用於上述第1發明之硬化性樹脂組成物B者相同之熱陽離子聚合 起始劑。 A compound which is activated by heat to initiate cationic polymerization, that is, a thermal cationic polymerization initiator, can also be used for the curable resin composition 2B of the present invention. As the compound, the same thermal cationic polymerization as that of the curable resin composition B of the above first invention can be mentioned. Starting agent.

於第2發明之硬化性樹脂組成物中，將聚合觸媒用作必須成分之情況可應用由硬化劑引起之熱硬化(硬化性樹脂組成物2A)與以酸作為硬化觸媒之陽離子硬化(硬化性樹脂組成物2B)兩種方法。 In the curable resin composition of the second aspect of the invention, when a polymerization catalyst is used as an essential component, thermosetting (hardening resin composition 2A) by a curing agent and cation hardening using an acid as a curing catalyst can be applied ( Curable resin composition 2B) Two methods.

與上述第1發明之硬化性樹脂組成物同樣地，於硬化性樹脂組成物2A及硬化性樹脂組成物2B中，本發明之環氧樹脂可單獨地或與其他環氧樹脂併用而使用。於併用之情形時，關於可併用之其他環氧樹脂之使用量，作為具體例，與上述第1發明之硬化性樹脂組成物相同。 In the same manner as the curable resin composition of the first aspect of the invention, the epoxy resin of the present invention can be used alone or in combination with other epoxy resins in the curable resin composition 2A and the curable resin composition 2B. In the case of use in combination, the amount of the other epoxy resin which can be used in combination is the same as the curable resin composition of the first invention described above as a specific example.

以下，對各個硬化性樹脂組成物進行說明。 Hereinafter, each of the curable resin compositions will be described.

由硬化劑引起之熱硬化(硬化性樹脂組成物2A) Thermal hardening by hardener (curable resin composition 2A)

作為本發明之硬化性樹脂組成物2A所含有之硬化劑，與可用於上述第1發明之硬化性樹脂組成物A之羧酸類或可與該羧酸類併用之其他硬化劑相同。 The curing agent contained in the curable resin composition 2A of the present invention is the same as the carboxylic acid which can be used in the curable resin composition A of the first invention or the other curing agent which can be used in combination with the carboxylic acid.

於本發明中，尤佳為以上述酸酐、羧酸樹脂為代表之具有酸酐結構、及或羧酸結構之化合物。 In the present invention, a compound having an acid anhydride structure or a carboxylic acid structure typified by the above acid anhydride or carboxylic acid resin is particularly preferred.

於本發明之硬化性樹脂組成物2A中，硬化劑之使用量亦與上述第1發明之硬化性樹脂組成物A相同。 In the curable resin composition 2A of the present invention, the amount of the curing agent used is also the same as that of the curable resin composition A of the first invention.

於本發明之硬化性樹脂組成物2A，亦可與硬化劑一併使用硬化促進劑。作為可使用之硬化促進劑之具體例，可列舉上述者。於使用硬化促進劑之情形時，其使用量與上述第1發明之硬化性樹脂組成物A相同。 In the curable resin composition 2A of the present invention, a curing accelerator may be used together with the curing agent. Specific examples of the hardening accelerator which can be used include the above. When a hardening accelerator is used, the amount used is the same as that of the curable resin composition A of the above first invention.

於本發明之硬化性樹脂組成物2A，亦可與上述第1發明之 硬化性樹脂組成物A同樣地含有含磷之化合物作為阻燃性賦予成分。關於含磷之化合物之具體例及使用量，亦與上述第1發明之硬化性樹脂組成物A相同。 The curable resin composition 2A of the present invention may be combined with the first invention described above. The curable resin composition A similarly contains a phosphorus-containing compound as a flame retardancy imparting component. Specific examples and amounts of use of the phosphorus-containing compound are also the same as those of the curable resin composition A of the first invention.

進而，於本發明之硬化性樹脂組成物2A，亦可與上述第1發明之硬化性樹脂組成物A同樣地視需要添加抗氧化劑。關於可使用之抗氧化劑之具體例及使用量，亦與上述第1發明之硬化性樹脂組成物A相同。 Furthermore, in the curable resin composition 2A of the present invention, an antioxidant may be added as needed in the same manner as the curable resin composition A of the first invention. Specific examples and amounts of the antioxidants that can be used are also the same as those of the curable resin composition A of the first invention.

進而，於本發明之硬化性樹脂組成物2A，亦可與上述第1發明之硬化性樹脂組成物A同樣地視需要添加光穩定劑。 Further, in the curable resin composition 2A of the present invention, a light stabilizer may be added as needed in the same manner as the curable resin composition A of the first invention.

作為光穩定劑之具體例，與上述第1發明之硬化性樹脂組成物A相同。 Specific examples of the light stabilizer are the same as those of the curable resin composition A of the first invention.

進而，於本發明之硬化性樹脂組成物2A，亦可與上述第1發明之硬化性樹脂組成物A同樣地視需要調配黏合劑樹脂。關於黏合劑樹脂之具體例及使用量，亦與上述第1發明之硬化性樹脂組成物A相同。 Further, in the curable resin composition 2A of the present invention, the binder resin may be blended as needed in the same manner as the curable resin composition A of the first invention. Specific examples and usage amounts of the binder resin are also the same as those of the curable resin composition A of the first invention.

於本發明之硬化性樹脂組成物2A，可與上述第1發明之硬化性樹脂組成物A同樣地視需要添加無機填充材。關於無機填充材之具體例及使用量，亦與上述第1發明之硬化性樹脂組成物A相同。 In the curable resin composition 2A of the present invention, an inorganic filler may be added as needed in the same manner as the curable resin composition A of the first invention. The specific examples and the amounts of use of the inorganic filler are also the same as those of the curable resin composition A of the first invention.

於將本發明之硬化性樹脂組成物2A用於光半導體密封劑之情形時，可與上述第1發明之硬化性樹脂組成物A同樣地視需要添加螢光體。關於螢光體之具體例及使用量，亦與上述第1發明之硬化性樹脂組成物A相同。 When the curable resin composition 2A of the present invention is used for a photo-semiconductor sealing agent, a phosphor may be added as needed in the same manner as the curable resin composition A of the first invention. The specific examples and the amount of use of the phosphor are also the same as those of the curable resin composition A of the first invention.

本發明之硬化性樹脂組成物2A與上述第1發明之硬化性樹脂組成物A同樣地可藉由均勻混合各成分而獲得，可藉由與習知之方法相同之方法容易地製作其之硬化物。 The curable resin composition 2A of the present invention can be obtained by uniformly mixing the components in the same manner as the curable resin composition A of the first aspect of the invention, and the cured product can be easily produced by the same method as the conventional method. .

又，本發明之硬化性樹脂組成物2A可藉由與上述第1發明之硬化性樹脂組成物A相同之手法製作硬化物。 Further, the curable resin composition 2A of the present invention can be produced into a cured product by the same method as the curable resin composition A of the first invention.

硬化性樹脂組成物2B(由酸性硬化觸媒引起之陽離子硬化) Curable resin composition 2B (cation hardening by acid hardening catalyst)

使用酸性硬化觸媒而進行硬化之本發明之硬化性樹脂組成物2B與上述第1發明之硬化性樹脂組成物B同樣地含有光聚合起始劑或熱聚合起始劑作為酸性硬化觸媒，進而亦可含有稀釋劑、聚合性單體、聚合性低聚物、聚合起始輔助劑、光敏劑等各種公知之化合物、材料等，又，亦可視需要含有無機填充材、著色顏料、紫外線吸收劑、抗氧化劑、穩定劑等各種公知之添加劑。 In the same manner as the curable resin composition B of the first aspect of the invention, the curable resin composition 2B of the present invention which is cured by an acidic curing catalyst contains a photopolymerization initiator or a thermal polymerization initiator as an acid curing catalyst. Further, various known compounds and materials such as a diluent, a polymerizable monomer, a polymerizable oligomer, a polymerization starting adjuvant, and a photosensitizer may be contained, and an inorganic filler, a coloring pigment, or an ultraviolet absorbing agent may be contained as needed. Various known additives such as agents, antioxidants, stabilizers, and the like.

與上述第1發明之硬化性樹脂組成物B同樣地，作為酸性硬化觸媒，較佳為陽離子聚合起始劑，尤佳為光或熱陽離子聚合起始劑。藉由調配利用活性能量射線而活化之陽離子聚合起始劑及/或利用熱而活化之陽離子聚合起始劑，可作為硬化性樹脂組成物2B而使用。 In the same manner as the curable resin composition B of the first aspect of the invention, the acid curing catalyst is preferably a cationic polymerization initiator, and more preferably a photo or thermal cationic polymerization initiator. A cationic polymerization initiator activated by an active energy ray and/or a cationic polymerization initiator activated by heat can be used as the curable resin composition 2B.

作為利用活性能量射線之照射而使本發明之硬化性樹脂組成物2B之陽離子聚合開始的陽離子聚合起始劑，可列舉與可用於上述第1發明之硬化性樹脂組成物B者相同之陽離子聚合起始劑。 The cationic polymerization initiator which starts the cationic polymerization of the curable resin composition 2B of the present invention by the irradiation of the active energy ray is the same as the cationic polymerization which can be used for the curable resin composition B of the first invention. Starting agent.

作為使本發明之硬化性樹脂組成物2B硬化時之活性能量射線，與上述第1發明之硬化性樹脂組成物B之情形相同。 The active energy ray when the curable resin composition 2B of the present invention is cured is the same as the case of the curable resin composition B of the first invention.

又，於本發明之硬化性樹脂組成物2B，與上述第1發明之硬化性樹脂組成物B同樣地，亦可視需要為了進一步提高光陽離子聚合起始劑之活性而併用增感劑。作為可用於本發明之增感劑，可列舉並較佳地使用與可用於上述第1發明之硬化性樹脂組成物B者相同之增感劑，關於 調配量，亦與上述第1發明之硬化性樹脂組成物B相同。 Further, in the curable resin composition 2B of the present invention, similarly to the curable resin composition B of the first aspect of the invention, a sensitizer may be used in combination in order to further increase the activity of the photocationic polymerization initiator. As the sensitizer which can be used in the present invention, the same sensitizer as that which can be used for the curable resin composition B of the above first invention can be mentioned and used. The blending amount is also the same as that of the curable resin composition B of the first invention.

於對本發明之硬化性樹脂組成物2B添加增感劑之情形時，關於調配量、活性能量射線之照射條件等，亦與上述第1發明之硬化性樹脂組成物B相同。 In the case where a sensitizer is added to the curable resin composition 2B of the present invention, the amount of the preparation, the irradiation conditions of the active energy ray, and the like are the same as those of the curable resin composition B of the first invention.

亦可將利用熱而活化而使陽離子聚合開始之化合物、即熱陽離子聚合起始劑用於本發明之硬化性樹脂組成物2B，作為該化合物，關於具體例或調配比率等，亦與上述第1發明之硬化性樹脂組成物B相同。 The curable resin composition 2B of the present invention, which is a compound which initiates cationic polymerization by activation with heat, can also be used as the compound, and the specific example or the blending ratio can also be used as the compound. The curable resin composition B of the invention is the same.

進而，於本發明之硬化性樹脂組成物2B，可與上述第1發明之硬化性樹脂組成物B同樣地視需要添加如上所述之無機填充材或矽烷偶合劑、脫模劑、顏料等各種調配劑、各種熱硬化性樹脂。 Further, in the curable resin composition 2B of the present invention, as described above, the inorganic filler, the decane coupling agent, the release agent, the pigment, and the like may be added as needed in the same manner as the curable resin composition B of the first invention. Formulation, various thermosetting resins.

本發明之硬化性樹脂組成物2B與上述第1發明之硬化性樹脂組成物A同樣地可藉由均勻混合各成分而獲得、使用並硬化。 In the same manner as the curable resin composition A of the first aspect of the invention, the curable resin composition 2B of the present invention can be obtained, used, and cured by uniformly mixing the components.

使第2發明之硬化性樹脂組成物2A及硬化性樹脂組成物2B硬化而成之硬化物可用於各種用途。 The cured product obtained by curing the curable resin composition 2A of the second invention and the curable resin composition 2B can be used for various purposes.

可列舉使用有硬化性樹脂組成物2A或硬化性樹脂組成物2B之一般用途，例如除接著劑、塗料、塗佈劑、成形材料(包括片材、膜、FRP等)、絕緣材料(包括印刷基板、電線覆層等)、密封劑以外，可列舉對其他樹脂等之添加劑等。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。作為該等之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、固晶劑、底膠等半導體用接著劑、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。 The general use using the curable resin composition 2A or the curable resin composition 2B, for example, an adhesive, a coating, a coating agent, a molding material (including a sheet, a film, an FRP, etc.), an insulating material (including printing) Other than the sealant, additives such as other resins and the like may be mentioned. Examples of the adhesive include an adhesive for electronic materials other than those for civil engineering, construction, automotive, general service, and medical use. Examples of the adhesive for the electronic material in the above-mentioned materials include an interlayer adhesive for a multilayer substrate such as a build-up substrate, a semiconductor adhesive such as a die bond or a primer, a BGA reinforcing primer, and an anisotropic conductive film ( ACF), an adhesive for mounting such as an anisotropic conductive paste (ACP), and the like.

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(包括加強用底膠)及封裝基板等。又，亦適宜地用於網路基板、或模塊基板等要求功能性之基板用途。 Examples of the sealing agent and the substrate include a capacitor, a transistor, a diode, a light-emitting diode, an IC, an LSI, etc., which are used for infusion, immersion, transfer molding, IC, LSI, COB, COF, TAB, etc. Seals for infusion sealing, flip chip, etc., QFP, BGA, CSP and other IC packages for sealing (including reinforcing primer) and package substrates. Moreover, it is suitably used for a substrate which requires a functional property such as a network board or a module board.

實施例 Example

以下，藉由合成例、實施例更詳細地說明本發明。再者，本發明並不限定於該等合成例、實施例。再者，實施例中之各物性值係藉由以下方法測定。 Hereinafter, the present invention will be described in more detail by way of Synthesis Examples and Examples. Furthermore, the present invention is not limited to the above-described synthesis examples and examples. Further, each physical property value in the examples was measured by the following method.

以下，記載實施例中使用之各種分析方法。 Hereinafter, various analysis methods used in the examples will be described.

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 ion: according to JIS K 7243-1 (ISO 21672-1)

鈉離子：藉由離子層析法進行測定 Sodium ion: determined by ion chromatography

鐵成分：ICP發光分光分析 Iron composition: ICP emission spectrometry

折射率：依據ISO 5661 Refractive index: according to ISO 5661

加德納色數：依據ISO 4630-1 Gardner color number: according to ISO 4630-1

GPC：管柱(Shodex KF-603、KF-602×2、KF-601×2) GPC: pipe column (Shodex KF-603, KF-602×2, KF-601×2)

連結溶離液為四氫呋喃 Linked dissolving solution to tetrahydrofuran

流速為0.5ml/min. The flow rate is 0.5ml/min.

管柱溫度為40℃ Column temperature is 40 ° C

檢測：RI(示差折射檢測器) Detection: RI (differential refraction detector)

合成例1 Synthesis Example 1

將具備攪拌機、回流冷卻管、攪拌裝置之燒瓶暫時抽真空並進行氮氣置換後，一面實施氮氣沖洗(2L/hr)一面添加酚系化合物(DPPI1)(於上述式(1)中取代基R均為氫原子之化合物SABIC PPPBP純度99%以上，殘留酚酞200ppm，鐵成分<5ppm)255份、表氯醇842份、甲醇168份，並將水浴升溫至75℃。於內溫超過65℃時以90分鐘分批添加薄片狀之氫氧化鈉21份後，進而於70℃進行1小時後續反應。反應結束後進行水洗，使用旋轉蒸發器於140℃減壓下自油層將過量之表氯醇等溶劑蒸餾去除。對殘留物中添加甲基異丁基酮200份並溶解，升溫至70℃。於攪拌下添加30重量%之氫氧化鈉水溶液26份並進行1小時反應後，進行水洗直至洗淨水成為中性，對所獲得之溶液使用旋轉蒸發器於180℃減壓下將甲基異丁基酮等蒸餾去除，藉此獲得環氧樹脂(EP1)301份。所獲得之環氧樹脂之環氧當量為266g/eq.，軟化點為88℃，ICI熔融黏度為0.44Pa‧s(150℃)，氯離子為2ppm，鈉離子為0.5ppm，色相為0.2以下(加德納40%THF溶液)。又，上述式(1)之結構為93面積%(GPC)。再者，折射率為1.63(通常之環氧樹脂、甲酚酚醛清漆型環氧樹脂為1.59，因此顯示出非常大之折射率)。 After the flask equipped with the stirrer, the reflux cooling tube, and the stirring device was temporarily evacuated and replaced with nitrogen, the phenol compound (DPPI1) was added while nitrogen purge (2 L/hr) was applied (the substituent R in the above formula (1) The compound of the hydrogen atom SABIC PPPBP was 99% or more, the residual phenolphthalein 200 ppm, the iron component <5 ppm) 255 parts, the epichlorohydrin 842 parts, and the methanol 168 parts, and the water bath was heated to 75 °C. When the internal temperature exceeded 65 ° C, 21 parts of flaky sodium hydroxide was added in portions over 90 minutes, and then the reaction was further carried out at 70 ° C for 1 hour. After completion of the reaction, water washing was carried out, and an excess of a solvent such as epichlorohydrin was distilled off from the oil layer using a rotary evaporator under reduced pressure at 140 °C. To the residue, 200 parts of methyl isobutyl ketone was added and dissolved, and the temperature was raised to 70 °C. After adding 26 parts of a 30% by weight aqueous sodium hydroxide solution under stirring and performing a reaction for 1 hour, the mixture was washed with water until the washing water became neutral, and the obtained solution was subjected to a rotary evaporator at 180 ° C under reduced pressure to give a methyl group. Dibutyl ketone or the like was distilled off, whereby 301 parts of an epoxy resin (EP1) was obtained. The epoxy resin obtained has an epoxy equivalent of 266 g/eq., a softening point of 88 ° C, an ICI melt viscosity of 0.44 Pa ‧ (150 ° C), a chloride ion of 2 ppm, a sodium ion of 0.5 ppm, and a hue of 0.2 or less. (Gardner 40% THF solution). Further, the structure of the above formula (1) is 93 area% (GPC). Further, the refractive index was 1.63 (normally, the epoxy resin and the cresol novolak type epoxy resin were 1.59, and thus showed a very large refractive index).

合成例2 Synthesis Example 2

一面對具備攪拌機、回流冷卻管、攪拌裝置之1L之燒瓶實施氮氣沖洗(2L/hr)一面添加酚系化合物(DPPI1)(上述式(1)中取代基R均為氫原 子之化合物SABIC PPPBP純度99%以上，殘留酚酞200ppm，鐵成分<5ppm)255份、表氯醇601份、甲醇180份，並將水浴升溫至75℃。開始氮氣沖洗後經過1.5小時(吹入燒瓶之約3倍之氮氣量)，進而確認到內溫超過65℃後，以90分鐘分批添加薄片狀之氫氧化鈉21份。其後，進而以70℃進行1小時後續反應。反應結束後進行水洗，並使用旋轉蒸發器於140℃減壓下自油層將過量之表氯醇等溶劑蒸餾去除。向殘留物中添加甲基異丁基酮200份並溶解，升溫至70℃。於攪拌下添加30重量%之氫氧化鈉水溶液5份並進行1小時反應後，進行水洗至洗淨水成為中性為止，對所獲得之溶液使用旋轉蒸發器於180℃減壓下將甲基異丁基酮等蒸餾去除，藉此獲得環氧樹脂(EP2)300份。所獲得之環氧樹脂之環氧當量為270g/eq.，軟化點為90℃，ICI熔融黏度為0.46Pa‧s(150℃)，氯離子為2ppm，鈉離子為0.5ppm，色相為0.2以下(加德納40%THF溶液)。又，上述式(1)之結構為93面積%(GPC)。再者，折射率為1.63。 A phenol-based compound (DPPI1) was added to a 1 L flask equipped with a stirrer, a reflux cooling tube, and a stirring device while the substituent R in the above formula (1) was a hydrogen source. The compound SABIC PPPBP has a purity of 99% or more, residual phenolphthalein 200 ppm, iron component <5 ppm) 255 parts, epichlorohydrin 601 parts, and methanol 180 parts, and the water bath was heated to 75 °C. After the nitrogen purge was started, 1.5 hours (about three times the amount of nitrogen gas blown into the flask) was passed, and after confirming that the internal temperature exceeded 65 ° C, 21 parts of flaky sodium hydroxide was added in portions over 90 minutes. Thereafter, the subsequent reaction was further carried out at 70 ° C for 1 hour. After completion of the reaction, water washing was carried out, and excess solvent such as epichlorohydrin was distilled off from the oil layer using a rotary evaporator under reduced pressure at 140 °C. To the residue, 200 parts of methyl isobutyl ketone was added and dissolved, and the temperature was raised to 70 °C. 5 parts of a 30% by weight aqueous sodium hydroxide solution was added under stirring, and the reaction was carried out for 1 hour, and then washed with water until the washing water became neutral, and the obtained solution was subjected to a methyl group under reduced pressure at 180 ° C using a rotary evaporator. Isobutyl ketone or the like was distilled off, whereby 300 parts of an epoxy resin (EP2) was obtained. The epoxy resin obtained has an epoxy equivalent of 270 g/eq., a softening point of 90 ° C, an ICI melt viscosity of 0.46 Pa ‧ (150 ° C), a chloride ion of 2 ppm, a sodium ion of 0.5 ppm, and a hue of 0.2 or less. (Gardner 40% THF solution). Further, the structure of the above formula (1) is 93 area% (GPC). Furthermore, the refractive index was 1.63.

合成例3 Synthesis Example 3

向具備攪拌機、回流冷卻管、攪拌裝置之燒瓶中添加酚系化合物(DPPI1)(上述式(1)中取代基R均為氫原子之化合物SABIC PPPBP純度99%以上，殘留酚酞200ppm，鐵成分<5ppm)256份、表氯醇661份、苄基三甲基氯化銨3份，並將水浴升溫至70℃。以90分鐘向其中滴加49%氫氧化鈉水溶液100份後，進而以70℃進行4小時後續反應。反應結束後進行水洗，使用旋轉蒸發器於140℃減壓下自油層將過量之表氯醇等溶劑蒸餾去除，藉此獲得環氧樹脂(EP3)290份。所獲得之環氧樹脂之環氧當量為297g/eq.，軟化點為95℃，ICI熔融黏度為0.70Pa‧s(150℃)，總氯量為10450 ppm，水解性氯為9700ppm，氯離子為0.5ppm，鈉離子為0.5ppm，色相為3(加德納40%THF溶液)。又，上述式(1)之結構為65面積%(GPC)。 A phenol-based compound (DPPI1) is added to a flask equipped with a stirrer, a reflux cooling tube, and a stirring device (the compound of the formula (1) wherein the substituent R is a hydrogen atom, the purity of the compound SABIC PPPBP is 99% or more, and the residual phenolphthalein 200 ppm, the iron component < 5 ppm) 256 parts, 661 parts of epichlorohydrin, 3 parts of benzyltrimethylammonium chloride, and the temperature of the water bath was raised to 70 °C. After 100 parts of a 49% sodium hydroxide aqueous solution was added dropwise thereto over 90 minutes, the reaction was further carried out at 70 ° C for 4 hours. After completion of the reaction, water washing was carried out, and excess solvent such as epichlorohydrin was distilled off from the oil layer under reduced pressure at 140 ° C using a rotary evaporator, whereby 290 parts of an epoxy resin (EP3) was obtained. The obtained epoxy resin has an epoxy equivalent of 297 g/eq., a softening point of 95 ° C, an ICI melt viscosity of 0.70 Pa ‧ (150 ° C), and a total chlorine content of 10450. P, hydrolyzable chlorine was 9700 ppm, chloride ion was 0.5 ppm, sodium ion was 0.5 ppm, and hue was 3 (Gardner 40% THF solution). Further, the structure of the above formula (1) is 65 area% (GPC).

合成例4 Synthesis Example 4

一面對具備攪拌機、回流冷卻管、攪拌裝置之燒瓶實施氮氣沖洗一面添加三環癸烷二甲醇15份、甲基環己烷二羧酸酐(新日本理化製造之RIKACID MH)70份、環己烷-1,2,4-三羧酸-1,2-酐(三菱瓦斯化學製造之H-TMAn)15份，並以40℃反應3小時後，以70℃進行1小時加熱攪拌(藉由GPC確認到三環癸烷二甲醇之消失(1面積%以下))，藉此獲得含有羧酸類與酸酐之硬化劑組成物(H-1)100份。所獲得之硬化劑組成物(H-1)為無色之液狀樹脂，關於藉由GPC獲得之純度，羧酸類(下述式6)為37面積%，酸酐(環己烷-1,2,4-三羧酸-1,2-酐)為11面積%，酸酐(甲基環己烷羧酸酐)為52面積%。又，官能基當量為171g/eq.。 One side of a flask equipped with a stirrer, a reflux cooling tube, and a stirring device was subjected to a nitrogen purge, and 15 parts of tricyclodecane dimethanol, methylcyclohexane dicarboxylic anhydride (RIKACID MH manufactured by Nippon Chemical and Chemical Co., Ltd.), and cyclohexane were added. 15 parts of alkane-1,2,4-tricarboxylic acid-1,2-anhydride (H-TMAn, manufactured by Mitsubishi Gas Chemical Co., Ltd.), and reacted at 40 ° C for 3 hours, then heated and stirred at 70 ° C for 1 hour (by GPC confirmed the disappearance of tricyclodecane dimethanol (1 area% or less), thereby obtaining 100 parts of the hardener composition (H-1) containing a carboxylic acid and an acid anhydride. The hardener composition (H-1) obtained was a colorless liquid resin, and regarding the purity obtained by GPC, the carboxylic acid (Formula 6 below) was 37% by area, and the acid anhydride (cyclohexane-1, 2, The 4-tricarboxylic acid-1,2-anhydride) was 11% by area, and the acid anhydride (methylcyclohexanecarboxylic anhydride) was 52% by area. Further, the functional group equivalent was 171 g/eq.

實施例1、比較例1 Example 1 and Comparative Example 1

對作為實施例之合成例1中所獲得之環氧樹脂(EP1)、作為比較例之雙酚A型環氧樹脂(jER828，三菱化學製造)，分別以53：47：2之比率調配脂環式環氧樹脂(Celloxide 3150，Daicel工業股份有限公司製造)與陽離子硬化觸媒(SI-150L，三新化學工業股份有限公司製造)，而製作甲基乙基 酮55%之溶液。將厚度40微米之E玻璃之玻璃布(UNITIKA製造)浸漬於所獲得之溶液中，並於150℃以4分鐘使溶劑揮發而製作預浸體。其後，以150℃進行1分鐘之預熱後，於150℃以30kg/cm2進行15分鐘加壓按壓，最後於150℃以3小時進行硬化。將所獲得之膜切成10×40mm之大小，並對作為雙折射之指標之延遲進行測定。再者，膜之厚度為56μm。 The epoxy resin (EP1) obtained in Synthesis Example 1 of the Example, and the bisphenol A type epoxy resin (jER828, manufactured by Mitsubishi Chemical Corporation) as a comparative example were blended at a ratio of 53:47:2, respectively. An epoxy resin (Celloxide 3150, manufactured by Daicel Industrial Co., Ltd.) and a cationic hardening catalyst (SI-150L, manufactured by Sanshin Chemical Industry Co., Ltd.) were used to prepare a 55% solution of methyl ethyl ketone. A glass cloth of E glass having a thickness of 40 μm (manufactured by UNITIKA) was immersed in the obtained solution, and the solvent was volatilized at 150 ° C for 4 minutes to prepare a prepreg. Thereafter, the film was preheated at 150 ° C for 1 minute, and then pressed at 150 ° C for 15 minutes at 30 kg/cm 2 , and finally cured at 150 ° C for 3 hours. The obtained film was cut into a size of 10 × 40 mm, and the retardation as an index of birefringence was measured. Further, the thickness of the film was 56 μm.

延遲之測定方法係以下述條件進行。 The measurement method of the delay was carried out under the following conditions.

測定機器：Ellipso M-220[日本分光製造] Measuring machine: Ellipso M-220 [Japan Spectroscopic Manufacturing]

入射角：90度 Incidence angle: 90 degrees

帶寬：1.0nm Bandwidth: 1.0nm

測定範圍：0.1~0.4kgf Measuring range: 0.1~0.4kgf

測定波長：550nm Measurement wavelength: 550nm

其結果為，使用環氧樹脂EP1者顯示出0.4~0.8μm之延遲，使用作為比較之雙酚A型環氧樹脂者於0.7~1.6μm之範圍顯示出延遲。 As a result, the epoxy resin EP1 showed a retardation of 0.4 to 0.8 μm, and the comparative bisphenol A epoxy resin showed a retardation in the range of 0.7 to 1.6 μm.

再者，所謂延遲係指相位差，其越小越好，根據本結果，可確認到本發明之環氧樹脂組成物為低延遲，即低雙折射。 Further, the term "delay" means a phase difference, and the smaller the better, according to the results, it was confirmed that the epoxy resin composition of the present invention has low retardation, that is, low birefringence.

實施例2、3、4、比較例2 Examples 2, 3, 4, Comparative Example 2

使用作為實施例之合成例1、2中所獲得之環氧樹脂(EP1)及(EP2)、作為比較例之合成例3中所獲得之環氧樹脂(EP3)，以下述表1所記載之調配比進行調配。所獲得之硬化性樹脂組成物係以如下方式獲得：於實施例2、3、比較例2中係於Teflon(註冊商標)板上以80℃、20分鐘使溶劑揮發，並切割所形成之膜，又，於實施例4中係以150℃、3分鐘之溶劑揮 發條件使其揮發，切出所形成之膜，將0.9g重疊塞入橫7mm、縱5cm之試片用模具中，並以150℃、30kg/cm2進行15分鐘加壓按壓，最後於160℃以3小時進行硬化。均為成型為0.7~0.8mm之厚度。對所獲得之板進行透明性之評價。再者，關於透明性之評價係使用日本電色製造之色彩-濁度同步測定器COH400，以YI之測定值進行比較。將結果示於表1。 The epoxy resins (EP1) and (EP2) obtained in Synthesis Examples 1 and 2 of the examples and the epoxy resin (EP3) obtained in Synthesis Example 3 of the comparative example were used as shown in Table 1 below. The ratio is adjusted. The obtained curable resin composition was obtained in the following manner: in Examples 2, 3, and Comparative Example 2, the solvent was volatilized at 80 ° C for 20 minutes on a Teflon (registered trademark) plate, and the formed film was cut. Further, in Example 4, the solvent was volatilized under the conditions of solvent volatilization at 150 ° C for 3 minutes, and the formed film was cut out, and 0.9 g of the overlap was placed in a mold for test pieces having a width of 7 mm and a length of 5 cm, and was 150. The pressure was pressed for 15 minutes at ° C and 30 kg/cm 2 , and finally hardened at 160 ° C for 3 hours. Both are formed to a thickness of 0.7 to 0.8 mm. The board obtained was evaluated for transparency. Further, the evaluation of the transparency was carried out by using the color-turbidity synchronization measuring device COH400 manufactured by Nippon Denshoku Co., Ltd., and comparing the measured values of YI. The results are shown in Table 1.

合成例2-1 Synthesis Example 2-1

將具備攪拌機、回流冷卻管、攪拌裝置之1L之四口燒瓶暫時抽真空，並進行氮氣置換後(氧濃度4.9%)，一面實施氮氣沖洗(2L/hr)一面添加酚系化合物(DPPI1)(上述式(1)中取代基R均為氫原子之化合物SABIC PPPBP純度99%以上，殘留酚酞200ppm，鐵成分<5ppm)256份、表氯醇 842份、甲醇180份，並將水浴升溫至75℃。於內溫超過65℃時以90分鐘分批添加薄片狀之氫氧化鈉21份後，進而以70℃進行1小時後續反應。反應結束後進行水洗，使用旋轉蒸發器於140℃減壓下自油層將過量之表氯醇等溶劑蒸餾去除。向殘留物中添加甲基異丁基酮600份並溶解，升溫至70℃。於攪拌下添加30重量%之氫氧化鈉水溶液26份，進行1小時反應後，進行水洗至洗淨水成為中性為止，對所獲得之溶液使用旋轉蒸發器於180℃減壓下將甲基異丁基酮等蒸餾去除，藉此獲得環氧樹脂(EP2-1)305份。所獲得之環氧樹脂之環氧當量為266g/eq.，軟化點為89℃，ICI熔融黏度為0.42Pa‧s(150℃)，總氯量為1600ppm，水解性氯為1540ppm，氯離子為2ppm，鈉離子為0.5ppm，色相為0.2以下(加德納40%MEK(甲基乙基酮)溶液)。又，上述式(1)之結構為93面積%(GPC)。 A four-necked flask of 1 L equipped with a stirrer, a reflux cooling tube, and a stirring device was temporarily evacuated, and after nitrogen substitution (oxygen concentration: 4.9%), a phenol-based compound (DPPI1) was added while performing nitrogen purge (2 L/hr). The compound of the formula (1) in which the substituent R is a hydrogen atom, the purity of the compound SABIC PPPBP is 99% or more, the residual phenolphthalein 200 ppm, the iron component <5 ppm), 256 parts, epichlorohydrin 842 parts, 180 parts of methanol, and the water bath was raised to 75 °C. When the internal temperature exceeded 65 ° C, 21 parts of flaky sodium hydroxide was added in portions over 90 minutes, and then the reaction was further carried out at 70 ° C for 1 hour. After completion of the reaction, water washing was carried out, and an excess of a solvent such as epichlorohydrin was distilled off from the oil layer using a rotary evaporator under reduced pressure at 140 °C. To the residue, 600 parts of methyl isobutyl ketone was added and dissolved, and the temperature was raised to 70 °C. 26 parts of a 30% by weight aqueous sodium hydroxide solution was added under stirring, and after reacting for 1 hour, the mixture was washed with water until the washing water became neutral, and the obtained solution was subjected to a methyl group under reduced pressure at 180 ° C using a rotary evaporator. Isobutyl ketone or the like was distilled off, whereby 305 parts of an epoxy resin (EP2-1) was obtained. The obtained epoxy resin has an epoxy equivalent of 266 g/eq., a softening point of 89 ° C, an ICI melt viscosity of 0.42 Pa ‧ (150 ° C), a total chlorine content of 1600 ppm, and a hydrolyzable chlorine of 1540 ppm. The chloride ion is 2 ppm, sodium ion 0.5 ppm, hue 0.2 or less (Gardner 40% MEK (methyl ethyl ketone) solution). Further, the structure of the above formula (1) is 93 area% (GPC).

合成例2-2 Synthesis Example 2-2

將具備攪拌機、回流冷卻管、攪拌裝置之1L之四口燒瓶暫時抽真空並進行氮氣置換後(氧濃度5.3%)，一面實施氮氣沖洗(2L/hr)一面使用酚系化合物(DPPI2)(於上述式(1)中取代基R均為氫原子之化合物SABIC PPPBP純度99%以上，殘留酚酞200ppm，鐵成分<5ppm中添加有酚酞500ppm者)，除此以外與合成例2-1同樣地進行反應。所獲得之環氧樹脂(EP2-2)之環氧當量為266g/eq.，軟化點為90℃，ICI熔融黏度為0.44Pa‧s(150℃)，總氯量為2000ppm，水解性氯為1950ppm，氯離子為1ppm，鈉離子為0.3ppm，色相為0.2(加德納40%MEK溶液)。又，上述式(1)之結構為93面積%(GPC)。 A 4-liter four-necked flask equipped with a stirrer, a reflux cooling tube, and a stirring device was temporarily evacuated and replaced with nitrogen (oxygen concentration: 5.3%), and a phenol-based compound (DPPI2) was used while performing nitrogen purge (2 L/hr). In the same manner as in Synthesis Example 2-1, except that the compound of the formula (1) wherein the substituent R is a hydrogen atom, the purity of the compound SABIC PPPBP is 99% or more, the residual phenolphthalein is 200 ppm, and the iron component is less than 5 ppm, the phenolphthalein is added in an amount of 500 ppm. reaction. The obtained epoxy resin (EP2-2) has an epoxy equivalent of 266 g/eq., a softening point of 90 ° C, an ICI melt viscosity of 0.44 Pa s (150 ° C), a total chlorine content of 2000 ppm, and hydrolyzable chlorine. 1950 ppm, chloride ion 1 ppm, sodium ion 0.3 ppm, hue 0.2 (Gardner 40% MEK solution). Further, the structure of the above formula (1) is 93 area% (GPC).

合成例2-3 Synthesis Example 2-3

對具備攪拌機、回流冷卻管、攪拌裝置之1L之四口燒瓶以4L/h進行30分鐘氮氣置換後(氧濃度6.5%)，一面實施氮氣沖洗(2L/hr)一面添加酚系化合物(DPPI1)(上述式(1)中取代基R均為氫原子之化合物SABIC PPPBP純度99%以上，殘留酚酞200ppm，鐵成分<5ppm)256份、表氯醇661份、甲醇165份，並將水浴升溫至75℃。於內溫超過65℃時以90分鐘分批添加薄片狀之氫氧化鈉57份後，進而以70℃進行1小時後續反應。反應結束後進行水洗，使用旋轉蒸發器於140℃減壓下自油層將過量之表氯醇等溶劑蒸餾去除。向殘留物中添加甲基異丁基酮600份並溶解，升溫至70℃。於攪拌下添加30重量%之氫氧化鈉水溶液5份並進行1小時反應後，進行水洗至洗淨水成為中性為止，對所獲得之溶液使用旋轉蒸發器於180℃減壓下將甲基異丁基酮等蒸餾去除，藉此獲得環氧樹脂(EP2-3)297份。所獲得之環氧樹脂之環氧當量為277g/eq.，軟化點為96℃，ICI熔融黏度為0.62Pa‧s(150℃)，總氯量為2230ppm，水解性氯為2100ppm，氯離子為0.5ppm，鈉離子為0.5ppm，色相為0.2以下(加德納40%MEK溶液)。又，上述式(1)之結構為82面積%(GPC)。 A four-liter flask equipped with a stirrer, a reflux cooling tube, and a stirring device was subjected to nitrogen substitution at 4 L/h for 30 minutes (oxygen concentration: 6.5%), and a phenol-based compound (DPPI1) was added while performing nitrogen purge (2 L/hr). (In the above formula (1), the substituent R is a hydrogen atom, the compound SABIC PPPBP has a purity of 99% or more, the residual phenolphthalein 200 ppm, the iron component is <5 ppm) 256 parts, the epichlorohydrin 661 parts, and the methanol 165 parts, and the water bath is heated to a temperature of 75 ° C. When the internal temperature exceeded 65 ° C, 57 parts of flaky sodium hydroxide was added in portions over 90 minutes, and then the reaction was further carried out at 70 ° C for 1 hour. After completion of the reaction, water washing was carried out, and an excess of a solvent such as epichlorohydrin was distilled off from the oil layer using a rotary evaporator under reduced pressure at 140 °C. To the residue, 600 parts of methyl isobutyl ketone was added and dissolved, and the temperature was raised to 70 °C. 5 parts of a 30% by weight aqueous sodium hydroxide solution was added under stirring, and the reaction was carried out for 1 hour, and then washed with water until the washing water became neutral, and the obtained solution was subjected to a methyl group under reduced pressure at 180 ° C using a rotary evaporator. Isobutyl ketone or the like was distilled off, whereby 297 parts of an epoxy resin (EP2-3) was obtained. The obtained epoxy resin has an epoxy equivalent of 277 g/eq., a softening point of 96 ° C, an ICI melt viscosity of 0.62 Pa ‧ (150 ° C), a total chlorine content of 2230 ppm, a hydrolyzable chlorine of 2100 ppm, and a chloride ion of 0.5 ppm, sodium ion 0.5 ppm, hue 0.2 or less (Gardner 40% MEK solution). Further, the structure of the above formula (1) is 82 area% (GPC).

合成例2-4 Synthesis Example 2-4

將具備攪拌機、回流冷卻管、攪拌裝置之1L之四口燒瓶暫時抽真空並進行氮氣置換後(氧濃度5.2%)，一面實施氮氣沖洗(2L/hr)一面添加酚系化合物(DPPI1)(上述式(1)中取代基R均為氫原子之化合物SABIC PPPBP純度99%以上，殘留酚酞200ppm，鐵成分<5ppm)256份、表氯醇661份、二甲基亞碸200份，將水浴升溫至45℃。於內溫超過40℃時以90分鐘分批添加薄片狀之氫氧化鈉57份後，進而以70℃進行1小時後續反 應。反應結束後進行水洗，使用旋轉蒸發器於140℃減壓下自油層將過量之表氯醇等溶劑蒸餾去除。向殘留物中添加甲基異丁基酮600份並升溫至70℃。於攪拌下添加30重量%之氫氧化鈉水溶液16份並進行1小時反應後，進行水洗至洗淨水成為中性為止，對所獲得之溶液使用旋轉蒸發器於180℃減壓下將甲基異丁基酮等蒸餾去除，藉此獲得環氧樹脂(EP2-4)300份。所獲得之環氧樹脂之環氧當量為270g/eq.，軟化點為92℃，ICI熔融黏度為0.48Pa‧s(150℃)，總氯量為1050ppm，水解性氯為960ppm，氯離子為0.3ppm，鈉離子為0.1ppm，色相為0.6(加德納40%MEK溶液)。又，上述式(1)之結構為90面積%(GPC)。 A four-necked flask of 1 L equipped with a stirrer, a reflux cooling tube, and a stirring device was temporarily evacuated and replaced with nitrogen (oxygen concentration: 5.2%), and a phenol-based compound (DPPI1) was added while performing nitrogen purge (2 L/hr). In the formula (1), the substituent R is a hydrogen atom, the compound SABIC PPPBP has a purity of 99% or more, the residual phenolphthalein 200 ppm, the iron component <5 ppm) 256 parts, the epichlorohydrin 661 parts, and the dimethyl hydrazine 200 parts, and the water bath is heated. To 45 ° C. When the internal temperature exceeds 40 ° C, 57 parts of flaky sodium hydroxide are added in portions over 90 minutes, and then further reacted at 70 ° C for 1 hour. should. After completion of the reaction, water washing was carried out, and an excess of a solvent such as epichlorohydrin was distilled off from the oil layer using a rotary evaporator under reduced pressure at 140 °C. 600 parts of methyl isobutyl ketone was added to the residue and the temperature was raised to 70 °C. 16 parts of a 30% by weight aqueous sodium hydroxide solution was added under stirring, and the reaction was carried out for 1 hour, and then washed with water until the washing water became neutral, and the obtained solution was subjected to a methyl group under reduced pressure at 180 ° C using a rotary evaporator. Isobutyl ketone or the like was distilled off, whereby 300 parts of an epoxy resin (EP2-4) was obtained. The epoxy resin obtained has an epoxy equivalent of 270 g/eq., a softening point of 92 ° C, an ICI melt viscosity of 0.48 Pa ‧ (150 ° C), a total chlorine content of 1050 ppm, and a hydrolyzable chlorine of 960 ppm. 0.3 ppm, sodium ion 0.1 ppm, and hue 0.6 (Gardner 40% MEK solution). Further, the structure of the above formula (1) is 90 area% (GPC).

實施例2-1、2-2、2-3及比較例2-1 Examples 2-1, 2-2, 2-3 and Comparative Example 2-1

使用上述中所獲得之環氧樹脂，以下述表2所示之調配比例進行調配，以120℃ 2小時、160℃ 2小時、180℃ 4小時進行硬化，並進行阻燃性之試驗。再者，阻燃性之試驗方法如下所示。 Using the epoxy resin obtained above, it was blended at a mixing ratio shown in the following Table 2, and was cured at 120 ° C for 2 hours, 160 ° C for 2 hours, and 180 ° C for 4 hours, and the flame retardancy test was carried out. Further, the test method of flame retardancy is as follows.

阻燃性 Flame retardancy

‧阻燃性之判定：依據UL94進行。其中，以樣品尺寸設為寬度12.5mm×長度150mm，厚度為0.8mm進行試驗。 ‧ Determination of flame retardancy: According to UL94. Among them, the test was carried out with a sample size of 12.5 mm in width × 150 mm in length and a thickness of 0.8 mm.

由以上結果闡明，本發明之硬化性樹脂組成物可同時實現較高之耐熱性與阻燃性。 From the above results, it is clarified that the curable resin composition of the present invention can simultaneously achieve high heat resistance and flame retardancy.

以上，參照特定態樣對本發明進行了詳細說明，但從業者明瞭可於不脫離本發明之精神及範圍之情況下實施各種變更及修正。 The present invention has been described in detail above with reference to the specific embodiments thereof. It is understood that various modifications and changes can be made without departing from the spirit and scope of the invention.

再者，本申請係基於2012年6月7日提出申請之日本專利特願(日本特願2012-129406及日本特願2012-129408)，藉由引用而援用其整體。又，此處所引用之所有參考係視為整體而併入。 In addition, the present application is based on Japanese Patent Application No. 2012-129406 and Japanese Patent Application No. 2012-129408, filed on Jun. Again, all references cited herein are incorporated as a whole.

[產業上之可利用性] [Industrial availability]

第1發明之環氧樹脂組成物可用於以光學零件材料為首之各種用途。又，第2發明之硬化性樹脂組成物除了接著劑、塗料、塗佈劑、成形材料(包括片材、膜、FRP等)、絕緣材料(包括印刷基板、電線覆層等)、密封劑以外，亦可用於對其他樹脂等之添加劑等。 The epoxy resin composition of the first invention can be used for various purposes including optical component materials. Further, the curable resin composition of the second aspect of the invention is other than an adhesive, a paint, a coating agent, a molding material (including a sheet, a film, an FRP, etc.), an insulating material (including a printed board, a wire coating, etc.), or a sealant. It can also be used as an additive to other resins and the like.

Claims (11)

一種環氧樹脂組成物，其係含有藉由下述式(1)所表示之酚系樹脂與表鹵醇之反應而獲得之環氧樹脂、與羧酸類及/或陽離子聚合觸媒者，並且上述環氧樹脂於加德納比色法(40%甲基乙基酮溶液)中之色相為2以下， (式中，存在複數個之R分別獨立地表示氫原子、碳數1~6之烷基或碳數1~6之烷氧基)。 An epoxy resin composition containing an epoxy resin obtained by a reaction of a phenolic resin represented by the following formula (1) and an epihalohydrin, and a carboxylic acid and/or a cationic polymerization catalyst, and The hue of the above epoxy resin in the Gardner colorimetric method (40% methyl ethyl ketone solution) is 2 or less. (In the formula, a plurality of R independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms). 如申請專利範圍第1項之環氧樹脂組成物，其中與表鹵醇反應之酚系樹脂中之殘留酚酞衍生物之量為2%以下。 The epoxy resin composition of claim 1, wherein the amount of the residual phenolphthalein derivative in the phenolic resin reacted with the epihalohydrin is 2% or less. 如申請專利範圍第1項之環氧樹脂組成物，其中與表鹵醇反應之酚系樹脂中之殘留鐵成分為50ppm以下。 The epoxy resin composition according to claim 1, wherein the residual iron component in the phenol resin reacted with the epihalohydrin is 50 ppm or less. 如申請專利範圍第3項之環氧樹脂組成物，其含有過渡金屬鹽。 An epoxy resin composition according to claim 3, which contains a transition metal salt. 如申請專利範圍第3項之環氧樹脂組成物，其含有四級鏻鹽。 An epoxy resin composition according to claim 3, which contains a quaternary phosphonium salt. 如申請專利範圍第3項之環氧樹脂組成物，其含有陽離子聚合起始劑。 An epoxy resin composition as claimed in claim 3, which contains a cationic polymerization initiator. 一種環氧樹脂硬化物，其係使申請專利範圍第4至6項中任一項之環氧樹脂組成物硬化而成者。 An epoxy resin cured product obtained by hardening an epoxy resin composition according to any one of claims 4 to 6. 如申請專利範圍第1至6項中任一項之環氧樹脂組成物，其係玻璃代替用環氧樹脂組成物。 The epoxy resin composition according to any one of claims 1 to 6, which is a glass substitute for an epoxy resin composition. 一種硬化性樹脂組成物，其含有下述式(2)所表示之環氧樹脂、與酚系樹脂及/或聚合觸媒， (式中，存在複數個之R分別獨立地表示氫原子、碳數1~6之烷基、或碳數1~6之烷氧基)。 A curable resin composition containing an epoxy resin represented by the following formula (2), a phenol resin, and/or a polymerization catalyst, (In the formula, a plurality of R independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms). 如申請專利範圍第9項之硬化性樹脂組成物，其中酚系樹脂為酚芳烷基樹脂(具有芳香族伸烷基結構之樹脂)。 The sclerosing resin composition of claim 9, wherein the phenolic resin is a phenol aralkyl resin (a resin having an aromatic alkylene structure). 如申請專利範圍第9項之硬化性樹脂組成物，其中聚合觸媒為陽離子聚合觸媒。 The sclerosing resin composition of claim 9, wherein the polymerization catalyst is a cationic polymerization catalyst.
TW102120279A 2012-06-07 2013-06-07 Epoxy resin composition, cured product thereof, and curable resin composition TW201412804A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2012129406 2012-06-07
JP2012129408 2012-06-07

Publications (1)

Publication Number Publication Date
TW201412804A true TW201412804A (en) 2014-04-01

Family

ID=49712123

Family Applications (2)

Application Number Title Priority Date Filing Date
TW106141641A TWI647248B (en) 2012-06-07 2013-06-07 Epoxy resin composition, cured product thereof, and curable resin composition
TW102120279A TW201412804A (en) 2012-06-07 2013-06-07 Epoxy resin composition, cured product thereof, and curable resin composition

Family Applications Before (1)

Application Number Title Priority Date Filing Date
TW106141641A TWI647248B (en) 2012-06-07 2013-06-07 Epoxy resin composition, cured product thereof, and curable resin composition

Country Status (7)

Country Link
JP (1) JP6240069B2 (en)
KR (1) KR101913603B1 (en)
CN (1) CN104395371B (en)
MY (1) MY169102A (en)
SG (1) SG11201408155RA (en)
TW (2) TWI647248B (en)
WO (1) WO2013183736A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI643741B (en) * 2015-11-04 2018-12-11 琳得科股份有限公司 Curable resin film and sheet for forming first protective film
TWI706003B (en) * 2016-03-28 2020-10-01 日商積水化學工業股份有限公司 Resin composition and multilayer substrate

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6239599B2 (en) * 2013-04-25 2017-11-29 日本化薬株式会社 Phenol resin, epoxy resin composition containing the phenol resin, and cured product thereof
JP6550843B2 (en) * 2014-03-31 2019-07-31 三菱ケミカル株式会社 Epoxy resin, epoxy resin composition, cured product, and laminate for electric / electronic circuit
WO2015159781A1 (en) * 2014-04-15 2015-10-22 三菱瓦斯化学株式会社 Fiber-reinforced composite material
JP2015209509A (en) * 2014-04-28 2015-11-24 京セラケミカル株式会社 Epoxy resin composition and resin-sealed electronic component device
KR102327347B1 (en) 2014-08-22 2021-11-16 닛뽄 가야쿠 가부시키가이샤 Epoxy(meth)acrylate compound, resin composition containing the same and cured product thereof, color filter and display device
WO2016031643A1 (en) * 2014-08-26 2016-03-03 日本化薬株式会社 Reactive polyester compound and active energy ray-curable resin composition using same
JP6428147B2 (en) * 2014-10-22 2018-11-28 味の素株式会社 Resin composition
US20180009935A1 (en) * 2015-03-18 2018-01-11 Mitsubishi Gas Chemical Company, Inc. Resin composition, prepreg, metal foil-clad laminate, resin sheet, and printed wiring board
JP2017071706A (en) * 2015-10-08 2017-04-13 日本化薬株式会社 Epoxy resin composition, curable resin composition and cured product thereof
CN105714857A (en) * 2016-02-03 2016-06-29 袁根木 Method for replacing template with steel wire mesh during prefabricating longest sea-crossing river bottom pipe section
US10487077B1 (en) 2018-06-14 2019-11-26 Sabic Global Technologies B.V. Bis(benzoxazinyl)phthalimidine and associated curable composition and composite
CN109401707B (en) * 2018-11-01 2020-12-08 烟台信友新材料有限公司 Single-component high-temperature-resistant impact-resistant flame-retardant structural adhesive and preparation method thereof
JP7184002B2 (en) 2019-09-13 2022-12-06 味の素株式会社 resin composition
JP7491741B2 (en) 2020-05-27 2024-05-28 住友化学株式会社 Epoxy resin composition and its cured product
CN112379546B (en) * 2020-11-23 2022-08-19 珠海兴业新材料科技有限公司 Polymer disperse dye liquid crystal material, electrochromic dimming film and preparation method
WO2024024620A1 (en) * 2022-07-26 2024-02-01 三井化学株式会社 Sealing material for display device, sealing material, organic el display, and led display

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH496021A (en) * 1966-03-10 1970-09-15 Ciba Geigy Preparation of polyglycidyl ethers
JPH01108218A (en) * 1987-10-21 1989-04-25 Mitsui Petrochem Ind Ltd Purification of epoxy resin
JPH01108217A (en) * 1987-10-21 1989-04-25 Mitsui Petrochem Ind Ltd Purification of epoxy resin
JP2556366B2 (en) * 1988-11-25 1996-11-20 日本化薬株式会社 High-purity epoxy resin and method for producing the same
JPH0892231A (en) * 1994-09-22 1996-04-09 Mitsui Toatsu Chem Inc Spirobiindan diglycidyl ether and its production
JPH11255864A (en) * 1998-03-09 1999-09-21 Toshiba Corp Liquid epoxy rein composition and resin-sealed type semiconductor apparatus
JP2000007757A (en) * 1998-04-22 2000-01-11 Asahi Chiba Kk New epoxy resin
JP2002114835A (en) * 2000-10-06 2002-04-16 Asahi Denka Kogyo Kk Curing agent composition for epoxy resin and coating composition
JP2004099744A (en) * 2002-09-10 2004-04-02 Mitsui Chemicals Inc Method for purifying epoxy resin
JP4675777B2 (en) * 2003-02-03 2011-04-27 新日鐵化学株式会社 Epoxy resin, production method thereof, epoxy resin composition and cured product using the same
JP2005154719A (en) 2003-04-25 2005-06-16 Mitsui Chemicals Inc Epoxy resin composition and its application
JP2007063565A (en) * 2006-10-17 2007-03-15 Sumitomo Bakelite Co Ltd Resin paste for semiconductor and semiconductor device
EP2143718B1 (en) * 2007-05-08 2012-11-21 Mitsubishi Gas Chemical Company, Inc. Process for producing tetraglycidylamino compound
JP4782870B2 (en) * 2008-07-31 2011-09-28 積水化学工業株式会社 Cured body, sheet-like molded body, laminated board and multilayer laminated board
JP5153000B2 (en) * 2009-04-01 2013-02-27 新日鉄住金化学株式会社 Epoxy resin, production method thereof, epoxy resin composition and cured product
WO2010119960A1 (en) * 2009-04-17 2010-10-21 日本化薬株式会社 Olefin resin, epoxy resin, curable resin composition, and material resulting from curing same
US20130009327A1 (en) * 2010-03-15 2013-01-10 Yusuke Tanaka Resin composition for semiconductor encapsulation, and semiconductor device using same
JP5404514B2 (en) * 2010-04-19 2014-02-05 日本化薬株式会社 Epoxy resin production method, epoxy resin, and curable resin composition
JP5732774B2 (en) * 2010-08-16 2015-06-10 Dic株式会社 Epoxy resin composition, curable resin composition, cured product thereof, and printed wiring board
JP5745248B2 (en) * 2010-10-08 2015-07-08 株式会社ダイセル Curing agent composition for epoxy resin, curable resin composition and cured product thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI643741B (en) * 2015-11-04 2018-12-11 琳得科股份有限公司 Curable resin film and sheet for forming first protective film
US10717901B2 (en) 2015-11-04 2020-07-21 Lintec Corporation Curable resin film and first protective film forming sheet
TWI706003B (en) * 2016-03-28 2020-10-01 日商積水化學工業股份有限公司 Resin composition and multilayer substrate

Also Published As

Publication number Publication date
KR101913603B1 (en) 2018-10-31
KR20150030645A (en) 2015-03-20
TW201809054A (en) 2018-03-16
WO2013183736A1 (en) 2013-12-12
JPWO2013183736A1 (en) 2016-02-01
JP6240069B2 (en) 2017-11-29
MY169102A (en) 2019-02-18
CN104395371A (en) 2015-03-04
CN104395371B (en) 2017-03-15
TWI647248B (en) 2019-01-11
SG11201408155RA (en) 2015-01-29

Similar Documents

Publication Publication Date Title
TWI647248B (en) Epoxy resin composition, cured product thereof, and curable resin composition
JP5713898B2 (en) Polyvalent carboxylic acid, composition thereof, curable resin composition, cured product, and method for producing polyvalent carboxylic acid
TWI579313B (en) Epoxy resin, epoxy resin composition and hardened material
JP5517237B2 (en) Method for producing epoxy compound, epoxy compound, curable resin composition and cured product thereof
JP5559154B2 (en) Olefin resin, epoxy resin, curable resin composition and cured product thereof
JP5430337B2 (en) Diolefin compound, epoxy resin, curable resin composition and cured product thereof
JP6239587B2 (en) Polyvalent carboxylic acid composition, curing agent composition for epoxy resin, epoxy resin composition and cured product thereof
JP5780627B2 (en) Method for producing epoxy compound
TWI572666B (en) An epoxy resin mixture, an epoxy resin composition and a cured product thereof
JP5505960B2 (en) Diolefin compound, epoxy resin, curable resin composition and cured product thereof
TWI659974B (en) Epoxy resin, curable resin composition, and cured product thereof
JP6016647B2 (en) Epoxy resin and curable resin composition
TWI642700B (en) Phenolic resin, epoxy resin, epoxy resin composition, and cured product thereof
JP5878865B2 (en) Diolefin compound, epoxy resin, curable resin composition and cured product thereof
JP2011225654A (en) Diolefin resin, epoxy resin, and composition for the same
JP5196663B2 (en) Diolefin compound, epoxy resin, curable resin composition and cured product thereof
JP5796916B2 (en) Production method of epoxy resin
JP2010254628A (en) Diolefin compound, epoxy compound, curable resin composition and cured product thereof