1268940 九、發明說明： 【發明所屬之技術領域】 之高:::係有崎環氧樹脂、其製法及含此環崎 【先前技術】 合物（如電路板）、IC封裝材等電氣元件， 寸由方：¾承受因大量電流通過而產生之古埶 耐熱性材料作為彼等元件之基底材料。…、、’ 口此需要 習知係以環氧樹脂如四溴雙盼a作為電氣元件所用 '、、材的基底材料，然其耐熱性不令人滿意。 中華民國專利申請號791 04628號案揭示利 環氧化合物與多昱氰酸旨人 ^扪用夕 基之-卩亏唾咬，(為一種改質環氧樹脂）。此種改 而 樹脂據稱具有優良的耐熱性（高玻璃轉移溫度）。Η =而’前揭中華民國專利案及其相關前案揭示之改質 衣乳树脂皆係以多異氰酸酉旨化合物如甲院二異氛酸酉旨、 aDi)、甲苯：異氰酸g|(TDI)作為反應原料。由於此 亂=酉曰化合物多具有高毒性及高反應性，對人體健康及反 應"又備、儀益皆有不利的影響，因此，蛋需開發以低毒性 原料製造具有高耐熱性能之材料。 本叙明者為解決上述問題，進行深入研究，發現以毒 f較〃氰I酗低之胺基酸酯化合物與縮水甘油醚類環氧樹 脂，2適當的觸媒及常壓或減壓下反應，可製得具有高耐 熱性能之含氮雜環改質樹脂，而解決前述使用異氰酸靡為 5 15633D] 1268940 原料，產生之對人及反應儀器、設傷的 角的不良影響。 【發明内容】 本發明之—目的係提供—種改質環氧樹脂，該 氧樹脂係由胺基曱酸酯化合物與縮次 ^ ^ 應而得者。 甘油_類環氧樹脂反 月之另一目的係提供一種改質環氧樹脂之製法， 係使胺基甲酸酯化合物與縮水甘油醚 ^ 觸媒存在下，於常塵或減屋下進行縮合=树脂在適當的 子ί發明之又一目的係提供-種高耐熱材，特別是電 子电氧領域使用之高耐埶材，竽古斛#α 用以合成本發明改質環氧樹脂 尤其是具有如4 f T ， A — g此基化合物，1268940 IX. Description of the invention: [Technical field to which the invention pertains] High::: Osaki epoxy resin, its production method, and electrical components including this ring-shaped [pre-technical compound (such as circuit board), IC packaging materials, etc. , Into the square: 3⁄4 with the heat-resistant materials generated by the passage of a large amount of current as the base material of their components. ...,, 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The Republic of China Patent Application No. 791 04628 discloses that the epoxy compound and the polyheptanoic acid are used in a singularity, which is a modified epoxy resin. Such a modification is said to have excellent heat resistance (high glass transition temperature). Η = and the 'previously disclosed in the Republic of China patent case and its related pre-existing modified latex resin are based on polyisocyanate compounds such as a hospital, adi), toluene: isocyanic acid g|(TDI) is used as a reaction raw material. Due to the high toxicity and high reactivity of the cockroaches, the cockroach compound has adverse effects on human health and reaction, and therefore, the egg needs to be developed to produce materials with high heat resistance with low toxicity materials. . In order to solve the above problems, the present inventors conducted in-depth research and found that the amino acid ester compound and the glycidyl ether epoxy resin which are lower than the toxic cyanide I oxime, 2 suitable catalyst and under normal pressure or reduced pressure By reacting, a nitrogen-containing heterocyclic modified resin having high heat resistance can be obtained, and the above-mentioned use of cesium isocyanate is 5 15633 D] 1268940 raw material, which has an adverse effect on the angle of humans, reaction equipment, and wounds. SUMMARY OF THE INVENTION The object of the present invention is to provide a modified epoxy resin which is obtained from an amino phthalate compound and a shrinkage. Another purpose of glycerol-based epoxy resin is to provide a modified epoxy resin by condensing the urethane compound with a glycidyl ether catalyst under normal or reduced atmosphere. = Resin in another object of the invention is to provide a high-heat-resistant material, especially a high-resistance material used in the field of electronic electro-oxidation, which is used to synthesize the modified epoxy resin of the present invention, especially Has a compound such as 4 f T , A — g,
Rj'0~c(=〇)-m~R2-m^C(=〇y〇^R] p有式⑴或⑴之化學結構者: ⑷ (式中 示相同或不同 R2 ^ c r ,, a-c6 烷基或 C3_c〇f 烷基； K2不c广c】8伸垸基 個^(：4垸基取代 C3~C8伸環烧基、可任意經1至 伸環烷基或可任咅姑本基或-U-R3-，其中Rs表示^ w表示Ci_C4 =基至4個烧基取代之伸苯基， 式（I)中，以 、普…S〇2—)。 不之Cl-Cg烧基，包含直鏈或支在 15633D] 6 1268940 燒基例如甲基、乙基、正丙基、異丙基、正丁基 基、第二丁基、正戊基、異戊基、新戊基、己基等。 m式（\)中，以R]表示C3_C8環燒基包含例如環丙基、 % 丁基、環戊基、環己基等，較佳為環己基。 式（I)中’以R2表示之CrCis仲焓其4入士 .… 烷基包含直鏈或支鏈 伸烧基，例如：亞甲基、伸乙基、伸丙基、伸丁基、伸戍 基、伸己基、伸庚基、伸辛基、伸壬基、伸癸基、伸十二 烧基、伸十六絲、伸十人烧基等。較佳為^伸烧其 如亞甲基、伸乙基、伸丙基、伸丁基、伸戊基或伸己基t 式（I )中，以L表示之C3-Cs伸環烷基甲包含例如： 伸環丙基、伸環丁基、伸環戊基、伸環己基等，較為 環己基。 Τ 、式（I )中，以R2表示之可任意經！至4個Ci_C4烷基 取代之伸苯基包含例如，伸苯基、單曱基伸笨基、二甲其 伸苯基、單乙基伸苯基等。較佳為伸苯基及單甲基伸苯 式（I )中，以R2表示之-r3-W-r3一中之r3所示之 伸裱烷基的定義，與上述R2所定義者同。 式（I )中，以R2表示之一R3一W—R3—中之R3所示之可任意 經1至4個Cl-C4烷基取代之伸苯基的定義，與上述匕所 定義者同。 式（I)中，以R2表示之-r3-w-r3一中之w所示之Ci—C4 伸k基包含直鏈或支鏈伸烷基，例如亞曱基、伸乙基、伸 丙基、伸丁基等，較佳為亞曱基。 適用於本發明之胺基曱酸酯化合物具體實例包含二官 7 15633D1 1268940 能基之胺基曱酸酯化合物例如：曱烧二胺基曱酸曱酯、甲 烷二胺基曱酸乙酯、曱烷二胺基曱酸丙酯、曱烷二胺基甲 酸丁酯、乙烧-1，2-二胺基曱酸曱酯、乙坑—1，2-二胺基曱 酸乙酯、乙烷-1，2-二胺基曱酸丙酯、乙烷—丨，2一二胺基甲 酸丁酯、丙烷-1，3-二胺基曱酸曱酯、丙烷―丨，3一二胺基曱 酸乙酯、丙烷-1，3-二胺基曱酸丙酯、丙烷Η，3一二胺基曱 酸丁酯、丁烷-1，卜二胺基曱酸曱酯、丁烷―丨，丨一二胺基曱 西文乙S曰、丁少元-1，1 -一胺基曱酸丙酷、丁烧-1，；[一二胺基曱 ί酸丁 S曰、丁烧-1，2-二胺基曱酸曱|旨、丁烧-1，2一二胺基曱 酉义乙酉曰、丁烧-1，2 -二胺基曱酸丙g旨、丁烧_ 1，2 一二胺基曱 酸丁酯、丁烷-1，4-二胺基曱酸曱酯、丁烷一二胺基曱 酸乙酯、丁烷-1，4-二胺基曱酸丙酯、丁烷―丨，4一二胺基曱 酸丁酯、戊烷-1，5-二胺基曱酸曱酯、戊烷-丨，5-二胺基曱 酸乙酯、戊烷-1，5-二胺基曱酸丙酯、戊烷一】，5一二胺基曱 酸丁酯、戊烷-1，5-二胺基甲酸環己酯、2-曱基—丁烷—；[，4一 鲁二胺基曱酸甲酯、2-曱基-丁烷-1，4-二胺基曱酸乙酯、2-曱基-丁烷-1，4-二胺基曱酸丙酯、2-曱基-丁烷-!，4一二胺 基曱酸丁酯、2-曱基-丁烷—1，4-二胺基曱酸環己酯、2, 2-二曱基戊烷-1，5-二胺基曱酸曱酯、2, 2-二曱基戊烷一1，5一 二胺基曱酸乙酯、2, 2-二曱基戊烷-1，5-二胺基曱酸丙酯、 2, 2-二曱基戊垸—1，5一二胺基甲酸丁酯、2, 2-二曱基戊烧 -1，5-一胺基曱酸環己酯、己烧—1，6-二胺基曱酸曱酯、己 烧-1，6-二胺基曱酸乙酯、己烷―丨，6_二胺基.曱酸丙酯、己 坑-1，6-二胺基曱酸丁酯、己烷—丨，6一二胺基曱酸戊酯、己 8 15633D1 1268940 烷-1，6-二胺基曱酸己酯、己烷-丨，6一二胺基甲酸環己酯、 環己:-1，3-一胺基曱酸曱酯、環己烧—1，3一二胺基曱酸乙 酯、環己烷-1，3-二胺基甲酸丙酯、環己烷—丨，3-二胺基甲 酸丁酯、環己烷-1，3-二胺基甲酸戊酯、環己烷-丨，3-二胺 基甲酸己酯、環己烷-1，3-二胺基曱酸環己酯、環己烷-丨，4一 二胺基曱酸曱酯、環己烷—1，4-二胺基甲酸乙酯、環己烷 -1，4-二胺基曱酸丙酯、環己烷一l 4一二胺基甲酸丁酯、環 己烷-1，4-二胺基甲酸戊酯、環己烷一丨，4一二胺基甲酸己 齡酯、環己烷-1，4-二胺基曱酸環己酯、庚烷-二胺基曱 酸曱酯、庚烷-1，7-二胺基甲酸乙酯、庚烷―丨，7一二胺基甲 酸丙酯、庚烷-1，7-二胺基曱酸丁酯、庚烷一〗，7一二胺基甲 酸環己酯、辛烷-1，8-二胺基曱酸甲酯、辛烷— it二胺基 曱酉义乙S曰、辛：)：元-1，8-二胺基曱酸丙酯、辛烷u一二胺基 曱酸丁酯、辛烷〜1，8 —二胺基甲酸環己酯、壬烷-二胺 基曱酸曱酯、壬烷d，9一二胺基曱酸乙酯、壬烷一二胺 φ基曱酸丙酯，壬烷4,9 —二胺基曱酸丁酯、壬烷— i，9一二胺 基曱酸％己酯、癸烷一1，10一二胺基曱酸曱翁、癸烷一^ 1〇一 二胺基曱酸乙酯、癸烷-i，丨0一二胺基曱酸丙酯、癸烷一 i，10一 二胺基曱酸丁酯、癸烷一丨，10—二胺基曱酸環己酯、二環己 基曱烷-4, 4 -一胺基曱酸甲酯、二環己基甲烷一4, 4，一二胺 基曱酸乙酯、二環己基曱烷一4, 4,-二胺基曱酸丙褊、二環 己基曱烷-4, 4 -二胺基曱酸丁酯、二環己基曱烷一4, 4，一二 胺基曱酸戊酯、二環己基曱烷—4, 4，—二胺基曱酸己酯、二 環己基曱烷-4, 4’ -二胺基曱酸環己酯、i —曱基苯—2, 4一二胺 9 15633D1 1268940 基曱酸曱酯、1-曱基苯-2, 4-二胺基甲酸乙酯、卜甲基苯 -2, 4-二胺基甲酸丙脂、i 一曱基苯一2,4 一二胺基甲酸丁"醋、 1-甲基苯-2, 4-二胺基甲酸戊酯、卜甲基苯—2,4一二胺基曱 酸己酉曰、1-甲基苯-2, 4 -二胺基甲酸環己酯、1 —甲基苯一 2, 6一 二胺基曱酸甲-曱基苯一 2,6一二胺基甲酸乙酯、丨—甲基 苯-2, 6-二胺基甲酸丙酯、；[一曱基苯-2,6 —二胺基甲酸丁 酯、卜曱基苯-2, 6-二胺基曱酸戊酯、j 一甲基苯一 2，β-二胺 基曱酸己酯、1-甲基苯一2, 6-二胺基曱酸環己酯、二苯基甲 烷-4, 4’ -二胺基曱酸曱酯、二苯基甲烷一4, 4，一二胺基甲酸 乙S曰一本基甲烧-4, 4 -二胺基曱酸丙酉旨、二苯基甲烧 -4, 4’-二胺基曱酸丁酯、二苯基曱烷一4,4，-二胺基甲酸戊 酯、二苯基曱烷-4, 4’二胺基曱酸己酯、二苯基甲烷一4, 4，一 二胺基曱酸環己酯、二苯基曱烷一2, 4, 一二胺基甲酸甲酯、 二苯基曱烷-2, 4’-二胺基甲酸乙酯、二苯基甲烷—2, 4，二二 胺基曱酸丙酯、二苯基甲烷一2, 4, 一二胺基曱酸丁酯、二笨 基曱烷-2, 4’ -二胺基曱酸戊酯、二苯基曱烷一2, 4，一二胺基 曱酸己酯、二苯基曱烷—2, 4，—二胺基酸環己酯、二笨基^ -4, 4’-二胺基曱酸曱酯、二苯基醚一4,4，一二胺基甲酸乙 酯、二苯基醚-4, 4’-二胺基甲酸丙酯、二苯基醚一4, 4，〜二 胺基曱酸丁酯、二苯基醚—4, 4,—二胺基甲酸戊酯、二笨基 醚-4, 4 -二胺基曱酸己酯、二笨基醚—4, 4，-二胺基甲酸環 己酯、二笨基醚-2, 4’ -二胺基曱酸曱酯、二苯基醚4,〜 二胺基曱酸乙酯、二苯基醚一2, 4，一二胺基曱酸丙酯、二笨 基醚-2, 4’ -二胺基曱酸丁酯、二苯基醚一2,4, 一二胺基曱酸 10 15633D] 1268940 戍能、二笨基醚-2, 4,-二胺基曱酸己酯、二苯基醚-2, 4, -一胺基曱酸環己酯、3, 3,-二甲基二苯基曱烷一 4, 4, -二胺基 甲酸曱酿、3, 3’ -二曱基二苯基曱烷-4, 4, -二胺基甲酸乙 隨、3, 3’ -二曱基二苯基曱烷一4, 4’ 一二胺基曱酸丙酯、3, 3’ 一 —曱基二苯基曱烷-4, 4,-二胺基曱酸丁酯、3, 3, -二甲基二 苯基曱烷-4, 4,-二胺基曱酸戊酯、3, 3,-二曱基二苯基甲烷 4, 4 -二胺基曱酸己酯、3, —二曱基二苯基曱烧—4, 4’ 一 一月女基甲酸環己酯、二苯基亞楓-4, 4, -二胺基甲酸甲酯、 ®二苯基亞楓-4, 4，-二胺基曱酸乙酯、二苯基亞楓一4, 4,-二 月女基曱酸丙跪、二苯基亞楓一4, 4’ -二胺基曱酸丁酯、二苯 基亞楓-4, 4’ -二胺基曱酸戊酯、二苯基亞楓-4, 4，—二胺基 曱酸己酯、二苯基亞楓—4, 4’ -二胺基曱酸環己酯、二苯基 楓4，4 -一胺基曱酸曱ί旨、二苯基楓-4，4’ -二胺基曱酸乙 酉旨、一本基楓- 4，4 ’ -二胺基曱酸丙醋、二苯基楓一 4，4 ’ -二 胺基曱酸丁酯、二苯基楓-4, 4’ -二胺基曱酸戊酯、二苯基 籲楓-4, 4’ -二胺基曱酸己酯、二苯基楓—4, 4,—二胺基甲酸環 己酉旨等；及三官能基之胺基曱酸酉旨例如；三苯基曱烧三胺 基曱酸曱醋、三苯基曱烷三胺基曱酸乙酯、三苯基曱烧三 胺基曱酸丙酯、三苯基曱烷三胺基甲酸丁酯、三苯基甲烧 三胺基曱酸戊酯、三苯基曱烷三胺基曱酸己酯、三苯基甲 烷三胺基曱酸環己酯。 較佳的胺基曱酸酯化合物為例如二苯基曱烧-4，4，-二 胺基曱酸曱酯、二苯基曱燒-4, 4’ -二胺基曱酸乙醋、二苯 基曱烷-4, 4’ -二胺基曱酸丙酯、二笨基曱烷-4, 4,-二胺基 15633D1 11 1268940 曱酸丁酯、丨―曱基苯—2, 4-二胺基曱酸甲酯、i —曱基苯一2, 4-一月女基甲酸乙酯、卜曱基苯-2, 4-二胺基甲酸丙酯、1-曱基 苯2,4〜二胺基曱酸丁酯、卜曱基苯—2,4-二胺基曱酸戊 酯、1 —甲基苯-2,4-二胺基曱酸己酯、卜曱基苯—2, 4-二胺 基甲酸環己酯、卜曱基苯-2, 6-二胺基曱酸曱酯、卜曱基苯 -2, 6-二胺基曱酸乙酯、卜曱基苯-2, β一二胺基甲酸丙酯、 1-曱基苯-2, 6-二胺基曱酸丁酯、卜曱基苯一2, 6一二胺基曱 酸戍酿、；1 一曱基苯—2,6一二胺基曱酸己酯、卜甲基苯—2,6一 二胺基甲酸環己酯。其中又以例如二苯基甲烷—4, 4,-二胺 基曱酸乙酯、1一曱基苯一2, 4一二胺基曱酸乙酯更佳。 。成本發明改質環氧樹脂所用之縮水甘油醚類環氧樹 ，，如：雙酚系二縮水甘油醚、雙酚縮水甘油醚、酚 醚聚縮水甘油醚、多酚系聚縮水甘油醚類等。 雒雙I系二縮水甘油醚包括例如雙酉分A二縮水甘油鍵、 又酉分F二縮水甘油醚、雙酚AD -始p 1、 U—鈿水甘油醚、雙酚S二縮 义甘油醚、四曱基雙酚A二缩波斗、丄 ^ , “百水甘油醚、四曱基雙酚F二Rj'0~c(=〇)-m~R2-m^C(=〇y〇^R] p has the chemical structure of formula (1) or (1): (4) (where the same or different R2 ^ cr ,, a -c6 alkyl or C3_c〇f alkyl; K2 is not c widely c] 8 is extended to a group of ^ (: 4 fluorenyl substituted C3 ~ C8 stretching ring, can be optionally 1 to Cycloalkyl or can be used Or a group of -U-R3-, wherein Rs represents ^w represents a phenyl group substituted with a group of four alkyl groups, and in the formula (I), a group of s... 2〇). a group comprising a straight chain or a branch at 15633D] 6 1268940 alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-pentyl, isopentyl, neopentyl , hexyl, etc. In the formula (\), R] represents a C3_C8 cycloalkyl group, for example, cyclopropyl, % butyl, cyclopentyl, cyclohexyl, etc., preferably cyclohexyl. In the formula (I) R2 represents CrCis 焓 焓 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 Heptyl, octyl, exfoliation, exfoliation, extension of twelve burning base, extension of sixteen filaments, extension of ten people to burn base, etc. Such as methylene, ethyl, propyl, butyl, pentyl or hexyl t. In the formula (I), the C3-Cs cycloalkyl group represented by L contains, for example, a cyclopropyl group. Cyclopentene, cyclopentylene, cyclohexyl, etc., more cyclohexyl. Τ, in formula (I), R2 can be arbitrarily passed! to 4 Ci_C4 alkyl substituted phenyl group includes, for example, Phenyl, monodecyl extended, dimethyl phenyl, monoethyl phenyl, etc., preferably phenyl and monomethyl benzene (I), represented by R2 -r3-W- The definition of the alkylene group represented by r3 in r3 is the same as defined in the above R2. In the formula (I), R2 represents one of R3, W-R3, and R3 is optional. The definition of the phenyl group substituted to four Cl-C4 alkyl groups is the same as defined in the above hydrazine. In the formula (I), the Ci-C4 represented by w in the -r3-w-r3 group represented by R2 The k-group includes a linear or branched alkyl group, such as an anthracenylene group, an ethylidene group, a propyl group, a butyl group, etc., preferably a fluorenylene group. The amino phthalate compound suitable for use in the present invention is specifically Examples include the uranyl group of the 2nd official 7 15633D1 1268940 The ester compound is, for example, decyl diamine decanoate, ethyl methane diamine decanoate, propyl decyl diamine decanoate, butyl decane diamine carboxylate, acetonitrile-1,2-di Ethyl decanoate, Ethyl-1,2-diaminoethyl decanoate, ethane-1,2-diamino decanoate, ethane-hydrazine, butyl 2-diaminocarbamate , propane-1,3-diaminodecyl decanoate, propane-oxime, ethyl 3-diamine decanoate, propane-1,3-diaminopropyl citrate, propane oxime, 3-diamine Based on butyl phthalate, butane-1, bis-diamine decanoate, butane-hydrazine, hydrazine-diamine-based hydrazine, succinyl-1, 1-amino citrate ,丁丁-1,;[monodiamine 曱 酸 曰 曰 丁 丁 丁 丁 丁 丁 丁 丁 丁 丁 丁 丁 丁 丁 丁 丁 -1 -1 -1 -1 -1 -1 , , , , , , , , , , butadiene-1,2-diamino decanoic acid propyl g, butadiene _ 1,2 diamino phthalic acid butyl ester, butane-1,4-diamino decanoic acid decyl ester, butane one Ethyl diamine decanoate, propyl butane-1,4-diamino decanoate, butane-oxime, butyl 4-diamine phthalate, pentane-1,5-diamino decanoic acid Oxime ester, pentane - , 5-diamino decanoic acid ethyl ester, pentane-1,5-diamino decanoic acid propyl ester, pentane one], 5-diamino phthalic acid butyl ester, pentane-1,5-diamine Cyclohexyl carbamate, 2-mercapto-butane-; [, 4-di-diamino decanoic acid methyl ester, 2-mercapto-butane-1,4-diamino decanoic acid ethyl ester, 2- Mercapto-butane-1,4-diamino decanoate, 2-mercapto-butane-!, 4-diamino phthalate, 2-mercapto-butane-1,4- Cyclohexyl diamine decanoate, decyl 2,2-didecylpentane-1,5-diamine decanoate, 2,2-didecylpentane-1,5-diamino decanoic acid Ethyl ester, propyl 2, 2-didecylpentane-1,5-diamino decanoate, 2,2-dimercaptopurine-butyl 1,5-diaminocarbamate, 2, 2- Dimercaptopurine-1,5-monoaminodecanoic acid cyclohexyl ester, hexyl-1,6-diaminodecanoic acid decanoate, hexyl-1,6-diaminoethyl decanoate Alkyl-hydrazine, 6-diamino-based propyl citrate, butyl-1,6-diamino decanoate, hexane-oxime, amylamine hexanoate, hexene 8 15633D1 1268940 -1,6-diaminodecyl decanoate, hexane-oxime, cyclohexyl 6-diaminocarbamate, cyclohexyl:-1,3-monoamine oxime Ethyl ester, cyclohexanol - 1,3 - diamino decanoic acid ethyl ester, cyclohexane - 1,3-diaminocarbamic acid propyl ester, cyclohexane - hydrazine, 3-diaminocarbamic acid butyl ester, ring Hexane-1,3-diaminocarbamic acid amyl ester, cyclohexane-indole, 3-diaminocarbamic acid hexyl ester, cyclohexane-1,3-diaminodecanoic acid cyclohexyl ester, cyclohexane-丨, 4-diamino decyl decanoate, cyclohexane-1,4-diaminocarbamate, cyclohexane-1,4-diamino decanoate, cyclohexane-l-4 Butyl diaminecarboxylate, amyl cyclohexane-1,4-diaminocarbamate, cyclohexane monodecyl, 4-diaminocarbamic acid hexyl ester, cyclohexane-1,4-diamine hydrazine Cyclohexyl acrylate, decyl-diamino decanoate, ethyl heptane-1,7-dicarbamate, heptane- hydrazine, propyl 7-diaminocarbamate, heptane-1,7 - butyl diamine decanoate, heptane y, cyclohexyl succinate, methyl octane-1,8-diamino decanoate, octane - it diamine S曰, 辛:): propyl-1,8-diamino decanoate, octane UD-butyl decanoate, octane~1,8-diaminocarbamic acid cyclohexyl ester, decane -diamine decanoate Decane d,9-diaminoethyl decanoate, decane-diamine propyl decanoate, decane 4,9-diaminodecanoate, decane-i,9-diamino曱% hexyl hexanoate, decane-1,10-diamino phthalic acid decanoate, decane- 〇1 〇-diamino decanoic acid ethyl ester, decane-i, 丨0-diamino decanoic acid Ester, decane-i, 10-diamino phthalic acid butyl acrylate, decane monodecyl, 10-diamino decanoic acid cyclohexyl ester, dicyclohexyl decane-4, 4-amino decanoic acid methyl ester , dicyclohexylmethane-4,4,diaminoethyl decanoate, dicyclohexyldecane-4,4,-diaminophosphonium phthalate, dicyclohexyldecane-4,4-diamine Butyl phthalate, dicyclohexyldecane-4,4,monoammonium decanoate, dicyclohexyldecane-4,4,diaminodecyl decanoate, dicyclohexyldecane- 4, 4'-diamino decanoic acid cyclohexyl ester, i-mercaptobenzene-2,4-diamine 9 15633D1 1268940 decyl decanoate, 1-mercaptobenzene-2, 4-diaminocarbamate Ester, m-methylbenzene-2,4-diaminocarbamate propyl ester, i-mercaptobenzene-2,4-diaminocarbamic acid butyl vinegar, 1-methylbenzene-2,4-diaminocarbamate ester, Methylbenzene-2,4-diaminophosphonium hexanoate, 1-methylbenzene-2,4-dicarbamic acid cyclohexyl ester, 1-methylbenzene-2,6-diamino decanoic acid Methyl-mercaptobenzene-ethyl 2,6-diaminocarbamate, propyl-methylbenzene-2,6-diaminocarbamic acid propyl ester; [monodecylbenzene-2,6-diaminocarbamic acid butyl Ester, decyl benzene-2,6-diaminodecyl decanoate, j-methyl phenyl-2,β-diaminodecyl decanoate, 1-methylphenyl-2,6-diaminodecanoic acid Cyclohexyl ester, diphenylmethane-4,4'-diaminodecyl decanoate, diphenylmethane-4,4,diaminocarbamic acid, ethyl sulfonate, 4-carboyl-4, 4-di Amino phthalic acid, butyl butyl 4-, 4'-diamino phthalate, diphenyl decane, amyl 4,4,-diaminocarboxylate, diphenyl decane -4,4'diamino decanoic acid hexyl ester, diphenylmethane-4,4,diamino decanoic acid cyclohexyl ester, diphenyl decane-2,4, methyl diaminocarbamate, Diphenyldecane-2,4'-diaminocarbamate, diphenylmethane-2,4,didiaminopropyl citrate, diphenylmethane-2,4,monodiamine hydrazine Butyl acrylate, dipyridyl hexane-2, 4' - two Amyl decyl phthalate, diphenyl decane - 2, 4, dimethyl decanoate, diphenyl decane - 2, 4, diamino acid cyclohexyl ester, diphenyl group ^ -4 , 4'-diaminodecyl decanoate, diphenyl ether-4,4,diaminocarbamate, diphenyl ether-4,4'-dicarbamic acid propyl ester, diphenyl ether a 4,4,~diamino phthalic acid butyl ester, diphenyl ether-4,4,-diaminoformic acid pentyl ester, diphenyl ether-4,4-diamino decanoic acid hexyl ester, two stupid Ethyl ether-4,4,-dicarbamic acid cyclohexyl ester, diphenyl ether-2, 4'-diamino decanoic acid decyl ester, diphenyl ether 4, ~ diamino decanoic acid ethyl ester, two Phenyl ether-2,4,monodiamine decanoate, diphenyl ether-2,4'-diamino phthalate, diphenyl ether-2,4, monoamino decanoic acid 10 15633D] 1268940 戍, diphenyl ether-2, 4,-diaminodecyl decanoate, diphenyl ether-2, 4,-amino decanoic acid cyclohexyl ester, 3, 3,-two Methyl diphenyl decane-4,4,-diaminocarboxylic acid broth, 3,3'-dimercaptodiphenyl decane-4,4,-diaminocarbamate, 3, 3' - Dimercaptodiphenyldecane-4,4'-diaminopropyl citrate, 3, 3'-Mercaptodiphenyldecane-4,4,-diaminodecanoic acid butylate, 3,3,-dimethyldiphenylnonane-4,4,-diaminodecanoic acid pentane Ester, 3,3,-dimercaptodiphenylmethane 4,4-diaminodecanoic acid hexyl ester, 3,-didecyldiphenyl fluorene- 4, 4'-one-month female carbamic acid ring Ester, methyl diphenyl sulfoxide-4, 4,-diaminocarbamate, ethyl diphenyl sulfoxide-4, 4,-diamino decanoic acid, diphenyl sulfoxide-4, 4, -February female bismuth phthalate, diphenyl sulfoxide-4, 4'-diamino phthalate, diphenyl sulfite-4, 4'-diaminopentanoic acid, diphenyl Kia Maple-4, 4,-diaminodecyl decanoate, diphenyl sulfite-4,4'-diaminodecanoic acid cyclohexyl ester, diphenyl maple 4,4-amino decanoic acid曱 旨, Diphenyl Maple-4,4'-diamino decanoic acid, a base of Maple - 4,4 '-diamino citrate propyl vinegar, diphenyl maple a 4,4 ' Butyl diamine phthalate, amyl diphenyl maple-4,4'-diaminodecanoate, diphenyl sulfa-4, 4'-diaminodecyl decanoate, diphenyl maple - 4, 4,-diaminocarbamic acid cyclohexanyl; and trifunctional amine hydrazine For example; triphenylsulfonium triamine decanoic acid vinegar, triphenyl decane triamine decanoic acid ethyl ester, triphenyl sulfonium triamine decanoate, triphenyl decane triamine Butyl methacrylate, amyl trimethyl sulfonate, hexyl phenyl trialkyl decanoate, cyclohexyl triphenylmethane triamine decanoate. Preferred amino phthalate compounds are, for example, diphenyl sulfonium-4,4,-diaminodecanoate decanoate, diphenyl sulfonium-4,4'-diamino decanoic acid vinegar, Phenylnonane-4,4'-diamino decanoic acid propyl ester, diphenyl decane-4,4,-diamine 15633D1 11 1268940 butyl phthalate, hydrazine-mercaptobenzene-2, 4- Methyl diamine decanoate, i-mercaptobenzene-2-Ethyl 4-ethyl benzoate, propyl phenyl-2,4-diaminocarbamate, 1-mercaptobenzene 2,4~2 Butyl amino phthalate, amyl benzene-2,4-diamino decanoate, 1-methylbenzene-2,4-diaminodecyl decanoate, diphenyl benzene-2,4-diamino Cyclohexyl formate, decyl benzene-2,6-diamino decanoate, decyl benzene-2,6-diamino decanoate, decyl benzene-2, 1,4-diaminocarbamate, 1 - mercaptobenzene-2,6-diaminodecanoic acid butyl ester, diterpene benzene-2,6-diamino phthalic acid decocting; 1-mercaptobenzene-2,6-diaminodecyl decanoate , m-methylbenzene-2,6-diaminocarbamic acid cyclohexyl ester. Further, for example, ethyl diphenylmethane-4,4,-diamine decanoic acid or ethyl decyl benzene-2,4-diamino decanoic acid is more preferred. . The invention relates to a glycidyl ether epoxy tree used for modifying an epoxy resin, such as bisphenol diglycidyl ether, bisphenol glycidyl ether, phenol ether polyglycidyl ether, polyphenol polyglycidyl ether, etc. .雒 double I diglycidyl ether includes, for example, biguanide A diglycidyl bond, bismuth F diglycidyl ether, bisphenol AD-starting p 1, U-glycidyl ether, bisphenol S diglyceride Ether, tetradecyl bisphenol A double shrinking bucket, 丄^, "Hexyl glyceryl ether, tetradecyl bisphenol F II
备百水甘油醚、四曱基雙酚AD二缩皮斗、丄 一 、嗰水甘油醚、四甲基雙酚S 一鈿水甘油醚、四溴雙酚A二缩7|c # 、、伯水甘油醚、四氯雙酚A二 对百水甘油_。 雙酚縮水甘油醚包括例如· / Q ,, m / · 4,4〜雙酚縮水甘油醚、 1 二曱基—4, 4’-雙酚縮水甘％ 〇 ,^ 甘油喊、3,3，，5, 5，-四曱基 4，4 -雙酿縮水甘油謎。 酚醛聚縮水甘油醚包括你u 田 ·恥曱S筌聚縮水甘油醚、 曱既曱S筌聚縮水甘油醚、雙|分A田 "A—曱醛聚縮水甘油醚、四溴 ]2 15633D1 1268940 雙驗A〜甲醛聚縮水甘油醚。 多盼系聚縮水甘油_，’ k、 甲々取 包括例如：參（苯基-4- 曱烷忒縮水甘油醚、參（笨基 二土） 來（茉其/1〜苴、石取 工土）乙烧聚縮水甘油醚、 ^、本基-4 -經基）丙力元聚縮欢斗、丄;^ 栌取… ^甘油趟、參（苯基-4-羥基）丁 少兀來鈿水甘油醚、參（苯基 t土）丁 油驗、參（苯基_3, 5-二甲基其—經基）甲燒聚縮水甘 ( ^ M: 、 《工土）甲丈元聚縮水甘油ii|、 肆“基+經基)乙烧聚縮水甘油，肆(苯基_3,5二 一4-羥基）乙烷聚縮水甘油醚等。 一丁土 本發明使用之縮水甘油醚類環氧樹脂中，較佳 能基的雙酚A二縮水甘油醚、四溴雙 ”、、又 一 夫又购A —备目水甘油醚及 二B能基的參（苯基-4-經基）f烧聚縮水甘油_以及四官 能基的肆（笨基-4-羥基）乙烷聚縮水甘油醚。 合成本發明改質樹脂時，該等縮水甘油醚類氧庐 可以單獨使用或混合兩種或多種合併使甩。/ 曰 製造本發明改質環氧樹脂時，胺基曱酸酯化合物之用 量，佔胺基曱酸酯化合物與縮水甘油醚類環氧樹脂總重之 5至95重量百分比（重量％)，較佳為10至9〇重量^更佳 為10至80重量％，特佳為15至60重量％。 製造本發明改質環氧樹脂時，縮水甘油醚類環氧樹脂 之用量，佔胺基酸酯化合物與縮水甘油醚類環氧樹脂脂總 重之95至5重量％，較佳90至10重量％，更佳9〇至2〇 重量％，特佳85至40重量％。 本發明縮合反應需於適宜的觸媒存在下進行。 適用於製造本發明改質環氧樹脂的觸媒有三級胺、三 15633D1 13 1268940 級膦、季錄鹽、季鐫鹽、二翁 唾化合物等。 4化蝴的錯合鹽、經化物、畔 三級胺例如三乙基胺、三丁基胺、二甲基甲胺 乙知、蒼（N，N-二曱基一胺基曱基） 基紛等； ν5ν-_ψ^-,^ψ 三級膦例如三苯基膦等； 季=例如氯化四甲基銨、溴化四甲基錢/项化四甲 ，三乙基苯甲基録等； —乙基本甲基叙、硬化 季鱗鹽例如氯化四丁基鱗、漠化四丁基鱗、破化 =二基鱗乙酸鹽乙酸錯合物、氯化四苯基鎳心 四本絲、碘化四苯基鱗、氯化乙基 三苯基鱗、碘化乙美二絮其减 ^ 牛/吴化乙基 錯合物、乙美-策二:ά '乙基三苯基鱗乙酸鹽乙酸 土二本基釦乙酸鹽磷酸錯合物、氯化丙基 基鎮、溴化丙某：r贫装乂半 ▲十 二裳其_、、自 叙、碘化丙基三苯基鱗，氯化丁基 > ^ 土 Η溴化丁基三苯基鱗、碘化丁基三苯基鱗等.又 :::合物例如:2_甲基，唾、2_苯基他 、 十一石反基咪唑、2〜十七碳基咪唑等。 ^述用方;合成本發明改質環氧樹脂的觸媒中，唑 化3物與季鱗鹽為較佳；特別是2_甲基味哇、2_苯基味 唑、乙基二苯基鱗乙酸鹽乙酸錯合物、溴化 該等觸媒可α 口田口供，土 ^Sh 用。 “早獨使用，或者混合兩種或多種一併使 成本k明改質環氧樹脂之縮合反應中之觸媒用量係 I5633D] 14 1268940 相對於胺基曱酸酯化合物與縮水甘油醚類環氧樹脂總重之 50至5000ppm，較佳為1〇〇至30000ppn]，更佳為2⑽至 l〇〇〇〇Ppm，最佳為500至2000ppm。若觸媒添加量太大， 雖可細短反應時間，但易生成副產物，且對往後的應用如 就電路板層合體而言，會對電氣性質、抗濕性、吸水性質 產生不良的影響；若觸媒添加量太小，反應速度過慢，較 無效率。 適於進行本發明改質環氧樹脂縮合反應的反應溫度j 2J)至30CTC，較佳為50至25〇。〇，更佳為1〇〇至22〇。〔， 最佳為⑽至2_。溫度過高易產生副反應且較難控制 心心度而且可此促使樹脂劣化的速度增快；溫度過伯 除效：差外，所產生的樹脂特性較難符合高溫使用的需求 衣造本發明改賀環氧樹脂日寺，較好係於常壓或減塵 合反應。但由於胺基甲酸g旨化合物和縮水甘油鍵類 fΜ脂反應時會產生有機醇類，為使反應趨向正反應方 向進仃，選擇於減壓下進行反應，或先於㈣下進行反應 ^減壓时有_則㈣的反應步雜佳。適於财 :應：壓力為。至76〇毫米汞柱’較佳為1〇至7 : 水柱’更佳為50至600毫米汞柱。 水 含氣Ϊ ΪI方法製得之改質環氧樹脂係帶有—NHC=0之 構者，此種結構賦與所得環氧樹脂 命 … 支叮使用方；咼耐熱材料之領域，特別是 %上电乳領域使用之高耐熱材，如電氣層合體、ΙΓ私士 材、高耐熱粉體塗料等。 ° 子裝 15633D1 15 1268940 當使用本發明改f環氧樹脂 合體時，係使本發明改所 〃、同、…、材例如電氣層 乃改貝％乳樹脂與適宜的、夭 劑、觸媒、溶劑等摻入 〜、、加劑如硬化 卞杉口，依習知方法製得所 適於與本發明改所 > 阿耐熱材。 文貝3展氧樹脂摻合形成高+ 劑可包含胺類、多σ 、’、、材的硬化 '貞竭類及㈣類化合物等。1 適宜的胺類包含例如：二氛基甲 二胺 基甲烷； 一胺基二笨 適宜的多酚類包含例如:參(苯基_4_Preparation of hexahydroglyceryl ether, tetradecyl bisphenol AD double shrinking bucket, hydrazine, hydrazine glyceryl ether, tetramethyl bisphenol S monohydrhydryl glyceryl ether, tetrabromobisphenol A bis 7|c # , Primary glycidyl ether, tetrachlorobisphenol A two pairs of water glycerol _. Bisphenol glycidyl ethers include, for example, · / Q , , m / · 4,4~bisphenol glycidyl ether, 1 dimercapto-4, 4'-bisphenol glycosaminoglycan, ^ glycerol shout, 3, 3, , 5, 5, - tetradecyl 4, 4 - double brewed glycidol mystery. Phenolic polyglycidyl ether includes you u Tian·Shame S曱 polyglycidyl ether, 曱 曱 S筌 polyglycidyl ether, bis | A field " A-furfural polyglycidyl ether, tetrabromo] 2 15633D1 1268940 Double test A ~ formaldehyde polyglycidyl ether. Poly-glycidyl _, 'k, formazan, for example: ginseng (phenyl-4-decane 忒 glycidyl ether, ginseng (stupid base soil) to (Muqi / 1 ~ 苴, stone to work Earth) Ethylene-fired polyglycidyl ether, ^, Benthyl-4 - thiol-based propylene condensate, 丄; ^ 取取... ^Glycerol 趟, ginseng (phenyl-4-hydroxy) 丁少兀Glycidyl ether, ginseng (phenyl t-soil) butan oil test, ginseng (phenyl_3, 5-dimethyl-----)---------------------------- Polyglycidol ii|, 肆 "based + trans group" Ethylene polyglycidyl, hydrazine (phenyl_3,5 di- 4-hydroxy) ethane polyglycidyl ether, etc. Among the ether epoxy resins, a preferred energy group of bisphenol A diglycidyl ether, tetrabromobis", and a further purchase of A-formed glycidyl ether and a di-B-based group (phenyl-4-menu) Base) f burnt polyglycidol - and a tetrafunctional fluorene (stupyl-4-hydroxy) ethane polyglycidyl ether. In the synthesis of the modified resin of the present invention, the glycidyl ether-based oxime may be used singly or in combination of two or more kinds. / 曰 When manufacturing the modified epoxy resin of the present invention, the amount of the amino phthalate compound is 5 to 95% by weight (% by weight) based on the total weight of the amino phthalate compound and the glycidyl ether epoxy resin. It is preferably 10 to 9 Å by weight, more preferably 10 to 80% by weight, particularly preferably 15 to 60% by weight. When the modified epoxy resin of the present invention is produced, the amount of the glycidyl ether epoxy resin is 95 to 5% by weight, preferably 90 to 10% by weight based on the total weight of the amino acid ester compound and the glycidyl ether epoxy resin grease. %, more preferably 9 to 2% by weight, particularly preferably 85 to 40% by weight. The condensation reaction of the present invention needs to be carried out in the presence of a suitable catalyst. Catalysts suitable for use in the manufacture of the modified epoxy resin of the present invention are tertiary amines, three 15633D1 13 1268940 grade phosphines, quarterly salts, quaternary phosphonium salts, diterpenoids, and the like. a compound of a butterfly, a mesogen, a tertiary amine such as triethylamine, tributylamine, dimethylformamide, and argon (N,N-didecylmonoaminoindenyl) Ν5ν-_ψ^-,^ψ tertiary phosphines such as triphenylphosphine; etc.; season = for example tetramethylammonium chloride, tetramethyl bromide / thiolated tetramethyl, triethyl benzyl Etc.; - ethyl methyl sulphate, hardened quaternary salt such as tetrabutyl sulphate, desertified tetrabutyl sulphate, broken = dibasic acetate acetate complex, tetraphenyl nickel tetrachloride Silk, iodinated tetraphenyl sulphate, ethyl triphenyl sulphate chloride, iodine acetonitrile bismuth reduction ^ bovine / Wuhua ethyl complex, yum-technical: ά 'ethyl triphenyl sulphate Saline-acetic acid soil, two-base deacetate phosphate complex, propyl chloride-based, brominated, propyl: r-poor 乂 half ▲ twelve-strip _, self-synthesis, iodized propyl triphenyl scale, Chlorinated butyl > ^ Η Η butyl triphenyl sulphate, iodide butyl triphenyl squam, etc. Also::: compound: for example: 2 - methyl, saliva, 2 - phenyl he, ten One stone anti-imidazole, 2 to heptacarbonylimidazole, and the like. In the catalyst for synthesizing the modified epoxy resin of the present invention, the azole compound 3 and the quaternary salt are preferred; in particular, 2-methyl odor, 2-phenyl benzoxazole, ethyl diphenyl The ketone acetate acetate complex and the bromination of these catalysts can be supplied by the mouth of the mouth of the mouth of the mouth. "The amount of catalyst used in the condensation reaction of two or more types and the cost of modifying the epoxy resin is I5633D] 14 1268940 Relative to the amino phthalate compound and the glycidyl ether epoxy The total weight of the resin is from 50 to 5000 ppm, preferably from 1 to 30,000 ppn, more preferably from 2 (10) to 10 pm Ppm, most preferably from 500 to 2000 ppm. If the amount of the catalyst added is too large, the reaction may be short. Time, but easy to produce by-products, and for subsequent applications, such as circuit board laminates, will have adverse effects on electrical properties, moisture resistance, water absorption properties; if the amount of catalyst added is too small, the reaction rate is too high Slow, less efficient. The reaction temperature suitable for the condensation reaction of the modified epoxy resin of the present invention is from 2 2) to 30 CTC, preferably from 50 to 25 Torr, more preferably from 1 Torr to 22 Torr. Jiawei (10) to 2_. Excessive temperature is easy to produce side reactions and it is difficult to control the center of gravity and can accelerate the deterioration of the resin. Demand clothing, the invention is to congratulate the epoxy temple, better system Atmospheric pressure or dust reduction reaction, but the organic acid is generated when the amino carboxylic acid gram compound and the glycidyl bond type f oxime react, and the reaction is carried out under reduced pressure in order to make the reaction progress toward the positive reaction direction, or The reaction is carried out before (4). When the pressure is reduced, there are _ (4). The reaction step is good. Suitable for: should be: pressure: to 76 〇 mm Hg 'preferably 1 〇 to 7: water column 'more preferably 50 Up to 600 mm Hg. Water contains gas Ϊ The modified epoxy resin obtained by the ΪI method has a structure of -NHC=0, and this structure gives the obtained epoxy resin... In the field, especially high-heat-resistant materials used in the field of electric-powered milk, such as electric laminates, smugglers, high-heat-resistant powder coatings, etc. ° Sub-assembly 15633D1 15 1268940 When using the present invention to modify the epoxy resin combination , the invention is modified, the same, ..., the electrical layer, such as the electrical layer is modified, the milk resin and the appropriate, bismuth, catalyst, solvent, etc. are mixed into ~, and additives such as hardened cedar mouth, according to It is known that the method is suitable for the invention and the heat-resistant material. The blending to form a high+ agent may include amines, poly-σ, ', hardening's of the materials, and (4) compounds, etc. 1 Suitable amines include, for example, diarylmethyldiaminomethane; Two stupid suitable polyphenols include, for example: ginseng (phenyl_4_
基-4-羥基）乙烷、表（装 ^ ^ U 丁烧、參〔笼其-/ )丙炫、參（苯基―4—經基: 一 土曱基一4 一羥基）甲烷、參（苯基-3 5_ 一甲 一 _(本基-4-羥基）乙烷、肆（苯基—3,5 — 一 r暴-4-羥基）乙烷； 過且的齡酸類包含例如：齡甲·縮合體、甲齡甲路縮 & 又鉍A曱路指合體、四溴雙齡A-曱醛縮合體等。 上述硬化劑的添加量係依所用硬化劑中的總反應活性 鲁氣當量與本發明改質環氧樹脂之總環氧當量而定。-般而 言’所硬化劑之總反應活似當量為本發㈣質環氧樹 脂之總環氧當量的20至95%，較佳為4〇至9〇%，更佳為 50 至 90〇/〇 〇 適於與本發明改質環氧樹脂一起摻合形成高耐熱材之 觸媒例如二級胺、三級膦、季鎮鹽及咪唑化合物。 彼等觸媒中適合的三級胺例如三乙基胺、三丁基胺、 一曱基月女乙醇、參（N，N一二曱基-胺基曱基）酚、N，N-二曱基 -胺基曱基酚等； 16 15633D] 1268940 適合的三級膦例如三苯基膦等； 適合的季錢鹽例如氯化四甲基銨、漠化四甲基錄、蛾 化四:基錄、氯化三乙基苯甲基錢、演化三乙基苯曱基錄、 峨化三乙基苯甲基銨等； 適合的季鎸鹽例如氯化四丁基鱗、溴化四丁基鎸、碘 皇丁基鱗、四丁基鱗乙酸鹽乙酸錯合物、氯化四苯基鱗、 /乙匕鱗、破化四苯基鱗、氯化乙基三苯基鎮、溴化 乙鱗、硬化!：基三苯基鱗、乙基三苯基鱗乙酸鹽 —、乙基二苯基鱗乙酸鹽鱗酸錯合物、氯化丙基 3 = Γ基三苯基鱗观丙基三苯基鱗、氯化 ^二本基_、漠化丁基三苯基鱗、峨化丁基三苯基鱗等； 已卷4-甲基口米哇、2一 + 一山| 上H , 十—反基味唑、2~十七碳基咪唑等。 处可與本發明改質環氧樹脂— 二苯美护 土本土1科乙酉夂鹽乙酸錯合物、溴化丁美 用。 ^^獨使用或混合兩種或多種合併使 以本發明改質環氧樹脂製造 時，所用之觸媒量，係㈣用改_^2電氣層合物 量計之0 005 貝衣虱树月曰與硬化劑總重 更佳為。.1=量%’較佳為。，至“㈣， 改貝每乳樹脂製備電氣層合物時，通常係使 15633D1 17 1268940 = :::質環氧樹腊與前述硬化劑、觸媒及適當的溶劑 作匕合成清漆的型式格y 、、天Λ旦广 仃彳呆作，為使清漆便於操作，觸媒的 ^ 30 ^ time^ 環氧樹脂、硬化凝日咖在使本發卿 量清漆於⑽下摻混成清漆後，取少 硬化反應時間，m m㈣添加量太大，雖可縮短 生不良的影響;若觸上1對硬化反惠… 效率。 1媒添加！太小，反應速度過慢，較無 之溶劑二::1=:環:樹脂之清漆的黏度可藉所添加 ,,、，。正、&之溶劑例如笨類、酮類、質子性、、容 :二醚類或醋類。其中，適合的苯類例如：曱苯、二甲苯。 二==:丙酮、甲基乙基酮、曱基異咖 口的貝子性喻丨如:Ν，Ν_二甲基 醯胺、二甲基亞楓。適合嶋例：甲7:基二 彻。適合的_、例如：乙酸乙ι 係將含改質環氧樹脂清、、夫 /、 s曰。較好 (黏度係依-二5— -二環氧樹脂製造高耐熱材，如^觀 一，：，由—般業界已知之方法進行。例如: 發明改質Μ樹脂之清漆含浸玻璃纖維布，、人: ;璃纖維布加熱乾燥，使之成為預浸潰體，再使 體興其他層合材料（如此種預浸潰體或含仙、/又/貝 浸潰體）互相層合，綱，更可與1购銅m 156331)1 18 1268940 合，並於加壓加熱下，使彼等層合材料之組合物硬化，得 電氣層合體。 上述硬化反應所用之壓力範圍係5至1〇〇公斤7厘米 2又，上述硬化反應所的溫度範圍宜於20至350°C，較 佳為50至30(TC，更佳為1〇〇至25(rc，特佳為12〇至22〇 C^。溫度過高易產生副反應，且較難控制反應速度，而且 可能促使樹脂劣化的速度增快；溫度過低除效率差外，所 產生的樹脂特性較難符合高溫使用的需求。 藝 下文將以實施例進一步說明本發明，惟該等貧例僅係 用以e兄明’熟習技藝之人士應悉知本發明範疇不受彼等 例所限。' 百'先對本案實例及比較例中所用縮水甘油醚類環氧樹 脂(即下文之環氧樹脂A、B、c、D)、胺基曱酸酯化合物、 硬化劑及觸媒進行說明。其中所用之環氧樹脂m為市 售電氣層合物中所慣用之環氧樹脂。 Φ 代表長春人造樹脂廠所生產，以商品名 BE188EL出售之雙酉分A二縮水甘油_，其環氧當量為咖 95克/田里，所含可水解氣為以下，黏度11000 至 1 5000cps/25°C。 代表長春人造樹脂廠所生產，以商品名 BEB350出售之四漠雙紛A二縮水甘油喊，其環氧當量為 340-380克/重量，漠含量為46-49.5重量％。 代表長春人造樹脂廠所生產，以商品名 ΒΕΒ530Α80出隹之、、鱼雔、Λ α之四/臭雙酚Α二縮水甘油醚，其環氧當量 19 15633D] 1268940 為430至450克/當量，溴含量為18· 5至20. 5重量％ 。 里_墓，樹脂i代表長春人造樹脂廠所生產，以商品名 ΒΕΒ526Α80出售之四溴雙酚a二縮水甘油醚，其環氧當量 為410至430克/重量，溴含量為19· 〇至21· 〇重量％ 。 腿1代表二苯基曱烷-4, 4，-二胺基曱酸乙酯。 星<匕觜11 A代表春人造樹脂廠所生產，以商品名pfi 1 2〇h 出售之酚-曱醛縮合樹脂。 毯-化劑L代表二氰基二醯胺〇 • 里差Jl_代表2-苯基咪唑。 觸媒B代表2-甲基咪峻。 里娣C—代表2-曱基-4苯基咪唑。 盤_·媒D-代表溴化丁基三苯基鱗。 有關本文中所用的環氧當量（EEW)、清漆黏度及膠凝時 間、改夤環氧樹脂之固含量，以及電氣層合物的耐熱性係 依下述測試法測定者·· φ 1 · EEW ·使環氧樹脂溶解於氯苯：氯仿=1 : 1的溶劑中， • 用HBr/冰醋酸進行滴定，依ASTM D1 652的方法測得，其 • 中指示劑為結晶紫。 2 ·黏度：將含有改質環氧樹脂之清漆置於2 5 恆溫槽 中4小時，用布魯克菲爾德（Br〇〇kf ieid)黏度計於25。〇測 量者。 3·膠凝時間（Geiiing Time):依 JISK-7233 的方法， 使含環氧樹脂的请漆樣品50克與15· 24克混合溶劑[由二 氰基二酸胺（10· 〇〇克）、2-曱基咪唑（〇· 54克）與曱基纖維 20 15633D1 1268940 素（14】· 83克）混合而得]混合， 熱板滴7滴，60秒後開始以尖的木棒=鐘於⑽的 時間(由最初開始滴至熱板上起算)：糊量樹脂膠凝之 品，=二取之含本發明改質環一 ^ 重量百分比。 .^，、性.將所得之電氣層合物浸置 中，_爽甘卜音』r，1 夏瓦Z⑽C 4干錫槽 示通過。 ）τ間。超過180秒者表 【實施方式】 (Έ：)含氮雜環改質環氧樹脂之製備 气气乂備有：熱為Μ度控制器、電動攪拌機、攪拌磁石、 …口、熱電偶、冷凝器及加料口之五頸瓶反應 ^ 5 4(EEW)=1^] ^ b(68〇克，腿367)與_24G克，通人氮氣並將 =職’待環氧樹η、環氧樹脂B與祕完全炫解後力， 〃空使以上原料乾燥，然後再通人氮氣，重複上 兩次。加入觸媒A(1.4克)，使混合物於氮氣圍下援 時加熱至I抓，並保持此溫度約1G分鐘。待發現有液㉗ 顧出後’將反應爸_，並經冷凝收集該鶴出4匆；持續^ 壓升溫至16(TC ’並於此溫度保持3小時，待鶴出物不再 增加，即反應完成。收集反應爸中之殘質，得常溫下呈固 態之本發明改質環氧樹脂，重1 632克，環氧當量為⑽， 以FTIR(傳里葉轉換遠紅外線光譜儀）分析，發現於 15633D1 21 1268940 有含氮雜環結構_NH_c(=〇)_的特性吸收。 士恭，了使所得改質垓氧樹脂更易於操作製得高耐熱材， ^電氣層合物，將曱基乙基酉同546克緩緩加入反應爸底 戶顺質環氧樹脂溶解，並授拌均勾。所得含此改 衣氧树知之，谷液，為樹脂w。經分析，測得固含量為Μ μ 重量％。 · 鲁Α β重複實施例1之操作，但以觸媒B(1. 4克）取代觸媒 戸j寻常溫下為固體，軟化點為73 9t，重⑽克之改質 Z樹脂’環氧當量為娜，以咖分析，發現於⑺时】 :含氮雜環結構普C(=〇)_的特性吸收。如實施例I ^將甲基乙基_ 53〇克緩緩加入反應爸中，使所得改質 溶解，並麟均勾。所得含此改質環氧樹脂之溶 "”、、树脂U。經分析，測得固含量為74. 57重量％ 。 重複實施例1之操作，但環氧樹脂Α、β 分別改為肌4克、639.〇克及24〇3克 ^化點為65.rc，重1541克之改質環氧樹月旨，環 :置為376.5，以聰分析，發現於丨备^ 二 刪，浙的特性吸收。如實施^ =、51U克緩緩加人反應蒼中，使所得改質環氧樹脂溶 :=斤料均勾。所得含此改f環氧樹脂之溶液為樹脂V。 、，工刀析’測得固含量為74· 67重量％ 。 156331)] 22 1268940 八重棱實施例1之操作，但環氧樹脂a、B及MDU的重量 =別改為654.9克、627. 3克及270.0克。得常溫下為固 去旦软化點為86. 5〇C，重1478克之改質環氧樹脂，環氧 二里為436’以FTIR分析，發現於1 755〇^處有含氮雜環 二構-NH-C(=0)-的特性吸收。如實施例i般，將曱基乙基 酮的3克緩緩加入反應釜中，使所得改質環氧樹脂溶解， =攪拌均勻。所得含此改質環氧樹脂之溶液為樹脂X。經 刀析’測得固含量為75· 02重量％ 。 重複實施例1之操作，但環氧樹脂A、B及mdu的重量 :別改為675.0克、633.〇克及255 3克。得常溫下為固 二軟化點為82.代，重149〇克之改質環氧樹腊，環氧 =為412，以而分析，發現於1 755‘，處有含氮雜環 、、，°構一NH_C(=0)—的特性吸收。如實施例1般，將甲基乙基 :二=緩加：反應爸中’使所得改質環氧樹脂溶解， 見=二。所侍含此改質環氧樹脂之溶液為樹脂1。經 分析，測得固含量為75. 13重量％ 。 、 (貳）3本發明改質環氧樹脂之清漆及電氣層合體之製 備 實施例6及7 於室溫下，配備有攪拌器的容器内，將如下，一 :例:=、觸媒及溶液與本發明改質， s ，形成3本發明改質環氧樹脂之清漆。 將上述清漆與破璃纖维布（台灣玻璃股份有限公司 J5633D] 23 1268940 ::等級E~glaSS，型號7628)含浸，經輥乳壓，於150 c下乾燥，得預浸潰m預浸潰體4合，並於其上 Lt置—片35//的銅羯’在溫度175°C、壓力25Κ_2 芦^下麼合’成為本發明改質環氧樹脂與玻璃纖維布之 ^肢二得的層合體㈣動掃描熱量計⑽，購自德州 孓唬TA 2910)測試其玻璃轉移溫度。 生致教丄較例2 如同貫施例6及實施你丨7 % _ 内，财―从L只"例7所不，配備有攪拌器的容器 硬化^納據^例方；至溫下，分別將環氧樹脂c及D與 成的環氧樹脂清# ^减“漆，將已調合 乾燥，得二：維布含浸’經_，在150 置—片％ 又"貝版，將八片預浸潰體疊合，其上下夂放 直片35間銅箔，於溫度 下口放 下壓合而成為俨尽糾匕 C、壓力25Kg/cm2的條件 合體經差时=破簡維布之層合體，所得的層 φ試其破螭轉移溫度。 自“川儀裔，型號TA 2910)測 15633D1 24 1268940 表1Base-4-hydroxy)ethane, table (supporting ^ ^ U butyl burning, ginseng [ cage - - / ) propyl sulphate, ginseng (phenyl -4- 4 - thiol: a sulfhydryl group - 4 hydroxy) methane, ginseng (Phenyl-3 5_ monomethyl-(benyl-4-hydroxy)ethane, hydrazine (phenyl-3,5-a-violet-4-hydroxy)ethane; and aged acids include, for example, age A condensate, aging ampule & A 曱A 曱 road finger combination, tetrabromo double age A-furfural condensate, etc. The amount of the above hardener added depends on the total reactivity in the hardener used. The equivalent weight is determined by the total epoxy equivalent of the modified epoxy resin of the present invention. Generally speaking, the total reaction of the hardener is equivalent to 20 to 95% of the total epoxy equivalent of the epoxy resin of the hair (4). It is preferably from 4 to 9%, more preferably from 50 to 90 Å/〇〇, which is suitable for blending with the modified epoxy resin of the present invention to form a high heat resistant material such as a secondary amine, a tertiary phosphine, and a season. S-alkali and imidazole compounds. Suitable tertiary amines in their catalysts such as triethylamine, tributylamine, monohydrazone, ethanol, ginseng (N,N-didecyl-aminodecyl)phenol ,N,N-didecyl-aminononylphenol 16 15633D] 1268940 Suitable tertiary phosphines such as triphenylphosphine; etc. Suitable quarter salt salts such as tetramethylammonium chloride, desert tetramethyl, moths: base, triethylbenzene chloride Methyl money, evolution of triethyl phenyl hydrazino, triethyl benzyl ammonium hydride, etc.; suitable quaternary phosphonium salts such as tetrabutyl sulphate, tetrabutyl bromo, iodine butyl scale, Tetrabutyl squamous acetate complex, tetraphenyl sulphate, / sulphate scale, broken tetraphenyl sulphate, ethyl triphenyl chloride, bromide scale, hardened!: triphenyl Keel, ethyl triphenyl sulphate acetate, ethyl diphenyl squaternary acid sulphate complex, chloropropyl 3 = decyl triphenyl scale propyl triphenyl scale, chlorinated ^ Two base _, desertified butyl triphenyl scale, decyl butyl triphenyl scale, etc.; has been rolled 4-methyl-mimi, 2 one + one mountain | upper H, ten-anti- oxazole, 2~17-carbenyl imidazole, etc. It can be used together with the modified epoxy resin of the present invention - diphenyl sulphate native 1 acetamidine acetate acetic acid complex, brominated butyl phthalate. ^^ alone or mixed Or a plurality of combinations to modify the epoxy tree with the present invention When the fat is manufactured, the amount of the catalyst used is (4) Preferably, the total weight of the 0 005 eucalyptus eucalyptus and the hardener is changed by using the _^2 electrical laminate amount. 1 = the amount %' is preferably. To "(4), when changing the electrical laminate of each latex resin, it is usually used to make 15633D1 17 1268940 = ::: epoxy wax with the aforementioned hardener, catalyst and appropriate solvent as a synthetic varnish. y,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, Less hardening reaction time, m m (four) addition amount is too large, although it can shorten the adverse effects; if you touch a pair of hardening benefits... efficiency. 1 media add! Too small, the reaction rate is too slow, less solvent 2::1=: Ring: The viscosity of the resin varnish can be added by, ,,,. Positive, & solvents such as stupid, ketone, proton, or: diether or vinegar. Among them, suitable benzenes are, for example, toluene and xylene. Two ==: Acetone, methyl ethyl ketone, thiophene keis, such as Ν, Ν _ dimethyl decylamine, dimethyl sulfoxide. Suitable for example: A 7: Base two. Suitable _, for example: acetic acid ethylene will contain modified epoxy resin, Fu /, s 曰. It is preferred that the viscosity is based on a high-resistance material, such as a two-epoxy resin, such as: 1., by a method known in the art. For example: Inventing a modified enamel varnish impregnated with a glass fiber cloth, , person: ; glass fiber cloth heating and drying, so that it becomes a pre-impregnated body, and then make other laminate materials (such a kind of pre-impregnated body or containing immortal, / / / shell impregnation) to each other, Further, it can be combined with 1 purchased copper m 156331) 1 18 1268940, and the composition of the laminates is hardened under pressure heating to obtain an electrical laminate. The pressure range used in the above hardening reaction is 5 to 1 〇〇 kg 7 cm 2 , and the temperature range of the above hardening reaction is preferably 20 to 350 ° C, preferably 50 to 30 (TC, more preferably 1 Torr to 25 (rc, especially good is 12〇 to 22〇C^. If the temperature is too high, it is easy to produce side reactions, and it is difficult to control the reaction speed, and it may promote the rate of deterioration of the resin; if the temperature is too low, the efficiency will be poor. The resin properties are more difficult to meet the needs of high temperature use. The following is a further description of the invention by way of example only, and those who are only used to e-learning skills should be aware that the scope of the invention is not limited by their examples. Limited. 'Hundred' first to the examples and comparative examples used in the glycidyl ether epoxy resin (ie epoxy resin A, B, c, D below), amino phthalate compounds, hardeners and catalysts The epoxy resin m used therein is an epoxy resin conventionally used in commercially available electrical laminates. Φ represents a bismuth A diglycidyl _ which is produced by the Changchun Synthetic Resin Factory and sold under the trade name BE188EL. The epoxy equivalent is 95 g/field, and the hydrolyzable gas is as follows Viscosity 11000 to 1 5000cps/25°C. Represented the Changchun Synthetic Resin Factory, which is sold under the trade name BEB350. It has an epoxy equivalent of 340-380 g/weight and a moisture content of 46. -49.5 wt%. Represented by Changchun Synthetic Resin Factory, under the trade name ΒΕΒ530Α80, 雔, fish 雔, Λ α / / odor bisphenol bis diglycidyl ether, its epoxy equivalent 19 15633D] 1268940 is 430 to 450 g / equivalent, bromine content of 18. 5 to 20.5 wt%. Li _ tomb, resin i represents the Changchun artificial resin plant, sold under the trade name ΒΕΒ Α Α Α Α Α ΒΕΒ ΒΕΒ , , , , , , The oxygen equivalent weight is 410 to 430 g/weight, and the bromine content is 19·〇 to 21·〇% by weight. Leg 1 represents diphenyldecane-4,4,-diaminoethyl decanoate. Star <匕觜11 A represents the phenol-furaldehyde condensation resin produced by the spring artificial resin factory under the trade name pfi 1 2〇h. The blanket-chemical agent L represents dicyanodiamine oxime • Lid Jl_ represents 2-phenyl Imidazole. Catalyst B represents 2-methyl mirram. Li 娣 C—represents 2-mercapto-4 phenylimidazole. Disc _·media D- represents brominated butyl Triphenyl scales. The epoxy equivalent (EEW), varnish viscosity and gel time used in this article, the solid content of the epoxy resin, and the heat resistance of the electrical laminate are determined by the following test methods. · φ 1 · EEW · Dissolve epoxy resin in chlorobenzene: chloroform = 1 : 1 solvent, • Titrate with HBr / glacial acetic acid, measured according to ASTM D1 652, the indicator is crystal violet 2 · Viscosity: The varnish containing the modified epoxy resin was placed in a 25 ° bath for 4 hours, and a Brookfield (Br〇〇kf ieid) viscometer at 25. 〇 Measurer. 3·Geiiing Time: According to the method of JISK-7233, make 50g of epoxy resin-containing paint sample and 15·24g mixed solvent [from dicyandiamide (10· gram) , 2-mercaptoimidazole (〇·54 g) mixed with sulfhydryl fiber 20 15633D1 1268940 (14·· 83 g)] mixed, hot plate drops 7 drops, 60 seconds later began with a pointed stick = clock At the time of (10) (from the beginning of the initial drop to the hot plate): paste resin resin, = two containing the modified ring of the present invention. .^,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, ) τ. Tables over 180 seconds [Embodiment] (Έ:) Preparation of nitrogen-containing heterocyclic modified epoxy resin: heat is a temperature controller, electric mixer, stirring magnet, port, thermocouple, condensation Five-necked bottle reaction of the device and the feeding port ^ 5 4(EEW)=1^] ^ b (68 gram, leg 367) and _24G gram, pass the nitrogen and will be the 'waiting epoxy tree η, epoxy Resin B and the secret completely smashed the force, hollowed out the above raw materials, and then passed the nitrogen, repeated twice. Catalyst A (1.4 g) was added and the mixture was heated to I under a nitrogen blanket and maintained at this temperature for about 1 G minutes. After the liquid 27 is found, it will react to the father, and collect the crane for 4 hurs after condensation; continue to pressurize the temperature to 16 (TC ' and keep it at this temperature for 3 hours, until the crane product no longer increases, ie The reaction was completed. The residue of the reaction dad was collected, and the modified epoxy resin of the present invention was solid at room temperature, weighing 1 632 g, and the epoxy equivalent was (10), and analyzed by FTIR (Turning-infrared conversion far-infrared spectrometer). At 15633D1 21 1268940, there is a characteristic absorption of the nitrogen-containing heterocyclic structure _NH_c(=〇)_. Shigong, the improved modified oxirane resin is easier to handle to produce a high heat-resistant material, ^Electrical laminate, sulfhydryl Ethyl hydrazine and 546g were slowly added to the reaction, and the mixture was mixed with the epoxy resin, and the mixture was mixed. The obtained oxidized tree containing the modified oxygen tree was found to be the resin w. After analysis, the solid content was determined. Μ μ% by weight · Luke β repeats the operation of Example 1, but with catalyst B (1.4 g) instead of the catalyst 戸j is solid at ordinary temperature, softening point is 73 9t, weight (10) gram of modified Z The resin's epoxy equivalent is Na, analyzed by coffee, and found at (7): Characteristic absorption of the nitrogen-containing heterocyclic structure C(=〇)_ As in Example I, methyl ethyl _ 53 gram was slowly added to the reaction dad, and the obtained modified solution was dissolved, and the mixture was homogenized. The obtained solvent containing the modified epoxy resin was obtained, and the resin U was obtained. After analysis, the measured solid content was 74.57 wt%. The operation of Example 1 was repeated, but the epoxy resin Α and β were changed to muscle 4 g, 639. gram and 24 〇 3 g, respectively. Rc, weighing 1541 grams of modified epoxy tree month, ring: set to 376.5, with Cong analysis, found in the preparation of ^ ^ delete, Zhejiang characteristics absorption. Such as implementation ^ =, 51U gram slowly add people to react So that the obtained modified epoxy resin is dissolved: = the material is hooked. The solution containing the modified epoxy resin is the resin V. The measured solid content is 74.67 wt%. 156331)] 〇 软化 软化 65 65 〇 〇 〇 〇 〇 〇 〇 〇 〇 65 65 65 65 65 65 65 65 65 65 65 65 65 65 65 65 65 65 65 65 65 65 65 65 65 65 65 65 65 65 65 65 65 65 65 65 65 65 65 65 C, a weight-changing epoxy resin weighing 1478 g, and 436' of epoxy eliquot was analyzed by FTIR, and it was found to have a characteristic absorption of nitrogen-containing heterocyclic di-conducting-NH-C(=0)- at 1 755 〇. Like the example i, 3 g of mercaptoethyl ketone was slowly added to the reaction vessel to dissolve the obtained modified epoxy resin, and the mixture was stirred uniformly. The solution containing the modified epoxy resin was obtained as resin X. The solid content was determined by knife analysis. 75.0% by weight. The operation of Example 1 was repeated, but the weights of the epoxy resins A, B and mdu were changed to 675.0 g, 633. g, and 255 3 g. The solid softening point was obtained at room temperature. 82. Generation, weighing 149 grams of modified epoxy tree wax, epoxy = 412, and analysis, found in 1 755 ', with nitrogen-containing heterocyclic ring, , ° ° NH_C (=0) - Characteristic absorption. As in Example 1, methyl ethyl group: two = slow addition: reaction dad' dissolved the resulting modified epoxy resin, see = two. The solution containing the modified epoxy resin is the resin 1.重量重量。 The solid content was determined to be 75. 13% by weight. (贰)3 Preparation Examples 6 and 7 of the varnish and electric laminate of the modified epoxy resin of the present invention are placed in a container equipped with a stirrer at room temperature as follows: Example: =, catalyst and The solution is modified with the present invention, s to form a varnish of the modified epoxy resin of the present invention. The above varnish and glass fiber cloth (Taiwan Glass Co., Ltd. J5633D) 23 1268940 :: Grade E~glaSS, model 7628) are impregnated, dried by roller pressing, and dried at 150 c to obtain prepreg m pre-impregnation. The body 4 is combined, and the copper bismuth on the Lt-sheet 35// is at a temperature of 175 ° C and a pressure of 25 Κ 2 芦 ^ 下 成为 成为 成为 成为 本 本 本 本 本 本 本 本 改 改 改 改 改 改 改 改 改 改 改 改 改 改The laminate (4) dynamic scanning calorimeter (10), purchased from Texas 孓唬TA 2910) was tested for its glass transition temperature. The teachings of the students are better than the example 2, as in the case of the example 6 and the implementation of your 丨 7 % _, the money - from the L only " example 7 does not, the container equipped with a stirrer hardens ^ ^ according to the example; to the temperature , respectively, the epoxy resin c and D and the epoxy resin clear # ^ minus "paint, will have been blended and dried, get two: Weibu impregnation 'jing _, at 150 sets - piece % " shell version, will Eight pieces of pre-impregnated body are superimposed, and 35 pieces of copper foil are placed on the upper and lower sides of the sheet. The lower part of the copper foil is placed under the temperature and the pressure is reduced. C, the pressure is 25Kg/cm2, and the condition is poor. The laminate is obtained, and the obtained layer φ is tested for breaking the transfer temperature. From "Chuan Yi, model TA 2910", 15633D1 24 1268940 Table 1
·: S施例6 茛施例7 比較例1 比較例2 環氣樹脂c(^) 1250 環氣樹脂D (克） 1250 環氧樹脂W(克） 1050 1500 硬化劑A (克） 175 硬化劑B (兎） 25 25 26 觭媒B(克） 0.625 0.625 «媒C(克） 1.05 2.25 甲基乙基酮（克） 140 235 二甲基甲醢胺（克） 260 260 淸漆黏度（CPS) 127 125 116 145 清漆膠凝時間（秒） 140 244 225 194 ®合物硬化後 玻璃轉移溫度（t) 160 159 132 150 曆合物硬化後 附熱試驗 (>180 秒） 通過 通過 不通遇 不通過1 丨 1 1 25 15633D1 ^6^94() 由表1結果可見，經本蛴日B ^ W較習知制0,m 方法製得之改質環氧樹脂 知製造電齓層合物所用之避〆 坡、切盘._ 衣乳树脂C、D具有更高的 之:;！：度，其耐熱性佳，而有利於製造需高耐熱性質 之”养件。更有甚者，依本發明 氣 ρ影塑。 、+寸產生之對人體健康及儀器設備之不 (本案無圖式）·: Example 6 茛 Example 7 Comparative Example 1 Comparative Example 2 Cyclo Resin c (^) 1250 Cyclo Resin D (g) 1250 Epoxy Resin W (g) 1050 1500 Hardener A (g) 175 Hardener B (兎) 25 25 26 觭媒B(克) 0.625 0.625 «媒C(克) 1.05 2.25 methyl ethyl ketone (g) 140 235 dimethylformamide (g) 260 260 lacquer viscosity (CPS) 127 125 116 145 Varnish gel time (sec) 140 244 225 194 ® glass hardening temperature after hardening (t) 160 159 132 150 Adhesive hardening test (>180 seconds) 1 丨1 1 25 15633D1 ^6^94() It can be seen from the results in Table 1 that the modified epoxy resin obtained by the conventional method of 0, m is known to be used in the manufacture of electrodeposites. 〆坡,切盘._ Latex resin C, D has a higher:;! : Degree, its heat resistance is good, and it is conducive to the manufacture of "reinforcing parts that require high heat-resistance properties. What's more, according to the invention, the gas ρ shadow plastic. The + inch produces the human health and equipment and equipment. figure)
26 15633D126 15633D1