TW524813B - Polynuclear epoxy compound, resin obtained therefrom curable with actinic energy ray, and photocurable/thermosetting resin composition containing the same - Google Patents
Polynuclear epoxy compound, resin obtained therefrom curable with actinic energy ray, and photocurable/thermosetting resin composition containing the same Download PDFInfo
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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- C08F269/00—Macromolecular compounds obtained by polymerising monomers on to polymers of heterocyclic oxygen-containing monomers as defined in group C08F24/00
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- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1494—Polycondensates modified by chemical after-treatment followed by a further chemical treatment thereof
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4292—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof together with monocarboxylic acids
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- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/285—Permanent coating compositions
- H05K3/287—Photosensitive compositions
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/46—Manufacturing multilayer circuits
- H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
- H05K3/4673—Application methods or materials of intermediate insulating layers not specially adapted to any one of the previous methods of adding a circuit layer
- H05K3/4676—Single layer compositions
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Abstract
Description
524813 A7 五、發明説明(1 ) 發明所屬技術領域 本發明係有關含規則重複之相異芳環之線狀新穎多手亥 環氧化合物,及該多核環氧化合物所衍生之多核環氧丙嫌 酸酯化合物,及含有其之硬化性樹脂組成物。 本發明首先係有關,衍生自上述多核環氧化合物或多 核環氧丙烯酸酯化合物之線狀且鹼可溶之新穎活性能量,線 硬化性樹脂。 進而本發明係有關,使用上述活性能量線硬化性樹脂 的液態’鹼可顯影之光硬化性•熱硬化性樹脂.組成物,及 使用其之硬化皮膜形成技術。 先行技術 雙酚A型環氧樹脂所代表之環氧樹脂,因具優良密合 性、耐熱性、耐樂品性、電絕緣性,向來廣泛用於粘著劑 、注模劑、層合材、塗料、封裝劑等用途。 關於該環氧樹脂,隨最近電器、半導體產業之發展, 有例如耐熱性、靭度、耐水性、耐藥品性等特性的提升之 要求,而有爲滿足相關特性的種種新穎環氧化合物之提議 〇 例如,耐熱性優之環氧化合物者,有甲酚淸漆型環氧 樹脂,酚淸漆型環氧樹脂等之多核環氧樹脂之提議。但是 ’追些環氧樹脂,其耐熱性雖確屬優良,因硬化時收縮大 ’伸展小’靭度不足,有易因熱衝擊發生龜裂之缺點。 對此,爲消除上述缺點,有於環氧樹脂摻以橡膠成分 ^----- (請先閲讀背面之注意事項再填寫本頁) 計 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -4 524813 A7 B7 五、發明説明(2 ) (請先聞讀背面之注意事項再填寫本頁} 之方法(日本專利特開昭6 3 — 1 9 9 2 1 8號公報), 混摻二種環氧樹脂之方法(日本專利第2 7 8 3 1 1 6號 公報)’聯苯骨架與雙酚骨架之共聚環氧樹脂(日本專利 第2789325號公報)等之提議。 .然而,以這些方法,目前依然無法提供同時滿足耐熱 性及_度之環氧化合物。 另一方面,已知的硬化性、操作性等成形性優之樹脂 、有雙酚型樹脂、淸漆型環氧樹脂等之多元酚型環氧樹脂 與(甲基)丙烯酸所衍生之環氧(甲基)丙烯.酸酯,或不 飽和聚酯等之自由基聚合型樹脂,通常,這些樹脂係配合 以如苯乙烯等之自由基交連劑,作爲乙烯酯樹脂或不飽和 聚酯樹脂廣泛應用。可是,這些樹脂在高溫下熱安定性方 面未必可達滿意之水準,且硬化時收縮大,伸展小,靭度 不足,有易因熱衝擊發生龜裂之缺點。 經濟部智慧財產局員工消費合作社印製 對此,爲消除上述缺點,有以改質芳族胺、聚合性交 連劑、及具丙烯醯基及/或甲基丙烯醯基之丁二烯丙烯腈 共聚物組成之樹脂組成物(日本專利第2 5 3 9 8 7 3號 鏈),以改質芳族聚胺及/或改質芳族二胺,環氧化合物 ,及自由基聚合性交連劑所組成之樹脂組成物(特開平1 一 2 9 7 4 2 3號公報)等之提議。然而,這些方法在滿 足耐熱性及靭度方面仍多少所使不足。 再者,目前部份消費用印刷電路板及幾乎所有的產業 用印刷電路板之焊料阻劑,從高精確度、高密度之觀點, 係使用紫外線照射後,以顯影形成圖像,經熱及光照射作 本紙張尺度適用中國國家標準(CNS ) A4規格(210 X 297公釐)-5 - 524813 A7 _____B7 五、發明説明(3 ) (請先閲讀背面之注意事項再填寫本頁) 最後硬化(正式硬化)之液狀顯影型焊料阻劑。又從環境 問題之顧慮’用稀鹼水溶液作顯影.液之鹼顯影型液狀焊料 阻劑已成主流。如此之用稀鹼水溶液之鹼顯影型液狀焊料 阻劑者,有例如特開昭6 1 - 2 4 3 8 6 9號公報之淸漆 型環氧化合物與不飽和一元酸之反應產物,以酸酐加成爲 感光性樹脂,與光聚合啓始劑、稀釋劑及環氧化合物所組 成之焊料阻劑組成物,以及特開平3 - 2 5 3 0 9 3號公 報之淸漆型環氧化合物與不飽和一元酸之反應產物,以酸 酐加成爲感光性樹脂,與光聚合啓始劑、稀釋.劑、乙烯三 畊或乙烯三哄與雙氰胺之鹿合物及三聚氰胺樹脂所組成的 焊料阻劑之揭示。 但是,此類感光性樹脂,其光硬化性及鹼顯影性雖優 .,然高溫下之熱安定性仍難謂已達滿意水準,並且,硬化 時趨於收縮•伸展小靭度差,故有因熱衝擊易起龜裂之缺 點。 經濟部智慧財產局員工消費合作社印製 又,隨近年來電子設備之輕薄短小化,對應於印刷電 路板之高密度化,對焊料阻劑亦有高性能化之要求。而且 最近,使用引線架及封裝樹脂之所謂的Q F P (四邊扁平 封裝)、S〇P (小外型封裝)等之I C封裝已爲所取代 ,而於印刷電路板之一面施以焊料阻劑,面狀配置焊料等 金屬,於另一面將I C晶片以絲焊法或凸塊等直接連接, 再以封裝樹脂封裝之I C封裝已出現,即所謂之B G A ( 球柵陣列封裝)、C S P (晶片尺寸封裝)等·。這些封裝 較之同大小的Q F P等之封裝易於多腳數化、小形化。又 本紙張尺度適用中關家標準(CNS ) A4胁{ 210X297公釐)7^ " 524813 A7 _ B7 五、發明説明(4 ) ,構裝時因球狀焊料之自行對準效果可提高良率,已快速 受到採用。 (請先閲讀背面之注意事項再填寫本頁) 然而,使用以往市售之鹼顯影型焊料阻劑之印刷電路 板,封裝之長期可靠性試驗的耐P C T性差,有焊料阻劑 皮膜之剝離發生。又,因焊料阻劑之吸濕,封裝構裝時再 流動當中內部所吸水分沸騰,於封裝內焊料阻劑之皮膜及 周圍產生龜裂,所謂爆玉米花現象是一問題。類此之耐吸 濕性及長期可靠性的缺失,不限於上述構裝技術之情況, 即使在一般印刷電路板之焊料阻劑,或積累式基板等之多 層線路板的層間絕緣層等;其它用途之產品中亦不欲其發 生。 發明所欲解決之課題 本發明鑒於上述現況,其一目的在提供具均衡之耐熱 性及靭度,並且對基材之密合性、耐水性、耐藥品性、電 絕緣性等優良,而具良好之成形性的多核環氧化合物,以 及含有其之熱硬化性樹脂組成物。 經濟部智慧財產局員工消費合作社印製 本發明之另一目的在提供,衍生自具如上述優良特性 之多核環氧化合物,以活性能量線照射硬化及熱硬化之任 一均可的多核環氧丙烯酸酯化合物,及含其之硬化性樹脂 組成物。 本發明之又一目的在提供,高溫下熱安定性優良,具 均衡之耐熱性及靭性,同時光硬化性及鹼顯影性均優之活 性能量線硬化性樹脂。 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐)~Γ^Τ 524813 A7 B7 五、發明説明(5 ) (請先閲讀背面之注意事項再填寫本莧) 本發明之又另一目的在提供,維持或提升以往之印刷 電路板的焊料阻劑及多層線路板之層間絕緣層等所要求的 耐熱性、密合性、耐無電解電鍍性、電特性、可撓性等特 性’並且,可得尤其是I c封裝所要求之耐吸濕性及耐 P C T (壓力鍋試驗)性等特性優良之硬化皮膜,可對應 印刷電路板之高密度化、表面構裝化的鹼可顯影之液狀光 硬化性•熱硬化性樹脂組成物。 用__以解決課題之手段 爲達上述目的,根據本發明之第一方面,可以提供下 述一般式(1 )所表多核環氧化合物(a ),及含其之熱 硬化性樹脂組成物。 0M ,524813 A7 V. Description of the Invention (1) Technical Field of the Invention The present invention relates to linear novel multi-handed epoxy compounds containing regularly repeated dissimilar aromatic rings, and polynuclear propylene oxide derived from the multi-core epoxy compound. Acid ester compounds, and curable resin compositions containing the same. The present invention relates first to a linear active alkali-soluble novel linear energy-hardening resin derived from the above-mentioned polynuclear epoxy compound or polynuclear epoxy acrylate compound. Further, the present invention relates to a liquid'alkali developable photo-curable / thermosetting resin. Composition using the above-mentioned active energy ray-curable resin, and a hardened film formation technique using the same. The epoxy resin represented by the prior art bisphenol A epoxy resin has been widely used in adhesives, injection molding agents, and laminates due to its excellent adhesion, heat resistance, resistance to music, and electrical insulation. , Coatings, sealants and other uses. With regard to the epoxy resin, with recent developments in the electrical appliance and semiconductor industries, there is a demand for improvements in properties such as heat resistance, toughness, water resistance, and chemical resistance, and various novel epoxy compounds have been proposed to satisfy the related characteristics. 〇 For example, epoxy resins having excellent heat resistance include multi-core epoxy resins such as cresol lacquer type epoxy resin and phenol lacquer type epoxy resin. However, although some epoxy resins have excellent heat resistance, they have a large shrinkage during curing and a small stretch, and their toughness is not sufficient, and they have the disadvantage of easily cracking due to thermal shock. For this reason, in order to eliminate the above-mentioned shortcomings, epoxy resin is mixed with rubber components ^ ----- (Please read the precautions on the back before filling this page) The paper size printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Planning and Economics Applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) -4 524813 A7 B7 V. Description of invention (2) (Please read the precautions on the back before filling in this page} Method (Japanese Patent Laid-Open Sho 6 3 — 1 9 9 2 1 8), a method of blending two kinds of epoxy resins (Japanese Patent No. 2 7 8 3 1 1 6) 'Copolymerized epoxy resin of biphenyl skeleton and bisphenol skeleton (Japanese patent No. 2789325), etc. However, with these methods, it is not currently possible to provide an epoxy compound that satisfies both heat resistance and temperature. On the other hand, known resins with excellent moldability such as hardenability and handleability are known. Free radicals such as bisphenol-type resins, lacquer-type epoxy resins and polyphenol-type epoxy resins and epoxy (meth) acrylic acid, acid esters, or unsaturated polyesters derived from (meth) acrylic acid Polymeric resins, these resins are usually formulated Combined with free-radical cross-linking agents such as styrene, they are widely used as vinyl ester resins or unsaturated polyester resins. However, these resins may not reach a satisfactory level in terms of thermal stability at high temperatures, and they shrink and stretch when hardened. Small, insufficient toughness, and shortcomings due to thermal shock. The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed this. In order to eliminate the above shortcomings, there are modified aromatic amines, polymeric crosslinkers, and Resin composition composed of acryl fluorenyl and / or methacryl fluorinated butadiene acrylonitrile copolymer (Japanese Patent No. 2 5 3 9 8 7 3 chain) to modify aromatic polyamines and / or Proposed resin compositions (Japanese Patent Application Laid-Open No. Hei 1- 2 9 7 4 2 3) composed of high-quality aromatic diamines, epoxy compounds, and radical polymerizable cross-linking agents. However, these methods are in Toughness is still insufficient. Furthermore, the solder resist of some consumer printed circuit boards and almost all industrial printed circuit boards is from the point of view of high precision and high density. Yi Xian The image is formed by shadowing, and the paper size is determined by heat and light. The paper size applies the Chinese National Standard (CNS) A4 (210 X 297 mm)-5-524813 A7 _____B7 V. Description of the invention (3) Please fill in this page again for details) Liquid hardened solder resist that is finally hardened (formally hardened). From the consideration of environmental issues, use a dilute aqueous alkali solution for development. Liquid alkali developed hard solder resist has become mainstream. The alkali-developed liquid solder resist using a dilute aqueous alkali solution is, for example, the reaction product of a lacquer type epoxy compound disclosed in JP 6 1-2 4 3 8 6 9 and an unsaturated monobasic acid. It is a solder resist composition composed of a photosensitive resin, a photopolymerization initiator, a diluent, and an epoxy compound, and a lacquer-type epoxy compound disclosed in Japanese Patent Laid-Open No. 3-2 5 3 0 9 3 The reaction product of the saturated monobasic acid is added to the photosensitive resin with acid anhydride, and a photopolymerization initiator, a diluent, an ethylene triglyceride or an ethylene trio deer compound with dicyandiamide and a melamine resin. Revealed. However, although this type of photosensitive resin has excellent light-hardening properties and alkali developability, it is still difficult to say that the thermal stability at high temperatures has reached a satisfactory level, and it tends to shrink and harden when stretched. It has the disadvantage of cracking easily due to thermal shock. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. With the thinning and thinning of electronic equipment in recent years, corresponding to the increase in density of printed circuit boards, there is also a demand for higher performance of solder resist. And recently, so-called QFP (Quad Flat Package), SoP (Small Form Factor Package) IC packages that use lead frames and packaging resins have been replaced, and solder resist is applied to one side of the printed circuit board. Metals such as solder are arranged on the surface, and IC chips are directly connected by wire bonding or bumps on the other side, and then IC packages with resin encapsulation have appeared, so-called BGA (ball grid array package), CSP (chip size) Package) and so on. These packages are easier to count and miniaturize than Q F P packages of the same size. And this paper size applies the Zhongguanjia standard (CNS) A4 threat {210X297 mm) 7 ^ " 524813 A7 _ B7 V. Description of the invention (4), the self-alignment effect of the ball solder can be improved during construction. Rate has been quickly adopted. (Please read the precautions on the back before filling this page.) However, the printed circuit board using the conventionally available alkali-developed solder resist has a poor PCT resistance in the long-term reliability test of the package, and peeling of the solder resist film occurs. . In addition, due to the moisture absorption of the solder resist, the water absorbed inside the package boils during the reflow, and cracks occur in the film and surroundings of the solder resist in the package. The so-called popcorn phenomenon is a problem. The lack of moisture absorption and long-term reliability like this is not limited to the above-mentioned assembly technology, even in solder resists of general printed circuit boards, or interlayer insulation layers of multilayer circuit boards such as accumulation substrates; etc .; other uses The products do not want it to happen. Problems to be Solved by the Invention In view of the above-mentioned circumstances, one object of the present invention is to provide balanced heat resistance and toughness, and to have excellent adhesion to a substrate, water resistance, chemical resistance, electrical insulation, and the like. A polynuclear epoxy compound having good moldability, and a thermosetting resin composition containing the same. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, another purpose of the present invention is to provide a multi-core epoxy compound derived from a multi-core epoxy compound having excellent characteristics as described above, and irradiated with active energy rays for hardening and thermal curing An acrylate compound and a curable resin composition containing the same. Still another object of the present invention is to provide a flexible energy-curing resin which is excellent in thermal stability at high temperatures, has balanced heat resistance and toughness, and is excellent in both photo-hardening and alkali developability. This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) ~ Γ ^ Τ 524813 A7 B7 V. Description of the invention (5) (Please read the precautions on the back before filling in this 苋) Another invention The purpose is to provide, maintain or improve the heat resistance, adhesion, electroless plating resistance, electrical characteristics, flexibility and other characteristics required for conventional solder resists of printed circuit boards and interlayer insulation layers of multilayer wiring boards. In addition, hardened films with excellent characteristics such as moisture absorption resistance and PCT (pressure cooker test) resistance required for I c packaging are available, and they are compatible with alkali-developable liquids for high density printed circuit boards and surface structure. Photocurable and thermosetting resin composition. In order to achieve the above-mentioned object by means of __, according to the first aspect of the present invention, a polynuclear epoxy compound (a) represented by the following general formula (1) and a thermosetting resin composition containing the same can be provided. . 0M,
- I CH2 -CH-CH2 -0-X-〇--CH2 -CH-CH2 -O-Y--I CH2 -CH-CH2 -0-X-〇--CH2 -CH-CH2 -O-Y-
\ / L 〇\ / L 〇
OM I Ί 一〇一CH2 —CH-CH2-O-X—0--CH2—CH—CH2 · · · (1) -n \ / 0 經濟,部智慧財產局員工消費合作社印製 式中,X及Y表不同芳環,X表選自聯酚型二環氧丙 醚、聯二甲酚型二環氧丙醚、雙酚型二環氧丙醚及萘型二 環氧丙醚所成群之至少一種一分子中有二環氧丙基的芳族 環氧化合物之芳環餘基,Y表選自二羥基萘及其衍生物、 聯酚及其衍生物、聯二甲酚及其衍生物、雙酚及其衍生物 ,以及氫醌及其衍生物所成群之至少一種一分子中有二酚 式羥基之芳族醇的芳環餘基,Μ表環氧丙基、甲基環氧丙 尺度適用中國國家標準(CNS ) Α4規格< 210X297公釐)~ΤβΖ' 524813 A7 _________ B7_ 五、發明説明(6 ) 基及/或氫原子,n表1至2 0之整數。 如上述之本發明的多核環氧化合物,因係含規則重複 (請先閲讀背面之注意^項再填寫本頁) 之不同芳環的線狀多核環氧化合物,尤其是高軟化點之聯 苯骨架及萘骨架、或聯酚骨架及萘骨架之交互共聚的交互 共聚型線狀多核環氧化合物,該多核環氧化合物之硬化物 具均衡的高水準之耐熱性及靭度,對基材之密合性優,且 耐水性、耐藥品性、電絕緣性等優良。 根據本發明之第二方面,可以提供下述一般式(2 a )或(2 b )所示多核環氧丙烯酸酯化合物(b )及含其 之熱硬化性樹脂組成物。·OM I 〇 一一 CH2 —CH-CH2-OX—0--CH2—CH—CH2 · · · (1) -n \ / 0 Economy, Ministry of Intellectual Property Bureau Employee Cooperative Cooperative Printing System, X and Y The different aromatic rings are shown, and the X is at least selected from the group consisting of biphenol-type diglycidyl ether, bixylenol-type diglycidyl ether, bisphenol-type diglycidyl ether, and naphthalene-type diglycidyl ether. An aromatic ring residue of an aromatic epoxy compound having diglycidyl in one molecule, Y is selected from dihydroxynaphthalene and its derivatives, biphenol and its derivatives, bixylenol and its derivatives, Bisphenol and its derivatives, and at least one aromatic ring residue of an aromatic alcohol having a diphenolic hydroxyl group in one molecule of a group of hydroquinone and its derivatives, where M represents an epoxy propyl group and a methyl propylene oxide group Dimensions are applicable to China National Standard (CNS) A4 specification < 210X297 mm) ~ TβZ '524813 A7 _________ B7_ 5. Description of the invention (6) Base and / or hydrogen atom, n is an integer from 1 to 20 in the table. As mentioned above, the polynuclear epoxy compound of the present invention is a linear polynuclear epoxy compound with different aromatic rings (especially high softening point biphenyls) because it contains regular repeats (please read the note on the back before filling this page). Cross-linked cross-linked linear polynuclear epoxy compound having a skeleton and a naphthalene skeleton, or an interpolymerization of a biphenol skeleton and a naphthalene skeleton. The hardened product of the polynuclear epoxy compound has a balanced high level of heat resistance and toughness. Excellent adhesion, excellent water resistance, chemical resistance, electrical insulation, etc. According to a second aspect of the present invention, a polynuclear epoxy acrylate compound (b) represented by the following general formula (2a) or (2b) and a thermosetting resin composition containing the same can be provided. ·
0Z0Z
r I V -0-X—〇--ch2 —ch-ch2 -o-y-o- oz I Ί 一CH2 —CH一CH2 ""*〇kX一Ο-~Z’ · · ·(2a) ozr I V -0-X—〇--ch2 —ch-ch2 -o-y-o- oz I Ί 一 CH2 —CH 一 CH2 " " * 〇kX 一 〇- ~ Z ’· · · (2a) oz
Γ I CH2 —CH—CH2 -o-x—ο--ch2 —ch-ch2 -o-y-o-Γ I CH2 —CH—CH2 -o-x—ο--ch2 —ch-ch2 -o-y-o-
\ / L 〇 oz 經濟部智慧財產局員工消費合作社印製 I η ~CH2 一CH—CH2 —0_?C_O-——CH一CH2 · · · (2b) 」n \ / 〇 式中’ X、Y及n同上述,Z係相互無關,表下述一 般式(3 )或.(4 )所示之基或氫原子,且Z之至少其一 表一般式(3 )所示之基,Z ’係相互無關,表下述一般 式(3.)或(4,)所示之基。 本紙張尺度適用中周國家標準(CNS ) A4規格(210X29*7公釐)-9 - 524813 A7 B7 五、發明説明(7 ) R1\ / L 〇oz Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs I η ~ CH2 One CH—CH2 —0_? C_O -—— CH One CH2 And n are the same as above, Z is independent of each other, and the base or hydrogen atom represented by the following general formula (3) or. (4) is shown, and at least one of Z is the base represented by the general formula (3), Z ' They are independent of each other, and the bases shown in the following general formulae (3.) or (4,) are shown. This paper size is applicable to Mid-week National Standard (CNS) A4 specification (210X29 * 7mm) -9-524813 A7 B7 V. Description of invention (7) R1
一CH2 —0-CH2 -〇—C一 R-CH2 —0-CH2 -〇-C-R
0H0H
一CH2 »CH — CH2 — 〇 — C-R I 0H R1 (3) -CH2 -C· —CH2 \ / 0 (3 ) 一CHa -CH-CH2 0 (4) (4,) 式中,R1表氫原子或甲基,R2表不飽和單羧酸餘基 如上述的本發明之多核環氧丙烯酸酯化合物,可藉活 性能量線之照射而硬化,或熱硬化,其硬化物.具均衡之高 水準耐熱性及靭度,對基材之密合性優,且耐水性、耐藥 品性、電絕緣性等優良。 根據本發明之第三方面,可以提供下述一般式(5 ) (請先閲讀背面之注意事項再填寫本頁)-CH2 »CH — CH2 — 〇— CR I 0H R1 (3) -CH2 -C · —CH2 \ / 0 (3) -CHa -CH-CH2 0 (4) (4,) where R1 represents a hydrogen atom Or the methyl, R2 unsaturated unsaturated monocarboxylic acid residues of the above-mentioned multi-core epoxy acrylate compound of the present invention can be hardened by the irradiation of active energy rays, or heat hardened, and its hardened products have a high level of heat resistance in balance. It has excellent toughness and toughness, excellent adhesion to the substrate, and excellent water resistance, chemical resistance, and electrical insulation. According to the third aspect of the present invention, the following general formula (5) can be provided (please read the precautions on the back before filling this page)
’)與含不飽和基之單羧酸(C 以多元酸酐(d )反應而得之活 .0M 所示多核環氧化合物(a )之反應產物(b ’ ), 性能量線硬化性樹脂。 CHa —CH-CH2 —0—X* -0- CH2 -CH-CH2 -0-Yf -0- 〇 經濟部智慧財產局員工消費合作社印製 0M I -CH2 —CH—CH2 —0—X’ 一0· -CH: -CH—CH: \ / 0 (5) 式中,X’及Y’表不同的二價芳環,M表環氧丙基 、甲基環氧丙基及/或氫原子,η表1至2 0之整數。 又根據.本發明之第四方面可以提供,含(.A )上述活 性能量線硬化性樹脂、(B )感光性(甲基)丙傑酸酯化 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) · - 524813 A7 _____B7_ 五、發明説明(8 ) (請先閲讀背面之注意事項再填寫本頁) 合物、(C)光聚合啓始劑、及(D) —分子中具二個以 上之環氧基的環氧化合物(以下稱多官能環氧化合物)’ 可藉鹼水溶液顯影之光硬化性•熱硬化性樹脂組成物。 各成分之配合比例不限於特定比例,而對(A )上述 活性能量線硬化性樹脂1 〇 〇質量份,(B )上述感光性 (甲基)丙烯酸酯化合物宜用1 0至6 0質量份,較佳者 爲1 5至5 0質量份,(C )上述光聚合啓始劑宜用 0 · 1至25重量份,較佳者爲0 · 5至20質量份,( D )上述多官能環氧化合物宜用1 0至1 0 0.質量部,更 於必要時之(E )環氧硬化觸媒宜用0 · 1至2 0質量部 之比例。 經濟部智慧財產局員工消費合作社印製 本發明之活性能量線硬化性樹脂,因係含規則重複之 不同芳環的線狀多核環氧丙烯酸酯化合物,尤其是高軟化 點之聯苯骨架及萘骨架、或聯酚骨架及萘骨架交互共聚之 交互共聚型線狀多核環氧丙烯酸酯化合物之多元酸酐加成 物,具光硬化性、鹼可溶性外,高溫下熱安定性優,具均 衡的高水準之耐熱性及靭度。又,含如此之活性能量線硬 化性樹脂作爲光硬化性成分之本發明的光硬化性•熱硬化 性樹脂組成物,可得光硬化性、鹼顯影性及對基材之密合 性優,且耐熱性、耐水性、耐無電解電鍍性、耐藥品性、 電絕緣性、可撓性、耐P c T性等優良之硬化物。 圖面之簡單說明 第1圖係合成例2所得之多核環氧化合物(a — 2 ) 本紙張尺度適用中國國家標準(CNS ) A4規格(21〇><297公釐) .^ " 524813 A7 B7 五、發明説明(9 ) 之紅外線吸收圖譜; 第2圖係合成例2所得之多核環氧化合物(3 - 2 ) 之核磁共振圖譜; 第3圖係合成例8所得之多核環氧丙烯酸酯化合物( b - 1 )之紅外線吸收圖譜; 桌4圖係合成例8所得之多核環氧丙燃酸酯化合物( b — 1 )之核磁共振圖譜; 第5.圖係合成例1 4所得之活性能量線硬化性樹脂( A - 1 )之紅外線吸收圖譜;而 第6圖係合成例1 4所得之活性能量線硬化性樹脂( A - 1 )之核磁共振圖譜。 .發明之實施形態 本發明人等爲達上述目的一再精心探討,結果發現, 含規則重複之上述X及Y所表不同芳環之線狀環氧化合物 ’尤其是高軟化點之聯苯骨架及萘骨架、或雙酚骨架與萘 骨架交互共聚之共聚型線狀環氧化合物中之醇性羥基,以 環氧鹵丙垸反應所得之多核環氧化合物,可導致兼具優良 耐熱性及靭度之硬化物。 亦即,本發明之多核環氧化合物(a ),因係如下述 一般式(1 )所表,含規則重複之不同芳環,可得高機械 強度之硬化物,又因具線狀構造,更因係與環氧鹵丙烷之 反應而得的多核環氧化合物,可得高耐熱性之硬化物,同 時可得對基材之密合性、耐水性、耐藥品性、電絕緣性、 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) .12- (請先閲讀背面之注意事項再填寫本頁) •裝· 訂 經濟部智慧財產局員工消費合作社印製 524813 A7 B7 _____ 五、發明説明(1〇 ) 唉形性等優良之硬化物The reaction product (b ') of the polynuclear epoxy compound (a) shown by 0M is a reaction product (b') with a monocarboxylic acid (C) containing an unsaturated group and a polyacid anhydride (d). CHa —CH-CH2 —0—X * -0- CH2 -CH-CH2 -0-Yf -0- 〇 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 0M I -CH2 —CH—CH2 —0—X '1 0 · -CH : -CH—CH: \ / 0 (5) In the formula, X 'and Y' represent different divalent aromatic rings, and M represents an epoxy group, a methyl epoxy group, and / or a hydrogen atom. Η is an integer of 1 to 20. According to the fourth aspect of the present invention, it can be provided, containing (.A) the above-mentioned active energy ray-curable resin, (B) a photosensitive (meth) propionate ester. Paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) ·-524813 A7 _____B7_ V. Description of the invention (8) (Please read the notes on the back before filling this page) Compounds, (C) Photopolymerization start Initiator and (D) —Epoxy compounds with two or more epoxy groups in the molecule (hereinafter referred to as polyfunctional epoxy compounds) 'Photocuring and thermosetting properties that can be developed by aqueous alkaline solution The composition ratio of each component is not limited to a specific ratio, and (A) 100 parts by mass of the above active energy ray-curable resin, and (B) the above-mentioned photosensitive (meth) acrylate compound are preferably used in an amount of 10 to 60 parts by mass, preferably 15 to 50 parts by mass, (C) The above-mentioned photopolymerization initiator is preferably from 0.1 to 25 parts by weight, and more preferably from 0.5 to 20 parts by mass, (D ) The above-mentioned multifunctional epoxy compounds should be used in the range of 10 to 100. More than necessary (E) Epoxy curing catalyst should be used in the proportion of 0. 1 to 20. The Ministry of Economic Affairs Intellectual Property Bureau The consumer energy cooperative printed the active energy ray-curable resin of the present invention, because it is a linear polynuclear epoxy acrylate compound with regularly repeated different aromatic rings, especially a high-softening point biphenyl skeleton and a naphthalene skeleton, or biphenol Cross-copolymerized linear polynuclear epoxy acrylate compound of polybasic acid anhydride adduct of cross-copolymerization of skeleton and naphthalene skeleton, in addition to photo-hardening and alkali-solubility, excellent thermal stability at high temperature, balanced high-level heat resistance and Toughness. Also, with such active energy ray hardening The photocurable and thermosetting resin composition of the present invention, which is a photocurable component, is excellent in photocurability, alkali developability, and adhesion to a substrate, and has heat resistance, water resistance, and non-resistance. Hardened products with excellent electrolytic plating, chemical resistance, electrical insulation, flexibility, P c T resistance, etc. Brief illustration of the drawing Figure 1 shows the polynuclear epoxy compound (a-2) obtained in Synthesis Example 2. This paper size is in accordance with China National Standard (CNS) A4 specification (21〇 > < 297mm). ^ &Quot; 524813 A7 B7 V. Infrared absorption spectrum of invention description (9); Figure 2 is obtained from Synthesis Example 2 The nuclear magnetic resonance spectrum of the polynuclear epoxy compound (3-2); Figure 3 is the infrared absorption spectrum of the polynuclear epoxy acrylate compound (b-1) obtained in Synthesis Example 8; The nuclear magnetic resonance spectrum of the glycidyl epoxide compound (b-1); Figure 5. is the infrared absorption spectrum of the active energy ray hardening resin (A-1) obtained in Synthesis Example 14; and Figure 6 is the synthesis Of the active energy ray hardening resin (A-1) obtained in Example 14 Magnetic resonance spectra. The embodiment of the invention The inventors have repeatedly and carefully studied in order to achieve the above-mentioned purpose, and as a result, have found that the linear epoxy compounds including the aromatic rings represented by the above-mentioned X and Y which are repeated repeatedly, especially the biphenyl skeleton with a high softening point and A polynuclear epoxy compound obtained by the reaction of an alcoholic hydroxyl group in a copolymerized linear epoxy compound in which a naphthalene skeleton or a bisphenol skeleton and a naphthalene skeleton are co-polymerized, and a halogenated propylene oxide reaction can result in both excellent heat resistance and toughness. Of hardened. That is, the polynuclear epoxy compound (a) of the present invention, as shown in the following general formula (1), contains regularly repeated different aromatic rings, can obtain a hardened product with high mechanical strength, and because of its linear structure, In addition, the polynuclear epoxy compound obtained by the reaction with epihalohydrin can obtain hardened products with high heat resistance, and at the same time can obtain the adhesion to the substrate, water resistance, chemical resistance, electrical insulation, and cost. Paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm). 12- (Please read the notes on the back before filling out this page) • Binding and printing printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Consumption Cooperative 524813 A7 B7_____ V. Description of the invention (1〇) Hardened materials with excellent formability
0M0M
- I CH2 -CH-CH2 —0-X—0--CH2 -CH-CH2 -0-Y- (請先閲讀背面之注意事項再填寫本頁)-I CH2 -CH-CH2 —0-X—0--CH2 -CH-CH2 -0-Y- (Please read the precautions on the back before filling this page)
\ / L 〇\ / L 〇
0M I _ 一0—CH2 —CH—CH2—0—X—0--CHs —CH—CH8 · · · (1) 」n \ / 〇 式中,X及Y表不同芳環,X表選自聯酚型二環氧丙 醚、聯二甲酚型二環氧丙醚、雙酚型二環氧丙醚及萘型二 環氧丙醚所成群之至少一種一分子中有二環氧.丙基的芳族 環氧化合物之芳環餘基,γ表選自二羥基萘及其衍生物’ 聯酚及其衍生物、聯二甲酚及其衍生物、雙酚及其衍生物 ,以及氫醌及其衍生物所成群之至少一種一分子中有二酚 .式羥基之芳族醇的芳環餘基,Μ表環氧丙基、甲基環氧丙 基及/或氫原子,η表1至2 0之整數。 上述多核環氧化合物,可用種種方法製造,而尤以使 下述一般式(6 )所表環氧化合物之醇性羥基,與環氧鹵 丙烷反應而得之多核環氧化合物爲佳,且較易於製造。 0Η 經濟部智慧財產局員工消費合作社印製 Γ | CH2 —CH—CH2 —ο--CHa —CH—CH2 —0—Y—Ο0M I _ 1 0—CH2 —CH—CH2—0—X—0—CHs —CH—CH8 Diepoxy is present in at least one of the groups of biphenol-type diglycidyl ether, bixylenol-type diglycidyl ether, bisphenol-type diglycidyl ether, and naphthalene-type diglycidyl ether. Aryl ring residues of propyl aromatic epoxy compounds, γ is selected from the group consisting of dihydroxynaphthalene and its derivatives' biphenol and its derivatives, bixylenol and its derivatives, bisphenol and its derivatives, and Hydroquinone and its derivatives have at least one group of diphenols. The aromatic ring residues of aromatic alcohols of the formula hydroxy, M represents an epoxy propyl group, a methyl epoxy propyl group and / or a hydrogen atom, η is an integer from 1 to 20. The above-mentioned polynuclear epoxy compound can be produced by various methods, and especially the polyhydric epoxy compound obtained by reacting the alcoholic hydroxyl group of the epoxy compound represented by the following general formula (6) with epihalohydrin is preferred, Easy to manufacture. 0Η Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Γ | CH2 —CH—CH2 —ο--CHa —CH—CH2 —0—Y—〇
Χ / L 〇Χ / L 〇
OH I Ί ~CH2 -CH-CH2 -0-x-o--GH2 -CH-CH2 · · · (6) J n \ / 式中,X、Y、及n同上述。 ο 更具體之合適樣態係,下述一般式(7 a.)或(7 b )所表環氧化合物之醇式羥基與環氧鹵丙烷反應所得之下 本紙張尺度適用中國國家標準(CNS ) A4規格(210父297公釐1 -13- 524813 A7 B7 五、 發明説明(11OH I Ί ~ CH2 -CH-CH2 -0-x-o--GH2 -CH-CH2 (6) J n \ / where X, Y, and n are the same as above. ο A more specific suitable aspect is the reaction between the alcoholic hydroxyl group of the epoxy compound represented by the general formula (7 a.) or (7 b) below and the epoxy halopropane. ) A4 specification (210 father 297 mm 1 -13- 524813 A7 B7 V. Description of the invention (11
述~ 一般式( 8 a ) 或 (8 b ) 所表 R3 / R6 t C Η : \ 2 ~CH—CH / 2 一 $ > <x —0— —CHa 0 R4 、Re 0H R3 R5 0H I -CH2 _CH~CHa 一〇— CH2 — CH—CH2 —0Remarks ~ R3 / R6 t C 表 as shown in the general formula (8 a) or (8 b): \ 2 ~ CH—CH / 2 1 $ > < x —0— —CHa 0 R4, Re 0H R3 R5 0H I -CH2 _CH ~ CHa 10— CH2 — CH—CH2 —0
R7 R11 R9 k I CH2 一CH-CHa -0~之〇 0 R8 R12 R10 0H CHa -CH-CH2 -0- (請先閱讀背面之注意事項存填寫本頁) -装· 〇R7 R11 R9 k I CH2 One CH-CHa -0 ~ of 〇 0 R8 R12 R10 0H CHa -CH-CH2 -0- (Please read the precautions on the back first and fill in this page) -Installation · 〇
•CH—CH* · · · (7b) / 0M 0 4 I •CH* -CH-CH2 —〇—〇- \ / 0 訂 (8 a) .秦 經濟部智慧財產局員工消費合作杜印製• CH—CH * · · · (7b) / 0M 0 4 I • CH * -CH-CH2 —〇—〇- \ / 0 Order (8 a)
CH2 —CH—CH2 n \ / ΟΜ CΗ2 一CH—CΗ2 一0- R8 R12 H10 0 式中,R3、R 4 R5、r6表相同或互異之氫原子或 CHa -CH-CH2 -〇—0- (8b) 碳原子數1至4之烷基,R 7、R 8、R 9、R 1。表相同或 互異之氫原子或不同之氫原子、碳原子數1至4之院基、 本紙張尺度適用中國國家標準(CNS ) A4規格(210 X 297公釐)-14 - 524813 A7 B7_ 五、發明説明(12 ) (請先閲讀背面之注意事項再填寫本頁) 或鹵素原子,Rll、R^2表相同或不同之氫原子、甲基或 鹵化甲基,Μ表環氧丙基、甲基環氧丙基及/或氫原子, η表1至2 0之整數。 合適樣態的上述一般式(7 a )、 (7b)、 ( 8 a )及(8 b )所表環氧化合物中,R 3至R 6全係氫原子或 R3至R6全係甲基,且R7至R1Q全係氫原子,R11及 R12全係甲基,另一方面,二價之萘環餘基爲1 ,5 —, 1 ’ 6 -,2,6 -,或2,7 —之取代體。尤爲合適之 樣態中,上述R 3至R 6全係由基,且上述二價之萘環餘基 係1,5 —,1,6 —,或2,Θ —取代體。 又,上述一般式(6 )所表之環氧化合物,隨數平均 分子量增大則藉環氧鹵丙烷之環氧化收率降低,而本發明 對於此點,利用調整作爲觸媒的鹼金屬氫氧化物之量,亦 可將醇式羥基以所欲之比率環氧化。 以下詳細說明本發明之多核環氧化合物。 首先,說明上述一般式(6)、 (7a)或(7b) 所表之環氧化合物。 經濟部智慧財產局員工消費合作社印製 上述一般式(6 )所表之環氧化合物,可用一分子中 有二環氧丙基之芳族環氧化合物(下稱二官能芳族環環氧 化合物),及一分子中有二酚式羥基之芳族醇(下稱二官 能芳族醇)爲原料,使用如下述之已知酯化觸媒,在溶劑 中或無溶劑下,交互聚合而簡便製造。 上述二官能芳族環氧化合物,適用者有選自具如下述 式(A )至(D )所示之芳環的聯酚型二環氧丙醚、聯二 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐)-15 - 524813 A7 五、發明説明(13 ) (請先閲讀背面之注意事項再填寫本頁} 甲酚型二環氧丙醚、雙酚型二環氧丙醚及萘型二環氧丙醚 所成群之至少一種二官能芳族環氧化合物。以如此之二官 能芳族環氧化合物’與二官能芳族醇行交互共聚,可得硬 化物之強度、耐熱性、電絕緣性等優良之多核環氧化合物CH2 —CH—CH2 n \ / OM CΗ2 —CH—CΗ2 — 0- R8 R12 H10 0 In the formula, R3, R 4 R5, r6 represent the same or different hydrogen atoms or CHa -CH-CH2 -〇-0- (8b) an alkyl group having 1 to 4 carbon atoms, R 7, R 8, R 9, R 1. Table of the same or different hydrogen atoms or different hydrogen atoms, the number of carbon atoms 1 to 4, the basis of this paper applies the Chinese National Standard (CNS) A4 specifications (210 X 297 mm) -14-524813 A7 B7_ 5 2. Description of the invention (12) (Please read the notes on the back before filling this page) or halogen atom, Rll, R ^ 2 are the same or different hydrogen atom, methyl group or halogenated methyl group, M means epoxypropyl group, Methylglycidyl and / or hydrogen atom, η is an integer of 1 to 20 in Tables. Among the epoxy compounds represented by the general formulae (7a), (7b), (8a), and (8b) in a suitable aspect, all of R 3 to R 6 are hydrogen atoms or all of R 3 to R 6 are methyl groups, And R7 to R1Q are all hydrogen atoms, and R11 and R12 are all methyl groups. On the other hand, the divalent naphthalene ring residue is 1, 5 —, 1 '6-, 2, 6-, or 2, 7 — Substitute. In a particularly suitable form, all of the above R 3 to R 6 are radicals, and the above-mentioned divalent naphthalene ring residual group is a 1,5 —, 1, 6 —, or 2, Θ — substituent. In addition, the epoxy compound represented by the above general formula (6) decreases the epoxidation yield of epoxy halopropane as the number average molecular weight increases, and the present invention uses this to adjust the alkali metal hydrogen as a catalyst. The amount of oxide can also epoxidize the alcoholic hydroxyl group at a desired ratio. Hereinafter, the polynuclear epoxy compound of the present invention will be described in detail. First, the epoxy compound represented by the general formula (6), (7a) or (7b) will be described. The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints the epoxy compound represented by the above general formula (6). An aromatic epoxy compound (hereinafter referred to as a bifunctional aromatic cyclic epoxy compound) having diglycidyl group in one molecule can be used. ), And an aromatic alcohol with a diphenolic hydroxyl group in one molecule (hereinafter referred to as a difunctional aromatic alcohol) as a raw material, using a known esterification catalyst as described below, in a solvent or without a solvent, interactive polymerization is simple and convenient Manufacturing. The above-mentioned difunctional aromatic epoxy compounds are applicable to those selected from the group consisting of bisphenol-type dipropylene oxide ethers having aromatic rings as shown in the following formulae (A) to (D), and the size of the paper is subject to Chinese national standards ( CNS) A4 specification (210X297 mm) -15-524813 A7 V. Description of the invention (13) (Please read the precautions on the back before filling out this page} Cresol dipropylene oxide, bisphenol dipropylene oxide Ether and naphthalene-type dipropylene oxide ether group of at least one difunctional aromatic epoxy compound. With such a difunctional aromatic epoxy compound 'and a difunctional aromatic alcohol cross-copolymerization, the strength of the hardened material can be obtained Polynuclear epoxy compounds with excellent heat resistance, electrical insulation, etc.
_Q_s〇2^Qk- (C) (D) 式中,R3、R4、R5、R6表相同或互異之氫原子或 碳原子數1至4之烷基’ R 7、R 8、R 9、R 1 Q表相同或 互異之氫原子、碳原子數1至4之烷基或鹵素原子’ R11 、R12表相同或不同之氫原子、甲基或鹵化甲基。 經濟部智慧財產局員工消費合作社印製 上述聯酚型、聯二甲酚型、雙酚型或萘型二環氧丙醚 ,可用由例如聯酚化合物、聯二甲酚化合物、雙酚化合物 或二羥基萘、與環氧鹵丙烷反應所製造者。又’亦可使用 市售之環氧化合物’可舉例如’聯酚型二環氧丙醚的曰本 環氧樹脂(股)製之商品名「Epicote YL — 6 0 5 6」等 ,聯二甲酚型二環氧丙醚的日本環氧樹脂(股)製之商品 名「Ep1C〇te YX - 4 0 0 0」等,雙酚型二環氧丙醚的旭 化成環氧(股)製之商品名「Araldite #260」、.「Araldite #607 1」等之雙酚A型環氧化合物、或大日本油墨化學工 本紙張尺度適用中國國家標準(CNS ) A4規格(210 X297公釐)-16 - 經濟部智慧財產局員工消費合作社印製 524813 A7 B7 ___ 五、發明説明(14 ) 業(股)製之商品名「Epklon 830S」等之雙酚^^型環 氧化合物、或大日本油墨化學工業(股)製之商品名「 Epiclon EXA15 14」等之雙酚S型環氧化合物等,萘型二環 氧丙醚的大日本油墨化學工業(股)製之商品名「Epic Ion HP — 40 3 2 (D)」等,這些可單獨或二種以上組合 使用。 本發明所使用之二官能芳族醇具有其構造特徵之’能 提高耐熱性之芳環,可使用具對稱構造或剛直構造者。如 此之化合物,可舉例如,1 ,4 一二羥基萘、.1 ,5 -二 羥基萘、1,6 —二羥基萘、2,6 -二羥基萘、2,7 —二羥基萘、2 ,8 —二羥基萘等之二羥基萘衍生物、聯 二甲酚、聯酚等之聯酚衍生物、雙酚A、雙酚F、雙酚S 、烷基取代雙酚等之雙酚衍生物、氫醌、甲基氫醌、三甲 基氫醌等之氫醌衍生物,這些可單獨或二種以上組合使用 〇 上述一般式(6)所表環氧化合物中,尤以上述一般 式(7 a )或(7b)所表之環氧化合物爲佳。該一般式 (7 a )或(7 b )所表環氧化合物,可藉聯苯型及/或 聯二甲酚型環氧化合物或雙酚型環氧化合物,與1 ,5 一 、1 ,6 -、2,6 -、2,7 —取代體等的至少一種二 羥基萘爲原料,用醚化觸媒,於溶劑中或無溶劑交互聚合 之方法簡便製造。二羥基萘係以使用高軟化點之1 ,5 - 、1 ’ 6 -或2,6 -取代體,尤以對稱之1 ,5 -及2 ,6 -取代體爲佳。 本紙張尺度適用中國國家標準(CNS ) ( 210X297公後)1^| 7 - '~" I----·---------、玎------0r (請先閲讀背面之注意事項再填寫本頁) 524813 A7 __B7 五、發明説明(彳5 ) 用於上述一般式(6 )及(7 a )、 ( 7 b )所表環 (請先閱讀背面之注意事項再填寫本頁) 氧化合物之合成的觸媒,係以環氧丙基與酣式經基定量反 應之膦類、鹼金屬化合物、胺類之單獨或合併使用爲佳。 其它觸媒因凝膠化之發生而不佳。 膦類者可舉三丁基膦、三苯基膦等之三院基或三芳基 膦、或其與氧化合物之鹽類等。 鹼金屬化合物可舉鈉、鋰、鉀等之鹼金屬的氫氧化物 、鹵化物、醇化物、醯胺等,這些可單獨或二種以上混合 使用。 胺類可舉脂族或芳族之一級、二級、三級、四級胺類 等,這些可單獨或二種以上組合使用。胺類之具體例可舉 、三乙醇胺、N,N —二甲基哌哄、二乙胺、三正丙胺、 .六甲撐四胺、吡啶、溴化四甲銨等。 經濟部智慧財產局員工消費合作社印製 這些觸媒,相對於上述二官能芳族環氧化合物及二官 能芳族醇之總入料量1 0 0質量份,以用〇 . 〇 〇 1至1 質量份爲佳,0 . 〇 1至1質量份爲更佳。其理由係,若 觸媒之用量不及0 . 0 0 1質量份,所應所需時間不經濟 ’另一方面,若超過1質量份,反因反應太快難以控制。 又,二官能芳族環氧化合物與二官能芳族醇之反應, 係以在上述觸媒之存在下,於惰性氣體氣流中或空氣中, 於1 3 0至1 8 0 °C之溫度範圍進行爲佳。 其次,說明上述一般式(1 )或(8 a )、 (8b) 所表之本發明的多核環氧化合物。 上述一般式(1)或(8a)、 (8b)所表之本發 本紙張尺度適用中國國家榡準(CNS ) A4規格(210X297公釐)-18 - 524813 經濟部智慧財產局員工消費合作社印製 A7 _B7 五、發明説明(16 ) 明的多核環氧化合物,可於如下述之已知溶劑中或無溶劑 下,在鹼金屬氫氧化物的存在下,利用上述一般式(6 ) 或(7a)、 (7b)之環氧化合物中的醇式羥基與環氧 鹵丙烷之反應而製造。 上述環氧鹵丙烷者可用例如,環氧氯丙烷、環氧溴丙 烷、環氧碘丙烷、/5 -甲基環氧氯丙烷、/3 —甲基環氧溴 丙烷、/5 —甲基環氧碘丙烷等。 上述一般式(1)及(8a)、 (8b)所表示本發 明之多核環氧化合物中,環氧鹵丙烷之使用量.爲相對於一 般式(6 )或(7 a )、 X 7 b )中之醇式羥基1當量, 以0 · 1倍當量爲佳。但若相對於上述羥基1當量,使用 超過1 5倍當量則容積效率差而不佳。 又,溶劑可用二甲亞碾、N,N —二甲基甲醯胺、N ,N -二甲基乙醯胺等之質子惰性極性溶劑、甲苯、二甲 苯等之芳族烴類等已知溶劑,而其中以質子惰性極性溶劑 ,尤以二甲亞碾爲佳。該溶劑之使用量,以對一般式(6 )或(7a)、 (7b)所表之環氧化合物5至300質 量%爲佳。其理由係,不足5質量%則醇式羥基與環氧鹵 丙烷之反應慢,另一方面,若超過3 0 0質量%則容積效 率變差之故。 又,鹼金屬氫氧化物可用氫氧化鈉、氫氧化鉀、氫氧 化鉀、氫氧化鈣等,尤以氫氧化鈉爲佳。該鹼金屬氫氧化 物之使用量,以對一般式(6 )或(7 a )、 ( 7 b )所 表環氧化合物中欲予環氧化之醇式羥基1當量,在0 · 5 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐] -19 - ----.---^ ------IT------" (請先閲讀背面之注意事項再填寫本頁) 524813 A7 B7 五、發明説明(17 ) 至2倍當量爲佳。 上述一般式(6)或(7a)、 (7b)所表之環氧 (請先閲讀背面之注意事項再填寫本頁) 化合物中的醇式羥基與環氧鹵丙烷之反應溫度,以在2 0 °C以上,較佳者爲3 0 °C以上,1 0 0 °C以下之範圍爲佳 。其理由係,若反應溫度不足2 0 °C,則反應慢,反應所 需時間長,另一方面,若反應溫度超過1 0 0 t則多有副 反應發生而不佳之故。 上述一般式(6 )或(7 a )、 ( 7 b )所表環氧化 合物中之醇式羥基與環氧鹵丙烷之反應,可於二甲亞砸或 四級銨鹽等之四級鹼性鹽化合物,或1 ,3 —二甲基一 2 -咪唑啉及鹼金屬氫氧化物之共存下,經該鹼金屬氫氧化 物之量的調整而進行。此時,溶劑可倂用甲醇或乙醇等之 醇類,甲苯、二甲苯等之芳族烴類、甲基異丁基甲醇、甲 基乙基甲酮等之酮類、四氫呋喃等之環狀醚類化合物等。 經濟部智慧財產局員工消費合作社印製 可用之四級鹼性鹽化合物之具體例,可舉例如,氯化 四甲銨、溴化四丁銨、三甲基甲苯基銨鹵化物、碳酸氫四 甲銨、苯甲酸四甲銨、氫氧化四甲銨、氫氧化四乙銨、氫 氧化四甲鐵等。而上述觸媒可單獨或二種以上混合使用。 其使用量以對上述上述一般式(6)或(7a)、 (7b )所表環氧化合物之羥基1當量,在Ο · Ο Ο 1至2當量 之範圍爲佳。更佳者爲在0 · 0 5至0 · 2當量之範圍。 不足0 · 0 0 1當量時效果難以呈顯,且原料環氧化合物 之環氧丙醚基與環氧化合物之羥基反應而高分子量化,故 不爲佳。另一方面,添加超過2當量時,亦不見效果之格 本紙張尺度適用中國國家標準(CNS ) Α4規格(210X297公釐) - 20- 524813 A7 ---- —_ B7 ___ 五、發明説明(18 ) 外提升。 (請先閲讀背面之注意事項再填寫本頁) 可如此製得之本發明的多核環氧化合物,數平均分子 量在400至5〇〇〇,以5〇〇至3000爲佳,以 5 0 0至2 0 0 0爲更佳。該環氧化合物之數平均分子量 不足4 0 0時,所得硬化物之靭度不充分,另一方面,若 超過5 0 0 0 ’則溶劑之溶解性降低而爲不佳。 環氧化率可依目的(依所需之物性)適當選擇,以 10至100%爲適當,以30至90%爲佳,以4至 8〇%爲更佳。 本發明之多核環氧化合物,可單獨或與其它環氧樹脂 組合使用,與通常之環氧樹脂同,可添加硬化劑,必要時 甚至於硬化促進劑,而硬化。 環氧樹脂可將以下例示之向來已知的各種環氧樹脂( D),單獨或二種以上組合使用。 經濟部智慧財產局員工消費合作社印製 所用硬化劑可舉胺系化合物、酸酐系化合物、醯胺系 化合物、酚系化合物等。具體例可舉,二胺基二苯基甲烷 、二乙撐三胺、二胺基二苯基硕、異佛爾酮二胺、雙氰胺 、亞油精之二聚物與乙二胺合成之聚醯胺樹脂、苯酐、偏 苯三酸酐、均苯四酸酐、馬來酸酐、四氫苯酐、四基四氫 苯酐、甲基降冰片烯二酸酐、六氫苯酐、甲基六氫苯酐、 酚醛淸漆,及這些之改質物,咪唑、B F 3 -胺絡合物、胍 衍生物等。這些硬化劑可各予單獨使用,或二種以上組合 使用。. 硬化促進劑可舉例如,咪唑類、三級胺類、酚類、金 本紙張尺度適用中國國家標準(CNS ) A4規格(210X29*7公釐) -21 - 經濟部智慧財產局員工消費合作社印製 524813 A 7 ___B7_ 五、發明説明(19 ) )运i ill合物等 ° 如此,本發明之多核環氧化合物、硬化劑、必要時之 硬化促進劑等所配合成之環氧樹脂組成物’可用向來已知 方法同樣之條件,簡便製成環氧樹脂組成物硬化物。例如 ,混合本發明之多核環氧化合物、硬化劑、充塡劑及其它 添加劑,必要時用擠出機、揑合機或輥筒等充分混練均勻 ’得環氧樹脂組成物5將該環氧樹脂組成物熔融後’以注 模或傳遞成形機等成形,再以8 0至2 0 0 t加熱,可得 硬化物。又,溶解環氧樹脂組成物於溶劑,含浸於玻纖、 碳纖、聚酯纖維、聚醯胺纖維、氧化鋁纖維、紙等基材, 加熱乾燥得膠片,其熱壓成形亦可得硬化物。 又,於上述環氧樹脂組成物,必要時可添加無機充塡 劑或有機充塡劑等之種種配合劑。 而本發明之多核環氧化合物、硬化劑、及必要時之硬 化促進劑所配合成之樹脂組成物,可溶於溶劑,調整爲適 合於塗布方法之粘度。 如此之溶劑,可舉例如,甲乙酮、環己酮等之酮類; 甲苯、二甲苯、四甲苯等芳族烴類、溶纖劑、甲基溶纖劑 、丁基溶纖劑、卡必醇、甲基卡必醇、丁基卡必醇、丙二 醇單甲醇、丙二醇單乙醚、二丙二醇二乙醚、三乙二醇單 乙醚等之二醇醚類;醋酸乙酯、醋酸丁酯、溶纖劑醋酸酯 、了基溶纖劑醋酸酯、卡必醇醋酸酯、丁基卡必醇醋酸酯 、丙二醇單甲醇醋酸酯、二丙二醇單甲醚醋酸醋等之醋酸 酯類;乙醇、丙醇、乙二醇、丙二醇等之醇類;辛烷、癸 本紙張尺度適用中國國家樣準(CNS )八4胁(210X 297公慶)=22 - 一 IT (請先閲讀背面之注意事項再填寫本頁) 524813 A7 ___ B7五、發明説明(20 ) 烷等之酯族烴類;石油醚、石油腦、氫化石油腦、溶劑輕 油等之石油系溶劑等。這些有機溶劑,可以單獨或二種以 上混合使用。 又根據本發明人等之硏究發現,將如上述之線狀多核 環氧化合物,尤以高軟化點之聯苯骨架與萘骨架,或雙酚 骨架與萘骨架交互共聚之交互共聚型線狀多核環氧化合物 ’以含不飽和基之一元酸(C )反應而得之下述一般式( 2 a )或(2 b )所表之多核環氧丙烯酸酯化合物(b ) ,可光硬化或熱硬化,且因如此的硬化處理可.導致兼具優 良耐熱性及靭度之硬化物。’ Z’ 一0—X—〇- 0Z I CH2 一CH—CH2 ~0—Y —〇— 0Z I 一 d — CH—CH2 —0—一〇-_Q_s〇2 ^ Qk- (C) (D) In the formula, R3, R4, R5, R6 represent the same or different hydrogen atom or alkyl group having 1 to 4 carbon atoms' R 7, R 8, R 9, R 1 Q represents the same or different hydrogen atom, alkyl group or halogen atom having 1 to 4 carbon atoms' R 11, R 12 represents the same or different hydrogen atom, methyl group or halogenated methyl group. The above-mentioned biphenol-type, bixylenol-type, bisphenol-type or naphthalene-type diglycidyl ether is printed by the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, and can be used for example by biphenol compounds, bixyphenol compounds, bisphenol compounds, or Dihydroxynaphthalene, produced by the reaction with epihalohydrin. Also, a “commercially available epoxy compound” may be used, for example, “Epicote YL — 6 0 5 6”, a brand name of “Epiote YL — 6 0 5 6” made of Bisphenol-type dipropylene oxide ether. Cresol type diglycidyl ether made by Japan Epoxy Resin Co., Ltd. under the trade name "Ep1C〇te YX-4 0 0", etc., bisphenol type diglycidyl ether manufactured by Asahi Kasei Epoxy Co., Ltd. Product names "Araldite # 260", "Araldite # 607 1" and other bisphenol A epoxy compounds, or Dainippon Ink Chemical Co., Ltd. Paper size applies Chinese National Standard (CNS) A4 specifications (210 X297 mm) -16 -Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 524813 A7 B7 ___ V. Description of the invention (14) Bisphenol ^^ epoxy compounds such as the trade name "Epklon 830S", or Dainippon Ink Chemistry Industrial products (Epiclon EXA15 14) and other bisphenol S-type epoxy compounds, etc., naphthalene-type dipropylene oxide ether, and product names "Epic Ion HP — 40" 3 2 (D) ", etc. These can be used alone or in combination of two or more. The bifunctional aromatic alcohol used in the present invention has a structural feature, an aromatic ring capable of improving heat resistance, and can be used for symmetrical structure or rigid structure. Examples of such a compound include 1,4-dihydroxynaphthalene, .1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2 Dihydroxy naphthalene derivatives such as 8-dihydroxynaphthalene, biphenol derivatives, biphenol derivatives, biphenol derivatives, bisphenol A, bisphenol F, bisphenol S, alkyl-substituted bisphenol derivatives, etc. Derivatives, hydroquinone, methylhydroquinone, trimethylhydroquinone, etc. These can be used alone or in combination of two or more. Among the epoxy compounds represented by the general formula (6), the general formula The epoxy compound represented by (7a) or (7b) is preferred. The epoxy compound represented by the general formula (7a) or (7b) may be a biphenyl-type and / or bixylenol-type epoxy compound or a bisphenol-type epoxy compound, and 1, 5, 1, 1, At least one dihydroxynaphthalene such as 6-, 2,6-, 2,7-substituent and the like is used as a raw material, and is easily produced by an etherification catalyst, in a solvent or solvent-free cross-polymerization. The dihydroxynaphthalene is preferably a 1,5-, 1 '6-or 2,6 -substituent having a high softening point, and particularly a symmetrical 1,5-and 2,6 -substituent. This paper size applies Chinese National Standard (CNS) (210X297 male) 1 ^ | 7-'~ " I ---- · ---------, 玎 ------ 0r (Please (Please read the precautions on the back before filling this page) 524813 A7 __B7 V. Description of the invention (5) is used for the rings of the above general formulae (6) and (7a), (7b) (please read the notes on the back first) Please fill in this page for more details.) The catalyst for the synthesis of oxygen compounds is preferably used alone or in combination with phosphine, alkali metal compounds, and amines based on the quantitative reaction of glycidyl group and hydrazone formula. Other catalysts are not good because of gelation. Examples of the phosphines include trialkylphosphine or triarylphosphine such as tributylphosphine and triphenylphosphine, or salts thereof with oxygen compounds. Examples of the alkali metal compound include hydroxides, halides, alcoholates, and amidines of alkali metals such as sodium, lithium, and potassium. These may be used alone or in combination of two or more. Examples of the amines include aliphatic, aromatic one-, two-, three-, and four-stage amines, and these may be used alone or in combination of two or more. Specific examples of the amines include triethanolamine, N, N-dimethylpiperazine, diethylamine, tri-n-propylamine, hexamethylenetetramine, pyridine, and tetramethylammonium bromide. The consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints these catalysts, with respect to the above-mentioned total amount of the difunctional aromatic epoxy compound and difunctional aromatic alcohol of 100 parts by mass, in order to use 0.001 to 1 Part by mass is preferable, and 0.01 to 1 part by mass is more preferable. The reason is that if the amount of catalyst used is less than 0.01 parts by mass, the time required should be uneconomical. 'On the other hand, if it exceeds 1 part by mass, the reaction is too fast and difficult to control. In addition, the reaction between a difunctional aromatic epoxy compound and a difunctional aromatic alcohol is in the temperature range of 130 to 180 ° C in an inert gas stream or in the air in the presence of the above catalyst. Better to proceed. Next, the polynuclear epoxy compound of the present invention represented by the general formulae (1), (8a), and (8b) will be described. The paper size shown in the general formulae (1) or (8a) and (8b) above is applicable to China National Standards (CNS) A4 specifications (210X297 mm) -18-524813 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Preparation A7 _B7 V. Description of the invention (16) The polynuclear epoxy compound described in (16) can be used in a known solvent as described below or in the absence of a solvent in the presence of an alkali metal hydroxide using the general formula (6) or ( 7a) and (7b) are produced by reacting an alcoholic hydroxyl group with an epoxy halopropane. The epihalohydrin can be used, for example, epichlorohydrin, epibromopropane, iodopropane, / 5-methylepoxychloropropane, / 3-methylepoxybromopropane, / 5-methylcyclopropane Oxyiodopropane and the like. In the polynuclear epoxy compound of the present invention represented by the general formulae (1), (8a), and (8b), the amount of epihalohydrin used is relative to the general formulae (6) or (7a), X 7 b 1 equivalent of the alcoholic hydroxyl group is preferably 0.1 times equivalent. However, if it is more than 15 times equivalent to 1 equivalent of the above-mentioned hydroxyl group, the volumetric efficiency is poor and unsatisfactory. As the solvent, known are aprotic polar solvents such as dimethylarylene, N, N-dimethylformamide, N, N-dimethylacetamide, and aromatic hydrocarbons such as toluene and xylene. Solvents, among which aprotic polar solvents, especially dimethyl arylene, are preferred. The solvent is preferably used in an amount of 5 to 300% by mass based on the epoxy compound represented by the general formulae (6) or (7a) and (7b). The reason is that if the content is less than 5% by mass, the reaction between the alcoholic hydroxyl group and the epihalohydrin is slow. On the other hand, if the content exceeds 300% by mass, the volumetric efficiency is deteriorated. As the alkali metal hydroxide, sodium hydroxide, potassium hydroxide, potassium hydroxide, calcium hydroxide and the like can be used, and sodium hydroxide is particularly preferred. The alkali metal hydroxide is used in an amount of 1 equivalent to the alcoholic hydroxyl group to be epoxidized in the epoxy compound represented by the general formulae (6) or (7a) and (7b). Standards are applicable to China National Standard (CNS) A4 specifications (210X297 mm) -19-----.--- ^ ------ IT ------ " (Please read the notes on the back first Fill out this page again) 524813 A7 B7 V. Description of the invention (17) to 2 times the equivalent is better. Epoxy represented by the above general formula (6) or (7a), (7b) (please read the precautions on the back first) (Fill in this page) The reaction temperature of the alcoholic hydroxy group and the epihalohydrin in the compound is preferably above 20 ° C, preferably above 30 ° C, and preferably below 100 ° C. The reason is In other words, if the reaction temperature is lower than 20 ° C, the reaction is slow and the time required for the reaction is long. On the other hand, if the reaction temperature exceeds 100 t, side reactions often occur and are not good. The above general formula (6) Or (7a), (7b) the alcoholic hydroxyl groups in the epoxy compounds shown in the table and the epoxy halopropane reaction, can be used in quaternary ammonium salt or quaternary ammonium salt, etc. , The coexistence of 3-dimethyl-2-imidazoline and an alkali metal hydroxide is carried out by adjusting the amount of the alkali metal hydroxide. At this time, the solvent may be an alcohol such as methanol or ethanol, or toluene Aromatic hydrocarbons such as xylene, ketones such as methyl isobutyl methanol and methyl ethyl ketone, cyclic ether compounds such as tetrahydrofuran, etc. Printed and available for use by employees' cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Specific examples of the quaternary basic salt compound include, for example, tetramethylammonium chloride, tetrabutylammonium bromide, trimethyltolylammonium halide, tetramethylammonium bicarbonate, tetramethylammonium benzoate, and tetrahydroxide. Methylammonium, tetraethylammonium hydroxide, tetramethyl iron hydroxide, etc. The catalyst can be used singly or in combination of two or more. The amount used is based on the above general formula (6) or (7a), (7b). The epoxy group has 1 equivalent of the hydroxyl group, preferably in the range of 0 to 0. 0 to 1 equivalent. More preferably, it is in the range of 0 to 0.5 to 2 equivalents. The effect is less than 0 to 0 to 1 equivalent. It is obvious, and the propylene oxide ether group of the raw material epoxy compound reacts with the hydroxyl group of the epoxy compound to be high Molecular weight, it is not good. On the other hand, when adding more than 2 equivalents, the effect of the standard paper size is applicable to China National Standard (CNS) A4 specifications (210X297 mm)-20- 524813 A7 ---- — _ B7 ___ V. Description of the invention (18) Outside promotion (Please read the notes on the back before filling this page) The polynuclear epoxy compound of the present invention, which can be prepared in this way, has a number average molecular weight of 400 to 5000, It is preferably 500 to 3000, and more preferably 500 to 2000. When the number-average molecular weight of the epoxy compound is less than 400, the toughness of the obtained cured product is insufficient. On the other hand, when it exceeds 5000 ', the solubility of the solvent is reduced and it is not good. The epoxidation rate can be appropriately selected according to the purpose (depending on the required physical properties), 10 to 100% is appropriate, 30 to 90% is preferable, and 4 to 80% is more preferable. The polynuclear epoxy compound of the present invention can be used alone or in combination with other epoxy resins. Like ordinary epoxy resins, a hardener can be added, and if necessary, a hardening accelerator can be used to harden. As the epoxy resin, various conventionally known epoxy resins (D) exemplified below can be used alone or in combination of two or more. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economics The hardener used can be amine compounds, acid anhydride compounds, amidine compounds, phenol compounds, etc. Specific examples include the synthesis of diamine diphenylmethane, diethylenetriamine, diaminodiphenyl master, isophorone diamine, dicyandiamide, linolein dimer and ethylenediamine Polyamine resin, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, tetrayltetrahydrophthalic anhydride, methylnorbornene anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, phenolic lacquer , And these modified products, imidazole, BF 3 -amine complex, guanidine derivatives and the like. These hardeners can be used individually or in combination of two or more. Hardening accelerators can be, for example, imidazoles, tertiary amines, phenols, and gold paper. Applicable to China National Standard (CNS) A4 specifications (210X29 * 7 mm) -21-Employees' Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs Printed 524813 A 7 ___B7_ V. Description of the invention (19)) I ill compound, etc. In this way, the polynuclear epoxy compound, hardener, hardening accelerator, etc. of the present invention is an epoxy resin composition 'The hardened | cured material of an epoxy resin composition can be manufactured easily under the same conditions as a conventionally known method. For example, the polynuclear epoxy compound, hardener, filler, and other additives of the present invention are mixed, and if necessary, thoroughly mixed with an extruder, kneader, or roller to obtain an epoxy resin composition 5 After the composition is melted, it is formed by injection molding or transfer molding, and then heated at 80 to 200 t to obtain a hardened product. In addition, the epoxy resin composition is dissolved in a solvent, impregnated with glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper and other substrates, and dried by heating to obtain a film, and a hardened product can also be obtained by hot pressing. . In addition, various additives such as inorganic fillers and organic fillers may be added to the epoxy resin composition as necessary. The resin composition made of the multi-core epoxy compound, the hardener, and the hardening accelerator when necessary can be dissolved in a solvent and adjusted to a viscosity suitable for the coating method. Examples of such solvents include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetra toluene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, and methylformate. Glycolol, butylcarbitol, propylene glycol monomethanol, propylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether and other glycol ethers; ethyl acetate, butyl acetate, cellosolve acetate Acetates such as cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethanol acetate, dipropylene glycol monomethyl ether acetate, etc .; ethanol, propanol, ethylene glycol Alcohols such as propylene glycol and propylene glycol; octane and decane paper standards are applicable to China National Standards (CNS) Ya 4 threats (210X 297 public holidays) = 22-one IT (Please read the precautions on the back before filling this page) 524813 A7 ___ B7 V. Description of the invention (20) Ester hydrocarbons such as alkanes; petroleum solvents such as petroleum ether, petroleum brain, hydrogenated petroleum brain, solvent light oil, etc. These organic solvents can be used singly or in combination of two or more kinds. According to the research conducted by the inventors, it is found that the linear polynuclear epoxy compound as described above, especially a high-softening point biphenyl skeleton and a naphthalene skeleton, or an interactive copolymerization type of a linear copolymerization of a bisphenol skeleton and a naphthalene skeleton. The polynuclear epoxy compound 'is obtained by reacting an unsaturated monobasic acid (C) with a polynuclear epoxy acrylate compound (b) represented by the following general formula (2a) or (2b), which can be photo-hardened or Heat hardening, and because of this hardening treatment, it can lead to hardened products with excellent heat resistance and toughness. ’Z’-0—X—〇— 0Z I CH2—CH—CH2 ~ 0—Y —〇— 0Z I—d — CH—CH2 — 0— 一 〇-
0Z -Z, (2a) CH2 —CH—CH2 —0— X — 〇- 〇0Z -Z, (2a) CH2 —CH—CH2 —0— X — 〇- 〇
0Z I _CH2 —CH—CH2 一0—Y—〇— -----.--------------IT------0 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 -CHa —CH-CHj (2b) 〇 式中,X及Y表不同芳環,X表選自聯酚型二環氧丙 醚、聯二甲酚型二環氧丙醚、雙酚型二環氧丙醚及萘型二 環氧丙醚所成群之至少一種一分子中有二環氧丙基的芳族 環氧化合物之芳環餘基、Y表選自二羥基萘及.其衍生物、 聯酚及其衍生物、聯二甲酚及其衍生物、雙酚及其衍生物 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐)-23 524813 A 7 B7 五、發明説明(21 ) ’以及氣酷及其衍生物所成群之至少一'種一分子中有二酣 式羥基之芳族醇的芳環餘基,z係相互無關,表下述一般 (請先閲讀背面之注意事項再填寫本頁) 式(3 )或(4)所示之基或氫原子,且Z之至少其一係 一般式(3)所示之基,Z’係相互無關,表下述一般式 (3’ )或(4’ )所示之基,η表1至20之整數。 R1 0 R10Z I _CH2 —CH—CH2 — 0—Y—〇— -----.-------------- IT ------ 0 (Please read the precautions on the back first (Refill this page) -CHa —CH-CHj (2b) printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, where X and Y are different aromatic rings, and X is selected from biphenol-type dipropylene oxide, Aryl ring of at least one aromatic epoxy compound having diglycidyl group in one molecule of at least one group formed by xylenol type diglycidyl ether, bisphenol type diglycidyl ether, and naphthalene type diglycidyl ether Residual and Y are selected from dihydroxynaphthalene and its derivatives, biphenol and its derivatives, bixylenol and its derivatives, bisphenol and its derivatives. The paper size applies to Chinese National Standard (CNS) A4 specifications. (210X297 mm) -23 524813 A 7 B7 V. Description of the invention (21) and at least one of the groups of qiku and its derivatives are aromatic ring residues of aromatic alcohols with difluorene hydroxyl groups in one molecule. The base and z are independent of each other. The following table is general (please read the notes on the back before filling this page) The base or hydrogen atom shown by formula (3) or (4), and at least one of Z is the general formula ( 3) The base shown, Z 'is independent of each other The bases shown in the following general formulae (3 ') or (4') are shown, and η is an integer from 1 to 20. R1 0 R1
I II I -CH2 -C-CH2 -0-C-R2 · · · (3) — CH2 -C ——CH2 · · · (4) I \ / OH 0I II I -CH2 -C-CH2 -0-C-R2 · · · (3) — CH2 -C ——CH2 · · · (4) I \ / OH 0
0 II 一CH2 — CH — CH2 —0 — C-R2 · · · (3,) -CH2 -CH-CHa · · · (4,) I \ / OH 0 式中,R1表氫原子或甲基、R2表不飽和一元酸餘基 0 經濟部智慧財產局員工消費合作社印製 亦即,本發明之多核環氧丙烯酸酯化合物(b ),因 含規則重複之上述一般式(2 a )或(2 b )所表的不同 芳環,係可得高機械強度之硬化物,又因呈線狀構造,且 因以含不飽和基之一元酸與多核環氧化合物反應,可藉光 硬化或熱硬化得高耐熱性之硬化物,同時,可得對基材之 密合性、耐水性、耐藥品性、電絕緣性、成形性優良之硬 化物者。 更具體的合適樣態爲,下述一般式(9 a )至(9 d )所示之多核環氧丙烯酸酯化合物。 本紙張尺度適用中國國家標準(CNS〉A4規格(210 X 297公釐)-24 - 524813 A7 B7 五、發明説明(22 R8 Z,一〇0 II a CH2 — CH — CH2 —0 — C-R2 · · · (3,) -CH2 -CH-CHa · · · (4,) I \ / OH R2 represents unsaturated monobasic acid residues. 0 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. That is, the multi-core epoxy acrylate compound (b) of the present invention contains the above-mentioned general formula (2a) or (2) b) The different aromatic rings shown are hardened products with high mechanical strength, and because of the linear structure, and because of the reaction of unsaturated monobasic acids with polynuclear epoxy compounds, they can be hardened by light or heat. A hardened product having high heat resistance and a hardened product having excellent adhesion to a substrate, water resistance, chemical resistance, electrical insulation, and formability can be obtained. A more specific suitable aspect is a polynuclear epoxy acrylate compound represented by the following general formulae (9a) to (9d). This paper size applies to Chinese national standard (CNS> A4 specification (210 X 297 mm) -24-524813 A7 B7 V. Description of the invention (22 R8 Z, 1〇
0Z CΗ2 —CH一CΗ2 一0——〇- 0Ζ I 一 CH2 — CH—CH2 — 00Z CΗ2 —CH—CΗ2 — 0—〇— 0Z I—CH2 — CH—CH2 — 0
(9a) R3 R6 〇(9a) R3 R6.
一CH2 一CH一CH2 一0One CH2 one CH one CH2 one 0
0Z -CHa --CH-CΗ2 -0——〇-0Z -CHa --CH-CΗ2 -0——〇-
CH2 -CH—CHa n \ / 0 (9b) (請先閲讀背面之注意事項再填寫本頁)CH2 -CH—CHa n \ / 0 (9b) (Please read the precautions on the back before filling this page)
R7 R11 R9 〇ZR7 R11 R9 〇Z
經濟部智慧財產局員工消費合作社印製 式中,R3至R12,Z及n同上述。 合適之樣態中,或R 3至R 6全係氫原子,或R 3至R 6 全係甲基、又R7至R1Q全係氫原子,R11及R12全係甲 本紙張尺度適用中國國家標準(CNS ) A4規格(210 X297公釐) -25 - 524813 A7 B7 五、發明説明(23 ) 基,另一方面,二價之萘環餘基係1 ,5 —、 1 ,6 —、 (請先閲讀背面之注意事項再填寫本頁) 2 ,6 -、或2 ,7 —取代體。尤爲合適之樣態中,上述 R 3至R 6全係甲基,且上述二價之萘環餘基係1 ,5 —、 1,6 -,或2,6 —取代體。 上述一般式(2 a )或(2b)所示多核環氧丙烯酸 酯化合物(b ),可將下述一般式(1 0 )所示多核環氧 化合物以含不飽和基之一元酸(c ),於前述有機溶劑之 存在下或不存在下,在聚合抑制劑及反應觸媒之共存下, 反應而得。 0Z1In the printed format of the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, R3 to R12, Z and n are the same as above. In a suitable state, either R 3 to R 6 are all hydrogen atoms, or R 3 to R 6 are all methyl groups, and R 7 to R 1 Q are all hydrogen atoms. R 11 and R 12 are all paper sizes. The national paper standards are applicable to Chinese standards. (CNS) A4 specification (210 X297 mm) -25-524813 A7 B7 V. Description of the invention (23) group, on the other hand, the divalent naphthalene ring residual group is 1, 5 —, 1, 6 —, (please Read the notes on the back before filling out this page) 2, 6-, or 2, 7 —substitute. In a particularly suitable aspect, the aforementioned R 3 to R 6 are all methyl groups, and the aforementioned divalent naphthalene ring residual group is a 1,5-—, 1,6-—, or 2,6-—substituent. The polynuclear epoxy acrylate compound (b) represented by the general formula (2a) or (2b) may be an unsaturated monobasic acid (c) containing the polynuclear epoxy compound represented by the following general formula (1 0). It is obtained by reacting in the presence or absence of the aforementioned organic solvent in the coexistence of a polymerization inhibitor and a reaction catalyst. 0Z1
厂 I CH2 —CH—CHz —Ο—X—Ο--CH2 —CH-CH2 —ο- γ-ο—Factory I CH2 —CH—CHz — 0—X—〇--CH2 —CH-CH2 —ο- γ-ο—
\ / L 〇 OZ1 -ch2 -ch-ch2 -0-x-o——ch2 -ch-ch2 · · · (1 0) -n \ / 0 式中,X、Y及n同上述,Z1係相互無關之氫原子或 上述一般式(4 )所示之基。 經濟部智慧財產局員工消費合作社印製 爲驗證上述一般式(1 〇 )所示之多核化合物,以含 +飽和I基之單羧酸(c )反應可得不飽和多核環氧丙烯酸 酯化合物(.b ),於上述一般式(1 〇 )所示多核環氧化 合物’配合以對該化合物中所含環氧基i莫耳,〇 · 8至 1 · 3莫耳之比例的含不飽和基之單羧酸,在惰性溶劑中 或無溶劑’於約6 0至1 5 0 °C,較佳者爲7 0至1 3 0 °C加熱,較佳者爲於空氣存在下進行反應。爲防止反應中 因聚合而凝膠化,以使用甲基氫醌、氫醌等之氫醌類;對 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -26 - 524813 A7 _____B7 五、發明説明(24 ) (請先閲讀背面之注意事項再填寫本頁) 苯醌、’對甲苯醌等之苯醌類等之已知常用聚合抑制劑爲佳 。又爲縮短反應時間,以使用酯化觸媒爲佳。酯化觸媒可 用,例如,N,N —二甲基苯胺、吡啶、三乙胺等之三級 胺及其鹽酸鹽或溴酸鹽;氯化四甲銨、氯化三乙基苯甲基 錶等四級銨鹽;對甲苯磺酸等之磺酸;二甲亞硕、甲基亞 砸等之銃鹽;2 -乙基一 4 —甲基咪唑等之咪唑化合物; 三苯膦、三正丁基膦等之膦類;氯化鋰、溴化鋰、氯化亞 錫、氯化鋅等之金屬鹵化物等已知常用者。惰性溶劑可用 ,例如,甲苯、二甲苯等。 經濟部智慧財產局員工消費合作社印製 上述含不飽和基之單羧酸(c )之代表物,可列舉丙 烯酸、甲基丙烯酸、(甲基)丙烯酸羥基乙酯、(甲基) 丙烯酸羥基丙酯、(甲基)丙烯酸羥基丁酯、三羥甲基丙 烷二(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、 二季戊四醇五(甲基)丙烯酸酯、(甲基)丙烯酸苯基環 氧丙酯、(甲基)丙烯酸己內酯加成物等含羥基之丙烯酸 酯的不飽和二元醇酐加成物等。其中特佳者爲丙烯酸、甲 基丙烯酸。這些含不飽和基之單羧酸可單獨或二種以上混 合使用。 本發明之多核環氧丙烯酸酯化合物(b)之數平均分 子量爲400至10, 000,以500至7, 000爲 佳’以5 0 0至5,0 0 0爲更佳。環氧化合物之數平均 分子量不足4 0 0時,所得硬化物之靭度不充分,另一方 面,若超過1 0,0 0 0則於溶劑之溶解度下降而不佳。 本發明之多核環氧丙烯酸酯化合物,可單獨或與其它 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -27 - 524813 A7 B7 五、發明説明(25 ) 環氧樹脂倂用,如同一般之環氧化合物,可添加硬化劑進 而必要時之硬化促進劑等使其硬化。 (請先閲讀背面之注意事項再填寫本頁) 環氧樹脂可將以下例示之以往已知的各種環氧樹脂( D )單獨或二種以上組合使用。又硬化劑及硬化促進劑可 用先前例示之以往已知的各種化合物。 又,本發明之多核環氧丙烯酸酯化合物,可單獨或與 其它感光性(甲基)丙烯酸酯化合物倂用,如同一般之感 光性(甲基)丙烯酸酯時,配合以光聚合啓始劑,以活性 能量線之照射而硬化。 其它感光性(甲基)丙烯酸酯化合物及光聚合啓始劑 ,可用以下例示之以往已知的各種感光性(甲基)丙烯酸 酯化合物(B )及光聚合啓始劑(C )。 再者,上述多核環氧丙烯酸酯化合物,可單獨或與其 它感光性(甲基)丙烯酸酯化合物倂用,以有機過氧化物 或偶氮化合物等之加熱聚合法、有機過氧化物與促進劑之 常溫聚合法使其硬化。 經濟部智慧財產局員工消費合作社印製 有機過氧化物可舉三級丁基過苯甲酸酯、三級丁基過 2 -乙基己酸酯、過氧化苯甲醯、過氧化環己酮、過氧化 甲乙酮、雙- 4 -三級丁基環己基過氧二碳酸酯等,這些 可單獨或二種以上組合使用。偶氮化合物可將偶氮雙異丁 腈等已知物單獨或二種以上組合使用。 促進劑可用鈷、鐵、錳等之辛酸、環烷酸等之多價金 屬的鹽類、二甲基苯胺、二乙基苯胺、對甲苯胺、乙醇胺 等之有機胺類等已知物,可單獨或二種以上組合使用。 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐)-28 524813 A7 B7 五、發明説明(26 ) (請先閲讀背面之注意事項再填寫本頁) 如此,本發明之多核環氧丙烯酸酯化合物、光聚合啓 始劑、硬化劑,甚至於必要時之硬化促進劑等所配合成之 環氧丙烯酸酯樹脂組成物,可用向來已知方法同樣之方法 簡便製得環氧丙烯酸酯樹脂組成物之硬化物。例如,將本 發明之多核環氧丙烯酸酯化合物、硬化劑、充塡劑及其它 添加劑,必要時用擠出機、捏合機、輥筒等充分均勻混合 ,得環氧丙烯酸酯樹脂組成物,將該組成物熔融後,用注 模或傳遞成形機等成形,再於2 0至2 0 0 °C加熱可得硬 化物。又,溶解環氧丙烯酸酯樹脂組成物,含.浸於玻纖、 碳纖、聚酯纖維、聚醯胺纖維、氧化鋁纖維、紙等基材、 加熱乾燥得膠片,其熱壓成形、或以活性能量線照射亦可 得硬化物。 而於上述環氧丙烯酸酯樹脂組成物,必要時可混合以 無機或有機充塡劑等之種種配合劑。 經濟部智慧財產局員工消費合作社印製 又,本發明之多核環氧丙烯酸酯化合物,光聚合啓始 劑、硬化劑,甚至於必要時之硬化促進劑等所配合成之環 氧丙烯酸酯樹脂組成物,可溶於溶劑,調整爲適合於塗布 方法之粘度。 又根據本發明人等之硏究發現,如上述之含規則重複 芳環的線狀環氧化合物,尤以高軟化點之聯苯骨架及萘骨 架、或雙酚骨架及萘骨架交互聚合的共聚型線狀環氧化合 物中側鏈之醇式羥基,於溶劑存在下與環氧鹵丙烷反應而 得之環氧化合物,以含不飽和基的單羧酸反應,以多元酸 酐與所得之環氧丙烯酸酯化合物反應而得的鹼可溶性之活 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -29 · 524813 Α7 Β7 五、發明説明(27) 性能量線硬化性樹脂,高溫 性及靭性,且含如此之活性 成分之樹脂組成物,可導致 鍍性、電特性、可撓性、吸 )性等特性優良之硬化物。 亦即,本發明之活性能 述一般式(5)所示多核環 基之單羧酸.C c )反應,更 b ’ )以多元酸酐(d )反 之物,並係因含規則重複之 化物,又因具線狀構造可得 對基材之密合性、耐無電解 吸濕性及耐P C 丁(壓力鍋 下熱安定性優,具均衡的耐熱 能量線硬化性樹脂爲光硬化性 耐熱性、密合性、耐無電解電 濕性及耐P c T (壓力鍋試驗 量線硬化性樹脂(A ),係下 氧化合物(a ’ )以含不飽和 於所得環氧丙烯酸酯化合物( 應,而具光硬化性及鹼顯影性 不同芳環可得高機械強度之硬 高耐熱性之硬化物,同時可得 電鍍性、電特性、可撓性、耐 試驗)性等優良的硬化物之物 (請先閲讀背面之注意事項再填寫本頁)\ / L 〇OZ1 -ch2 -ch-ch2 -0-xo——ch2 -ch-ch2 A hydrogen atom or a group represented by the general formula (4). Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs to verify the polynuclear compound shown in the above general formula (10), the unsaturated polynuclear epoxy acrylate compound can be obtained by reacting a monocarboxylic acid (c) containing a + saturated I group ( .b), the polynuclear epoxy compound 'shown in the general formula (10) above is compounded to contain an epoxy group in the compound, in which the molar ratio of the epoxy group is 0.8 to 1.3 moles and the unsaturated group is contained. The monocarboxylic acid is heated in an inert solvent or without a solvent at about 60 to 150 ° C, preferably 70 to 130 ° C, and preferably in the presence of air. In order to prevent gelation due to polymerization during the reaction, hydroquinones such as methylhydroquinone, hydroquinone and the like are used; the Chinese national standard (CNS) A4 specification (210X297 mm) is applied to this paper size -26-524813 A7 _____B7 5 2. Description of the invention (24) (Please read the notes on the back before filling this page) Known commonly used polymerization inhibitors such as benzoquinone, benzoquinone, etc. To shorten the reaction time, it is better to use an esterification catalyst. Esterification catalysts can be used, for example, tertiary amines such as N, N-dimethylaniline, pyridine, triethylamine and their hydrochloride or bromate; tetramethylammonium chloride, triethylbenzyl chloride Quaternary ammonium salts such as bases; sulfonic acids such as p-toluenesulfonic acid; sulfonium salts such as dimethyl arsenate and methyl sulfamate; imidazole compounds such as 2-ethyl-4-methylimidazole; triphenylphosphine, Phosphines such as tri-n-butylphosphine; metal halides such as lithium chloride, lithium bromide, stannous chloride, zinc chloride and the like are known and commonly used. Inert solvents are available, for example, toluene, xylene and the like. Representatives of the above-mentioned unsaturated monocarboxylic acids (c) printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs include acrylic acid, methacrylic acid, hydroxyethyl (meth) acrylate, and hydroxypropyl (meth) acrylate Ester, hydroxybutyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, phenyl (meth) acrylate Unsaturated diol anhydride adducts of hydroxyl-containing acrylates such as propylene oxide, caprolactone (meth) acrylate, and the like. Particularly preferred are acrylic acid and methacrylic acid. These unsaturated monocarboxylic acids may be used alone or in combination of two or more. The number average molecular weight of the polynuclear epoxy acrylate compound (b) of the present invention is 400 to 10,000, preferably 500 to 7,000 ', and more preferably 500 to 5,000. When the number-average molecular weight of the epoxy compound is less than 400, the toughness of the obtained cured product is insufficient. On the other hand, if it exceeds 10, 000, the solubility in the solvent decreases, which is not good. The multi-core epoxy acrylate compound of the present invention can be used alone or in combination with other paper sizes of the Chinese National Standard (CNS) A4 (210X297 mm) -27-524813 A7 B7 V. Description of the invention (25) Epoxy resin Like ordinary epoxy compounds, a hardener can be added to harden it if necessary. (Please read the precautions on the back before filling out this page) Epoxy resins can be used individually or in combination of two or more of the conventionally known epoxy resins (D) illustrated below. As the hardening agent and the hardening accelerator, various conventionally known compounds exemplified previously can be used. In addition, the multi-core epoxy acrylate compound of the present invention can be used alone or in combination with other photosensitive (meth) acrylate compounds. When the photosensitive (meth) acrylate is used in common, a photopolymerization initiator is added. Hardened by irradiation with active energy rays. For other photosensitive (meth) acrylate compounds and photopolymerization initiators, various conventionally known photosensitive (meth) acrylate compounds (B) and photopolymerization initiators (C) can be used as exemplified below. Furthermore, the above-mentioned multi-core epoxy acrylate compound can be used alone or in combination with other photosensitive (meth) acrylate compounds. The organic peroxide or azo compound can be used for thermal polymerization, organic peroxide, and accelerator. It is hardened by normal temperature polymerization. Organic peroxides printed by employees' cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs include tertiary butyl perbenzoate, tertiary butyl per 2-ethylhexanoate, benzamidine peroxide, and cyclohexanone peroxide , Methyl ethyl ketone peroxide, bis-4-tertiary-butylcyclohexyl peroxydicarbonate, etc. These can be used alone or in combination of two or more. The azo compound may be a known compound such as azobisisobutyronitrile alone or in combination of two or more. As the accelerator, known salts of polyvalent metals such as octanoic acid and naphthenic acid such as cobalt, iron, and manganese, organic amines such as dimethylaniline, diethylaniline, p-toluidine, and ethanolamine can be used. Use alone or in combination of two or more. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -28 524813 A7 B7 V. Description of the invention (26) (Please read the precautions on the back before filling this page) So, the multi-core epoxy of the present invention An epoxy acrylate resin composition composed of an acrylate compound, a photopolymerization initiator, a hardener, or even a hardening accelerator when necessary, can be easily prepared by the same method as the conventional method. A hardened composition. For example, the polynuclear epoxy acrylate compound, hardener, filler, and other additives of the present invention are thoroughly and uniformly mixed with an extruder, a kneader, a roller, etc. as necessary to obtain an epoxy acrylate resin composition. After the composition is melted, it is formed by injection molding or transfer molding machine, and then heated at 20 to 200 ° C to obtain a hardened product. In addition, the epoxy acrylate resin composition is dissolved, and it is impregnated with glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper and other substrates, and dried by heating to obtain a film, which is formed by hot pressing or The hardened material can also be obtained by irradiation with active energy rays. The epoxy acrylate resin composition may be mixed with various additives such as inorganic or organic fillers, if necessary. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the multi-core epoxy acrylate compound, photopolymerization initiator, hardener, and even hardening accelerator when necessary It is soluble in solvents and adjusted to a viscosity suitable for the coating method. According to the research of the inventors, it is found that, as described above, the linear epoxy compound containing a regular repeating aromatic ring is a copolymerization of a biphenyl skeleton and a naphthalene skeleton with a high softening point, or a bisphenol skeleton and a naphthalene skeleton. The alcoholic hydroxyl group of the side chain in the linear epoxy compound is an epoxy compound obtained by reacting with an epoxy halopropane in the presence of a solvent, reacting with an unsaturated monocarboxylic acid, and using a polybasic acid anhydride with the obtained epoxy Alkali-soluble active paper obtained from the reaction of acrylate compounds The paper size is applicable to Chinese National Standard (CNS) A4 (210X297 mm) -29 · 524813 Α7 Β7 V. Description of the invention (27) Performance line hardening resin, high temperature resistance A resin composition having toughness and containing such an active ingredient can lead to a hardened product having excellent plating properties, electrical properties, flexibility, and absorption properties. That is, the activity of the present invention can be described as a monocarboxylic acid of the polynuclear ring group represented by the general formula (5). C c), and b ') is the opposite of polybasic acid anhydride (d), and is a compound containing regular repetition Because of the linear structure, it can obtain the adhesion to the substrate, non-electrolytic hygroscopicity and PC resistance (excellent thermal stability under pressure cooker, balanced heat-resistant energy ray-curable resin is light-curable heat resistance) , Adhesiveness, resistance to electroless electrowetting, and resistance to P c T (pressure cooker test line hardening resin (A), the oxygen compound (a ') contains unsaturated unsaturated epoxy acrylate compound (should, Aromatic rings with different light-hardening and alkali-developing properties can be used to obtain hardened products with high mechanical strength and high heat resistance. At the same time, excellent hardened products such as electroplating, electrical properties, flexibility, and test resistance can be obtained. (Please read the notes on the back before filling this page)
0M CH2 —CH—CH2 —0—X,一〇 •CH2 —CH—CH2 —0—Ύ*’ 一〇— 〇0M CH2 —CH—CH2 —0—X, -10 • CH2 —CH—CH2 —0—Ύ * ’one 〇— 〇
0M 經濟部智慧財產局員工消費合作社印製 一CH2 —CH—CH2 —0—X ’ 一〇- -CH2 —CH—CH2 \ / 0 (5) 式中,X’及Y’表互不相同之二價芳環,Μ表環氧 丙基、甲基環氧丙基及/或氫原子,η表1至之整數 以下詳細說明本發明之活性能量線硬化性.樹脂,及使 用其之光硬化性•熱硬化性組成物之各成分。首先說明本 本紙張尺度適用中國國家標準(CNS ) Α4規格(210X297公釐)-30 - 524813 A7 _B7 五、發明説明(28 ) 發明的活性能量線硬化性樹脂。 (請先閲讀背面之注意事項再填寫本頁) 上述一般式(5 )所示之多核環氧化合物(3,), 係以二官能芳族環氧化合物及二官能芳族醇爲原料,如前 述般,用已知酯化觸媒,在溶劑中或無溶劑下交互聚合, 將所得之醇式二級經基以環氧鹵丙院,於二甲亞硕、N, N -二甲基甲醯胺、N,N —二甲基乙醯胺等之質子惰性 極性溶劑、甲苯、二甲苯等之芳族烴類等已知溶劑中,在 氫氧化鈉等鹼金屬氫氧化物之存在下反應而得。二官能芳 族環氧化合物及二官能芳族醇者,在上述活性能量線硬化 性樹脂的合成中,固不限於先前例示者,但當然係以使用 先前例示之二官能芳族環氧化合物及二官能芳族醇爲佳。 其次,於上述一般式(5 )所示之多核環氧化合物( a ’ )以含不飽和基之單殘酸,如前述般,在有機溶劑之 經濟部智慧財產局員工消費合作社印製 存在下或不存在下,在氫醌、氧等之聚合抑制劑、及三乙 胺等之三級胺、氯化三乙基苯甲基銨等之四級銨鹽、2 — 乙基-4-甲基咪唑等之咪唑化合物、三苯膦等之磷化合 物等之反應觸媒的共存下,通常於約8 0至1 3 0 °C反應 ’可得多核環氧丙烯酸酯化合物(b ’ )。 以上述反應生成之環氧丙烯酸酯化合物(b’ )之醇 式羥基,用多元酸酐(d )與之反應可得本發明之活性能 量線硬化性樹脂(A ),而該反應中,多元酸酐(d )之 用量,對於上述反應產物中之醇式羥基、酐基係以9 9 : 1至1 .·· 9之比例爲宜,而酸値範圍宜在5 0 .至2 0 0毫 克/KOH/克,以50至120毫克KOH/克爲佳。 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐)-31 - 524813 A 7 B7 五、發明説明(29 ) (請先閲讀背面之注意事項再填寫本頁) 活性能量線硬化性樹脂(A )之酸値低於5 0毫克K〇Η /克時,鹼水溶液之溶解性差,形成之塗膜難以顯影。另 一方面,若高於2 0 0毫克Κ〇Η/克,不依曝光條件連 曝光部之表面亦致顯影而不佳。 .反應係在前述有機溶劑之存在下或不存在下,於氫醌 、氧等聚合抑制劑的存在下,通常在約5 0至1 3 0 °C進 行。此時若必要,亦可添加三乙胺等三級胺、氯化三乙基 苯甲基銨等之四級銨鹽、2-乙基-4一甲基咪唑等之咪 唑化合物、三苯膦等之磷化合物等作爲觸媒。. 經濟部智慧財產局員工消費合作社印製 上述多元酸酐,可舉甲基四氫苯酐、四氫苯酐、六氫 苯酐、甲基六氫苯酐,降冰片烯二酸酐、3 ,6 —橋甲撐 四氫苯酐、甲基橋甲撐四氫苯酐、四溴苯酐等之脂環式二 元酸酐;琥珀酸酐、馬來酸酐、衣康酸酐、辛烯基琥珀酸 酐、十五烯基琥珀酸酐、苯酐、苯偏三酸酐等之脂族或芳 族二元酸酐、或聯苯四甲酸二酐、二苯醚四甲酸二酐、丁 烷四甲酸二酐、環戊烷四甲酸二酐、均苯四酸酐、二苯甲 酮四甲酸二酐等之脂族或芳族四元酸二酐,這些可以一種 或二種以上使用。其中係以脂環式二元酸酐爲特佳。 本發明之活性能量線硬化性樹脂(A )之數平均分子 量在400至10, 000,以500至7, 000爲佳 ,以5 0 0至3,0 0 0爲更佳。活性能量線硬化性樹脂 之數平均分子量不及4 0 0時,所得之硬化物靭度不充分 ,另一.方面,若超過1 0,0 0 0,則於溶劑之溶解性下 降而不佳。 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -32 - 524813 A7 B7 五、發明説明(30 ) (請先閲讀背面之注意事項再填寫本頁) 本發明之鹼可顯影光硬化性•熱硬化性樹脂組成物, 除上述活性能量線硬化性樹脂(A )外,亦可含作爲感光 性(甲基)丙烯酸酯化合物(B )之一分子中有一個以上 之(甲基)丙烯醯氧基,在室溫爲液體、固體或半固態之 感光性(甲基)丙烯酸酯化合物。這些感光性(甲基)丙 烯酸酯化合物之使用目的,在提升組成物的光反應性。室 溫爲液狀之感光性(甲基)丙烯酸酯化合物,除提升組成 物的光反應性以外,亦可達有助於將組成物調整爲適合各 種塗布方法之粘度,及於鹼水溶液之溶解性的效果。但是 ’若大量使用室溫下爲液狀之感光性(甲基)丙烯酸酯化 合物,則無法獲致所形成的塗膜之指觸乾燥性,而塗膜之 特性亦趨於惡化之故,大量使用並不佳。感光性(甲基) 丙烯酸酯化合物(B )之配合量,對於上述活性能量線硬 化性樹脂(A ) 1 〇 〇質量份(以固體成分計,下同)在 1〇至60質量份,以1 5至50質量份爲佳。 經濟部智慧財產局員工消費合作社印製 上述感光性(甲基)丙烯酸酯化合物,可舉例如,丙 烯酸2 -羥基乙酯、丙烯酸2 -羥基丙酯、季戊四醇三丙 烯酸酯、二季戊四醇五丙烯酸酯等之含羥基的丙烯酸酯類 ;聚乙二醇二丙烯酸酯、聚丙二醇二丙烯酸酯等之水溶性 丙烯酸酯類;三羥甲基丙烷三丙烯酸酯、季戊四醇四丙烯 酸酯、二季戊四醇六丙烯酸酯等之多官能醇之多官能聚酯 丙烯酸酯類;三羥甲基丙烷、氫化雙酚A等之多官能醇或 雙酚A、聯酚等之多官能酚的氧化乙烯加成物.、氧化丙烯 加成物之丙烯酸酯類;上述含羥基之丙烯酸酯的異氰酸酯 本纸張尺度適用中國ϋ家標準(CNS ) A4· ( 210X297公羡)-33 - " 524813 A7 B7 五、發明説明(31 ) (請先閲讀背面之注意事項再填寫本頁) 改質物之多官能或單官能聚氨酯丙烯酸酯;雙酚A二環氧 丙醚、氫化雙酣A二環氧丙醚或酚醛淸漆型環氧樹脂之( 甲基)丙烯酸加成物的環氧丙烯酸酯類、及對應於上述丙 烯酸酯類之甲基丙烯酸酯類等,這些可以單獨或二種以上 組合使用。這些之中,係以一分子中有二個以上之(甲基 )丙烯醯氧基的多官基(甲基)丙烯酸酯化合物爲佳。 上述光聚合啓始劑(C ),可舉例如,苯偶因、苯偶 因甲醚、苯偶因乙醚、苯偶因丙醚等之苯偶因及苯偶因院 基醚類;乙醯苯、2,2 —二甲氧基一 2 —苯基乙醯苯、 2 ,2 —二乙氧基一2 —苯基乙醯苯、1 ,1—二氯乙醯 苯等之乙醯苯類;2 —甲基—1— 〔4 一 (甲硫基)苯基 〕_2 -嗎啉胺基丙酮一 1 ,2 —苯甲基一 2 —二甲胺基 經濟部智慧財產局員工消費合作社印製 一 1— (4 一嗎啉苯基)—1 一 丁酮、N,N —二甲胺基 乙醯苯等之胺基乙醯苯類;2 -甲基蒽醌、2 —乙基蒽醌 、2 -三級丁基蒽醌、1 —氯化蒽醌等之蒽醌類;2,4 一二甲基硫蒽酮、2,4 一二乙基硫蒽酮、2 —氯硫蒽酮 、2 ,4 —二異丙基硫蒽酮等硫蒽酮類;乙醯酮縮二甲醇 、苯甲基二甲基縮酮等之縮酮類;苯甲基過氧化物、異丙 苯過氧化物等之有機過氧化物;2,4,5 -三芳基咪唑 二聚物、四丁醇核黃素、2 -锍基苯并咪唑、2 —疏基苯 并鸣唑、2 —锍基苯并噻唑等之硫醇化合物;2 , 4 , 6 —參一 S —三哄、2,2,2 -三溴乙醇、三溴甲基苯基 硕等有.機鹵化物;二苯甲酮、4,4 ’ 一雙二乙胺基二苯 甲酮等二苯甲酮類或氧蒽酮類;2 ,4,6 —三甲基苯甲 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -34 - 524813 A7 __ B7 五、發明説明(32 ) 基苯基膦氧化物等。 (請先閲讀背面之注意事項再填寫本頁) 這些已知常用之光聚合啓始劑,可單獨或二種以上混 合使用,可進而加用N,N —二甲胺基安息香酸乙酯、N ’ N -二甲胺基安息香酸異戊酯、戊基一 4 一二甲胺基苯 甲酸酯、三乙胺、三乙醇胺等三級胺類等之光啓始助劑^ 又,亦可添加在可見光範圍有吸收之CG I — 7 8 4等( 汽巴特用化學品公司製)的二茂鈦化合物等,以促進光反 應。尤佳之光聚合啓始劑有2 -甲基一 1 一〔 4 一(甲基 硫基)苯基〕一 2 —嗎啉胺基丙酮—1 ,2—.苯甲基一 2 一二甲胺基一 1 一(4 一嗎啉苯基)丁一 1 一酮等,但非 特定於這些,只要在紫外線或可見光之範圍有吸收,而使 (甲基)丙烯醢基等不飽和基作自由基聚合者,不限於光 聚合啓始劑、光啓始助劑、可單獨或多數倂用。 上述光聚合啓始劑之用量(用光啓始助劑時則爲其合 計量),對上述活性能量線硬化性樹脂(A ) 1 〇 〇質量 份宜在0 · 1至2 5質量份,以0 · 5至20質量份爲佳 經濟部智慧財產局員工消費合作社印製 。光聚合啓始劑之配合量少於上述範圍時,活性能量線之 照射亦無法硬化,或必須延長照射時間,難以獲致恰當之 塗膜物性。另一方面,光聚合啓始劑之添加量多於上述範 圍,光硬化性亦無變化,經濟上不佳。 又,本發明之光硬化性·熱硬化性組成物,爲將上述 活性能量線硬化性樹脂(A )及感光性(甲基)丙烯酸酯 化合物(B )溶解,並將組成物調整爲適於塗布方法之粘 度,可用先前例示之有機溶劑單獨或組合二種以上予以配 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公嫠) -35 - 524813 A7 B7 五、發明説明(33 ) 合。· (請先閲讀背面之注意事項再填寫本頁) 上述多官能環氧化合物(D).,具體可舉日本環氧樹 聘(股)製之 Epicote 8 2 8、 Epicote 8 3 4、 EPic〇te 10 0 1、 Epicote 1 0〇4 ’大曰本油墨化學 ^ 業(股)製之 Epicolon 8 4 0、 Epicolon 8 5 0、 ^Piclon 1 0 5 0、Epiclon 2 0 5 5’ 東都化成(股) 製之 Epotote YD — 011、YD — 013、YD — 1 27、YD— 1 28,道爾化學公司製之D·E·R· 317、D.E.R.331、D.E.R.661、D • E · r · 6 6 4,汽巴特用化學品公司製之Araldite 6 〇 7 1、Araldite 6 0 8 4、Araldite GY 250 、Araldite Y G 2 6 0,住友化學工業(股)製之Sumi EP〇xy ESA—011、 ESA—014、 ELA— 1 1 5、ELA— 1 28 ’旭化成工業(股)製之A · E •R.330、A . E . R . 3 3 1 > A.E.R. 經濟部智慧財產局員工消費合作社印製 6 61、A.E.R.664等(均屬商品名)之雙酚A 型環氧樹脂;日本環氧樹脂(股)製之Epicote Y L 9 0 3,大日本油墨化學工業(股)製之Epotote YDB - 400、YDB — 500,道爾化學公司製之 D . E . R . 542 ,汽巴特用化學品公司製之Araldite 8 0 1 1 ,住友化學工業(股)製之Sumi Epoxy E S B — 400、E SB - 700,旭化成工業(股)製之A. E · R · 7 1 1、A · E · R · 7 1 4 等(均爲商品名) 之溴化環氧樹脂;日本環氧樹脂(股)製之Epicote 本紙張尺度適用中國國家標準(CNS ) A4規格{ 210X297公釐) -36 - 524813 A7 B7_ 五、發明説明(34 ) (請先閲讀背面之注意事項再填寫本頁)0M Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, a CH2 —CH—CH2 —0—X '10— -CH2 —CH—CH2 \ / 0 (5) where X' and Y 'tables are different from each other Divalent aromatic ring, M represents an epoxy propyl group, methyl glycidyl group and / or a hydrogen atom, η is an integer from Table 1 to the following. The active energy ray hardenability of the present invention is described in detail. The resin, and light hardening using the same Each component of the thermosetting composition. First of all, the paper size of this paper applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -30-524813 A7 _B7 V. Description of the invention (28) The active energy ray hardening resin of the invention. (Please read the precautions on the back before filling this page) The polynuclear epoxy compound (3,) shown by the general formula (5) above is based on difunctional aromatic epoxy compounds and difunctional aromatic alcohols, such as As mentioned above, a known esterification catalyst is used for cross-polymerization in a solvent or without a solvent. In a known aprotic polar solvent such as formamidine, N, N-dimethylacetamide, and aromatic hydrocarbons such as toluene and xylene, in the presence of an alkali metal hydroxide such as sodium hydroxide Derived from the reaction. In the synthesis of the above-mentioned active energy ray-curable resin, the bifunctional aromatic epoxy compound and the difunctional aromatic alcohol are not limited to those previously exemplified, but of course, the bifunctional aromatic epoxy compounds and Difunctional aromatic alcohols are preferred. Secondly, the polynuclear epoxy compound (a ') represented by the above general formula (5) is a monoresidue containing unsaturated group, as described above, in the presence of the organic solvent of the Intellectual Property Bureau employee consumer cooperative printed by the Ministry of Economic Affairs In the absence or presence, polymerization inhibitors such as hydroquinone, oxygen, tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzyl ammonium chloride, 2-ethyl-4-methyl In the coexistence of reaction catalysts such as imidazole compounds such as imidazole and phosphorus compounds such as triphenylphosphine, the 'multinuclear epoxy acrylate compound (b') is usually reacted at about 80 to 130 ° C. According to the alcoholic hydroxyl group of the epoxy acrylate compound (b ') formed by the above reaction, the active energy ray-curable resin (A) of the present invention can be obtained by reacting it with the polybasic acid anhydride (d). In this reaction, the polybasic acid anhydride The amount of (d) is suitable for the alcoholic hydroxyl group and the anhydride group in the above reaction product at a ratio of 9 9: 1 to 1... 9, and the range of the acid hydrazone is preferably 50. 0 to 200 mg / KOH / g, preferably 50 to 120 mg KOH / g. This paper size applies Chinese National Standard (CNS) A4 (210X297 mm) -31-524813 A 7 B7 V. Description of the invention (29) (Please read the precautions on the back before filling this page) Active energy ray hardening resin When the acid sulfonium (A) is less than 50 mg KOH / g, the solubility of the alkaline aqueous solution is poor, and the formed coating film is difficult to develop. On the other hand, if it is higher than 200 mg KOH / g, the surface of the exposed portion will not develop well regardless of the exposure conditions. The reaction is carried out in the presence or absence of the aforementioned organic solvent in the presence of polymerization inhibitors such as hydroquinone and oxygen, usually at about 50 to 130 ° C. In this case, if necessary, tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzyl chloride, imidazole compounds such as 2-ethyl-4 monomethylimidazole, and triphenylphosphine may be added. And other phosphorus compounds as catalysts. The above-mentioned polybasic acid anhydrides are printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Examples include methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, norbornene dianhydride, 3,6 —bridged Tetrahydrophthalic anhydride, methyl bridged tetrahydrophthalic anhydride, tetrabromophthalic anhydride and other alicyclic dibasic anhydrides; succinic anhydride, maleic anhydride, itaconic anhydride, octenyl succinic anhydride, pentaenyl succinic anhydride, phthalic anhydride , Trimellitic anhydride, aliphatic or aromatic dibasic anhydride, or biphenyltetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, pyromellitic acid Aliphatic or aromatic quaternary acid dianhydrides such as acid anhydride, benzophenone tetracarboxylic dianhydride, etc., These can be used singly or in combination of two or more. Among them, alicyclic diacid anhydride is particularly preferable. The number-average molecular weight of the active energy ray-curable resin (A) of the present invention is 400 to 10,000, more preferably 500 to 7,000, and more preferably 500 to 3,000. When the number-average molecular weight of the active energy ray-curable resin is less than 400, the toughness of the obtained hardened product is insufficient. On the other hand, if it exceeds 10, 000, the solubility in the solvent decreases, which is not good. This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) -32-524813 A7 B7 V. Description of the invention (30) (Please read the precautions on the back before filling this page) The alkali of this invention can develop light The curable and thermosetting resin composition may contain, in addition to the above-mentioned active energy ray-curable resin (A), one or more (methyl) groups of one of the molecules of the photosensitive (meth) acrylate compound (B). ) Acrylic fluorenyloxy, a photosensitive (meth) acrylate compound that is liquid, solid, or semi-solid at room temperature. These photosensitive (meth) acrylate compounds are used for the purpose of improving the photoreactivity of the composition. The photosensitive (meth) acrylate compound is a liquid at room temperature. In addition to improving the photoreactivity of the composition, it can also help adjust the composition to a viscosity suitable for various coating methods and dissolve in an alkaline aqueous solution. Sexual effect. However, if a large amount of a photosensitive (meth) acrylate compound that is liquid at room temperature is used, the touch dryness of the formed coating film cannot be obtained, and the characteristics of the coating film tend to deteriorate. Not good. The blending amount of the photosensitive (meth) acrylate compound (B) is 10 to 60 parts by mass based on 100 parts by mass of the active energy ray-curable resin (A) (in terms of solid content, the same below), and 15 to 50 parts by mass is preferred. The above-mentioned photosensitive (meth) acrylate compounds are printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, for example, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, etc. Hydroxyl-containing acrylates; water-soluble acrylates such as polyethylene glycol diacrylate, polypropylene glycol diacrylate, etc .; trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, etc. Polyfunctional polyester acrylates of polyfunctional alcohols; polyfunctional alcohols such as trimethylolpropane and hydrogenated bisphenol A, or ethylene oxide adducts of polyfunctional phenols such as bisphenol A and biphenol. Acrylates of finished products; the isocyanates of the above-mentioned hydroxyl-containing acrylates are applicable to Chinese paper standard (CNS) A4 · (210X297 public envy) -33-" 524813 A7 B7 V. Description of the invention (31) ( (Please read the precautions on the back before filling this page) Modified polyfunctional or monofunctional polyurethane acrylate; bisphenol A diglycidyl ether, hydrogenated bis-A dipropylene oxide Qing or phenolic type epoxy paint (meth) acrylate, epoxy acrylate adduct, and said the acrylate of methacrylate and the like corresponding to these may be used alone or in combination of two or more kinds. Among these, a polyfunctional (meth) acrylate compound having two or more (meth) acryloxy groups in one molecule is preferred. The photopolymerization initiator (C) can be exemplified by benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin ethyl ethers; acetamidine Benzene, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, etc. Category; 2-methyl-1— [4-mono (methylthio) phenyl] _2-morpholinaminoacetone-1, 2-benzyl-2-dimethylamino group Consumer Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs Printing 1- (4-morpholinophenyl) -1 monomethyl ethyl ketone, N, N-dimethylamino ethyl acetophenone and other amino ethyl acetophenones; 2-methyl anthraquinone, 2- ethyl Anthraquinones, 2-tert-butylanthraquinone, 1-anthraquinone chloride, and other anthraquinones; 2,4-dimethylthioanthone, 2,4-diethylthioanthone, 2-chlorosulfan Anthrone, 2,4-diisopropylthioxanthone and other thioanthones; acetone ketal, benzyl dimethyl ketal and other ketals; benzyl peroxide, isopropyl Organic peroxides such as benzene peroxide; 2,4,5-triarylimidazole dimer, tetra Thiol compounds such as alcohol riboflavin, 2-fluorenyl benzimidazole, 2-sulfobenzimidazole, 2-fluorenylbenzothiazole, etc .; 2, 4, 6—reference 1S—trioxine, 2, Organic halides such as 2,2-tribromoethanol, tribromomethylphenyl, etc .; benzophenones, benzophenones such as benzophenone, 4,4'-bisdiethylaminobenzophenone or oxanthracene Ketones; 2,4,6-trimethylbenzene This paper is sized for the Chinese National Standard (CNS) A4 (210X297 mm) -34-524813 A7 __ B7 V. Description of the invention (32) Phenylphosphine oxidation Things. (Please read the precautions on the back before filling this page) These known commonly used photopolymerization initiators can be used alone or in combination of two or more. N, N-dimethylaminobenzoic acid ethyl ester, Light-starting auxiliaries such as tertiary amines such as N'N-dimethylaminoisobenzoate, pentyl-4, dimethylaminobenzoate, triethylamine, triethanolamine, etc. Titanocene compounds, such as CG I — 7 8 4 (Cibaite Chemical Co., Ltd.) that absorb in the visible range can be added to promote photoreaction. A particularly good initiator for photopolymerization is 2-methyl-1 1- [4-mono (methylthio) phenyl] -2 2-morpholinaminoacetone-1, 2-benzyl-1 2-dimethyl. Amino-1,1- (4-morpholinylphenyl) butan-1, one-ketone, etc., but not specific to them, as long as there is absorption in the ultraviolet or visible light range, and unsaturated groups such as (meth) acrylfluorenyl are used as The radical polymerizer is not limited to a photopolymerization initiator and a photoinitiator, and can be used alone or in a large amount. The amount of the photopolymerization initiator (the total amount when the photoinitiator is used) is preferably 0.1 to 25 parts by mass to 100 parts by mass of the active energy ray-curable resin (A), Printed with 0.5 to 20 parts by mass as a consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. When the blending amount of the photopolymerization initiator is less than the above range, the irradiation with active energy rays cannot be hardened, or the irradiation time must be extended, and it is difficult to obtain proper coating film properties. On the other hand, the addition amount of the photopolymerization initiator is more than the above range, and the photohardenability does not change, which is not economically good. The photocurable and thermosetting composition of the present invention is to dissolve the active energy ray-curable resin (A) and the photosensitive (meth) acrylate compound (B), and adjust the composition to be suitable The viscosity of the coating method can be formulated with the organic solvents previously exemplified alone or in combination of two or more. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 cm) -35-524813 A7 B7 V. Description of the invention (33) · (Please read the notes on the back before filling this page) The above-mentioned multifunctional epoxy compound (D). Specific examples are Epicote 8 2 8, Epicote 8 3 4, EPic. te 10 0 1, Epicote 1 0〇4 'Epicolon 8 4 0, Epicolon 8 5 0, ^ Piclon 1 0 5 0, Epiclon 2 0 5 5' ) Epotote YD — 011, YD — 013, YD — 1 27, YD — 1 28, D · E · R · 317, DER331, DER661, D • E · r · 6 6 4. Araldite 6 〇7 manufactured by Cibaite Chemicals Company 1, Araldite 6 0 8 4, Araldite GY 250, Araldite YG 2 60, Sumi EP〇xy ESA—011, ESA— manufactured by Sumitomo Chemical Industry Co., Ltd. 014, ELA— 1 1 5. ELA— 1 28 'A.E.R.330, A.E.R. 3 3 1 > Asahi Kasei Industrial Co., Ltd. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 6 61, AER664, etc. (all are trade names) Bisphenol A epoxy resin; Epicote YL 9 0 3 made by Japan Epoxy Resin Co., Ltd. Epotote YDB-400, YDB — 500 made by (stock), D. E.R. 542 made by Dow Chemical Company, Araldite 8 0 1 1 made by Cibaite Chemicals, and Sumitomo Chemical Industry (stock) made Sumi Epoxy ESB — 400, E SB-700, A. E · R · 7 1 1, A · E · R · 7 1 4 and other (all trade names) brominated epoxy resins manufactured by Asahi Kasei Corporation Epicote made by Japan Epoxy Resin Co., Ltd. This paper size is applicable to Chinese National Standard (CNS) A4 specifications {210X297 mm) -36-524813 A7 B7_ V. Description of the invention (34) (Please read the precautions on the back before (Fill in this page)
15 2·、 Epicote 154’道爾化學公司製之D.E.N • 43 1、D · E · N · 438 ’大曰本油墨化學工業( 股)製之 Epiclon N — 7 3 0、 Epiclon N — 7 7 0、 Epiclon N— 865,東都化成(股)製之 EP〇tote 丫[)〇1^—70 1、丫〇〇]^ — 7 04,汽巴特用化學品 公司製之 Araldite E C N 1 2 3 5、 Araldite E C N 12 7 3、Araldite E C N 1 2 9 9. Araldite XPY 307,曰本化藥(股)製之EPPN 一 201、 E〇CN— 1025、 E〇CN — 1020、.E〇CN — 1〇4S、RE — 3〇6;住友化學工業(股)製之Sumi Epoxy eSCN - 195X、ESCN - 2 20 ’ 旭化成 工業(股)製之 A.E.R.ECN — 235、ECN — 經濟部智慧財產局員工消費合作社印製 2 9 9等(均爲商品名)之淸漆型環氧樹脂;大日本油墨 化學工業(股)製之Epicolon 8 3 0,日本環氧樹脂( 股)製之Epicote 8 0 7,東都化成(股)製之Epitote YDF - 170、YDF-175、YDF-2004 » 汽巴特用化學品公司製之Araldite XPY306等(均爲 商品名)之雙酚F型環氧樹脂;東都化成(股)製之 Epocote ST- 2004、ST - 2007、ST- 3 0 0 0 (商品名)等之氫化雙酚A型環氧樹脂;日本環 氧樹脂(股)製之Epicote 6 0 4 ’東都化成(股)製之 Epotote γ Η — 4 3 4 ,汽巴特用化學品公司製之15 2. · Epicote 154 'DEN by Dow Chemical Company • 43 1. D · E · N · 438' Epiclon N — 7 3 0, Epiclon N — 7 7 0 Epiclon N—865, EP〇tote ya [) 〇1 ^ —70 1, Dong 〇00] ^ — 7 04, Araldite ECN 1 2 3 5 by Cibate Chemical Co., Ltd. Araldite ECN 12 7 3. Araldite ECN 1 2 9 9. Araldite XPY 307, EPPN-201, E-CN-1025, E-CN-1020, .E-CN-104 , RE — 3 06; Sumi Epoxy eSCN-195X, ESCN-2 20 'manufactured by Sumitomo Chemical Industries (stock) Printed by ARECEN of Asahi Kasei Corporation (235), ECN — Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 2 9 9 and other (both trade names) lacquer-type epoxy resins; Epicolon 8 3 0 manufactured by Dainippon Ink Chemical Industry Co., Ltd .; Epicote 8 0 7 manufactured by Japan Epoxy Resins (stock); Stock) made by Epitote YDF-170, YDF-175, YDF-2004 »Araldite XPY306 made by Cibaite Chemicals Co., Ltd. (all are Trade name) of bisphenol F-type epoxy resin; Hydrogenated bisphenol A type of epoxy resin such as Epocote ST-2004, ST-2007, ST-3 0 0 0 (trade name) manufactured by Toto Kasei Co., Ltd .; Japan Epicote 6 0 4 'made by epoxy resin (stock)' Epotote made by Toto Kasei (stock) γ Η — 4 3 4, manufactured by Cibato Chemical Co., Ltd.
Araldite MY720,住友化學工業(股)製之S Umi Epoxy E LM — 1 2 0等(均爲商品名)之環氧丙胺型環 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -37 - 524813 五、發明説明(35 ) 氧樹脂;汽巴特用化學品公司製之Araldite C Y - 3 5 〇 (商品名)等之海因型環氧樹脂;Daicel化學工業(股) 製之CeloxWe 2 0 2 1 ,汽巴特用化學品公司製之Araldite MY720, S Umi Epoxy E LM made by Sumitomo Chemical Industry Co., Ltd. — 1 2 0, etc. (both trade names) Epoxy amine type ring This paper is sized to Chinese National Standard (CNS) A4 (210X297 mm) -37-524813 V. Description of the invention (35) Oxygen resin; Araldite CY-3 50 (trade name) and other Hein-type epoxy resins made by Cibaite Chemicals; CeloxWe made by Daicel Chemical Industry Co., Ltd. 2 0 2 1, manufactured by Cibaite Chemical Company
Araldite CY175、CY179等(均爲商品名)之脂 環式環氧樹脂;日本環氧樹脂(股)製之Y L — 9 3 3, 道爾化學公司製之Τ·Ε·Ν·、EPPN— 501、 E P PN — 5 0 2等(均爲商品名)之三羥基苯基甲院型 環氧樹脂;日本環氧樹脂(股)製之YL — 6056、 YX — 4000、YL — 6 121 (均爲商品名)等之聯 股 甲酚型或聯酚型環氧樹脂,或其混合物;日本化藥 )製EBPS — 200、旭電化工業(股)製EPX〜3 經濟部智慧財產局員工消費合作社印製 (請先閲讀背面之注意事項再填寫本頁,> 0、大日本油墨化學工業(股)製之EXA — 1514 ( 商品名)等之雙酚S型環氧樹脂;日本環氧樹脂·(股)製 之Epicote 1 5 7 S (商品名)等之雙酚A型淸漆型環氧 樹脂;日本環氧樹脂(股)製之Epkote Y L - 9 3 1, 汽巴特用化學品公司製之Araldhe 1 6 3等(均爲商品名 )之四羥苯基乙烷型環氧樹脂;汽巴特用化學品公司製之 Araldite PT810,日產化學工業(股)製之 TE P I C等(均爲商品名)之雜環式環氧樹脂;曰本油 脂(股)製Blenmer - D G T等之二環氧丙基酞酸酯樹脂; 東都化成(股)製ZX— 1 〇 6 3等之四環氧丙基二甲酚 乙烷樹脂;新日鐵化學(股)製E S N — 1 9 0、ESN 一 3 6 0,大日本油墨化學工業(股)製Η P. - 4 0 3 2 、ΕΧΑ - 4750、ΕΧΑ — 4700等之含萘基的環 本紙張尺度適用中國國家標準(CNS ) Α4規格(210X297公釐)-38 524813 A7 B7_ 五、發明説明(36 ) (請先閲讀背面之注意事項再填寫本頁) 氧樹脂,大日本油墨化學工業(股)製HP - 7 2 0 0、 HP — 7 2 0 0H等之具二環戊二烯骨架的環氧樹脂;日 本油脂(股)製CP — 50S、CP — 50M等之環氧丙 基甲基丙烯酸酯共聚系環氧樹脂;以至於環己基馬來醯亞 胺及環氧丙基甲基丙烯酸酯之共聚環氧樹脂等,但不限於 這些。這些環氧樹脂可單獨或二種以上倂用。其中尤以聯 酚型或聯二甲酚型環氧樹脂、或其混合物爲佳,使用其它 環氧樹脂時,亦以對組成物中上述活性能量線硬化性樹脂 (A ) 1 0 0質量份,含5質量份以上之比例爲佳。 如上述之多官能環氧樹脂(D),因熱硬化,可提升 焊料阻劑之密合性、耐熱性等特性。其配合量,對上述活 性能量線硬化性樹脂(A ) 1 〇 〇質量份,在1 〇質量份 以上、1 0 0質量份以下即可,以2 5至6 0質量份爲佳 。多官能環氧化合物(D)之配合量不足1 〇質量%時, 硬化皮膜之吸濕性高、耐P C T性易降低,且焊枓耐熱性 、耐無電解電鍍性易於降低。另一方面,若超過1 0 0質 量份,塗膜之顯影性及硬化皮膜之耐無電解電鍍性惡化, 且耐P C T性也變差。 經濟部智慧財產局員工消費合作社印製 上述硬化觸媒(E )可舉例如,咪唑、2 -甲基咪嗤 、2 —乙基咪唑、2 —乙基—4 —甲基咪唑、2 —苯基咪 唑、4 —苯基咪唑、1 一氰胺乙基一 2 —苯基咪唑、1 一 (2 -氰胺乙基)一 2 -乙基—4 -甲基咪唑等之咪唑衍 生物:雙氰胺、苯甲基二甲胺、4 —(二甲胺基)一 N, N —二甲基苯甲基胺、4 一甲氧基一N,N —二甲基苯甲 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -39 - 524813 Α7 Β7 五、發明説明(37 ) (請先閱讀背面之注意事項再填寫本頁) 基胺、‘4 一甲基一 N,N -二甲基苯甲基胺等之胺化合物 、己二酸醯肼、癸二酸醯肼等之肼化合物;三苯基膦等之 磷化物等,而市售者有例如四國化成(股)製之2!^12 — A、2MZ-0K、2PHZ、2P4BHZ、 2 P 4 Μ Η Z (均爲咪唑系化合物之商品名),Sunapro公 司製之 U — CAT3503X、U— CAT3502X( 均爲二甲胺之阻絕異氰酸酯化合物的商品名)、D B U、 DBN、U-CATSA10 2、U — CAT5002 ( 均爲二環式脒化合物及其鹽)等。不特定於此,只要是環 氧樹脂之硬.化觸.媒、或促進環氧基與羧基之反應者即佳, πί甲·獨或二種以上混合使用。又,亦可用具密合性賦予機 能之胍胺、乙醯胍胺、苯并胍胺、三聚氰胺、2,4 —二 胺基一6—甲基丙醯氧基乙基一S—三畊、2-乙烯基一 2 ,4 一二氨基—S —三哄、2 —乙烯基一4,6 —二氨 經濟部智慧財產局員工消費合作社印製 基一 S —三哄·三聚異氰酸加成物、2,4 一二氨基一 6 -甲基丙烯醯氧基乙基- S -三哄•三聚異氰酸加成物等 之S -三畊衍生物,較佳者爲倂用這些密合性賦予性化合 物及上述硬化觸媒。上述硬化觸媒之配合量以通常之比例 量即可,例如對上述活性能量線硬化性樹脂(A ) 1〇〇 重量份,在0 · 1至2 0質量份,以0 · 5至1 5 · 0質 量份爲佳。 於本發明之光硬化性•熱硬化性樹脂組成物,必要時 可更以硫酸鋇、鈦酸鋇、氧化矽粉、微粉狀氧化矽、不定 形氧化矽、結晶氧化矽、熔融氧化砂、球狀氧化矽、滑石 本紙張尺度適用中國國家標準(CNS ) A4規格(210Χ297公釐) -40 _ 524813 A7 __B7 五、發明説明(38 ) (請先閲讀背面之注意事項再填寫本頁) 、黏土、碳酸鎂、碳酸鈣、氧化鋁、氫氧化鋁、雲母等已 知常用之無機充塡劑單獨或二種以上配合。使用目的在抑 制這些塗膜之硬化收縮,提升密合性、硬度等特性。無機 恆充塡劑之配合量,上述活性能量線硬化性樹脂(A )每 1 〇 0質量份爲1 0至3 0 0質量份,較佳者爲3 0至 2 0 0質量份。 本發明之組成物’必要時可更配合以酞菁藍、酞菁綠 、碘綠、二重氮黃、結晶紫、氧化鈦、碳黑、萘黑等已知 常用著色劑、氫醌、氫醌單甲醚、三級丁基兒.茶酚、焦掊 酚、吩噻哄等已知常用之熱聚合抑制劑、微粉氧化矽、有 機膨潤土等已知常用之增粘劑、矽酮系、氟系、高分子系 等之消泡劑及/或流平劑、咪唑系、噻唑系、三唑系等矽 烷偶合劑等已知常用添加劑類。 經濟部智慧財產局員工消費合作社印製 具以上組成之本發明的光硬化性•熱硬化性樹脂組成 物’可於必要時稀釋而調整爲適於塗布方法之粘度,將之 於例如’經已形成電路之印刷電路板之網版印刷法,簾塗 法、噴塗法、輥塗法等塗布,於例如約6 0至1 0 0 °C之 溫度將組成物中所含有機溶劑揮發乾燥,形成無龜裂塗膜 。其後’透過形成有圖樣之光罩以活性能量線作選擇性曝 光’未曝光部份以稀鹼水溶液顯影可形成阻劑圖樣,更於 活性能量線之照射後以加熱硬化或加熱硬化後以活性能量 線照射’或僅加熱硬化後作最終硬化(正式硬化),形成 耐熱性.、密合性、耐無電解電鍍性、電特性、.可撓性、耐 吸濕性及耐P C T (壓力鍋試驗)性優之硬化皮膜(焊料 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐)-41 - 524813 A7 B7 五、發明説明(39 ) 阻劑皮膜).° (請先閱讀背面之注意事項再填寫本頁) 上述鹼水溶液,可用氫氧化鉀、氫氧化鈉、碳酸鈉、 碳酸鉀、磷酸鈉、矽酸鈉、氨、胺類等之鹼水溶液。 又,爲作光硬化之照射光源,合適者有低壓水銀燈、 中壓水銀燈、局壓水銀燈、超局壓水銀燈、氣燈或金屬鹵 化物燈等。此外,亦可用雷射光等作爲活性能量線。 以下用實施例及比較例具體說明本發明,惟以下實施 例僅以例示本發明爲目的,不甩以限定本發明。又,以下 之「份」及「%」,除另指明外全係以質量爲準。 合成例1 於配備氣體導入管、攪拌裝置、冷卻管及溫度計之燒 瓶,加入1 ,5 —二羥基萘1 6 9份,及環氧當量1 9 4 克/當量之3 ’3’ ,5,5’ 一四甲基一4,4’ 一二 經濟部智慧財產局員工消費合作社印製 羥基聯苯二環氧丙醚1 1 3 0份,在氮氣中攪拌下於 1 2 0 t溶解。其後,添加三苯膦0 · 6 5份,將燒瓶內 之溫度升溫至1 5 0 t,一面保持於1 5 0 °C —面反應約 9 0分鐘,得環氧當量4 0 2克/當量之環氧化合物(工 )。其次,將燒瓶內之溫度冷卻至7 0 °C以下,加入環氧 氯丙烷1 9 2 2份,二甲亞砸1 6 9 0份,攪拌下升溫至 7〇°C並保持。其後,分散於9 0分鐘加入9 6 %氫氧化 鈉1 1 4份。添加後再反應3小時。反應結束後,將過剩 的環氧.氯丙烷及二甲亞硕之大半於1 2 0 °C、 5 0毫米录 柱減壓蒸餾,將含副生鹽及二甲亞碾之反應產物溶解於甲 本紙張尺度適用中國國家標準(CNS ) A4規格{ 210X297公釐) .42 - 524813 A7 B7 五、發明説明(40 ) (請先閲讀背面之注意事項再填寫本頁) 基異丁基甲_作水洗。其後,從油層蒸觀回收甲基異丁基 甲酮,得環氧當量3 〇 4克/當量之多核環氧化合物(a ~ 1 )。所得多核環氧化合物(a — 1 ),若從環氧當量 s十算,則上述一般式(7 a )中之醇式羥基1 · 7 6個中 有〇 · 7 9個環氧化。因此,醇式羥基之環氧化率爲4 5 °() 台成例2 - 於配備氣體導入管、攪拌裝置、冷卻管及溫度計之燒 瓶,加入1 ,5 -二羥基萘232份,及環氧當量194 克/當量之3 ’3, ,5,5’ 一四甲基一 4,4’ 一二 經基聯苯二環氧丙醚1 〇 6 7份,在氮氣中攪拌下於 1 2 〇 t:溶解。其後,添加三苯膦〇 · 6 5份,將燒瓶內 經濟部智慧財產局員工消費合作社印製 之溫度升溫至1 5 0 t,一面保持於1 5 0 t —面反應約 9 0分鐘,得環氧當量5 4 4克/當量之環氧化合物(2 }。其次,將燒瓶內之溫度冷卻至7 0 °C以下,加入環氧 氯丙烷1 8 3 9份,二甲亞碾1 6 9 0份,攪拌下升溫至 7 0 °C並保持。其後,分散於9 0分鐘加入9 6 %氫氧化 鈉1 5 9份。添加後再反應3小時。反應結束後,將過剩 之環氧氯丙烷及二甲亞硕之大半於12 0°C、 50毫米求 柱減壓蒸餾,將含副生鹽及二甲亞硕之反應產物溶解於甲 基異丁基甲酮作水洗。其後,從油層蒸餾回收甲基異丁基 甲酮,得環氧當量3 7 6克/當量之多核環氧化合物(a 一 2 )。所得多核環氧化合物(a — 2 ),若從環氧當量 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐)-43 - 524813 A7 B7 五、發明説明(41 ) 計算,則上述一般式(7 a )中之醇式羥基2 · 2 8個之 中約1 · 0 5個環氧化。因此’醇式羥基之環氧化率爲4 (請先閲讀背面之注意事項再填寫本頁)Araldite CY175, CY179, etc. (both trade names) are alicyclic epoxy resins; YL — 9 3 3 made by Japan Epoxy Resin (stock), Τ · Ε · Ν · made by Dow Chemical Company, EPPN — 501 , EP PN — 502, etc. (both trade names) trihydroxyphenyl methyl formaldehyde epoxy resin; YL — 6056, YX — 4000, YL — 6 121 (both are made by Japan Epoxy Resins) (Brand name) and other cresol-type or biphenol-type epoxy resins, or mixtures thereof; EBPS-200 manufactured by Nippon Kayaku), EPX ~ 3 manufactured by Asahi Kasei Kogyo Kogyo Co., Ltd., printed by employees of the Intellectual Property Bureau, Ministry of Economy (Please read the precautions on the back before filling in this page, > 0, EXA-1514 (trade name) made by Dainippon Ink Chemical Industry Co., Ltd.) and other bisphenol S epoxy resins; Japanese epoxy resins · Epicote 1 5 7 S (trade name) and other bisphenol A type lacquer-type epoxy resins; Epkote YL-9 3 1 made by Japan Epoxy Resins (stocks), made by Cibaite Chemicals Co., Ltd. Araldhe 1 6 3 etc. (both trade names) tetrahydroxyphenylethane type epoxy resin; Cibat Chemical Co., Ltd. Araldite PT810, TE PIC, etc. (both trade names) made by Nissan Chemical Industries, Ltd. (both trade names) heterocyclic epoxy resins; Diepoxypropylphthalate resins, such as Blenmer-DGT, made by Ben Fats & Oils Co., Ltd. ; Tetsu epoxy xylenol ethane resins such as ZX-1 0 6 3 manufactured by Toto Kasei Co., Ltd .; ESN-1 90, ESN 3 6 0 manufactured by Nippon Steel Chemical Co., Ltd., Dainippon Ink Chemical industry (stock) system Η P.-4 0 3 2, ΕΑΑ-4750, ΕΑΑ-4700 and other naphthalene-based ring paper sizes apply Chinese National Standard (CNS) A4 specifications (210X297 mm) -38 524813 A7 B7_ V. Description of the invention (36) (Please read the precautions on the back before filling in this page) Oxygen resin, HP-7 2 0 0, HP — 7 2 0 0H, etc. made by Dainippon Ink Chemical Industry Co., Ltd. Cyclopentadiene-based epoxy resins; epoxy methacrylate copolymer epoxy resins such as CP — 50S, CP — 50M made by Japan Oils & Fats Co., Ltd .; even cyclohexylmaleimide and cyclic Copolymer epoxy resin of oxypropyl methacrylate, etc., but is not limited to these. These epoxy resins may be It can be used alone or in combination of two or more. Among them, biphenol type or bixylenol type epoxy resin, or a mixture thereof is preferred. When other epoxy resins are used, the above active energy ray-curable resin in the composition is also used. (A) 100 parts by mass, preferably a proportion of 5 parts by mass or more. The multifunctional epoxy resin (D) as described above can improve the adhesiveness and heat resistance of the solder resist due to heat curing. The blending amount is preferably 100 parts by mass or more and 100 parts by mass or less, and preferably 25 to 60 parts by mass, with respect to the above-mentioned active energy line curable resin (A). When the blending amount of the polyfunctional epoxy compound (D) is less than 10% by mass, the cured film has a high hygroscopicity, and the PCT resistance is liable to decrease, and the heat resistance of the solder and the electroless plating resistance are liable to decrease. On the other hand, if it exceeds 100 parts by mass, the developability of the coating film and the electroless plating resistance of the cured film are deteriorated, and the P C T resistance is also deteriorated. For example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-benzene, etc. are printed by the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Imidazole derivatives such as imidazole, 4-phenylimidazole, 1-cyanamide ethyl-2-phenylimidazole, 1- (2-cyanaminoethyl) -2-ethyl-4-methylimidazole: bis Cyanamide, benzyl dimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzyl China National Standard (CNS) A4 Specification (210X297 mm) -39-524813 Α7 Β7 V. Invention Description (37) (Please read the notes on the back before filling this page) Base amine, '4 monomethyl-N, Amine compounds such as N-dimethylbenzylamine, hydrazine compounds such as hydrazine adipate and hydrazine sebacate; phosphides such as triphenylphosphine and the like; 2) ^ 12 — A, 2MZ-0K, 2PHZ, 2P4BHZ, 2 P 4 Μ Η Z (all are trade names of imidazole compounds), U — CAT3503X, U — CAT made by Sunapro 3502X (both trade names of dimethylamine barrier isocyanate compounds), D B U, DBN, U-CATSA10 2, U — CAT5002 (both bicyclic fluorene compounds and their salts), etc. It is not limited to this, as long as it is an epoxy resin, a catalyst, or a catalyst that promotes the reaction between an epoxy group and a carboxyl group, it is preferably used alone or in combination. In addition, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methylpropionyloxyethyl-S-three farming, guanidamine, acetoguanamine, melamine, adhesion-improving functions can also be used, 2-vinyl-1,2,4-diamino-S—three-coated, 2-vinyl-4,6—di-amino-printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Employees ’Cooperatives, printed base-S—three-coated, trimeric isocyanate Adducts, 2,4-diamino-6-methacrylic acid, ethoxyethyl-S-trioxine, trimeric isocyanate adducts, etc., S-three cultivated derivatives are preferred These adhesion-imparting compounds and the above-mentioned curing catalyst. The blending amount of the hardening catalyst may be a normal proportion, for example, 100 parts by weight of the active energy ray-curable resin (A), 0. 1 to 20 parts by mass, and 0. 5 to 1 5 · 0 parts by mass is preferred. In the photocurable and thermosetting resin composition of the present invention, barium sulfate, barium titanate, silicon oxide powder, fine powdered silicon oxide, amorphous silicon oxide, crystalline silicon oxide, fused oxide sand, Spherical silicon oxide, talc This paper size is applicable to Chinese National Standard (CNS) A4 specification (210 × 297 mm) -40 _ 524813 A7 __B7 V. Description of the invention (38) (Please read the precautions on the back before filling this page), Clay, magnesium carbonate, calcium carbonate, alumina, aluminum hydroxide, mica and other known inorganic fillers are commonly used alone or in combination of two or more. The purpose of use is to suppress the hardening and shrinkage of these coating films, and improve the properties such as adhesion and hardness. The blending amount of the inorganic constant filling tincture is 10 to 300 parts by mass per 100 parts by mass of the active energy ray-curable resin (A), and preferably 30 to 200 parts by mass. The composition of the present invention can be further blended with phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, and other commonly used colorants, hydroquinone, hydrogen, etc. if necessary. Known and commonly used thermal polymerization inhibitors such as quinone monomethyl ether, tertiary butyl catechin, catechol, pyrogallol, phenothiazine, micronized silica, organic bentonite and other known commonly used thickeners, silicones, Defoamers and / or leveling agents such as fluorine-based polymers and / or leveling agents, silane coupling agents such as imidazole-based, thiazole-based, and triazole-based additives are commonly known. The photo-curable / thermo-curable resin composition of the present invention, which is composed of the above-mentioned composition by the Consumers' Cooperative of the Ministry of Economic Affairs and the Ministry of Economic Affairs, can be diluted as necessary to adjust the viscosity suitable for the coating method. The screen printing method, curtain coating method, spray coating method, roll coating method, etc. of the printed circuit board forming the circuit are applied, and the organic solvent contained in the composition is evaporated to dryness at a temperature of about 60 to 100 ° C to form No cracking coating. Thereafter, the selective exposure of the active energy rays through a mask formed with the pattern is used to develop the resist pattern by developing the unexposed portion with a dilute aqueous alkali solution. Active energy ray irradiation 'or final hardening (formal hardening) only after heating and hardening to form heat resistance, adhesion, electroless plating resistance, electrical properties, flexibility, moisture absorption resistance, and PCT resistance (pressure cooker test) ) Hardened film with excellent properties (The size of this paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm)-41-524813 A7 B7 V. Description of the invention (39) Resist film)) (Please read the first Please fill in this page for the matters needing attention) The above alkaline aqueous solution can be potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines and other alkaline aqueous solutions. In addition, for the light source for light hardening, suitable ones include a low-pressure mercury lamp, a medium-pressure mercury lamp, a local-pressure mercury lamp, an ultra-local-pressure mercury lamp, a gas lamp, or a metal halide lamp. In addition, laser light or the like may be used as the active energy ray. Hereinafter, the present invention will be specifically described using examples and comparative examples. However, the following examples are only for the purpose of illustrating the present invention and are not intended to limit the present invention. In addition, the following "parts" and "%" are based on quality unless otherwise specified. Synthesis Example 1 In a flask equipped with a gas introduction tube, a stirring device, a cooling tube, and a thermometer, 169 parts of 1,5-dihydroxynaphthalene, and epoxy equivalent 194 g / equivalent 3'3 ', 5, 5 130 parts of 5′-tetramethyl-1, 4 ′ 12 printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed 1,130 parts of hydroxybiphenyl dipropylene oxide, and dissolved in 120 t under stirring in nitrogen. Thereafter, 0.65 parts of triphenylphosphine was added, and the temperature in the flask was raised to 150 t, while the temperature was maintained at 150 ° C. The surface reaction was performed for about 90 minutes to obtain an epoxy equivalent of 4.02 g / Equivalent epoxy compound. Next, the temperature in the flask was cooled to below 70 ° C, and 192 parts of epichlorohydrin and 169 parts of dimethylene were added. The temperature was raised to 70 ° C with stirring and maintained. Thereafter, it was dispersed in 90 minutes, and 114 parts of 96% sodium hydroxide was added. After the addition, it was reacted for another 3 hours. After the reaction, the excess of epoxy, chloropropane and dimethylacetone were distilled under reduced pressure at 120 ° C and 50mm column to dissolve the reaction products containing parasalt and dimethylacetate in The paper size of this paper applies the Chinese National Standard (CNS) A4 specification (210X297 mm). 42-524813 A7 B7 V. Description of the invention (40) (Please read the precautions on the back before filling this page) Isobutyl A . Thereafter, methyl isobutyl ketone was recovered from the oil layer by evaporation, and an epoxy equivalent of 3.0 g / equivalent polynuclear epoxy compound (a to 1) was obtained. The obtained polynuclear epoxy compound (a-1) is epoxidized in the alcoholic hydroxyl groups 1.76 in the general formula (7a) described above when calculated from the epoxy equivalent s. Therefore, the epoxidation rate of alcoholic hydroxyl groups is 45 ° (). Example 2-In a flask equipped with a gas introduction tube, a stirring device, a cooling tube, and a thermometer, add 232 parts of 1,5-dihydroxynaphthalene, and epoxy 194 g / equivalent 3'3,3,5,5'-tetramethyl-1,4,4'-dioxetylbiphenylenedioxypropyl ether 7 parts, 1 2 under stirring under nitrogen. t: dissolved. After that, 0.65 parts of triphenylphosphine was added, and the temperature printed by the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs in the flask was raised to 150 t, while the temperature was kept at 150 t. The reaction took about 90 minutes. An epoxy equivalent of 5 4 4 g / equivalent epoxy compound (2) was obtained. Next, the temperature in the flask was cooled to below 70 ° C, 1 8 3 9 parts of epichlorohydrin was added, and dimethylene was ground 16 Ninety parts, heated to 70 ° C with stirring and maintained. After that, disperse in 90 minutes and add 159 parts of 96% sodium hydroxide. After the addition, react for 3 hours. After the reaction is completed, the excess ring Most of the oxychloropropane and dimethylarsox were distilled under reduced pressure at 120 ° C, 50 mm, and the reaction product containing parasalt and dimethylarsox was dissolved in methyl isobutyl ketone for washing. Thereafter, The methyl isobutyl ketone was recovered by distillation from the oil layer to obtain an epoxy equivalent of 376 g / equivalent polynuclear epoxy compound (a-2). The obtained polynuclear epoxy compound (a-2) was obtained from the epoxy equivalent of this paper Applicable to China National Standard (CNS) A4 specification (210X297 mm) -43-524813 A7 B7 V. Description of invention (41) Calculation, Then about 1 · 0 5 of the alcoholic hydroxyl groups in the general formula (7 a) above are epoxidized. Therefore, the epoxidation rate of the alcoholic hydroxyl groups is 4 (please read the precautions on the back before filling in (This page)
6 %。而本合成例所得之多核環氧化合物(a 一 2 )之紅 外線吸收圖譜(用傅立葉轉換紅外分光光度計F T - I R 測定)及核磁共振圖譜(溶劑C D C 1 3,參考物質T M S (四甲基矽烷))各示於第1及第2圖。 合成例3 於配備氣體導入管、攪拌裝置、冷卻管及.溫度計之燒 瓶,加入1 ,5 -二羥基萘274份’及環氧當量194 克/當量之3,3’ ,5,5’一四甲基一4,4’一二 羥基聯苯二環氧丙醚1 0 2 5份,在氮氣中攪拌下於 .1 2 0 °C溶解。其後,添加三苯膦〇 · 6 5份,將燒瓶內 之溫度升溫至1 5 0 °C,一面保持於1 5 0 °C —面反應約 9 0分鐘,得環氧當量7 2 3克/當量之環氧化合物(3 )。其次,將燒瓶內之溫度冷卻至7 0 °C以下,加入環氧 氯丙烷1 7 7 9份,二甲亞碾1 6 9 0份,攪拌下升溫至 經濟部智慧財產局員工消費合作社印製 7 0 °C並保持。其後,分散於9 0分鐘加入9 6 %氫氧化 鈉1 9 2份。添加後再反應3小時。反應結束後,將過剩 的環氧氯丙烷及二甲亞硕之大半於1 2 0 °C、 5 0毫米汞 柱減壓蒸餾,將含副生鹽及二甲亞砸之反應產物溶解於甲 基異丁基甲酮作水洗。其後,從油層蒸餾回收甲基異丁基 甲酮,.得環氧當量4 5 8克/當量之多核環氧化合物(a —3 )。所得多核環氧化合物(a - 3 ),若從環氧當量 本紙張尺度適用中國國家標準(CNS ) A4規格(210Χ297公釐) -44 - " ~ 524813 A7 B7 五、發明説明(42 ) 計算,則上述一般式(7a)中之醇式羥基2 · 93個中 約1 . 3 2個環氧化。因此,醇式羥基之環氧化率爲4 5 (請先閲讀背面之注意事項再填寫本頁) %。 合成例4 於配備氣體導入管、攪拌裝置、冷卻管及溫度計之燒 瓶,加入2 ,6 -二羥基萘169份,及環氧當量194 克/當量之3,3’ ,5,5’ 一四甲基一4,4’ 一二 經濟部智慧財產局員工消費合作社印製 羥基聯苯二環氧丙醚1 1 3 0份,在氮氣中攪拌下於 1 2 0 t:溶解。其後,添加三苯膦0 . 6 5份,將燒瓶內 之溫度升溫至1 5 0 °C,一面保持於1 5 Ο T: —面反應約 9〇分鐘,得環氧當量3 7 1克/當量之環氧化合物(4 )。其次,將燒瓶內之溫度冷卻至7 0 °C以下,加入環氧 氯丙烷1 9 5 2份,二甲亞碾1 6 9 0份,攪拌下升溫至 7 0 °C並保持。其後,分散於9 0分鐘加入9 6 %氫氧化 鈉2 3 1份。添加後再反應3小時。反應結束後,將過剩 之環氧氯丙烷及二申亞硕之大半於12 0°C、50毫米汞 柱減壓蒸飽,將含副生鹽及二甲亞硕之反應產物溶解於甲 基異丁基甲酮作水洗。其後,從油層蒸餾回收甲基異丁基 甲酮,得環氧當量2 6 7克/當量之多核環氧化合物(a 一 4 )。所得多核環氧化合物(a — 4 ),若從環氧當量 計算,則上述一般式(7 a )中之醇式羥基1 · 6 5個中 有0 ·. 9 9個環氧化。因此,醇式經基之環氧化率爲6 0 % 〇 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐1 -45 · 一 524813 A7 B7 五、發明説明(43 ) 合成例5 . (請先閲讀背面之注意事項再填寫本頁) 除9 6 %氫氧化鈉之使用量爲5 8份以外,同合成例 4得環氧當量3 〇 9克/當量之多核環氧化合物(a — 5 )。所得多核環氧化合物(a - 5 ),若從環氧當量計算 ’則上述一般式(7 a )中之醇式羥基1 · 6 5個中有 〇 · 50個環氧化。因此,醇式羥基之環氧化率爲30% 合成例6 * 於配備氣體導入管、攪拌裝置、冷卻管及溫度計之反 應容器’加入羥基當量80克/當量之1 ,5 —二羥基萘 經濟部智慧財產局員工消費合作社印製 2 2 4 · 2份,及日本環氧樹脂(股)製環氧當量1 8 9 克/當量之雙酸A型環氧化合物(商品名「Epicote 828」)1075 . 8份,在氮氣中攪拌下於1 10 °C 溶解。其後,添加三苯膦0 · 6 5份,將反應容器內之溫 度升溫至1 5 0 °C,一面保持於1 5 0 °C —面反應約9 0 分鐘’得環氧當量452克/當量之環氧化合物(6)。 其次,將反應容器內之溫度冷卻至4 0 °C,加入環氧 氯丙烷1 9 2 0份,甲苯1 6 9 0份溶解後,添加溴化四 甲銨7 0份,攪拌下升溫至6 0 °C並保持。其後,於6 0 分鐘連續滴入4 8 %氫氧化鈉水溶液3 6 4份。滴入後再 反應6小時。反應結束後,將過剩之未反應環氧氯丙烷及 甲苯之大半減壓蒸餾回收,將含副生鹽及甲苯之反應產物 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -46 - 524813 A7 B7 五、發明説明(44) (請先閲讀背面之注意事項再填寫本頁) 溶於甲基異丁基甲酮作水洗。將有機溶劑層及水層分離後 ,從有機溶劑層以減壓蒸餾餾出甲基異丁基甲酮,得環氧 當量2 7 7克/當量之多核環氧化合物(a — 6 )。所得 多核環氧化合物(a - 6 ) ’若從環氧當量計算,則環氧 化合物(6 )中醇性羥基1 · 9 8個中約1 · 5 9個環氧 化。因此,醇式羥基之環氧化率約爲8 0 %。 合成例7 於配備氣體導入管、攪拌裝置、冷卻管及.溫度計之反 應容器,加入羥基當量8 0克/當量之1 ,5 —二羥基萘 219 . 2份,及日本環氧樹脂(股)製環氧當量19 2 克/當量之聯二甲酚型環氧化合物(商品名「Epicote YX4000」)1080·8份,在氮氣中攪样下於 1 1 0 t:溶解。其後,添加三苯膦0 · 6 5份,將反應容 器內之溫度升溫至1 5 0 °C,一面保持於1 5 0 t: —面反 應約9 0分鐘,得環氧當量4 5 1克/當量之環氧化合物 (7 )。 經濟部智慧財產局員工消費合作社印製 其次,將反應容器內之溫度冷卻至4 0 °C,加入環氧 氯丙烷1 8 9 9份,甲苯1 6 9 0份溶解後,添加溴化四 甲銨6 9份,攪拌下升溫至6 0 t並保持。其後,於6 0 分鐘連續滴入4 8 %氫氧化鈉水溶液3 6 0份。滴入後再 反應6小時。反應結束後,將過剩之未反應環氧氯丙烷及 甲苯的大半以減壓蒸餾回收,將含副生鹽及甲.苯之反應產 物溶解於甲基異丁基甲酮作水洗。將有機溶劑層及水層分 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -47 - 524813 A7 _____ B7 五、發明説明(45 ) 離後,以減壓蒸餾從有機溶劑層餾出甲基異丁基甲酮’得 環氧當量278克/當量之多核環氧化合物(a-7) ° 所得多核環氧化合物(a - 7 ),若從環氧當量計算,貝【J 環氧化合物(7 )中醇性羥基1 · 9 5個中約1 · 5 6個 環氧化。因此,醇式羥基之環氧化率約爲8 0 %。 實施例1至7及比較例1至4 實施例1至7係各用上述合成例1至7中合成之多核 環氧化合物(a — 1 )至(a - 7 ),而比較.例1至4各 用上述合成例1至4所得之環氧化合物(1 )至(4 ), 以表1所示比例配合酚樹脂(酚醛淸漆,羥基當量1 0 6 克/當量),硬化促進劑-苯基—4,5 —二羥基甲 .基咪唑,簡稱P D Μ I )及溶劑(卡必醇醋酸酯),以三 輥機混練得熱硬化性樹脂組成物。 (請先閲讀背面之注意事項再填寫本頁} 經濟部智慧財產局員工消費合作社印製 準 標 家 國 國 中 用 I適一錄 Α4 S Ν 公 97 2 48 5248136%. The infrared absorption spectrum (determined by Fourier transform infrared spectrophotometer FT-IR) and nuclear magnetic resonance spectrum (solvent CDC 1 3, reference substance TMS (tetramethylsilane) of the polynuclear epoxy compound (a-2) obtained in this synthesis example. )) Each is shown in Figures 1 and 2. Synthesis Example 3 In a flask equipped with a gas introduction pipe, a stirring device, a cooling pipe, and a thermometer, 274 parts of 1,5-dihydroxynaphthalene 'and 194 g / equivalent of epoxy resin were added to 3,3', 5,5'- 10 2 5 parts of tetramethyl-1,4'-dihydroxydiphenyl dipropylene oxide were dissolved in .120 ° C under stirring under nitrogen. Thereafter, 0.65 parts of triphenylphosphine was added, and the temperature in the flask was raised to 150 ° C, while maintaining the temperature at 150 ° C for about 90 minutes, and an epoxy equivalent of 7 2 3 g was obtained. / Equivalent epoxy compound (3). Next, cool the temperature in the flask to below 70 ° C, add 179 parts of epichlorohydrin, and 190 parts of dimethylamine, and heat up to the printing of the employee's consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs with stirring. 70 ° C and hold. Thereafter, it was dispersed in 90 minutes, and 92% of 96% sodium hydroxide was added. After the addition, it was reacted for another 3 hours. After the reaction, the excess of epichlorohydrin and dimethyl arsenate were distilled under reduced pressure at 120 ° C and 50 mm Hg to dissolve the reaction product containing para-salt and dimethyl arylene in formazan. Isobutyl ketone was washed with water. Thereafter, methyl isobutyl ketone was recovered by distillation from the oil layer to obtain an epoxy equivalent of 4.8 g / equivalent polynuclear epoxy compound (a-3). The obtained multi-core epoxy compound (a-3), if the Chinese equivalent standard (CNS) A4 specification (210 × 297 mm) is applied from the epoxy equivalent of the paper size, -44-" ~ 524813 A7 B7 V. Description of the invention (42) calculation Then, about 1.3 2 of the alcoholic hydroxyl groups 2.93 in the general formula (7a) are epoxidized. Therefore, the epoxidation rate of alcoholic hydroxyl groups is 4 5 (Please read the precautions on the back before filling this page)%. Synthesis Example 4 In a flask equipped with a gas introduction pipe, a stirring device, a cooling pipe, and a thermometer, 169 parts of 2,6-dihydroxynaphthalene, and epoxy equivalent 194 g / equivalent of 3, 3 ', 5, 5', and 14 were added. Methyl-4,4'12 Printed 1,130 parts of hydroxydiphenyl dipropylene oxide by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, dissolved in nitrogen at 120 t under stirring. Thereafter, 0.65 parts of triphenylphosphine was added, and the temperature in the flask was raised to 150 ° C, while maintaining the temperature at 150 ° C:-The side reaction was performed for about 90 minutes, and epoxy equivalent of 37.1 g was obtained. / Equivalent epoxy compound (4). Next, the temperature in the flask was cooled to below 70 ° C, and 195 parts of epichlorohydrin and 169 parts of dimethyl arylene were added, and the temperature was raised to 70 ° C with stirring and maintained. Thereafter, it was dispersed in 90 minutes, and 23% of 96% sodium hydroxide was added. After the addition, it was reacted for another 3 hours. After the reaction was completed, the excess epichlorohydrin and the majority of Ershen Yashuo were evaporated under reduced pressure at 120 ° C and 50 mm Hg to dissolve the reaction products containing parasalt and dimethyl Yasuo in methyl isobutyl formamide Ketone was washed with water. Thereafter, methyl isobutyl ketone was recovered by distillation from the oil layer to obtain a polynuclear epoxy compound (a-4) having an epoxy equivalent of 267 g / equivalent. If the obtained polynuclear epoxy compound (a-4) is calculated from the epoxy equivalent, there are 0 ·· 9 9 epoxidation of the alcoholic hydroxyl groups 1. 6 of the general formula (7 a). Therefore, the epoxidation rate of alcoholic radicals is 60%. ○ This paper size applies Chinese National Standard (CNS) A4 specifications (210X297 mm 1 -45 · 524813 A7 B7. V. Description of the invention (43) Synthesis example 5. (Please read the precautions on the back before filling in this page) Except that the use amount of 96% sodium hydroxide is 58 parts, the epoxy equivalent of 3.09 g / equivalent polynuclear epoxy compound (a — 5). If the obtained polynuclear epoxy compound (a-5) is calculated from the epoxy equivalent, then 0.5 to 50 of the alcoholic hydroxyl groups 1.65 in the general formula (7a) described above are epoxidized. The epoxidation rate of alcoholic hydroxyl groups is 30% Synthesis Example 6 * In a reaction vessel equipped with a gas introduction pipe, a stirring device, a cooling pipe and a thermometer, '80 equivalents of hydroxyl groups / equivalent of 1, 5-dihydroxynaphthalene are wisdom 2 2 4 · 2 copies printed by the employees' cooperative of the property bureau, and 189 g / equivalent bis-acid A type epoxy compound (trade name "Epicote 828") made by Japan Epoxy Resin (stock) 1075. 8 parts, dissolved under stirring at 1 10 ° C. After that, triphenylphosphine 0.65 parts was added The temperature in the reaction vessel was raised to 150 ° C, and the temperature was kept at 150 ° C while the reaction was carried out for about 90 minutes to obtain an epoxy equivalent of 452 g / equivalent epoxy compound (6). The temperature in the reaction vessel was cooled to 40 ° C, 192 parts of epichlorohydrin was added, and 169 parts of toluene were dissolved. Then 70 parts of tetramethylammonium bromide was added, and the temperature was raised to 60 ° C with stirring. After that, 364 parts of 48% sodium hydroxide aqueous solution was continuously added dropwise over 60 minutes. After the dropwise addition, the reaction was continued for 6 hours. After the reaction was completed, excess unreacted epichlorohydrin and most of toluene were added. Recovered under reduced pressure, the reaction products containing by-product salt and toluene will be used. The paper size is applicable to Chinese National Standard (CNS) A4 (210X297 mm) -46-524813 A7 B7 V. Description of the invention (44) (Please read the back first Note: Please fill in this page again) Dissolve in methyl isobutyl ketone for washing. After separating the organic solvent layer and water layer, distill off the methyl isobutyl ketone from the organic solvent layer under reduced pressure to obtain epoxy equivalent 2 7 7 g / equivalent polynuclear epoxy compound (a-6). The obtained polynuclear epoxy compound (a-6) ) 'If calculated from the epoxy equivalent, about 1.59 of the alcoholic hydroxyl groups of 1.98 in the epoxy compound (6) are epoxidized. Therefore, the epoxidation rate of the alcoholic hydroxyl groups is about 80%. Synthesis Example 7 In a reaction vessel equipped with a gas introduction pipe, a stirring device, a cooling pipe, and a thermometer, hydroxy equivalent 80 g / equivalent 1,25-dihydroxynaphthalene 219.2 parts, and Japanese epoxy resin (stock) were added. An epoxy equivalent of 19 2 g / equivalent xylenol type epoxy compound (trade name "Epicote YX4000") was made into 1080 · 8 parts, and the sample was dissolved at 1 10 t under nitrogen stirring. Thereafter, 0.65 parts of triphenylphosphine was added, and the temperature in the reaction vessel was raised to 150 ° C, while maintaining the temperature at 150 ° C:-The reaction was carried out for about 90 minutes to obtain an epoxy equivalent of 4 5 1 G / equivalent of epoxy compound (7). Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs followed by cooling the temperature in the reaction vessel to 40 ° C, adding 189 parts of epichlorohydrin, and 169 parts of toluene dissolved, and then adding tetramethyl bromide 6-9 parts of ammonium were heated to 60 t with stirring and kept. Thereafter, 360 parts of a 48% sodium hydroxide aqueous solution was continuously added dropwise over 60 minutes. After dropping, the reaction was continued for another 6 hours. After completion of the reaction, most of the excess unreacted epichlorohydrin and toluene were recovered by distillation under reduced pressure, and the reaction product containing by-product salt and methylbenzene was dissolved in methyl isobutyl ketone for washing. Separate the organic solvent layer and water layer into paper. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -47-524813 A7 _____ B7 V. Description of the invention (45) After separation, remove the organic solvent layer by vacuum distillation. Distilling out the methyl isobutyl ketone 'gives an epoxy equivalent of 278 g / equivalent polynuclear epoxy compound (a-7) ° The obtained polynuclear epoxy compound (a-7). About 1.56 of the alcoholic hydroxyl groups of 1.95 in the compound (7) are epoxidized. Therefore, the epoxidation rate of the alcoholic hydroxyl group is about 80%. Examples 1 to 7 and Comparative Examples 1 to 4 Examples 1 to 7 are each a comparison of the polynuclear epoxy compounds (a-1) to (a-7) synthesized in the above Synthesis Examples 1 to 7, respectively. Examples 1 to 7 4 Each of the epoxy compounds (1) to (4) obtained in the above Synthesis Examples 1 to 4 was blended with a phenol resin (phenolic lacquer, hydroxyl equivalent of 106 g / equivalent) in the ratio shown in Table 1, Phenyl-4,5-dihydroxymethyl.imidazole (PDM I for short) and a solvent (carbitol acetate) were kneaded with a three-roller machine to obtain a thermosetting resin composition. (Please read the notes on the back before filling out this page} Printed by the Consumers' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, Standard State, State, China, and China I ー 4 S Ν Publication 97 2 48 524813
AA
7 B 五、發明説明(46 ) 經濟部智慧財產局員工消費合作社印製 i 比較例 寸 o r—H 28.6 寸 S m 〇 i ,mi ▼—H 寸 S csl o. r··· i a\ 寸 g r—Ή 〇 r— i 26.4 寸 〇 實施例 Ο- Ο 40.0 寸 〇 Ο 「< 40.6 寸 uo MP υη ο f'' i 34.3 寸 〇 寸 ο f i 39.7 寸 un v〇 cn Ο ι " 1 Η 23.1 寸 Ο r—Η Csl Ο ι i 28.2 寸 g τ—Η Ο τ· Λ 34.9 寸 Ο 組成 (a_l) (a-2) (a-3) (a-4) (a-5) (a-6) (a-7) 〆^\ /^N —oi cn 寸 >w/ 酚樹脂 硬化促進劑 (PDMI) 溶劑 (卡必醇醋酸酯) I .----------— (請先閲讀背面之注意事項再填寫本頁) 訂 Φ 平 网. 丁 一 -7 B V. Description of the invention (46) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs i Comparative example inch—H 28.6 inch S m 〇i, mi ▼ —H inch S csl o. R ··· ia \ inch gr —Ή 〇r— i 26.4 inches 〇 Example 〇- 〇 40.0 inches 〇〇 "< 40.6 inches uo MP υη ο f '' i 34.3 inches 〇 inches ο fi 39.7 inches un v〇cn Ο ι " 1 Η 23.1 Inch 〇 r—Η Csl Ο ι i 28.2 Inch g τ—Η Ο τ · Λ 34.9 Inch 〇 Composition (a_l) (a-2) (a-3) (a-4) (a-5) (a-6 ) (a-7) 〆 ^ \ / ^ N —oi cn inch > w / Phenol resin hardening accelerator (PDMI) solvent (carbitol acetate) I .----------— ( (Please read the notes on the back before filling out this page) Order Φ Flat Screen. Ding Yi-
公 97 2 X 49 524813 A7 B7 五、發明説明(47 ) (請先閲讀背面之注意事項再填寫本頁) 將上述各實施例及比較例之組成物於8 Ο X:,3 0分 鐘,再於1 8 0 °C,1小時硬化,測定玻璃轉移點,拉伸 強度、伸展率、拉伸彈性率、吸水率、電絕緣性、鉛筆硬 度,並評估密合性、耐酸性、耐鹼性。 各物性之評價係以如下方法進行。 <玻璃轉移溫度> 於預先水洗•乾燥之鐵氟龍板以網版印刷塗布上述各 實施例及比較例之組成物,於熱風循環式乾燥爐以8 0 °C 乾燥4 0分鐘。冷卻至室溫後,以曝光量5 0毫焦耳/平 方公分之條件曝光,於熱風循環式乾燥爐以1 8 0 °C硬化 6 0分鐘。冷卻至室溫後,從鐵氟龍板剝下硬化塗膜,得 評估樣本。以D Μ A法測定該樣本之玻璃轉移點。 <拉伸強度(拉伸破壞強度)、伸展率(拉伸破壞伸展) 、拉伸彈性率> 依JIS K 7172求出。 經濟部智慧財產局員工消費合作社印製 <吸水率、鉛筆硬度> 依Jis K 5400求出。 <密合性> 依.J I s D 0 2 0 2以目視判定。判定標準如下 〇 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -50- 524813 A7 _______B7_ 五、發明説明(48 ) 〇:全無剝落可見者 A:僅只輕微剝落者 X :完全剝落者 (請先閲讀背面之注意事項再填寫本頁) <電絕緣性 將上述各實施例及比較例之組成物,於I P C B -2 5之梳型電極B試片,用Pilot精工(股)製輥塗機全面 塗布,於8 0 °C以3 0分鐘,再於1 8 0 °C以1小時硬化 ’製成評估基板。施加D C 5 0 0伏特之偏壓.於該梳型電 極,測定絕緣電阻値。 · <耐酸性試驗> 同電絕緣性用之評估基板,於2 0 °C 1 0容量%硫酸 水溶液浸泡3 0分鐘後取出,綜合判定塗膜之狀態及密合 性。判定標準如下。 經濟部智慧財產局員工消費合作社印製 〇:無可見變化者 △:僅只輕微變化者 X:塗膜脹起或膨潤脫落者 <耐鹼性試驗〉 除1 0容量%硫酸水溶液換成1 0容量%氫氧化鈉水 溶液外,同耐酸性試驗作評價。 所得結果示於表2。 本紙張尺度適用中國國家橾準(CNS ) A4規格(210X297公釐) -51 - 524813 A7 B7 五、發明説明(49 ) 經濟部智慧財產局員工消費合作社印製 比較例 寸 I 丨 172.4 1942.9 62.5 1_ 1 i r—^ 〇 cn CO 〇 〇 CO 165.1 1882.6 60.8 5.69 oo i 1 i t—H < CO cn κ Csl <] 〇 166.3 1907.5 61.6 5.66 〇 ^ 1 i t—H 〇 cn cn cn 〇 〇 ......m,i 168.1 1936.5 3 5.64 1.05 〇 Ά K CO 〇 〇 實施例 卜 213.1 2340.5 70.2 5.32 r_H 〇 E VO 〇 〇 VO 204.5 2320.3 69.4 f i r—H un 0.66 〇 CO K VO 〇 〇 un 190.5 1956.3 62.8 5.62 0.60 〇 o K 〇 〇 寸 198.8 1961.8 63.2 5.58 0.58 〇 p 〇 〇 CO 173.5 1892.4 61.6 5.71 0.73 〇 wo cn K 〇 〇 CNl 180.1 1924.2 62.3 5.64 0.66 〇 E 〇 〇 τ—Η 189.4 1955.7 62.9 0.61 〇 tc 〇 〇 特性 玻璃轉移點 (°〇 拉伸彈性率 (N/mm2) 拉伸強度 (N/mm2) 伸展率 (%) 吸水率 (%) 密合性 電絕緣電阻 (X 10,3Ω ) 鉛筆硬度 耐酸性 耐鹼性 (請先閱讀背面之注意事項再填寫本頁) -裝· 訂 1^ 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -52 - 524813 A7 B7 五、發明説明(5〇 ) (請先閲讀背面之注意事項再填寫本頁) 由表2所示結果可知,得自本發明之多核環氧化合物 之硬化物’玻璃轉移溫度局’機械強度優,具吸水率、密 合性、電絕緣電阻、硬度、耐藥品性等亦優之特性。相對 於此,得自比較例之芳族環氧化合物的硬化物,玻璃轉移 點低,吸水率、硬度等差。 合成例8 於配備氣體導入管、攪拌裝置、冷卻管及溫度計之燒 瓶,加入1 ,5 —二經基萘1 6 9份,及環氧當量1 9 4 克/當量之3,3’ ,5,5’ 一四甲基一 4,4, 一二 經濟部智慧財產局員工消費合作社印製 羥基聯苯二環氧丙醚1 1 3 0份,在氮氣中攪拌下於 1 2 0 t溶解。其後,添加三苯膦0 · 6 5份,將燒瓶內 之溫度升溫至1 5 0 t:,一面保持於1 5 0 °C —面反應約 9〇分鐘,得環氧當量3 5 0克/當量之環氧化合物(8 )。其次將燒瓶內溫度冷卻至7 0 °C,以下,加入環氧氯 丙烷2 0 8 0份,二甲亞硕1 6 9 0份,攪拌下升溫至 7 0 °C並予保持。其後,分散於9 0分鐘添加9 6 %氫氧 化鈉1 8 0份。添加後再反應3小時。反應結束後,將過 剩之環氧氯丙烷及二甲亞硕之大半於12 0°C、 50毫米 汞柱減壓蒸餾,將含副生鹽及二甲亞硕之反應產物溶解於 甲基異丁基甲酮作水洗。其後,從油層蒸餾回收甲基異丁 基甲酮,得環氧當量2 6 2克/當量之多核環氧化合物( a - 8 )。所得多核環氧化合物(a - 8 ),若從環氧當 量計算,則一般式(7 a )中醇式羥基1 . 5 7個中約0 本紙張尺度適用中國國家標準(CNS ) A4規格(21〇Χ297公釐)^53 - -- 524813 A7 ___B7_ 五、發明説明(51 ) .8 6個環氧化。因此,醇式羥基之環氧化率爲5 5 %。 (請先閲讀背面之注意事項再填寫本頁) 其次,將多核環氧化合物(a - 8 ) 4 7 1份,置入 配備攪拌裝置、冷卻管及溫度計之燒瓶,加入卡必醇醋酸 酯4 0 〇份,加熱溶解並加入甲基氫醌〇 . 4 6份,及三 苯膦1 · 3 8份,於9 5至1 0 5 °C加熱,緩慢滴入丙烯 酸1 2 9份,反應1 6小時。以下,該反應溶液稱作b -1淸漆。而本合成例所得之多核環氧丙烯酸酯化合物(b - 1 )的紅外線吸收圖譜(用傅立葉轉換紅外分光光度計 F T - I R測定)及核磁共振圖譜(溶劑c D C 1 3,參考 物質T M S (四甲基矽烷V各示於第3及第4圖。 合成例9 將合成例8所得之多核環氧化合物(a — 8 ) 5 2 8 份,置入配備攪拌裝置、冷卻管及溫度計之燒瓶,加入卡 必醇醋酸酯4 0 0份加熱溶解,加入甲基氫醌0 · 4 6份 及三苯膦1 · 3 8份,於9 5至1 0 5 °C加熱,緩慢滴入 經濟部智慧財產局員工消費合作社印製 丙烯酸7 2份,反應1 6小時。以下稱此反應溶液爲b -2淸漆。 合成例1〇 將合成例3所得之多核環氧化合物(a — 3 ) 5 1 8 份,置入配備攪拌裝置、冷卻管及溫度計之燒瓶,加入卡 必醇醋.酸酯4 0 0份加熱溶解,加入甲基氫醞0 · 4 6份 及三苯膦1 · 3 8份,於9 5至1 0 5 °C加熱,緩慢滴入 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) Γ54 - ' 524813 A7 B7 五、發明説明(52) 丙烯酸8 2份,反應1 6小時。以下稱此反應溶液爲b - 3淸漆。 (請先閲讀背面之注意事項再填寫本頁} 合成例1 1 將合成例4所得之多核環氧化合物(a — 4 ) 4 7 3 份,置入配備攪拌裝置、冷卻管及溫度計之燒瓶,加入卡 必醇醋酸酯4 0 〇份加熱溶解,加入甲基氫醌0 · 4 6份 及三苯膦1 · 3 8份,於9 5至1 0 5 t加熱,緩慢滴入 丙烯酸1 2 7份,反應1 6小時。以下稱此反.應溶液爲b 一 4淸漆。 . 合成例1 2 經濟部智慧財產局員工消費合作社印製 將合成例6所得之多核環氧化合物(a — 6 ) 2 7 7 份,置入配備攪拌裝置、冷卻管及溫度計之燒瓶,加入卡 必醇醋酸酯2 3 3份加熱溶解,加入甲基氫醌〇 · 4 6份 及三苯膦1 · 3 8份,於9 5至1 0 5 °C加熱,緩慢滴入 丙烯酸7 2份,反應1 6小時。以下稱此反應溶液爲b — 6淸漆。 比較合成例1 將甲酚淸漆型環氧樹脂(Epiclon N — 6 9 5,大日 本油墨化學工業(股)製,環氧當量2 2 0克/當量) 5 2 7 .份,置入配備氣體導入管、攪拌裝置、.冷卻管及溫 度計之燒瓶,加入卡必醇醋酸酯3 0 0份加熱溶解,加入 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) _ 55 經濟部智慧財產局員工消費合作社印製 524813 A7 ------—B7_ 五、發明説明(53 ) 氫醌0 · 4 6份及二苯膦;[· 3 8份。將該混合物於9 5 至1 0 5。(:加熱,緩慢滴入丙烯酸丨7 3份,反應i 6小 時。以下稱此反應溶液爲b, — i 7淸漆。 比較合成例2 將甲酚淸漆型環氧樹脂(Epiclon N — 6 9 5,大曰 本油墨化學工業(股)製’環氧當量2 2 〇克/當量) 6 0 2份’置入配備氣體導入管、攪拌裝置、冷卻管及溫 度計之燒瓶,加入卡必醇醋酸酯3 〇 〇份加熱溶解,加入 氫醌0 . 4 6份及三苯膦1 · 3 8份。將該混合物於9 5 至1 0 5 °C加熱,緩慢滴入丙烯酸9 8份,反應1 6小時 。以下稱此反應溶液爲b ’〜2淸漆。 比較合成例3 將酚醛淸漆型環氧樹脂(E P P N — 2 0 1 ,日本油 化藥(股)製,環氧當量190克/當量)508份,置 入配備氣體導入管、攪拌裝置、冷卻管及溫度計之燒瓶, 加入卡必醇醋酸酯3 0 0份加熱溶解,加入氫醌0 · 4 6 份及三苯膦1 · 3 8份。將該混合物於9 5至1 0 5 t加 熱,緩慢滴入丙烯酸1 9 2份,反應1 6小時。以下稱此 反應溶液爲b 一 3淸漆。 比較合成例4 於配備氣體導入管、攪拌裝置、冷卻管及溫度計之燒 --------ΓΙΦ·^------、訂----- (請先閲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規格(210X297公釐) -56 - 524813 A7 ___ B7_ 五、發明説明(54 ) (請先閲讀背面之注意事項再填寫本頁) 瓶,加入雙酚A 3 1 3份及雙酚A型環氧樹脂(Epiclon 一 840,大日本油墨化學工業(股)製,環氧當量 180克/當量)987份,在氮氣中攪拌下於120 °C 溶解。其後,添加三苯膦〇 · 6 5份,將燒瓶內之溫度升 溫至1 5 0 °C,一面保持於1 5 0 C —^面反應約9 0分鐘 ,得環氧當量4 7 5克/當量之環氧化合物(g)。其次 將燒瓶內之溫度冷卻至7 0 °C以下’加入環氧氯丙烷 1 8 5 1份,二甲亞硕1 6 9 0份’攪拌下升溫至70^: 並保持。其後,分散於9 0分鐘添加9 6 %氫氧化鈉 1 1 0份。添加後再反應3小時。反應結束後,將過剩之 環氧氯丙烷及二甲亞硕之大半於12 0°C、50毫米汞柱 減壓蒸餾,將含副生鹽及二甲亞碩之反應產物溶解於甲基 異丁基甲酮作水洗。其後,從油層蒸餾回收甲基異丁基甲 酮,得環氧當量3 3 6克/當量之環氧化合物(h )。所 得之環氧化合物(h ),若從環氧當量計算,則一般式( 6)(其中X = Y)中醇式羥基2 · 00個中約0 · 9個 環氧化。因此,醇式羥基之環氧化率爲4 5 %。 經濟部智慧財產局員工消費合作社印製 其次,將環氧化合物(h ) 4 9 4份置入配備攬拌裝 置、冷卻管及溫度計之燒瓶,加入卡必醇醋酸酯4 0 0份 ,加熱溶解,加入甲基氫醌〇 · 4 6份及三苯膦1 · 3 8 份,於9 5至1 〇 5 °C加熱,緩慢滴入丙烯酸1 0 6份, 反應1 6小時。以下稱此反應溶液爲b ’ 一 4淸漆。 實施例8至1 3及比較例5至8 i紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐)-57 - 524813 A 7 B7 五、發明説明(55 ) 將表3所示之使用上述合成例8至1 3及比較合成例 1至4所得之各淸漆的配合成分,以三輥機混練,得光硬 化性及熱硬化性樹脂組成物。 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -58 - 524813 A7 B7 五、發明説明) 表3 組成 f :(質量份) 實a 剛 比較例 8 9 10 11 12 13 5 6 7 8 b-1 167 - b-2 • 167 - - - - - - b-3 - - 167 - - - - - - 樹 b-4 - - - 167 - - - - - - 脂 b-5 - - - - 167 '- - - - - 淸 b-6 - - - - - 167 - - - - 漆 b,-l - - - - 143 - - - b,-2 - - - - - - - 143 - - b,-3 - 143 - 1 b,-4 167 Irgacure-907 12 12 12 12 12 12 12 12 12 12 ITX 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 雙氰胺 - 1 - - - - - 1 - - KS-66 15 15 15 15 15 15 15 15 15 15 R-974 1 1 1 1 1 1 1 1 1 1 卡必醇醋酸酯 10 10 10 10 10 10 10 10 10 10 j 硫酸鋇 20 20 20 20 20 20 20 20 20 20 | 80 80 80 80 80 80 80 80 80 80 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 備 註Publication 97 2 X 49 524813 A7 B7 V. Description of the invention (47) (Please read the precautions on the back before filling out this page) Put the composition of each of the above examples and comparative examples at 80 ×: 30 minutes, then Hardened at 180 ° C for 1 hour, measured glass transition point, tensile strength, elongation, tensile elasticity, water absorption, electrical insulation, pencil hardness, and evaluated adhesion, acid resistance, and alkali resistance . The evaluation of each physical property was performed by the following method. < Glass transition temperature > The composition of each of the above Examples and Comparative Examples was screen-printed on a Teflon sheet washed and dried in advance, and dried in a hot air circulation drying oven at 80 ° C for 40 minutes. After cooling to room temperature, exposure was performed at an exposure amount of 50 mJ / cm², and it was hardened in a hot air circulation drying oven at 180 ° C for 60 minutes. After cooling to room temperature, the hardened coating film was peeled from the Teflon board to obtain an evaluation sample. The glass transition point of the sample was measured by the DM method. < Tensile strength (tensile failure strength), elongation (tensile failure elongation), and tensile modulus of elasticity > Calculated in accordance with JIS K 7172. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs < Water absorption, pencil hardness > Calculated based on Jis K 5400. < Adhesiveness > J I s D 0 2 0 2 was judged visually. The judging standards are as follows: ○ This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -50- 524813 A7 _______B7_ V. Description of the invention (48) 〇: No peeling visible A: Only slight peeling X: Complete Peeler (please read the precautions on the back before filling in this page) < Electrical insulation The composition of each of the above examples and comparative examples was applied to a comb electrode B test piece of IPCB-2 5 using Pilot Seiko (stock ) The roll coater was used for full coating, and it was cured at 80 ° C for 30 minutes, and then cured at 180 ° C for 1 hour to make an evaluation substrate. A bias voltage of DC 500 volts was applied. The comb electrode was used to measure the insulation resistance 値. ≪ Acid resistance test > The substrate for evaluation of the same electrical insulation property was taken out after immersing in a 10% by volume sulfuric acid aqueous solution at 20 ° C for 30 minutes, and the state and adhesion of the coating film were comprehensively judged. The judgment criteria are as follows. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 〇: No visible change △: Only slight changes X: Coating film swelled or swelled off < Alkali resistance test〉 Except 10% by volume sulfuric acid aqueous solution was replaced by 10 Except for the volume% sodium hydroxide aqueous solution, it was evaluated by the same acid resistance test. The results obtained are shown in Table 2. This paper size applies to China National Standard (CNS) A4 (210X297 mm) -51-524813 A7 B7 V. Description of invention (49) Comparative example printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs I 丨 172.4 1942.9 62.5 1_ 1 ir- ^ 〇cn CO 〇〇CO 165.1 1882.6 60.8 5.69 oo i 1 it-H < CO cn κ Csl <] 〇166.3 1907.5 61.6 5.66 〇 ^ 1 it-H 〇cn cn cn 〇〇 ... ..m, i 168.1 1936.5 3 5.64 1.05 〇K K 〇〇 Example 213.1 2340.5 70.2 5.32 r_H 〇E VO 〇〇VO 204.5 2320.3 69.4 fir-H un 0.66 〇CO K VO 〇〇un 190.5 1956.3 62.8 5.62 0.60 〇o K 〇〇inch 198.8 1961.8 63.2 5.58 0.58 〇p 〇〇CO 173.5 1892.4 61.6 5.71 0.73 〇w cn K 〇CN1 180.1 1924.2 62.3 5.64 0.66 〇E 〇〇τ—Η 189.4 1955.7 62.9 0.61 〇tc 〇〇 Transfer point (° 〇 Tensile elasticity (N / mm2) Tensile strength (N / mm2) Elongation (%) Water absorption (%) Adhesive electrical insulation resistance (X 10,3Ω) Pencil hardness Acid and alkali resistance Sex (Please read the note on the back first Please fill in this page again)-Binding and ordering 1 ^ This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) -52-524813 A7 B7 V. Description of the invention (50) (Please read the note on the back first Please fill in this page again from the results) From the results shown in Table 2, it can be seen that the hardened product of the multi-core epoxy compound of the present invention 'glass transition temperature board' has excellent mechanical strength, water absorption, adhesion, electrical insulation resistance, hardness, It also has excellent properties such as chemical resistance. On the other hand, the cured product of the aromatic epoxy compound obtained from the comparative example has a low glass transition point and poor water absorption and hardness. Synthesis Example 8 A gas introduction tube and a stirring device are provided. , A cooling tube and a flask of a thermometer, add 169 parts of 1,5-di-naphthylnaphthalene, and epoxy equivalent of 194 g / equivalent of 3,3 ', 5,5'-tetramethyl-1,4 1,130 copies of hydroxybiphenyl dipropylene oxide were printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs of the Ministry of Economic Affairs of the People's Republic of China, and dissolved in 120 t under stirring in nitrogen. Thereafter, 0.65 parts of triphenylphosphine was added, and the temperature in the flask was raised to 150 t: while maintaining the temperature at 150 ° C for about 90 minutes, the epoxy equivalent was 350 grams. / Equivalent epoxy compound (8). Next, the temperature in the flask was cooled to 70 ° C, and then, 8.0 parts of epichlorohydrin and 169 parts of dimethyl asus were added, and the temperature was raised to 70 ° C with stirring and maintained. Thereafter, it was dispersed in 90 minutes, and 180% of 96% sodium hydroxide was added. After the addition, it was reacted for another 3 hours. After the reaction was completed, the excess epichlorohydrin and dimethyl arsenic were distilled under reduced pressure at 120 ° C, 50 mm Hg, and the reaction product containing parasalt and dimethyl arsenic was dissolved in methyl isopropyl alcohol. Butyl ketone was washed with water. Thereafter, methyl isobutyl ketone was recovered by distillation from the oil layer to obtain an epoxy equivalent of 262 g / equivalent polynuclear epoxy compound (a-8). The obtained polynuclear epoxy compound (a-8), if calculated from the epoxy equivalent, then the alcoholic hydroxyl group in the general formula (7 a) 1.5 5 out of about 7 This paper size applies the Chinese National Standard (CNS) A4 specification ( 21〇 × 297 mm) ^ 53--524813 A7 ___B7_ 5. Description of the invention (51) .8 6 epoxidation. Therefore, the epoxidation rate of the alcoholic hydroxyl group is 55%. (Please read the precautions on the back before filling this page.) Secondly, put 1 part of the polynuclear epoxy compound (a-8) 4 7 into a flask equipped with a stirring device, a cooling tube and a thermometer, and add carbitol acetate 4 0 〇parts, heat to dissolve and add 0.46 parts of methylhydroquinone, and 1.38 parts of triphenylphosphine, heat at 95 to 105 ° C, slowly add 129 parts of acrylic acid, reaction 1 6 hours. Hereinafter, this reaction solution is referred to as b-1 lacquer. The infrared absorption spectrum of the polynuclear epoxy acrylate compound (b-1) obtained by this synthesis example (determined by FT-IR with a Fourier transform infrared spectrophotometer) and nuclear magnetic resonance spectrum (solvent c DC 1 3, reference substance TMS (four Methylsilane V is shown in Figures 3 and 4. Synthesis Example 9 5 2 8 parts of the polynuclear epoxy compound (a-8) obtained in Synthesis Example 8 were placed in a flask equipped with a stirring device, a cooling tube, and a thermometer. Add 400 parts of carbitol acetate and heat to dissolve, add 0.46 parts of methylhydroquinone and 1.8 parts of triphenylphosphine, heat at 95 to 105 ° C, slowly drip into the Ministry of Economic Affairs wisdom 72 copies of acrylic acid were printed by the consumer cooperative of the property bureau and reacted for 16 hours. This reaction solution is hereinafter referred to as b-2 lacquer. Synthesis Example 10 The polynuclear epoxy compound (a-3) 5 1 obtained in Synthesis Example 3 8 parts, put into a flask equipped with a stirring device, a cooling tube and a thermometer, add carbitol vinegar. Ethyl acetate 400 parts heat to dissolve, add methyl hydrogen to prepare 0.46 parts and triphenylphosphine 1. 3 8 parts , Heating at 95 to 105 ° C, slowly dripping into the paper standard applicable Chinese national standard (CN S) A4 size (210X297 mm) Γ54-'524813 A7 B7 V. Description of the invention (52) 8 parts of acrylic acid, reacted for 16 hours. This reaction solution is hereinafter referred to as b-3 lacquer. (Please read the back Please fill in this page again for preparation} Synthesis Example 1 1 Put 4 7 3 parts of the polynuclear epoxy compound (a-4) obtained in Synthesis Example 4 into a flask equipped with a stirring device, a cooling tube and a thermometer, and add carbitol acetate Dissolve 400 parts by heating, add 0.46 parts of methylhydroquinone and 1.8 parts of triphenylphosphine, heat at 95 to 105 t, slowly add 127 parts of acrylic acid, and react for 16 hours. The reaction solution is hereinafter referred to as b-4 lacquer. Synthetic Example 1 2 The consumer cooperative of the Intellectual Property Bureau of the Ministry of Economy printed 2 7 7 copies of the polynuclear epoxy compound (a-6) obtained in Synthetic Example 6, Put in a flask equipped with a stirring device, a cooling tube and a thermometer, add 233 parts of carbitol acetate and heat to dissolve, add 0.46 parts of methylhydroquinone and 1.8 parts of triphenylphosphine. Heat at 105 ° C, slowly add 72 parts of acrylic acid, and react for 16 hours. This reaction solution is hereinafter referred to as b-6 lacquer. Compared to Synthesis Example 1, 5 2 7. Parts of cresol lacquer-type epoxy resin (Epiclon N — 6 9 5 manufactured by Dainippon Ink Chemical Industry Co., Ltd., epoxy equivalent 2 220 g / equivalent) was placed in the equipment. Gas introduction tube, stirring device, cooling tube and thermometer flask, add 300 parts of carbitol acetate to heat and dissolve. Add this paper to the standard of China National Standard (CNS) A4 (210X297 mm) _ 55 Ministry of Economy Printed by the Intellectual Property Bureau's Consumer Cooperatives 524813 A7 -------- B7_ V. Description of the Invention (53) Hydroquinone 0 · 4 6 parts and diphenylphosphine; [· 3 8 parts. Mix the mixture between 9 5 and 105. (: Heat, slowly drip 3 parts of acrylic acid, and react for 6 hours. This reaction solution is hereinafter referred to as b, — i 7 lacquer. Comparative Synthesis Example 2 A cresol lacquer-type epoxy resin (Epiclon N — 6 9 5. "Epoxy equivalent of 220 g / equivalent" manufactured by Daikoku Ink Chemical Industry Co., Ltd. 602 parts' is placed in a flask equipped with a gas introduction tube, a stirring device, a cooling tube and a thermometer, and carbitol is added. 3,000 parts of acetate was dissolved by heating, 0.46 parts of hydroquinone and 1.38 parts of triphenylphosphine were added. The mixture was heated at 95 to 105 ° C, and 98 parts of acrylic acid was slowly added dropwise to the reaction. 16 hours. This reaction solution is hereinafter referred to as b '~ 2 lacquer. Comparative Synthesis Example 3 A phenolic lacquer-type epoxy resin (EPPN — 2 01), manufactured by Nippon Oil Chemical Co., Ltd., has an epoxy equivalent weight of 190 g. (Equivalent) 508 parts, put in a flask equipped with a gas introduction tube, a stirring device, a cooling tube and a thermometer, add 300 parts of carbitol acetate and heat to dissolve, add 0 · 4 6 parts of hydroquinone and 1 · triphenylphosphine 38 parts. The mixture was heated at 95 to 105 t, and 192 parts of acrylic acid was slowly added dropwise and reacted for 16 hours. This reaction solution is hereinafter referred to as b-3 lacquer. Comparative Synthesis Example 4 Burning with a gas introduction tube, a stirring device, a cooling tube, and a thermometer -------- ΓΙΦ · ^ ------, order ----- (Please read the notes on the back before filling this page) This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -56-524813 A7 ___ B7_ V. Description of the invention (54) ( Please read the notes on the back before filling this page) Bottle, add bisphenol A 3 1 3 parts and bisphenol A type epoxy resin (Epiclon 840, made by Dainippon Ink Chemical Industry Co., Ltd., epoxy equivalent 180 grams (Equivalent) 987 parts, dissolved under stirring at 120 ° C under nitrogen. Then, 65 parts of triphenylphosphine was added, and the temperature in the flask was raised to 150 ° C while maintaining the temperature at 150 ° C. The surface reaction takes about 90 minutes to obtain an epoxy equivalent of 475 g / equivalent epoxy compound (g). Next, the temperature in the flask is cooled to below 70 ° C. 'Epichlorohydrin is added 1 8 5 1 Parts, dimethyl asus 1690 parts' heated to 70 ^ with stirring: and kept. After that, disperse in 90 minutes and add 96% sodium hydroxide 110 parts. After adding After 3 hours of reaction, after the reaction, the excess of epichlorohydrin and dimethyl arsenic were distilled under reduced pressure at 120 ° C and 50 mm Hg to dissolve the reaction products containing byproduct salt and dimethyl arsenic. It was washed with methyl isobutyl ketone in water, and then methyl isobutyl ketone was recovered by distillation from the oil layer to obtain an epoxy equivalent of 3 36 g / equivalent epoxy compound (h). If the obtained epoxy compound (h) is calculated from the epoxy equivalent, about 0 · 9 of the alcoholic hydroxyl groups of 2 · 00 in the general formula (6) (where X = Y) are epoxidized. Therefore, the epoxidation rate of the alcoholic hydroxyl group is 45%. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The epoxy compound (h) 4 9 4 parts were placed in a flask equipped with a stirring device, a cooling tube and a thermometer. 400 parts of carbitol acetate was added, and dissolved by heating. Add 0.46 parts of methylhydroquinone and 1.38 parts of triphenylphosphine, heat at 95 to 105 ° C, slowly add 106 parts of acrylic acid, and react for 16 hours. This reaction solution is hereinafter referred to as b'-4 lacquer. Examples 8 to 13 and Comparative Examples 5 to 8 i The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -57-524813 A 7 B7 V. Description of the invention (55) Use as shown in Table 3 The compounding components of each of the varnishes obtained in the above Synthesis Examples 8 to 13 and Comparative Synthesis Examples 1 to 4 were kneaded with a three-roller to obtain a photocurable and thermosetting resin composition. (Please read the notes on the back before filling out this page) The paper size printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs applies to the Chinese National Standard (CNS) A4 (210X297 mm) -58-524813 A7 B7 V. Description of the invention ) Table 3 Composition f: (parts by mass) Actual a Just Comparative Example 8 9 10 11 12 13 5 6 7 8 b-1 167-b-2 • 167------b-3--167--- ---Tree b-4---167------Fat b-5----167 '-----淸 b-6-----167----Lacquer b,- l----143---b, -2-------143--b, -3-143-1 b, -4 167 Irgacure-907 12 12 12 12 12 12 12 12 12 12 ITX 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Dicyandiamine-1-----1--KS-66 15 15 15 15 15 15 15 15 15 15 R-974 1 1 1 1 1 1 1 1 1 1 card Betanol acetate 10 10 10 10 10 10 10 10 10 10 j Barium sulfate 20 20 20 20 20 20 20 20 20 20 20 | 80 80 80 80 80 80 80 80 80 80 (Please read the precautions on the back before filling this page ) Printed Notes for Employee Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs
Irgacure-907:2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉胺基丙酮-1 (汽巴特用化學品公司製光聚合啓始劑) ITX:異丙基硫蒽酮(日本化藥(股)製) DPHA:二季戊四醇六丙烯酸酯(日本化藥(股)製) KS-66:砂酮系消泡劑(信越化學工業(股)製) R-974:微粉氧化矽(日本AerosiK股)製) 羊紙張尺度適用中國國家標準(CNS ) A4規格< 210X297公釐)一:5 524813 A7 五、發明説明(57 ) 將上述各實施例及比較例之組成物於8 0 t乾燥3 〇 # ^ ’以曝光量5 0 〇毫焦耳/平方公分之條件曝光、硬 化’並於有關實施例9及比較例6曝光後,於1 5 〇。(:硬 化1小時,以上述同樣方法測定玻璃轉移點、拉伸彈性率 、拉伸強度、伸展率、吸水率、鉛筆硬度、電絕緣電阻, 並評估密合性、耐酸性、耐鹼性。評估結果示於表4。 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 本紙張尺度逍用中國國家標準(CNS ) A4規格(210X 297公釐)-60 - 524813 A7 B7 五、發明説明(58 ) 經濟部智慧財產局員工消費合作社印製 比較例 〇〇 120.4 2018.9 r—H oi \o r—H On 1 PC csi 〇 wn csi 〇 〇 1 »"·^ un CNl 1 ^ 2249.6 oo ON CN r — PC cn <] < 〇 \〇 134.3 2307.5 r- r < f "丨丨4 寸 <] 〇 ν/Ί t—H OO CN γ_··Η 2293.5 i i cs CN r—^ 寸 < S < 〇 實施例 cn r—Η 162.5 2349.5 CNj i i un ON 寸· o E 〇 r-H cn 〇 〇 CN| r—Η 160.7 2340.1 to o OO CTs 寸· CN E 〇 CN cn 〇 〇 \ ..... i ! m4 160.8 1 1998.8 CNl oo un un o E \o 〇 〇 〇 〇 150.5 1920.4 m cn uo m oo o 〇 VO CO 〇 〇 ON 167.2 2015.2 cn s 寸 T—t wo } i X 〇 ON CN 〇 〇 oo 155.4 1975.7 On S un oo X 〇 〇 〇 特性 an- 感a S P i 拉伸彈性率 (N/mm2) 拉伸強度 (N/mm2) 伸展率 (%) 吸水率 (%) 鉛筆硬度 密合性 電絕緣電阻 (X 10丨3Ω ) 耐酸性 耐鹼性 I-------------IT------0 (請先閲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規格(210X297公釐) -61 - 524813 A7 _B7_ 五、發明説明(59 ) (請先閲讀背面之注意事項再填寫本頁) 從表4所示之結果可知’得自本發明之多核環氧丙嫌 酸酯化合物之硬化物有高玻璃轉移點’機械強度優’並且 吸水率、密合性、電絕緣電阻、硬度、耐藥品性等優良之 特性。相對於此,得自比較例之芳族環氧丙烯酸酯化合物 之硬化物,其玻璃轉移點、吸水率、硬度等差。 合成例1 4 經濟部智慧財產局員工消費合作社印製 將合成例8所得之多核環氧化合物(a — 8 ) 3 4 1 份,置入配備攪拌裝置、冷卻管及溫度計之燒.瓶,加入卡 必醇醋酸酯.4 0 0份,反應溶解,加入甲基氫醌〇 · 4 6 份,及三苯膦1 · 3 8份,於9 5至1 0 5 °C加熱,緩慢 滴入丙烯酸9 4份,反應1 6小時。將該反應產物冷卻至 80至90 °C,加入四氫苯酐166份,反應8小時。反 應中以電位差滴定測定反應液之氧化、全氧化。以所得加 成率作追蹤,以及反應率9 5 %以上爲終點。如此而得之 含羧基活性能量線硬化性樹脂,固體物之酸値在1 〇 2毫 克K〇Η /克。以下稱此反應溶液爲A — 1淸漆。而本合 成例所得之含羧基活性能量線硬化性樹脂(A - 1 )之紅 外線吸收圖譜(用傅立葉紅外分光光度計F T - I R測定 )及核磁共振圖譜{溶劑C D C i 3,參考物質T M S (四 甲基矽烷)}各示於第5及第6圖。 合成例.1 5 於配備氣體導入管、攪拌裝置、冷卻管及溫度計之燒 本紙張尺度適用中國國家標準(CNS ) Α4規格{ 210X297公釐)-62 - 524813 A7 B7 五、發明説明(6〇 ) 瓶,加入1 ,5 -二羥基萘203份,及雙酚A型環氧樹 (請先閲讀背面之注意事項再填寫本頁) 脂(Epiclon — 840,大曰本油墨化學工業(股)製,環 氧當量180克/當量)1097份,在氮氣中攪拌下於 1 2 0 °C溶解。其後,添加三苯膦〇 . 6 5份,將燒瓶內 之溫度升溫至1 5 0°C,一面保持於1 5 0°C —面反應約 9 0分鐘,得環氧當量3 6 5克/當量之環氧化合物( 15)。其次,將燒瓶內之溫度冷卻至7 0 °C以下,加入 環氧氯丙烷2 0 5 8份,二甲亞硕1 6 9 0份,攪拌下升 溫至7 0 °C並保持。其後,分散於9 0分鐘添.加9 6 %氫 氧化鈉1 2 2份。添加後再反應3小時。反應結束後,將 過剩之環氧氯丙烷及二甲亞硕的大半於1 2 0 t、5 0毫 米汞柱減壓蒸餾,將含副生鹽及二甲亞硕之反應產物溶解 於甲基異丁基甲酮作水洗。其後,從油層蒸餾回收甲基異 丁基甲酮,得環氧當量2 7 5克/當量之多核環氧化合物 (a - 1 5 )。所得之多核環氧化合物(a — ί 5 ),若 從環氧當量計算,則上述一般式(7 b )中醇式羥基1 · 7 1個中約〇 · 8 2個環氧化。因此,醇式羥基之環氧化 率爲4 8 %。 經濟部智慧財產局員工消費合作社印製 其次,將多核環氧化合物(a — 1 5 ) 3 4 7份置入 配備攪拌裝置、冷卻管及溫度計之燒瓶’加入卡必醇醋酸 酯4 0 0份,加熱溶解’加入甲基氫醌〇 · 4 6份及三苯 膦1 · 3 8份,於9 5至1 0 5 °C加熱,緩慢滴入丙烯酸 9 1份.,反應1 6小時。將該反應產物冷卻到· 8 0至9 0 t:,加入四氫苯酐1 6 3份,反應8小時。反應中以電位 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐)~~- 63 - 524813 A7 B7 五、發明説明(61 ) (請先閱讀背面之注意事項再填寫本頁) 差滴定測定反應液之氧化、全氧化而以所得之加成率作追 蹤,以反應率9 5 %以上爲終點。如此而得之含殘基的活 性能量線硬化性樹脂’其固體物之酸値爲1 〇 〇毫克 K〇Η /克。以下稱此反應溶液爲A — 2淸漆。 合成例1 6 於配備氣體導入管、攪拌裝置、冷卻管及溫度計之燒 瓶,加入雙酚A 2 2 2份及環氧當量1 9 4克/當量之3 ,3 ,5.,5 ’ —四甲基一 4,4 ,—二羥基聯苯二環 氧丙醚1 0 7 8份,在氮氣中攪拌下於1 2 0°C溶解。其 後’添加三苯膦0 · 6 5份,將燒瓶內之溫度升溫至 1 5 0 °C,一面保持於1 5 0 °C —面反應約9 0分鐘,得 環氧當量3 6 0克/當量之環氧化合物(1 6 )。其次, 將燒瓶內之溫度冷卻至7 0 °C以下,加入環氧氯丙烷 1 8 77份,二甲亞硕1 6 9 0份,攪拌下升溫至70 t: 經濟部智慧財產局員工消費合作社印製 並保持。其後,分散於9 0分鐘添加9 6 %氫氧化鈉 1 1 1份。添加後再反應3小時。反應結束後,將過剩的 環氧氯丙烷及二甲亞碾之大半於12 0°C、50毫米汞柱 減壓蒸餾,將含副生鹽及二甲亞硕之反應產物溶解於甲基 異丁基甲酮作水洗。其後,從油層蒸餾回收甲基異丁基甲 酮,得環氧當量2 7 6克/當量之多核環氧化合物(a -16)。所得之多核環氧化合物(a-16),若從環氧 當量計算,則上述一般式(6 )中醇式羥基1 · 5 4個中 約0 · 7 7個環氧化。因此,醇式羥基之環氧化率爲5 0 本紙張尺度逍用中國國家標準(CNS ) A4規格(210X297公釐)-64 - 524813 A7 B7 五、發明説明(62 ) %。 (請先閲讀背面之注意事項再填寫本頁) 其次’將多核環氧化合物(a - 16) 349份,置 λ配備攪拌裝置、冷卻管及溫度計之燒瓶,加入卡必醇醋 酉变_ 4 0 0份’加熱溶解,加入甲基氫醌〇 · 4 6份及三 苯膦1 · 3 8份,於9 5至1 0 5 °C加熱,緩慢滴入丙烯 酸9 1份’反應1 6小時。將該反應產物冷卻到8 0至 9 0 °C,加入四氫苯酐1 5 9份,反應8小時。反應中以 電位差滴定測定反應液之氧化、全氧化而以所得之加成率 作追蹤,以反應率9 5 %以上爲終點。如此而.得之含羧基 的活性能量線硬化性樹脂,·其固體物之酸値爲9 8毫克 K〇Η /克。以下稱此反應溶液爲a 一 3淸漆。 合成例1 7 經濟部智慧財產局員工消費合作社印製 將合成例1 2所得之反應產物冷卻到8 0至0 t,加 入四氫苯酐1 3 0份,反應8小時。反應中以電位差滴定 測定反應液之氧化、全氧化,以所得之加成率作追蹤,以 反應率9 5 %以上爲終點。如此而得之含羧基之活性能量 線硬化性樹脂’其不揮發成份占6 7 %,固體物之酸値爲 1 0 2毫克Κ Ο Η /克。以下稱此反應溶液爲a — 4淸漆 合成例1 8 將合成例1 3所得之反應產物冷卻到8 0.至0 °C,加 入四氫苯酐1 3 0份,反應8小時。反應中以電位差滴定 本紙張尺度適用中國國家標準(CNS ) A4規格(21〇父297公着) 524813 A7 _— B7_ 五、發明説明(63 ) (請先閲讀背面之注意事項再填寫本頁) 測定反應液之氧化、全氧化,以所得之加成率作追蹤,以 反應率9 5 %以上爲終點。如此而得之含羧基活性能量線 硬化性樹脂,其不揮發成份占6 7 %,固體物之酸値爲1 〇3毫克KOH/克。以下稱此反應溶液爲a — 5淸漆。 比較合成例5 將甲酚淸漆型環氧樹脂(.Epiclon N — 6 9 5,大日 本油墨化學工業(股)製,環氧當量2 2 0克/當量) 3 3 0份,置入配備氣體導入管、攪拌裝置、冷卻管及溫 度計之燒瓶,加入卡必醇醋酸酯4 0 0份,加熱溶解,加 入氫醌0 · 4 6份及三苯膦1 · 3 8份。將該混合物於 9 5至1 0 5 °C加熱,緩慢滴入丙烯酸1 〇 8份,反應 1 6小時。將該反應產物冷卻到8 0至8 0 °C,加入四氫 苯酐1 6 3份,反應8小時。反應中以電位差滴定測定反 應液之氧化、全氧化,以所得之加成率作追蹤,以反應率 9 5 %以上爲終點。如此而得之含羧基感光性樹脂,其固 體物之酸値爲1 0 0毫克K〇Η /克。以下稱此反應溶液 爲Β - 1淸漆。 經濟部智慧財產局員工消費合作社印製 比較合成例Θ 將酚醛淸漆型環氧樹脂(Ε Ρ Ρ Ν — 2 0 1 ,日本化 藥(股)製,環氧當量190克/當量)322份’置入 配備氣體導入管、攪拌裝置、冷卻管及溫度計之燒瓶’加 入卡必醇醋酸酯4 0 0份,加熱溶解,加入氫醌〇 · 4 6 本紙張尺度適用中國國家標準(CNS ) Α4規格(210X297公釐) -66 - 524813 Α7 Β7 五、發明説明(64 ) (請先閲讀背面之注意事項再填寫本頁) 份’三苯膦1 . 3 8份。將該混合物於9 5至1 0 5 °C加 熱’緩慢滴入丙烯酸1 2 2份,反應1 6小時。將該反應 產物冷卻到8 0至8 0 °C,加入四氫苯酐1 5 6份,反應 8小時。反應中以電位差滴定測定反應液之氧化、全氧化 ’以所得之加成率作追蹤,以反應率9 5 %以上爲終點。 如此而得之含羧基的感光性樹脂,其固體物之酸値爲9 6 毫克K〇Η /克。以下稱此反應溶液爲B — 2淸漆。 比較合成例.7 經濟部智慧財產局員工消費合作社印製 將比較合成例4所得之多核環氧化合物(h ) 3 5 2 份’置入配備攪拌攪拌裝置、冷卻管及溫度計之燒瓶,加 入卡必醇醋酸酯4 0 0份,加熱溶解,加入甲基氫醌 〇 · 4 6份,三苯膦1 · 3 8份。於9 5至1 0 5 °C加熱 ’緩慢滴入丙烯酸7 5份,反應1 6小時。將該反應產物 冷卻到8 0至8 0 °C,加入四氫苯酐1 7 2份,反應8小 時。反應中以電位差滴定測定反應液之氧化、全氧化,以 所得之加成率作追蹤,以反應率9 5 %以上爲終點。如此 而得之含羧基感光性樹脂,其固體物之酸値爲1 〇 6毫克 K〇Η /克。以下稱此反應溶液爲B — 3淸漆。 實施例1 4至1 8及比較例9至1 1 將表5所示之使用上述合成例1 4至1 8及比較合成 例5至7所得之各淸漆的配合成分,以三輥機混練,得光 硬化性.·熱硬化性樹脂組成物。各組成物之特性値示於表 本紙張尺度適用中國國家標準(CNS ) Α4規格(210X297公釐) -67 - 524813 A7 B7 I五、發明説明(α) 經濟部智慧財產局員工消費合作社印製 表5 I 組成 (質量份) 實施例 比較例 14 15 16 17 18 9 10 11 A-l 167 - - - - - - - Α·2 - 167 - - - - - Α-3 - - 167 - - - - - 樹 Α-4 - - 149 - - - - 脂 Α-5 - - 讎 - 149 - - - 主 ί円 Β-1 - - - - - 167 - - 漆 Β-2 - - - - - - 167 - Β-3 _ - - - - - - 167 Irgacure-907 12 12 12 12 12 12 12 12 ί 1 ί ΙΤΧ 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 ! i - ί 雙氰胺 1 1 1 1 1 1 1 1 DPHA 15 15 15 15 15 15 15 15 KS-66 1 1 1 1 . 1 1 1 1 ΥΧ4000 36 35 34 35 36 35 34 37 R-974 10 10 10 10 10 10 10 10 卡必醇醋酸酯 20 20 20 20 20 20 20 20 硫酸鋇 80 80 80 80 80 80 80 80 備 i i註 ΥΧ4000:聯二甲酚型環氧樹脂 (日本環氧樹脂(股)製) (請先閲讀背面之注意事項再填寫本頁) A \—/ S N C //V 準 標 家 國 國 中 用 適 I度 尺 張 紙 • r^丨 ξ I釐 公 7 9 2 X ο /b - 524813Irgacure-907: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinaminoacetone-1 (Photopolymerization initiator from Cibat Chemical Co., Ltd.) ITX: isopropyl Thioanthrone (manufactured by Nippon Kayaku Co., Ltd.) DPHA: dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) KS-66: a ketone defoamer (by Shin-Etsu Chemical Co., Ltd.) 974: Micronized silicon oxide (manufactured by Japan AerosiK shares) The size of the sheep paper is applicable to the Chinese National Standard (CNS) A4 specifications < 210X297 mm) 1: 5 524813 A7 5. Description of the invention (57) The above examples and comparative examples The composition was dried at 80 t for 30 ° ^ 'exposed and hardened at an exposure amount of 500 millijoules per square centimeter', and after exposure to Example 9 and Comparative Example 6, it was at 150 °. (: Hardened for 1 hour. The glass transition point, tensile elasticity, tensile strength, elongation, water absorption, pencil hardness, electrical insulation resistance were measured in the same manner as described above, and adhesion, acid resistance, and alkali resistance were evaluated. The evaluation results are shown in Table 4. (Please read the precautions on the back before filling out this page) Printed by the Intellectual Property Bureau Staff Consumer Cooperative of the Ministry of Economic Affairs This paper is scaled to the Chinese National Standard (CNS) A4 (210X 297 mm)- 60-524813 A7 B7 V. Description of the invention (58) Comparative example printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 〇〇120.4 2018.9 r—H oi \ or—H On 1 PC csi 〇wn csi 〇〇1 »" · ^ un CNl 1 ^ 2249.6 oo ON CN r — PC cn <] < 〇 \ 〇134.3 2307.5 r- r < f " 丨 丨 4 inch <] 〇ν / Ί t—H OO CN γ_ ·· Η 2293.5 ii cs CN r- ^ inch < S < 〇 Example cn r-Η 162.5 2349.5 CNj ii un ON inch · o E 〇rH cn 〇〇CN | r-Η 160.7 2340.1 to o OO CTs inch · CN E 〇CN cn 〇〇 \ ..... i! M4 160.8 1 1998.8 CNl oo un un o E \ o 〇〇〇 150.5 1920.4 m cn uo m oo o 〇VO CO 〇〇ON 167.2 2015.2 cn s inch T—t wo} i X 〇ON CN 〇〇oo 155.4 1975.7 On S un oo X 〇〇〇Characteristic an-a SP i Pull Elongation (N / mm2) Tensile strength (N / mm2) Elongation (%) Water absorption (%) Pencil hardness Adhesive electrical insulation resistance (X 10 丨 3Ω) Acid and alkali resistance I ---- --------- IT ------ 0 (Please read the precautions on the back before filling out this page) This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) -61- 524813 A7 _B7_ V. Description of the invention (59) (Please read the notes on the back before filling this page) From the results shown in Table 4, it can be seen that the hardened product of the polynuclear epoxy propionate compound obtained from the present invention has a high The glass transition point is 'excellent in mechanical strength' and has excellent properties such as water absorption, adhesion, electrical insulation resistance, hardness, and chemical resistance. On the other hand, the hardened | cured material of the aromatic epoxy acrylate compound obtained from the comparative example has inferior glass transition point, water absorption, hardness, etc. Synthetic Example 1 4 The consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed the 3 4 1 parts of the polynuclear epoxy compound (a-8) obtained in Synthetic Example 8 and put it in a bottle equipped with a stirring device, a cooling pipe and a thermometer. Add 400 parts of carbitol acetate, dissolved in the reaction, added 0.46 parts of methylhydroquinone, and 1.8 parts of triphenylphosphine, heated at 95 to 105 ° C, slowly dripped acrylic acid 9 4 parts, reaction for 16 hours. The reaction product was cooled to 80 to 90 ° C, 166 parts of tetrahydrophthalic anhydride was added, and the reaction was performed for 8 hours. During the reaction, the oxidation and total oxidation of the reaction solution were measured by potentiometric titration. The obtained addition rate was used for tracking, and the response rate was above 95% as the end point. In this way, a carboxyl group-containing active energy ray-curable resin was obtained, and the acid content of the solid matter was 102 mg / kg. This reaction solution is hereinafter referred to as A-1 lacquer. The infrared absorption spectrum of the carboxyl group-containing active energy ray-curable resin (A-1) obtained in this synthesis example (measured by Fourier infrared spectrophotometer FT-IR) and the nuclear magnetic resonance spectrum {solvent CDC i 3, reference substance TMS (4 Methylsilane)} are shown in Figures 5 and 6, respectively. Synthetic example. 1 5 For the paper size of this paper equipped with gas introduction tube, stirring device, cooling tube and thermometer, the Chinese National Standard (CNS) A4 specification {210X297 mm) -62-524813 A7 B7 V. Description of the invention (6〇 ) Bottle, add 203 parts of 1,5-dihydroxynaphthalene and bisphenol A epoxy resin (please read the precautions on the back before filling this page) grease (Epiclon — 840, Daiyoshi Ink Chemical Industry Co., Ltd.) System, epoxy equivalent 180 g / equivalent) 1097 parts, dissolved at 120 ° C under stirring in nitrogen. Thereafter, 0.65 parts of triphenylphosphine was added, the temperature in the flask was raised to 150 ° C, and the temperature was kept at 150 ° C while the surface was reacted for about 90 minutes to obtain an epoxy equivalent of 3 65 grams. / Equivalent of epoxy compound (15). Next, the temperature in the flask was cooled to below 70 ° C, and 2058 parts of epichlorohydrin and 169 parts of dimethyl asus were added, and the temperature was raised to 70 ° C with stirring and maintained. Thereafter, it was dispersed over 90 minutes, and 96% sodium hydroxide was added in 12 parts. After the addition, it was reacted for another 3 hours. After the reaction was completed, the excess epichlorohydrin and dimethyl arsenic were distilled under reduced pressure at 120 t, 50 mm Hg, and the reaction product containing parasalt and dimethyl arsenic was dissolved in methyl. Isobutyl ketone was washed with water. Thereafter, methyl isobutyl ketone was recovered by distillation from the oil layer to obtain an epoxy equivalent of 275 g / equivalent polynuclear epoxy compound (a-1 5). If the obtained polynuclear epoxy compound (a-5) is calculated from the epoxy equivalent, about 0.82 of the alcoholic hydroxyl groups of 1.71 in the general formula (7b) are epoxidized. Therefore, the epoxidation rate of the alcoholic hydroxyl group is 48%. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Secondly, put 3 4 7 parts of the polynuclear epoxy compound (a-15) into a flask equipped with a stirring device, a cooling tube and a thermometer. Add carbitol acetate 4.0 parts , Heat to dissolve. Add 0.46 parts of methylhydroquinone and 1.8 parts of triphenylphosphine, heat at 95 to 105 ° C, slowly add 91 parts of acrylic acid, and react for 16 hours. The reaction product was cooled to 80 to 90 t: 163 parts of tetrahydrophthalic anhydride was added and reacted for 8 hours. In the reaction, the paper size applies the Chinese national standard (CNS) A4 specification (210X297 mm) ~~-63-524813 A7 B7 V. Description of the invention (61) (Please read the precautions on the back before filling this page) Poor The oxidation and total oxidation of the reaction solution were determined by titration, and the obtained addition rate was used for tracking. The reaction rate was 95.5% or higher as the end point. The thus obtained residue-containing active energy line curable resin 'has a acid content of 1,000 mg of KOH / g. This reaction solution is hereinafter referred to as A-2 lacquer. Synthesis Example 16 In a flask equipped with a gas introduction pipe, a stirring device, a cooling pipe, and a thermometer, bisphenol A 2 2 parts and epoxy equivalent 194 g / equivalent 3,3,5,5'-4 were added. 1,078 parts of methyl 4,4, -dihydroxydiphenyl dipropylene oxide were dissolved at 120 ° C under stirring in nitrogen. After that, 0.65 parts of triphenylphosphine was added, and the temperature in the flask was raised to 150 ° C, while the temperature was maintained at 150 ° C. The reaction was carried out for about 90 minutes, and epoxy equivalent of 360 grams was obtained. / Equivalent epoxy compound (1 6). Next, cool the temperature in the flask to below 70 ° C, add 187 parts of epichlorohydrin and 690 parts of dimethyl arso, and heat up to 70 t under stirring: Employees' Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs Print and keep. Thereafter, it was dispersed in 90 minutes, and 96% sodium hydroxide was added in 11 parts. After the addition, it was reacted for another 3 hours. After the reaction, the excess of epichlorohydrin and dimethyl arylene were distilled under reduced pressure at 120 ° C and 50 mm Hg to dissolve the reaction product containing by-product salt and dimethyl arsenic in methyl isopropyl. Butyl ketone was washed with water. Thereafter, methyl isobutyl ketone was recovered by distillation from the oil layer to obtain an epoxy equivalent of 276 g / equivalent polynuclear epoxy compound (a-16). If the obtained polynuclear epoxy compound (a-16) is calculated from the epoxy equivalent, about 0.77 of the alcoholic hydroxyl groups of 1.5 to 4 in the general formula (6) are epoxidized. Therefore, the epoxidation rate of alcoholic hydroxyl groups is 50. This paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm)-64-524813 A7 B7. 5. Description of the invention (62)%. (Please read the precautions on the back before filling this page.) Next, 349 parts of the polynuclear epoxy compound (a-16) are placed in a flask equipped with a stirring device, a cooling tube and a thermometer, and carbitol vinegar is added. 4 0 0 parts' heat to dissolve, add 0.46 parts of methylhydroquinone and 1.8 parts of triphenylphosphine, heat at 95 to 105 ° C, slowly add 9 1 parts of acrylic acid, and react for 16 hours . The reaction product was cooled to 80 to 90 ° C, 159 parts of tetrahydrophthalic anhydride was added, and the reaction was performed for 8 hours. During the reaction, potentiometric titration was used to measure the oxidation and total oxidation of the reaction solution, followed by the addition rate obtained, and the end point was a reaction rate of 95% or more. In this way, the obtained active energy ray-curable resin containing a carboxyl group has a solid acidity of 98 mg / kg / g. This reaction solution is hereinafter referred to as a 3 lacquer. Synthetic Example 17 Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs The reaction product obtained in Synthetic Example 12 was cooled to 80 to 0 t, and 130 parts of tetrahydrophthalic anhydride was added for 8 hours. During the reaction, potentiometric titration was used to measure the oxidation and total oxidation of the reaction solution, followed by the addition rate obtained, and the end point was a reaction rate of 95% or more. The carboxyl group-containing active energy linear hardening resin 'thus obtained had a non-volatile content of 67%, and the acid hydration of the solid matter was 102 mg K0Η / g. This reaction solution is hereinafter referred to as a-4 lacquer. Synthesis Example 1 8 The reaction product obtained in Synthesis Example 13 was cooled to 80 ° to 0 ° C, 130 parts of tetrahydrophthalic anhydride was added, and the reaction was performed for 8 hours. Potentiometric titration during the reaction. The paper size applies the Chinese National Standard (CNS) A4 specification (21 ° parent 297) 524813 A7 _ — B7_ V. Description of the invention (63) (Please read the precautions on the back before filling this page) The oxidation and total oxidation of the reaction solution were measured, followed by the addition rate obtained, and the end point was a reaction rate of 95% or more. The carboxyl group-containing active energy ray-curable resin thus obtained had a non-volatile content of 67%, and the acid content of the solid matter was 103 mg KOH / g. This reaction solution is hereinafter referred to as a-5 lacquer. Comparative Synthesis Example 5 A cresol lacquer-type epoxy resin (.Epiclon N — 6 95, manufactured by Dainippon Ink Chemical Industry Co., Ltd., epoxy equivalent 2 220 g / equivalent) 3 3 0 parts was placed in the equipment Add 400 parts of carbitol acetate to the gas introduction tube, stirring device, cooling tube and thermometer flask, heat to dissolve, add 0.46 parts of hydroquinone and 1.8 parts of triphenylphosphine. The mixture was heated at 95 to 105 ° C, 108 parts of acrylic acid was slowly added dropwise, and reacted for 16 hours. The reaction product was cooled to 80 to 80 ° C, 163 parts of tetrahydrophthalic anhydride was added, and reacted for 8 hours. During the reaction, the oxidation and total oxidation of the reaction solution were measured by potentiometric titration, followed by the addition rate obtained, and the end point was a reaction rate of 95% or more. The carboxyl group-containing photosensitive resin thus obtained had a solid acid acidity of 100 mg Kom / g. This reaction solution is hereinafter referred to as Beta-1 lacquer. A comparative synthesis example printed by the Employees ’Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 'Place in a flask equipped with a gas introduction tube, stirring device, cooling tube, and thermometer' Add 400 parts of carbitol acetate, heat to dissolve, add hydroquinone. 0.46 This paper applies Chinese National Standard (CNS) Α4 Specifications (210X297 mm) -66-524813 Α7 Β7 V. Description of the invention (64) (Please read the precautions on the back before filling this page). This mixture was heated at 95 to 105 ° C and slowly added 122 parts of acrylic acid, and reacted for 16 hours. The reaction product was cooled to 80 to 80 ° C, 156 parts of tetrahydrophthalic anhydride was added, and the reaction was performed for 8 hours. During the reaction, the oxidation and peroxidation of the reaction solution were measured by potentiometric titration, followed by the addition rate obtained, and the end point was a reaction rate of 95% or more. The carboxyl group-containing photosensitive resin thus obtained had a solid acid acidity of 96 mg K0Η / g. This reaction solution is hereinafter referred to as B-2 lacquer. Comparative Synthesis Example. 7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. The polynuclear epoxy compound (h) 3 5 2 parts obtained in Comparative Synthesis Example 4 were placed in a flask equipped with a stirring device, a cooling tube and a thermometer, and the card was added. 400 parts of acetol acetate were dissolved by heating, 0.46 parts of methylhydroquinone, and 1.8 parts of triphenylphosphine were added. Heat at 95 to 105 ° C and slowly add 75 parts of acrylic acid, and react for 16 hours. The reaction product was cooled to 80 to 80 ° C, 172 parts of tetrahydrophthalic anhydride was added, and the reaction was performed for 8 hours. During the reaction, potentiometric titration was used to measure the oxidation and total oxidation of the reaction solution, and the resulting addition rate was used for tracking. The reaction rate was 95% or more as the end point. The carboxyl group-containing photosensitive resin thus obtained had a solid acid acidity of 106 mg KO / g. This reaction solution is hereinafter referred to as B-3 lacquer. Example 1 4 to 18 and Comparative Examples 9 to 1 1 The compounding components of each lacquer obtained in Table 5 using the above Synthesis Examples 14 to 18 and Comparative Synthesis Examples 5 to 7 were kneaded with a three-roller machine. , To obtain photo-hardenable. · Thermosetting resin composition. The characteristics of each composition are shown in the paper. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -67-524813 A7 B7 I V. Description of the invention (α) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Table 5 I Composition (parts by mass) Example Comparative Example 14 15 16 17 18 9 10 11 Al 167-------Α · 2-167-----Α-3--167----- Tree Α-4--149----Zhi Α-5--雠-149---Lord ί 円 Β-1-----167--Lacquer Β-2------167-Β -3 _-------167 Irgacure-907 12 12 12 12 12 12 12 12 12 ί 1 ί ΙΤχ 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5! I-ί dicyandiamide 1 1 1 1 1 1 1 1 DPHA 15 15 15 15 15 15 15 15 KS-66 1 1 1 1. 1 1 1 1 40004000 4000 36 35 34 35 36 35 34 37 R-974 10 10 10 10 10 10 10 10 Carbitol acetate 20 20 20 20 20 20 20 20 Barium sulfate 80 80 80 80 80 80 80 80 Remark Υ4000: Bixylenol epoxy resin (made by Japan Epoxy Resin (stock)) (Please read the precautions on the back before filling this page) A \ — / SNC // V Standard home country Suitable sheets of paper I graduated scale • r ^ I [xi] Shu PCT well 7 9 2 X ο / b - 524813
7 B 經濟部智慧財產局員工消費合作社印製 五、發明説明(66 ) 表6 特性 實施例 比較例 14 15 16 17 18 9 10 11 顯影性 40分鐘乾燥 〇 〇 〇 〇 〇 〇 〇 〇 50分鐘乾燥 〇 〇 〇 〇 〇 〇 〇 〇 60分鐘乾燥 〇 〇 〇 〇. 〇 〇 〇 Δ 70分鐘乾燥 〇_ 〇 〇 〇 〇 Δ Δ X 玻璃轉移點 165.4 157.2 150.5 161.2 167.3 150.7 150.5 125.6 (°C) 拉伸彈性率 2475.7 2415.2 2390.4 2432.7 2464.1 2891.3 2820.5 2451.8 ;(N/mm2) 拉伸強度 63.9 64.3 68.6 68.9 70.5 48.3 49.1 64.1 (N/mm2) 伸展率 4.90 5.04 5.76 6.17 5.93 2.75 3.10 5.11 (%) 吸水率 0.71 0.78 0.83 0.78 0.80 1.32 1.35 1.47 (%) 鉛筆硬度 6H 6H 5H 6H 6H 6H 6H 2H 密合性 〇 〇 〇 〇 〇 X X 〇 電絕緣電阻 3.6 3.4 3.5 3.5 3.3 2.1 1.9 0.8 (X 101?Ω ) i 耐酸性 〇 〇 〇 〇 〇 Δ Δ 〇 耐鹼性 〇 〇 〇 〇 〇 〇 〇 〇 耐PCT性 〇 〇 〇 〇 〇 X X Δ (請先閲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規格(210X297公釐) -69 - 經濟部智慧財產局員工消費合作社印製 524813 A7 __B7 五、發明説明(67 ) 而上述表6中之性能試驗方法如下。 <顯影性> : 將上述各實施例及比較例之組成物,於形成有圖樣之 銅箔基板上以網版印刷全面塗布,於8 〇 t以4 〇 50 、6 0或7 0分鐘乾燥,放冷至室溫後,以3 〇 c之丄% 碳酸鈉水溶液,噴霧壓力2公斤/平方公分作6 〇秒顯影 ’以目視確認乾燥塗膜之有無顯影殘餘。判定標準如下。 〇:完全顯影。 △:部份塗膜殘留。 X :塗膜完全保留。 <玻璃轉移點> : 於預先水洗•乾燥之鐵氟龍板,將上述各實施例及比 較例之組成物,以網版印刷法塗布,於熱風循環式乾燥爐 以8 0 °C乾燥4 0分鐘。將之冷卻至室溫後,以曝光量 5 0 〇毫焦耳/平方公分之條件曝光,於熱風循環式乾燥 爐以1 5 0 °C硬化6 0分鐘。將之冷卻至室溫後,從鐵氟 龍板剝下硬化塗膜,得評估樣本。以;D Μ A法測定該評估 樣本之玻璃轉移點。 <拉伸彈性率、.拉伸強度(拉伸破壞強度)、伸展率(拉 伸破壞伸展)> 以拉伸一壓縮試驗機(島津製作所股份有限公司製) 本紙張尺度適用中國國家樣準(CNS ) A規210X297公瘦)-70 - ----·---------IT------ (請先閲讀背面之注意事項再填寫本頁) 524813 A7 ___ _B7 ___ 五、發明説明(68 ) 測定上述評估樣本之拉伸彈性率、拉伸強度(拉伸破壞強 度)、伸展率(拉伸破壞伸展)。 (請先閲讀背面之注意事項再填寫本頁) <吸水率> : 於預先測定質量之玻璃板,將上述各實施例及比較例 之組成物以網版印刷塗布,於熱風循環式乾燥爐以8 0 °C 乾燥4 0分鐘。冷卻至室溫後,以曝光量5 0 0毫焦耳/ 平方公分之條件曝光,於熱風循環式乾燥爐以1 5 0 °C硬 化6 0分鐘’得評估樣本。將之冷卻至室溫後.測定i平估樣 本之質量。其次,用P CT裝置(TABAI ESPEC HAST SYSTEM T.PC-412MD )將該評估樣本於 1 2 1 °C、 1 0 0 R . Η .處理2 4小時,測定處理後的硬化物之質量, 以下述計算式求出硬化物之吸水率。 吸水率=(W2 — W1)/(W1— Wg) 其中,W 1係評估樣本之質量,W 2爲P C T處理後 的評估樣本之質量,W g爲玻璃板之質量。 <鉛筆硬度 > :依J I S K 5 4 0 0求出。 經濟部智慧財產局員工消費合作社印製 <密合性> ··依〗I S D 0 2 0以目視判定。判定標 準如下。 〇:全無剝離可見者 △:僅只輕微剝落者 X :完全剝落者 紙張尺中國國家標準(CNS ) A4規格(210 x297公釐)^71 - 524813 A7 _ B7 五、發明説明(69 ) 〈電絕緣性> : (請先閲讀背面之注意事項再填寫本頁) 於I PC B_2 5之梳型電極B試片將上述各實施 例及比較例之組成物用Pilot精工(股)製輥塗機全面塗布 ’於熱風循環式乾燥爐以8 0 °C乾燥4 0分鐘,冷卻至室 溫後,以曝光量5 〇 〇毫焦耳/平方公分之條件曝光,於 熱風循環式乾燥爐以1 5 0 硬化6 0分鐘,得評估樣本 。於該梳型電極施加D C 5 0 0伏特之偏壓,測定絕緣電 阻値。 <耐酸性試驗> 將電絕緣性用同樣之評估基板於1 0容量%硫酸水溶 液在2 〇 °C浸泡3 0分鐘後取出,作塗膜之狀態及密合性 之綜合判定評估。判定標準如下。 〇:無可見變化者 △:僅只輕微變化者 X :塗膜有脹起或膨潤脫落者 經濟部智慧財產局員工消費合作社印製 〈耐驗性試驗 > :除將1 0容量%硫酸水溶液換爲1 0容 量%氫氧化鈉水溶液以外,與耐酸性試驗同樣試驗評估。 <耐P C Τ性> : 於印刷電路板將上述各實施例及比較例之組成物,以 網版印刷法塗布,於熱風循環式乾燥爐以8 〇 °C乾燥4 0 本紙張尺度適用中國國家標準(CNS ) A4規格(21〇χ297公釐)-72 - 524813 A7 B7 五、發明説明(70) (請先閲讀背面之注意事項再填寫本頁)7 B Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (66) Table 6 Characteristic Examples Comparative Examples 14 15 16 17 18 9 10 11 Developing 40 minutes drying 50,000 50,000 drying 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇 △ △ X Glass transition point 165.4 157.2 150.5 161.2 167.3 150.7 150.5 125.6 (° C) Tensile elasticity Rate 2475.7 2415.2 2390.4 2432.7 2464.1 2891.3 2820.5 2451.8; (N / mm2) Tensile strength 63.9 64.3 68.6 68.9 70.5 48.3 49.1 64.1 (N / mm2) Elongation 4.90 5.04 5.76 6.17 5.93 2.75 3.10 5.11 (%) Water absorption 0.71 0.78 0.83 0.78 0.80 1.32 1.35 1.47 (%) Pencil hardness 6H 6H 5H 6H 6H 6H 6H 2H Adhesiveness 〇〇〇〇XX 〇 Electrical insulation resistance 3.6 3.4 3.5 3.5 3.3 2.1 1.9 0.8 (X 101? Ω) i Acid resistance 〇〇〇 〇〇Δ Δ 〇 Alkali resistance 0.0000000 〇 PCT resistance 〇〇〇〇〇XX Δ (Please first Read the notes on the back and fill in this page again) This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) -69-Printed by the Intellectual Property Bureau Employee Consumer Cooperative of the Ministry of Economic Affairs 524813 A7 __B7 V. Description of Invention (67) The performance test method in Table 6 is as follows. < Developability >: The composition of each of the above Examples and Comparative Examples was fully coated by screen printing on a copper foil substrate on which a pattern was formed, and the coating was applied at 80 t at 4050, 60 or 70 minutes. After drying and cooling to room temperature, the solution was developed in 30% 丄% sodium carbonate aqueous solution at a spray pressure of 2 kg / cm 2 for 60 seconds to visually confirm the presence or absence of development residue in the dried coating film. The judgment criteria are as follows. ○: Completely developed. △: Part of the coating film remains. X: The coating film is completely retained. < Glass transfer point >: The composition of each of the above Examples and Comparative Examples was coated on a Teflon board washed and dried in advance by screen printing, and dried in a hot air circulation drying oven at 80 ° C. 40 minutes. After it was cooled to room temperature, it was exposed at an exposure amount of 500 millijoules per square centimeter, and hardened in a hot-air circulation drying furnace at 150 ° C for 60 minutes. After it was cooled to room temperature, the hardened coating film was peeled from the Teflon board to obtain an evaluation sample. The glass transition point of the evaluation sample was determined by the DM method. < Tensile elasticity, tensile strength (tensile failure strength), elongation (tensile failure strength) > A tensile-compressive tester (manufactured by Shimadzu Corporation). (CNS) A Regulation 210X297 Male Thin) -70----- · --------- IT ------ (Please read the precautions on the back before filling this page) 524813 A7 ___ _B7 ___ V. Description of the invention (68) Determine the tensile elastic modulus, tensile strength (tensile failure strength), and elongation (tensile failure extension) of the above evaluation samples. (Please read the precautions on the back before filling in this page) < Water absorption >: The composition of each of the above Examples and Comparative Examples was screen-printed on a glass plate whose quality was measured in advance, and dried in a hot air cycle The oven was dried at 80 ° C for 40 minutes. After cooling to room temperature, exposure was performed at an exposure amount of 500 mJ / cm², and the specimen was hardened at 150 ° C for 60 minutes in a hot air circulation drying oven to obtain an evaluation sample. After cooling to room temperature, determine the mass of the sample. Next, a P CT device (TABAI ESPEC HAST SYSTEM T. PC-412MD) was used to evaluate the sample at 121 ° C, 100 R. Η. After processing for 24 hours, the mass of the hardened material after processing was measured. Determine the water absorption of the hardened material using the following calculation formula. Water absorption rate = (W2 — W1) / (W1 — Wg) Among them, W 1 is the quality of the evaluation sample, W 2 is the quality of the evaluation sample after PCT treatment, and W g is the quality of the glass plate. < Pencil hardness >: Calculated based on J I S K 5 4 0 0. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs < Adhesiveness > ·· Visually judge according to I S D 0 2 0. The judgment criteria are as follows. 〇: No peeling visible △: Only slight peeling X: Fully peeling paper rule Chinese national standard (CNS) A4 specification (210 x 297 mm) ^ 71-524813 A7 _ B7 V. Description of the invention (69) Insulation >: (Please read the precautions on the back before filling out this page) On the comb electrode B test piece of I PC B_2 5 The composition of each of the above examples and comparative examples was coated with a roller made by Pilot Seiko Co., Ltd. The machine is fully coated in a hot air circulation drying oven at 80 ° C for 40 minutes. After cooling to room temperature, it is exposed at an exposure of 5000 mJ / cm2. The hot air circulation drying oven is exposed at 1 5 0 Harden for 60 minutes, the sample must be evaluated. A DC bias voltage of 500 C was applied to the comb electrode, and the insulation resistance 値 was measured. < Acid resistance test > The substrate with the same evaluation for electrical insulation was immersed in a 10% by volume sulfuric acid aqueous solution at 20 ° C for 30 minutes, and was taken out for comprehensive evaluation of the state of the coating film and adhesion. The judgment criteria are as follows. 〇: No visible change. △: Only slight changes. X: Those with swelling or swelling of the coating. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Except for a 10% by volume sodium hydroxide aqueous solution, the test was evaluated in the same manner as in the acid resistance test. < PC T resistance >: The composition of each of the above Examples and Comparative Examples was coated on a printed circuit board by screen printing, and dried in a hot air circulation drying oven at 80 ° C for 40 °. China National Standard (CNS) A4 Specification (21 × 297 mm) -72-524813 A7 B7 V. Invention Description (70) (Please read the precautions on the back before filling this page)
分鐘。冷卻至室溫後,以曝光量5 0 0毫焦耳/平方公分 之條件曝光,於熱風循環式乾燥爐以1 5 0 °C硬化6 0分 鐘’得評估樣本。冷卻至室溫後,用P C T裝置(TABAI ESPEC HAST SYSTEM TPC-412MD )於 1 2 1 t:、2 氣壓之 條件下處理1 6 8小時,評估硬化皮膜之狀態。判定標準 如下。 〇:無剝落、變色或溶出。 △:有剝落、變色或溶出之任一。 X :多有剝落、變色、溶出。 由表6所示結果可知,得自本發明之光硬化性•熱硬 化性樹脂組成物的硬化物有高玻璃轉移點,機械強度優, 具吸水率、密合性、電絕緣電阻、硬度、耐藥品性、耐 P C T性等亦優之特性。相對於此,得自比較例之芳族環 氧丙烯酸酯化合物的硬化物,其玻璃轉移點、吸水率、硬 度、耐P C T性等差。 發明之效果 經濟部智慧財產局員工消費合作社印製 本發明之多核環氧化合物可熱硬化,並且,本發明之 多核環氧丙烯酸酯化合物,可用活性能量線照射而硬化或 熱硬化亦可,這些硬化物具均衡之高度耐熱性及靭度,對 基材之密合性優,同時耐水性、耐藥品性、電絕緣性等優 良之故,可有利地使用於各種阻劑、粘著劑、注模劑、層 合材、塗料、封裝劑等用途,更可適用作本發.明的活性能 量線硬化性樹脂之出發原料。 本紙張尺度適用中國國家標準(CNS ) A4規格< 210X297公釐)-73 - 524813 A7 B7 五、發明説明(71 ) 又,含有本發明之活性能量線硬化性樹脂作爲光硬化 性成分之本發明的光硬化性•熱硬化性樹脂組成物,可得 光硬化性、鹼顯影性及對基材之密合性優,同時,耐熱性 、耐水性、耐無電解電鍍性、耐藥品性、電絕緣性、可撓 性、耐P C T性等優之硬化物之故,除上述用途外,可極 有利地使用於印刷電路板之焊料阻劑,多層印刷電路板之 層間絕緣層等。 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準(CNS ) A4規格{ 210 X 297公釐)-74 -minute. After cooling to room temperature, exposure was performed at an exposure amount of 500 mJ / cm², and the specimen was hardened at 150 ° C for 60 minutes' in a hot air circulation drying oven to obtain an evaluation sample. After cooling down to room temperature, a PC device (TABAI ESPEC HAST SYSTEM TPC-412MD) was used for 1 to 8 hours at a pressure of 1 2 1 t: 2 to evaluate the state of the hardened film. The judgment criteria are as follows. 〇: No peeling, discoloration or dissolution. △: Any of peeling, discoloration, or dissolution. X: There are many peeling, discoloration and dissolution. From the results shown in Table 6, it can be seen that the hardened material obtained from the photocurable / thermosetting resin composition of the present invention has a high glass transition point, excellent mechanical strength, water absorption, adhesion, electrical insulation resistance, hardness, It is also excellent in chemical resistance and PCT resistance. On the other hand, the hardened | cured material of the aromatic epoxy acrylate compound obtained from the comparative example has inferior glass transition point, water absorption, hardness, PCT resistance, etc. Effect of the Invention The multi-core epoxy compound printed by the employee's cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs can be thermally hardened, and the multi-core epoxy acrylate compound of the present invention can be hardened or heat-cured by irradiation with active energy rays. The hardened material has a balance of high heat resistance and toughness, excellent adhesion to the substrate, and excellent water resistance, chemical resistance, and electrical insulation. It can be advantageously used in various resists, adhesives, Injection molding agents, laminates, coatings, encapsulants, etc. can be used as starting materials for active energy ray-curable resins. This paper size applies the Chinese National Standard (CNS) A4 specification < 210X297 mm) -73-524813 A7 B7 V. Description of the invention (71) In addition, it contains the active energy ray curable resin of the present invention as the basis of the photocurable component The photocurable and thermosetting resin composition of the invention is excellent in photocurability, alkali developability, and adhesion to the substrate, and also has heat resistance, water resistance, electroless plating resistance, chemical resistance, In addition to the above-mentioned uses, the hardened products are excellent in electrical insulation, flexibility, and PCT resistance. In addition to the above-mentioned applications, they can be very advantageously used as solder resists for printed circuit boards, interlayer insulation layers of multilayer printed circuit boards, and the like. (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper is sized to the Chinese National Standard (CNS) A4 specification {210 X 297 mm) -74-
Claims (1)
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JP2000008505 | 2000-01-18 | ||
JP2000081036 | 2000-03-22 | ||
JP2000090931A JP3723036B2 (en) | 2000-03-29 | 2000-03-29 | Active energy ray-curable resin and photocurable / thermosetting resin composition using the same |
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TW524813B true TW524813B (en) | 2003-03-21 |
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ID=27342072
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TW90101202A TW524813B (en) | 2000-01-18 | 2001-01-17 | Polynuclear epoxy compound, resin obtained therefrom curable with actinic energy ray, and photocurable/thermosetting resin composition containing the same |
Country Status (3)
Country | Link |
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CN (1) | CN1193056C (en) |
TW (1) | TW524813B (en) |
WO (1) | WO2001053375A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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TWI791500B (en) * | 2017-03-28 | 2023-02-11 | 日商味之素股份有限公司 | Photosensitive resin composition |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
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CN100358932C (en) * | 2003-08-21 | 2008-01-02 | 旭化成化学株式会社 | Photosensitive composition and cured product thereof |
SG110189A1 (en) * | 2003-09-26 | 2005-04-28 | Japan Epoxy Resins Co Ltd | Epoxy compound, preparation method thereof, and use thereof |
KR100845657B1 (en) * | 2004-07-07 | 2008-07-10 | 다이요 잉키 세이조 가부시키가이샤 | Photocurable/thermosetting resin composition, dry film using same, and cured product thereof |
JP4683182B2 (en) * | 2004-09-28 | 2011-05-11 | 山栄化学株式会社 | Photosensitive thermosetting resin composition, resist-coated printed wiring board and method for producing the same |
JP4849860B2 (en) * | 2005-10-04 | 2012-01-11 | 太陽ホールディングス株式会社 | Photocurable / thermosetting resin composition, cured product thereof, and printed wiring board obtained using the same |
TW200728917A (en) * | 2005-10-27 | 2007-08-01 | Toppan Printing Co Ltd | Alkali development-type photosensitive resin composition, substrate with projections for liquid crystal division alignment control formed using the same, and liquid crystal display device |
CN101591423B (en) * | 2008-05-29 | 2012-09-05 | 新日铁化学株式会社 | Alkaline water-soluble resin and manufacture method, as well as photosensitive resin composition, cured resin and color filter |
WO2013077307A1 (en) * | 2011-11-22 | 2013-05-30 | 日本ペイント株式会社 | Hard coating composition |
KR102541614B1 (en) * | 2015-03-04 | 2023-06-09 | 다이요 홀딩스 가부시키가이샤 | Etching resist composition and dry film |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2879860B2 (en) * | 1991-05-31 | 1999-04-05 | 日本化薬株式会社 | Epoxy resin, epoxy resin composition and cured product thereof |
JP3233222B2 (en) * | 1991-07-31 | 2001-11-26 | 大日本インキ化学工業株式会社 | Epoxy resin composition |
JP3190251B2 (en) * | 1995-06-06 | 2001-07-23 | 太陽インキ製造株式会社 | Photocurable and thermosetting resin composition for alkali-developed flexible printed wiring boards |
-
2001
- 2001-01-17 CN CN 01803841 patent/CN1193056C/en not_active Expired - Lifetime
- 2001-01-17 TW TW90101202A patent/TW524813B/en not_active IP Right Cessation
- 2001-01-17 WO PCT/JP2001/000268 patent/WO2001053375A1/en active Application Filing
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI791500B (en) * | 2017-03-28 | 2023-02-11 | 日商味之素股份有限公司 | Photosensitive resin composition |
Also Published As
Publication number | Publication date |
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CN1396937A (en) | 2003-02-12 |
WO2001053375A1 (en) | 2001-07-26 |
CN1193056C (en) | 2005-03-16 |
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