1307707： 九、發明說明： 【發明所屬之技術領域】 本發明係—種在積層板製程中，具有良好的反應性、寬廣的加 w=^indQW)之賴制㈣高補_溫度之縣麟清漆組成物。= 二其所壓合的板材具有高玻璃轉移溫度(Tg)、低吸水率、優良 = ⑽4㈣試。可有效降㈣或祕用量，即可達到ί 【先前技術】 環氧樹脂因本身之化學結構關係，在反應性 二31越，硬化後的環鑛脂不僅仍保有縣之特性，對於水氣及辟物 資更八阻隔性’且具有質輕’成本低等優點。所以環氧樹脂廣泛的使用於 ίί 輸騎料觀路板基料。尤其在近_印刷 電路板減邁向輕、薄、小型及精密化，對此材料之要求亦愈迫切。 【發明内容】 【擬解決之技術課題】 就印刷！路之積層板而言’隨著環保意識提升，目前國際規範 i=eadfrce)，所崎基板的加王性要求特砸格，尤其是對觀之玻ϋ =溫度(Tg)及基板於錫爐中之财雛等已成為此技㈣者必須克服之重要^ 【解決課題之技術手段】 有鑑於上述課題，本發明人經研究、試驗後發現，在環氧樹 混一種具有合適反應性、寬廣的壓合加工區間、高 t 低吸水性《«紐f ^料⑽ 隱樹脂’將可達到所要求之特性。由於二氫苯并熱固性樹脂，=化=盖 ϋ減含氮元素之結構，因此具有優良耐熱性、高Tg及耐ϋ . 反應性及較高崎麟轉度，純寬廣之壓合加工師嫌^優 1307707 二氫苯并_x)熱固性樹脂本身為一含氮的雜環化合物_㈣ydic ⑽p_ds)，並在其樹脂中導人有少量之獻素，可以藉由魏協同效應 (synergistic effect) ’而得到更好之難燃積層板用樹脂材料。 由之本發明之目的’係提供—絲層細高麵轉移溫度之環氧樹脂清漆 組成物’包括：（A)-種新型二氫苯并（ΝΡΒχ)熱固性；^脂，此樹脂係利用下 歹二匕合，，應所得’其成份包含：⑷―種二官能基或二官能基以上之環氧樹 月曰與一 g旎基之酚類化合物反應所得之酚類產物；（b 合之-級麵化她(e)二官驗之麵化她及⑷帽錢帽化;^ ⑻一或以上環氧樹脂；（C)祕細旨硬化劑；（D)硬化促進劑等所組成。 此環氧樹脂清漆配方組成物’經由硬化後，可財效提騎狀玻璃轉移1307707: IX. Description of the invention: [Technical field to which the invention pertains] The present invention is a kind of system which has good reactivity and wide plus w=^indQW in the process of laminated board (4) high-filling Varnish composition. = 2 The plate to be pressed has a high glass transition temperature (Tg), low water absorption, and excellent = (10) 4 (four) test. Can effectively reduce (four) or secret amount, can reach 【 [Prior Art] Epoxy resin due to its own chemical structure, in the reactivity of the second 31, hardened ring petrolatum not only retains the characteristics of the county, for water vapor and The material has a more eight barrier property and has the advantages of light weight and low cost. Therefore, epoxy resin is widely used in ίί. Especially in the near-printed circuit board, the lighter, thinner, smaller and more precise, the requirements for this material are more urgent. [Summary of the Invention] [Technical issues to be solved] Just print! In terms of the laminate of the road, 'with the increasing awareness of environmental protection, the current international standard i=eadfrce), the king of the Saki substrate requires special specifications, especially for the glass of the glass = temperature (Tg) and the substrate in the tin furnace In the light of the above-mentioned problems, the inventors discovered that the epoxy resin mixed with a suitable reactivity is broad and broad. The press-fit processing interval, high t-low water absorption "«纽料(10) hidden resin" will achieve the required characteristics. Due to the structure of the dihydrobenzo-thermosetting resin, which has the structure of nitrogen-containing elements, it has excellent heat resistance, high Tg and resistance to hydrazine. Reactivity and high-spinning rotation. Excellent 1307707 Dihydrobenzo-x) thermosetting resin itself is a nitrogen-containing heterocyclic compound _(d) ydic (10) p_ds), and has a small amount of succulent in its resin, which can be achieved by the synergistic effect A resin material for a better flame retardant laminate is obtained. The purpose of the present invention is to provide an epoxy resin varnish composition for the fine layer transfer temperature of the silk layer, which comprises: (A) a novel dihydrobenzo (fluorene) thermosetting property;歹 二匕,, should be obtained as 'the composition of: (4) - a phenolic product obtained by reacting a difunctional or difunctional epoxy resin ruthenium with a fluorenyl phenolic compound; - Leveling her (e) second officer to face her and (4) cap money cap; ^ (8) one or more epoxy resin; (C) secret fine hardener; (D) hardening accelerator. The epoxy resin varnish formula composition can be transferred to the glass by the hardening
溫度(Tg)，降低基板吸轉並提升耐熱性，並可以有效降低成本及優異之加工 性0 、 本發日狀卿輔板用高_齡溫度之觀樹脂清雜成物，因播混有 (鹏x)熱固性樹脂，使其有著比—般環氧樹脂更好的機械、化 學^物理性質，如低吸難'高賴轉移温度、尺寸紋性經好的電氣性質； 聚合時可孙促進舰能自身_聚合，而其開環聚合並無 ^，質(啦物)誠生，獨板雛等優點，但高溫下硬化反應速率過 快不易控制。若能在硬化過程中，加入適量酉分系結構化合物，不但可促進硬化 速度、降低硬化溫度’同時促使開環聚合完全，使得板具有更優良物性。 上述，發明所摻混之新型二氫苯#(NPBX)熱固性樹脂，美國專利第 4,6〇7,091说曾披露利用苯胺、丙^(Bisphen〇1A)及情製備，而美國專利第 6,〇〇5,〇64細利騎贿脂、苯胺及甲喊備，彻上述美 ^氫苯并(NPBX)樹脂’由於溶解度不佳，於室溫儲存易因過飽和，而^成大 析出’在後續之制很不方便。本發明為避免晶體析出，採用經由 &、之新型一虱苯并(npbx)樹脂，因其化學結構已經過修飾，於儲存 =會造f*大量晶體析出，可適用於工f上之A量生產。另美國專利第 ，，484號是利用笨并（Benz〇xazine )直接高溫硬化，並添加A⑽H)3耐辦 W等級。而錢專利第5,443,911號是利㈣_azin^ ^化％補轻硬_ ’可減料個量，硬化後積層板亦可逹耐燃等級 Ϊ 1而t華民國專利第_253"號，是利用芳香族二胺化合物、義化合物 ，胺及經類化合物’提丨製備Dihydrobenzoxazine細性細旨之方法，、但利用 方香族二胺化合物，成本昂貴，不適合工業上生產。 1307707 【發明之詳細說明】 士=明if 3提供—種環氧樹脂摻混二氫苯并㈣呵熱_樹脂清漆 Tf、、且成，二且成包括：⑻—種新型二氫苯并卿x)熱固性樹脂，⑼-或夕種以上％氧樹脂’（〇樹脂硬化劑，⑼硬化促進劑等；將⑷、⑹、 (C)及(D)以疋比例混合均勻後，即可得積層板用之含二氮苯并⑽明熱固 性樹脂清漆配方。 ”' ^成份⑷新型二氫苯并(ΝΡΒχ)’係利用⑷一種二官能基或二官能基以 上之環讀脂與二官能基之賴化合物反顧得之_產物；⑻―種單官能 基及二官能基混合之-級麵化合物；（e)H能基之賴化合物；及⑷ 曱越或聚帽化合物’且在觸溶劑下反應製得。經由改質後可 式，詳述其合成例於下： i (A-l) NPBX-610是於備有加熱包、控溫器、電動麟機、冷凝管之虬 四頸玻璃反應槽中’置入171〇克丙二_isphedA，BpA)、5 脂(NPEL-篇），在少量溶劑下加入四級鱗鹽觸媒於15叱反應2小時，Z 後，加入782克聚曱醛(parafbrmaldehyde：^麵克甲苯攪拌溶解，並將· 克苯胺(amhne)緩慢滴入上述溶液中，溫度控制於6〇〜n(rc之間，反應*〜6 時’再利用真空將溶劑及未反應物抽出，再將9〇〇克丙g同加人予以溶 知固形伤80%之改質一氫苯并化合物，以下簡稱ΝρΒχ_6ΐ〇。 (A-2)NPBX-62〇是於備有加熱包、控溫器、電動授拌機、冷凝管之几四 頸玻璃反應槽中’置入17H)克丙二酚(BisphedA，BpA)、27 (NPEL指E)，在少量溶劑下加入四級麟鹽觸媒於15叱反應' 2小^展二曰 再加入880克聚甲醛(parafonnaldehyde)、148克二胺基二苯基曱浐 (Diaminodiphenylmethane^ 1000 克甲苯半溶解，並將 ni6 克苯 = 緩慢滴入上述溶液中，溫度控制於6(M1(rc之間，反應4〜6 d、時，再 空將溶劑及未反應物抽出’再將_克丙嗣加人予赌解，即可制形份 之改質二氫苯并化合物，以下簡稱NPBX-620。 。 —(A-3)NPBX-630是於備有加熱包、控溫器、電動攪拌機、冷凝管之5 頸玻璃反應槽巾，i人1710克!^二零丨_。丨^職）、_克四 樹脂(NPPN，，在少量溶劑下加入四級顧觸媒於15(Γ(：反應2小時，$ 後再加入782克聚曱路(paraf0rmaldehyde)及卿〇克曱苯獅溶解，並將= 克苯胺(aniline)緩慢滴入上述溶液中，溫度控制於6〇〜11〇(>c之間，反應4 時’再利用真空將溶劑及未反應物抽出，再將9〇〇克丙_加入予以溶^ $ 付固形伤80%之改負一鼠本并化合物，以下簡稱]s^pbX-630。 1307707 η x/A-4)腦^640是於備有加熱包、控溫器、電動授拌機、冷凝管之5L四 ，匕璃反應槽中’置人171〇克丙二齡(BisphedA，BpA)、3〇〇克四官能基環氧 a(NPPN_431) ’在少量溶冑彳下加人四級雜觸媒於i5(rc反應2小時，降溫 <再加入880克聚酽路(paraf〇rmaidehycje)、Mg克二胺基二苯基甲烧 (Dmmmodiphenyl methane)&丨_克甲苯授摔溶解，並將〗丨丨6克苯胺㈣㈣ '，慢，入上述溶液t，溫度控制於㈣丨。。。之間，反應4〜6小時，再利用真 空將溶劑，未反應物抽出，再將9⑻克丙酮加人予以溶解，即可卵形份8〇〇/。 之改質二氫苯并化合物，以下簡稱NPBX440。 一 述A·1 ’ A·2’A_3及A-4之合成例中，其製備二氫苯并化合物之⑻一 種了官能基或二官能基以上之魏翻旨與二官能基之_化合物反應所得之 酌類^物’ -^：係使職祕氧舰制二祕合物，反應後·_之贿產物。 製備二氫苯并化合物之(b)一種單官能基及二官能基混合之一級胺類化合 物.Γ般f使用一級胺如甲基胺、苯胺、鄰甲苯胺(toluidine)、甲氧苯胺 (anisidine)專’可以為脂月樣或芳香族胺類化合物，最佳為苯胺二二 基曱烷。 製備二氫苯并化合物之(c)一種二官能基之酚類化合物，一般係使用鄰-曱 酚、丙一酚A、丙二酚F、丙二酚s、美耐皿(melamine)或酚醛樹脂等，最佳 為丙二酚或酚醛樹脂。 製備二氫苯并化合物之(d)甲醛或聚甲醛化合物，一般係使用曱醛、聚甲 盤或情蒸氣等’最佳為聚甲盤，因為聚甲路會隨著一級胺的滴加而緩慢溶解 反應，促使二氫苯并（NPBX)樹脂環形成。 而製備二氫苯并化合物化合物之溶劑並無特別限制，只要可以溶解各反應 物即可j例如.醇類、酮類、醚類、醋類或烴類溶劑，以烴類溶劑如甲苯，二 节苯等最佳’ 1U為聚合反應後會產生水分子，而其反應生成水與甲苯不互溶， 可迴流蒸鶴後重覆使用。 本發明樹脂清漆配方組成物中之成份(B)，其環氧樹脂可為含膦環氧樹脂 係將有機膦化合物(如’ 9,10-二氫-9-氧雜-10-磷菲_1〇氧化合物(簡稱D〇p〇)) 與 o-cresol formaldehyde n_lac ep〇xy(NPCN-703)環氧樹脂反應，形成含膦環 氧樹脂(破含量為2〜5重量％);或為溴化環氧樹脂係利用四溴丙二酚(TBB/ 與液態環氧樹脂(NPEL-128E)反應，並摻混多官能基環氧樹脂，所製備之 樹脂(溴含量為14〜21重量°/〇)。 9 1307707 本發明樹脂清漆配方組成物中之成份(c)，其樹脂硬化劑包括酚醛樹脂硬 化劑’如多價胺(Polyvalent amines)、多價叛酸(polyvalent carboxylic acids)、氰 二醯酸(dicyano diamide)、酸酐(anhydrides)、酌·甲越樹脂(Phenol Novolac Epoxy， 簡稱 PN)' 三聚氰胺酌甲趁(Melamine Phenol Novolac,簡稱 MPN)、BPA Phenol Novolac(簡稱BPA-PN)及四酚乙烷樹脂(簡稱TPN，南亞塑膠生產)等，其中最佳 為四齡乙烧樹脂。 本發明樹脂清漆配方組成物中之成份(D)，其硬化促進劑包括三級膦、三 級胺、季鱗鹽、季銨鹽、味吐(imwazo】e)化合物，其中三級膦包括：三苯基膦 等；三級胺包括：三甲基苯胺、三乙基胺、三丁基胺、二曱基胺乙醇等；季鱗 φ 鹽包括：四丁基溴化鑄、四苯基溴化鱗、乙基三苯基溴化鎮、丙基三苯基氣化 鐫、丁基三苯基溴化鱗等含鹵化物季鱗鹽；季銨鹽包括：四曱基溴化銨、四乙 基溴化銨、四丁基溴化銨、三乙基苯甲基溴化録、三乙基苯乙基溴化銨等含鹵 化物季銨鹽；咪唑(imidazole)化合物包括：2-甲基咪唑、2-乙基咪唑、2-十二 烷基咪唑、2-苯基咪唑、4-甲基咪唑、4-乙基咪唑、4-十二烷基咪唑、2-乙基_4· 曱基咪唑、2-乙基-4-羥甲基咪唑等，最適合為2_甲基咪唑或孓乙基_4_甲基咪 唑。該促進劑可以單獨使用或同時使用兩種以上混合使用，其使用量相對於 脂總量之0,01〜1PHR，最適量為0.04〜0.15PHR。Temperature (Tg), which reduces substrate absorption and improves heat resistance, and can effectively reduce cost and excellent processability. (Peng x) thermosetting resin, which has better mechanical and chemical properties than ordinary epoxy resin, such as low absorption, high transfer temperature, good linear properties, and good electrical properties. The ship can self-polymerize, and its open-loop polymerization has no advantages, such as quality, quality, and sapling. However, the hardening reaction rate at high temperature is too fast to control. If a proper amount of the quinone structure compound is added during the hardening process, not only the hardening speed but also the hardening temperature can be promoted, and the ring-opening polymerization is promoted at the same time, so that the plate has better physical properties. In the above, the novel dihydrobenzene #(NPBX) thermosetting resin blended by the invention, U.S. Patent No. 4,6,7,091, the disclosure of which is incorporated herein by reference to U.S. Pat. 〇5, 〇64 finely bribed fat, aniline and a shouting, the above-mentioned US Hydrazine (NPBX) resin 'because of poor solubility, storage at room temperature is easy to over-saturation, and ^ into a large precipitation' in the follow-up The system is very inconvenient. In order to avoid crystal precipitation, the invention adopts a novel bismuth benzo (npbx) resin via &, because its chemical structure has been modified, and it can be used for the precipitation of a large amount of crystals in the storage = Volume production. Another U.S. Patent No. 484 is a direct high temperature hardening using Benz〇xazine and adding A(10)H)3 toughness. And the money patent No. 5, 443, 911 is profit (four) _azin ^ ^ %% light and hard _ 'can reduce the amount of material, the hardened laminated board can also be 逹 逹 Ϊ Ϊ 而 而 而 华 华 华 华 民 华 华 华 华 华 华 , , The diamine compound, the compound, the amine and the compound-like compound are prepared by the method of preparing the Dihydrobenzoxazine, but the use of the scented diamine compound is expensive and is not suitable for industrial production. 1307707 [Detailed description of the invention] Shi = Ming if 3 provides - an epoxy resin blended with dihydrobenzo (4) heat _ resin varnish Tf, and into, and includes: (8) - a new type of dihydrobenzoic x) thermosetting resin, (9)- or more than 70% oxygen resin' (an epoxy resin hardener, (9) hardening accelerator, etc.; (4), (6), (C) and (D) are uniformly mixed in a ratio of bismuth, and then a laminate can be obtained. Formulation of diazonium benzo (10) bright thermosetting resin varnish for board. "'Component (4) new dihydrobenzo(ΝΡΒχ)' utilizes (4) a difunctional or difunctional or higher cyclic read and difunctional a compound that is counterproductive; (8) a mono- and di-functional mixed-grade compound; (e) a H-based compound; and (4) a thixo- or poly-cap compound' and in a solvent The reaction is prepared. The synthesis example is described below by modifying the formula: i (Al) NPBX-610 is a four-neck glass reaction tank equipped with a heating pack, a temperature controller, an electric machine, and a condenser. In the middle of 'insert 171 grams of propylene _isphedA, BpA), 5 lipids (NPEL- articles), adding a four-stage scale salt catalyst in a small amount of solvent 15 叱 reaction for 2 hours, after Z, add 782 g of polyfurfural (parafbrmaldehyde: ^ gram of toluene stirred to dissolve, and gram of aniline (amhne) slowly drip into the above solution, the temperature is controlled at 6 〇 ~ n (rc During the reaction, when the reaction is *6, the solvent and the unreacted material are extracted by vacuum, and then 9 g of the g-g is added to the human to dissolve the modified monohydrogen benzo compound, which is hereinafter referred to as ΝρΒχ_6ΐ〇. (A-2) NPBX-62〇 is placed in a four-neck glass reaction tank equipped with a heating pack, a temperature controller, an electric mixer, and a condenser tube. [Implanted 17H) gram bisphenol (Bisphed A, BpA) 27 (NPEL refers to E), adding a four-stage sulphate catalyst to a 15 叱 reaction in a small amount of solvent. 2 2 small 展 曰 曰 曰 880 880 880 880 880 880 880 880 880 880 880 880 880 880 880 880 880 880 880 880 880 880 880 880 880 880 880 880 880 880 880 (Diaminodiphenylmethane^ 1000 g of toluene is semi-dissolved, and ni6 g of benzene = slowly dropped into the above solution, the temperature is controlled at 6 (M1 (rc, reaction 4~6 d, when the solvent and unreacted materials are taken out again) 'Additional _ 克 嗣 嗣 嗣 嗣 赌 赌 , , , , , , , , , , 改 改 改 改 改 改 改 改 改 改 改 改 改 改 改 改 改(A-3) NPBX-630 is a 5-neck glass reaction sump equipped with a heating pack, a temperature controller, an electric mixer, and a condensing tube. It is 1710g for i people! ^20丨_.丨^)),_克Four resins (NPPN, in a small amount of solvent, add a four-stage catalyst to 15 (Γ:: reaction for 2 hours, then add 782 g of paraf0rmaldehyde and 〇 〇 曱 曱 溶解 溶解 ,, and will = The aniline is slowly dropped into the above solution, and the temperature is controlled between 6 〇 and 11 〇 (>c, and when the reaction is 4', the solvent and the unreacted material are extracted by vacuum, and then 9 gram of propyl _ Add a compound that is dissolved and dissolved by 80% of the solid form, and the compound is hereinafter referred to as s^pbX-630. 1307707 η x/A-4) Brain ^640 is equipped with a heating pack, a temperature controller, an electric mixer, a condenser tube, 5L, and a glass reaction tank, which is set to 171 grams of B2 (BisphedA). BpA), 3 gram of tetrafunctional epoxy a (NPPN_431) 'Add a four-stage heterocatalyst to i5 under a small amount of solution (rc reaction for 2 hours, cooling < then add 880 g of poly-parallel (paraf 〇rmaidehycje), Mgmmodidiphenyl methane & 丨 gram of toluene to dissolve and dissolve, and 〗 6 g of aniline (four) (four) ', slow, into the above solution t, temperature control (4) Between the reaction, the reaction is carried out for 4 to 6 hours, and then the solvent is taken out by vacuum, and the unreacted material is extracted, and then 9 (8) g of acetone is added to dissolve, and the aliquot of the dihydrobenzene can be obtained. And a compound, hereinafter referred to as NPBX440. In the synthesis example of A·1 'A·2'A_3 and A-4, the preparation of the dihydrobenzo compound (8) is a functional group or a difunctional group or more. The difunctional base compound obtained by the reaction of the compound '-^: is the second secret compound of the oxygen-based ship, and the brittle product after the reaction. Preparation of dihydrobenzoate (b) a monofunctional and difunctional mixed mono-amine compound. The use of a primary amine such as methylamine, aniline, toluidine, anisidine can be a lipid The moon-like or aromatic amine compound is preferably aniline dioxane. The dihydrobenzo compound is prepared as (c) a difunctional phenolic compound, generally using o-nonylphenol or propanol A. , propylene glycol F, propylene glycol s, melamine or phenolic resin, etc., preferably propylene glycol or phenolic resin. Preparation of dihydrobenzo compound (d) formaldehyde or polyoxymethylene compound, generally The use of furfural, polyacetal disk or steam is the best as a polystyrene disc, because the polymethylene will slowly dissolve the reaction with the dropwise addition of the primary amine, prompting the formation of a dihydrobenzo (NPBX) resin ring. The solvent of the dihydrobenzo compound compound is not particularly limited as long as it can dissolve each reactant, for example, an alcohol, a ketone, an ether, a vinegar or a hydrocarbon solvent, and a hydrocarbon solvent such as toluene or a benzene. Waiting for the best '1U for the polymerization reaction will produce water molecules, and the reaction produces water It is incompatible with toluene and can be re-used after reflowing. The component (B) of the resin varnish formulation of the present invention may be a phosphine-containing epoxy resin-based organic phosphine compound (eg '9, 10 -Dihydro-9-oxa-10-phosphaphenanthracene oxide (abbreviated as D〇p〇)) reacts with o-cresol formaldehyde n_lac ep〇xy(NPCN-703) epoxy resin to form a phosphine-containing epoxy Resin (breaking content is 2~5% by weight); or brominated epoxy resin using tetrabromopropanol (TBB/ with liquid epoxy resin (NPEL-128E) and blending polyfunctional epoxy resin , prepared resin (bromine content of 14 to 21 weight ° / 〇). 9 1307707 The component (c) of the resin varnish formulation composition of the present invention, the resin hardener comprising a phenolic resin hardener such as polyvalent amines, polyvalent carboxylic acids, cyanamide ( Dicyano diamide), anhydrides, Phenol Novolac Epoxy (PN) melamine Phenol Novolac (MPN), BPA Phenol Novolac (BPA-PN) and tetraphenol ethane Resin (referred to as TPN, South Asia plastic production), etc., the best of which is four-year-old E-burn resin. The component (D) in the resin varnish formulation of the present invention, the hardening accelerator comprises a tertiary phosphine, a tertiary amine, a quaternary salt, a quaternary ammonium salt, an imwazo e compound, wherein the tertiary phosphine comprises: Triphenylphosphine or the like; tertiary amines include: trimethylaniline, triethylamine, tributylamine, dinonylamine ethanol, etc.; quarter scale φ salt includes: tetrabutyl bromide cast, tetraphenyl bromide a quaternary salt containing a halide such as scaly, ethyl triphenyl bromide, propyl triphenyl gasification ruthenium, butyl triphenyl bromination scale, etc.; quaternary ammonium salt includes: tetradecyl ammonium bromide, four a halide-containing quaternary ammonium salt such as ethyl ammonium bromide, tetrabutylammonium bromide, triethylbenzyl bromide, triethyl phenethyl ammonium bromide or the like; imidazole compound includes: 2-A Imidazole, 2-ethylimidazole, 2-dodecylimidazole, 2-phenylimidazole, 4-methylimidazole, 4-ethylimidazole, 4-dodecylimidazole, 2-ethyl-4 Mercaptoimidazole, 2-ethyl-4-hydroxymethylimidazole and the like are most suitable as 2-methylimidazole or indoleethyl-4-methylimidazole. The accelerator may be used singly or in combination of two or more kinds, and the amount thereof is 0,01 to 1 PHR, and the optimum amount is 0.04 to 0.15 PHR, based on the total amount of the fat.
本發0月積層板用高玻璃轉移溫度之環氧樹脂清漆配方組成物，係包 基，二氫苯并（npbx_610、620、630或64〇)，含量為2〇〜7〇滅、⑼含 人^旨(NPEP ’鱗含量為2〜5%)或含演環氧樹脂_3，溪含量為14〜25%)， I目硬化劑，含量為1〜2G爾及(D)硬化促進劑，其使用量 t ^ 〜腿；並可添加無機填充材(二氧切、氫氧化銘等） 劑、光f㈣、熱安㈣及紫外光吸收劑等），利用溶劑包 曱I 、質子洛劑、嗣類溶舞 1、鱗類溶劑及_溶劑(適當溶劑有 二曱基甲酿胺、丙綱1基乙基酉同、1-甲氧基-2-丙醇、乙酸^ ’將此配彳纟嫩隸璃纖維布， 面或Ϊ聽^㈡，糊浸潰體之-片，製得銅縣板。 預次漬體疊成層’最後在加壓下加熱該疊 _氧樹脂清漆配方組成物之硬化溫度可為3〇至·。c，較佳為⑼至 1307707 〇 c ’若硬化度太低’硬化速率太慢，需延長硬化時 · ϊ^ί'解，硬化反應速率職《控制之缺ϋ ΐ ^J7二風苯并(卿χ)，可以降低成本；添加雜硬化劑物質， 了~低反應&度雜使硬化交聯完全，提高基板Tg及其他雛。 、 實施例·· 其成較佳之實施例詳述本發明，實補耻較射所狀各代號及 %氧樹脂A ;代表南亞塑膠所生產之含磷環氧樹脂， NPEP-200LA70 ’其環氧當量介於34〇〜38〇g/eq，璃含量為2 6%。° ’’’、 Ϊίΐΐ。表南亞塑膠所生產之含磷環顧脂，商品名為顧咖錢， 其裱氧當3：介於440〜480g/eq，鱗含量為4%。 ，巧脂c;代表南亞_所生產之含演環氧樹脂，商品名為观肌45彻， 其壤軋當量介於420〜455g/eq，溴含量為19%。 代表南亞卿所生產之含漠環氧樹脂，商品名為NPEB-485A80， 其％氧當量介於385〜405g/eq，溴含量為19〇/〇。 硬化劑A ;代表雙I胺(DICY)，14.7%溶於DMp。 硬化劑B ;代表南亞塑膠所生產之酚醛樹脂，商品名為BpA_pN。 硬化劑C ;代表南亞塑膠所生產之四酚乙烷樹脂，商品名為τρΝ。 促進劑2MI ;代表2-甲基咪唑，14.2°/。溶於DMF。 【實施例1〜8】 使用不同比例之含礎環氧樹脂、新型二氫苯并⑽欣)及硬化劑.，並添加 無機填充材(Al(OH)3與Si〇2)及硬化促進劑’其配方組成詳於表一，將之利用 丙酮’以調整m形份為65%之清漆翻旨組成物；以習知方法製備積層板。該 法係將7628玻璃纖維布含浸上述清漆無液，然後於17〇t(含浸機溫 f分鐘’藉由破㈣賴日销而調整乾、職職潰體之制^度^ 4000~10000poise間’最後將8片膠片層層相疊於兩片μ.厚之銅猪間，在 25kg/Cm壓力下’其控制升溫程式如下，經熱壓後即可得到積層壓合板。 85°C~^ 85〇C —~^ 200°C — 20min 30min 120minThe epoxy resin varnish formulation of the high-glass transfer temperature of the laminate of the present month is a base, dihydrobenzo (npbx_610, 620, 630 or 64 〇), the content is 2〇~7 annihilation, (9) People's purpose (NPEP 'scale content is 2~5%) or contains epoxy resin _3, stream content is 14~25%), I mesh hardener, content is 1~2G and (D) hardening accelerator , its use amount t ^ ~ leg; and can add inorganic filler (dioxo, hydrazine, etc.) agent, light f (four), heat (four) and ultraviolet light absorber, etc., using solvent coating I, proton嗣 溶 溶 1、 1, scaly solvent and _ solvent (appropriate solvent is dimercapto amylamine, propyl 1 yl ethyl hydrazine, 1-methoxy-2-propanol, acetic acid ^ ' this match彳纟 隶 隶 隶 纤维 纤维 , , , 隶 隶 隶 隶 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( The hardening temperature of the object may be from 3 〇 to · c, preferably from (9) to 1307707 〇c 'If the degree of hardening is too low, the hardening rate is too slow, and the hardening is required. ϊ^ί' solution, hardening reaction rate Shortcoming ΐ ^J7 二风苯和(清χ), can reduce the cost; add the hardener material, ~ low reaction & degree of hardening cross-linking completely, improve the substrate Tg and other chicks., Example · · DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT The present invention, the actual shame is more than the code name and % oxygen resin A; represents the phosphorus-containing epoxy resin produced by South Asia Plastics, NPEP-200LA70 'its epoxy equivalent is between 34〇~38 〇g/eq, the glass content is 2 6%. ° ''', Ϊίΐΐ. Table South Asia Plastics produced phosphorus ring Gu Gu, the product name is Gu coffee, its oxygen 3: between 440~480g / eq , the scale content is 4%., Qiaozhi c; represents the South Asia _ produced epoxy resin, the trade name is 45 muscles, the soil rolling equivalent is between 420~455g / eq, the bromine content is 19%. Representing the epoxy resin produced by Nanyaqing, trade name is NPEB-485A80, its % oxygen equivalent is between 385~405g/eq, and the bromine content is 19〇/〇. Hardener A; represents double I amine (DICY) , 14.7% dissolved in DMp. Hardener B; represents the phenolic resin produced by South Asia Plastics, trade name is BpA_pN. Hardener C; represents the tetraphenol produced by South Asia Plastics Ethane resin, trade name: τρΝ. Promoter 2MI; represents 2-methylimidazole, 14.2 ° /. Dissolved in DMF. [Examples 1 to 8] Using different proportions of base epoxy resin, new dihydrobenzene (10) Xin) and hardener. Add inorganic filler (Al(OH)3 and Si〇2) and hardening accelerator'. The composition of the formula is detailed in Table 1. Use acetone to adjust the m-shaped fraction to 65%. The varnish is turned into a composition; a laminate is prepared by a conventional method. The system is to impregnate the 7628 glass fiber cloth with the above varnish without liquid, and then adjust the dryness of the 7 〇t (the impregnation machine temperature f minutes) by breaking (four) Lai's sales, the degree of the occupational body ^ ^ ^ 4000 ~ 10000poise 'At the end, 8 layers of film are layered on two pieces of μ. Thick copper pigs. Under the pressure of 25kg/cm, the temperature control program is as follows. After hot pressing, the laminate can be obtained. 85°C~^ 85〇C —~^ 200°C — 20min 30min 120min
200°C200 ° C
130°C 慢慢冷卻 1307707 而可得到1.6mm厚之銅箔基板。 【比較例1〜2】使用不同比例之含磷環氧樹脂及硬化劑，並添加無機填充材 (AfOH)3與SiCb)及硬化促進劑，但不添加二氫苯并，將其利用丙酮， 以。周整固形份為65°/。之清漆樹脂組成物；再與實施例丨_8製備積層板相 進行製備積層壓合板。 / 【實關9〜Ιό】使用不同比例之漠化環氧樹脂 '新型二氩笨并(腦乂)及硬化 劑，並添加硬化促進劑，其清漆配方組成詳如表二，將之利用丙嗣，以調整固 形份為65%之清漆旨組成物，再與實補Μ製備板_方 積層壓合板。 1农1有 【比較例3〜4】 一〆=使用不同比例之溴化環氧樹脂及硬化劑，並添加硬化促進劑，但不添加 二氫笨并(ΝΡΒΧ) ’將其利用丙酮，以調整固形份為之清漆樹脂組成物； 再與實施例1-8製備積層板相同方法進行製備積層壓合板。 【量測說明】 1 ·清漆膠化時間(Vamish gel time，VGT^)A 130 mm thick copper foil substrate was obtained by slowly cooling 1307707 at 130 °C. [Comparative Examples 1 to 2] Different ratios of phosphorus-containing epoxy resin and hardener were used, and inorganic filler (AfOH) 3 and SiCb) and a hardening accelerator were added, but dihydrobenzene was not added, and acetone was used. To. The weekly solid content is 65°/. A varnish resin composition; and a laminate sheet prepared in the same manner as in Example 丨8 to prepare a laminate. / [Shiguan 9 ~ Ιό] use different proportions of desertified epoxy resin 'new di-argon stupid (brain sputum) and hardener, and add hardening accelerator, the varnish formula composition is detailed as Table 2, which uses C嗣, to adjust the solid content of the composition of 65% of the varnish composition, and then with the real preparation of the _ _ laminated laminate. 1 Agriculture 1 has [Comparative Examples 3 to 4] One 〆 = use different proportions of brominated epoxy resin and hardener, and add hardening accelerator, but do not add dihydro cumin (ΝΡΒΧ) 'use it with acetone, The solid component was adjusted to be a varnish resin composition; and a laminate laminate was prepared in the same manner as in the preparation of the laminate of Examples 1-8. [Measurement Description] 1 · Varnish gel time (Vamish gel time, VGT^)
f漆反應性測試為將環氧樹脂溶液與各種不同硬化劑及促進劑，配製清漆 此合液，將清漆混合物約〇.3ml滴於熱板上，熱板溫度為17yc，記錄至 膠化所需時間，稱之VGT。 2.吸水率測試 吸水率測試方法為將以蚀刻後基板裁成5 cm2正方形試片，於i〇yc洪箱 内烘2hr後，將試片置於壓力鍋内，壓力銷條件為2atmxi2〇t：，經過壓 3. 力銷30min後，記錄試片於壓力鍋前後重量麵以試片初重即為吸水率。 288 C对焊錫耐熱性 記錄試片爆 測試方法則為將上述經過壓力鍋試片，浸入288(>(：銲錫爐中 板分層所需時間。 表一；常溫下攪拌配製含磷環氧樹脂清漆組成之百分比表 12 1307707 實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 實施例7 實施例8 比較例1 比較例2 環氧樹脂A 58 54 57 58 97 環氧樹脂B 41 39 37 38 79 NPBX-610 26 47 NPBX-620 30 47 NPBX-630 26 50 NPBX-640 28 45 硬化劑A 3 硬化劑B 16 17 13 21 硬化劑C 16 14 12 14 17 填充材 Si02/ATH 30 30 30 30 30 30 30 30 30 30 促進劑 2MI(PHR) 0.11 0.08 0.06 0.1 0.1 0.08 0.07 0.07 0.05 0.08f paint reactivity test is to prepare the varnish solution with epoxy resin solution and various hardeners and accelerators. Drip the varnish mixture to about 3 ml on a hot plate. The temperature of the hot plate is 17yc, and record it at the gelatinization station. It takes time, called VGT. 2. Water absorption test The water absorption test method is to cut the substrate after etching into a 5 cm2 square test piece, and after drying in the i〇yc container for 2 hr, the test piece is placed in a pressure cooker, and the pressure pin condition is 2 atmxi2〇t: After pressing for 30 minutes, the test piece is recorded on the weight surface before and after the pressure cooker, and the initial weight of the test piece is the water absorption rate. The test method for the 288 C solder heat resistance recording test piece is to immerse the above-mentioned pressure cooker test piece in 288 (>(: time required for delamination of the plate in the soldering furnace. Table 1; stirring and preparing phosphorus-containing epoxy resin at normal temperature) Percentage of varnish composition Table 1 1307707 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Comparative Example 1 Comparative Example 2 Epoxy Resin A 58 54 57 58 97 Epoxy Resin B 41 39 37 38 79 NPBX-610 26 47 NPBX-620 30 47 NPBX-630 26 50 NPBX-640 28 45 Hardener A 3 Hardener B 16 17 13 21 Hardener C 16 14 12 14 17 Filler Si02/ATH 30 30 30 30 30 30 30 30 30 30 Accelerator 2MI (PHR) 0.11 0.08 0.06 0.1 0.1 0.08 0.07 0.07 0.05 0.08
表二；常溫下攪拌配製含溴環氧樹脂清漆組成之百分比表 13 1307707 實施例9 實施例10 實施例11 實施例12 實施例13 實施例14 實施例15 實施例16 比較例3 比較例4 環氧樹脂C 53 50 49 50 97 環氧樹脂D 46 44 45 47 78 NPBX-610 31 38 NPBX-620 33 44 NPBX-630 37 42 NPBX-640 35 39 硬化劑A 3 硬化劑B 16 14 12 22 硬化劑C 17 15 16 13 14 促進劑 2MI(PHR) 0.06 0.07 0.05 0.06 0.09 0.05 0.04 0.06 0.08 0.1Table 2: Percentage of composition of bromine-containing epoxy resin varnish stirred at room temperature Table 13 1307707 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Comparative Example 3 Comparative Example 4 Ring Oxygen resin C 53 50 49 50 97 Epoxy resin D 46 44 45 47 78 NPBX-610 31 38 NPBX-620 33 44 NPBX-630 37 42 NPBX-640 35 39 Hardener A 3 Hardener B 16 14 12 22 Hardener C 17 15 16 13 14 Accelerator 2MI (PHR) 0.06 0.07 0.05 0.06 0.09 0.05 0.04 0.06 0.08 0.1
表三；各配方之基板特性評估 14 1307707Table 3; Evaluation of substrate characteristics of each formulation 14 1307707
分析項目 實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 實施例7 實施例8 比較例1 比較例2 清漆膠化 時間sec*1 320 330 350 300 380 290 330 340 310 340 玻璃轉移 溫度11*2 170 182 173 186 192 189 182 195 150 153 吸水率％ 本3 0.21 0.19 0.15 0.20 0.21 0.18 0.17 0.16 030 0.28 焊錫时熱 性 sec*4 400 600 450 500 400 460 480 590 380 390 耐燃性 (UL-94) V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 說明： *1.取0.3ml樹脂清漆於170°C加熱板上，量測其膠化時間。 *2.使用微差掃瞄熱分析儀(DSC)，升溫速率=20°C/min。 *3.試樣在120°C及2atm壓力鍋中加熱30分鐘。 *4.試樣在120°C及2atm壓力鍋中加熱30分鐘後，浸入288t焊錫爐，記錄試樣爆板分層所需時 間。 表四；各配方之基板特性評估 15 1307707 分析項目 實施例9 實施例10 實施例11 實施例12 實施例13 實施例14 實施例15 實施例】6 比較例3 比較例4 清漆膠化 310 320 340 295 320 295 310 330 320 310 時間sec*1 玻璃轉移 溫度°c*2 165 173 168 176 177 182 180 179 149 151 吸水率°/〇 氺3 0.20 0.21 0.19 0.22 0.16 0.17 0.19 0.19 0.28 0.30 焊錫耐熱 性 sec*4 600 560 500 600 500 600 520 590 400 500 耐燃性 (UL-94) V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 ->·£> βΟ · ------J. *1.取0.3ml樹脂清漆於170°C加熱板上，量測其膠化時間β *2.使用微差掃瞄熱分析儀(DSC)，升溫速率=2〇°〇/ηύη。 *3·試樣在120°C及2atm壓力鍋中加熱3〇分鐘。 *4.試樣在120°C及2atm壓力鍋中加熱3〇分鐘後，浸入2 。 問。 C焊錫爐，記錄試樣爆板分層所需時 由表二之基板測試結果可知，本發明無_樹 物，且可以降低磷含量，即可達到職需添加齒化 物性。而表四之_航方域物，也可臀 Μ 11絲板其他 (ΝΡΒΧ)熱固性樹脂於樹脂清漆配方中，不斤風本并 越樹脂硬化劑，更可崎低反應硬化溫度 低成本’又配合紛 物性。 ^，旨交縣度，提昇基板 16Analysis Item Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Comparative Example 1 Comparative Example 2 Varnishing time sec*1 320 330 350 300 380 290 330 340 310 340 Glass Transfer temperature 11*2 170 182 173 186 192 189 182 195 150 153 Water absorption % This 3 0.21 0.19 0.15 0.20 0.21 0.18 0.17 0.16 030 0.28 Soldering heat sec*4 400 600 450 500 400 460 480 590 380 390 Flame resistance (UL -94) V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 Description: *1. Take 0.3ml of resin varnish on a hot plate at 170 °C , measure the gelation time. *2. Using a differential scanning thermal analyzer (DSC), the heating rate = 20 ° C / min. *3. The sample was heated in a 120 ° C and 2 atm pressure cooker for 30 minutes. *4. The sample was heated in a 120 ° C and 2 atm pressure cooker for 30 minutes, and then immersed in a 288 t soldering furnace to record the time required for the sample to blast. Table 4; Evaluation of substrate characteristics of each formulation 15 1307707 Analysis item Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Example 6 Comparative Example 3 Comparative Example 4 Varnish gel 310 310 340 295 320 295 310 330 320 310 Time sec*1 Glass transition temperature °c*2 165 173 168 176 177 182 180 179 149 151 Water absorption rate °/〇氺3 0.20 0.21 0.19 0.22 0.16 0.17 0.19 0.19 0.28 0.30 Solder heat resistance sec* 4 600 560 500 600 500 600 520 590 400 500 Flame resistance (UL-94) V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 -> ;·£> βΟ · ------J. *1. Take 0.3ml of resin varnish on a hot plate at 170 ° C, measure the gelation time β * 2. Use a differential scanning thermal analyzer ( DSC), heating rate = 2 〇 ° 〇 / η ύ η. *3. The sample was heated in a 120 ° C and 2 atm pressure cooker for 3 minutes. *4. The sample was heated in a 120 ° C and 2 atm pressure cooker for 3 minutes and then immersed in 2 . ask. C soldering furnace, when recording the delamination of the sample blasting board According to the test results of the substrate of Table 2, the present invention has no _ tree, and can reduce the phosphorus content, and can achieve the toothing property of the occupation. And the table _ 航方域, can also be hip Μ 11 silk plate other (ΝΡΒΧ) thermosetting resin in the resin varnish formulation, not the wind and the resin hardener, but also the low reaction hardening temperature low cost Cooperate with the nature. ^, the purpose of the county, lifting the substrate 16