TW307779B

TW307779B -

Info

Publication number: TW307779B
Application number: TW83101274A
Authority: TW
Original assignee: Mitsui Petroleum Chemicals Ind
Priority date: 1993-02-18
Filing date: 1994-02-17
Publication date: 1997-06-11
Also published as: SG64861A1; GB2275682A; GB9403012D0; MY131546A; GB2275682B; CN1095728A; CN1037972C; CN1176262A; CN1219546A

Description

經濟部中央標準局貞工消费合作社印製 307779 A7 ______B7 五、發明説明（1 ) 發明背暑本發明有關一種環氧樹脂以及包含有該環氧樹脂之環氧樹脂組成物。本發明特別有關一種在與硬化劑混合時粘性極低以便於操作，且在硬化後即具有優越之耐熱性及高機械強度之環氧樹脂。本發明亦有關一種對諸如玻璃布等材料具有優越滲透性，且在硬化後即具優越之耐熱性及抗起泡性，以用於生產印刷電路板（尤其是多層型印刷電路板）所用之銅覆膜環氧樹脂層稹板的環氧樹脂組成物^ 摻和塑料基質與強化材料所製之塑性複合材料在工業上有廣泛之用途’因爲其耐熱性、耐候性，抗化學性或機械強度皆極優越。環氧樹脂則廣泛用爲塑性複合材料之基質，因爲其動態性質較佳，且對具有強化用途之強化纖維的粘著性極高，且形成之複合材料易成型。在此種塑性複合材料中，包含有環氧樹脂及碳纖維者因具優越之耐熱性及機械強度，故爲航空太空、汽車及其他高科技工業中所最需要之新生代結構材料。但是，仍希望該複合材料具有更高之耐熱性及更佳之成型性或模製性，以作爲該高科技工業之結構材料。近來，電子裝置大量增加，多層型印刷電路板不但可應用於與電腦有關之設備，亦可用於自動化控制機器，通訊裝置，商務機器，遊樂器等設備中，以改善其性能並縮減其尺寸。另一方面，在電腦工業中，系統結構已有明顯之變化 (通稱爲迷你化），而工作場所裝置之周邊系統也已普及本紙張尺度適用中國國家標準（CNS ) Λ4現格（2IOX 297公釐） (請先閱讀背面之注意事項再填寫本頁) 訂 4Printed by the Zhengong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 307779 A7 ______B7 V. Description of the invention (1) The invention is related to an epoxy resin and an epoxy resin composition containing the epoxy resin. The present invention is particularly concerned with an epoxy resin which has a very low viscosity when mixed with a hardener to facilitate handling, and which has excellent heat resistance and high mechanical strength after hardening. The invention also relates to a material having superior permeability to materials such as glass cloth, and having excellent heat resistance and blistering resistance after hardening, for use in the production of printed circuit boards (especially multilayer printed circuit boards) The epoxy resin composition of copper-coated epoxy resin layered board ^ The plastic composite material made of plastic matrix and reinforced material has a wide range of applications in industry because of its heat resistance, weather resistance, chemical resistance or mechanical The strength is extremely superior. Epoxy resins are widely used as the matrix of plastic composite materials because of their better dynamic properties and extremely high adhesion to reinforcing fibers with reinforcing applications, and the resulting composite materials are easy to form. Among such plastic composite materials, those containing epoxy resin and carbon fiber have excellent heat resistance and mechanical strength, so they are the most needed new generation structural materials in aerospace, automobiles and other high-tech industries. However, the composite material is still desired to have higher heat resistance and better formability or moldability as a structural material for the high-tech industry. Recently, the number of electronic devices has increased significantly. Multilayer printed circuit boards can be used not only in computer-related equipment, but also in automatic control machines, communication devices, business machines, game instruments, etc. to improve their performance and reduce their size. On the other hand, in the computer industry, the system structure has changed significantly (commonly known as miniaturization), and the peripheral systems of workplace devices have also been popularized. This paper standard is applicable to the Chinese National Standard (CNS) Λ4 cash (2IOX 297 () (Please read the precautions on the back before filling out this page) Order 4

從猫申請案民阶年修正五、發明説明（2) 化。該周邊系統中所用之印刷電路板的發展方向並非增加層稹板之層數，其通常包括具有4至1〇層之層積板。在此種印刷電路板中，所致力硏究的是可產生高密度組件以及減少厚度之細致圖型。爲符合印刷電路板之此種需求，印刷電路板所用之基板需具有更佳之耐熱性及抗起泡性。 ‘在技藝界中已知之改善環氧樹脂耐熱性的方法係添加多官能性環氧樹脂，以增加樹脂之交聯密度。線型酚醛環氧清漆樹脂因爲不昂貴，故廣泛應用於該改良法中。但是，線型酚醛瓚氧清漆樹脂之分子量分佈相當廣泛，添加大量線型酚醛環氧清漆樹脂時，或使用高分子量線型酚醛環氧清漆樹脂時，形成之樹脂的粘度極高。使用此種高粘度樹脂爲塑性複合材料之基質時，則該基質樹脂難以完全浸透强化嫌維，亦難以將形成之塑性複合材料成型。而且，僅添加多官能性環氧樹脂不能滿足印刷電路板所用之層積板對耐熱性之要求。例如，大量添加此種多官能性環氧樹脂以改善耐熱性時，會使組成物欒硬而脆化，由該組成物生產之層稹板在沸煮後進焊接時，經常會有積層分離而致起泡的情況。發明槪沭本發明第一個目的是提出一種易成型之環氧樹脂，其在與硬化劑混合時粘度低，而一旦硬化，則具有優越之耐熱性以及高機械强度。本紙張尺度適用中國國家橾準（CNS) A4规格（210X297公釐） (請先M讀背面之注意事項再填寫本頁) 訂绨經濟部中央樣準局貞工消费合作社印製經濟部中央標準局員工消费合作社印裝 307779 at _____B7_ 五、發明説明（3 ) 本發明第二個目的是提出一種環氧樹脂組成物，其對諸如玻璃布等材料具有優越之浸透性，而一旦硬化，則具有優越之耐熱性，抗起泡性，及銅覆膜粘著性，因此，極適合生產印刷電路板所用之銅覆膜環氧樹脂層積板，尤其是多層型印刷電路板。本發明者針對上述第一個目的進行徹底研究，發現一旦硬化即具優越耐熱性以及高機械強度之低粘度易成型環氧樹脂的製法係在線型酚醛清漆存在下，以表醇或甲基表鹵醇將雙酚縮水甘油醚化，同時使雙酚及線型酚醛清漆縮水甘油醚化。在本發明中用以達成上述第一個目的者係環氧樹脂（ A)，其製法係以至少一種選自表鹵醇及甲基表鹵醇中者將雙酚（I )及線型酚醛清漆（I I )縮水甘油醚化。此外，在本發明中達成上述第二目的者係一種環氧樹脂組成物，其主要包含加成聚合反應（polyadduct)環氧樹脂（B )，此者之製法係以選自表鹵醇及甲基表鹵醇中之至少一種化合物將雙酚（I )及線型酚醛清漆（I I ) 縮水甘油醚化，產生環氧樹脂（A)，然後在鏘鹽或鹼觸媒存在下，使環氧樹脂（A)與經鹵化之雙酚（I I I ) 反應’產生加成聚合反應（polyadduct)樹脂（B )。本發明達成上述第二目的者係一種環氧樹脂組成物，其主要包含加成聚合反應（polyadduct)環氧樹脂（D ) ，此者之製法係以表鹵醇或甲基表鹵醇將雙酚（I )，線型酚醛清漆（I I )，及經鹵化之雙酚（I I I )縮水甘本紙張尺度適用中國國家標準（CNS ) Λ4規格（210X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 訂From the cat application case to the civil order year amendment V. Invention description (2). The development direction of the printed circuit board used in the peripheral system is not to increase the number of layers of the pegboard, which usually includes a laminated board having 4 to 10 layers. In this type of printed circuit board, the focus is on detailed patterns that produce high-density components and reduce thickness. In order to meet this demand for printed circuit boards, the substrates used for printed circuit boards need to have better heat resistance and blistering resistance. ‘A method known in the art to improve the heat resistance of epoxy resins is to add multifunctional epoxy resins to increase the crosslink density of the resin. Novolac epoxy resins are widely used in this improved method because they are inexpensive. However, the molecular weight distribution of the novolac varnish resin is quite broad. When a large amount of novolac epoxy varnish resin is added, or when a high molecular weight novolac epoxy varnish resin is used, the viscosity of the resin formed is extremely high. When using such a high-viscosity resin as the matrix of the plastic composite material, it is difficult for the matrix resin to fully penetrate and strengthen the dimension, and it is difficult to mold the formed plastic composite material. Moreover, the addition of multifunctional epoxy resin alone cannot meet the heat resistance requirements of the laminates used in printed circuit boards. For example, when a large amount of such multifunctional epoxy resin is added to improve the heat resistance, the composition will be hard and brittle. When the layered plate produced from the composition is boiled and then welded, there will often be layer separation. Causes blistering. Invention of the invention The first object of the present invention is to propose an easily-formable epoxy resin which has a low viscosity when mixed with a hardener, and once hardened, has excellent heat resistance and high mechanical strength. This paper standard applies to China National Standard (CNS) A4 (210X297mm) (please read the notes on the back before filling in this page) Order the Central Standards Bureau of the Ministry of Economic Affairs to print the Central Standards of the Ministry of Economy Bureau employee consumer cooperative printed 307779 at _____B7_ V. Description of the invention (3) The second object of the present invention is to propose an epoxy resin composition, which has superior permeability to materials such as glass cloth, and once hardened, it has Excellent heat resistance, blistering resistance, and copper film adhesion, therefore, it is very suitable for the production of copper film epoxy resin laminates for printed circuit boards, especially multilayer printed circuit boards. The inventors conducted a thorough research on the first object mentioned above, and found that once hardened, the production method of a low-viscosity, easily-formable epoxy resin with excellent heat resistance and high mechanical strength is based on the presence of novolac or methyl alcohol Halohydrin etherifies bisphenol glycidol, and at the same time etherifies bisphenol and novolac glycidol. In the present invention, the first epoxy resin (A) is used to achieve the above-mentioned first object, and its preparation method is to use at least one selected from epihalohydrin and methylepihalohydrin to bisphenol (I) and novolac (II) Glycidyl etherification. In addition, in the present invention, those who achieve the above second object are an epoxy resin composition, which mainly includes an addition polymerization (polyadduct) epoxy resin (B). At least one compound in the base epihalohydrin etherifies bisphenol (I) and novolac (II) glycidol to produce an epoxy resin (A), and then in the presence of a salt or alkali catalyst, the epoxy resin (A) Reaction with halogenated bisphenol (III) produces polyadduct resin (B). The present invention achieves the above-mentioned second object is an epoxy resin composition, which mainly includes an addition polymerization (polyadduct) epoxy resin (D), the preparation method of this is to use epihalohydrin or methyl epihalohydrin Phenol (I), novolac (II), and halogenated bisphenol (III) shrunken glycerin paper. The standard of China National Standard (CNS) Λ4 (210X 297mm) is applicable (please read the precautions on the back first Fill in this page)

I I 經濟部中央標準局貝工消費合作社印製 307779 A7 ___^__________ _ B7_ 五、發明説明（4 ) 油醚化’產生環氧樹脂（C)，然後在_鹽或鹼觸媒存在下使環氧樹脂（A)與經鹵化之雙酚（I I )反應，產生加成聚合反應（polyadduct)樹脂（D)。發明詳述茲以下文詳述本發明之環氧樹脂及含有該環氧樹脂之環氧樹脂組成物。本發明環氧樹脂（A)之製法係使用雙酚（I )及線型酚醛清漆（I I )作爲原料。本發明環氧樹脂組成物主要包含有加成聚合反應（polyadduct )環氧樹脂（B )或 (D) ’其製法個別係使由雙酚（I)，線型酚醛清漆（ I I )及經鹵化之雙酚（I I I )縮水甘油醚化所製之環氧樹脂（A )或環氧樹脂（C )與加成聚合反應所用之經鹵化雙酚（I I I )反應。雙酚（I ) 用以製備環氧樹脂（A)或環氧樹脂（c )之原料雙酚（I)係具有通式（i)之化合物： FT η R, ηII Printed 307779 A7 ___ ^ __________ _ B7_ by the Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs V. Description of the invention (4) Oil etherification 'produces epoxy resin (C), and then makes the ring in the presence of _ salt or alkali catalyst Oxygen resin (A) reacts with halogenated bisphenol (II) to produce polyadduct resin (D). DETAILED DESCRIPTION OF THE INVENTION The epoxy resin of the present invention and the epoxy resin composition containing the epoxy resin of the present invention are described in detail below. The production method of the epoxy resin (A) of the present invention uses bisphenol (I) and novolac (I I) as raw materials. The epoxy resin composition of the present invention mainly includes an addition polymerization (polyadduct) epoxy resin (B) or (D). Its preparation method is made up of bisphenol (I), novolac (II) and halogenated The epoxy resin (A) or epoxy resin (C) prepared by glycidyl etherification of bisphenol (III) reacts with the halogenated bisphenol (III) used in the addition polymerization reaction. Bisphenol (I) The raw material used to prepare epoxy resin (A) or epoxy resin (c) Bisphenol (I) is a compound of general formula (i): FT η R, η

式中R係選自—CH2—，—CHCH 泰紙張尺度適用中國國家橾準（CNS ) A4規格（21 OX 297公釐） (讀先閱讀背面之注意事項再填寫本頁) 、訂 307779 A7 __B7 五、發明説明（5〉 -C ( C Η 3 ) 2 - , ~ S Ο 2 -，及 —C(CH3) (C6H5) —中之二價基；R -各選自氫原子及含有1至5個碳原子的烴基；且η係整數0至4 β 雙酚（I)之實例有雙酚Α，雙酚F，及雙酹AD。其中最佳者係雙酸A ’其係上式（i )中R爲亞異丙基且R，爲氫原子之雙酚。線铟酚醛清漆（I I ) 用以製備本發明環氧樹脂（A )或環氧樹脂（c )( 其用以製造本發明環氧樹脂組成物）之線型酣酸清漆（ I I)係甲酸與上述雙酚（I)或下列通式（i i)所示之苯酚：In the formula, R is selected from —CH2—, —CHCH Thai paper standard is applicable to the Chinese National Standard (CNS) A4 specification (21 OX 297 mm) (read the precautions on the back and then fill out this page), order 307779 A7 __B7 V. Description of the invention (5> -C (C Η 3) 2-, ~ S Ο 2-, and —C (CH3) (C6H5) — the divalent group in R; each R is selected from a hydrogen atom and contains 1 to A hydrocarbon group of 5 carbon atoms; and η is an integer from 0 to 4. Examples of bisphenol (I) are bisphenol A, bisphenol F, and bisphenol AD. The best one is bisacid A ′, which is represented by the above formula ( i) in which R is isopropylidene and R is a bisphenol of hydrogen atom. The indium novolac (II) is used to prepare the epoxy resin (A) or epoxy resin (c) of the present invention (which is used to produce The linear epoxy acid varnish (II) of the invention epoxy resin composition) is formic acid and the bisphenol (I) or the phenol represented by the following general formula (ii):

OHOH

(ii), 經濟部中央樣準局貝工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁) (式中R1及R 2各選自氫原子及含有2至1 〇個碳原子之烴）的縮合產物。通式（i i )所示之較佳苯酚實例有苯酚，鄰一甲酚，對一第三辛苯酚，及對—甲酚。可與甲醛縮合產生線型酚醛清漆（I I )之雙酚（I )可爲通式（i )所示之雙酚。而用以製備線型酚醛清漆 (I I)之較佳雙酚（I)可爲雙酚A或雙酚AD。本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐）(ii), Printed by the Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling in this page) (where R1 and R 2 are each selected from hydrogen atoms and contain 2 to 10 carbon atoms Of hydrocarbons). Examples of preferred phenols represented by the general formula (i i) are phenol, o-cresol, p-third octylphenol, and p-cresol. The bisphenol (I) that can be condensed with formaldehyde to produce a novolak (I I) can be the bisphenol represented by the general formula (i). The preferred bisphenol (I) used to prepare the novolak (I I) can be bisphenol A or bisphenol AD. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X 297mm)

I I 307779 A7 B7 五、發明説明（6 ) 線型酚醛清漆（I I )之較佳軟化點最高1 Ο 0 °c，而更佳之軟化點係介於3 0至1 Ο 0 °C間。使用軟化點超過1 1 0°C之雙酚（I I )製造環氧樹脂時，因爲高分子量種類之含量太高，使粘度太高，故形成之環氧樹脂不能輕易成型。此種環氧樹脂再與經鹵化之雙酚（III)反應，製得環氧樹脂（B)或（D)，形成之樹脂的高分子量種類的含量太高，故無法充分滲透玻璃布。線型酚醛清漆（I I )之較佳數量平均分子量係 300至1000，更佳係300至700，而由350 至600尤佳。較佳之線型酚醛清漆（I I)亦可具有最高2之分子量分佈，而由1.1至1. 8最佳。本發明中所用之分子量分佈係重量平均分子量對數量平均分子量之比例，即M w /Μ η。線型酚醛清漆（I I )之製法係在不使用溶劑或在諸如二甲苯或甲苯等溶劑中，酸性觸媒存在下，使上述雙酚及/或苯酚與甲醛反應。可使用多聚甲醛取代甲醛。甲醛用量可爲每1莫耳雙酚及/或苯酣總量由〇. 2至0. 8 莫耳，以使軟化點及平均分子量最佳化。當在上述反應中使用溶劑時，可使用之比例係每 1 0 0重量％上述雙酚及/或苯酚由2 0至1 0 0重量％〇所用之酸性觸媒一般係無機酸，諸如硫酸，鹽酸，硝酸，或磷酸；或有機酸，諸如對-甲苯磺酸或草酸。其中，對甲苯磺酸具有髙酸度且與反應受質相容性良好之優點本紙張尺度適用中國國家標準（CNS ) Α4規格（2丨Ο X 297公釐） 1' 1 n n n n m I L. %^—*· I I _ 丁 --斗-δ (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消费合作社印製經濟部中央標準局貝工消費合作杜印裝 A7 ________ B7 五、發明説明（7 ) 。酸性觸媒之較佳比例係每1 0 0重量％上述雙酚及/或酚總量0. 05至2重量％)，而0. 1至1重量％更佳。酸性觸媒用量太少時則無法反應，故無法生產具有所需之分子量的線型酚醛清漆（I I )。酸性觸媒用量太少時導致反應失敗，故不能製出所欲分子量之線型酚醛清漆（ II)，酸性觸媒用量太多時導致難以控制反應，使所形成之線型酚醛清漆分子量太高。一般反應方式係將反應混合物加熱至由7 0至1 0 0 °<：之溫度經1_ 5至4小時，然後到達脫水縮合所用之 1 0 0至1 2 0°C之溫度。促進脫水縮合之方法係減壓或在溶劑（諸如二甲苯或甲苯）中回流共沸去除縮合之水。較佳反應係進行到不再產生縮合之水。一般反應時間係3 至5小時。反應完成後，在反應混合物中添加與所用之酸性觸媒化學計量相等之鹼化合物，使酸性觸媒中和。所用之_般鹼化合物有氫氧化鈉，氫氧化鉀及三乙醇胺嗎琳。或考·，在反應混合物中添加非水性溶劑形成均勻溶液，然後& 7欠性鹼溶液洗滌溶液，而中和之。使用溶劑製造線型酚醛清漆（I I )時，飽劑，留下線型酚醛清漆。官能性，3或更大之線型酚醛清漆（I I )中所含之多環組份可佔在雙酚（I )與線型酚醛清漆（I I )中酣組份之3至5 0重量％，而5至4 0重量％更佳，以產生環氧樹脂（A )或在雙酚I ’線型酚醛清漆（I I )及經本紙張尺度逋用中國國家標隼（CNS > A4規格（210 ;< 297公t ) ' —-- (請先閲讀背面之注意事項再填寫本頁)I I 307779 A7 B7 5. Description of the invention (6) The better softening point of the novolac (I I) is up to 100 ° C, and the better softening point is between 30 and 100 ° C. When bisphenol (I I) with a softening point exceeding 110 ° C is used to produce epoxy resins, because the content of high molecular weight species is too high and the viscosity is too high, the resulting epoxy resin cannot be easily molded. This epoxy resin is then reacted with halogenated bisphenol (III) to prepare epoxy resin (B) or (D). The content of the formed polymer is too high to fully penetrate the glass cloth. The preferred number average molecular weight of the novolak (I I) is 300 to 1000, more preferably 300 to 700, and particularly preferably 350 to 600. The best novolac (II) can also have a molecular weight distribution of up to 2, and from 1.1 to 1.8 is best. The molecular weight distribution used in the present invention is the ratio of weight average molecular weight to number average molecular weight, that is, M w / M η. Novolac (I I) is produced by reacting the above bisphenol and / or phenol with formaldehyde without using a solvent or in the presence of an acidic catalyst such as xylene or toluene. Paraformaldehyde can be used instead of formaldehyde. The amount of formaldehyde can be from 0.2 to 0.8 mol per 1 mol bisphenol and / or benzene benzene to optimize the softening point and average molecular weight. When a solvent is used in the above reaction, the ratio that can be used is from 20 to 100% by weight per 100% by weight of the above bisphenol and / or phenol. The acid catalyst used is generally an inorganic acid, such as sulfuric acid, Hydrochloric acid, nitric acid, or phosphoric acid; or organic acids, such as p-toluenesulfonic acid or oxalic acid. Among them, p-toluenesulfonic acid has the advantages of high acidity and good compatibility with the reaction substrate. This paper scale is applicable to the Chinese National Standard (CNS) Α4 specifications (2 丨 Ο X 297 mm) 1 '1 nnnnm I L.% ^ — * · II _ Ding-Dou-δ (Please read the precautions on the back before filling out this page) Printed by the Ministry of Economic Affairs Central Standards Bureau Employee Consumer Cooperative Printed by the Ministry of Economic Affairs Central Standards Bureau Beigong Consumer Cooperative Du Printed A7 ________ B7 5 3. Description of the invention (7). The preferred ratio of the acid catalyst is 0.05 to 2% by weight per 100% by weight of the total amount of the above bisphenol and / or phenol, and 0.1 to 1% by weight is more preferable. When the amount of the acid catalyst is too small, it cannot react, so it is impossible to produce a novolak (I I) having a desired molecular weight. When the amount of acid catalyst is too small, the reaction will fail, so the novolac (II) of the desired molecular weight cannot be produced. When the amount of acid catalyst is too large, it is difficult to control the reaction, so that the molecular weight of the formed novolak is too high. The general reaction method is to heat the reaction mixture to a temperature of from 70 to 100 ° <:: for 1 to 5 to 4 hours, and then to a temperature of 100 to 120 ° C for dehydration condensation. The method to promote dehydration condensation is to remove the condensation water by decompressing or refluxing in a solvent (such as xylene or toluene) azeotropically. The preferred reaction is such that condensation water is no longer produced. The general reaction time is 3 to 5 hours. After the reaction is completed, an alkali compound equal to the stoichiometric amount of the acid catalyst used is added to the reaction mixture to neutralize the acid catalyst. The basic compounds used are sodium hydroxide, potassium hydroxide and triethanolamine moline. Or, consider adding a non-aqueous solvent to the reaction mixture to form a homogeneous solution, and then wash the solution with < 7 < When a solvent is used to manufacture the novolak (I I), it is saturated, leaving novolak. Functionality, the polycyclic component contained in the novolac (II) of 3 or more can account for 3 to 50% by weight of the bisphenol (I) and the novolac (II) in the volatile component, and 5 to 40% by weight is better to produce epoxy resin (A) or bisphenol I 'novolac (II) and the Chinese national standard falcon (CNS > A4 specification (210; < 297 Gong t) '--- (Please read the notes on the back before filling this page)

、1T 10 A7 _ 五、發明説明（8 ) (請先閲讀背面之注意事項再填寫本頁) 鹵化之雙酚（I I I )中佔上述比例以產生可溶可溶性樹脂（C)。該多環組份含量少於3重量％時，無法有效改善硬化後之環氧樹脂玻璃化溫度。另一方面，當多環組份含量超過5 0重量％時，使環氧樹脂（A )或（C )再與經齒化之雙酚（I I )反應所產生之環氧樹脂（B)或（ D )之分子量太高，故不能充分浸透玻璃布。經鹵化之雙酚（I I I ) 用以製備環氧樹脂（C )之較佳原料經鹵化雙酚（ I I I )係經溴化之雙酚。最佳者有四溴雙酚A，四溴雙酚F，及1 ，1—雙（3，5 —二溴一 4 —羥苯基）乙烷〇縮水甘油化經濟部中央標準局員工消費合作社印製雙酚（I)及線型酚醛清漆（I I)與表鹵醇或甲基表鹵醇反應產生環氧樹脂（A);而雙酚（I)，線型酚醛清漆（I I)，及經鹵化之雙酚（I I I)與表鹵醇或甲基表鹵醇反應產生環氧樹脂（C)之方法可使用各種已知方法。但是，較佳者係接著進行醚化步驟及脫鹵化氫步驟，以產生品質可信之經縮水甘油醚化之環氧樹脂（A ) 或（C)。較佳表鹵醇有表氯醇，而較佳甲基表_醇係2 一甲基表氯醇》進行醚化步驟時之醚化觸媒用量係每1當量酚羥基（存於雙酚（I )與線型酚醛清漆（I I )之混合物中者，本紙張尺度遑用中國國家標準（CNS ) A4規格（210 :<297公釐Ί -11 - A7 B7 五、發明説明（9 ) 或存於雙酚（I )，線型酚醛清漆（I I )與經鹵化雙酌 (III)之混合物中）有0. 1至5莫耳％。一般醚化觸媒有三級胺，諸如三甲胺，三乙胺等；三級膦，諸如三苯膦，三丁膦等；季銨鹽，諸如氯化四甲銨，溴化四甲胺，氯化四乙銨，氯化膽鹼等；季錢鹽，諸如溴化四甲鐵，碘化四甲鱗，溴化四苯鱗，溴化三苯基丙鐵等；季銃鹽，諸如氯化苄基二丁銃，氯化苄基二甲銃等；及無機鹼，諸如氫氧化鈉，氫氧化鉀等。而其中較佳者係氯化四甲銨。醚化步驟中，反應係進行至有至少約5 0莫耳％ (較佳至少約7 0莫耳％)之酚羥基被醚化。一般反應溫度係 6 0至1 1 0 °C，而時間係1至1 2小時且使用惰性氣氛。系統中較佳水含量係以不超過3. 0重量％爲佳。可在包含有未反應之表_醇的醚化反應產物上進行後續之脫鹵化氫步驟。反應中，較好使用同於醚化步驟所用之鹼化合物（諸如鹼金屬氫氧化物）爲觸媒。在脫鹵化氫步驟中，一般鹼化合物使用比例係每1當量在線型酚醛清漆（I I )之酚羥基有0. 5莫耳或更高之比例，而 0 . 8莫耳或更高爲佳。較佳鹼化合物使用比例係每1當量酚羥基最多1莫耳，以減少諸如反應產物凝膠化所致之不便。一般反應溫度係6 0至1 0 〇°C，而時間係1至3 小時。使用氫氧化鈉時，較佳反應方式係去除副產物水。去除水之方法係將反應混合物脫水，例如，使表鹵醇水共沸’並將表鹵醇再送回反應系統中。反應完成後，可在諸如真空蒸餾去除未反應之表鹵醇，以諸如水洗等處理去除本紙張尺度關巾關sMf準（CNS ) Λ4規格（210X297公慶)' — -12 -、 1T 10 A7 _ V. Description of invention (8) (Please read the notes on the back before filling in this page) Halogenated bisphenol (I I I) accounts for the above proportion to produce soluble soluble resin (C). When the content of the polycyclic component is less than 3% by weight, the glass transition temperature of the cured epoxy resin cannot be effectively improved. On the other hand, when the polycyclic component content exceeds 50% by weight, the epoxy resin (B) or the epoxy resin (B) produced by reacting the epoxy resin (A) or (C) with the denatured bisphenol (II) or (D) The molecular weight is too high, so it cannot fully penetrate the glass cloth. Halogenated bisphenol (III) The preferred raw material for preparing epoxy resin (C). Halogenated bisphenol (III) is brominated bisphenol. The best ones are tetrabromobisphenol A, tetrabromobisphenol F, and 1,1-bis (3,5-dibromo-4-hydroxyphenyl) ethane. Glycidylation Ministry of Economic Affairs Central Standards Bureau Employee Consumer Cooperative Printed bisphenol (I) and novolac (II) react with epihalohydrin or methyl epihalohydrin to produce epoxy resin (A); and bisphenol (I), novolac (II), and halogenated Various known methods can be used to produce epoxy resin (C) by reacting bisphenol (III) with epihalohydrin or methylepihalohydrin. However, it is preferred that the etherification step and the dehydrohalogenation step be followed to produce a glycidyl etherified epoxy resin (A) or (C) of reliable quality. The preferred epihalohydrin is epichlorohydrin, and the preferred methylepi-alcohol is 2-methylepichlorohydrin. The amount of etherification catalyst used in the etherification step is per 1 equivalent of phenolic hydroxyl group (stored in bisphenol ( I) In the mixture of novolac (II), the paper size is in accordance with the Chinese National Standard (CNS) A4 specification (210: < 297 mm Ί -11-A7 B7 V. Description of the invention (9) or stored In the mixture of bisphenol (I), novolac (II) and halogenated bisphenol (III), there is 0.1 to 5 mol%. Generally the etherification catalyst has tertiary amines, such as trimethylamine, tri Ethylamine, etc .; tertiary phosphines, such as triphenylphosphine, tributylphosphine, etc .; quaternary ammonium salts, such as tetramethylammonium chloride, tetramethylammonium bromide, tetraethylammonium chloride, choline chloride, etc .; quaternary salt , Such as tetramethyl iron bromide, tetramethyl iodide scales, tetraphenyl bromide scales, triphenyl propyl ferric bromide, etc .; quaternary beryllium salts, such as benzyl dibutyl benzyl chloride, benzyl dimethyl benzyl chloride, etc. ; And inorganic bases, such as sodium hydroxide, potassium hydroxide, etc. and the preferred one is tetramethylammonium chloride. In the etherification step, the reaction system is carried out to at least about 50 mole% (preferably at least about 7 0 0%) The phenolic hydroxyl group is etherified. The general reaction temperature is 60 to 110 ° C, and the time is 1 to 12 hours and an inert atmosphere is used. The preferred water content in the system is not to exceed 3.0 weight % Is better. The subsequent dehydrohalogenation step can be carried out on the etherification reaction product containing unreacted epi-alcohol. In the reaction, it is preferable to use the alkali compound (such as alkali metal hydroxide) used in the etherification step ) Is a catalyst. In the dehydrohalogenation step, the general alkali compound is used in a ratio of 0.5 mol or more per 1 equivalent of the phenolic hydroxyl group of the novolac (II), and 0.8 mol or Higher is better. The use ratio of the preferred alkali compound is at most 1 mole per 1 equivalent of phenolic hydroxyl group to reduce inconveniences such as gelation of the reaction product. The general reaction temperature is 60 to 100 ° C, and the time 1 to 3 hours. When using sodium hydroxide, the preferred reaction method is to remove by-product water. The method of removing water is to dehydrate the reaction mixture, for example, to azeotrope the epihalohydrin water and send the epihalohydrin back to the reaction After the reaction is completed, it can be removed by vacuum distillation The reaction of epihalohydrin, processing such as washing with water to remove the present paper towel Off Scale Off sMf registration (CNS) Λ4 size (210X297 Qing well ') ---12--

V (請先閱讀背面之注意事項再填寫本頁) 訂經濟部中央梂準局員工消費合作社印袈 307779 經濟部中央梂準局貝工消費合作社印製 A7 B7五、發明説明（i〇) 副產物鹽，並視情況以弱酸（諸如磷酸或磷酸二氫鈉中和反應混合物等後處理後’過濾並乾燥製得本發明環氧樹脂 °此外，若需減少可水解氯之量，則可再進行第二次脫鹵化氫。使用鹼化合物以減少可水解氯之量，其比例係每1 莫耳殘留之可水解氯1至3莫耳’較佳者係1_ 2至3莫耳。反應溫度係60至1 00°C，而時間約1至3小時。反應可使用或不使用溶劑。使用溶劑時，較佳者係二甲苯 ’甲苯，MEK，甲基異丁基酮。製造環氧樹脂（A)時，雙酚（I )與線型酚醛清漆之使用重量比係1至99 · 99至5，較佳者係5至95 至5 ’而10至90 : 90至10更佳。當線型酚醛清漆過量使用時，形成之環氧樹脂的高分子量組份含量太高，在製造預浸漬體時不能充分浸透玻璃布，故形成之層積板的耐衝擊性差。當線型酚醛清漆之比例太低，形成之環氧樹脂的耐熱性不足。具有耐熱性之複合材料中，雙酚（I )與線型酚醛清漆（I Ϊ)之使用重量比係50至90 : 50至10 ，而 65至90 : 35至10較佳。當線型酚醛清漆（I I) 比例太低時，形成之環氧樹脂的耐熱性不足。若過量使用可溶可溶性酚醛組份，則形成之環氧樹脂的粘度太高，且不易成型。製造環氧樹脂（C )時，雙酚（I )，線型酹醛清漆 (I I )及經鹵化雙酚（I I I )之使用重量比係5 — 80 : 94 — 5 : 1 - 15，較佳者係 7 - 80 : 90 — •r (請先閱讀背面之注意事項再填寫本頁) 訂. 本紙張义度適用中國國家標隼（CNS ) Λ4%格（210 X 297公釐） 13 A7 ___________ B7 五、發明説明（11 ) 1 0 : 3 — 1 〇。上述反應所製之經縮水甘油醚化環氧樹脂（A)的環氧當量係1 7 0至2 2 o/e q而用於印刷電路板時，軟心點最高50°C，環氧當量170_220g/eq ，鹵化物含量最高0.1重量％。上述反應所製之經縮水甘油酸化環氧樹脂（C )軟化點最高4 0°C，環氧當量爲 170 — 22〇g/eq，而鹵化物含量最高1〇重量％〇加成聚合反應個別爲本發明環氧樹脂組成物之主組份之加成聚合反應物樹脂（B)及（D)之製法係個別地使環氧樹脂（A )及（C)與經鹵化之雙酚（I I I)反應。環氧樹脂（A)或環氧樹脂（B)與經鹵化雙酚（ I I〗）之加成聚合反應時的溫度係由1 20 °C至1 70 °C，而時間係4至1 5小時，使用惰性氣氛，並選擇性地採用1 0至3 0 0 p pm之觸媒，諸如季銨鹽或季銃鹽。反應所用之溶劑係諸如甲苯，二甲苯及環己酮，使反應混合物中之固體含量最高3 0重量％。可用於加成聚合反應之經鹵化雙酚（I I I )可同於縮水甘油醚化所用者》在此種經鹵化之雙酚（I I I )中，較佳者係溴化雙酚，尤其是四溴雙酚A，四溴雙酚F，及1 ，1—雙（3 ，5—二溴—4 —羥苯基）乙烷。環氧樹脂（A)與經鹵化雙酚（I I I )反應產生加本紙張尺度適用中國國家樣隼（CNS) A4規格（210X297公釐） — -14 -V (Please read the precautions on the back before filling out this page) Order the Employee Consumer Cooperative of the Central Bureau of Economics of the Ministry of Economic Affairs to print 袈 307779 Printed by the Central Bureau of Economic Affairs of the Ministry of Economic Affairs of the Beigong Consumer Cooperative. The product salt is optionally treated with a weak acid (such as phosphoric acid or sodium dihydrogen phosphate to neutralize the reaction mixture, etc.), filtered and dried to prepare the epoxy resin of the present invention. In addition, if the amount of hydrolyzable chlorine needs to be reduced, the Carry out the second dehydrohalogenation. Use an alkali compound to reduce the amount of hydrolyzable chlorine, the ratio of which is 1 to 3 moles per 1 mole of hydrolyzable chlorine remaining, preferably 1 to 2 to 3 moles. Reaction temperature It is 60 to 100 ° C, and the time is about 1 to 3 hours. The reaction can be used with or without a solvent. When using a solvent, it is preferably xylene 'toluene, MEK, methyl isobutyl ketone. Manufacture of epoxy resin (A), the weight ratio of bisphenol (I) to novolak is 1 to 99 · 99 to 5, preferably 5 to 95 to 5 'and 10 to 90: 90 to 10 is better. When the line type When the novolac is used in excess, the content of high molecular weight components of the epoxy resin formed is too high When the prepreg is manufactured, the glass cloth cannot be sufficiently penetrated, so the formed laminate has poor impact resistance. When the ratio of the novolak is too low, the formed epoxy resin has insufficient heat resistance. In heat-resistant composite materials, The weight ratio of bisphenol (I) to novolak (I Ϊ) is 50 to 90: 50 to 10, and 65 to 90: 35 to 10. Preferably, when the ratio of novolak (II) is too low, it forms The epoxy resin has insufficient heat resistance. If the soluble phenolic component is used excessively, the viscosity of the formed epoxy resin is too high and it is not easy to mold. When manufacturing epoxy resin (C), bisphenol (I), linear The weight ratio of aldehyde varnish (II) and halogenated bisphenol (III) is 5-80: 94-5: 1-15, preferably 7-80: 90-• r (please read the notes on the back first Please fill out this page again. Order. This paper is applicable to the Chinese National Standard Falcon (CNS) Λ4% grid (210 X 297mm) 13 A7 ___________ B7 5. Description of the invention (11) 1 0: 3 — 1 〇. The epoxy equivalent of the glycidyl etherified epoxy resin (A) prepared by the reaction is 1 7 0 to 2 2 o / eq when used in printed circuit boards, the soft core point is up to 50 ° C, the epoxy equivalent is 170_220g / eq, and the halide content is up to 0.1% by weight. The glycidated epoxy resin (C ) The softening point is up to 40 ° C, the epoxy equivalent is 170-22〇g / eq, and the halide content is up to 10% by weight. The addition polymerization reaction is the addition of the main component of the epoxy resin composition of the present invention. The preparation method of the polymerization reactant resins (B) and (D) is to separately react the epoxy resins (A) and (C) with the halogenated bisphenol (III). The temperature during the addition polymerization of epoxy resin (A) or epoxy resin (B) and halogenated bisphenol (II〗) is from 1 20 ° C to 1 70 ° C, and the time is from 4 to 15 hours , Use an inert atmosphere, and selectively use a catalyst of 10 to 300 p pm, such as quaternary ammonium salt or quaternary cymbium salt. The solvents used in the reaction are such as toluene, xylene and cyclohexanone, so that the solid content in the reaction mixture is up to 30% by weight. Halogenated bisphenols (III) that can be used for addition polymerization can be used for the etherification of glycidol. Among such halogenated bisphenols (III), the preferred ones are brominated bisphenols, especially tetrabromo Bisphenol A, tetrabromobisphenol F, and 1,1-bis (3,5-dibromo-4-hydroxyphenyl) ethane. Epoxy resin (A) reacts with halogenated bisphenol (I I I) to produce additional paper. The paper size is applicable to China National Falcon (CNS) A4 specification (210X297 mm) — -14-

V (請先閱讀背面之注意事項再填寫本頁) 訂經濟部中央揉準局員工消費合作社印製 A7 ______B7_ 五、發明説明（l2 ) 成聚合反應環氧樹脂（B)之程序中，環氧樹脂（A)與經鹵化雙酚（I I I )之較佳比例係7 4 : 2 6至5 5 : 45 »環氧樹脂（c)與經鹵化雙酚（I I I)反應產生加成聚合反應環氧樹脂（D)之程序中，環氧樹脂（C ) 與經鹵化雙酚（I I I )之較佳比例係90 : 1 0至58 :42。使用過量之經鹵化雙酚（I I I )時，產生過量之高分子量組份，故在製造預浸漬體時，樹脂組成物不能充分浸透該布》經鹵化之雙酚（III)之比例太低時，形成之環氧樹脂組成物的阻燃性不足，加成聚合反應之方法係使用一般環氧樹脂及以表鹵醇或甲基表_醇將上述經鹵化雙酚（III)縮水甘油醚化所得之經環氧化經鹵化雙酚。使用經環氧化經鹵化之雙酚進行加成聚合反應時，較佳比例係每1 〇〇重量％總含量有1至1 5重量％，以防止層積板在加熱時變色。本發明環氧樹脂組成物（主要包含加成聚合反應樹脂 (B) ’其製法係使環氧樹脂（A)與經鹵化之雙酚.（經濟部中央標準局貝工消费合作社印製 {請先閱讀背面之注意事項再填寫本頁) I ϊ I)如上述般地反應）之環氧當量係300至500 g/eq ’數量平均分子量Μη爲500至1 ，0〇〇，而Mn/Mw比例係1_ 7至3. 0，鹵化物含量爲15 至2 5重量％，而多官能性組份之含量爲3至4 0重量％。此者爲分子量分佈集中且低及高分子量組份含量皆小之粘性產物》主要包含加成聚合反應樹脂（D)(製法係上述使環氧樹脂（C )與經鹵化之雙酚（I I I )反應）之本發明 (張尺度逋用中國國家棟準（CNS ) A<t規格（21〇χ；297公釐） "~ 15 A7 ___B7_ 五、發明説明（l3) 環氧樹脂組成物的環氧當量爲3 0 0至5 0 0 g/e q，數量平均分子量Μη爲500至1 ，000，而Μη/ Mw比例爲1. 5至2. 5，鹵化物含量爲15至2 5重量％，而多官能性組份之含量爲3至4 0重量％。此者係分子量分佈集中且低及高分子量組份之含量皆極低的粘性產物。使用諸如雙氰胺或線型酚醛清漆等硬化劑將本發明環氧樹脂組成物硬化時，形成之硬化產物具有較佳之抗起泡性，而玻璃化溫度T g約比採用非本發明環氧樹脂（A ) 或（C )之習用環氧樹脂所製之環氧樹脂的硬化產品高 1 o°c。而且，本發明環氧樹脂組成物對玻璃布之滲透性良好。如前述者，經縮水甘油醚化之環氧樹脂（A)或（C )係用於製造本發明環氧樹脂組成物。製造本發明環氧樹脂組成物時，環氧樹脂（A)或（C )可單獨或與其他在分子中具有兩個或多個環氧基之環氧樹脂組合使用。此種額外環氧樹脂實例有雙酚- A環氧樹脂，線型酚醛清漆，可溶可溶性甲酚醛環氧樹脂及其他經縮水甘油醚化環氧樹脂縮水甘油酯環氧樹脂，縮水甘油胺環氧樹脂，直鏈脂族環氧樹脂，脂環族環氧樹脂，雜環環氧樹脂，經_化之環氧樹脂及其他多官能性環氧樹脂》此種額外環氧樹脂之用量係每1 0 0重量％環氧化物總含量（即，環氧樹脂與額外環氧樹脂之總含量）最多5 0重量％。使用過量之額外環氧樹脂時，形成之組成物不再擁有本發明特性。 p張尺度適用中國國家標隼（CNS ) Λ4坭格（210X297公釐Ί 1 (請先閱讀背面之注意事項再填寫本頁) 笨· 訂經濟部中央標準局員工消费合作社印製V (Please read the precautions on the back before filling in this page) Order A7 ______B7_ printed by the Employee Consumer Cooperative of the Central Bureau of Economic Development of the Ministry of Economic Affairs. 5. Description of the Invention (l2) In the procedure for forming the polymerization epoxy resin (B), epoxy The preferred ratio of resin (A) to halogenated bisphenol (III) is 7 4: 2 6 to 5 5: 45 »Epoxy resin (c) reacts with halogenated bisphenol (III) to produce addition polymerization epoxy In the procedure of resin (D), the preferred ratio of epoxy resin (C) to halogenated bisphenol (III) is 90:10 to 58:42. When using an excessive amount of halogenated bisphenol (III), an excessive amount of high molecular weight components are generated, so when the prepreg is manufactured, the resin composition cannot sufficiently penetrate the cloth. When the ratio of halogenated bisphenol (III) is too low The flame retardancy of the formed epoxy resin composition is insufficient, and the method of addition polymerization reaction is to etherify the halogenated bisphenol (III) glycidol using general epoxy resin and epihalohydrin or methylepi-alcohol The resulting epoxidized halogenated bisphenol. When epoxidized and halogenated bisphenol is used for the addition polymerization reaction, the preferred ratio is 1 to 15% by weight per 100% by weight of the total content to prevent the laminated board from discoloring when heated. The epoxy resin composition of the present invention (mainly including an addition polymerization resin (B) 'is prepared by a method of making epoxy resin (A) and halogenated bisphenol. (Printed by Beigong Consumer Cooperative of Central Bureau of Standards, Ministry of Economic Affairs {please Read the precautions on the back before filling this page) I ϊ I) React as described above) The epoxy equivalent weight is 300 to 500 g / eq 'and the number average molecular weight Mn is 500 to 1,000, while Mn / Mw The ratio is 1-7 to 3.0, the halide content is 15 to 25% by weight, and the content of the polyfunctional component is 3 to 40% by weight. This is a viscous product with a concentrated molecular weight distribution and low content of low and high molecular weight components. It mainly contains addition polymerization resin (D) (preparation method is the above-mentioned epoxy resin (C) and halogenated bisphenol (III) Reaction) of the present invention (Zhang Jiexing uses China National Building Standard (CNS) A < t specification (21〇χ; 297 mm) " ~ 15 A7 ___B7_ V. Description of the invention (l3) Ring of epoxy resin composition Oxygen equivalent is 300 to 5000 g / eq, the number average molecular weight Mn is 500 to 1,000, and the Mn / Mw ratio is 1.5 to 2.5, the halide content is 15 to 25% by weight, The content of the multifunctional component is 3 to 40% by weight. This is a viscous product with concentrated molecular weight distribution and low content of both low and high molecular weight components. Use hardeners such as dicyandiamide or novolac When the epoxy resin composition of the present invention is hardened, the hardened product formed has better blistering resistance, and the glass transition temperature T g is about 20% higher than that of conventional epoxy resins not using the epoxy resin (A) or (C) of the present invention. The hardened product of the produced epoxy resin is 1 o ° c high. Furthermore, the epoxy tree of the present invention The composition has good permeability to glass cloth. As mentioned above, the glycidyl etherified epoxy resin (A) or (C) is used to manufacture the epoxy resin composition of the present invention. The epoxy resin composition of the present invention is manufactured , Epoxy resin (A) or (C) can be used alone or in combination with other epoxy resins having two or more epoxy groups in the molecule. Examples of such additional epoxy resins are bisphenol-A epoxy Resin, novolac, soluble cresol novolac epoxy resin and other glycidyl etherified epoxy resin glycidyl ester epoxy resin, glycidylamine epoxy resin, linear aliphatic epoxy resin, alicyclic ring Oxygen resins, heterocyclic epoxy resins, modified epoxy resins and other multifunctional epoxy resins. The amount of such additional epoxy resins is the total epoxide content per 100% by weight (ie, epoxy The total content of the resin and additional epoxy resin) is at most 50% by weight. When an excessive amount of additional epoxy resin is used, the resulting composition no longer possesses the characteristics of the present invention. The p-scale is applicable to the Chinese National Standard Falcon (CNS) Λ4 (210X297mm Ί 1 (please read first Note to fill out the back of this page) stupid · Order Ministry of Economic Affairs Bureau of Standards staff printed consumer cooperatives

經濟部中央標準局員工消合作社印裝五、發明説明（l4) 與本發明環氧樹脂組成物組合使用之硬化劑不限於特定種類。一般硬化劑係酸酐，芳族多胺’脂族多胺’咪哩，及酚類樹脂。酸酐實例有酞酐，六氫酞酐，甲基四氫酞酐’甲基六氫酞酐，甲基耐地酐（methylnadic anhydride)，甲基棻二甲酸，苯均四酸酐，苯偏三酸酐，二苯甲酮四甲酸酐，十二基號拍酐，可若酸酐（chlorendic anhydride)及氯原冰片烯二甲酸酐。脂族多胺實例有三伸乙基四胺，二伸乙基三胺，甲二胺，N—胺乙基哌啶，異佛爾酮二胺，3 ，9 —雙（3 — 胺丙基）一2，4，8，10—四螺〔5 ，〕十一烷，胺加合物。咪唑實例有2_甲基咪唑，2 —乙基一 4_甲基咪哩，2_苯基咪唑，2 —十一基咪唑，2 —乙基一 4_甲基咪唑吖嗪，及1 _笮基—2 _甲基咪唑。酚類樹脂實例係線型酚醛清漆及經烷基取代之線型酣醛清漆。本發明亦可使用諸如雙氰胺，間一苯二胺等硬化劑。在本發明中，該硬化劑可單獨或二或多種組合使用。硬化劑可與硬化加速劑一起使用。硬化加速劑實例有上述咪唑，例如，1—苄基—2 —甲基咪唑及2 —乙基一 4 —甲基咪唑；胺，諸如三級胺，例如，N，N —笮基二甲胺及2 ’ 4 ，6 —三（二甲胺甲基）苯酚；及三級膦，諸如三苯膦。本紙张尺度適用中國國家橾準（CNS ) A4規格（2丨0 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) -aPrinted by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of the Invention (l4) The hardener used in combination with the epoxy resin composition of the present invention is not limited to a specific type. Common hardeners are acid anhydrides, aromatic polyamines, aliphatic polyamines, and phenolic resins. Examples of acid anhydrides are phthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride 'methylhexahydrophthalic anhydride, methylnadic anhydride, methyldicarboxylic acid, pyromellitic anhydride, trimellitic anhydride , Benzophenone tetracarboxylic anhydride, twelve-base rac anhydride, chlorendic anhydride and chlorogenic norbornene dicarboxylic anhydride. Examples of aliphatic polyamines are triethylidenetetraamine, diethylidenetriamine, methylenediamine, N-aminoethylpiperidine, isophoronediamine, 3,9-bis (3-aminopropyl) A 2,4,8,10-tetraspiro [5,] undecane, amine adduct. Examples of imidazole are 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-ethyl-4-methylimidazoleazine, and 1_笮基 -2_Methylimidazole. Examples of phenolic resins are novolacs and novolacs substituted with alkyl groups. The present invention can also use hardeners such as dicyandiamide, m-phenylenediamine and the like. In the present invention, the hardener may be used alone or in combination of two or more. Hardeners can be used with hardening accelerators. Examples of hardening accelerators are the above-mentioned imidazoles, for example, 1-benzyl-2-methylimidazole and 2-ethyl-4-methylimidazole; amines, such as tertiary amines, for example, N, N-dimethyldiamine And 2'4,6-tris (dimethylaminomethyl) phenol; and tertiary phosphines, such as triphenylphosphine. This paper scale is applicable to China National Standard (CNS) A4 (2 丨 0 X 297mm) (please read the precautions on the back before filling this page) -a

-17 — 經濟部中央標準局負工消費合作社印裝 A7 _B7_ 五、發明説明（is) 其他硬化加速劑有1 ，8 —氮雜二環—〔5 , 4， 1 0〕一 --烯一 7辛酸酯，單乙胺與三氟硼之錯合物，及Sun Abbot Inc.所售之商標爲 Ucat SA102的化合物〇在本發明中，硬化加速劑可單獨或二或多種組合使用〇本發明環氧樹脂組成物可與溶劑（諸如丙酮，甲基乙基酮，甲苯，二甲苯，甲基異丁基酮，乙酸乙酯，乙二醇單甲醚，N，N —二甲基甲醯胺，N ，N —二甲基乙醯胺，甲醇，乙醇等單獨使用之溶劑或二或多種組合之混合溶劑）摻和。本發明環氧樹脂組成物可視情況根據組成物之用途含有其他添加劑，諸如如阻燃劑及填料。本發明環氧樹脂組成物相當適合藉習用方法製造銅覆膜環氧樹脂層積板。使用本發明環氧樹脂組成物製造銅覆膜環氧樹脂層積板的一般方法係先將環氧樹脂溶於溶劑中製得樹脂液，強化材料（諸如玻璃布）浸於所製之樹脂液中且/或於其上施加所製之樹脂液，並在高溫下乾燥去除溶劑得到預浸漬體。其次在單片或堆疊之預浸漬體的單或雙面上放置銅覆膜，以習用方法加熱或壓力以使環氧樹脂組成物硬化。茲以下列實例及比較例詳述本發明。但實例不限制本發明範瞒。本紙张尺度適用中國國家梯準（CNS ) A4規格（210X 297公釐） I - - ii— i*\^,f «I I I II —^ϋ m 1^1 ^ ^-兵 (請先閱讀背面之注意事項再填寫本頁) - 18 — 307779 A7 B7______ 五、發明説明（ie) 實施例 (請先閱讀背面之注意事項再填寫本頁) 下列實施例及比較例中，粘度，撓曲強度，撓曲模量及在負荷在之撓曲溫度的評估方法係下列方法。粘度粘度係在2 5 °C溫度以E型粘度計測量。撓曲強度及橈曲模量試樣大小爲4mmx 1 Ommx 9 7mm，而評估方法係JISK6911，使用T〇YO BALDWIN 所製之Tensilon,滑動橫樑速度lmm/mi η ’使用最大負荷爲5 0 Okg之檔次。負荷下之撓曲溫度試樣大小 12. 5 m m X 1 2 . 5mmxl25mm ，方法係 J I S K 6 9 1 1，而裝置係 Tester Industry K. K.所製者。經濟部中央標準局負工消费合作社印製合成例1 使用雙酚Α充作苯酚以合成線型酚醛清漆之方t 在裝有冷凝器，溫度計，攪拌器’及滴液容器之1升可分離式燒瓶中送入4 5 6 g雙酚A及3 3 5 g甲苯’內部材料在攪拌下加熱。瓶中溫度達7 Ot時’添加本紙張尺度適用中國國家標準（CNS > Μ規格（2丨0 X 297公釐） 19 - 經濟部中央樣準局負工消费合作社印製 A7 B7 五、發明説明（π)-17 — Printed and printed A7 _B7_ by the Negative Workers ’Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of the invention (is) Other hardening accelerators are 1,8 —azabicyclo— [5, 4, 1 0] mono-ene one 7 Octanoate, the complex compound of monoethylamine and trifluoroboron, and the compound sold by Sun Abbot Inc. under the trademark Ucat SA102. In the present invention, the hardening accelerator can be used alone or in combination of two or more. Invention epoxy resin composition can be combined with solvents (such as acetone, methyl ethyl ketone, toluene, xylene, methyl isobutyl ketone, ethyl acetate, ethylene glycol monomethyl ether, N, N-dimethyl methyl Acetamide, N, N-dimethylacetamide, methanol, ethanol and other solvents used alone or two or more combinations of mixed solvents) blended. The epoxy resin composition of the present invention may contain other additives such as flame retardants and fillers depending on the use of the composition, as the case may be. The epoxy resin composition of the present invention is quite suitable for manufacturing copper-clad epoxy resin laminates by conventional methods. The general method for manufacturing a copper-coated epoxy resin laminate using the epoxy resin composition of the present invention is to first dissolve an epoxy resin in a solvent to prepare a resin solution, and immerse a reinforcing material (such as glass cloth) in the prepared resin solution Medium and / or apply the prepared resin solution thereon, and dry at high temperature to remove the solvent to obtain a prepreg. Next, a copper film is placed on one or both sides of the single piece or stacked prepreg, and the epoxy resin composition is hardened by heating or pressure in a conventional manner. The following examples and comparative examples detail the present invention. However, the examples do not limit the scope of this invention. This paper scale is applicable to China National Standards (CNS) A4 specification (210X 297 mm) I--ii— i * \ ^, f «III II — ^ ϋ m 1 ^ 1 ^ ^ -Bing (please read the back (Notes and fill in this page)-18 — 307779 A7 B7______ V. Description of the invention (ie) Examples (please read the notes on the back before filling in this page) In the following examples and comparative examples, viscosity, flexural strength, flex The evaluation methods of flexural modulus and deflection temperature under load are the following methods. Viscosity Viscosity is measured with an E-type viscometer at 25 ° C. The flexural strength and radial modulus of the sample size is 4mmx 1 Ommx 9 7mm, and the evaluation method is JISK6911, using Tensilon manufactured by TOYO BALDWIN, the sliding beam speed lmm / mi η 'the maximum load is 50 Okg Grade. Deflection temperature under load Sample size 12. 5 mm x 1 2 .5mmxl25mm, the method is J I S K 6 9 11 and the device is made by Tester Industry K.K. Printed and synthesized example 1 by the National Bureau of Standards, Ministry of Economic Affairs, Consumer Cooperatives. Using bisphenol A as phenol to synthesize a novolac t. In a 1 liter separable type equipped with a condenser, thermometer, stirrer and drip container 4 5 6 g of bisphenol A and 3 3 5 g of toluene were fed into the flask and heated with stirring. When the temperature in the bottle reaches 7 Ot, the standard of this paper is added to the Chinese national standard (CNS > M specifications (2 丨 0 X 297 mm) 19-A7 B7 printed by the Consumer Labor Cooperative of the Central Bureau of Prototyping of the Ministry of Economic Affairs Description (π)

2. 5 2 g草酸二水合物以充作觸媒。瓶中溫度達90 °C 時，以2小時逐滴添加82. 7g37%之福馬林（ formal in )水溶液》內部材料再回流攪拌1小時》瓶內材料溫度再升高，以由系統去除水及甲苯。溫度達1 5 0°C 時，在常溫下使內部材料濃縮1小時，再於2 OmmHg 減壓下濃縮1小時，得到雙酚A線型酚醛清漆（以下稱爲線型酚醛清漆（1))。使用Metier Inc.之自動化軟化點測量儀所測之線型酚醛清漆（1 )軟化點係9 3 °C。亦根據：f I S K0070評估線型酚醛清漆之羥基當量，而其爲120g/ecj »而數量平均分子量爲450 ;分子量分佈爲1. 50。實施例1 在裝有攪拌器，回流冷凝器，滴液漏斗，及溫度計之反應器中送入4 0 0 g雙酚A，1 0 〇 g鄰一甲酚線型酚酸清漆（0 C N 8 0， Nippon Kayaku K.K.之產品·，軟化點，8 0°C ;羥基當量1 3 g/e q ;數量平均分子量 425;分子量分佈1. 30) ，1956g表氯醇，及 3 9 g水。內部材料溫度升高至6 5 °C。反應混合物變成均匀溶液時，添加2 3 · 1 g 5 0 %氯化四甲銨水溶液，並攪拌反應3小時。其次’在70 °C減壓下以2小時將331. 之 4 8%N a OH水溶液逐滴添加於混合物中，使表氯醇及水共沸由系統連續去除水，而反應系統中之水含量保持2 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） I - - .1 n I - I». -- ------"'水 I— I (請先閱讀背面之注意事項再填寫本頁) 訂經濟部中央揉準局貝工消费合作社印製 A7 ___B7_ 五、發明説明（is) 重量％。將與水一起餾出之表氯醇由水中分離出來並送回反應系統中。包括減壓程度及加熱之共沸蒸餾條件係控制在每單位時間所移出之水量等於添加於反應系統中之4 8 % N a Ο Η水溶液的水量與反應中所產生之水量的總和。添加4 8%N a 0Η水溶液後，反應系統再在相同溫度下攪拌0 . 5小時。反應完成後，在減壓下由反應混合物餾除未反應之表氯醇及水。在殘留混合物中添加7 5 0 g二甲苯及7 5 g 水。反應混合物在8 0 °C攪拌0. 5小時，靜置以分離二甲苯及水相》由二甲苯相收集之試樣分析的結果，可水解之氯濃度爲1. 45重量％。其次，在二甲苯相中添加6 2 g 4 8 %N a Ο Η水溶液，反應混合物在9 5 °C攪拌2小時。反應完成後，去除凝膠組份，添加7 5 0 g 2 5 %磷酸單鈉水溶以中和之。利用二甲苯-水共沸，由中和後之產物去除水，殘留混合物經玻璃濾器過濾，分離在中和產物中之無機鹽。濾液在 1 5 Ot：減壓下加熱去除二甲苯，產生6 8 0 g環氧樹脂。所製之環氧樹脂之環氧當量爲185g/eq ，而可水解之氯含量爲0. 06重量％。實施例2 重複例1 ，不同處係雙酚A之用量減少至2 6 0 S ’ 而以在參考合成例1所合成之線型酚醛清漆（1 )取代鄰 -甲酚線型酚醛清漆》產生4 5 0 ίί環氧樹脂，其環氧當本紙张尺度適用中國國家標準（CNS ) A4規格（2I0X297公釐） (請先聞讀背面之注意事項再填寫本頁) 衣. 訂 212. 5 2 g of oxalic acid dihydrate is used as a catalyst. When the temperature in the bottle reaches 90 ° C, 82. 7g of 37% formalin (formal in) aqueous solution is added dropwise over 2 hours. The internal materials are refluxed and stirred for another hour. The temperature of the materials in the bottle is increased again to remove water and water from the system. Toluene. When the temperature reached 150 ° C, the internal material was concentrated at room temperature for 1 hour, and then concentrated under reduced pressure of 2 OmmHg for 1 hour to obtain bisphenol A novolac (hereinafter referred to as novolac (1)). The softening point of the novolac (1) measured by the automatic softening point measuring instrument of Metier Inc. is 9 3 ° C. Also based on: f I S K0070 evaluated the hydroxyl equivalent of novolac, which is 120g / ecj »and the number average molecular weight is 450; the molecular weight distribution is 1.50. Example 1 In a reactor equipped with an agitator, a reflux condenser, a dropping funnel, and a thermometer, 400 g of bisphenol A and 100 g of o-cresol novolac phenolic varnish (0 CN 8 0 , Product of Nippon Kayaku KK ,, softening point, 80 ° C; hydroxyl equivalent of 13 g / eq; number average molecular weight 425; molecular weight distribution 1.30), 1956 g epichlorohydrin, and 39 g water. The internal material temperature rises to 65 ° C. When the reaction mixture became a homogeneous solution, 2 3 · 1 g of 50% tetramethylammonium chloride aqueous solution was added, and the reaction was stirred for 3 hours. Secondly, add 331. of 8% Na OH aqueous solution to the mixture dropwise at 70 ° C for 2 hours under reduced pressure to make epichlorohydrin and water azeotropic continuously remove water from the system, while the water in the reaction system Keep the content of 2 The paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) I--.1 n I-I ».------- " 'Water I— I (Please read first (Notes on the back and then fill out this page) Order A7 ___B7_ printed by the Beigong Consumer Cooperative of the Ministry of Economic Affairs, Central Bureau of Standardization V. Invention description (is) Weight%. The epichlorohydrin distilled with water is separated from the water and sent back to the reaction system. The azeotropic distillation conditions including the degree of decompression and heating are controlled. The amount of water removed per unit time is equal to the sum of the amount of water added to the 48% Na 0 Η aqueous solution added to the reaction system and the amount of water generated in the reaction. After adding 48% Na 0H aqueous solution, the reaction system was stirred at the same temperature for 0.5 hours. After the reaction was completed, unreacted epichlorohydrin and water were distilled off from the reaction mixture under reduced pressure. 7 500 g of xylene and 75 g of water were added to the residual mixture. The reaction mixture was stirred at 80 ° C for 0.5 hours, and allowed to stand to separate the xylene and water phase. The analysis result of the sample collected from the xylene phase showed that the hydrolyzable chlorine concentration was 1.45% by weight. Next, 6 2 g of 48% Na 0 H aqueous solution was added to the xylene phase, and the reaction mixture was stirred at 95 ° C for 2 hours. After the reaction was completed, the gel component was removed, and 7 50 g 25% monosodium phosphate was dissolved in water to neutralize it. Using xylene-water azeotrope, water is removed from the neutralized product, and the residual mixture is filtered through a glass filter to separate the inorganic salts in the neutralized product. The filtrate was heated at 15 Ot: under reduced pressure to remove xylene, producing 680 g of epoxy resin. 06 重量％。 The epoxy equivalent of the prepared epoxy resin is 185g / eq, and the hydrolyzable chlorine content is 0.06% by weight. Example 2 Example 1 was repeated, and the amount of bisphenol A was reduced to 2 6 0 S 'in different places, and the o-cresol novolac (1) was substituted with the novolac (1) synthesized in Reference Synthesis Example 1 to produce 4 5 0 ίί epoxy resin, the size of the epoxy paper is applicable to the Chinese National Standard (CNS) A4 specification (2I0X297 mm) (please read the precautions on the back before filling out this page) Clothing. Order 21

I I 經濟部中央梂準局属工消費合作杜印製 A7 ____B7___ 五、發明説明（I9 ) 量爲1 9 0 g/e q，而可水解之氯含量係0 . 0 5重量 %。實施例3 在5 0°C攪拌下混合8 0 g例1所合成之環氧樹脂’ 7 2 . 6 g 甲基六氫酞酐（Liquacid MH-700, Shin-I I Printed by the Ministry of Economic Affairs Central Bureau of Industry and Consumer Cooperation A7 ____B7___ V. Invention description (I9) The amount is 190 g / e q, and the hydrolyzable chlorine content is 0.05% by weight. Example 3 80 g of the epoxy resin synthesized in Example 1 was mixed under stirring at 50 ° C. 7 2. 6 g of methylhexahydrophthalic anhydride (Liquacid MH-700, Shin-

Nippon Rika K.K.之產品）及 Ο . 4 g 1，8 —二氮雜二環〔5 . 4 . 0〕一 7 — -f--嫌辛酸酯（octilate)(Nippon Rika K.K. product) and Ο. 4 g 1,8-diazabicyclo [5.4.0]-7--f--octilate (octilate) (

Ucat-102, Sun-Abbot Inc.之產品），製得均句樹脂_液. 。均勻溶液在2 5°C之粘度爲9 9 3 c p s。將所製之均匀溶液例入適於製造測量撓曲強度及撓曲模量所用之試樣的模具中，再倒入適於製造在測量負荷下撓曲溫度中所用之試樣的模具中，在1 2 0。0加熱2小時 ’加1 5 0 °C加熱2小時，最後，在1 7 0 °C加熱4小時硬化。經硬化之試樣個別評估其撓曲強度，撓曲模量及在負荷下之撓曲溫度。結果列於表1。實施你丨4 重複例3之方法’不同處係使用8 0 g由例2所合成之環氧樹脂取代環氧樹脂，而甲基六氫酞酸酐用量減少至 7〇_ 8g。形成之均勻溶液在25°C的粘度爲896 c P s 。亦將均匀溶液硬化成評估撓曲強度，撓曲模量及負荷下之撓曲溫度。結果列於表1。本紙^^^"適用中國國家標準（CNS ) A4規格（210X 297公釐) (請先閲讀背面之注意事項再填寫本頁)Ucat-102, a product of Sun-Abbot Inc.), the homogram resin_liquid was prepared. The viscosity of the homogeneous solution at 25 ° C is 9 9 3 c p s. Introduce the prepared homogeneous solution into a mold suitable for making samples for measuring flexural strength and flexural modulus, and then pour into a mold suitable for making samples for measuring deflection temperature under load, Heat at 1 2 0. 0 for 2 hours, add 1 5 0 ° C for 2 hours, and finally, heat at 1 7 0 ° C for 4 hours. The hardened specimens were individually evaluated for flexural strength, flexural modulus and deflection temperature under load. The results are shown in Table 1. Implement your method. 4 Repeat the method of Example 3. The difference is that 80 g of the epoxy resin synthesized in Example 2 is used instead of epoxy resin, and the amount of methylhexahydrophthalic anhydride is reduced to 70-8 g. The viscosity of the formed homogeneous solution at 25 ° C is 896 c P s. The homogeneous solution is also hardened to evaluate the flexural strength, flexural modulus and deflection temperature under load. The results are shown in Table 1. This paper ^^^ " applies to the Chinese National Standard (CNS) A4 specification (210X 297mm) (please read the precautions on the back before filling this page)

-22 - 307779 A7 B7 五、發明説明（2〇) 比齩例1 重複例1方法，不同處係不使用雙酚_A ’而僅使用鄰-甲酚線型酚醛清漆（0 c N 8 0，Nippon Kayaku K.K.之產物）（用量爲584g) ’產生65〇g可溶可溶性酚醛環氧樹脂。所製之線型酚醛清漆之環氧當量爲 -2 0 3 g/e q ，而可水解之氯含量爲 0 . 0 5重量％。比齩例2 重複例1方法，但是不使用雙酚A，而以5 0 4 g由參考合成例1所合成之雙酚A線型酚醛清漆取代鄰一甲酚線型酚醛清漆，產生6 0 5 g線型酚醛清漆。所製之可溶可溶性酚醛環氧樹脂之環氧當量爲1 9 7 g/e q ，而可水解之氯含量爲0.06重量％。 . 比齩例3 經濟部中央梂準局貝工消费合作社印製 n^i UJn-i I! I n n^i ^^^1 n n nn 一OJ (請先閲讀背面之注意事項再填寫本頁) 重複例3方法，不同處係使用1 6 g比較例1所合成之可溶可溶性酚醛環氧樹脂，6 4 g雙酚A型液體環氧樹月旨（環氧當量，188g/eq) ，71. 4g甲基六氫酞酸酐，及0. 4gl，8 —二氮雜二環〔5. 4. ◦〕 —7 ^ —稀辛酸酯（〇(：1;1131：6)(1]。31:-102，51111-人1313- ot Inc.產品）製造均勻樹脂液。均勻溶液在2 5 °C之粘度爲1 9 4 6 c p s 。所製之均匀溶液硬化成用於測量撓曲強度’擒曲模量’及負荷下之撓曲溫度的試樣。硬化產本紙张尺度適招中國困家揉串* ( CNS ) A4規格（210χ 297公着：） A7 A7 結氮雜 κ/ 五、發明説明（2ΐ) 物中雙酚A組份相對於線型酚醛清漆的比例同於例3 果列於表1 。 4 重複例3方法，不同處係使用3 7 . 4 g比較例2所合成之可溶可溶性酚醛環氧樹脂，42. 62雙酌A型液體環氧樹脂（環氧當量，i88g/eq)， 69. 8g甲基六氫酞酸酐，及〇. 4gl，8 —二 —環〔5 _ 4 · 0〕— 7 — ^--嫌辛酸酯（octilat'-22-307779 A7 B7 V. Description of the invention (2〇) Example 1 Repeat the method of Example 1, except that bisphenol_A 'is not used in different places but only o-cresol novolac (0 c N 8 0, Nippon Kayaku KK's product) (amount of 584g) 'produces 65〇g of soluble phenolic epoxy resin. The epoxy equivalent of the produced novolak is -203 g / e q, and the hydrolyzable chlorine content is 0.05% by weight. Comparative Example 2 The method of Example 1 was repeated, but bisphenol A was not used, and instead of o-cresol novolak, the bisphenol A novolak synthesized in Reference Synthesis Example 1 was replaced with 50 4 g, yielding 6 0 5 g Novolak. The epoxy equivalent of the prepared soluble phenol novolac epoxy resin was 197 g / e q, and the hydrolyzable chlorine content was 0.06% by weight. . Comparative example 3 Printed by the Ministry of Economic Affairs, Central Bureau of Economic Affairs, Beigong Consumer Cooperatives n ^ i UJn-i I! I nn ^ i ^^^ 1 nn nn one OJ (please read the precautions on the back before filling this page) Repeat the method of Example 3, using 16 g of soluble phenolic epoxy resin synthesized in Comparative Example 1, 6 4 g of bisphenol A liquid epoxy resin (epoxy equivalent, 188g / eq), 71 . 4g methyl hexahydrophthalic anhydride, and 0.4gl, 8-diazabicyclo [5. 4. ◦] -7 ^-dilute octanoate (〇 (: 1; 1131: 6) (1). 31: -102, 51111-Human 1313-ot Inc. product) to produce a uniform resin solution. The viscosity of the uniform solution at 2 5 ° C is 1 9 4 6 cps. The uniform solution prepared is hardened to measure the flexural strength. Specimen of flexural modulus' and deflection temperature under load. The size of the hardened paper is suitable for Chinese sleepers * (CNS) A4 specification (210χ 297 public :) A7 A7 azadiazepine κ / 5. Description of the invention (2) The ratio of the bisphenol A component to the novolac is the same as in Example 3 and the results are listed in Table 1. 4 The method of Example 3 was repeated, and 37.4 g of Comparative Example 2 was used in different places. Soluble phenolic ring Resin, 42.62 double-choice A-type liquid epoxy resin (epoxy equivalent, i88g / eq), 69.8g methylhexahydrophthalic anhydride, and 0.4gl, 8-di-cyclo [5_4 · 0] — 7 — ^-octilate

Ucat-102，Sun- Abbot Inc.產品）製造均勻樹脂液。均勻溶液在2 5 °C之粘度爲3 3 79 c p s。所製之均勻溶液硬化成用於測量撓曲強度，撓曲模量，及負荷下之撓曲溫度的試樣。硬化產物中雙酚A組份相對於線型酚醛清漆的比例同於例4。結果列於表1。比較例5 重複例3方法，不同處係使用8 0 g雙酚A型液體環氧樹脂（環氧當量，188g/eq) ，71. 5g甲基六氨駄肝’及0 . 4 g Ucat-102製造均勻樹脂液。所製之均勻溶液硬化成用以測量撓曲強度，撓曲模量及負荷τ 之撓曲溫度的試樣。結果列於表1。表1 __硬化產物之件菅Ucat-102, product of Sun-Abbot Inc.) manufactures uniform resin solution. The viscosity of the homogeneous solution at 2 5 ° C is 3 3 79 c p s. The prepared homogeneous solution is hardened into a sample for measuring flexural strength, flexural modulus, and deflection temperature under load. The ratio of the bisphenol A component to the novolak in the hardened product is the same as in Example 4. The results are shown in Table 1. Comparative Example 5 The method of Example 3 was repeated, using 80 g of bisphenol A liquid epoxy resin (epoxy equivalent, 188 g / eq), 71.5 g of methylhexamine and 0.4 g of Ucat- in different places. 102 Manufacture a uniform resin solution. The prepared homogeneous solution is hardened into a sample for measuring flexural strength, flexural modulus and deflection temperature of load τ. The results are shown in Table 1. Table 1 __ pieces of hardened products

Ex . 3 Ex. 4 Π . E . 3 C. E. 4 本紙张尺度逋用中國國家標準（CNS ) A4規格（210X 297公釐） I. —I . - I- - - I I- - In -1-4’^-- -- I m ml I \ 4 、v-e (請先閱讀背面之注意事項再填寫本頁) 經濟部中央椹準局負工消费合作社印製 24 五、發明説明（22 ) A7 B7 硬化前之樹脂液在 993 896 1946 3379 _ 25°C之粘度，cps 擦曲強度，kg/mm2 12. 9 12.9 12.0 12. 1 11. 撓曲模量，kg /mm2 279 292 280 280 277 在負荷下之撓曲 159 164 160 165 140 溫度，°C C. E.:比較例合成例2革5 合._成線型酚醛清漆之方法Ex. 3 Ex. 4 Π. E. 3 CE 4 This paper scale uses the Chinese National Standard (CNS) A4 specification (210X 297 mm) I. —I.-I---I I--In -1- 4 '^--I m ml I \ 4, ve (please read the precautions on the back before filling in this page) Printed by the Ministry of Economic Affairs Central Bureau of Accreditation Consumer Cooperative 24 24. Description of invention (22) A7 B7 The viscosity of the resin solution before hardening at 993 896 1946 3379 _ 25 ° C, cps flexural strength, kg / mm2 12. 9 12.9 12.0 12. 1 11. Flexural modulus, kg / mm2 279 292 280 280 277 under load The next flexure 159 164 160 165 140 temperature, ° C CE: Comparative Example Synthesis Example 2 leather 5 combination. _Method of forming novolac

在裝有冷凝器，溫度計，攪拌器，及滴液容器之1升可分離式燒瓶中送入4 5 6 g雙酚A及3 3 5 g甲苯，內部材料在攪拌下加熱。瓶中溫度達7 0°C時，添加 2. 5 2 g草酸二水合物以充作觸媒。瓶中溫度達9 0 °C 時，以2小時逐滴添加1 3 0 g 3 7%之福馬林（formalin) 水溶液，內部材料再回流攪拌 1 小時。瓶內材料溫度再升高，以由系統去除水及甲苯。溫度達1 5 0°C時，在常溫下使內部材料濃縮1小時，再於2 OmmHg減壓下濃縮1小時*得到含有殘留雙酚A之線型酚醛清漆（以下稱爲線型酌酸清漆（1 ))。使用Metier Inc.之自動化軟化點測量儀測置線型酚醛清漆（2 )軟化點。亦評估雙酚A單體殘留量以及其數量平均分子量與分子量分佈（ M w ./ Μη)(凝膠滲透層析（GPC)。評估雙酚A單本紙張尺度適用中國國家橾準（CNS ) A4規格（210X297公嫠) I 1. 4 -衣-- (請先閱讀背面之注意事項再填寫本頁) -9 經濟部中央橾準局負工消費合作社印裝 -25 - A7 _B7_ 五、發明説明（23) 體之殘留量時’串聯2支 Shin-pack-HSG 1 0管柱（3-h i m a d z u S e i s a k u s h 〇 L t d.產物）及各 1 支之 S h i m - p a c k -HSG 1 5及20，構成分離管柱。評估分子量時’串聯 HSG — 20 ，40 ，50 ，及60。使用四氫呋喃爲洗提溶液。而分子量分佈之測法如下。結果列於表2。重複上述參考合成例2之方法，不同處係使用雙酚A ，草酸二水合物，及3 7%福馬林（formal in )水溶液製得線型酚醛清漆（3 )至（5 )(用量列於表2 )。亦測量所製之線型酚醛清漆（3 )至（5 )之軟化點，雙酚A 單體殘留量，數量平均分子量，及分子量分佈。而合成例 5係使用3 2 4 g鄰—甲酚取代雙酚A。 4·^^ x^i d i n^i HA ^ m 1^1 lx >^^1— n^i 一 V .J4 i (請先閲讀背面之注意事項再填寫本頁) 經濟部中央梯準局貞工消费合作社印製 307779 A7 A7 ____B7 五、發明説明（24) 線型酚醛清漆淮料之原料重量 (2) ill (4) (5 ) 雙酚一 A 456 456 456 — 鄰一甲酚 - — - 324 草酸二水合物 2.52 2. 52 2. 52 3. 8 3 7 %福馬林 130 82.7 33.1 174 成之產物的件質軟化點，°c 110 93 72 80 雙酚-A單體殘留量，重量％ 22 39 57 231 數量平均分子量 556 450 374 425 分子量分佈，Mw/Mn 1.68 1.50 1.12 1. 30 (請先閱讀背面之注意事項再填寫本頁) 訂經濟部中央梂準局貝工消費合作社印製 1 兩環型鄰-甲酚之含量合成例6至1 5 經縮水甘1..醚化之環氧樹J旨的—合_^一（共同縮7k甘油化）在裝有溫度’搜拌器’分離器，冷凝器，及滴液容器之2升圓底燒瓶中置入雙Α單體殘留量爲22重量 2 ο 〇 (2)，及 1206g表氯醇 ’而內容物在攪拌下加熱至9 0°C之溫度。在9 0〇c '溫g 下’添加3 0 g水及3 g氯化四甲敍，而混合物搜拌4小本紙張尺度適用中國國家標準（CNS ) A4规格（210X297公釐)~~ --— -27 - 經濟部中央標準局貝工消費合作社印製 A7 ___B7_ 五、發明説明（25) 時。混合物溫度降至7 0°C並將壓力降至5 0 OmmHg ，在此壓力下，在3小時內由滴液容器將1 3 7 g 4 8% 氫氧化鈉水溶液添加於混合物中，同時以分離器去除系統中之水。氫氧化鈉逐滴添加完成後，持續去除水經3 0分鐘。將系統壓力降至20mmHg，混合物在1 20°C縮合1小時。恢復常壓，在混合物中添加3 5 0 g水及 2 5 0 g甲苯，形成之混合物再在9 Ot：攪拌3 0分鐘。放置混合物，促使其分離，並去除水層，殘留之樹脂層在 1 5 0°C 2 0 OmmHg濃縮得到2 6 4 g經縮水甘油醚化之環氧樹脂，此者以下稱爲環氧樹脂（6 )。使用鹽酸一二噁烷法評估所得之環氧樹脂（6)的環氧當量。亦以Meier Inc.之自動化軟化點測量儀評估環氧樹脂（6 )之軟化點，而以凝膠滲透層析（GP C )測其組成（合成例2至5)。結果列於表3» 重複合成例6之方法，不同處係使用線型酚醛清漆，雙酚A，表氯醇，及4 8%N a OH水溶液（用量示於表 3) ’製得環氧樹脂（7)至（15)。亦評估形成之環氧樹脂（7)至（1 5)之環氧當量，軟化點及組成。結果亦列於表3。本紙張尺度適用中國國家梯準（CNS) A4規格（21〇x 297公着） ^ .衣"------^ (請先閲讀背面之注意事項再填寫本頁) 五、發明説明（26) HU TFU (ΓΠ (ΤΠ (ΤΠ (·ϋττ ΤΪΤ 9 ΤΠ 刍 09 ocoCNl 16In a 1 liter separable flask equipped with a condenser, a thermometer, a stirrer, and a drip container, 4 5 6 g of bisphenol A and 3 3 5 g of toluene were fed, and the internal materials were heated with stirring. When the temperature in the bottle reached 70 ° C, 2.5 2 g of oxalic acid dihydrate was added as a catalyst. When the temperature in the bottle reached 90 ° C, 1 30 g 3 7% formalin aqueous solution was added dropwise over 2 hours, and the internal materials were refluxed and stirred for another 1 hour. The temperature of the material in the bottle rises again to remove water and toluene from the system. When the temperature reaches 150 ° C, the internal materials are concentrated for 1 hour at normal temperature, and then concentrated under reduced pressure of 2 OmmHg for 1 hour. * A novolac containing residual bisphenol A is obtained (hereinafter referred to as a linear novolac (1 )). Use the automatic softening point measuring instrument of Metier Inc. to measure the softening point of novolac (2). Also evaluate the residual amount of bisphenol A monomer and its number average molecular weight and molecular weight distribution (M w ./ Mn) (Gel Permeation Chromatography (GPC). The paper size of the bisphenol A sheet is applicable to China National Standard (CNS)) A4 specifications (210X297 gong) I 1. 4-clothing-(please read the precautions on the back before filling in this page) -9 Printed by the Ministry of Economic Affairs, Central Bureau of Preservation and Consumer Cooperatives -25-A7 _B7_ V. Invention Description (23) When the residual amount of the body is connected in series with 2 Shin-pack-HSG 1 0 columns (3-himadzu S eisakush 〇L t d. Product) and each of the 1 Shi-pack-HSG 1 5 and 20 , Constitute a separation column. When evaluating molecular weights, connect HSG-20, 40, 50, and 60 in series. Use tetrahydrofuran as the elution solution. The molecular weight distribution is measured as follows. The results are listed in Table 2. Repeat the above Reference Synthesis Example 2 Methods, bisphenol A, oxalic acid dihydrate, and 3 7% formalin aqueous solution were used to prepare novolacs (3) to (5) in different places (the dosage is listed in Table 2). The softening point of the novolac (3) to (5), the residual amount of bisphenol A monomer, the number Average molecular weight and molecular weight distribution. In Synthesis Example 5, 3 2 4 g o-cresol was used instead of bisphenol A. 4 · ^^ x ^ idin ^ i HA ^ m 1 ^ 1 lx > ^^ 1— n ^ i 一 V .J4 i (Please read the precautions on the back before filling out this page) Printed 307779 A7 A7 ____B7 by the Zhenggong Consumer Cooperative of the Central Escalation Bureau of the Ministry of Economic Affairs 5. Description of the invention (24) Raw material weight of novolac lacquer (2) ill (4) (5) Bisphenol-A 456 456 456-o-cresol-324 oxalic acid dihydrate 2.52 2. 52 2. 52 3. 8 3 7% formalin 130 82.7 33.1 174 The softening point of the product, ° c 110 93 72 80 Residual amount of bisphenol-A monomer, weight% 22 39 57 231 number average molecular weight 556 450 374 425 molecular weight distribution, Mw / Mn 1.68 1.50 1.12 1. 30 (please Read the precautions on the back before filling out this page) Printed by the Ministry of Economic Affairs, Central Bureau of Economics and Technology, Beigong Consumer Cooperative Printed 1 Content of two-ring o-cresol Synthesis examples 6 to 1 5 Shrinked 1. Etherified ring Oxygen tree J purpose-combined _ ^ one (together with 7k glycerolization) in a 2 liter round equipped with a temperature 'searcher' separator, condenser, and drip container The bottom flask was charged with a residual amount of bis-A monomer of 22 weight 2 ο (2), and 1206 g of epichlorohydrin, and the contents were heated to a temperature of 90 ° C with stirring. Add 90 g of water and 3 g of tetramethylchloride at 900 ° C '温 g 下', and the mixture is mixed with 4 small papers. The standard of China's national standard (CNS) A4 (210X297 mm) is applicable ~~- -— -27-A7 ___B7_ printed by the Beigong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs V. Invention description (25). The temperature of the mixture was lowered to 70 ° C and the pressure was lowered to 50 OmmHg. At this pressure, 1 3 7 g 4 8% aqueous sodium hydroxide solution was added to the mixture within 3 hours from the drip container, while separating Remove water from the system. After the completion of the dropwise addition of sodium hydroxide, the water was continuously removed for 30 minutes. The system pressure was reduced to 20 mmHg, and the mixture was condensed at 120C for 1 hour. After returning to normal pressure, 3 50 g of water and 25 50 g of toluene were added to the mixture, and the resulting mixture was stirred at 9 Ot for 30 minutes. Place the mixture to promote its separation and remove the water layer. The remaining resin layer is concentrated at 150 ° C 2 0 OmmHg to obtain 2 6 4 g of glycidyl etherified epoxy resin, which is hereinafter referred to as epoxy resin ( 6). The epoxy equivalent of the obtained epoxy resin (6) was evaluated using the hydrochloric acid-dioxane method. The softening point of the epoxy resin (6) was also evaluated by Meier Inc.'s automated softening point measuring instrument, and its composition was measured by gel permeation chromatography (GP C) (Synthesis Examples 2 to 5). The results are shown in Table 3 »The method of Synthesis Example 6 was repeated. Novolak, bisphenol A, epichlorohydrin, and 48% Na aOH aqueous solution were used in different places (the dosage is shown in Table 3). (7) to (15). The epoxy equivalent, softening point and composition of the formed epoxy resins (7) to (15) were also evaluated. The results are also listed in Table 3. This paper scale is applicable to China National Standards (CNS) A4 (21〇x 297 public) ^. 衣 " ------ ^ (Please read the precautions on the back before filling this page) V. Invention description (26) HU TFU (ΓΠ (ΤΠ (ΤΠ (· ϋττ ΤΪΤ 9 ΤΠ 鲁 09 ocoCNl 16

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HocdK St- Y®SK ^0 = =-5-11 恝袒ss CT3/3- _細祕酹本紙張尺度逋用中國國家橾準（CNS ) A4規格（210X297公釐） -29 - 經濟部中央揉準局只工消費合作杜印製 A7 B7 五、發明説明（27) 合成例1 6 — 2 7 加成聚合反應樹脂之合成法在裝有攪拌器及溫度計之1升可分離燒瓶中置入 171g雙酚A環氧樹脂（環氧當量，I88g/eq) ’29. 4g合成例6所製之環氧樹脂（6)，及 9 4. 3 g.四溴雙酚A，而內容物在攪拌下加熱。溫度達 100°C時，添加〇. 2g氯化四乙銨，在160°c促進反應5小時，得到加成聚合反應樹脂，此者以下稱爲加成聚合反應樹脂（1 6 )。利用上述方法評估加成聚合反應樹脂（16)之環氧當量。利用凝膠滲透層（G P C )使用串聯5。11113(^-HSG 20 ’ 40，50及60之管柱評估該樹脂之數量平均分子量’並以上方法測其分子量分佈。重複合成例1 6之方法，不同處係使用環氧樹脂，雙酚A環氧樹脂’及四溴雙酚a (用量示於表4 )製得加成聚合反應樹脂（17)至（25)。亦評估加成聚合反應樹脂（17)至（25)之環氧當量，數量平均分子量，及分子量分佈。亦重複合成例1 6之方法，不同處係以四溴雙酚A環氧樹脂（用量示於表4 )取代四溴雙酚A，而環氧樹脂及雙酚A環氧樹脂之用量示於表4，製得加成聚合反應樹脂 (26)及（27)。亦評估加成聚合反應樹脂（26) 及（27)之環氧當量，數量平均分子量，及分子量分佈。本紙张尺度適用中國國家梯準（CNS ) A4規格（210X29*/公釐） (請先閱讀背面之注意事項再填寫本頁) 訂 -30 - 307779 A7 B7 五、發明説明（28) Όϋ T^T 目麵(Ιϋ ΤΤϋ 義 TFTT WT Tin Τ5ϋ sHocdK St- Y®SK ^ 0 = = -5-11 條袒 ss CT3 / 3- _ fine secret paper size using the Chinese National Standard (CNS) A4 specification (210X297mm) -29-Central Ministry of Economic Affairs A7 B7 produced by the Ministry of Industry and Commerce for cooperation and cooperation. 5. Description of the invention (27) Synthesis Example 1 6-2 7 The synthesis method of the addition polymerization resin is placed in a 1 liter separable flask equipped with a stirrer and a thermometer 171g bisphenol A epoxy resin (epoxy equivalent, I88g / eq) '29. 4g epoxy resin (6) prepared in Synthesis Example 6, and 94.3 g. Tetrabromobisphenol A, and the content is Heat with stirring. When the temperature reached 100 ° C, 0.2 g of tetraethylammonium chloride was added, and the reaction was accelerated at 160 ° C for 5 hours to obtain an addition polymerization resin, which is hereinafter referred to as an addition polymerization resin (16). The epoxy equivalent of the addition polymerization resin (16) was evaluated by the above method. The gel permeable layer (GPC) was used to evaluate the number average molecular weight of the resin by using 5.11113 (^ -HSG 20 '40, 50 and 60 columns in series) and the molecular weight distribution was measured by the above method. The method of Synthesis Example 16 was repeated In different places, epoxy resins, bisphenol A epoxy resin 'and tetrabromobisphenol a (amounts shown in Table 4) were used to prepare addition polymerization resins (17) to (25). The addition polymerization reaction was also evaluated Epoxy equivalent, number average molecular weight, and molecular weight distribution of resins (17) to (25). The method of Synthesis Example 16 was also repeated, except that tetrabromobisphenol A epoxy resin was used in different places (amounts shown in Table 4). Tetrabromobisphenol A, and the amounts of epoxy resin and bisphenol A epoxy resin are shown in Table 4. Addition polymerization resins (26) and (27) were prepared. Addition polymerization resins (26) and (27) Epoxy equivalent, number-average molecular weight, and molecular weight distribution. The paper size is applicable to China National Standard (CNS) A4 specification (210X29 * / mm) (please read the precautions on the back before filling this page). -30-307779 A7 B7 5. Description of the invention (28) Όϋ T ^ T 目面 (Ιϋ ΤΤϋ meaning TFTT WT Tin Τ5ϋ s

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、1T 本紙浪尺度適用中國國家橾準（CNS ) A4規格（210X297公釐） 31 經濟部中央橾準局貝工消费合作社印製 A7 B7 五、發明説明（29)、 1T This paper wave scale is applicable to China National Standard (CNS) A4 (210X297mm) 31 Printed by Beigong Consumer Cooperative of Central Standardization Bureau of Ministry of Economic Affairs A7 B7 V. Description of invention (29)

實施例FS 在100g加成聚合反應樹脂（20)在25g甲基乙基酮中之溶液中添加2. 5g雙氰胺及0.15g2— 乙基一4 一甲基咪唑在2 0 g乙二醇單甲醚中之溶液，產生環氧樹脂組合成之樹脂液。將玻璃布（W E A -.1 8 W 1 〇 5 F，Nitto Boseki Co.，Ltd.之產物）浸入所製之樹脂液中，然後在1 4 0°C乾燥爐中乾燥6分鐘製得預浸漬體。預浸漬體之環氧樹脂組成物含量係4 9重量％。評估預浸潰體之外觀。壓皺預浸漬體以收集環氧樹脂組成物，將所收集之環氧樹脂組成物置入適於製造1 mm厚之試樣板的模具中。將試樣板置入Toyobo Co, Ltd.所製之Reolosolid中 ’以2°C/m i η加熱速度評估環氧樹脂組成物之玻璃化溫度，T g » 堆疊四片預浸漬體，並在1 7 0°C及2 〇kg/cm2 壓力下模製該堆疊物經1小時，製成層積板。層積板浸入 1 2 1°C水中且在2kg/cm2壓力下放置預定時間，並在2 6 0°C焊浴中浸漬2 0秒。層積板在加壓蒸缸試驗（ P C T )後，根據下列標準評估層積板之耐焊熱性：〇：不起泡亦不分層△:少許氣泡或稍有分層，且 X :有許多氣泡或有相當程度之分層》結果列於表5。本紙張尺度適用中國國家標準（CNS ) A4規格（2丨0 X 297公釐） (請先閱讀背面之注意事項再填寫本頁)Example FS In a solution of 100 g of addition polymerization resin (20) in 25 g of methyl ethyl ketone, add 2.5 g of dicyandiamide and 0.15 g of 2-ethyl-4-methylimidazole in 20 g of ethylene glycol The solution in monomethyl ether produces a resin solution composed of epoxy resin. The glass cloth (WEA-. 1 8 W 1 〇5 F, product of Nitto Boseki Co., Ltd.) was immersed in the prepared resin solution, and then dried in a drying oven at 140 ° C. for 6 minutes to prepare a pre-dip body. The epoxy resin composition content of the prepreg was 49% by weight. Evaluate the appearance of the prepreg. The prepreg was crimped to collect the epoxy resin composition, and the collected epoxy resin composition was placed in a mold suitable for manufacturing a 1 mm thick sample plate. Place the sample plate in Reolosolid manufactured by Toyobo Co, Ltd. 'Evaluate the glass transition temperature of the epoxy resin composition at a heating rate of 2 ° C / mi η, T g »stack four prepregs, and place in 1 The stack was molded at 70 ° C and 20 kg / cm2 pressure for 1 hour to make a laminate. The laminate was immersed in 1 2 1 ° C water and placed under a pressure of 2 kg / cm2 for a predetermined time, and immersed in a solder bath of 260 ° C for 20 seconds. After the pressurized steam cylinder test (PCT) of the laminated board, the soldering heat resistance of the laminated board was evaluated according to the following criteria: 〇: No blistering or delamination △: A few bubbles or slight delamination, and X: Many The bubbles may have a considerable degree of delamination. The results are listed in Table 5. The size of this paper is applicable to the Chinese National Standard (CNS) A4 (2 丨 0 X 297mm) (Please read the precautions on the back before filling this page)

，-IT A7 307779 ____ B7 ___ 五、發明説明（3〇 ) 實施例6至1 以個別示於表5中之加成聚合反應樹脂（21)至（ 27)取代加成聚合反應樹脂（20)，重複例5方法’ 製得樹脂液，然後製備預浸漬體。如例5般評估所製之樹脂液及預浸漬體之玻璃化溫度，P C T後之抗焊熱性，以及浸透性。結果亦列於表5中。 I---------^ ------IT (请先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局貝工消费合作社印装 I張紙一本 A S N C /(\ 準梂家國國中一用 ί適, -IT A7 307779 ____ B7 ___ V. Description of the invention (3〇) Examples 6 to 1 The addition polymerization resins (21) to (27) are replaced with the addition polymerization resins (21) shown separately in Table 5 , Repeat the method of Example 5 to prepare a resin solution, and then prepare a prepreg. The glass transition temperature of the prepared resin solution and prepreg, the soldering heat resistance after PCT, and the penetration were evaluated as in Example 5. The results are also listed in Table 5. I --------- ^ ------ IT (Please read the precautions on the back before filling out this page) Printed a copy of the I sheet of ASNC / ( \ The quasi-birth country junior high school with one suitable

|釐公 7 9 2 X 3 3 五、發明説明（31 ) SI u 01 001 oot 001 A7 B7 GOl oot is 001 001 001 0091 691 9S1 691 091 191 SI SI sroLOrotoloLOrolnrolorolnroιηΓΟ Lo.zLO.CJlo.OJLoco·lo.cmlo.nlo·》Lod 〇〇〇〇〇〇 ο 〇 ο 〇〇〇〇〇 V 〇 (請先閲讀背面之注意事項再填寫本頁) 、-° 經濟部中央橾準局貝工消費合作社印製 uesl u!曰 GZl 担癍败运-N班一3d 3。· 3,一埘額A3>溥鸹淨爹«iffi--T«lN)-s 逛减δ< (5s)s) (5(ss)m) (s)gg趄<n嵌啪茛133^2 本紙張尺度適用中國國家梂準（CNS ) A4規格（21〇X：297公釐）Ligong 7 9 2 X 3 3 V. Description of invention (31) SI u 01 001 oot 001 A7 B7 GOl oot is 001 001 001 0091 691 9S1 691 091 191 SI SI sroLOrotoloLOrolnrolorolnroιηΓΟ Lo.zLO.CJlo.OJLoco · lo.cmlo .nlo ·》 Lod 〇〇〇〇〇〇ο 〇ο 〇〇〇〇〇〇V 〇 (please read the notes on the back before filling out this page),-° Ministry of Economic Affairs Central Bureau of Industry and Commerce Cooperative Printed Uesl u! Said GZl to lose luck-N class one 3d 3. · 3, Azi> A3> Pujin net father «iffi--T« lN) -s wander minus δ < (5s) s) (5 (ss) m) (s) gg 趄 < n inlaid ranunculus 133 ^ 2 The paper size is applicable to China National Standards (CNS) A4 (21〇X: 297mm)

卩H 34 - A7 B7 五、發明説明（32 ) 比較例6至1 2 重複例5之方法，不同處係使用表3所列之環氧樹脂 (6 )至（9 )及表4所列之加成聚合反應樹脂（1 6 ) 至（19)(用量示於表6)，製得環氧樹脂組成物之樹脂液，接著製得預浸漬體。如例5般評估所製之樹脂液及預浸漬體的玻璃化溫度，P C T後之抗焊熱性，以及浸透性。結果列於表6。 (請先閱讀背面之注意事項再填寫本頁)卩 H 34-A7 B7 V. Description of invention (32) Comparative Examples 6 to 1 2 Repeat the method of Example 5, except that the epoxy resins (6) to (9) listed in Table 3 and those listed in Table 4 are used in different places The addition polymerization resins (16) to (19) (amounts shown in Table 6) were used to prepare a resin solution of an epoxy resin composition, followed by a prepreg. The glass transition temperature of the prepared resin solution and prepreg, solder heat resistance after PCT, and penetration were evaluated as in Example 5. The results are shown in Table 6. (Please read the notes on the back before filling this page)

J -0 經濟部中央橾準局貝工消费合作社印製本紙張尺度適用中國國家橾準（CNS ) A4規格（210X 297公釐） -35 - 五、發明説明（33) δΐ 01 一一 οιJ -0 Printed by the Beigong Consumer Cooperative of the Central Bureau of Economic Affairs of the Ministry of Economic Affairs. The paper size is applicable to China National Standard (CNS) A4 (210X 297 mm) -35-V. Description of the invention (33) δΐ 01 11.11

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I 001 A7 B7 srolnroLnroloroloro sc;tn.NLO.CJLOCNJLocvl 06 06 06 sro ιη·ζ X X X X X X 〇〇 V 〇〇 V/.sis【s ss»—*S一經濟部中央標準局員工消費合作杜印製槲-N垢溥海葙堵MS靼 X uesl V U0§ 坦疾败垢-N游iod 卜91 0/〇〇1«8|^洱海sro _#-蝴E--TttaKl-s SCS.·逛戚谢 k0^0 V 溢SK-N^^m SI)s)ul) 001 (91)®恝啪联啪君(6) S S (9)鋰靼晡sitol 。口9/39^赃_細祕酹 IrxIMttIS 赃 _<tIM-h!si靼喊一E V 豳粼忉与蟋窠. (請先閱讀背面之注意事項再填寫本頁) 訂本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 36 A7 307779 ______B7 五、發明説明（μ) 合成例2 8至3 8 (請先閱讀背面之注意事項再填寫本頁) 經縮水甘油酸化之環氧樹脂的合成法（此同縮水甘油化）在裝有溫度計’攪拌器，分離器，冷凝器，及滴液容器之2升圓底燒瓶中置入3 0 · 7 g合成例2所合成之線型酚醛清漆（2) ，17lg雙酚a，17. 5g四溴雙酣A及1 17 8 g表氯醇’而內容物在攪拌下加熱至9 〇 °C之溫度。在9 0 °C溫度下，添加3 〇 g水及3 g氯化四甲銨’而混合物攪拌4小時。混合物溫度降至7 〇。(：並將壓力降至5 0 OmmHg，在此壓力下，在3小時內由滴液容器將1 4 2 . 5 g 4 8%氫氧化鈉水溶液添加於混合經濟部中央標準局負工消费合作社印製物中，同時以分離器去除系統中之水。氫氧化鈉逐滴添加完成後，持續去除水經3 0分鐘。將系統壓力降至2 0 mmHg，混合物在1 2 0°C縮合1小時。恢復常壓，在混合物中添加3 5 0 g水及2 5 0 g甲苯，形成之混合物再在9 0°C攪拌3 0分鐘。放置混合物，促使水層分離，並去除水層，殘留之樹脂層在1 5 0°C 2 0 OmmHg濃縮得到1 g經縮水甘油醚化之環氧樹脂，此者以下稱爲環氧樹脂（2 8 )。使用鹽酸一二噁烷法評估所得之環氧樹脂（2 8 )的環氧當量。亦以Meier Inc.之自動化軟化點測量儀評估環氧樹脂（2 8 )之軟化點，而以凝膠滲透層析（G P C )測其組成（合成例2至5 )。重複合成例2 8之方法，不同處係使用線型酚醛清漆本紙張尺度適用中國國家橾準（CNS ) A4規格（210X297公釐） 37 - 307779 at __B7_ 五、發明説明（35 ) ，雙酚A，表氯醇，及48%NaOH水溶液（用量示於脂至。 lCT\1/ _γ 氧 9 表環 2 於得 C 列製脂亦 , 樹果 } 氧結 7 環。表之成 8 當 3 氧 C 環至之成組形及估點評化亦軟 (請先閱讀背面之注意事項再填寫本頁) J: 訂經濟部中央標準局員工消費合作社印製本紙張尺度適用中國國家橾準（CNS ) Α4規格（2丨Ο X 297公釐） 38 五、發明説明（36) (3 3) (3 s) 3) 9) (s (π)(詞)3) ο·ειο zoeI 001 A7 B7 srolnroLnroloroloro sc; tn.NLO.CJLOCNJLocvl 06 06 06 sro ιη · ζ XXXXXX 〇〇V 〇〇V / .sis 【s ss »— * S-Employee consumption cooperation of the Central Standards Bureau of the Ministry of Economic Affairs Du Printed Quercus- N Scale Pu Hai plug MS MS X uesl V U0 § Tan Jifei scale-N You iod bu 91 0 / 〇〇1 «8 | ^ Erhai sro _ #-蝶 E--TttaKl-s SCS. k0 ^ 0 V overflow SK-N ^^ m SI) s) ul) 001 (91) ® slap coupler (6) SS (9) lithium sitol.口 9/39 ^ 貹 _ 紅秘酹 IrxIMttIS 買 _ < tIM-h! Si 靼 Shou an EV 豳忉和蟋窠. (Please read the precautions on the back before filling in this page) The size of the revised paper is applicable to China National Standard (CNS) A4 specification (210X 297mm) 36 A7 307779 ______B7 V. Description of invention (μ) Synthesis Example 2 8 to 3 8 (Please read the precautions on the back before filling in this page) Ring of glycidylation Oxygen resin synthesis method (this is the same as glycidylation) In a 2 liter round bottom flask equipped with a thermometer 'stirrer, separator, condenser, and drip container, place 3 0 · 7 g of the compound synthesized in Synthesis Example 2 Novolac (2), 17lg of bisphenol a, 17.5g of tetrabromobisphenol A and 1 178g of epichlorohydrin 'and the contents were heated to a temperature of 90 ° C with stirring. At a temperature of 90 ° C, 30 g of water and 3 g of tetramethylammonium chloride were added and the mixture was stirred for 4 hours. The temperature of the mixture dropped to 70. (: Reduce the pressure to 50 OmmHg. Under this pressure, add 1 4 2.5 g 4 8% aqueous sodium hydroxide solution to the Negative Work Consumer Cooperative of the Central Bureau of Standards of the Ministry of Mixture within 3 hours. At the same time, remove the water in the system with a separator. After the sodium hydroxide is added dropwise, continue to remove the water for 30 minutes. The system pressure is reduced to 20 mmHg, the mixture is condensed at 120 ° C 1 After returning to normal pressure, add 3 50 g of water and 2 50 g of toluene to the mixture, and stir the resulting mixture for 30 minutes at 90 ° C. Place the mixture to promote separation of the water layer and remove the water layer. The resin layer was concentrated at 150 ° C 2 0 OmmHg to obtain 1 g of glycidyl etherified epoxy resin, which is hereinafter referred to as epoxy resin (2 8). The obtained ring was evaluated using the hydrochloric acid-dioxane method The epoxy equivalent of oxygen resin (2 8). The softening point of epoxy resin (2 8) was also evaluated by Meier Inc.'s automated softening point measuring instrument, and its composition was measured by gel permeation chromatography (GPC) (Synthesis Example 2 to 5). Repeat the method of Synthesis Example 2 to 8, using novolac paper in different places The standard is applicable to China National Standard (CNS) A4 (210X297mm) 37-307779 at __B7_ 5. Description of the invention (35), bisphenol A, epichlorohydrin, and 48% NaOH aqueous solution (the dosage is shown in fat to. LCT \ 1 / _γ Oxygen 9 Table ring 2 In column C, fat making, tree fruit} Oxygen knot 7 ring. Table formation 8 When 3 oxygen C ring to the group shape and evaluation is also soft (please read the back first Note: Please fill out this page again) J: The size of the paper printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs is applicable to the Chinese National Standard (CNS) Α4 specification (2 丨 Ο X 297 mm) 38 V. Invention description (36 ) (3 3) (3 s) 3) 9) (s (π) (word) 3) ο · ειο zoe

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06 脬芻 0 0卜1 I 0S (請先閱讀背面之注意事項再填寫本頁) os ΙΖ S S3 S ooAZf-η οε i寸 SI Acol cosl 經濟部中央標準局貝工消费合作社印製一一 00n^s0s 00'ss 60S ,cra/3·!:細碱略 in s 9SI 趣梂IK - y溢谢蟋a y豳细s s5 OS (2®靼娌溢担駐k锭&§ llaal-憩坦扣长锴u y -溢谢蟋£3赵®a«·路坦扣爷锔Η y溢谢 ίί.¥^Ν 本紙張尺度適用中國國家標準（CNS ) A4规格（210 X 297公釐） 39 307779 A7 B7 五、發明説明（37 ) 合成例3 9 — 4 9 (請先閱讀背面之注意事項再填寫本頁) 聚合反應樹脂之合成法在裝有攪拌器及溫度計之1升可分離燒瓶中置入 200g合成例28所製之環氧樹脂（28) ，及78g 四溴雙酚A，而內容物在攪拌下加熱。溫度達1 〇〇°c時 ’添加0 _.2 g氯化四乙銨，在1 6 0。(：促進反應5小時 ’得到加成聚合反應樹脂，此者以下稱爲加成聚合反應樹月旨（3 9 ) 〇利用合成例1 6之方法評估加成聚合反應樹脂（3 9 )之環氧當量。利用凝膠滲透層（GPC)使用串聯 Shim-pack- HSG 2 0，4 0，5 0 及 6 0 之管柱評估該加成聚合反應樹脂（3 9 )之數量平均分子量，並以合成例1 6之方法測其分子量分佈。結果列於表8中。經濟部中央揉準局員工消费合作社印裝重複合成例3 9之方法，不同處係使用環氧撞fjg旨，雙酚A環氧樹脂，及四溴雙酚A (用量示於表8 )製得加成聚合反應樹脂（40)至（49)。亦評估加成聚合樹脂（40)至（49)之環氧當量，數量平均#子_^ , 及分子量分佈。結果亦列於表8。本紙張尺度適用中國國家橾準（CNS ) A4说格（210X297公釐） -40 - 五、發明説明（38 ) A7 B7 經濟部中央標準局貝工消费合作社印製 (3 (3 (IF) (s (3 3) (3 § (π) (3 (s06 焬揬 0 0 卜 1 I 0S (Please read the precautions on the back before filling in this page) os ΙZO S S3 S ooAZf-η οε i inch SI Acol cosl Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Beigong Consumer Cooperative, 100n ^ s0s 00'ss 60S, cra / 3 · !: fine base slightly in s 9SI fun IK-y overflow Xie 蟋 ay 豳 fine s s5 OS (2® Tatar overflowing ingots & § llaal-rest Buckle long yu-overflow Xie Chong £ 3 Zhao®a «· Lutan buckle 鎔 HY y Xie ίί. ¥ ^ Ν This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 39 307779 A7 B7 5. Description of the invention (37) Synthesis Example 3 9 — 4 9 (Please read the precautions on the back before filling this page) The synthesis method of the polymerization resin is placed in a 1 liter separable flask equipped with a stirrer and thermometer 200 g of epoxy resin (28) prepared in Synthesis Example 28 and 78 g of tetrabromobisphenol A were added, and the contents were heated with stirring. When the temperature reached 100 ° C., 0 _.2 g of tetraethyl chloride was added Ammonium, at 160. (: Promotes the reaction for 5 hours' to obtain the addition polymerization resin, which is hereinafter referred to as the addition polymerization reaction tree purpose (3 9). ○ The addition polymerization is evaluated by the method of Synthesis Example 16 The epoxy equivalent of the reaction resin (3 9). The gel permeation layer (GPC) was used to evaluate the addition polymerization resin (3 9 using Shim-pack-HSG 2 0, 4 0, 50 0 and 60 columns in series). ) Number average molecular weight, and its molecular weight distribution was measured by the method of Synthesis Example 16. The results are listed in Table 8. The method of Synthesis Example 3 9 was repeated by the printing and printing of the Employees' Cooperative of the Central Bureau of Economic Cooperation of the Ministry of Economic Affairs. Oxygen impact fjg purpose, bisphenol A epoxy resin, and tetrabromobisphenol A (amounts shown in Table 8) were used to prepare addition polymerization resins (40) to (49). The addition polymerization resins (40) to (49) Epoxy equivalent, number average # 子 _ ^, and molecular weight distribution. The results are also listed in Table 8. This paper scale is applicable to the Chinese National Standard (CNS) A4 (210X297mm) -40-V. Description of the invention (38) A7 B7 Printed by the Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (3 (3 (IF) (s (3 3) (3 § (π) (3 (s

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I 經濟部中央標準局貝工消費合作社印袋 A 7 B7 _ — . 丨丨丨·— — "'"' 五、發明説明（39) 實施例1 3 在1 OOg加成聚合反應樹脂（46)在2 5 g甲基乙基酮中之溶液中添加2. 5g雙氰胺及0· 15g2〜乙基一4 一甲基咪唑在2 0 g乙二醇單甲醚中之溶液’產生環氧樹脂組合成之樹脂液。將玻璃布（WE A -1 8W1 〇 5 F，Nitto Boseki Co.，Ltd.之產物）浸入所製之樹脂液中，然後在1 4 0°C乾燥爐中乾燥6分鏟製得預浸漬體。預浸漬體之環氧樹脂組成物含量係4 9重量％。評估預浸漬體之外觀。使用同於例5至12之預浸漬體，評估玻璃化溫度， Tg。亦評估其浸透性及在加壓蒸缸試驗（PCT)後；^ 抗焊熱性。結果列於表9。實施例14至15 重複例1 3之方法，不同處係各以加成聚合反應樹月旨 (47)至（48)(用量示於表9)取代加成聚合樹脂（4 6 )，製得樹脂液，接著製得預浸漬體。如例 1 3般評估所製之樹脂液及預浸漬體的玻璃化溫度， P C T後之抗焊熱性，以及浸透性。結果列於表9。本紙張尺度適用中國國家橾準（CNS ) Λ4規格（2丨0X297公釐> (請先閲讀背面之注意事項再填寫本頁} -=° 丄I ! - 42 - 307779五、發明説明（4〇) ^_9 A7 B7 實施例 UL U. L5. 環氧樹脂組成物之組成加成聚合反應樹脂（46) 100 (47) 100 (48) 100 雙氰胺 2. 5 2.5 2.5 2-乙基-4-甲基咪唑 0. 15 0.15 0.1 硬化產物之件晳玻璃化溫度T g，°c 171 170 162 PCT後之抗焊熱性 120 min 〇〇〇 150 rain 〇〇 Δ 樹脂液對玻璃布之浸透性良好良好良好請先閱讀背 i 事項再填寫本頁I Printed bag A 7 B7 _ —. 丨丨丨 — — " '"' of the Central Standards Bureau of the Ministry of Economic Affairs. 5. "Description" (39) Example 1 3 Addition polymerization resin at 1 OOg ( 46) A solution of 2.5 g of dicyandiamide and 0.15 g of 2-ethylimidazole in 20 g of ethylene glycol monomethyl ether was added to a solution of 25 g of methyl ethyl ketone. Resin liquid composed of epoxy resin. The glass cloth (product of WE A -1 8W1 〇5 F, product of Nitto Boseki Co., Ltd.) was immersed in the prepared resin solution, and then dried in a drying oven at 140 ° C for 6 minutes to obtain a prepreg . The epoxy resin composition content of the prepreg was 49% by weight. Evaluate the appearance of the prepreg. Using the same prepregs as in Examples 5 to 12, the glass transition temperature, Tg, was evaluated. Also evaluated its permeability and after the pressurized steam cylinder test (PCT); ^ welding heat resistance. The results are shown in Table 9. Examples 14 to 15 The method of Example 13 was repeated, except that the addition polymerization resins (47) to (48) (amounts shown in Table 9) were used instead of the addition polymerization resin (4 6) to prepare The resin liquid is then prepared into a prepreg. The glass transition temperature of the prepared resin solution and prepreg, solder resistance after PCT, and penetration were evaluated as in Example 13. The results are shown in Table 9. This paper scale is applicable to China National Standard (CNS) Λ4 specifications (2 丨 0X297mm> (Please read the precautions on the back before filling out this page)-= ° 丄 I!-42-307779 V. Description of invention (4 〇) ^ _9 A7 B7 Example UL U. L5. Composition of epoxy resin composition addition polymerization resin (46) 100 (47) 100 (48) 100 dicyandiamide 2.5 5 2.5 2.5 2-ethyl- 4-Methylimidazole 0.15 0.15 0.1 Pieces of hardened product Clear glass transition temperature T g, ° c 171 170 162 Solder resistance after PCT 120 min 〇〇〇150 rain 〇〇Δ Resin liquid penetration of glass cloth Good good good please read the back i matters before filling this page

1T 經濟部中央標準局負工消费合作社印製 2 2 1 例較比1T Printed by the Consumer Labor Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 2 2 1 Case Comparison

樹氧環之列所 7 表用使係處同不法方之 3 1 例複一鼠 J C組gg 0 樹樹應氧反環合得聚製成’ 加 } 之 ο 列 1 所表 8 於表示及量 ο ( 3 ) ( 5 至 4 ) ( 8 至 2 ) ( 9 脂 3 製性所熱估焊評抗般之 3 後 1 T 例 C 如 P o t 體度。漬溫 ο 浸化 1 預璃表得玻於製的列著體果接漬結，浸。液預性脂及透樹液浸之脂及物樹以成之，本紙張尺度適用中國國家標率（CNS ) A4规格（210X297公釐） 307779 A7 ___B7五、發明説明（41)Table 7 of the oxygen ring of the tree is used in the same way as the illegal side. 3 1 case of the compound mouse JC group gg 0 The tree is formed by the combination of oxygen and reverse ring. Volume ο (3) (5 to 4) (8 to 2) (9 Grease 3 The thermal evaluation of welding resistance is generally 3 after 1 T Example C such as Pot body size. Stain temperature ο Infiltration 1 Pre-glass table It can be obtained by boiled and stained knots of fruit and fruit. It is made of liquid pre-fat and tree-soaked fat and trees. This paper scale is applicable to China National Standard Rate (CNS) A4 (210X297mm) 307779 A7 ___B7 V. Description of the invention (41)

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鋰靼减舷Y溢粼孕蟋截忉cra / 3 95岫細祕_坤％lws U _邻蟋· 砬砥鸠頰_ 賊蛑 _# 赋餵# 槲〇〇〇vxx XXX X 〇〇〇〇〇〇 v〇v V 疟溥谣葙铤si靼uesl ui 却癍酞拭-N班iod u°-DOlM_q>0F鸹Mss^0 φ!#«ιη--τ«8νι-ζs)5)5)(s(5 (5) (63鹊葙<0联<10后 s § (83)蠲恝碱酹本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ^——^------1 t- (請先閱讀背面之注意事項再填寫本頁) 、-° 44 A7 B7 307779 五、發明説明（42 ) 如前述者，本發明環氧樹脂因爲與硬化劑混合時之粘度相當低，故易成型。本發明環氧樹脂在硬化後具有優越之耐熱性以及髙機械強度。因此，適於與多種纖維組合而構成塑性複合材料。環氧樹脂組成物（以由本發明特定經共縮水甘油醚化之環氧樹脂加成聚合反應製得之加成聚合反應樹脂爲主組份）對諸如玻璃布等材料的滲透性優越，而一旦硬化’則熱化產物具有優越之耐熱性，抗起泡性，及對銅覆膜之粘著性。 (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局負工消费合作社印製準榡家國國中用適 .度尺一浪氏規 ¥ 公 7 9 2 -- i-y —307779 {由本局) 承辦人代碼大類 I PC分類Lithium-reducing flank Y overflowing pregnant cricket cut cra / 3 95 Xiuxi secret_ Kun% lws U _ neighbouring cricket · 砬砥鳥 Cheek _ 賑蛑 _ # 賵質 # 湯〇〇〇xxxx XXX X 〇〇〇〇〇〇v〇v V malaria rumors 铤 si ue uesl ui but phthalophthalate wipe-N class iod u ° -DOlM_q > 0F 鸹 Mss ^ 0 φ! # «Ιη--τ« 8νι-ζs) 5) 5) (s (5 (5) (63 magpie < 0 union < 10 after s § (83) copperine base paper size is applicable to China National Standard (CNS) A4 specification (210X297mm) ^ —— ^- ----- 1 t- (please read the precautions on the back before filling in this page),-° 44 A7 B7 307779 V. Description of the invention (42) As mentioned above, when the epoxy resin of the present invention is mixed with hardener The viscosity is relatively low, so it is easy to mold. The epoxy resin of the present invention has excellent heat resistance and high mechanical strength after hardening. Therefore, it is suitable for combining with a variety of fibers to form a plastic composite material. Addition polymerization resins prepared by the addition polymerization of certain co-glycidyl etherified epoxy resins are the main components). They have excellent permeability to materials such as glass cloth, but once hardened, the thermalized products have It has excellent heat resistance, blistering resistance, and adhesion to copper film. (Please read the precautions on the back side before filling out this page) Printed by the Central Standards Bureau of the Ministry of Economic Affairs, the Cooperative Consumer Cooperative Printed the quasi-home country Use a moderate degree ruler for a wave's rule ¥ public 7 9 2-iy — 307779 (by this bureau) undertaker code category I PC classification

6 6 A B 本案已向：國（地區）申請專利，申請日期：案號：，□有□無主張饅先權本本本曰曰曰 1993 年 1993 年 1994 年曰BB 8 8 2 111 月月月 2 2 1 5-28825 5- 28826 6- 1731 權權權先先先優優優張張張主主主 S 00 000 有關微生物已寄存於：，寄存日期：，寄存號碼: 4- ---,r---良--I---丁----L 11_ 象 -έ 髮 (請先閲讀背面之注意事項再填寫本頁各欄) 經濟部中央樣準局負工消費合作社印裝本紙張尺度適用中國國家標準（CNS ) A4规格（210X297公釐） -3 -6 6 AB This case has applied for a patent to: Country (region), application date: Case number:, □ Yes □ No claim for the first right of the manuscript The original version is 1993 1993 1993 1994 BB 8 8 2 111 month month month 2 2 1 5-28825 5- 28826 6- 1731 Quan Quan Quan Xian You You Xian Zhang Zhang Zhang Zhu Zhu S 00 000 The related microorganisms have been deposited in:, Date of deposit:, Number of deposit: 4- ---, r- -良 --I --- 丁 ---- L 11_ 象 -έ hair (please read the precautions on the back and then fill in the columns on this page) Printed copies of paper size of the Central Prototype Bureau of the Ministry of Economic Affairs Applicable to China National Standard (CNS) A4 specification (210X297mm) -3-

Claims

經濟部中夬橾準局員工消費合作社印製々、申請專利範圍附件二A : 第83 1 0 1 274號申請專利案中文申猜專利範園修正本民國84年10月修正 1. 一種環氧樹脂（A)，其係以至少一種選自表鹵醇及甲基表鹵醇中者將重置比例爲1_9 5 : 9 9 — 5之雙酚（I )與線型酚醛清漆（I I )縮水甘油醚化所製成 Ο 2 .如申請專利範圍第1項之環氧樹脂（A )，其中該雙酚（I )與胲線型酚醛清漆（I I )所用之重量比係 5〇 — 90 i 50 — 10° 3 .如申請專利範園第1或2項之環氧樹脂（A )，其中該線型酚醛清漆（I I )之軟化點最高1 1 〇°C，數量平均分子置爲1，0 0 0至3 0 0，而分子置分佈最高爲2。 4.—種加成聚合反應樹脂（B)，此樹脂之製法係以選自表鹵醇及甲基表鹵酵中之至少一者將重置比例爲1 一 95 : 99 — 5之雙酚（I)與線型酚醛清漆（I I) 縮水甘油醚化，製得環氣樹脂（A):然後使該環氧樹脂 (A)與經鹵化之雙酚（I I I)以74 — 55 : 26 — 4 5之重量比例反應而生成加成聚合反應樹脂（B )。 5 .如申猜專利範園第4項之加成聚合反應樹脂（B )，其中該環氧樹脂（A)與該經鹵化雙酚（I I I )間之反應係在選自環氣樹脂（E )與經環氧化經鹵化之雙酚本紙張尺度逋用中國國家標準（CNS)A4現格（210Χ297公釐）-1 - (請先閱讀背面之注意事項再填寫本頁) 、π 8 8 S 8 ABCD 307779 經濟部中央標準局真工消費合作社印製六、申請專利範圍 1 | ( F ) 中的至少一者存在下進行 0 1 I 6 • 如串請專利範圍第 5 項之加成聚合反應樹脂 ( B 1 I ) 9 其中該經環氧化經鹵化之雙酚 ( F ) 之用置爲 1 至 y—S 請 1 1 1 5 重量 % 0 先閱讀 1 1 7 如丰請專利範圍第 4 項之加成聚合反 rrtg 應樹脂 ( B 背 ιέ 1 I 之 1 I ) 9 係用作清漆中之主成份〇 >王意 1 1 事 1 8 如串請專利範圍第 7 項之加成聚合反 rrttf Μ 樹脂 ( B 項再 1 填 ) 9 其中清漆可被用來浸溃層稹板中之强化材料 0 罵本袈頁 9 * 一種加成聚合反應樹脂 ( D ) 9 其之製法係以 1 I 選白表鹵醇及甲基表鹵醇中之至少 — 者將重量比例爲 5 — 1 1 I 8 0 ： 9 4 一 5 ： 1 一 1 5 之雙酚 ( I ) > 線型酚醛清漆 1 1 訂 1 ( I I ) 9 及經鹵化之雙酚 ( I I I ) 縮水甘油醚化 9 製得環氧樹脂 ( C ) 再使環氧樹脂 ( C ) 與經鹵化之雙酚 1 1 ( I I I ) 以 9 0 — 5 8 ： 1 0 — 4 2 之重置比例反 nsig 應 9 1 I 製成加成聚合反應樹脂 ( D ) 0 1 1 0 • 如丰請專利範圍第 9 項之加成聚合反 rrtg 應樹脂 9 Γ 其中該環氧樹脂 ( C ) 與該經鹵化雙酚 ( I I I ) 間之反 1 ntg 應係在一種環氧樹脂 ( E ) 存在下進行 0 1 1 1 * 如串讅專利範圍第 9 項之環氧樹脂組成物 9 其 1 中該線型酚醛清漆 ( I I ) 之軟化點最高 1 1 0 °C 9 數量 1 I 平〇均分子量爲 1 0 0 0 至 3 0 0 9 而分子置分佈最高爲 1 1 1 I L· 1 2 如串請專利範園第 1 0 項之加成聚合反應樹脂 1 1 1 ( D ) y 係用作清漆中之主成份 0 1 1 本紙法尺度適用中國國家橾牟（CNS ) A4規格（210X297公釐） 307779 經濟部中央標準局員工消費合作社印裝 A8 B8 C8 D8 申請專利範圍 13.如申請專利範圍第12項之加成聚合反應樹脂 (D)，其中清漆可被用來浸漬層稹板中之强化材料。 I ί 裝訂 f .冰 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4规格（210X297公釐）Printed by the Employee Consumer Cooperative of the Ministry of Economic Affairs of the Ministry of Economic Affairs 々, the scope of patent applications Appendix II A: Patent Application No. 83 1 0 1 274 Resin (A), which is bisphenol (I) and novolac (II) glycidol with a reset ratio of at least one selected from epihalohydrin and methylepihalohydrin, with a reset ratio of 1_9 5: 9 9-5 Made by etherification Ο 2. The epoxy resin (A) as claimed in item 1 of the patent scope, in which the weight ratio of the bisphenol (I) to the novolac (II) is 50—90 i 50— 10 ° 3. For example, the epoxy resin (A) of item 1 or 2 of the patent application park, where the novolak (II) has a softening point of up to 1 10 ° C, and the number average molecule is set to 1, 0 0 0 Up to 300, and the molecular distribution is up to 2. 4. A kind of addition polymerization resin (B), the production method of this resin is based on at least one selected from epihalohydrin and methyl epihalogenase to reset the ratio of bisphenol 1 to 95: 99-5 (I) etherified with novolac (II) glycidol to prepare a ring gas resin (A): then the epoxy resin (A) and halogenated bisphenol (III) were 74-55: 26-4 The weight ratio of 5 reacts to form an addition polymerization resin (B). 5. For example, the addition polymerization resin (B) in item 4 of Shenchai Patent Fan Garden, wherein the reaction between the epoxy resin (A) and the halogenated bisphenol (III) is selected from the group consisting of ring gas resin (E) ) This paper is used in accordance with the Chinese National Standard (CNS) A4 (210Χ297 mm) -1-(please read the precautions on the back before filling out this page), π 8 8 S 8 ABCD 307779 Printed by the Genuine Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 6. Apply for patent scope 1 | (F) in the presence of at least one 0 1 I 6 • Addition polymerization if the patent scope item 5 is requested Resin (B 1 I) 9 where the use of the epoxidized and halogenated bisphenol (F) is set to 1 to y-S please 1 1 1 5 weight% 0 first read 1 1 7 Ruofeng patent scope item 4 The addition polymerization anti-rrtg resin (B back ιέ 1 I of 1 I) 9 is used as the main component in varnish. 〇> Wang Yi 1 1 Matter 1 8 Addition polymerization of anti-rrttf Μ resin (item B is filled in 1) as claimed in item 7 of the patent scope 9 where varnish can be used to impregnate the reinforced material in the layered plywood 0 Addition polymerization resin (D) 9 The preparation method is to select at least one of white epihalohydrin and methyl epihalohydrin with 1 I—the weight ratio is 5 — 1 1 I 8 0: 9 4 1 5: 1 1-5 of bisphenol (I) > novolac 1 1 order 1 (II) 9 and halogenated bisphenol (III) glycidyl etherification 9 to obtain epoxy resin (C) and then epoxy resin (C) C) With halogenated bisphenol 1 1 (III) at a reset ratio of 9 0-5 8: 1 0-4 2 anti-nsig should be 9 1 I to make addition polymerization resin (D) 0 1 1 0 • Addition polymerization reverse rrtg should be resin 9 Γ of this patent if the patent scope is in the scope of item 9 Γ where the epoxy resin (C) The reaction between the halogenated bisphenol (III) and 1 ntg should be carried out in the presence of an epoxy resin (E) 0 1 1 1 * For example, the epoxy resin composition 9 of the patent scope item 9 Among them, the softening point of the novolac (II) is up to 1 1 0 ° C 9 Quantity 1 I Flat 〇 The average molecular weight is 1 0 0 0 to 3 0 0 9 and the molecular distribution is up to 1 1 1 IL · 1 2 Addition polymerization resin 1 1 1 (D) y is used as the main component in varnish if the patent Fanyuan Item 10 is submitted 0 1 1 This paper method scale is applicable to China National Mous (CNS) A4 specification (210X297 C) 307779 Printed and printed A8 B8 C8 D8 of the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. Patent application scope 13. Addition polymerization resin (D), such as item 12 of the patent application scope, where varnish can be used to impregnate the layered board Of reinforced materials. I ί binding f. Ice (please read the precautions on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 specification (210X297mm)