TW202024105A - Phosphorus-containing curing agent, epoxy resin composition containing the phosphorus-containing curing agent and epoxy resin, and cured product thereof - Google Patents

Phosphorus-containing curing agent, epoxy resin composition containing the phosphorus-containing curing agent and epoxy resin, and cured product thereof Download PDF

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TW202024105A
TW202024105A TW108133840A TW108133840A TW202024105A TW 202024105 A TW202024105 A TW 202024105A TW 108133840 A TW108133840 A TW 108133840A TW 108133840 A TW108133840 A TW 108133840A TW 202024105 A TW202024105 A TW 202024105A
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epoxy resin
phosphorus
carbons
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TWI807099B (en
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秋葉圭太
佐藤洋
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日商日鐵化學材料股份有限公司
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    • 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
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    • B32B15/00—Layered products comprising a layer of metal
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    • B32—LAYERED PRODUCTS
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    • B32B27/00—Layered products comprising a layer of synthetic resin
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
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    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
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    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
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    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4071—Curing agents not provided for by the groups C08G59/42 - C08G59/66 phosphorus containing compounds
    • C—CHEMISTRY; METALLURGY
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2363/04—Epoxynovolacs
    • C—CHEMISTRY; METALLURGY
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Abstract

An objective of the present invention is to provide a phosphorus-containing curing agent having excellent solubility in a solvent and an epoxy resin, an epoxy resin composition containing the curing agent and having excellent heat resistance and flame resistance, and a cured product thereof.
The present invention is a phosphorus-containing curing agent represented by the following general formula (1), an epoxy resin composition, and a cured product thereof; the epoxy resin composition containing the phosphorus-containing curing agent and an epoxy resin, and the phosphorus content in the composition is 1.0 to 5.0 mass%.
Figure 108133840-A0202-11-0002-2
 In the formula, X is an aryl group having 2 to 4 substituents selected from a hydroxy group, a carboxy group or an amino group, R1 to R8 each represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and at least one of R1 to R8 is other than a hydrogen atom.

Description

含磷硬化劑、含有該含磷硬化劑及環氧樹脂的環氧樹脂組成物，以及其硬化物 Phosphorus-containing hardener, epoxy resin composition containing the phosphorus-containing hardener and epoxy resin, and hardened products thereof

本發明係關於改善對於含磷硬化劑之溶劑及環氧樹脂的溶解性，且阻燃性及耐熱性優異的環氧樹脂組成物及其硬化物；該硬化物適合使用於纖維強化塑料、半導體用液狀密封材及印刷電路板的電子電路基板絕緣材料、液狀密封材、接著劑、填孔材料等。 The present invention relates to an epoxy resin composition and its cured product that improve the solubility of phosphorus-containing hardener solvents and epoxy resins, and are excellent in flame retardancy and heat resistance; the cured product is suitable for use in fiber reinforced plastics and semiconductors Use liquid sealing materials and printed circuit board insulating materials for electronic circuit boards, liquid sealing materials, adhesives, and filling materials.

由於環氧樹脂具有優異的接著性、可撓性、耐熱性、耐化學性、絕緣性、硬化反應性等，因此被廣泛使用於電性材料、塗料、接著材料、複合材料等用途。 Since epoxy resin has excellent adhesion, flexibility, heat resistance, chemical resistance, insulation, curing reactivity, etc., it is widely used in electrical materials, coatings, adhesives, composite materials and other applications.

另一方面，環氧樹脂是易燃的，在作為製品的安全性方面有疑慮。於是為了解決該種易燃性，至今已經對以賦予環氧樹脂阻燃性為目的而使用的各種阻燃劑進行檢討/開發。因為如此的背景，至今為止多為使用廉價且物性平衡為優異的鹵素阻燃劑。 On the other hand, epoxy resin is flammable, and there are doubts about its safety as a product. Therefore, in order to solve this flammability, various flame retardants used for the purpose of imparting flame retardancy to epoxy resins have been reviewed and developed. Because of this background, halogen flame retardants that are inexpensive and have an excellent balance of physical properties have been used so far.

但是，鹵素阻燃劑在廢棄焚燒時產生的戴奧辛對人體為有害，且會對環境產生負面影響，而造成嚴重的社會問題。因此，近年來對於環氧樹脂的無鹵阻燃化之要求正在提高。 However, the dioxin produced when the halogen flame retardant is discarded and incinerated is harmful to the human body and has a negative impact on the environment, causing serious social problems. Therefore, the requirements for halogen-free flame retardancy of epoxy resins are increasing in recent years.

該無鹵阻燃化已有提案為磷系阻燃劑，例如使用屬於縮合磷酸酯的雙酚A-雙(磷酸二苯酯)[bisphenol A-bis(diphenyl phosphate)](大八化學工業股份有限公司製、CR-741)、間苯二酚雙(磷酸聯二甲苯基酯)(大八化學工業股份有限公司製、PX-200)等(專利文獻1)。但是，由於此等縮合磷酸酯系阻燃劑顯示塑化劑效果，使得成形品的耐熱性降低。 The halogen-free flame retardant has been proposed as a phosphorus-based flame retardant, such as the use of bisphenol A-bis(diphenyl phosphate) which is a condensed phosphate ester [bisphenol A-bis(diphenyl phosphate)] (Dahachi Chemical Industry Co., Ltd.) Co., Ltd. product, CR-741), resorcinol bis(bixylyl phosphate) (Dahachi Chemical Industry Co., Ltd. product, PX-200), etc. (Patent Document 1). However, since these condensed phosphate ester flame retardants exhibit a plasticizer effect, the heat resistance of the molded article is reduced.

此外，與環氧樹脂反應的磷系硬化劑，有提案是使屬於環狀有機磷化合物的9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物(三光股份有限公司製，HCA)與醌類反應而得到的多官能酚化合物等(專利文獻2、3)。但是，此等多官能酚化合物對於溶劑及環氧樹脂的溶解性低，在環氧樹脂組成物中溶解不完全而局部分佈，因此未能發揮出環氧樹脂組成物本身的阻燃性，且因為硬化不良而導致物性降低。 In addition, there is a proposal to make 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, which is a cyclic organophosphorus compound, a phosphorus-based hardener that reacts with epoxy resin (Sanko Co., Ltd. Company product, HCA), a polyfunctional phenol compound obtained by reacting with quinones, etc. (Patent Documents 2, 3). However, these polyfunctional phenol compounds have low solubility in solvents and epoxy resins, are incompletely dissolved in the epoxy resin composition and are locally distributed, and therefore fail to exhibit the flame retardancy of the epoxy resin composition itself, and The physical properties are reduced due to poor curing.

再者，作為含磷硬化劑，亦有提案為溶劑溶解性優異的含磷酚樹脂(專利文獻4、5)。但是，由於此等含磷酚樹脂的分子量高而會增加溶液中的黏度，因此對於預浸物的含浸性不佳，且未能去除在製作預浸物時所產生的氣泡，使得成形品的阻燃性劣化。 Furthermore, as a phosphorus-containing curing agent, there are also proposals for phosphorus-containing phenol resins having excellent solvent solubility (Patent Documents 4 and 5). However, due to the high molecular weight of these phosphorus-containing phenol resins, it will increase the viscosity in the solution, so the impregnation of the prepreg is not good, and the bubbles generated during the production of the prepreg cannot be removed, making the molded product The flame retardancy is deteriorated.

[先前技術文獻] [Prior Technical Literature] [專利文獻] [Patent Literature]

[專利文獻1]WO2010/082426號 [Patent Document 1] WO2010/082426

[專利文獻2]日本特開昭61-236787號公報 [Patent Document 2] JP 61-236787 A

[專利文獻3]日本特開2001-302686號公報 [Patent Document 3] JP 2001-302686 A

[專利文獻4]WO2005/118604號 [Patent Document 4] WO2005/118604

[專利文獻5]日本特開2010-215842號公報 [Patent Document 5] JP 2010-215842 A

本發明所欲解決之課題為提供一種含磷硬化劑以及一種環氧樹脂組成物，所述含磷硬化劑改善了對於溶劑及環氧樹脂的溶解性，所述環氧樹脂組成物與環氧樹脂的硬化物呈現優異的耐熱性及阻燃性。 The problem to be solved by the present invention is to provide a phosphorous-containing hardener and an epoxy resin composition, the phosphorous-containing hardener improves the solubility of solvents and epoxy resin, the epoxy resin composition and epoxy The cured resin exhibits excellent heat resistance and flame retardancy.

為了解決上述課題，本發明者針對含磷硬化劑進行精心探討，結果為發現具有特定取代基的環狀有機磷化合物會改善對於溶劑及環氧樹脂之溶解性，更發現當調配於環氧樹脂時所得到的硬化物之耐熱性及阻燃性優異，從而完成本發明。 In order to solve the above-mentioned problems, the inventors of the present invention conducted careful research on phosphorus-containing hardeners. As a result, they found that cyclic organophosphorus compounds with specific substituents would improve the solubility to solvents and epoxy resins, and also found that when formulated in epoxy resins The cured product obtained at this time is excellent in heat resistance and flame retardancy, thereby completing the present invention.

亦即，本發明為下述通式(1)所示之含磷硬化劑。 That is, the present invention is a phosphorus-containing hardener represented by the following general formula (1).

Figure 108133840-A0202-12-0003-4
式中，X為具有2至4個選自羥基、羧基或胺基之取代基的芳基，R1至R8 為氫原子、碳數1至12之烷基、碳數2至12之烯基、碳數6至20之芳基或碳數7至20之芳烷基，R1至R8中的至少一者為排除氫原子者。
Figure 108133840-A0202-12-0003-4
 In the formula, X is an aryl group having 2 to 4 substituents selected from the group consisting of hydroxyl, carboxyl or amino, and R 1 to R 8 are hydrogen atoms, alkyl groups with 1 to 12 carbons, and alkenes with 2 to 12 carbons. Group, an aryl group having 6 to 20 carbons, or an aralkyl group having 7 to 20 carbons, at least one of R 1 to R 8 excludes a hydrogen atom.

上述通式(1)的R1較佳為碳數6至20之芳基或碳數7至20之芳烷基。 R 1 of the general formula (1) is preferably an aryl group having 6 to 20 carbons or an aralkyl group having 7 to 20 carbons.

在高效能液相層析(HPLC)測定中，較佳為含有0.01至5.0面積%的下述通式(2)所示之環狀有機磷化合物。 In the high performance liquid chromatography (HPLC) measurement, it is preferable to contain 0.01 to 5.0 area% of the cyclic organophosphorus compound represented by the following general formula (2).

Figure 108133840-A0202-12-0004-5
式中，R11至R18為氫原子、碳數1至12之烷基、碳數2至12之烯基、碳數6至20之芳基或碳數7至20之芳烷基，R11至R18中的至少一者為排除氫原子者。
Figure 108133840-A0202-12-0004-5
 In the formula, R 11 to R 18 are hydrogen atoms, alkyl groups having 1 to 12 carbons, alkenyl groups having 2 to 12 carbons, aryl groups having 6 to 20 carbons, or aralkyl groups having 7 to 20 carbons, and R At least one of 11 to R 18 excludes a hydrogen atom.

上述通式(2)之R11較佳為碳數6至20之芳基或碳數7至20之芳烷基。 R 11 in the above general formula (2) is preferably an aryl group having 6 to 20 carbons or an aralkyl group having 7 to 20 carbons.

此外，本發明為一種環氧樹脂組成物，係含有上述含磷硬化劑及環氧樹脂，且組成物中之含磷率為1.0至5.0質量%。 In addition, the present invention is an epoxy resin composition containing the above-mentioned phosphorus-containing hardener and epoxy resin, and the phosphorus content of the composition is 1.0 to 5.0% by mass.

此外，本發明為一種預浸物、積層板、密封劑或澆注材，所述預浸物、積層板、密封劑或澆注材使用上述樹脂組成物，屬於將上述環氧樹脂組成物硬化而成的硬化物所述硬化物。 In addition, the present invention is a prepreg, laminate, sealant or casting material, the prepreg, laminate, sealant or casting material uses the above-mentioned resin composition and belongs to the hardening of the above-mentioned epoxy resin composition The hardened object said hardened object.

因為本發明之含磷硬化劑對於溶劑及環氧樹脂具有優異的溶解性，所以含有該含磷硬化劑的環氧樹脂組成物為均勻的液體，並具有優異的基材含浸性，而且該環氧樹脂組成物的硬化物具有優異的阻燃性及耐熱性。因此，有用於作為附樹脂的金屬箔材料、複合材料用基質樹脂、電子電路基板絕緣材料、液狀密封材料、接著劑、填孔材料等電路安裝基板領域以及電子電路基板的環氧樹脂組成物。 Because the phosphorus-containing hardener of the present invention has excellent solubility in solvents and epoxy resins, the epoxy resin composition containing the phosphorus-containing hardener is a uniform liquid and has excellent substrate impregnation properties, and the ring The cured product of the oxygen resin composition has excellent flame retardancy and heat resistance. Therefore, there are epoxy resin compositions used in the field of circuit mounting substrates such as metal foil materials with resins, matrix resins for composite materials, electronic circuit board insulating materials, liquid sealing materials, adhesives, and filling materials, and electronic circuit boards. .

第1圖為實施例1所獲得的含磷硬化劑之FTIR圖表。 Figure 1 is the FTIR chart of the phosphorus-containing hardener obtained in Example 1.

第2圖為實施例1所獲得的含磷硬化劑之HPLC圖表。 Figure 2 is an HPLC chart of the phosphorus-containing hardener obtained in Example 1.

本發明之含磷硬化劑如上述通式(1)所示，其含磷率較佳為4.0至9.0質量%，以5.0至8.0質量%為較佳，以6.0至7.5質量%為更佳，以6.5至7.2質量%為特佳。 The phosphorus-containing hardener of the present invention is represented by the above general formula (1), and its phosphorus content is preferably 4.0 to 9.0% by mass, more preferably 5.0 to 8.0% by mass, and more preferably 6.0 to 7.5% by mass, 6.5 to 7.2% by mass is particularly preferred.

上述通式(1)中，X為具有2至4個選自羥基、羧基或胺基之取代基的芳基。2至4個取代基可為相同或相異，但以相同為佳。較佳的取代基為羥基或胺基，特佳為羥基。 In the above general formula (1), X is an aryl group having 2 to 4 substituents selected from a hydroxyl group, a carboxyl group or an amino group. Two to four substituents may be the same or different, but the same is preferred. A preferred substituent is a hydroxyl group or an amino group, and a hydroxyl group is particularly preferred.

上述X中具有取代基的芳基為苯基、萘基和蒽環結構、菲環結構等，較佳為苯基、1-萘基、2-萘基、鄰甲苯基、間甲苯基、對甲苯基、二甲苯基，特佳為2-萘基。 The aryl groups having substituents in X are phenyl, naphthyl, anthracene ring structure, phenanthrene ring structure, etc., preferably phenyl, 1-naphthyl, 2-naphthyl, o-tolyl, m-tolyl, p- Tolyl and xylyl, particularly preferably 2-naphthyl.

上述通式(1)中，R1至R8為碳數1至12之烷基、碳數2至12之烯基、碳數6至20之芳基或碳數7至20之芳烷基，R1至R8中的至少一者為排除氫原子者，較佳的R1為碳數6至20之芳基或碳數7至20之芳烷基，特佳的R1為碳數7至20之芳烷基。 In the above general formula (1), R 1 to R 8 are alkyl groups having 1 to 12 carbons, alkenyl groups having 2 to 12 carbons, aryl groups having 6 to 20 carbons, or aralkyl groups having 7 to 20 carbons , At least one of R 1 to R 8 excludes the hydrogen atom, preferably R 1 is an aryl group with 6 to 20 carbons or an aralkyl group with 7 to 20 carbons, and particularly preferably R 1 is a carbon number Aralkyl from 7 to 20.

R1至R8中的烷基可列舉：甲基、乙基、正丙基、異丙基、正丁基、異丁基、二級丁基、三級丁基、正戊基、異戊基、新戊基、三級戊基、1-甲基丁基、正己基、2-甲基戊基、3-甲基戊基、2,2-二甲基丁基、2,3-二甲基丁基、正庚基、2-甲基己基、3-甲基己基、2,2-二甲基戊基、2,3-二甲基戊基、2,4-二甲基戊基、3,3-二甲基戊基、3-乙基戊基、2,2,3-三甲基丁基、正辛基、異辛基、2-乙基己基、壬基、癸基、十一基、十二基等。R1至R8中的烷基的碳數較佳為1至10，以1至7為更佳，以1至5為特佳。 Examples of alkyl groups in R 1 to R 8 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl, n-pentyl, isoamyl Base, neopentyl, tertiary pentyl, 1-methylbutyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 2,2-dimethylbutyl, 2,3-di Methylbutyl, n-heptyl, 2-methylhexyl, 3-methylhexyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl , 3,3-dimethylpentyl, 3-ethylpentyl, 2,2,3-trimethylbutyl, n-octyl, isooctyl, 2-ethylhexyl, nonyl, decyl, Eleven bases, twelve bases, etc. The carbon number of the alkyl group in R 1 to R 8 is preferably 1 to 10, more preferably 1 to 7, and particularly preferably 1 to 5.

R1至R8中的烯基可例示：乙烯基(vinyl；ethenyl)、烯丙基(allyl；2-丙烯基(2-propenyl))、甲基烯丙基(methallyl；2-甲基-2-丙烯基(2-methyl-2-propenyl))等碳數2以上的上述烷基的1個單鍵(C-C)經雙鍵(C=C)取代而成之基。R1至R8中的烯基之碳數較佳為2至10，以2至7為更佳，以2至5為特佳。 The alkenyl groups in R 1 to R 8 can be exemplified by vinyl (vinyl; ethenyl), allyl (allyl; 2-propenyl), methallyl (methallyl; 2-methyl- One single bond (CC) of the above-mentioned alkyl group with 2 or more carbon atoms, such as 2-propenyl (2-methyl-2-propenyl), is substituted with a double bond (C=C). The carbon number of the alkenyl group in R 1 to R 8 is preferably from 2 to 10, more preferably from 2 to 7, and particularly preferably from 2 to 5.

R1至R8中的芳基之碳數較佳為6至12，可例示：苯基、1-萘基、2-萘基、鄰甲苯基、間甲苯基、對甲苯基、二甲苯基(二甲基苯基)等。 The carbon number of the aryl group in R 1 to R 8 is preferably 6 to 12, and examples include phenyl, 1-naphthyl, 2-naphthyl, o-tolyl, m-tolyl, p-tolyl, and xylyl (Dimethylphenyl) and so on.

作為R1至R8中的芳烷基，可例示上述烷基的1個氫原子經上述芳基取代而成之一價基。芳烷基的碳數較佳為7至20，更具體而言，可例示苄基(苯基甲基)、鄰甲基苄基(鄰甲基苯基甲基)、間甲基苄基 (間甲基苯基甲基)、對甲基苄基(對甲基苯基甲基)、苯基乙基、萘基甲基、萘基乙基等。 As the aralkyl group in R 1 to R 8 , one hydrogen atom of the alkyl group is substituted with the aryl group to form a monovalent group. The carbon number of the aralkyl group is preferably 7 to 20. More specifically, benzyl (phenylmethyl), o-methylbenzyl (o-methylphenylmethyl), m-methylbenzyl ( M-methylphenylmethyl), p-methylbenzyl (p-methylphenylmethyl), phenylethyl, naphthylmethyl, naphthylethyl, etc.

本發明之含磷硬化劑可含有上述通式(2)所示之環狀有機磷化合物。其含量可從以HPLC測定而得的圖表之面積比率算出。其測定條件為溶析液：10mM醋酸銨水/四氫呋喃/乙腈=55/22.5/22.5(體積%)、管柱槽溫度：40℃、流量：1.0mL/分鐘、偵檢器：紫外可見分光(UV/VIS)偵檢器、波長：300nm。 The phosphorus-containing hardener of the present invention may contain the cyclic organophosphorus compound represented by the general formula (2). The content can be calculated from the area ratio of the graph obtained by HPLC measurement. The measurement conditions are eluent: 10mM ammonium acetate water/tetrahydrofuran/acetonitrile=55/22.5/22.5(vol%), column tank temperature: 40℃, flow rate: 1.0mL/min, detector: UV-visible spectroscopy ( UV/VIS) detector, wavelength: 300nm.

從對於溶劑及環氧樹脂的溶解性的觀點來看，相對於含磷硬化劑與環狀有機磷化合物之總計，本發明之含磷硬化劑中的上述環狀有機磷化合物的含量較佳為0.01至5.0面積%，以0.1至3.0面積%為更佳。 From the viewpoint of solubility in solvents and epoxy resins, the content of the cyclic organophosphorus compound in the phosphorus-containing curing agent of the present invention is preferably relative to the total of the phosphorus-containing curing agent and the cyclic organophosphorus compound 0.01 to 5.0 area%, more preferably 0.1 to 3.0 area%.

通式(2)中，R11至R18為氫原子、碳數1至12之烷基、碳數2至12之烯基、碳數6至20之芳基或碳數7至20之芳烷基，R11至R18中的至少一者為排除氫原子者，R11較佳為碳數6至20之芳基或碳數7至20之芳烷基，R11特佳係碳數7至20之芳烷基。 In the general formula (2), R 11 to R 18 are hydrogen atoms, alkyl groups having 1 to 12 carbons, alkenyl groups having 2 to 12 carbons, aryl groups having 6 to 20 carbons, or aromatic groups having 7 to 20 carbons. Alkyl, at least one of R 11 to R 18 excludes a hydrogen atom, R 11 is preferably an aryl group with 6 to 20 carbons or an aralkyl group with 7 to 20 carbons, and R 11 is particularly preferably a carbon number Aralkyl from 7 to 20.

作為R11至R18中的烷基可列舉上述通式(1)之R1至R8中所例示的烷基，較佳的烷基亦相同。 Examples of the alkyl group in R 11 to R 18 include the alkyl groups exemplified in R 1 to R 8 of the general formula (1), and the preferred alkyl groups are also the same.

作為R11至R18中的烯基可列舉上述通式(1)之R1至R8中所例示的烯基，較佳的烯基亦相同。 Examples of the alkenyl group in R 11 to R 18 include the alkenyl groups exemplified in R 1 to R 8 of the above general formula (1), and preferred alkenyl groups are also the same.

作為R11至R18中的芳基可列舉上述通式(1)之作為R1至R8中所例示的芳基，較佳的芳基亦相同。 Examples of the aryl group in R 11 to R 18 include the aryl groups exemplified as R 1 to R 8 in the general formula (1), and the preferred aryl groups are also the same.

作為R11至R18中的芳烷基可列舉上述通式(1)之R1至R8中所例示的芳烷基，較佳的芳烷基亦相同。 Examples of the aralkyl group in R 11 to R 18 include the aralkyl groups exemplified in R 1 to R 8 of the above general formula (1), and preferred aralkyl groups are also the same.

製造本發明之含磷硬化劑之方法並無特別限定，但能列舉使上述通式(2)表示之環狀有機磷化合物與視需要而經羥基、羧基及/或胺基取代的氫醌、萘醌、蒽醌或菲醌等醌類反應的方法。 The method for producing the phosphorus-containing hardener of the present invention is not particularly limited, but it can be exemplified by making the cyclic organophosphorus compound represented by the above general formula (2) and hydroquinone substituted with hydroxyl, carboxyl and/or amine groups as necessary, A method of reacting quinones such as naphthoquinone, anthraquinone or phenanthrenequinone.

具體的製造方法列舉如以下的方法。亦即，在具備攪拌裝置、溫度計、氮氣導入裝置、冷卻管及原料投入口的反應容器中，饋入有機溶劑與上述通式(2)表示之環狀有機磷化合物，將溫度保持在常溫至110℃(較佳為40至90℃)以溶解環狀有機磷化合物。溶解後，費時1至5小時以少量逐次添加醌類，添加後以100至130℃費時1至5小時使反應完成。 Specific manufacturing methods are as follows. That is, in a reaction vessel equipped with a stirring device, a thermometer, a nitrogen introduction device, a cooling tube, and a raw material input port, an organic solvent and the cyclic organophosphorus compound represented by the above general formula (2) are fed, and the temperature is maintained at room temperature to 110°C (preferably 40 to 90°C) to dissolve the cyclic organophosphorus compound. After the dissolution, it takes 1 to 5 hours to add the quinones in small amounts one by one, and after the addition, it takes 1 to 5 hours to complete the reaction at 100 to 130°C.

其中，通式(2)表示之環狀有機磷化合物可列舉例如：8-甲基-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物、8-乙基-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物、8-異丙基-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物、8-三級丁基-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物、8-環己基-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物、8-(3’-甲基環己基)-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物、8-苯基-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物、8-甲苯基-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物、8-苄基-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物、6,8-二甲基-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物、6,8-二乙基-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物、6,8-二-三級丁基-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物、6,8-二環己基-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物、6-甲基-8-苯基-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物、6-甲基-8-苄基-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物、2,6,8-三-三級丁基-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物等，惟並不限定於此等環狀有機磷化合物。此等環狀有機磷化合物中，較佳為8-苯基-9,10-二氫-9-氧雜-10-磷雜菲 -10-氧化物、6-甲基-8-苯基-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物、8-苄基-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物、6-甲基-8-苄基-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物，特佳為8-苯基-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物、8-苄基-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物。 Among them, the cyclic organophosphorus compound represented by the general formula (2) includes, for example, 8-methyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 8-ethyl -9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 8-isopropyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10- Oxide, 8-tertiary butyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 8-cyclohexyl-9,10-dihydro-9-oxa- 10-phosphaphenanthrene-10-oxide, 8-(3'-methylcyclohexyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 8-phenyl -9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 8-tolyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide , 8-benzyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6,8-dimethyl-9,10-dihydro-9-oxa- 10-phosphaphenanthrene-10-oxide, 6,8-diethyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6,8-di-tertiary Butyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6,8-dicyclohexyl-9,10-dihydro-9-oxa-10-phospha Phenanthrene-10-oxide, 6-methyl-8-phenyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-methyl-8-benzyl- 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,6,8-tris-tertiary butyl-9,10-dihydro-9-oxa-10- Phosphaphenanthrene-10-oxide, etc. are not limited to these cyclic organophosphorus compounds. Among these cyclic organophosphorus compounds, 8-phenyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene is preferred -10-oxide, 6-methyl-8-phenyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 8-benzyl-9,10-dihydro -9-oxa-10-phosphaphenanthrene-10-oxide, 6-methyl-8-benzyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, Especially preferred are 8-phenyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 8-benzyl-9,10-dihydro-9-oxa-10- Phosphaphenanthrene-10-oxide.

此外，上述醌類可列舉例如：苯醌、甲基苯醌、乙基苯醌、丁基苯醌、二甲基苯醌、二乙基苯醌、二丁基苯醌、甲基異丙基苯醌、二乙氧基苯醌、甲基二甲氧基苯醌、甲基甲氧基苯醌、苯基苯醌、甲苯基苯醌、乙氧基苯基苯醌、二苯基苯醌、羥基苯醌、胺基苯醌、二側氧苯甲酸等；及萘醌、甲基萘醌、環己基萘醌、甲氧基萘醌、乙氧基萘醌、二甲基萘醌、二甲基異丙基萘醌、甲基甲氧基萘醌、羥基萘醌、甲基羥基萘醌、二羥基萘醌、胺基萘醌、甲基胺基萘醌、羥基胺基萘醌、二胺基萘醌、二側氧二氫萘甲酸等；及蒽醌、甲基蒽醌、乙基蒽醌、甲氧基蒽醌、二甲氧基蒽醌、二苯氧基蒽醌、羥基蒽醌、甲基羥基蒽醌、二羥基蒽醌胺基蒽醌、二胺基蒽醌、蒽醌羧酸等；及菲醌、甲基菲醌、異丙基菲醌、甲氧基菲醌、丁氧基菲醌、二甲基菲醌、二甲氧基菲醌、甲氧基羥基菲醌等，惟並不限定於此等醌類。 In addition, the above-mentioned quinones include, for example, benzoquinone, methoquinone, ethyl benzoquinone, butyl benzoquinone, dimethyl benzoquinone, diethyl benzoquinone, dibutyl benzoquinone, methyl isopropyl Benzoquinone, diethoxybenzoquinone, methyldimethoxybenzoquinone, methylmethoxybenzoquinone, phenylbenzoquinone, tolylbenzoquinone, ethoxyphenylbenzoquinone, diphenylbenzoquinone , Hydroxybenzoquinone, aminobenzoquinone, dibenzoic acid, etc.; and naphthoquinone, menaquinone, cyclohexyl naphthoquinone, methoxy naphthoquinone, ethoxy naphthoquinone, dimethyl naphthoquinone, two Methyl isopropyl naphthoquinone, methyl methoxy naphthoquinone, hydroxy naphthoquinone, methyl hydroxy naphthoquinone, dihydroxy naphthoquinone, amino naphthoquinone, methyl amino naphthoquinone, hydroxyl amino naphthoquinone, two Amino naphthoquinone, dihydronaphthoic acid, etc.; and anthraquinone, methylanthraquinone, ethylanthraquinone, methoxyanthraquinone, dimethoxyanthraquinone, diphenoxyanthraquinone, hydroxyanthracene Quinone, methylhydroxyanthraquinone, dihydroxyanthraquinone aminoanthraquinone, diaminoanthraquinone, anthraquinone carboxylic acid, etc.; and phenanthrenequinone, methylphenanthrenequinone, isopropylphenanthrenequinone, methoxyphenanthrenequinone, Butoxyphenanthrenequinone, dimethylphenanthrenequinone, dimethoxyphenanthrenequinone, methoxyphenanthrenequinone, etc., but not limited to these quinones.

此等醌類之中，較佳為苯醌類、萘醌類，因阻燃性與耐熱性會顯著地變得良好，而以萘醌類為特佳。萘醌類具體上可列舉：1,4-萘醌、2-羥基-1,4-萘醌、5-羥基-1,4-萘醌、6-羥基-1,4-萘醌、2-羥基-3-甲基-1,4-萘醌、5-羥基-2-甲基-1,4-萘醌、5-羥基-7-甲基-1,4-萘醌、5,8-二羥基-1,4-萘醌、2,5-二羥基-1,4-萘醌、5-胺基-1,4-萘醌、2-甲基-5-胺基-1,4-萘醌、2-羥基-6-胺基-1,4-萘醌、2,5-二胺基-1,4-萘醌、5,8-二側氧-5,8-二氫-1-萘甲酸 等，較佳為1,4-萘醌、2-羥基-1,4-萘醌、5-羥基-1,4-萘醌。 Among these quinones, benzoquinones and naphthoquinones are preferred, since flame retardancy and heat resistance are remarkably improved, and naphthoquinones are particularly preferred. Specific examples of naphthoquinones include 1,4-naphthoquinone, 2-hydroxy-1,4-naphthoquinone, 5-hydroxy-1,4-naphthoquinone, 6-hydroxy-1,4-naphthoquinone, 2- Hydroxy-3-methyl-1,4-naphthoquinone, 5-hydroxy-2-methyl-1,4-naphthoquinone, 5-hydroxy-7-methyl-1,4-naphthoquinone, 5,8- Dihydroxy-1,4-naphthoquinone, 2,5-dihydroxy-1,4-naphthoquinone, 5-amino-1,4-naphthoquinone, 2-methyl-5-amino-1,4- Naphthoquinone, 2-hydroxy-6-amino-1,4-naphthoquinone, 2,5-diamino-1,4-naphthoquinone, 5,8-dioxo-5,8-dihydro-1 -Naphthoic acid Etc., preferably 1,4-naphthoquinone, 2-hydroxy-1,4-naphthoquinone, 5-hydroxy-1,4-naphthoquinone.

本發明之環氧樹脂組成物的必要成分含有上述含磷硬化劑與環氧樹脂。本發明能夠使用的環氧樹脂若為習知的環氧樹脂即無特別限定，惟較佳為分子中具有平均2至6個環氧基的環氧樹脂，更佳為分子中具有平均2.5至5個環氧基的環氧樹脂，又更佳為分子中具有平均3至4個左右的環氧基的環氧樹脂。特佳為酚醛清漆型的環氧樹脂。環氧基少則有對硬化物的耐熱性造成負面影響之虞，環氧基多則有對接著性造成負面影響之虞。 The essential components of the epoxy resin composition of the present invention contain the aforementioned phosphorus-containing hardener and epoxy resin. The epoxy resin that can be used in the present invention is not particularly limited as long as it is a conventional epoxy resin. However, it is preferably an epoxy resin having an average of 2 to 6 epoxy groups in the molecule, and more preferably an epoxy resin having an average of 2.5 to The epoxy resin having 5 epoxy groups is more preferably an epoxy resin having an average of 3 to 4 epoxy groups in the molecule. Particularly preferred is novolac type epoxy resin. A few epoxy groups may have a negative effect on the heat resistance of the cured product, and a large amount of epoxy groups may have a negative effect on the adhesion.

作為環氧樹脂之具體例可列舉：雙酚A型環氧樹脂(例如：Epotohto YD-128、YD-8125、YD-825GS(新日鐵住金化學股份有限公司製)等)、雙酚F型環氧樹脂(例如：Epotohto YDF-170、YDF-170B、YDF-8170、YDF-870GS(新日鐵住金化學股份有限公司製)等)、四甲基雙酚F型環氧樹脂(例如：YSLV-80XY(新日鐵住金化學股份有限公司製)等)、氫醌型環氧樹脂(例如：Epotohto YDC-1312(新日鐵住金化學股份有限公司製)等)、聯苯型環氧樹脂(例如：jERYX4000H(三菱化學股份有限公司製)等)、雙酚茀型環氧樹脂(例如：Epotohto ZX-1201(新日鐵住金化學股份有限公司製)等)、雙酚S型環氧樹脂(例如：TX-0710(新日鐵住金化學股份有限公司製)、EPICLON EXA-1515(DIC股份有限公司製)等)、萘二醇(naphthalenediol)型環氧樹脂(例如：Epotohto ZX-1355、Epotohto ZX-1711(新日鐵住金化學股份有限公司製)等)、雙硫醚型環氧樹脂(例如：YSLV-120TE(新日鐵住金化學股份有限公司製)等)、間苯二酚型環氧樹脂(例如：Epotohto ZX-1684(新日鐵住金化學股份有限公司 製)等)、酚酚醛清漆型環氧樹脂(例如：Epotohto YDPN-638、YDPN-6300(新日鐵住金化學股份有限公司製)等)、甲酚酚醛清漆型環氧樹脂(例如：Epotohto YDCN701(新日鐵住金化學股份有限公司製)等)、酚芳烷型環氧樹脂(例如：NC-3000(日本化藥股份有限公司製)等)、β-萘酚芳烷型環氧樹脂(例如：Epotohto ESN-155(新日鐵住金化學社製)等)、萘二醇芳烷型環氧樹脂(例如：Epotohto ESN-355、Epotohto ESN-375(新日鐵住金化學股份有限公司製)等)、α-萘酚芳烷型環氧樹脂(例如：Epotohto ESN-475V,Epotohto ESN-485(新日鐵住金化學股份有限公司製)等)、參苯基甲烷型環氧樹脂(例如：EPPN-501H(日本化藥股份有限公司製)、SUMI-EPOXY TMH-574(住友化學股份有限公司製)等)、二環戊二烯型環氧樹脂(例如：EPICLON HP-7200H(DIC股份有限公司製)等)、烷二醇型環氧樹脂(例如：TX-0929、TX-0934、TX-1032(新日鐵住金化學股份有限公司製)等)等環氧丙基醚化合物；及脂肪族環狀環氧樹脂(例如：CELLOXIDE 2021P(DAICEL股份有限公司製)等)；及酞酸二環氧丙酯、四氫酞酸二環氧丙酯、六氫酞酸二環氧丙酯、對羥基苯甲酸二環氧丙基酯、二體酸環氧丙酯等環氧丙酯型環氧樹脂；及二胺基二苯基甲烷四環氧丙基胺(diaminodiphenylmethane tetraglycidylamine)(例如：Epotohto YH-434(新日鐵住金化學股份有限公司製)等)、二環氧丙基苯胺、二環氧丙基甲苯胺等環氧丙基胺化合物；及胺基酚型環氧樹脂(例如：jER 630(三菱化學股份有限公司製)等)、二環氧丙基尿囊素、環氧丙基環氧丙氧基烷基尿囊素等之尿囊素型環氧樹脂、含磷的環氧樹脂(例如：Epotohto FX-289B、Epotohto FX-305、TX-0932A(新日鐵住金化學股份有 限公司製)等)、胺甲酸乙酯改質環氧樹脂、含

Figure 108133840-A0202-12-0012-12
唑啶酮環的環氧樹脂等，惟並不限定於此等環氧樹脂。此外，此等環氧樹脂可以單獨使用，亦可併用2種以上而使用。 Specific examples of epoxy resins include: bisphenol A type epoxy resins (e.g., Epotohto YD-128, YD-8125, YD-825GS (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), etc.), bisphenol F type Epoxy resin (for example: Epotohto YDF-170, YDF-170B, YDF-8170, YDF-870GS (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), etc.), tetramethyl bisphenol F epoxy resin (for example: YSLV -80XY (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), hydroquinone epoxy resin (for example: Eptohto YDC-1312 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), etc.), biphenyl epoxy resin ( For example: jERYX4000H (manufactured by Mitsubishi Chemical Co., Ltd.), bisphenol phenolic epoxy resin (for example: Epotohto ZX-1201 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), etc.), bisphenol S-type epoxy resin ( For example: TX-0710 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), EPICLON EXA-1515 (manufactured by DIC Co., Ltd.), naphthalenediol type epoxy resin (for example: Epotohto ZX-1355, Epotohto ZX-1711 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), disulfide epoxy resin (for example: YSLV-120TE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), etc.), resorcinol-type ring Oxygen resin (for example: Epotohto ZX-1684 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), etc.), phenol novolac type epoxy resin (for example: Epotohto YDPN-638, YDPN-6300 (Nippon Steel & Sumikin Chemical Co., Ltd.) ), etc.), cresol novolac type epoxy resin (e.g. Eptohto YDCN701 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), etc.), phenolarane type epoxy resin (e.g., NC-3000 (Nippon Kayaku Co., Ltd.) Co., Ltd.), etc.), β-naphthol arane type epoxy resin (e.g., Eptohto ESN-155 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), etc.), naphthalenediol arane type epoxy resin (e.g., Epotohto ESN -355, Epotohto ESN-375 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), α-naphthol arane type epoxy resin (for example: Epotohto ESN-475V, Epotohto ESN-485 (Nippon Steel & Sumikin Chemical Co., Ltd.) Co., Ltd.), etc.), ginseng phenyl methane type epoxy resin (e.g. EPPN-501H (manufactured by Nippon Kayaku Co., Ltd.), SUMI-EPOXY TMH-574 (manufactured by Sumitomo Chemical Co., Ltd.), etc.), Pentadiene epoxy resin (for example: EPICLON HP-7200H (manufactured by DIC Co., Ltd.) Etc.), alkanediol type epoxy resins (for example: TX-0929, TX-0934, TX-1032 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) and other glycidyl ether compounds; and aliphatic cyclic Epoxy resin (for example: CELLOXIDE 2021P (made by DAICEL Co., Ltd.), etc.); and diglycidyl phthalate, diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate, and p-hydroxybenzene Glycidyl epoxy resins such as diglycidyl formate and glycidyl dibasic acid; and diaminodiphenylmethane tetraglycidylamine (e.g., Epitohto YH-434) (Manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), etc.), epoxypropyl amine compounds such as diglycidyl aniline and diglycidyl toluidine; and aminophenol epoxy resins (e.g., jER 630 ( Mitsubishi Chemical Co., Ltd.), etc.), allantoin-type epoxy resins such as diglycidyl allantoin, glycidylglycidoxyalkyl allantoin, and phosphorus-containing epoxy resins ( For example: Epotohto FX-289B, Epotohto FX-305, TX-0932A (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), urethane modified epoxy resin,
Figure 108133840-A0202-12-0012-12
The epoxy resin of the oxazolidone ring, etc. are not limited to these epoxy resins. In addition, these epoxy resins may be used alone or in combination of two or more kinds.

本發明之環氧樹脂組成物中，硬化劑必須為上述通式(1)表示之含磷硬化劑，惟在不損及本發明目的的範圍內，可以併用上述通式(1)表示之含磷硬化劑以外的硬化劑。 In the epoxy resin composition of the present invention, the hardener must be the phosphorous-containing hardener represented by the above general formula (1), but within the range that does not impair the purpose of the present invention, the above-mentioned general formula (1) may be used in combination. Hardeners other than phosphorus hardeners.

若是要具體例示上述式(1)表示之含磷硬化劑以外的硬化劑，酚硬化劑可列舉：雙酚A、雙酚F、雙酚C、雙酚K、雙酚S、雙酚Z、雙酚茀、四甲基雙酚A、四甲基雙酚F、四甲基雙酚S、四甲基雙酚Z、二羥基二苯基硫醚、4,4’-硫代雙(3-甲基-6-三級丁基酚)、4,4’-聯苯酚(4,4’-biphenol)、3,3’,5,5’-四甲基-4,4’-二羥基聯苯、兒茶酚、間苯二酚、甲基間苯二酚、氫醌、單甲基氫醌、二甲基氫醌、三甲基氫醌、單-三級丁基氫醌、二-三級丁基氫醌、二羥基萘、二羥基甲基萘類等2價的酚類、三羥基萘、參-(4-羥基苯基)甲烷、1,1,2,2-肆(4-羥基苯基)乙烷、酚酚醛清漆、鄰甲酚酚醛清漆等3價以上的酚類、由二環戊二烯與酚類而得的共縮合系的酚類、由甲酚類與甲醛與烷氧基取代萘類而得的共縮合系的酚類、由酚類與二氯化對二甲苯(paraxylylene dichloride)等而得的酚芳烷系的酚類、由酚類與雙氯甲基聯苯等而得的聯苯基芳烷系的酚類、由萘酚類與二氯化對二甲苯等而合成的萘酚芳烷系的酚類等。 If it is necessary to specifically exemplify hardeners other than the phosphorus-containing hardener represented by the above formula (1), phenol hardeners include: bisphenol A, bisphenol F, bisphenol C, bisphenol K, bisphenol S, bisphenol Z, Bisphenols, tetramethyl bisphenol A, tetramethyl bisphenol F, tetramethyl bisphenol S, tetramethyl bisphenol Z, dihydroxy diphenyl sulfide, 4,4'-thiobis (3 -Methyl-6-tertiary butylphenol), 4,4'-biphenol (4,4'-biphenol), 3,3',5,5'-tetramethyl-4,4'-dihydroxy Biphenyl, catechol, resorcinol, methylresorcinol, hydroquinone, monomethylhydroquinone, dimethylhydroquinone, trimethylhydroquinone, mono-tertiary butyl hydroquinone, two -Divalent phenols such as tertiary butyl hydroquinone, dihydroxy naphthalene, dihydroxy methyl naphthalene, trihydroxy naphthalene, ginseng-(4-hydroxyphenyl) methane, 1,1,2,2-four ( 4-hydroxyphenyl) ethane, phenol novolac, o-cresol novolac and other phenols with more than 3 valence, co-condensed phenols derived from dicyclopentadiene and phenols, and phenols with cresols and phenols Co-condensed phenols obtained by substituting formaldehyde and alkoxy for naphthalenes, phenolic aralkyl phenols obtained from phenols and paraxylylene dichloride (paraxylylene dichloride), etc., phenols and dichloride Biphenylarane-based phenols obtained from methyl biphenyl, etc., naphtholarane-based phenols synthesized from naphthols and p-xylene dichloride, etc.

其他的環氧樹脂硬化劑可列舉：甲基四氫酞酸酐、六氫酞酸酐、焦蜜石酸二酐、酞酸酐、1,2,4-苯三甲酸酐、甲基納迪克酸(methylnadic acid)等酸酐類；二伸乙三胺、三伸乙四胺、間苯二甲二胺、異佛酮二胺、 二胺二苯甲烷、二胺二苯碸、二胺二苯醚、二氰二醯胺、二體酸等酸類與多胺類之縮合物的聚合物之聚醯胺基胺等胺系化合物等，三苯膦等膦化合物，溴化四苯鏻等鏻鹽，2-甲基咪唑、2-苯基咪唑、2-乙基-4甲基咪唑、2-十一基咪唑、1-氰基乙基-2-甲基咪唑等咪唑類及該等咪唑類與1,2,4-苯三甲酸、異三聚氰酸、硼等之鹽的咪唑鹽類，二甲苄胺、2,4,6-參(二甲基胺基甲基)酚等胺類，氯化三甲銨等的4級銨鹽類，二吖雙環化合物及該等二吖雙環化合物與酚類、酚酚醛清漆樹脂類等的鹽類3氟化硼與胺類、醚化合物等的錯合物，芳香族鏻或錪鹽等。 Other epoxy resin hardeners include: methyl tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic dianhydride, phthalic anhydride, 1,2,4- trimellitic anhydride, methylnadic acid (methylnadic acid ) And other acid anhydrides; diethylenetriamine, triethylenetetramine, metaxylylenediamine, isophoronediamine, Diamine diphenylmethane, diamine diphenyl methane, diamine diphenyl ether, dicyandiamide, dicyandiamide, dicyandiamide, diacid and other acids and polyamines, polyamines and other amine compounds, etc. , Phosphine compounds such as triphenylphosphine, phosphonium salts such as tetraphenylphosphonium bromide, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4methylimidazole, 2-undecylimidazole, 1-cyano Imidazoles such as ethyl-2-methylimidazole and imidazole salts of these imidazoles and salts of trimellitic acid, isocyanuric acid, boron, etc., dimethylbenzylamine, 2,4 ,6-Ginseng (dimethylaminomethyl) phenol and other amines, quaternary ammonium salts such as trimethylammonium chloride, diazed bicyclic compounds and these diazed bicyclic compounds and phenols, phenol novolac resins 3, complex compounds of boron fluoride with amines, ether compounds, etc., aromatic phosphonium or enoxon salts, etc.

此等上述式(1)表示之含磷硬化劑以外的硬化劑可以單獨使用，亦可併用2種類以上。此等含磷硬化劑以外之硬化劑的調配量相對於通式(1)表示之含磷硬化劑與此等以外之硬化劑的總計，為未達50質量%，較佳為未達40質量%，更佳為未達25質量%。 These curing agents other than the phosphorus-containing curing agent represented by the above formula (1) may be used alone, or two or more types may be used in combination. The blending amount of the hardeners other than these phosphorus-containing hardeners is less than 50% by mass, preferably less than 40% by mass relative to the total of the phosphorus-containing hardener represented by the general formula (1) and the other hardeners %, more preferably less than 25% by mass.

本發明之環氧樹脂組成物中的硬化劑之調配量相對於環氧樹脂之環氧基1莫耳，硬化劑之活性氫基較佳為0.4至1.2莫耳，以0.5至1.1莫耳為更佳，以0.7至1.1莫耳為又更佳。相對於環氧基之環氧樹脂硬化劑無論是多還是少，硬化皆會變得不充分且無法獲得良好的硬化物性。又，環氧樹脂硬化劑之活性氫基係表示與環氧基反應的官能基，具體上可列舉：羥基、胺基、羧基等。 The compounding amount of the hardener in the epoxy resin composition of the present invention is relative to 1 mol of the epoxy group of the epoxy resin. The active hydrogen group of the hardener is preferably 0.4 to 1.2 mol, 0.5 to 1.1 mol More preferably, it is even more preferably from 0.7 to 1.1 mol. Regardless of the amount of epoxy resin hardener, the hardening becomes insufficient and good hardening physical properties cannot be obtained. In addition, the active hydrogen group of the epoxy resin curing agent means a functional group that reacts with an epoxy group, and specifically, a hydroxyl group, an amino group, a carboxyl group, etc. can be mentioned.

本發明之環氧樹脂組成物中的含磷率為1.0至5.0質量%，較佳為1.2至4.7質量%，特佳為1.5至4.5質量%。 The phosphorus content in the epoxy resin composition of the present invention is 1.0 to 5.0% by mass, preferably 1.2 to 4.7% by mass, and particularly preferably 1.5 to 4.5% by mass.

本發明之環氧樹脂組成物中可視需要而使用硬化促進劑。若將可使用的硬化促進劑具體例，則可列舉：2-甲基咪唑、2-乙基咪唑、2-乙 基-4-甲基咪唑等咪唑類；2-(二甲基胺基甲基)酚、1,8-二吖-雙環(5,4,0)十一-7-烯等三級胺類；三苯膦、三環己膦、三苯膦三苯基硼烷等膦類；辛酸錫等金屬化合物。硬化促進劑可以單獨使用，亦可併用2種類以上。相對於本發明之環氧樹脂組成物中的環氧樹脂100質量份，可視需要而使用0.02至5.0質量份的硬化促進劑。藉由選擇性地使用此等硬化促進劑，可以降低硬化溫度或縮短硬化時間。 The epoxy resin composition of the present invention may optionally use a hardening accelerator. If specific examples of hardening accelerators that can be used include: 2-methylimidazole, 2-ethylimidazole, 2-ethyl Imidazoles such as 4-methylimidazole; tertiary amines such as 2-(dimethylaminomethyl)phenol, 1,8-diazine-bicyclo(5,4,0)undec-7-ene ; Triphenylphosphine, tricyclohexylphosphine, triphenylphosphine triphenylborane and other phosphines; tin octoate and other metal compounds. The hardening accelerator may be used alone, or two or more kinds may be used in combination. With respect to 100 parts by mass of the epoxy resin in the epoxy resin composition of the present invention, 0.02 to 5.0 parts by mass of a hardening accelerator can be used as needed. By selectively using these hardening accelerators, the hardening temperature or the hardening time can be reduced.

本發明之環氧樹脂組成物中，可使用有機溶劑或反應性稀釋劑作為黏度調整用。此等有機溶媒或反應性稀釋劑可以單獨使用，亦可併用2種類以上。 In the epoxy resin composition of the present invention, an organic solvent or a reactive diluent can be used for viscosity adjustment. These organic solvents or reactive diluents may be used alone, or two or more of them may be used in combination.

可使用的有機溶劑者並無特別規定，惟有機溶媒可列舉例如：N,N-二甲基甲醯胺、N,N-二甲基乙醯胺等醯胺類；及二

Figure 108133840-A0202-12-0014-13
烷、四氫呋喃、乙二醇單甲基醚、二甲氧基二乙二醇、乙二醇二乙基醚、二乙二醇二乙基醚、三乙二醇二甲基醚等醚類；及丙酮、甲基乙基酮、甲基異丁基酮、環己酮等酮類；及甲醇、乙醇、1-甲氧基-2-丙醇、2-乙基-1-己醇、苄基醇、乙二醇、丙二醇、丁基二醇、松油(pine oil)等醇類；及乙酸乙酯、乙酸丁酯、乙酸甲氧基丁酯、乙酸甲賽璐蘇(methyl cellosolve acetate)、乙酸賽璐蘇、二甘醇乙酸乙酸酯(ethyl diglycol acetate)、丙二醇單甲基醚乙酸酯、卡必醇乙酸酯、苄基醇乙酸酯等乙酸酯類；及苯甲酸甲酯、苯甲酸乙酯等苯甲酸酯類；及甲賽璐蘇、賽璐蘇、丁賽璐蘇等賽璐蘇類；及甲基卡必醇、卡必醇、丁基卡必醇等卡必醇類；及苯、甲苯、二甲苯等芳香族烴類；及二甲亞碸等亞碸類；及己烷、環己烷等烷烴類；及乙腈、N-甲基吡咯啶酮等。 There are no special regulations on the organic solvents that can be used, but organic solvents include, for example: N,N-dimethylformamide, N,N-dimethylacetamide and other amines; and two
Figure 108133840-A0202-12-0014-13
Alkanes, tetrahydrofuran, ethylene glycol monomethyl ether, dimethoxydiethylene glycol, ethylene glycol diethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether and other ethers; And ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; and methanol, ethanol, 1-methoxy-2-propanol, 2-ethyl-1-hexanol, benzyl Base alcohol, ethylene glycol, propylene glycol, butyl glycol, pine oil and other alcohols; and ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate , Cellulose acetate, ethyl diglycol acetate, propylene glycol monomethyl ether acetate, carbitol acetate, benzyl alcohol acetate and other acetates; and methyl benzoate Ester, ethyl benzoate and other benzoic acid esters; and celluloid such as methylcellulose, cellulose, butylcellulose; and carbitol such as methyl carbitol, carbitol, butyl carbitol, etc. Classes; and aromatic hydrocarbons such as benzene, toluene, xylene; and subsulfones such as dimethyl sulfoxide; and alkanes such as hexane and cyclohexane; and acetonitrile, N-methylpyrrolidone, etc.

可使用的有機溶劑並無特別規定，惟作為反應性稀釋劑可列舉例如：烯丙基環氧丙基醚、丁基環氧丙基醚、2-乙基己基環氧丙基醚、苯基環氧丙基醚、甲苯基環氧丙基醚等單官能環氧丙基醚類；及間苯二酚二環氧丙基醚、新戊二醇二環氧丙基醚、1,4-丁二醇二環氧丙基醚、1,6-己二醇二環氧丙基醚、環己烷二甲醇二環氧丙基醚、丙二醇二環氧丙基醚等二官能環氧丙基醚類；及丙三醇聚環氧丙基醚、三羥甲丙烷聚環氧丙基醚、三羥甲乙烷聚環氧丙基醚、新戊四醇聚環氧丙基醚等多官能環氧丙基醚類；及新癸酸環氧丙酯等環氧丙酯類；及苯基二環氧丙基胺、甲苯基二環氧丙基胺等環氧丙基胺類。 The organic solvent that can be used is not specifically defined, but as a reactive diluent, for example: allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl Monofunctional glycidyl ethers such as glycidyl ether and cresylglycidyl ether; and resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,4- Difunctional glycidyl groups such as butylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, cyclohexane dimethanol diglycidyl ether, propylene glycol diglycidyl ether, etc. Ethers; and polyfunctional glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, trimethylol ethane polyglycidyl ether, neopentylerythritol polyglycidyl ether, etc. Glycidyl ethers; and glycidyl esters such as glycidyl neodecanoate; and glycidyl amines such as phenyldiglycidylamine and tolyldiglycidylamine.

此等有機溶媒或反應性稀釋劑較佳為作為不揮發成分而以90質量%以下的量使用，其適當的種類及使用量能夠依用途而適當選擇。例如在印刷電路板用途中，較佳為甲基乙基酮、丙酮、1-甲氧基-2-丙醇等沸點為160℃以下的極性溶媒，其使用量較佳是不揮發成分計為40至80質量%。此外，在接著膜用途中，較佳為使用例如：酮類、乙酸酯類、卡必醇類、芳香族烴類、二甲基甲醯胺、二甲基乙醯胺、N-甲基吡咯啶酮等，其使用量較佳是以不揮發成分計為30至60質量%。 These organic solvents or reactive diluents are preferably used as non-volatile components in an amount of 90% by mass or less, and the appropriate type and amount of use can be appropriately selected according to the application. For example, in the use of printed circuit boards, polar solvents such as methyl ethyl ketone, acetone, 1-methoxy-2-propanol and the like having a boiling point of 160°C or less are preferred, and the amount used is preferably non-volatile. 40 to 80% by mass. In addition, in the adhesive film application, it is preferable to use, for example, ketones, acetates, carbitols, aromatic hydrocarbons, dimethylformamide, dimethylacetamide, N-methylpyrrole The amount of pyridone and the like is preferably 30 to 60% by mass in terms of non-volatile components.

在不損及特性之範圍內，本發明之環氧樹脂組成物可調配環氧樹脂以外的硬化性樹脂及熱塑性樹脂。就具體例示而言，可列舉：酚樹脂、丙烯酸樹脂、石油樹脂、茚樹脂、茚薰草酮樹脂(indene-coumarone resin)、苯氧樹脂、氰酸鹽樹脂、環氧丙烯酸酯樹脂(epoxy acrylate resin)、乙烯基(vinyl)化合物、聚胺甲酸乙酯、聚酯、聚醯胺、聚醯亞胺、聚醯胺醯亞胺、聚醚醯亞胺、雙順丁烯二醯亞胺三

Figure 108133840-A0202-12-0015-14
氮樹脂、聚醚碸、聚碸、聚醚醚酮、 聚苯硫醚、聚乙烯甲醛等，惟並不限定於此等例示。 The epoxy resin composition of the present invention can be blended with curable resins and thermoplastic resins other than epoxy resins within the range of not impairing the characteristics. Specific examples include: phenol resin, acrylic resin, petroleum resin, indene resin, indene-coumarone resin, phenoxy resin, cyanate resin, epoxy acrylate resin resin), vinyl compound, polyurethane, polyester, polyamide, polyimide, polyimide, polyetherimide, bismaleimide
Figure 108133840-A0202-12-0015-14
Nitrogen resin, polyether stubble, poly stubble, polyether ether ketone, polyphenylene sulfide, polyvinyl formaldehyde, etc. are not limited to these examples.

本發明之環氧樹脂組成物中可視需要而使用填料。具體上可列舉：氫氧化鋁、氫氧化鎂、滑石、煅燒滑石、黏土、高嶺土、氫氧化鈦、玻璃粉末、二氧化矽中空球(silica balloon)等無機填料，惟亦可調配有機系或無機系的耐濕顏料、鱗片狀顏料等顏料等。使用一般無機填充劑的理由可列舉：提高耐衝擊性。此外，可以調配玻璃纖維、紙漿纖維、合成纖維、陶質纖維等纖維質填充劑；及微粒子橡膠、熱塑性彈性體等有機填充劑等。 Fillers may be used in the epoxy resin composition of the present invention as needed. Specific examples include: aluminum hydroxide, magnesium hydroxide, talc, calcined talc, clay, kaolin, titanium hydroxide, glass powder, silica balloons and other inorganic fillers, but they can also be equipped with organic or inorganic fillers. Series of moisture-resistant pigments, flake pigments and other pigments. The reasons for using general inorganic fillers can be cited: improving impact resistance. In addition, fibrous fillers such as glass fiber, pulp fiber, synthetic fiber, ceramic fiber, etc.; and organic fillers such as fine particle rubber and thermoplastic elastomer can be formulated.

本發明之環氧樹脂組成物中，可視需要而調配阻燃劑、觸變賦予材料、流動性提升劑等添加劑。觸變賦予材料可列舉：矽系、蓖麻油系、脂肪族醯胺蠟、氧化聚乙烯蠟、有機膨土系等。再者，可視需要而於本發明之樹脂組成物中調配棕櫚蠟、OP蠟(OP Wax)等離型劑；碳黑等著色劑；三氧化二銻等阻燃助劑；矽油等低應力化劑；硬脂酸鈣等潤滑劑。 In the epoxy resin composition of the present invention, additives such as flame retardants, thixotropy imparting materials, fluidity enhancers, etc. may be blended as needed. Examples of the thixotropy imparting material include silicon-based, castor oil-based, aliphatic amide wax, oxidized polyethylene wax, and organic bentonite-based. Furthermore, if necessary, release agents such as palm wax and OP wax (OP Wax) can be blended into the resin composition of the present invention; coloring agents such as carbon black; flame retardant additives such as antimony trioxide; Agent; lubricants such as calcium stearate.

本發明之環氧樹脂組成物可藉由與習知的環氧樹脂組成物相同的方法進行硬化而獲得環氧樹脂硬化物。用以獲得硬化物的方法可採用與習知的環氧樹脂組成物相同的方法，可適合使用藉由以澆注、注入、灌封(potting)、浸漬、滴塗(drop-coating)、轉注成型(transfer-molding)、壓縮成型等；及作成樹脂片、附樹脂的銅箔、預浸物等形態而進行積層、加熱加壓硬化而製成積層板等的方法。此方法中的硬化溫度通常為100至300℃的範圍，硬化時間通常為1小時至5小時左右。 The epoxy resin composition of the present invention can be cured by the same method as the conventional epoxy resin composition to obtain a cured epoxy resin. The method used to obtain the hardened product can be the same method as the conventional epoxy resin composition, and can be suitably used by casting, injecting, potting, dipping, drop-coating, and transfer molding. (transfer-molding), compression molding, etc.; and methods such as forming a resin sheet, copper foil with resin, prepreg, etc., and laminating, heating and pressurizing hardening to make a laminated board. The curing temperature in this method is usually in the range of 100 to 300°C, and the curing time is usually about 1 hour to 5 hours.

針對使用本發明的環氧樹脂組成物而得到的預浸物進行說明。片狀基材可以使用：玻璃等無機纖維；及聚酯纖維等、多胺纖維、聚丙烯纖維、聚醯亞胺纖維、克維拉纖維(kevlar)等的有機材質纖維之織造布 或不織布，惟並不限定於此等片狀基材。從本發明的環氧樹脂組成物及基材來製造預浸物的方法並無特別限定，例如可以是藉由使上述基材浸漬並含浸樹脂清漆(此樹脂清漆是將上述環氧樹脂組成物調節黏度而製成)之後，加熱乾燥以使樹脂成分半硬化(B階段化)而得到，例如可以在100至200℃加熱乾燥1至40分鐘。其中，預浸物中的樹脂量較佳以樹脂成分的30至80質量%。 The prepreg obtained using the epoxy resin composition of the present invention will be described. Sheet-like substrates can be used: inorganic fibers such as glass; and woven fabrics of organic fibers such as polyester fibers, polyamine fibers, polypropylene fibers, polyimide fibers, and Kevlar fibers. Or non-woven fabrics, but not limited to these sheet-like substrates. The method for producing a prepreg from the epoxy resin composition and the substrate of the present invention is not particularly limited. For example, the substrate may be impregnated and impregnated with a resin varnish (the resin varnish is made of the epoxy resin composition After adjusting the viscosity), it is heated and dried to semi-harden the resin component (B-staged). For example, it can be heated and dried at 100 to 200°C for 1 to 40 minutes. Among them, the amount of resin in the prepreg is preferably 30 to 80% by mass of the resin component.

針對使用本發明的預浸物製造積層板的方法進行說明。首先，積層一片或複數片的預浸物，並於一側或兩側配置金屬箔而構成積層物，將該積層物進行加熱加壓以使積層一體化。其中，金屬箔可使用銅、鋁、黃銅、鎳等的單一金屬的金屬箔、合金的金屬箔或複合的金屬箔。積層物進行加熱加壓的條件，若是適當地調整成環氧樹脂組成物會硬化的條件來加熱加壓即可，惟若是加壓之加壓量過低，則會有於獲得的積層板內部殘留氣泡，且電性特性降低的情況，因此較佳為以滿足成型性的條件進行加壓。例如可分別設定成：溫度為160至220℃，壓力為49.0至490.3N/cm2(5至50kgf/cm2)，加熱時間為40至240分鐘。再者，可將如此而得的單層積層板作為內層材而作成多層板。此時，首先用添加(additive)法或減去(subtractive)法等對積層板實施電路形成，並使用酸溶液處理所形成的電路表面而實施黑化處理，以獲得內層材。在該內層材的單面或兩面之電路形成面配置積層有一片或複數片預浸物者，再於其外側配置金屬箔以形成積層物。然後，藉由將該積層物加熱加壓而一體成型，以形成預浸物的硬化物來作為絕緣層，同時將其外側的金屬箔形成作為導體層。其中，金屬箔亦可採用與使用作為內層板的積層板相同的金屬箔。而且，加熱加壓成形 可用與內層材的成型為相同的條件來進行。在以如此方式成形的多層積層板的表面，可進一步以添加法或減去法實施通孔形成、電路形成，以成型印刷電路板。再者，藉由再將該印刷電路板作為內層材而重複實施上述工序，可以形成更多層的多層印刷電路板。又，絕緣層的形成中，亦可使用絕緣接著片或附樹脂的金屬箔等來取代預浸物，也可以使用稱作鑄製(casting)法的將環氧樹脂組成物進行塗佈、乾燥以作成片狀的方法。 The method of manufacturing a laminated board using the prepreg of this invention is demonstrated. First, one or more prepregs are laminated, and metal foils are arranged on one or both sides to form a laminate, and the laminate is heated and pressurized to integrate the laminate. Among them, as the metal foil, a single metal metal foil such as copper, aluminum, brass, or nickel, an alloy metal foil, or a composite metal foil can be used. The conditions for the laminate to be heated and pressurized can be heated and pressurized if the epoxy resin composition is properly adjusted to the conditions that will harden, but if the amount of pressurization is too low, it will be in the interior of the obtained laminate In the case where air bubbles remain and electrical characteristics are reduced, it is preferable to pressurize to satisfy moldability conditions. For example, the temperature can be set to 160 to 220°C, the pressure is 49.0 to 490.3 N/cm 2 (5 to 50 kgf/cm 2 ), and the heating time is 40 to 240 minutes. Furthermore, the single-layer laminated board obtained in this way can be used as an inner layer material to make a multilayer board. At this time, first, circuit formation is performed on the laminate by an additive method or a subtractive method, and the surface of the formed circuit is treated with an acid solution to perform a blackening treatment to obtain an inner layer material. One or a plurality of prepregs are placed on the circuit forming surface of one or both sides of the inner layer material, and a metal foil is placed on the outside to form a laminate. Then, the laminate is integrally molded by heating and pressing to form a hardened prepreg as an insulating layer, and at the same time forming a metal foil on the outer side as a conductor layer. Among them, as the metal foil, the same metal foil as the laminated plate used as the inner layer plate can be used. In addition, the heating and pressing molding can be performed under the same conditions as the molding of the inner layer material. On the surface of the multilayer build-up board formed in this way, through hole formation and circuit formation can be further performed by an additive method or a subtractive method to form a printed circuit board. Furthermore, by repeating the above-mentioned steps by using the printed circuit board as an inner layer material, a multi-layer printed circuit board with more layers can be formed. In addition, in the formation of the insulating layer, an insulating adhesive sheet or a metal foil with resin can also be used instead of the prepreg, and the epoxy resin composition can also be coated and dried by a so-called casting method. In the method of making flakes.

此外，若是使本發明之環氧樹脂組成物加熱硬化，則可獲得阻燃性環氧樹脂硬化物，該硬化物的阻燃性及耐熱性為優異。該硬化物可以是藉由使用澆注、壓縮成型、轉注成型等方法將環氧樹脂組成物進行成型加工而獲得。此時的溫度通常為120至250℃的範圍。 In addition, if the epoxy resin composition of the present invention is heat-cured, a flame-retardant epoxy resin cured product can be obtained, and the cured product is excellent in flame retardancy and heat resistance. The hardened product can be obtained by molding the epoxy resin composition using methods such as casting, compression molding, and transfer molding. The temperature at this time is usually in the range of 120 to 250°C.

使用本發明的環氧樹脂組成物與其組成物而得到的預浸物、積層板、硬化物會顯示優異的阻燃性及耐熱性。 The prepreg, laminate, and cured product obtained by using the epoxy resin composition of the present invention and the composition thereof exhibit excellent flame retardancy and heat resistance.

[實施例] [Example]

以下是基於實施例及比較例來進一步具體的說明本發明，惟本發明並不限定於此等例。若無另行說明，則「份」表示質量份，「%」表示質量%。此外，試驗及測定分別是藉由以下的方法來進行。又，當量單位皆為「g/eq.」。 The following is a further detailed description of the present invention based on examples and comparative examples, but the present invention is not limited to these examples. Unless otherwise specified, "parts" means parts by mass, and "%" means mass%. In addition, the test and the measurement were respectively performed by the following methods. Also, the equivalent units are all "g/eq."

含磷率： Phosphorus rate:

在試料中加入硫酸、鹽酸、過氯酸，加熱至濕灰化(wet ashing)，使所有的磷原子為正磷酸。使偏釩酸鹽及鉬酸鹽在硫酸酸性溶液中反應，測定所產生的磷釩鉬酸(phosphovanadomolybdate)錯合物在420nm中的吸光度，並以%表示藉由預先作出的標準曲線求出的含磷率。 Sulfuric acid, hydrochloric acid, and perchloric acid are added to the sample, and heated to wet ashing, so that all phosphorus atoms are orthophosphoric acid. The metavanadate and molybdate are reacted in a sulfuric acid acid solution, and the absorbance of the produced phosphovanadomolybdate complex at 420nm is measured, and expressed in% as calculated by the standard curve prepared in advance Phosphorus rate.

酚性羥基當量： Phenolic hydroxyl equivalent:

依據JIS K 0070規格進行測定。 Measured according to JIS K 0070 standard.

熔點： Melting point:

依據JIS K 7121規格、示差掃描熱量法(DSC)進行測定。具體而言，是使用DSC裝置(日立High-tech science股份有限公司製，EXSTAR6000 DSC6200)，藉由從20℃至10℃/分鐘之升溫速度測定，並依據在第1循環所獲得的圖表的熔解峰值溫度(Tpm)求出。 It is measured in accordance with JIS K 7121 standard and differential scanning calorimetry (DSC). Specifically, a DSC device (manufactured by Hitachi High-tech Science Co., Ltd., EXSTAR6000 DSC6200) was used to measure the temperature rise rate from 20°C to 10°C/min, and the melting was based on the graph obtained in the first cycle The peak temperature (Tpm) is calculated.

含磷硬化劑的純度(環狀有機磷化合物的含量)： Purity of phosphorus-containing hardener (content of cyclic organic phosphorus compound):

以藉由HPLC所測定的各成分的面積百分率(面積%)來表示。 It is expressed as the area percentage (area %) of each component measured by HPLC.

HPLC的裝置及測定條件係如以下所示。 The HPLC apparatus and measurement conditions are as follows.

分析裝置：Agilent Technologies,Inc.製，型號：HP1200系列。 Analysis device: manufactured by Agilent Technologies, Inc., model: HP1200 series.

管柱：Sigma-Aldrich Co.LLC.製、型號：ASCENTISEXPRESS C18。 Column: manufactured by Sigma-Aldrich Co. LLC, model: ASCENTISEXPRESS C18.

管柱槽溫度：40℃。 Column tank temperature: 40℃.

溶析液：10mM醋酸銨水/四氫呋喃/乙腈=55/22.5/22.5體積% Eluent: 10mM ammonium acetate water/tetrahydrofuran/acetonitrile=55/22.5/22.5% by volume

流量：1.0mL/分鐘 Flow rate: 1.0mL/min

偵檢器：紫外可見分光(UV/VIS)偵檢器 Detector: Ultraviolet-visible spectroscopy (UV/VIS) detector

測定波長：300nm Measurement wavelength: 300nm

試料溶液注入量：100μL Injection volume of sample solution: 100μL

FTIR測定： FTIR measurement:

使用傅立葉轉換式紅外分光光度計(Perkinelmer Inc.製，Spectum One FT-IR Spectrometer 1760X)，藉由衰減全反射法(Attenuated Total Reflection method；ATR法)測定波數400至4000cm-1之吸光度。 A Fourier transform infrared spectrophotometer (manufactured by Perkinelmer Inc., Spectum One FT-IR Spectrometer 1760X) was used to measure the absorbance at a wavenumber of 400 to 4000 cm -1 by the Attenuated Total Reflection method (ATR method).

溶劑溶解性： Solvent solubility:

將環氧樹脂清漆在室溫下保管24小時後，確認有無析出物，並以下述判定方式表示。 After storing the epoxy resin varnish at room temperature for 24 hours, the presence or absence of precipitates was confirmed, and the result was indicated by the following judgment method.

無析出物而維持透明：○ Keep transparent without precipitate: ○

有析出物：x。 There are precipitates: x.

預浸物的狀態： State of prepreg:

目視觀察預浸物的表面狀態，並以下述判定方式表示。 The surface state of the prepreg was visually observed and expressed in the following judgment method.

沒有問題：○ No problem: ○

產生粗糙：x1 Produce roughness: x1

有氣泡殘留：x2 There are bubbles remaining: x2

阻燃性： Flame retardancy:

依據UL(Underwriters Laboratories Inc.)規格、UL94、垂直試驗法進行測定，並藉由同規格的判定基準V-0、V-1、V-2進行判定。 It is measured according to UL (Underwriters Laboratories Inc.) standards, UL94, and vertical test method, and judged by the same standards of judgment standards V-0, V-1, and V-2.

玻璃轉移溫度(Tg)： Glass transition temperature (Tg):

依據JIS K 7121、示差掃描熱量測定法進行測定。使用DSC裝置，以從20℃至10℃/分鐘的升溫速度測定，以第2循環所獲得的DSC圖表之外推玻璃轉移起始溫度(Tig)的溫度來表示。 It is measured in accordance with JIS K 7121 and differential scanning calorimetry. Using a DSC device, the temperature was measured at a temperature increase rate from 20°C to 10°C/min, and the glass transition initiation temperature (Tig) was extrapolated from the DSC chart obtained in the second cycle.

銅箔剝離強度及層間接著力： Copper foil peeling strength and layer indirect focus:

依據JIS C 6481規格進行測定，在第7層與第8層之間進行剝離而測定層間接著力。 Measured in accordance with the JIS C 6481 standard, peeled off between the 7th layer and the 8th layer, and measured the layer indirect adhesion.

實施例1 Example 1

在具備攪拌裝置、溫度計、氮氣導入裝置及冷卻管的反應容器中饋入 8-苄基-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物(三光股份有限公司製，Bz-HCA)100份、甲苯185份，加熱至90℃且完全溶解後，一邊注意反應熱一邊少量逐次地投入1,4-萘醌(川崎化成股份有限公司製)51份，之後以回流溫度保持3小時而終止反應。之後，將所產生的漿料進行乾式過濾並以熱甲苯重複洗淨10次，最後以甲基乙基酮洗淨後，以80℃進行乾燥，獲得為白色結晶的8-苄基-9,10-二氫-10-〔2’-(1’,4’-二羥基萘)〕-9-氧雜-10-磷雜菲-10-氧化物的含磷硬化劑(A-1)。含磷率為6.7%，酚性羥基當量為232，熔點為189℃，純度為99.2面積%(Bz-HCA的含量為0.8面積%)。將獲得的A-1的FTIR圖表顯示於第1圖。圖中，在2400cm-1附近的P-H譜峰消失，在3200cm-1附近可確認到寬的O-H譜峰。將HPLC圖表顯示於第2圖。 Feed 8-benzyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide into a reaction vessel equipped with a stirring device, a thermometer, a nitrogen introduction device, and a cooling tube (Sanko Co., Ltd. 100 parts of Bz-HCA), 185 parts of toluene, heated to 90°C and completely dissolved, add 51 parts of 1,4-naphthoquinone (manufactured by Kawasaki Chemical Co., Ltd.) in small amounts while paying attention to the reaction heat. The reaction was terminated by keeping the reflux temperature for 3 hours. After that, the resulting slurry was dry filtered and washed with hot toluene 10 times, and finally washed with methyl ethyl ketone, and dried at 80°C to obtain 8-benzyl-9 as white crystals. 10-Dihydro-10-[2'-(1',4'-dihydroxynaphthalene)]-9-oxa-10-phosphaphenanthrene-10-oxide phosphorus-containing hardener (A-1). The phosphorus content is 6.7%, the phenolic hydroxyl equivalent is 232, the melting point is 189°C, and the purity is 99.2 area% (Bz-HCA content is 0.8 area%). The FTIR chart of A-1 is shown in Figure 1. FIG, the PH of the peak near 2400cm -1 disappeared in the vicinity of 3200cm -1 was confirmed broad OH peak. The HPLC chart is shown in Figure 2.

實施例2 Example 2

除了將使用熱甲苯及甲基乙基酮的洗淨次數設為1次以外，進行與實施例1相同的操作，獲得含磷硬化劑(A-2)。含磷率為6.7%，酚性羥基當量為231，純度為95.5面積%(Bz-HCA的含量為4.5面積%)。 Except that the number of times of washing using hot toluene and methyl ethyl ketone was set to once, the same operation as in Example 1 was performed to obtain a phosphorus-containing hardener (A-2). The phosphorus content is 6.7%, the phenolic hydroxyl equivalent is 231, and the purity is 95.5 area% (Bz-HCA content is 4.5 area%).

實施例3 Example 3

除了省略了使用熱甲苯及甲基乙基酮的洗淨以外，進行與實施例1相同的操作，獲得含磷硬化劑(A-3)。含磷率為6.7%，酚性羥基當量為230，純度為94.0面積%(Bz-HCA的含量為6.0面積%)。 Except for omitting the washing with hot toluene and methyl ethyl ketone, the same operation as in Example 1 was performed to obtain a phosphorus-containing hardener (A-3). The phosphorus content is 6.7%, the phenolic hydroxyl equivalent is 230, and the purity is 94.0 area% (Bz-HCA content is 6.0 area%).

實施例4 Example 4

除了將1,4-萘醌變更為2-羥基-1,4-萘醌(試藥)56份以外，進行與實施例1相同的操作，獲得含磷硬化劑(A-4)。含磷率為6.4%，酚性羥基 當量為160，純度為99.1面積%(Bz-HCA的含量為0.9面積%)。 Except that 1,4-naphthoquinone was changed to 56 parts of 2-hydroxy-1,4-naphthoquinone (reagent), the same operation as in Example 1 was performed to obtain a phosphorus-containing hardener (A-4). Phosphorus content is 6.4%, phenolic hydroxyl The equivalent weight is 160, and the purity is 99.1 area% (the content of Bz-HCA is 0.9 area%).

比較例1 Comparative example 1

在與實施例1相同的裝置內饋入乙二醇單乙基醚100份、9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物(三光股份有限公司製、HCA)54份，加熱至70℃且完全溶解後，一邊注意反應熱一邊以少量逐次地投入2-羥基-1,4-萘醌42份，投入後以120℃保持5小時而終止反應。之後，減壓回收乙二醇單乙基醚並除去溶劑，用甲醇洗淨所產生的結晶物後，進行減壓乾燥而獲得白色結晶之含磷硬化劑(A-10)。含磷率為7.8%，酚性羥基當量為130。 In the same device as in Example 1, 100 parts of ethylene glycol monoethyl ether, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (manufactured by Sanko Co., Ltd., HCA) 54 parts were heated to 70°C and completely dissolved, while paying attention to the reaction heat, 42 parts of 2-hydroxy-1,4-naphthoquinone were sequentially added in small amounts, and the reaction was terminated by keeping it at 120°C for 5 hours. After that, ethylene glycol monoethyl ether was recovered under reduced pressure and the solvent was removed, the resulting crystals were washed with methanol, and then dried under reduced pressure to obtain white crystals of phosphorus-containing hardener (A-10). The phosphorus content is 7.8%, and the phenolic hydroxyl equivalent is 130.

實施例及比較例中所使用的代號的說明如下。 The description of the codes used in the examples and comparative examples is as follows.

〔硬化劑〕 〔hardener〕

A-1：實施例1所獲得的含磷硬化劑 A-1: Phosphorus-containing hardener obtained in Example 1

A-2：實施例2所獲得的含磷硬化劑 A-2: Phosphorus-containing hardener obtained in Example 2

A-3：實施例3所獲得的含磷硬化劑 A-3: Phosphorus-containing hardener obtained in Example 3

A-4：實施例4所獲得的含磷硬化劑 A-4: Phosphorus-containing hardener obtained in Example 4

A-5：二氰二醯胺(日本Carbide工業股份有限公司製，dicyandiamide，活性氫當量21) A-5: Dicyandiamide (manufactured by Carbide Industry Co., Ltd., dicyandiamide, active hydrogen equivalent 21)

A-6：酚酚醛清漆樹脂(Aica工業股份有限公司製，SHONOL BRG-557，酚性羥基當量105，軟化點80℃) A-6: Phenolic novolac resin (manufactured by Aica Industrial Co., Ltd., SHONOL BRG-557, phenolic hydroxyl equivalent weight 105, softening point 80°C)

A-7：9,10-二氫-10-〔2’-(1’,4’-二羥基萘)〕-9-氧雜-10-磷雜菲-10-氧化物(三光股份有限公司製，HCA-NQ，酚性羥基當量187，含磷率8.3%) A-7: 9,10-dihydro-10-[2'-(1',4'-dihydroxynaphthalene)]-9-oxa-10-phosphaphenanthrene-10-oxide (Sanguang Co., Ltd. Manufacture, HCA-NQ, phenolic hydroxyl equivalent 187, phosphorus content 8.3%)

A-8：9,10-二氫-10-〔2’-(1’,4’-二羥基苯基)〕-9-氧雜-10-磷雜菲-10-氧化物(三光股份有限公司製，HCA-HQ，酚性羥基當量162，含磷率9.3%) A-8: 9,10-dihydro-10-[2'-(1',4'-dihydroxyphenyl)]-9-oxa-10-phosphaphenanthrene-10-oxide (Sanguang Co., Ltd. Company made, HCA-HQ, phenolic hydroxyl equivalent weight 162, phosphorus content 9.3%)

A-9：含磷的酚硬化劑(SHIN-A T&C Co.ltd.製，LC-950MP60，酚性羥基當量341，含磷率9.2%) A-9: Phosphorus-containing phenol hardener (manufactured by SHIN-A T&C Co.ltd., LC-950MP60, phenolic hydroxyl equivalent 341, phosphorus content 9.2%)

A-10：比較例1所獲得的含磷硬化劑 A-10: Phosphorus-containing hardener obtained in Comparative Example 1

〔磷系阻燃劑〕 〔Phosphorus flame retardant〕

A-11：雙酚A雙(磷酸二苯酯)(大八化學工業股份有限公司製，CR-741，含磷率8.9%) A-11: Bisphenol A bis(diphenyl phosphate) (manufactured by Daha Chemical Industry Co., Ltd., CR-741, phosphorus content 8.9%)

〔環氧樹脂〕 〔Epoxy resin〕

B-1：酚酚醛清漆型環氧樹脂(新日鐵住金化學股份有限公司製，Epotohto YDPN-638，環氧當量177) B-1: Phenolic novolac type epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., Epotohto YDPN-638, epoxy equivalent 177)

B-2：甲酚酚醛清漆型環氧樹脂(新日鐵住金化學股份有限公司製，Epotohto YDCN-700-7，環氧當量202) B-2: Cresol novolac type epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., Epotohto YDCN-700-7, epoxy equivalent 202)

B-3：含磷的環氧樹脂(新日鐵住金化學股份有限公司製，Epotohto FX-289B，環氧當量330，含磷率2.0%) B-3: Phosphorus-containing epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., Eptohto FX-289B, epoxy equivalent 330, phosphorus content 2.0%)

實施例5至14、比較例2至7 Examples 5 to 14, Comparative Examples 2 to 7

使用表1或表2的調配量(份)調配環氧樹脂、硬化劑或阻燃劑，將其溶解於以甲基乙基酮、丙二醇單甲基醚、環戊酮調製成的混合溶劑中，以不揮發成分(樹脂成分)成為50%的方式調製而獲得環氧樹脂組成物清漆。使用獲得的環氧樹脂組成物清漆進行溶劑溶解性的確認。 Use the blending amount (parts) in Table 1 or Table 2 to prepare epoxy resin, hardener or flame retardant, and dissolve them in a mixed solvent prepared with methyl ethyl ketone, propylene glycol monomethyl ether, and cyclopentanone , Prepared so that the non-volatile component (resin component) became 50% to obtain an epoxy resin composition varnish. The solvent solubility was confirmed using the obtained epoxy resin composition varnish.

在獲得的環氧樹脂組成物清漆中添加作為硬化促進劑的2-乙基-4-甲基咪唑(四國化成工業股份有限公司製，CUREZOL 2E4MZ)，以170℃之膠化時間成為300秒左右的方式加以調整。將該調整後的環氧樹脂組成物清漆含浸於玻璃布(日東紡績股份有限公司製，WEA 7628 XS13，0.18mm厚)。將經含浸的玻璃布在150℃之熱風循環爐中乾燥8分鐘以獲得預浸物。觀察預浸物的表面狀態，並將其結果顯示於表1或表2。 Add 2-ethyl-4-methylimidazole (manufactured by Shikoku Chemical Industry Co., Ltd., CUREZOL 2E4MZ) as a hardening accelerator to the obtained epoxy resin composition varnish, and the gel time at 170°C is 300 seconds Adjust the way around. The adjusted epoxy resin composition varnish was impregnated into glass cloth (manufactured by Nittobo Co., Ltd., WEA 7628 XS13, 0.18mm thick). The impregnated glass cloth was dried in a hot air circulation oven at 150°C for 8 minutes to obtain a prepreg. Observe the surface state of the prepreg and show the results in Table 1 or Table 2.

將8片所獲得的預浸物的上下重疊銅箔(三井金屬礦業股份有限公司製，3EC-III，厚度35μm)，在以130℃、15分鐘再以210℃、90分鐘的溫度條件下進行2MPa的真空加壓，獲得1.6mm厚的積層板。藉由浸漬於蝕刻液以除去所獲得的積層板之銅箔部分，進行洗淨與乾燥後，切成127mm×12.7mm的大小以作為阻燃性測定用試驗片。將積層板之阻燃性、Tg、銅箔剝離強度及層間接著力的結果顯示於表1或表2。又，表中之含磷率為環氧樹脂組成物(除去溶劑成分)的值。 Put 8 pieces of the obtained prepreg on top and bottom of copper foil (manufactured by Mitsui Metals & Mining Co., Ltd., 3EC-III, thickness 35μm), under temperature conditions of 130°C for 15 minutes and 210°C for 90 minutes 2 MPa vacuum pressure to obtain a 1.6mm thick laminate. The copper foil part of the obtained laminated board was removed by immersing in an etching solution, washing|cleaning and drying, and cutting into a size of 127mm x 12.7mm as a flame-retardant measurement test piece. Table 1 or Table 2 shows the results of flame retardancy, Tg, copper foil peel strength, and layer adhesion of the laminate. In addition, the phosphorus content in the table is the value of the epoxy resin composition (excluding the solvent component).

Figure 108133840-A0202-12-0025-6
Figure 108133840-A0202-12-0025-6

Figure 108133840-A0202-12-0026-7
Figure 108133840-A0202-12-0026-7

依據表1、表2，從預浸物之表面狀態的觀察結果可知本發明之含磷硬化劑對於環氧樹脂具有優異的溶解性。此外，本發明之環氧樹脂組成物的硬化物亦具有優異的阻燃性及耐熱性。 According to Table 1 and Table 2, from the observation results of the surface state of the prepreg, it is known that the phosphorus-containing hardener of the present invention has excellent solubility for epoxy resin. In addition, the cured product of the epoxy resin composition of the present invention also has excellent flame retardancy and heat resistance.

Figure 108133840-A0202-11-0003-3
Figure 108133840-A0202-11-0003-3

Claims (8)

一種含磷硬化劑，為下述通式(1)所示之含磷的硬化劑，
Figure 108133840-A0202-13-0001-8
 式中，X為具有2至4個選自羥基、羧基或胺基之取代基的芳基，R1至R8為氫原子、碳數1至12之烷基、碳數2至12之烯基、碳數6至20之芳基或碳數7至20之芳烷基，R1至R8中的至少一者為排除氫原子者。 A phosphorus-containing hardener is a phosphorus-containing hardener represented by the following general formula (1),
Figure 108133840-A0202-13-0001-8
 In the formula, X is an aryl group having 2 to 4 substituents selected from the group consisting of hydroxyl, carboxyl or amino, and R 1 to R 8 are hydrogen atoms, alkyl groups with 1 to 12 carbons, and alkenes with 2 to 12 carbons. Group, an aryl group having 6 to 20 carbons, or an aralkyl group having 7 to 20 carbons, at least one of R 1 to R 8 excludes a hydrogen atom. 如申請專利範圍第1項所述之含磷硬化劑，其中，上述通式(1)之R1為碳數6至20之芳基或碳數7至20之芳烷基。 The phosphorus-containing hardener as described in the first item of the scope of patent application, wherein R 1 of the above general formula (1) is an aryl group having 6 to 20 carbons or an aralkyl group having 7 to 20 carbons. 如申請專利範圍第1或2項所述之含磷硬化劑，該含磷硬化劑在高效能液相層析測定中，含有0.01至5.0面積%的下述通式(2)所示之環狀有機磷化合物，
Figure 108133840-A0202-13-0001-9
 式中，R11至R18為氫原子、碳數1至12之烷基、碳數2至12之烯基、碳數6至20之芳基或碳數7至20之芳烷基，R11至R18中的至少一者為排除氫原子者。 The phosphorus-containing hardener as described in item 1 or 2 of the scope of patent application, the phosphorus-containing hardener contains 0.01 to 5.0 area% of the ring represented by the following general formula (2) in the high performance liquid chromatography measurement Like organophosphorus compounds,
Figure 108133840-A0202-13-0001-9
 In the formula, R 11 to R 18 are hydrogen atoms, alkyl groups having 1 to 12 carbons, alkenyl groups having 2 to 12 carbons, aryl groups having 6 to 20 carbons, or aralkyl groups having 7 to 20 carbons, and R At least one of 11 to R 18 excludes a hydrogen atom. 如申請專利範圍第3項所述之含磷硬化劑，其中，上述通式(2)之R11為碳數6至20之芳基或碳數7至20之芳烷基。 The phosphorus-containing hardener as described in item 3 of the scope of patent application, wherein R 11 of the above general formula (2) is an aryl group with 6 to 20 carbons or an aralkyl group with 7 to 20 carbons. 一種環氧樹脂組成物，係含有申請專利範圍第1至4項中任一項所述之含磷硬化劑及環氧樹脂，該組成物中的含磷率為1.0至5.0質量%。 An epoxy resin composition containing the phosphorus-containing hardener and epoxy resin described in any one of items 1 to 4 in the scope of patent application, and the phosphorus content of the composition is 1.0 to 5.0% by mass. 一種硬化物，該硬化物係申請專利範圍第5項所述之環氧樹脂組成物硬化而成者。 A hardened product obtained by hardening the epoxy resin composition described in item 5 of the scope of the patent application. 一種預浸物，該預浸物係使用了申請專利範圍第5項所述之環氧樹脂組成物。 A prepreg that uses the epoxy resin composition described in item 5 of the scope of patent application. 一種積層板，該積層板係使用了申請專利範圍第5項所述之環氧樹脂組成物。 A laminated board that uses the epoxy resin composition described in item 5 of the scope of patent application.
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