TWI422609B - A novel flame retardant epoxy resin, an epoxy resin composition containing the epoxy resin as an essential component and a cured product thereof - Google Patents

A novel flame retardant epoxy resin, an epoxy resin composition containing the epoxy resin as an essential component and a cured product thereof Download PDF

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TWI422609B
TWI422609B TW097118191A TW97118191A TWI422609B TW I422609 B TWI422609 B TW I422609B TW 097118191 A TW097118191 A TW 097118191A TW 97118191 A TW97118191 A TW 97118191A TW I422609 B TWI422609 B TW I422609B
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epoxy resin
integer
flame retardant
cyclic
branched
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TW097118191A
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TW200911864A (en
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Kazuo Ishihara
Tetsuya Nakanishi
Noriko Kishi
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Nippon Steel & Sumikin Chem Co
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • 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
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1405—Polycondensates modified by chemical after-treatment with inorganic compounds
    • C08G59/1422—Polycondensates modified by chemical after-treatment with inorganic compounds containing phosphorus
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0326—Organic insulating material consisting of one material containing O

Description

新穎難燃性環氧樹脂、以該環氧樹脂為必要成分之環氧樹脂組合物及其硬化物Novel flame retardant epoxy resin, epoxy resin composition containing the epoxy resin as an essential component, and cured product thereof

本發明係關於一種可用作製造電子電路基板中所使用之銅箔積層板、膜材、附樹脂之銅箔等的樹脂組合物或者電子零件中所使用之密封材、成形材、澆鑄材、接著劑、電氣絕緣塗料用材料等的新穎難燃性環氧樹脂、環氧樹脂組合物及其硬化物。The present invention relates to a resin composition for use in manufacturing a copper foil laminate, a film material, a copper foil with a resin, or the like, or a sealing material, a molding material, a casting material, or the like used in an electronic component. A novel flame retardant epoxy resin, an epoxy resin composition, and a cured product thereof, such as a binder or a material for electrical insulating coating.

環氧樹脂由於接著性、耐熱性、成形性優異，故而廣泛用於電子零件、電氣設備、汽車零件、FRP(Fiber Reinforced Plastics，纖維強化塑膠)、運動用品等中。其中，強烈要求在電子零件、電氣設備中所使用之銅箔積層板或密封材具有火災之防止、延遲等安全性，因此至今為止使用具有該等特性的溴化環氧樹脂等。雖具有比重大的問題，但自藉由在環氧樹脂中導入鹵素尤其是溴而賦予難燃性，以及環氧基具有高反應性而獲得優異之硬化物的方面考慮，溴化環氧樹脂類被確定為有用的電子、電氣材料。Since epoxy resin is excellent in adhesiveness, heat resistance, and moldability, it is widely used in electronic parts, electrical equipment, automobile parts, FRP (Fiber Reinforced Plastics), sporting goods, and the like. Among them, copper foil laminates or sealing materials used in electronic components and electrical equipment are strongly required to have safety such as fire prevention and delay, and thus brominated epoxy resins having such characteristics have been used until now. Although it has a problem of a large specific gravity, brominated epoxy resin is obtained by introducing a halogen, especially bromine, into an epoxy resin to impart flame retardancy, and an epoxy group having high reactivity to obtain an excellent cured product. Classes are identified as useful electronic and electrical materials.

但，觀察最近之電氣設備，將所謂輕薄短小視為最重要的傾向逐漸增強。在如此之社會要求下，從最近之輕量化傾向的觀點考慮，比重大之鹵化物為較佳材料，又，在高溫下長期使用時，鹵化物產生解離，由此而有產生配線腐蝕之虞。進而使用完畢之電子零件、電氣設備燃燒時產生鹵化物等有害物質，自環境安全性之觀點考慮，鹵素之利用成為問題，正在研究可代替其之材料。本發明者對該課 題進行潛心研究，發明了一種電子機器之輕薄短小化、無配線腐蝕之問題以及有害鹵化物產生的含磷之環氧樹脂(專利文獻1~2)。但，進一步謀求硬化物之耐熱性提高以及難燃性提高等。However, observing the recent electrical equipment, the so-called light and short is considered to be the most important tendency to gradually increase. Under the request of such a society, from the viewpoint of the recent lightening tendency, a halide of a larger ratio is a preferable material, and when it is used for a long period of time at a high temperature, the halide is dissociated, thereby causing corrosion of wiring. . Further, when electronic components and electrical equipment that have been used are burned, harmful substances such as halides are generated. From the viewpoint of environmental safety, the use of halogens has become a problem, and materials that can be substituted for them are being studied. The inventor of the class In particular, the invention has invented a thin and light electronic device, a problem of no wiring corrosion, and a phosphorus-containing epoxy resin which is harmful to halides (Patent Documents 1 to 2). However, the heat resistance of the cured product is improved and the flame retardancy is improved.

專利文獻1：日本專利特開平11－166035專利文獻2：日本專利特開平11－279258Patent Document 1: Japanese Patent Laid-Open No. Hei 11-166035 Patent Document 2: Japanese Patent Laid-Open No. 11-279258

為了進一步提高未使用鹵素且賦予難燃性的含磷之環氧樹脂的耐熱性及難燃性，本發明者進行潛心研究發現，可利用含有磷及氮之新穎難燃性環氧樹脂來提高耐熱性及難燃性，從而完成本發明，目的在於提供一種新穎難燃性環氧樹脂、新穎難燃性環氧樹脂組合物及其硬化物，該新穎難燃性環氧樹脂適合於電子電路基板中所使用之銅箔積層板或電子零件中所使用之密封材、成形材、澆鑄材、接著劑、電氣絕緣塗料用材料、電氣絕緣膜等。In order to further improve the heat resistance and flame retardancy of a phosphorus-containing epoxy resin which does not use a halogen and impart flame retardancy, the inventors of the present invention have conducted intensive studies and found that a novel flame retardant epoxy resin containing phosphorus and nitrogen can be used for improvement. The present invention has been made in view of heat resistance and flame retardancy, and aims to provide a novel flame retardant epoxy resin, a novel flame retardant epoxy resin composition and a cured product thereof, which are suitable for electronic circuits. A sealing material, a molding material, a casting material, an adhesive, a material for an electrical insulating coating material, an electrical insulating film, or the like used in a copper foil laminate or an electronic component used for a substrate.

即，本發明之要旨為以通式(1)所表示之含有氮及磷之新穎難燃性環氧樹脂、以該環氧樹脂為必要成分之新穎難燃性環氧樹脂組合物及其硬化物。That is, the gist of the present invention is a novel flame retardant epoxy resin containing nitrogen and phosphorus represented by the general formula (1), a novel flame retardant epoxy resin composition containing the epoxy resin as an essential component, and hardening thereof. Things.

具體而言係提供一種具有以通式(1) 所表示之特定結構的含有氮及磷之新穎難燃性環氧樹脂： (式中，X表示選自由後述通式(2)~(5)所組成之群中的至少1種化學結構；Y表示選自由後述通式(6)~(9)所組成之群中的至少1種化學結構；並且n表示1~10之整數)。Specifically, a novel flame retardant epoxy resin containing nitrogen and phosphorus having a specific structure represented by the general formula (1) is provided: (wherein X represents at least one chemical structure selected from the group consisting of the following general formulae (2) to (5); and Y represents a group selected from the group consisting of the following general formulae (6) to (9); At least one chemical structure; and n represents an integer from 1 to 10).

以上所引用之通式(2)~(28)具有下述結構： The above general formulae (2) to (28) have the following structures:

(式中，R1表示烴基，各自可相同亦可不同，亦可為直鏈狀、分支狀或者環狀；並且a表示0、1、2、3、4或5之整數)； (wherein R1 represents a hydrocarbon group, each of which may be the same or different, may be linear, branched or cyclic; and a represents an integer of 0, 1, 2, 3, 4 or 5);

(式中，R1表示烴基，各自可不同亦可相同，亦可為直鏈狀、分支狀或者環狀；a表示0、1、2、3、4或5之整數；並且Z表示亞甲基、氧、硫、苯、萘、蒽、菲、聯苯、或者後述通式(10)~(19)中之任一者： 通式(14) ：－SO－ (14) Wherein R1 represents a hydrocarbon group, each of which may be different or the same, and may be linear, branched or cyclic; a represents an integer of 0, 1, 2, 3, 4 or 5; and Z represents a methylene group. , oxygen, sulfur, benzene, naphthalene, anthracene, phenanthrene, biphenyl, or any of the following formulas (10) to (19): General formula (14) :-SO- (14)

通式(17)： -CH2 -(D)-CH2 - (17) General formula (17): -CH 2 -(D)-CH 2 - (17)

(式中，D表示苯、萘、蒽、菲或聯苯)； (wherein D represents benzene, naphthalene, anthracene, phenanthrene or biphenyl);

(式中，q表示0、1、2、3……之整數)； (where q represents an integer of 0, 1, 2, 3, ...);

(式中，W表示亞甲基、硫、苯、萘、蒽、菲、聯苯、或者通式(10)~(17)中之任一者))； (wherein W represents a methylene group, sulfur, benzene, naphthalene, anthracene, phenanthrene, biphenyl, or any one of the formulae (10) to (17));

(式中，R1表示烴基，各自可相同亦可不同，亦可為直 為直鏈狀、分支狀或者環狀；並且a表示0、1、2、3、4或5之整數)； (wherein R1 represents a hydrocarbon group, each of which may be the same or different, and may be straight linear, branched or cyclic; and a represents an integer of 0, 1, 2, 3, 4 or 5);

(式中，R1表示烴基，各自可相同亦可不同，亦可為直鏈狀、分支狀或者環狀；並且b表示0、1、2、3、4、5、6或7之整數)； (wherein R1 represents a hydrocarbon group, each of which may be the same or different, may be linear, branched or cyclic; and b represents an integer of 0, 1, 2, 3, 4, 5, 6 or 7);

(式中，R2表示烴基，各自可不同亦可相同，亦可為直鏈狀、分支狀或者環狀；c表示0、1、2、3或4之整數；G表示後述通式(20)~(23)中之任一者，1分子中至少1個表示式(21)或者後述通式(22)： (wherein R2 represents a hydrocarbon group, and each may be different or the same, and may be linear, branched or cyclic; c represents an integer of 0, 1, 2, 3 or 4; and G represents a formula (20) described later) In any one of (23), at least one of the molecules represents the formula (21) or the following formula (22):

(式中，j為0或1；並且R3及R4表示氫或烴基，各自可相同亦可不同，亦可為直鏈狀、分支鏈狀或者環狀，或者R3與R4亦可鍵結而形成環狀結構)； (wherein j is 0 or 1; and R3 and R4 represent hydrogen or a hydrocarbon group, each of which may be the same or different, may be linear, branched or cyclic, or R3 and R4 may be bonded to form Ring structure);

(式中，j為0或1；R3及R4表示氫或烴基，各自可相同亦可不同，亦可為直鏈狀、分支鏈狀或者環狀，或者R3與R4亦可鍵結而形成環狀結構；B表示苯、萘、蒽、菲以及該等之烴取代體；並且Y表示通式(6)~(9)中之任一者)； (wherein j is 0 or 1; R3 and R4 represent hydrogen or a hydrocarbon group, and each may be the same or different, and may be linear, branched or cyclic, or R3 and R4 may be bonded to form a ring. a structure; B represents benzene, naphthalene, anthracene, phenanthrene, and the like; and Y represents any one of the formulae (6) to (9);

(式中，r表示0、1、2、3……之整數；E表示苯、萘、蒽、菲、聯苯以及該等之烴取代體、通式(25)或(24)： (wherein, r represents an integer of 0, 1, 2, 3, ...; E represents benzene, naphthalene, anthracene, phenanthrene, biphenyl, and the like, or a hydrocarbon substituent of the formula (25) or (24):

(式中，R2表示烴基，各自可不同亦可相同，亦可為直鏈狀、分支狀或者環狀；c1及c2表示0、1、2、3或4之整數；Z表示亞甲基、氧、硫、苯、萘、蒽、菲、聯苯、或者通式(10)~(19)中之任一者；並且m表示1、2、3……之整數)； (wherein R2 represents a hydrocarbon group, each of which may be different or the same, may be linear, branched or cyclic; c1 and c2 represent an integer of 0, 1, 2, 3 or 4; Z represents a methylene group, Oxygen, sulfur, benzene, naphthalene, anthracene, phenanthrene, biphenyl, or any one of the formulae (10) to (19); and m represents an integer of 1, 2, 3...);

(式中，R2表示烴基，各自可相同亦可不同，亦可為直鏈狀、分支狀或者環狀； h1及h2表示0、1、2、3、4或5之整數；Z表示亞甲基、氧、硫、苯、萘、蒽、菲、聯苯、或者通式(10)~(19)中之任一者；並且l表示1、2、3……之整數)；並且Y表示通式(6)~(9)中之任一者)；d表示1、2、3、4或5之整數；並且c+d≦5)； (wherein R2 represents a hydrocarbon group, each of which may be the same or different, and may be linear, branched or cyclic; h1 and h2 represent an integer of 0, 1, 2, 3, 4 or 5; Z represents a Any of the formulae (10) to (19); and l represents an integer of 1, 2, 3, ...; and Y represents Any one of the general formulae (6) to (9); d represents an integer of 1, 2, 3, 4 or 5; and c + d ≦ 5);

(式中，R2表示烴基，各自可相同亦可不同，亦可為直鏈狀、分支狀或者環狀；c1及c2表示0、1、2、3或4之整數，d表示1、2、3、4或5之整數，e表示0、1、2、3或4之整數；c1+e≦4，c2+d≦5；並且G表示上述通式(20)~(23)中之任一者，1分子中至少1個表示上述通式(21)或者上述通式(22))； (wherein R2 represents a hydrocarbon group, and each may be the same or different, and may be linear, branched or cyclic; c1 and c2 represent an integer of 0, 1, 2, 3 or 4, and d represents 1, 2, An integer of 3, 4 or 5, e represents an integer of 0, 1, 2, 3 or 4; c1+e≦4, c2+d≦5; and G represents any of the above formulas (20) to (23) In one case, at least one of the molecules represents the above formula (21) or the above formula (22));

(式中，R2表示烴基，各自可不同亦可相同，亦可為直鏈狀、分支狀或者環狀；c1及c2表示0、1、2、3或4之整數，e表示0、1、2、3或4之整數，f表示1、2、3或4之整數；c1+e≦4，c2+f≦4；G表示上述通式(20)~(23)中之任一者，1分子中至少1個表示上述通式(21)或(22)；Z表示亞甲基、氧、硫、苯、萘、蒽、菲、聯苯、或者上述通式(10)~(19)中之任一者；並且m表示1、2、3……之整數)； (wherein R2 represents a hydrocarbon group, each of which may be different or the same, and may be linear, branched or cyclic; c1 and c2 represent an integer of 0, 1, 2, 3 or 4, and e represents 0, 1. An integer of 2, 3 or 4, f represents an integer of 1, 2, 3 or 4; c1+e≦4, c2+f≦4; G represents any one of the above formulae (20) to (23), At least one of 1 molecules represents the above formula (21) or (22); Z represents methylene, oxygen, sulfur, benzene, naphthalene, anthracene, phenanthrene, biphenyl, or the above formula (10) to (19) Any of; and m represents an integer of 1, 2, 3...);

(式中，R2表示烴基，各自可不同亦可相同，亦可為直鏈狀、分支狀或者環狀；G表示上述通式(20)~(22)中之任一者，1分子中至少1個表示上述通式(21)或(22)；g表示0、1、2、3、4、5或6之整數，h1及h2表示0、1、2、3、4或5之整數，i表示1、2、3、4、5或6之整數；g+h1≦6，i+h2≦6，Z表示亞甲基、氧、硫、苯、萘、蒽、菲、聯苯、或者上述式(10)~(19)中之任一者；並且l表示1、2、3……之整數)。(wherein R2 represents a hydrocarbon group, each of which may be different or the same, and may be linear, branched or cyclic; and G represents any one of the above formulas (20) to (22), and at least one molecule One represents the above formula (21) or (22); g represents an integer of 0, 1, 2, 3, 4, 5 or 6, and h1 and h2 represent an integer of 0, 1, 2, 3, 4 or 5, i represents an integer of 1, 2, 3, 4, 5 or 6; g+h1≦6, i+h2≦6, Z represents methylene, oxygen, sulfur, benzene, naphthalene, anthracene, phenanthrene, biphenyl, or Any one of the above formulas (10) to (19); and l represents an integer of 1, 2, 3, ...).

本發明亦提供一種新穎難燃性環氧樹脂，其含有如請求項1之化合物，該化合物係將以通式(26)所表示之胺化合物、環氧樹脂類、以通式(27)及/或通式(28)之所表示之有機磷化合物類進行反應而獲得。此處，通式(26)~(28)係由下述式表示： The present invention also provides a novel flame retardant epoxy resin comprising the compound of claim 1, which is an amine compound represented by the formula (26), an epoxy resin, and the formula (27) and / or an organophosphorus compound represented by the formula (28) is obtained by a reaction. Here, the general formulae (26) to (28) are represented by the following formula:

(式中，X表示通式(2)~(5)中之任一者；並且n表示1~10之整數)； (wherein, X represents any one of the general formulae (2) to (5); and n represents an integer of 1 to 10);

(式中，j為0或1；並且R3及R4表示氫或烴基，各自可不同亦可相同，亦可為直鏈狀、分支鏈狀或者環狀，或者R3與R4亦可鍵結而形成環狀結構)； (wherein j is 0 or 1; and R3 and R4 represent hydrogen or a hydrocarbon group, each of which may be different or the same, may be linear, branched or cyclic, or R3 and R4 may be bonded to form Ring structure);

(式中，j為0或1；R3及R4表示氫或烴基，各自可相同亦可不同，亦可為直鏈狀、分支鏈狀或者環狀，或者R3與R4亦可鍵結而形成環狀結構；並且B表示苯、萘、蒽、菲以及該等之烴取代體)。(wherein j is 0 or 1; R3 and R4 represent hydrogen or a hydrocarbon group, and each may be the same or different, and may be linear, branched or cyclic, or R3 and R4 may be bonded to form a ring. And B represents benzene, naphthalene, anthracene, phenanthrene and these hydrocarbon substituents).

於上述環氧樹脂中，較好的是環氧當量為200 g/eq~1000 g/eq，含磷率為0.2%~8.0%，且含氮率為0.1%~4.0%。Among the above epoxy resins, it is preferred that the epoxy equivalent is from 200 g/eq to 1000 g/eq, the phosphorus content is from 0.2% to 8.0%, and the nitrogen content is from 0.1% to 4.0%.

本發明亦提供一種新穎難燃性環氧樹脂組合物，其係以上述新穎難燃性環氧樹脂為必要成分，調配硬化劑而形成者。The present invention also provides a novel flame retardant epoxy resin composition which is formed by blending a hardener with the above-mentioned novel flame retardant epoxy resin as an essential component.

本發明亦提供一種環氧樹脂積層板，其係使用上述新穎 難燃性環氧樹脂組合物而獲得者。The invention also provides an epoxy resin laminated board which uses the above novel A flame retardant epoxy resin composition is obtained.

本發明亦提供一種環氧樹脂密封材，其係使用上述新穎難燃性環氧樹脂組合物而獲得者。The present invention also provides an epoxy resin sealing material obtained by using the above novel flame retardant epoxy resin composition.

本發明亦提供一種環氧樹脂澆鑄材，其係使用上述新穎難燃性環氧樹脂組合物而獲得者。The present invention also provides an epoxy resin casting material obtained by using the above novel flame retardant epoxy resin composition.

本發明亦提供一種新穎難燃性環氧樹脂硬化物，其係將上述難燃性環氧樹脂組合物進行硬化而獲得者。The present invention also provides a novel flame retardant epoxy resin cured product obtained by hardening the above flame retardant epoxy resin composition.

上述新穎難燃性環氧樹脂、環氧樹脂組合物及其硬化物，可用作電子電路基板中所使用之銅箔積層板的製造用樹脂組合物或電子零件中所使用之密封材、成形材、澆鑄材、接著劑、電氣絕緣塗料用材料等。The above-mentioned novel flame-retardant epoxy resin, epoxy resin composition, and cured product thereof can be used as a sealing material and a sealing material used in a resin composition for manufacturing a copper foil laminate used in an electronic circuit board or an electronic component. Materials, casting materials, adhesives, materials for electrical insulating coatings, etc.

[發明之效果][Effects of the Invention]

根據與後述實施例及比較例的對比可知，本發明之新穎難燃性環氧樹脂、新穎難燃性環氧樹脂組合物為低含磷率，具有難燃性，且兩者之耐熱性、反應性等物性均優異，因此最適合於尤其以電子電路基板中所使用之銅箔積層板為代表之電氣絕緣材料，適合於電子零件中所使用之密封材、成形材、澆鑄材、接著劑、膜材，進而作為電氣絕緣塗料用材料亦有效。According to comparison with the examples and comparative examples described later, the novel flame retardant epoxy resin and the novel flame retardant epoxy resin composition of the present invention have low phosphorus content, are flame retardant, and have heat resistance therebetween. It is excellent in physical properties such as reactivity, and is therefore most suitable for electrical insulating materials such as copper foil laminates used in electronic circuit boards, and is suitable for sealing materials, molding materials, casting materials, and adhesives used in electronic components. It is also effective as a material for electrical insulating coatings.

對本發明進行詳細說明。以通式(1)所表示之新穎環氧樹脂由於在同一分子內含有磷及氮，故難燃性提高。又，作為氮之導入效果，耐熱性亦提高，反應性亦得到顯著改良。作為合成如此之新穎環氧樹脂之方法，可藉由將以通 式(26)所表示之胺化合物，與以通式(27)及/或通式(28)所表示之含有機磷之化合物、環氧樹脂類進行反應而獲得。The invention will be described in detail. Since the novel epoxy resin represented by the general formula (1) contains phosphorus and nitrogen in the same molecule, the flame retardancy is improved. Moreover, as a nitrogen introduction effect, heat resistance is also improved, and reactivity is also remarkably improved. As a method of synthesizing such a novel epoxy resin, The amine compound represented by the formula (26) is obtained by a reaction with a compound containing an organic phosphorus represented by the formula (27) and/or the formula (28), or an epoxy resin.

作為本發明中所使用的以通式(26)所表示之胺化合物的具體例，(X)為通式(2)之例可列舉：苯胺、苯二胺、甲苯胺、二甲苯胺、二乙基甲苯二胺等。作為(X)為通式(3)、(4)之例，可列舉：二胺基二苯基甲烷、二胺基二苯基乙烷、二胺基二苯基丙烷、二胺基二苯基酮、二胺基二苯基硫醚、二胺基二苯基碸、雙(胺基苯基)茀、二胺基二乙基二甲基二苯基甲烷、二胺基二苯基醚、二胺基苯甲醯苯胺、二胺基聯苯、二甲基二胺基聯苯、聯苯四胺、雙胺基苯基蒽、雙胺基苯氧基苯、雙胺基苯氧基苯基醚、雙胺基苯氧基聯苯、雙胺基苯氧基苯基碸、雙胺基苯氧基苯基丙烷等。作為(X)為通式(5)之例，可列舉二胺基萘等。又，亦可列舉該等之具有烴取代基的化合物或異構物等。又，並不限定於該等，亦可為表示所有以通式(26)所表示之胺化合物者，亦可併用2種以上。Specific examples of the amine compound represented by the formula (26) used in the present invention, and (X) is an example of the formula (2): aniline, phenylenediamine, toluidine, xylylamine, and Ethyl toluene diamine and the like. Examples of the general formula (3) and (4) include diaminodiphenylmethane, diaminodiphenylethane, diaminodiphenylpropane, and diaminodiphenyl. Ketone, diaminodiphenyl sulfide, diaminodiphenylphosphonium, bis(aminophenyl)anthracene, diaminodiethyldimethylmethane, diaminodiphenyl ether , diamino benzilanilide, diaminobiphenyl, dimethyldiamine biphenyl, biphenyltetramine, bisaminophenyl hydrazine, bisaminophenoxybenzene, bisaminophenoxy Phenyl ether, bisaminophenoxybiphenyl, bisaminophenoxyphenyl hydrazine, bisaminophenoxyphenylpropane, and the like. Examples of the general formula (5) (X) include diaminonaphthalene and the like. Further, examples thereof include a compound having a hydrocarbon substituent, an isomer, and the like. Further, the present invention is not limited to these, and any of the amine compounds represented by the formula (26) may be used in combination.

所謂本發明中所使用之以通式(27)所表示之有機磷類，係指可與醌類或縮水甘油基、乙烯基等官能基進行反應之活性氫鍵結於磷原子之有機磷化合物類，具體而言可列舉：HCA(三光化學股份有限公司製造之9,10－二氫－9－側氧基－10－磷雜菲－10－氧化物)、二苯基氧化膦、CPHO(日本化學工業股份有限公司製造之環伸辛基氧化膦)等。The organophosphorus represented by the formula (27) used in the present invention means an organophosphorus compound in which an active hydrogen which is reactive with a functional group such as an anthracene or a glycidyl group or a vinyl group is bonded to a phosphorus atom. Specific examples include HCA (9,10-dihydro-9-sideoxy-10-phosphaphenanthrene-10-oxide manufactured by Sanko Chemical Co., Ltd.), diphenylphosphine oxide, CPHO ( Nippon Chemical Industry Co., Ltd. manufactured by cyclopentylphosphine oxide).

所謂本發明中所使用的以通式(28)所表示之有機磷化合物類，係指以通式(27)所表示之有機磷化合物類之活性氫 與醌類進行反應而獲得的含磷之酚化合物，具體而言可列舉：HCA－HQ(三光化學股份有限公司製造之10－(2,5－二羥基苯基)－10－二氫－9－側氧基－10－磷雜菲－10－氧化物)、10－(2,7－二羥基萘基)－10－二氫－9－側氧基－10－磷雜菲－10－氧化物、PPQ(北興化學工業股份有限公司之二苯基膦醯基對苯二酚)、二苯基膦醯基萘醌、CPHO－HQ(日本化學工業股份有限公司製造之環伸辛基膦醯基－14－苯二醇)、環伸辛基膦醯基－1,4－萘二醇、日本專利特開2002－265562中所揭示之含磷之酚化合物等。於本發明中若為以通式(27)及/或通式(28)所表示者即可，並不限定於該等，又，亦可使用2種以上。The organophosphorus compound represented by the formula (28) used in the present invention means an active hydrogen of an organophosphorus compound represented by the formula (27). Specific examples of the phosphorus-containing phenol compound obtained by the reaction with a hydrazine include HCA-HQ (10-(2,5-dihydroxyphenyl)-10-dihydro-9 manufactured by Sanko Chemical Co., Ltd. - side oxy-10-phosphaphenanthrene-10-oxide), 10-(2,7-dihydroxynaphthyl)-10-dihydro-9-sideoxy-10-phosphaphenanthrene-10-oxidation , PPQ (diphenylphosphonium quinone hydroquinone of Beixing Chemical Industry Co., Ltd.), diphenylphosphonium naphthoquinone, CPHO-HQ (Nippon Chemical Industry Co., Ltd. A phosphine-containing phenol compound disclosed in Japanese Patent Laid-Open No. 2002-265562, and the like. In the present invention, the compound represented by the formula (27) and/or the formula (28) is not limited thereto, and two or more kinds thereof may be used.

將鍵結於磷原子之活性氫與醌類反應而獲得的含磷之酚化合物，係利用例如日本專利特開平5－214068號公報、俄國之普通雜誌(Zh.Obshch.Khim.)的42(11)第2415~2418頁(1972)或者日本專利特開昭60－126293公報、日本專利特開昭61－236787公報、日本專利特開平5－331179號公報中所示之方法進行反應。此時，為了僅取出所生成之多官能的含磷之酚化合物，必須進行純化或再結晶等操作。但是，不僅不需要如使活性氫鍵結於磷原子之有機磷化合物適度殘存般之操作，反而可提高環氧樹脂之含磷率，且可使反應後之環氧樹脂黏度降低。A phosphorus-containing phenol compound obtained by reacting an active hydrogen bonded to a phosphorus atom with a hydrazine is used, for example, in Japanese Patent Laid-Open No. Hei 5-214068, and a general magazine of the Russian Journal (Zh. Obshch. Khim.) 42 ( 11) The reaction is carried out by the method shown in the Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. At this time, in order to take out only the generated polyfunctional phosphorus-containing phenol compound, it is necessary to perform operations such as purification or recrystallization. However, it is not necessary to operate the organic phosphorus compound in which the active hydrogen is bonded to the phosphorus atom as appropriate, and the phosphorus content of the epoxy resin can be increased, and the viscosity of the epoxy resin after the reaction can be lowered.

與以通式(26)所表示之胺化合物、及以通式(27)及/或通式(28)所表示的含有機磷之化合物進行反應的環氧樹脂類較理想的是具有縮水甘油醚基者。The epoxy resin which reacts with the amine compound represented by the formula (26) and the organophosphorus-containing compound represented by the formula (27) and/or the formula (28) preferably has glycidol. Ether based.

具體而言可列舉：Epotohto YDC－1312、ZX－1027(東都化成股份有限公司製造之對苯二酚型環氧樹脂)、ZX－1251(東都化成股份有限公司製造之聯苯酚型環氧樹脂)、Epotohto YD－127、Epotohto YD－128、Epotohto YD－8125、Epotohto YD－825GS、Epotohto YD－011、Epotohto YD－900、Epotohto YD－901(東都化成股份有限公司製造之BPA型環氧樹脂)、Epotohto YDF－170、Epotohto YDF－8170、Epotohto YDF－870GS、Epotohto YDF－2001(東都化成股份有限公司製造之BPF型環氧樹脂)、Epotohto YDPN－638(東都化成股份有限公司製造之苯酚酚醛型環氧樹脂)、Epotohto YDCN－701(東都化成股份有限公司製造之甲酚酚醛型環氧樹脂)、ZX－1201(東都化成股份有限公司製造之雙酚茀型環氧樹脂)、NC－3000(日本化藥股份有限公司製造之聯苯芳烷基酚型環氧樹脂)、EPPN－501H、EPPN－502H(日本化藥股份有限公司製造之多官能環氧樹脂)、ZX－1355(東都化成股份有限公司製造之萘二醇型環氧樹脂)、ESN－155、ESN－185V、ESN－175(東都化成股份有限公司製造之β萘酚芳烷基型環氧樹脂)、ESN－355、ESN－375(東都化成股份有限公司製造之二萘酚芳烷基型環氧樹脂)、ESN－475V、ESN－485(東都化成股份有限公司製造之α萘酚芳烷基型環氧樹脂)等，但並不限定於該等，亦可併用2種以上。Specific examples include Epotohto YDC-1312, ZX-1027 (hydroquinone epoxy resin manufactured by Dongdu Chemical Co., Ltd.), and ZX-1251 (biphenol epoxy resin manufactured by Dongdu Chemical Co., Ltd.) , Epotohto YD-127, Epotohto YD-128, Epotohto YD-8125, Epotohto YD-825GS, Epotohto YD-011, Epotohto YD-900, Epotohto YD-901 (BPA type epoxy resin manufactured by Dongdu Chemical Co., Ltd.), Epotohto YDF-170, Epotohto YDF-8170, Epotohto YDF-870GS, Epotohto YDF-2001 (BPF type epoxy resin manufactured by Dongdu Chemical Co., Ltd.), Epotohto YDPN-638 (phenolic phenolic type ring manufactured by Dongdu Chemical Co., Ltd.) Oxygen resin), Epotohto YDCN-701 (cresol novolac epoxy resin manufactured by Dongdu Chemical Co., Ltd.), ZX-1201 (bisphenol oxime epoxy resin manufactured by Tohto Kasei Co., Ltd.), NC-3000 (Japan) Biphenyl aralkyl phenol epoxy resin manufactured by Chemical Pharmaceutical Co., Ltd.), EPPN-501H, EPPN-502H (multifunctional epoxy resin manufactured by Nippon Kayaku Co., Ltd.), ZX-1355 (East) Naphthalenediol-type epoxy resin manufactured by Huacheng Co., Ltd.), ESN-155, ESN-185V, ESN-175 (beta naphthol aralkyl epoxy resin manufactured by Dongdu Chemical Co., Ltd.), ESN-355, ESN-375 (dinaphthol aralkyl type epoxy resin manufactured by Dongdu Chemical Co., Ltd.), ESN-475V, ESN-485 (α-naphthol aralkyl type epoxy resin manufactured by Dongdu Chemical Co., Ltd.), etc. However, it is not limited to these, and two or more types may be used together.

環氧樹脂類與以通式(26)所表示之胺化合物、以通式(27)及/或通式(28)所表示之含有機磷之化合物的反應可以 公知方法進行，作為反應溫度，可於100℃~200℃、更好的是120℃~180℃下進行攪拌。可使環氧樹脂類與胺化合物、或有機磷化合物反應後，使剩餘之胺化合物、或有機磷化合物進行反應，並且亦可使環氧樹脂類與胺化合物、有機磷化合物同時反應。The reaction of the epoxy resin with the amine compound represented by the general formula (26) and the organic phosphorus-containing compound represented by the general formula (27) and/or the general formula (28) may be used. The reaction is carried out by a known method, and the reaction can be carried out at 100 ° C to 200 ° C, more preferably at 120 ° C to 180 ° C. The epoxy resin may be reacted with an amine compound or an organophosphorus compound to cause a reaction between the remaining amine compound or the organophosphorus compound, and the epoxy resin may be simultaneously reacted with the amine compound or the organophosphorus compound.

反應時間可進行環氧當量之測定而確定。測定時可利用JIS K7236之方法進行測定。藉由環氧樹脂類與胺化合物、含有機磷之化合物的反應，環氧當量變大，可根據與理論環氧當量之比較來確定反應終點。The reaction time can be determined by measuring the epoxy equivalent. The measurement can be carried out by the method of JIS K7236. The reaction of the epoxy resin with the amine compound and the organic phosphorus-containing compound increases the epoxy equivalent, and the reaction end point can be determined based on comparison with the theoretical epoxy equivalent.

又，反應速度慢時，可視需要而使用觸媒來改善生產性。具體而言可使用：苄基二甲基胺等三級胺類；四甲基氯化銨等四級銨鹽類；三苯基膦、三(2,6－二甲氧基苯基)膦等膦類；乙基三苯基溴化鏻等鏻鹽類；2－甲基咪唑、2－乙基－4－甲基咪唑等咪唑類等各種觸媒。Further, when the reaction rate is slow, the catalyst can be used as needed to improve productivity. Specifically, tertiary amines such as benzyldimethylamine; quaternary ammonium salts such as tetramethylammonium chloride; triphenylphosphine and tris(2,6-dimethoxyphenyl)phosphine can be used. Other catalysts such as phosphines; sulfonium salts such as ethyltriphenylphosphonium bromide; and imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole.

反應時亦可在不損及本發明之物性的範圍內同時使用多元酚類等改質劑。作為多元酚類，可列舉：雙酚A、雙酚F、雙酚C、雙酚Z、雙酚S、聯苯酚等二元酚類；苯酚酚醛樹脂、甲酚酚醛樹脂、萘酚酚醛樹脂、萘酚芳烷基樹脂、苯酚芳烷基樹脂等多元酚類。In the reaction, a modifier such as a polyhydric phenol may be simultaneously used in a range that does not impair the physical properties of the present invention. Examples of the polyhydric phenols include dihydric phenols such as bisphenol A, bisphenol F, bisphenol C, bisphenol Z, bisphenol S, and biphenol; phenol novolac resin, cresol novolac resin, and naphthol phenol resin; A polyphenol such as a naphthol aralkyl resin or a phenol aralkyl resin.

作為本發明組合物之硬化劑，可使用以苯酚酚醛樹脂為代表之各種多元酚樹脂類及酸酐類、以DICY(Dicyandiamide，雙氰胺)為代表之胺類、醯肼類、酸性聚酯類等通常所使用的環氧樹脂用硬化劑，該等硬化劑可僅使用1種，亦可使用2種以上。As the curing agent of the composition of the present invention, various polyhydric phenol resins and acid anhydrides represented by phenol novolac resins, amines represented by DICY (Dicyandiamide), anthraquinones, and acidic polyesters can be used. The curing agent for an epoxy resin which is usually used may be used alone or in combination of two or more.

本發明組合物中可視需要而調配三級胺、四級銨鹽、膦類、咪唑類等硬化促進劑。又，亦可視需要而調配無機填充劑或者玻璃布及芳族聚醯胺纖維等強化材、填充材、顏料等。A hardening accelerator such as a tertiary amine, a quaternary ammonium salt, a phosphine or an imidazole may be blended in the composition of the present invention as needed. Further, an inorganic filler, a reinforcing material such as a glass cloth or an aromatic polyamide fiber, a filler, a pigment, or the like may be blended as needed.

對使用本發明之新穎難燃性環氧樹脂而獲得之積層板進行特性評價之結果可知，難燃性高且耐熱性高。由此可知，可獲得不含鹵化物的難燃性環氧樹脂組合物及其硬化物，該環氧樹脂、環氧樹脂組合物及其硬化物可用作電子電路基板中所使用之銅箔積層板的製造用樹脂組合物或電子零件中所使用之密封材、成形材、澆鑄材、接著劑、膜材、電氣絕緣塗料用材料等。As a result of evaluation of the characteristics of the laminate obtained by using the novel flame retardant epoxy resin of the present invention, it was found that the flame retardancy was high and the heat resistance was high. From this, it is understood that a halogen-free flame retardant epoxy resin composition and a cured product thereof can be obtained, and the epoxy resin, the epoxy resin composition, and the cured product thereof can be used as a copper foil used in an electronic circuit substrate. A sealing material, a molding material, a casting material, an adhesive, a film material, a material for electrical insulating coating materials, and the like used in the resin composition for manufacturing a laminate or the electronic component.

實施例Example 一般事項General matters

列舉實施例及比較例來具體說明本發明，但本發明並不限定於該等。積層板係利用以下條件來製作。使用所得之環氧樹脂、硬化劑、視需要之硬化促進劑，製備具有如表1所示之組成的樹脂清漆，使該樹脂清漆含浸於玻璃布(日東紡績股份有限公司製造之WEA7628)中後，於150℃下加熱5分鐘，藉此進行乾燥而獲得預浸體。The present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited thereto. The laminate is produced using the following conditions. A resin varnish having a composition as shown in Table 1 was prepared by using the obtained epoxy resin, a hardener, and, if necessary, a hardening accelerator, and the resin varnish was impregnated into a glass cloth (WEA7628 manufactured by Ridong Textile Co., Ltd.). The mixture was heated at 150 ° C for 5 minutes, thereby being dried to obtain a prepreg.

將該預浸體積層4片，在其兩側配置厚度為35 μm之銅箔(三井金屬礦業股份有限公司製造之3EC－III)而製作積層物。藉由將該積層物於170℃、20 kgf/cm2 之條件下進行70分鐘之加熱加壓成形而製作積層板。難燃性係依據UL(Underwriter Laboratorics)規格進行測定。銅箔剝離強 度係依據JIS C 6481 5.7進行測定。又，硬化物的玻璃轉移溫度係利用SII NanoTechnology股份有限公司製造之Exster6000 DSC以10℃/分鐘之升溫速度進行測定。Four sheets of the prepreg layer were placed on both sides of the copper foil having a thickness of 35 μm (3EC-III manufactured by Mitsui Mining & Mining Co., Ltd.) to prepare a laminate. The laminate was produced by heat and pressure molding at 170 ° C and 20 kgf / cm 2 for 70 minutes. The flame retardancy is measured in accordance with UL (Underwriter Laboratorics) specifications. The copper foil peel strength was measured in accordance with JIS C 6481 5.7. Further, the glass transition temperature of the cured product was measured at a temperature increase rate of 10 ° C /min using an Exster 6000 DSC manufactured by SII NanoTechnology Co., Ltd.

實施例1.Example 1.

於具備攪拌裝置、溫度計、冷卻管、氮氣導入裝置之四口玻璃製可分離式燒瓶中，加入575.5重量份之YDPN－638、250.0重量份之YDF－170、140.0重量份之HCA、34.5重量份之Ethacure 100(Ethyl Corporation製造之二乙基甲苯二胺)，一面導入氮氣一面進行攪拌，進行加熱而溶解。添加0.1重量份之三苯基膦，於150℃下反應4小時。所得環氧樹脂之環氧當量為275.9 g/eq，含磷率為2.0重量%。所得環氧樹脂之GPC、FTIR示於圖1、圖2中。於所得環氧樹脂中以表1中所示之比例添加硬化劑(DICY)及硬化促進劑(2E4MZ)，利用實施例之一般事項之項中所記載之方法進行積層板評價。該積層板評價結果示於表1中。575.5 parts by weight of YDPN-638, 250.0 parts by weight of YDF-170, 140.0 parts by weight of HCA, and 34.5 parts by weight in a four-port separable flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introducing device. Ethacure 100 (diethyltoluenediamine manufactured by Ethyl Corporation) was stirred while introducing nitrogen gas, and heated and dissolved. 0.1 part by weight of triphenylphosphine was added and reacted at 150 ° C for 4 hours. The epoxy resin obtained had an epoxy equivalent of 275.9 g/eq and a phosphorus content of 2.0% by weight. The GPC and FTIR of the obtained epoxy resin are shown in Fig. 1 and Fig. 2 . A hardener (DICY) and a hardening accelerator (2E4MZ) were added to the obtained epoxy resin in the ratio shown in Table 1, and the laminate evaluation was carried out by the method described in the general item of the examples. The evaluation results of this laminate are shown in Table 1.

實施例2.Example 2.

除了在與實施例1相同之裝置中加入300.0重量份之YD－128、500.4重量份之YDPN－638、154.6重量份之HCA、15.0重量份之BPA(新日鐵科學股份有限公司製造之雙酚A)、30.0重量份之Ethacure 100、0.2重量份之三苯基膦以外，進行與實施例1相同之操作。所得環氧樹脂之環氧當量為299.8 g/eq，含磷率為2.2重量%。於所得環氧樹脂中以表1中所示之比例添加硬化劑(DICY)及硬化促進劑(2E4MZ)，利用實施例之一般事項之項中所記載之方法進 行積層板評價。該積層板評價結果示於表1中。In addition to the same apparatus as in Example 1, 300.0 parts by weight of YD-128, 500.4 parts by weight of YDPN-638, 154.6 parts by weight of HCA, and 15.0 parts by weight of BPA (Bisphenol manufactured by Nippon Steel Scientific Co., Ltd.) were added. The same operation as in Example 1 was carried out, except for A), 30.0 parts by weight of Ethacure 100, and 0.2 parts by weight of triphenylphosphine. The epoxy resin obtained had an epoxy equivalent of 299.8 g/eq and a phosphorus content of 2.2% by weight. A hardener (DICY) and a hardening accelerator (2E4MZ) were added to the obtained epoxy resin in the ratio shown in Table 1, and the method described in the general item of the examples was used. Line laminate evaluation. The evaluation results of this laminate are shown in Table 1.

實施例3.Example 3.

除了在與實施例1相同之裝置中加入299.6重量份之YD－128、504.5重量份之YDPN－638、143.7重量份之HCA、16.0重量份之HCA－HQ、15.0重量份之BPA、21.2重量份之Ethacure 100、0.2重量份之三苯基膦以外，進行與實施例1相同之操作。所得環氧樹脂之環氧當量為301.8 g/eq，含磷率為2.2重量%。於所得環氧樹脂中以表1中所示之比例添加硬化劑(DICY)及硬化促進劑(2E4MZ)，利用實施例之一般事項之項中所記載之方法進行積層板評價。該積層板評價結果示於表1中。In addition to the same apparatus as in Example 1, 299.6 parts by weight of YD-128, 504.5 parts by weight of YDPN-638, 143.7 parts by weight of HCA, 16.0 parts by weight of HCA-HQ, 15.0 parts by weight of BPA, and 21.2 parts by weight were added. The same operation as in Example 1 was carried out except that Ethacure 100 and 0.2 parts by weight of triphenylphosphine were used. The epoxy resin obtained had an epoxy equivalent of 301.8 g/eq and a phosphorus content of 2.2% by weight. A hardener (DICY) and a hardening accelerator (2E4MZ) were added to the obtained epoxy resin in the ratio shown in Table 1, and the laminate evaluation was carried out by the method described in the general item of the examples. The evaluation results of this laminate are shown in Table 1.

實施例4.Example 4.

在與實施例1相同之裝置中加入42.0重量份之HCA、98.0重量份之甲苯，進行加熱而溶解。將27.7重量份之1,4－萘醌一面注意反應發熱一面分割投入。反應發熱逐漸消失後進行升溫，於回流溫度下保持2小時而進行反應。添加895.3重量份之ESN－485及35.0重量份之TSB－HB(和歌山精化工業股份有限公司製造之3,3'－二甲基－4,4'－二胺基聯苯)，一面除去溶劑一面使其熔融。調配0.1重量份之三苯基膦，於160℃下反應4小時。所得環氧樹脂之環氧當量為458.3 g/eq，含磷率為0.6重量%。所得環氧樹脂之GPC、FTIR示於圖3、圖4中。於所得環氧樹脂中以表1中所示之比例添加硬化劑(DICY)及硬化促進劑(2E4MZ)，利用實施例之一般事項之項中所記載之方法進行積層板評價。該積 層板評價結果示於表1中。42.0 parts by weight of HCA and 98.0 parts by weight of toluene were added to the same apparatus as in Example 1, and the mixture was heated and dissolved. 27.7 parts by weight of 1,4-naphthoquinone was divided into inputs while paying attention to heat generation. After the reaction heat generation gradually disappeared, the temperature was raised, and the reaction was carried out by maintaining the temperature at the reflux temperature for 2 hours. 895.3 parts by weight of ESN-485 and 35.0 parts by weight of TSB-HB (3,3'-dimethyl-4,4'-diaminobiphenyl manufactured by Wakayama Seiki Co., Ltd.) were added, and the solvent was removed. Melt it on one side. 0.1 part by weight of triphenylphosphine was formulated and reacted at 160 ° C for 4 hours. The epoxy resin obtained had an epoxy equivalent of 458.3 g/eq and a phosphorus content of 0.6% by weight. The GPC and FTIR of the obtained epoxy resin are shown in Fig. 3 and Fig. 4 . A hardener (DICY) and a hardening accelerator (2E4MZ) were added to the obtained epoxy resin in the ratio shown in Table 1, and the laminate evaluation was carried out by the method described in the general item of the examples. The product The evaluation results of the laminates are shown in Table 1.

比較例1.Comparative Example 1.

除了在與實施例1相同之裝置中加入250.0重量份之YDF－170、547.5重量份之YDPN－638、140.0重量份之HCA、62.5重量份之BRG－557(昭和高分子股份有限公司製造之苯酚酚醛樹脂)、0.2重量份之三苯基膦以外，進行與實施例1相同之操作。所得環氧樹脂之環氧當量為297.5 g/eq，含磷率為2.0重量%。於所得環氧樹脂中以表1中所示之比例添加硬化劑(DICY)及硬化促進劑(2E4MZ)，利用實施例之一般事項之項中所記載之方法進行積層板評價。該積層板評價結果示於表1中。In addition to the same apparatus as in Example 1, 250.0 parts by weight of YDF-170, 547.5 parts by weight of YDPN-638, 140.0 parts by weight of HCA, and 62.5 parts by weight of BRG-557 (phenol manufactured by Showa Polymer Co., Ltd.) were added. The same operation as in Example 1 was carried out, except that phenolic resin) and 0.2 parts by weight of triphenylphosphine were used. The epoxy resin obtained had an epoxy equivalent of 297.5 g/eq and a phosphorus content of 2.0% by weight. A hardener (DICY) and a hardening accelerator (2E4MZ) were added to the obtained epoxy resin in the ratio shown in Table 1, and the laminate evaluation was carried out by the method described in the general item of the examples. The evaluation results of this laminate are shown in Table 1.

比較例2.Comparative Example 2.

除了在與實施例1相同之裝置中加入761.0重量份之YDPN－638、209.0重量份之HCA、30.0重量份之BPA、0.2重量份之三苯基膦以外，進行與實施例1相同之操作。所得環氧樹脂之環氧當量為327.4 g/eq，含磷率為3.0重量%。於所得環氧樹脂中以表1中所示之比例添加硬化劑(DICY)及硬化促進劑(2E4MZ)，利用實施例之一般事項之項中所記載之方法進行積層板評價。該積層板評價結果示於表1中。The same operation as in Example 1 was carried out except that 761.0 parts by weight of YDPN-638, 209.0 parts by weight of HCA, 30.0 parts by weight of BPA, and 0.2 parts by weight of triphenylphosphine were added in the same apparatus as in Example 1. The epoxy resin obtained had an epoxy equivalent of 327.4 g/eq and a phosphorus content of 3.0% by weight. A hardener (DICY) and a hardening accelerator (2E4MZ) were added to the obtained epoxy resin in the ratio shown in Table 1, and the laminate evaluation was carried out by the method described in the general item of the examples. The evaluation results of this laminate are shown in Table 1.

比較例3.Comparative Example 3.

在與實施例1相同之裝置中加入42.0重量份之HCA、98.0重量份之甲苯，進行加熱而溶解。將27.7重量份之1,4－萘醌一面注意反應發熱一面分割投入。反應發熱逐漸消失後 進行升溫，於回流溫度下保持2小時而進行反應。添加930.3重量份之ESN－485，一面除去溶劑一面使其熔融。調配0.1重量份之三苯基膦，於160℃下反應4小時。所得環氧樹脂之環氧當量為315.2 g/eq，含磷率為0.6重量%。於所得環氧樹脂中以表1中所示之比例添加硬化劑(DICY)及硬化促進劑(2E4MZ)，利用實施例之一般事項之項中所記載之方法進行積層板評價。該積層板評價結果示於表1中。42.0 parts by weight of HCA and 98.0 parts by weight of toluene were added to the same apparatus as in Example 1, and the mixture was heated and dissolved. 27.7 parts by weight of 1,4-naphthoquinone was divided into inputs while paying attention to heat generation. After the reaction fever gradually disappears The temperature was raised, and the reaction was carried out by maintaining at reflux temperature for 2 hours. 930.3 parts by weight of ESN-485 was added, and the solvent was removed while being removed. 0.1 part by weight of triphenylphosphine was formulated and reacted at 160 ° C for 4 hours. The epoxy resin obtained had an epoxy equivalent of 315.2 g/eq and a phosphorus content of 0.6% by weight. A hardener (DICY) and a hardening accelerator (2E4MZ) were added to the obtained epoxy resin in the ratio shown in Table 1, and the laminate evaluation was carried out by the method described in the general item of the examples. The evaluation results of this laminate are shown in Table 1.

以上，由實施例及比較例之試驗結果、以及表1之比較例中所記載之物性值可知，藉由使用本發明之新穎難燃性環氧樹脂，即使含磷量相等亦可獲得高難燃性，耐熱性亦高。於實施例1與比較例1之比較中，將Ethacure 100進行反應而獲得之本發明環氧樹脂即使含磷率改變，亦具有高難燃性，且根據玻璃轉移溫度之比較，耐熱性亦變高。又，於實施例4與比較例3中，同樣地將TSB－HB進行反應而獲得之本發明環氧樹脂的難燃性、耐熱性均得到顯著改良。As described above, from the test results of the examples and the comparative examples and the physical property values described in the comparative examples of Table 1, it is understood that by using the novel flame retardant epoxy resin of the present invention, even if the phosphorus content is equal, it is difficult to obtain high difficulty. Flammability and heat resistance are also high. In the comparison between Example 1 and Comparative Example 1, the epoxy resin of the present invention obtained by reacting Ethacure 100 has high flame retardancy even if the phosphorus content is changed, and the heat resistance is also changed according to the comparison of the glass transition temperature. high. Further, in Example 4 and Comparative Example 3, the flame retardancy and heat resistance of the epoxy resin of the present invention obtained by reacting TSB-HB in the same manner were remarkably improved.

又，如以所使用之硬化觸媒2E4MZ之調配量可瞭解般，可知本發明之環氧樹脂的反應性亦得到改良。如此，本發明之新穎難燃性環氧樹脂、新穎難燃性環氧樹脂組合物為低含磷率，具有難燃性，且兩者之耐熱性、反應性等物性均優異，因此最適合於尤其以電子電路基板中所使用之銅箔積層板為代表之電氣絕緣材料，且適合於電子零件中所使用之密封材、成形材、澆鑄材、接著劑、膜材，進而亦可用作電氣絕緣塗料用材料。Further, as can be understood from the blending amount of the curing catalyst 2E4MZ used, the reactivity of the epoxy resin of the present invention is also improved. Thus, the novel flame retardant epoxy resin and the novel flame retardant epoxy resin composition of the present invention have low phosphorus content, are flame retardant, and have excellent physical properties such as heat resistance and reactivity, and thus are most suitable. It is an electrical insulating material typified by a copper foil laminate used in an electronic circuit board, and is suitable for a sealing material, a molding material, a casting material, an adhesive, a film used in an electronic component, and can also be used as a film. Materials for electrical insulation coatings.

[產業上之可利用性][Industrial availability]

由本發明獲得之新穎難燃性環氧樹脂、新穎難燃性環氧樹脂組合物為低含磷率且具有難燃性，耐熱性、反應性等物性優異，因此適合用作尤其以電子電路基板中所使用之銅箔積層板為代表之電氣絕緣材料以及電子零件中所使用之密封材、成形材、澆鑄材、接著劑、膜劑，進而適合用作電氣絕緣塗料用材料。The novel flame retardant epoxy resin and the novel flame retardant epoxy resin composition obtained by the present invention have low phosphorus content and are flame retardant, and are excellent in physical properties such as heat resistance and reactivity, and thus are suitable for use as an electronic circuit substrate in particular. The copper foil laminate used in the present invention is an electrical insulating material and a sealing material, a molding material, a casting material, an adhesive, and a film used in an electronic component, and is suitable as a material for electrical insulating coating.

圖1係表示實施例1中所獲得之環氧樹脂的GPC圖。Fig. 1 is a GPC chart showing the epoxy resin obtained in Example 1.

圖2係表示實施例1中所獲得之環氧樹脂的FTIR圖。2 is a FTIR chart showing the epoxy resin obtained in Example 1.

圖3係表示實施例4中所獲得之環氧樹脂的GPC圖。Fig. 3 is a GPC chart showing the epoxy resin obtained in Example 4.

圖4係表示實施例4中所獲得之環氧樹脂的FTIR圖。4 is a FTIR chart showing the epoxy resin obtained in Example 4.

Claims (8)

一種新穎難燃性環氧樹脂，其具有以通式(1)所表示之特定結構且含有氮及磷： (式中，X表示選自由後述通式(2)~(5)所組成群中的至少1種化學結構，Y表示選自由後述通式(6)~(9)所組成群中的至少1種化學結構；並且n表示1~10之整數)： (式中，R1表示烴基，各自可相同亦可不同，亦可為直鏈狀、分支狀或者環狀；並且a表示0、1、2、3、4或5之整數)； (式中，R1表示烴基，各自可相同亦可不同，亦可為直鏈狀、分支狀或者環狀；a表示0、1、2、3、4或5之整數，並且Z表示亞甲基、氧、硫、苯、萘、蒽、菲、聯苯、或者後述通式(10)~(19)中之任一者： 通式(14)： -SO- (14) 通式(17)： -CH2 -(D)-CH2 - (17)(式中，D表示苯、萘、蒽、菲或聯苯)； (式中，q表示0、1、2、3……之整數)； (式中，W表示亞甲基、硫、苯、萘、蒽、菲、聯苯、或者通式(10)~(17)中之任一者))； (式中，R1表示烴基，各自可相同亦可不同，亦可為直鏈狀、分支狀或者環狀；並且a表示0、1、2、3、4或5之整數)； (式中，R1表示烴基，各自可相同亦可不同，亦可為直鏈狀、分支狀或者環狀；並且b表示0、1、2、3、4、5、6或7之整數)； (式中，R2表示烴基，各自可相同亦可不同，亦可為直鏈狀、分支狀或者環狀；c表示0、1、2、3或4之整數； G表示後述通式(20)~(23)中之任一者，1分子中至少1個表示式(21)或者後述通式(22)： (式中，j為0或1；並且R3及R4表示氫或烴基，各自可不同亦可相同，亦可為直鏈狀、分支鏈狀或者環狀，或者R3與R4亦可鍵結而形成環狀結構)； (式中，j為0或1；R3及R4表示氫或烴基，各自可相同亦可不同，亦可為直鏈狀、分支鏈狀或者環狀，或者R3與R4亦可鍵結而形成環狀結構； B表示苯、萘、蒽、菲以及該等之烴取代體；並且Y表示通式(6)~(9)中之任一者)； (式中，r表示0、1、2、3……之整數；E表示苯、萘、蒽、菲、聯苯以及該等之烴取代體、通式(24)或(25)： (式中，R2表示烴基，各自可相同亦可不同，亦可為直鏈狀、分支狀或者環狀；c1及c2表示0、1、2、3或4之整數；Z表示亞甲基、氧、硫、苯、萘、蒽、菲、聯苯、或者通式(10)~(19)中之任一者；並且m表示1、2、3……之整數)； (式中，R2表示烴基，各自可相同亦可不同，亦可為直鏈狀、分支狀或者環狀；h1及h2表示0、1、2、3、4或5之整數；Z表示亞甲基、氧、硫、苯、萘、蒽、菲、聯苯、或者通式(10)~(19)中之任一者；並且l表示1、2、3……之整數)；並且Y表示通式(6)~(9)中之任一者)；d表示1、2、3、4或5之整數；並且c+d≦5)； (式中，R2表示烴基，各自可相同亦可不同，亦可為直鏈狀、分支狀或者環狀；c1及c2表示0、1、2、3或4之整數，d表示1、2、3、4或5之整數， e表示0、1、2、3或4之整數；c1+e≦4，c2+d≦5；並且G表示上述通式(20)~(23)中之任一者，1分子中至少1個表示上述通式(21)或者上述通式(22))； (式中，R2表示烴基，各自可不同亦可相同，亦可為直鏈狀、分支狀或者環狀；c1及c2表示0、1、2、3或4之整數，e表示0、1、2、3或4之整數，f表示1、2、3或4之整數；c1+e≦4，c2+f≦4；G表示上述通式(20)~(23)中之任一者，1分子中至少1個表示上述通式(21)或(22)；Z表示亞甲基、氧、硫、苯、萘、蒽、菲、聯苯、或者上述通式(10)~(19)中之任一者；並且m表示1、2、3……之整數)； (式中，R2表示烴基，各自可相同亦可不同，亦可為直鏈狀、分支狀或者環狀；G表示上述通式(20)~(23)中之任一者，1分子中至少1個表示上述通式(21)或(22)；g表示0、1、2、3、4、5或6之整數，h1及h2表示0、1、2、3、4或5之整數，i表示1、2、3、4、5或6之整數；g+h1≦6，i+h2≦6；Z表示亞甲基、氧、硫、苯、萘、蒽、菲、聯苯、或上述式(10)~(19)中之任一者；並且l表示1、2、3……之整數)。A novel flame retardant epoxy resin having a specific structure represented by the general formula (1) and containing nitrogen and phosphorus: (wherein X represents at least one chemical structure selected from the group consisting of the following general formulae (2) to (5), and Y represents at least one selected from the group consisting of the following general formulae (6) to (9). Chemical structure; and n represents an integer from 1 to 10): (wherein R1 represents a hydrocarbon group, each of which may be the same or different, may be linear, branched or cyclic; and a represents an integer of 0, 1, 2, 3, 4 or 5); (wherein R1 represents a hydrocarbon group, and each may be the same or different, and may be linear, branched or cyclic; a represents an integer of 0, 1, 2, 3, 4 or 5, and Z represents a methylene group; , oxygen, sulfur, benzene, naphthalene, anthracene, phenanthrene, biphenyl, or any of the following formulas (10) to (19): General formula (14): -SO- (14) Formula (17): -CH 2 -(D)-CH 2 - (17) (wherein D represents benzene, naphthalene, anthracene, phenanthrene or biphenyl); (where q represents an integer of 0, 1, 2, 3, ...); (wherein W represents a methylene group, sulfur, benzene, naphthalene, anthracene, phenanthrene, biphenyl, or any one of the formulae (10) to (17)); (wherein R1 represents a hydrocarbon group, each of which may be the same or different, may be linear, branched or cyclic; and a represents an integer of 0, 1, 2, 3, 4 or 5); (wherein R1 represents a hydrocarbon group, each of which may be the same or different, may be linear, branched or cyclic; and b represents an integer of 0, 1, 2, 3, 4, 5, 6 or 7); (wherein R2 represents a hydrocarbon group, and each may be the same or different, and may be linear, branched or cyclic; c represents an integer of 0, 1, 2, 3 or 4; and G represents a formula (20) described later) In any one of (23), at least one of the molecules represents the formula (21) or the following formula (22): (wherein j is 0 or 1; and R3 and R4 represent hydrogen or a hydrocarbon group, each of which may be different or the same, may be linear, branched or cyclic, or R3 and R4 may be bonded to form Ring structure); (wherein j is 0 or 1; R3 and R4 represent hydrogen or a hydrocarbon group, and each may be the same or different, and may be linear, branched or cyclic, or R3 and R4 may be bonded to form a ring. B represents benzene, naphthalene, anthracene, phenanthrene and these hydrocarbon substituents; and Y represents any one of the general formulae (6) to (9); (wherein, r represents an integer of 0, 1, 2, 3, ...; E represents benzene, naphthalene, anthracene, phenanthrene, biphenyl, and the like, or a hydrocarbon substituent of the formula (24) or (25): (wherein R2 represents a hydrocarbon group, and each may be the same or different, and may be linear, branched or cyclic; c1 and c2 represent an integer of 0, 1, 2, 3 or 4; Z represents a methylene group, Oxygen, sulfur, benzene, naphthalene, anthracene, phenanthrene, biphenyl, or any one of the formulae (10) to (19); and m represents an integer of 1, 2, 3...); (wherein R2 represents a hydrocarbon group, and each may be the same or different, and may be linear, branched or cyclic; h1 and h2 represent an integer of 0, 1, 2, 3, 4 or 5; and Z represents a Any of the formulae (10) to (19); and l represents an integer of 1, 2, 3, ...; and Y represents Any one of the general formulae (6) to (9); d represents an integer of 1, 2, 3, 4 or 5; and c + d ≦ 5); (wherein R2 represents a hydrocarbon group, and each may be the same or different, and may be linear, branched or cyclic; c1 and c2 represent an integer of 0, 1, 2, 3 or 4, and d represents 1, 2, An integer of 3, 4 or 5, e represents an integer of 0, 1, 2, 3 or 4; c1+e≦4, c2+d≦5; and G represents any of the above formulas (20) to (23) In one case, at least one of the molecules represents the above formula (21) or the above formula (22)); (wherein R2 represents a hydrocarbon group, each of which may be different or the same, and may be linear, branched or cyclic; c1 and c2 represent an integer of 0, 1, 2, 3 or 4, and e represents 0, 1. An integer of 2, 3 or 4, f represents an integer of 1, 2, 3 or 4; c1+e≦4, c2+f≦4; G represents any one of the above formulae (20) to (23), At least one of 1 molecules represents the above formula (21) or (22); Z represents methylene, oxygen, sulfur, benzene, naphthalene, anthracene, phenanthrene, biphenyl, or the above formula (10) to (19) Any of; and m represents an integer of 1, 2, 3...); (wherein R2 represents a hydrocarbon group, and each may be the same or different, and may be linear, branched or cyclic; and G represents any one of the above formulas (20) to (23), and at least one molecule One represents the above formula (21) or (22); g represents an integer of 0, 1, 2, 3, 4, 5 or 6, and h1 and h2 represent an integer of 0, 1, 2, 3, 4 or 5, i represents an integer of 1, 2, 3, 4, 5 or 6; g+h1≦6, i+h2≦6; Z represents methylene, oxygen, sulfur, benzene, naphthalene, anthracene, phenanthrene, biphenyl, or Any one of the above formulas (10) to (19); and l represents an integer of 1, 2, 3, ...). 一種新穎難燃性環氧樹脂，其含有如請求項1之新穎難燃性環氧樹脂，其中請求項1之新穎難燃性環氧樹脂係將以通式(26)所表示之胺化合物、環氧樹脂類、與以通式(27)及/或通式(28)所表示之有機磷化合物類進行反應而獲得者： (式中，X表示通式(2)~(5)中之任一者；並且n表示1~10之整數)； (式中，j為0或1；並且R3及R4表示氫或烴基，各自可相同亦可不同，亦可為直鏈狀、分支鏈狀或者環狀，或者R3與R4亦可鍵結而形成環狀結構)； (式中，j為0或1；R3及R4表示氫或烴基，各自可不同亦可相同，亦可為直鏈狀、分支鏈狀或者環狀，或者R3與R4亦可鍵結而形成環狀結構；並且 B表示苯、萘、蒽、菲以及該等之烴取代體)。A novel flame retardant epoxy resin containing the novel flame retardant epoxy resin of claim 1, wherein the novel flame retardant epoxy resin of claim 1 is an amine compound represented by the general formula (26), The epoxy resin is obtained by reacting with an organophosphorus compound represented by the general formula (27) and/or the general formula (28): (wherein, X represents any one of the general formulae (2) to (5); and n represents an integer of 1 to 10); (wherein j is 0 or 1; and R3 and R4 represent hydrogen or a hydrocarbon group, each of which may be the same or different, may be linear, branched or cyclic, or R3 and R4 may be bonded to form Ring structure); (wherein j is 0 or 1; R3 and R4 represent hydrogen or a hydrocarbon group, each of which may be different or the same, may be linear, branched or cyclic, or R3 and R4 may be bonded to form a ring. And B represents benzene, naphthalene, anthracene, phenanthrene and these hydrocarbon substituents). 如請求項1或2之新穎難燃性環氧樹脂，其中環氧當量為200g/eq~1000g/eq，含磷率為0.2%~8.0%，且含氮率為0.1%~4.0%。 The novel flame retardant epoxy resin according to claim 1 or 2, wherein the epoxy equivalent is from 200 g/eq to 1000 g/eq, the phosphorus content is from 0.2% to 8.0%, and the nitrogen content is from 0.1% to 4.0%. 一種新穎難燃性環氧樹脂組合物，其係以如請求項1、2或3之新穎難燃性環氧樹脂作為必要成分，調配硬化劑而形成者。 A novel flame retardant epoxy resin composition formed by blending a hardener with a novel flame retardant epoxy resin as claimed in claim 1, 2 or 3. 一種環氧樹脂積層板，其係使用如請求項4之新穎難燃性環氧樹脂組合物而獲得者。 An epoxy resin laminate obtained by using the novel flame retardant epoxy resin composition of claim 4. 一種環氧樹脂密封材，其係使用如請求項4之新穎難燃性環氧樹脂組合物而獲得者。 An epoxy resin sealing material obtained by using the novel flame retardant epoxy resin composition of claim 4. 一種環氧樹脂澆鑄材，其係使用如請求項4之新穎難燃性環氧樹脂組合物而獲得者。 An epoxy resin casting material obtained by using the novel flame retardant epoxy resin composition of claim 4. 一種新穎難燃性環氧樹脂硬化物，其係將如請求項4之難燃性環氧樹脂組合物進行硬化而獲得者。A novel flame retardant epoxy resin cured product obtained by hardening the flame retardant epoxy resin composition of claim 4.
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