TW201441280A - Thermosetting resin, its composition, its use and an epoxy resin composition - Google Patents
Thermosetting resin, its composition, its use and an epoxy resin composition Download PDFInfo
- Publication number
- TW201441280A TW201441280A TW102114286A TW102114286A TW201441280A TW 201441280 A TW201441280 A TW 201441280A TW 102114286 A TW102114286 A TW 102114286A TW 102114286 A TW102114286 A TW 102114286A TW 201441280 A TW201441280 A TW 201441280A
- Authority
- TW
- Taiwan
- Prior art keywords
- group
- resin
- thermosetting resin
- divalent hydrocarbon
- epoxy
- Prior art date
Links
Landscapes
- Epoxy Resins (AREA)
Abstract
Description
本發明提供一種熱固性樹脂、熱固性樹脂組成物、環氧樹脂組成物可以採用含浸、塗佈、印刷、澆鑄、模塑等加工方式，其係用於製造黏合片、積層板、增厚法之基板、銅箔用之接著劑、密封劑、預浸漬片、可撓性基板、半導體構裝材、FCCL、覆蓋膜、高頻基板等。 The invention provides a thermosetting resin, a thermosetting resin composition and an epoxy resin composition, which can be processed by impregnation, coating, printing, casting, molding, etc., and is used for manufacturing a substrate of a bonding sheet, a laminated board and a thickening method. An adhesive for copper foil, a sealant, a prepreg, a flexible substrate, a semiconductor package, an FCCL, a cover film, a high frequency substrate, and the like.
1972年H.Schreiber以紙含浸苯并噁嗪(Benzoxazine)，硬化做電器絕緣材料；1994年後各種不同結構之苯并噁嗪陸續被合成出來；苯并噁嗪固化物具有接近零的尺寸安定性、低吸水性、低介電特性、自熄性、低內硬力，可做成複合材料及電子材料應用於航太、電子、汽車、切削等領域。 In 1972, H. Schreiber was impregnated with Benzoxazine as a mechanical insulating material. After 1994, various structures of benzoxazine were synthesized. The benzoxazine cured product has a dimensional stability close to zero. Properties, low water absorption, low dielectric properties, self-extinguishing, low internal hardness, can be made into composite materials and electronic materials used in aerospace, electronics, automotive, cutting and other fields.
近年來電子產品進入信號傳輸高速化、電子元件小型化、基板高密度化時代，對於電子材料用之樹脂要求低介電常數、低介電損失、可承受內外部應力導致裂痕之柔韌性，及軟性電子產品要求之可撓性。 In recent years, electronic products have entered the era of high-speed signal transmission, miniaturization of electronic components, and high-density substrates. The resin used for electronic materials requires low dielectric constant, low dielectric loss, and can withstand internal and external stresses, resulting in crack flexibility. Flexible electronics require flexibility.
中華民國專利公告I321139號揭示一種介電特性較先前改善之二胺/單酚型苯并噁嗪，其二胺具有降冰片烯骨架、二環戊二烯骨架、金剛烷骨架之結構(C9~C12)，其缺點在於因導入剛性結構，合成時需採用毒性強之氯仿為溶劑，其苯并噁嗪缺乏韌性，其溶劑溶解性、樹脂相容性不佳，無法進行含浸、塗佈等加工，產業用途因此受限。 The Republic of China Patent Publication No. I321139 discloses a diamine/monophenol type benzoxazine having improved dielectric properties, and the diamine has a structure of a norbornene skeleton, a dicyclopentadiene skeleton, and an adamantane skeleton (C9~). C12), the disadvantage is that the rigid structure is introduced, and the toxic chloroform is used as a solvent in the synthesis. The benzoxazine lacks toughness, and its solvent solubility and resin compatibility are not good, and processing such as impregnation and coating cannot be performed. Industrial use is therefore limited.
中華民國專利公告I332514號揭示一種二胺/二酚型苯并噁嗪聚合物，其二胺採用雙(胺甲基)三環癸烷(C12)、降冰片烷二胺(C9)其缺點在於因導入剛性結構，合成時仍需採用毒性強之氯仿為溶劑，其苯并噁嗪聚合物柔韌性仍不理想，其溶劑溶解性、樹脂相容性不佳。 The Republic of China Patent Publication No. I332514 discloses a diamine/diphenol type benzoxazine polymer whose diamine is bis(aminomethyl)tricyclodecane (C12) or norbornanediamine (C9). Due to the introduction of the rigid structure, it is still necessary to use toxic chloroform as a solvent in the synthesis, and the flexibility of the benzoxazine polymer is still not satisfactory, and the solvent solubility and resin compatibility are not good.
目前公知技術範圍之苯并噁嗪，例如雙酚A型苯并噁、雙酚F型苯并噁嗪、二苯胺基甲烷型苯并噁嗪其介電特性無法達到低介電常數、低介電損失之要求，其硬化物較脆，先前技術中苯并噁嗪採用(C9~C12)之脂肪多環結構雖然可以降低介電性質，但其溶劑溶解性、介電性質、樹脂相容性、可撓性仍不理想，在合成時仍須採用高環境危害性之氯仿。 The benzoxazines currently known in the art, such as bisphenol A type benzoxime, bisphenol F type benzoxazine, and diphenylaminomethane type benzoxazine, cannot have low dielectric constant and low dielectric properties. The electric loss is required to be brittle. In the prior art, the benzoxazine adopts the (C9~C12) aliphatic polycyclic structure, although it can lower the dielectric properties, but its solvent solubility, dielectric properties, and resin compatibility. The flexibility is still not ideal, and high environmentally harmful chloroform must be used in the synthesis.
本發明所欲解決之問題在於目前公知技術範圍之苯并噁嗪(Benzoxazine)，其存在的問題在於傳統苯并噁嗪具脆性，開環後酚羥基當量較小，容易吸收水分造成介電常數及介電損失不能有效降低；其被忽略的問題在於先前技術之苯并噁嗪開環後酚羥基未做適當處理，苯并噁嗪與環氧樹脂反應後產生吸水性更強之醇羥基，傳統苯并噁嗪之可撓性、介電常數及介電損失特性仍存在許多改善空間。 The problem to be solved by the present invention is that Benzoxazine, which is currently known in the technical field, has a problem in that the conventional benzoxazine is brittle, the phenolic hydroxyl equivalent after opening is small, and the dielectric constant is easily absorbed. And the dielectric loss can not be effectively reduced; the neglected problem is that the phenolic hydroxyl group of the prior art benzoxazine is not properly treated after the ring opening, and the benzoxazine reacts with the epoxy resin to produce a more water-absorbing alcoholic hydroxyl group. There are still many room for improvement in the flexibility, dielectric constant and dielectric loss characteristics of conventional benzoxazines.
鑑於上述問題，本發明所欲解決問題之技術手段，在於將苯并噁嗪導入脂肪族側鏈，可改善溶劑溶解性、可撓性，並使酚羥基當量變大，開環後樹脂中含有之酚羥基數降低，該固化物之吸水性可以降低，介電性常數與介電損失亦能有效降低，可再以噁唑啉(oxazoline)與苯并噁嗪之酚羥基反應，產生醯胺酯鍵結，可以去除或減少苯并噁嗪之酚羥基，同時也可提供 交聯架橋效果改善物性，降低介電常數、介電損失。 In view of the above problems, the technical means for solving the problem of the present invention is to introduce benzoxazine into an aliphatic side chain, thereby improving solvent solubility and flexibility, and increasing the phenolic hydroxyl equivalent, and containing the resin after ring opening. The number of phenolic hydroxyl groups is lowered, the water absorption of the cured product can be lowered, the dielectric constant and the dielectric loss can be effectively reduced, and the oxazoline can be reacted with the phenolic hydroxyl group of the benzoxazine to produce the guanamine. Ester bond can remove or reduce the phenolic hydroxyl group of benzoxazine, and also provide cross-linking bridging effect to improve physical properties, reduce dielectric constant and dielectric loss.
本發明在提供一種熱固性樹脂，該樹脂為一種苯并噁嗪，其具低介電常數、低介電損失特性，其化學結構如式(一)所示：
本發明提供一種熱固性樹脂組成物，該組成物至少含有：(a)具有噁唑啉環之化合物；(b)熱固性樹脂，其化學結構如式(一)所示：
本發明提供一種環氧樹脂組成物，該組成物至少含有：(a)每一分子至少含有兩個環氧官能基之環氧樹脂；(b)熱固性樹脂，其化學結構如式(一)所示：
本發明提供一種熱固性樹脂之用途，係用於製造黏合片、積 層板、增厚法之基板、銅箔用之接著劑、密封劑、預浸漬片、可撓性基板、半導體構裝材、FCCL、覆蓋膜、高頻基板等。 The invention provides a use of a thermosetting resin, which is used for manufacturing adhesive sheets and products. A laminate, a substrate for a thickening method, an adhesive for a copper foil, a sealant, a prepreg, a flexible substrate, a semiconductor package, an FCCL, a cover film, a high frequency substrate, and the like.
對照先前技術之功效，本發明在提供一種熱固性樹脂、熱固性樹脂組成物、環氧樹脂組成物比一般傳統苯并噁嗪及其組成物有更佳之低介電常數、低介電損失、可撓性，本發明之一種熱固性樹脂之用途，係於製造黏合片、積層板、增厚法之基板、銅箔用之接著劑、密封劑、預浸漬片、可撓性基板、半導體構裝材、FCCL、覆蓋膜、高頻基板等，可以符合產業殷切之需求。 Compared with the efficacy of the prior art, the present invention provides a thermosetting resin, a thermosetting resin composition, and an epoxy resin composition which have better low dielectric constant, low dielectric loss, and flexibility than conventional benzoxazines and their compositions. The use of a thermosetting resin of the present invention is for producing an adhesive sheet, a laminate, a substrate for a thickening method, an adhesive for a copper foil, a sealant, a prepreg, a flexible substrate, a semiconductor structure, FCCL, cover film, high-frequency substrate, etc., can meet the needs of the industry.
本發明提供一種熱固性樹脂，該熱固性樹脂其化學結構如式(一)所示：
本發明提供一種熱固性樹脂組成物，該組成物至少含有：(a)具有噁唑啉環之化合物；(b)熱固性樹脂，其化學結構如式(一)所示：
本發明提供一種環氧樹脂組成物，該組成物至少含有：(a)每一分子至少含有兩個環氧官能基之環氧樹脂；(b)熱固性樹脂，其化學結構如式(一)所示：式(一)
本發明提供一種熱固性樹脂之用途，係用於製造黏合片、積層板、增厚法之基板、銅箔用之接著劑、密封劑、預浸漬片、可撓性基板、半導體構裝材、FCCL、覆蓋膜、高頻基板等。 The present invention provides a use of a thermosetting resin for producing an adhesive sheet, a laminate, a substrate for a thickening method, an adhesive for a copper foil, a sealant, a prepreg, a flexible substrate, a semiconductor package, and a FCCL. , cover film, high frequency substrate, etc.
本發明之一種熱固性樹脂，該熱固性樹脂之合成是將雙酚類、單酚類、單醛類、二胺類在溶劑中反應脫水後取得，較佳之反應溫度為80℃~120℃。 In the thermosetting resin of the present invention, the thermosetting resin is obtained by reacting and dehydrating bisphenols, monophenols, monoaldehydes, and diamines in a solvent, and preferably has a reaction temperature of 80 ° C to 120 ° C.
本發明一種熱固性樹脂，其合成使用之二胺類包括：二(胺基環己基)甲烷、4,4’-亞甲基雙(2,6-二己基環己胺)、4,4’-亞甲基雙(2,6-二戊基環己胺)、4,4’-亞甲基雙(2,6-二丁基環己胺)、4,4’-亞甲基雙(2,6-二異丙基環己胺)、4,4’-亞甲基雙(2,6-二乙基環己胺)、4,4’-亞甲基雙(2,6-二甲基環己胺)、4,4’-亞甲基雙(2-甲基6-乙基環己胺)、4,4’-亞甲基雙(2-甲基6-異丙基環己胺)、4,4’-亞甲基雙(2-甲基6-丁基
環己胺)、C32二聚胺、C36二聚胺、C40二聚胺、C44二聚胺、C48二聚胺、
本發明之一種熱固性樹脂，其合成使用之二酚類包括：雙酚A、雙酚B、雙酚E、雙酚F、雙酚Z、雙酚M、雙酚P、聯苯二酚、芴二酚、碳酸二酚、甲酸酯二酚等。 A thermosetting resin of the present invention, which comprises diphenols, bisphenol B, bisphenol E, bisphenol F, bisphenol Z, bisphenol M, bisphenol P, biphenyldiol, hydrazine Diphenol, carbonic acid diphenol, formic acid diphenol, and the like.
本發明之一種熱固性樹脂，其合成使用之單酚類包括：酚、甲基酚、乙基酚、異丙基酚、第三丁基酚、戊酚、己酚、庚酚、辛基酚、壬基酚、癸基酚、十二烷基酚、腰果酚、萜烯酚、對苯基酚等。 The thermosetting resin of the present invention, the monophenols used in the synthesis thereof include: phenol, methylphenol, ethylphenol, isopropylphenol, tert-butylphenol, pentanol, hexanol, heptol, octylphenol, Nonylphenol, nonylphenol, dodecylphenol, cardanol, terpene phenol, p-phenylphenol, and the like.
本發明一種熱固性樹脂，其合成所使用之單醛類包括：甲醛、三聚甲醛、多聚甲醛、乙醛、三聚乙醛等。 The thermosetting resin of the present invention, the monoaldehydes used in the synthesis thereof include: formaldehyde, trioxane, paraformaldehyde, acetaldehyde, paraldehyde, and the like.
本發明一種熱固性樹脂，其合成使用之溶劑包括：苯、甲苯、二甲苯、均三甲苯、偏三甲苯、環己烷、1-丁醇、2-丁醇、異丁醇、甲基異 丁基酮、二異丁酮、四氫呋喃、甲基異戊基酮、環戊酮、環己酮、二異丁酮、二咢烷、γ-丁內酯、γ-戊內酯、γ-己內酯、β-丁內酯、β-戊內酯、β-己內酯、γ-丁內酯、3-甲基辛醯-4-內酯、4-羥基-3-戊烯酸γ-內酯、氯仿、二氯甲烷、二乙二醇單己基醚、丙二醇單甲基醚、丙二醇單乙基醚、丙二醇單丙基醚、乙酸正丁酯、二乙二醇單丁基醚乙酸酯、甲氧基乙醇、乙氧基乙醇等之單一或混合溶劑。 The invention relates to a thermosetting resin, which comprises the following solvents: benzene, toluene, xylene, mesitylene, trimellitic acid, cyclohexane, 1-butanol, 2-butanol, isobutanol and methyl Butyl ketone, diisobutyl ketone, tetrahydrofuran, methyl isoamyl ketone, cyclopentanone, cyclohexanone, diisobutyl ketone, dioxane, γ-butyrolactone, γ-valerolactone, γ-hexyl Lactone, β-butyrolactone, β-valerolactone, β-caprolactone, γ-butyrolactone, 3-methyloctyl-4-lactone, 4-hydroxy-3-pentenoic acid γ- Lactone, chloroform, dichloromethane, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, n-butyl acetate, diethylene glycol monobutyl ether acetate A single or mixed solvent of ester, methoxyethanol, ethoxyethanol or the like.
本發明提供一種熱固性樹脂組成物，該組成物之具有噁唑啉(oxazoline)環之化合物包括：1,3亞苯基雙噁唑啉(1,3phenylene bis oxazoline)、1,4亞苯基雙噁唑啉(1,4phenylene bis oxazoline)、苯基噁唑啉、甲基噁唑啉、乙基噁唑啉等。 The present invention provides a thermosetting resin composition, the composition having the oxazoline (oxazoline) compounds comprising a ring of: 1,3-phenylene bisoxazoline (1,3phenylene bis oxazoline), 1,4-phenylene bis 1,4phenylene bis oxazoline , phenyloxazoline, methyloxazoline, ethyloxazoline, and the like.
發明提供一種熱固性樹脂組成物，該組成物之熱固性樹脂為一種苯并噁嗪(Benzoxazine)，經熱開環可以產生酚羥基，其熱開環較佳溫度為100℃~270℃，開環後熱固性樹脂中含有酚羥基愈低，其介電性質會愈好，噁唑啉在120℃~180℃開環與苯并噁嗪之酚羥基反應，產生醯胺酯鍵結，可以降低苯并噁嗪之酚羥基，使熱固性樹脂組成物之固化物保有難燃性、抑煙性、耐熱性、可撓性，更降低原有介電損失，更適合用於半導體構裝材料及低介電特性需求之電子材料。 The invention provides a thermosetting resin composition, wherein the thermosetting resin of the composition is a benzooxazine, which can generate a phenolic hydroxyl group by thermal ring opening, and the hot-opening ring preferably has a temperature of 100 ° C to 270 ° C. The lower the phenolic hydroxyl group in the thermosetting resin, the better the dielectric properties. The oxazoline ring-opening at 120 ° C ~ 180 ° C reacts with the phenolic hydroxyl group of benzoxazine to produce a guanamine linkage, which can reduce benzoin The phenolic hydroxyl group of the azine makes the cured product of the thermosetting resin composition have flame retardancy, smoke suppressing property, heat resistance and flexibility, and further reduces the original dielectric loss, and is more suitable for use in semiconductor packaging materials and low dielectric properties. Electronic materials for demand.
本發明提供一種環氧樹脂組成物，該組成物之每一分子至少含有兩個環氧官能基之環氧樹脂包括：雙酚A型縮水甘油醚、雙酚F型縮水甘油醚、雙酚S型縮水甘油醚、氫化雙酚A型縮水甘油醚、氫化雙酚A型縮水甘油醚、鄰苯二甲酸縮水甘油酯、海因環氧樹脂、醯亞胺環氧樹脂、雙(2,3環氧基環戊基)醚、3,4環氧基-6-甲基環己基甲酸-3’,4’-環氧基-6’-甲基 環己基甲酯、乙烯基環己烯二環氧化合物、3,4環氧基環己基甲酸-3’,4’-環氧基環己基甲酯、二異戊二烯二環氧化物、二丁二烯二環氧化物、己二酸二(3,4環氧基-6-甲基環己基甲酯)、二縮水甘油醚、聚乙醇二縮水甘油醚、聚丙醇二縮水甘油醚、聚丁醇二縮水甘油醚、丁醇二縮水甘油醚、二縮水甘油基苯胺、對苯二甲酸二縮水甘油酯、內次甲基四氫鄰苯二甲酸二縮水甘油酯、鄰苯二甲酸二縮水甘油酯、四氫鄰苯二甲酸二縮水甘油酯、間苯二甲酸二縮水甘油酯、4,5環氧環己烷1,2-二甲酸二縮水甘油酯、鄰苯二辛酸二環氧丙酯、二氧化戊烯、二氧化雙環戊二烯多元醇醚、其它二個環氧基之環氧樹脂、二個環氧基之環氧樹脂稀釋劑、酚醛型環氧樹脂、萘酚醛型環氧樹脂、甲酚醛型環氧樹脂、雙酚A醛型環氧樹脂、四苯基縮水甘油醚基乙烷、三苯基縮水甘油醚基甲烷、三縮水甘油基對胺基苯酚、三縮水甘油基三聚異氰酸酯、四縮水甘油基二胺基二苯基甲烷、四縮水甘油基二甲苯二胺、四縮水甘油基1,3-雙氨基甲基環己烷、三甲醇基丙烷三縮水甘油醚、丙三醇三縮水甘油醚、其它二個以上環氧基之環氧樹脂、二個以上環氧基之環氧樹脂稀釋劑等。 The present invention provides an epoxy resin composition, the epoxy resin having at least two epoxy functional groups per molecule of the composition, including: bisphenol A glycidyl ether, bisphenol F glycidyl ether, bisphenol S Glycidyl ether, hydrogenated bisphenol A glycidyl ether, hydrogenated bisphenol A glycidyl ether, glycidyl phthalate, hydantoin epoxy resin, quinone imine epoxy resin, double (2, 3 ring Oxycyclopentyl)ether, 3,4 epoxy-6-methylcyclohexylcarboxylic acid-3',4'-epoxy-6'-methyl Cyclohexyl methyl ester, vinyl cyclohexene diepoxide, 3,4 epoxycyclohexylcarboxylic acid-3',4'-epoxycyclohexyl methyl ester, diisoprene diepoxide, two Butadiene diepoxide, bis(3,4 epoxy-6-methylcyclohexylmethyl) adipate, diglycidyl ether, polyglycol diglycidyl ether, polyglycol diglycidyl ether, poly Butanol diglycidyl ether, butanol diglycidyl ether, diglycidyl aniline, diglycidyl terephthalate, endomethyltetrahydrophthalic acid diglycidyl ester, phthalic acid condensed water Glyceryl ester, diglycidyl tetrahydrophthalate, diglycidyl isophthalate, 4,5 epoxy cyclohexane 1,2-dicarboxylic acid diglycidyl ester, phthalic acid diepoxypropionate Ester, pentene oxide, dicyclopentadiene polyol ether, two other epoxy epoxy resins, two epoxy epoxy resin diluents, novolac epoxy resin, naphthol type ring Oxygen resin, cresol novolac epoxy resin, bisphenol A aldehyde type epoxy resin, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether group Alkane, triglycidyl-p-aminophenol, triglycidyl trimer isocyanate, tetraglycidyldiaminodiphenylmethane, tetraglycidyl xylylenediamine, tetraglycidyl1,3-diamino Methylcyclohexane, trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, two or more epoxy epoxy resins, two or more epoxy epoxy resin diluents, and the like.
本發明之一種種環氧樹脂組成物可使用之硬化促進劑包括已知之三級胺、四級銨鹽、咪唑類、金屬有機鹽、膦類化合物、三氟硼胺錯合物、酚類等。 The hardening accelerator which can be used for the epoxy resin composition of the present invention includes known tertiary amines, quaternary ammonium salts, imidazoles, metal organic salts, phosphine compounds, trifluoroboramine complexes, phenols, and the like. .
本發明之熱固性樹脂、熱固性樹脂組成物、環氧樹脂組成物可以採用含浸、塗佈、印刷、澆鑄、模塑等加工方式，其係用於製造黏合片、積層板、增厚法之基板、銅箔用之接著劑、密封劑、預浸漬片、可撓性基板、半導體構裝材、FCCL、覆蓋膜、高頻基板等。 The thermosetting resin, the thermosetting resin composition and the epoxy resin composition of the present invention can be processed by impregnation, coating, printing, casting, molding, etc., and are used for manufacturing a bonded sheet, a laminated board, a substrate for thickening, An adhesive for a copper foil, a sealant, a prepreg, a flexible substrate, a semiconductor package, an FCCL, a cover film, a high frequency substrate, or the like.
本發明將以下列實施例與比較例進一步說明，唯不因此而限制本發明範圍。 The invention will be further illustrated by the following examples and comparative examples, which are not intended to limit the scope of the invention.
將C36二聚胺53.6g(0.10mole)、甲苯100g、異丁醇100g，置入裝有機械攪拌、戴氏冷凝管、迪恩-斯達克蒸餾受器、氮氣管、等壓滴液漏斗之四口反應瓶中，將37%甲醛32.4g(0.40mole)滴入反應瓶中，溫度控制在20~30℃反應5小時，再將酚18.8g(0.20mole)加入，溫度加熱到90~120℃以共沸方式去除生成水，之後以減壓蒸餾去除溶劑，可得到A樹脂，經由HPLC分析C36二聚胺殘量為0.031%，酚殘量為0.023%。 53.6g (0.10mole) of C36 dipolyamine, 100g of toluene, 100g of isobutanol, placed in a mechanical stirring, Daisy condenser, Dean-Stark distillation receiver, nitrogen tube, isobaric dropping funnel In the four reaction bottles, 37% formaldehyde (32.4g (0.40mole)) was dropped into the reaction flask, the temperature was controlled at 20~30 °C for 5 hours, then the phenol 18.8g (0.20mole) was added, and the temperature was heated to 90~ The produced water was removed azeotropically at 120 ° C, and then the solvent was distilled off under reduced pressure to obtain an A resin. The residual amount of C36 diamine was analyzed by HPLC to be 0.031%, and the residual amount of phenol was 0.023%.
將4,4’-亞甲基雙(2,6-二乙基環己胺)31.8g(0.10mole)、甲苯200g，置入裝有機械攪拌、戴氏冷凝管、迪恩-斯達克蒸餾受器、氮氣管、等壓滴液漏斗之四口反應瓶中，將37%甲醛32.4g(0.40mole)滴入反應瓶中，溫度控制在20~30℃反應5小時，再將腰果酚60.0g(0.20mole)加入，溫度加熱到90~120℃以共沸方式去除生成水，之後以減壓蒸餾去除溶劑，可得到A樹脂，經由HPLC分析4,4’-亞甲基雙(2,6-二乙基環己胺)殘量為0.031%，腰果酚殘量為0.025%。 41.8 g (2,6-diethylcyclohexylamine) 31.8 g (0.10 mole), 200 g of toluene, placed in a mechanical stirring, Daisy condenser, Dean-Stark In a four-reaction reaction flask of a distillation receiver, a nitrogen tube, and an equal pressure dropping funnel, 32.4 g (0.40 mole) of 37% formaldehyde was dropped into the reaction flask, and the temperature was controlled at 20 to 30 ° C for 5 hours, and then cardanol was added. 60.0g (0.20mole) was added, the temperature was heated to 90-120 ° C to remove the formed water by azeotropic method, and then the solvent was distilled off under reduced pressure to obtain A resin, and 4,4'-methylene double (2) was analyzed by HPLC. The residual amount of 6-diethylcyclohexylamine was 0.031%, and the residual amount of cardanol was 0.025%.
將C36二聚胺107.2g(0.20mole)、甲苯200g、異丁醇300g，置入裝有機械攪拌、戴氏冷凝管、迪恩-斯達克蒸餾受器、氮氣管、等壓滴液漏斗之四口反應瓶中，將37%甲醛64.8g(0.80mole)滴入反應瓶中，溫度控 制在20~30℃反應5小時，再將丁基酚30.0g(0.20mole)、雙酚Z 26.8g(0.1mole)加入，溫度加熱到90~120℃以共沸方式去除生成水，之後以減壓蒸餾去除溶劑，可得到A樹脂，經由HPLC分析C36二聚胺殘量為0.036%，丁基酚殘量為0.011%、雙酚Z殘量為0.024。 107.6g (0.20mole) of C36 dipolyamine, 200g of toluene, 300g of isobutanol, placed in a mechanical stirring, Daisy condenser, Dean-Stark distillation receiver, nitrogen tube, isobaric dropping funnel In the four reaction bottles, 37% formaldehyde 64.8g (0.80mole) was dropped into the reaction flask, temperature control The reaction was carried out at 20 to 30 ° C for 5 hours, and then butylphenol 30.0 g (0.20 mole), bisphenol Z 26.8 g (0.1 mole) was added, and the temperature was heated to 90-120 ° C to remove the formed water by azeotropy. The solvent was distilled off under reduced pressure to obtain an A resin. The residue of C36 diamine was analyzed by HPLC to be 0.036%, the residual amount of butylphenol was 0.011%, and the residual amount of bisphenol Z was 0.024.
將C36二聚胺107.2g(0.20mole)、甲苯200g、異丁醇300g，置入裝有機械攪拌、戴氏冷凝管、迪恩-斯達克蒸餾受器、氮氣管、等壓滴液漏斗之四口反應瓶中，將37%甲醛64.8g(0.80mole)滴入反應瓶中，溫度控制在20~30℃反應5小時，再將丁基酚30.0g(0.20mole)、聯苯二酚18.6g(0.1mole)加入，溫度加熱到90~120℃以共沸方式去除生成水，之後以減壓蒸餾去除溶劑，可得到A樹脂，經由HPLC分析C36二聚胺殘量為0.031%，丁基酚殘量為0.015%、雙酚Z殘量為0.025。 107.6g (0.20mole) of C36 dipolyamine, 200g of toluene, 300g of isobutanol, placed in a mechanical stirring, Daisy condenser, Dean-Stark distillation receiver, nitrogen tube, isobaric dropping funnel In the four reaction bottles, 37% formaldehyde (64.8g (0.80mole)) was dropped into the reaction flask, the temperature was controlled at 20~30 °C for 5 hours, and then butylphenol 30.0g (0.20mole), biphenyldiol 18.6g (0.1mole) was added, the temperature was heated to 90-120 ° C to remove the formed water by azeotropic method, and then the solvent was distilled off under reduced pressure to obtain A resin, and the residual amount of C36 di-polyamine was determined by HPLC to be 0.031%. The residual amount of phenol is 0.015%, and the residual amount of bisphenol Z is 0.025.
將C36二聚胺107.2g(0.20mole)、甲苯200g、異丁醇300g，置入裝有機械攪拌、戴氏冷凝管、迪恩-斯達克蒸餾受器、氮氣管、等壓滴液漏斗之四口反應瓶中，將37%甲醛64.8g(0.80mole)滴入反應瓶中，溫度控制在20~30℃反應5小時，再將丁基酚30.0g(0.20mole)、甲酸酯二酚23.0g(0.1mole)加入，溫度加熱到90~120℃以共沸方式去除生成水，之後以減壓蒸餾去除溶劑，可得到A樹脂，經由HPLC分析C36二聚胺殘量為0.028%，丁基酚殘量為0.017%、甲酸酯二酚殘量為0.031。 107.6g (0.20mole) of C36 dipolyamine, 200g of toluene, 300g of isobutanol, placed in a mechanical stirring, Daisy condenser, Dean-Stark distillation receiver, nitrogen tube, isobaric dropping funnel In the four reaction bottles, 37% formaldehyde (64.8g (0.80mole)) was dropped into the reaction flask, the temperature was controlled at 20~30 °C for 5 hours, and then butylphenol 30.0g (0.20mole), formate two Phenol 23.0g (0.1mole) was added, the temperature was heated to 90-120 ° C to remove the formed water by azeotropic method, and then the solvent was distilled off under reduced pressure to obtain A resin, and the residual amount of C36 dimeramine was 0.028% by HPLC. The residual amount of butyl phenol was 0.017%, and the residual amount of formic acid diphenol was 0.031.
實施例6~10依序為：將A樹脂、B樹脂、C樹脂、D樹脂、E 樹脂各取10g在150℃下烘烤2小時，再180℃下脫氣壓鑄成形2小時，最後以210℃下固化2小時，得到膜厚1.0mm之固化物，測量其玻璃轉移溫度、介電常數、介電損失，其數據如表一所示。 Examples 6 to 10 are sequentially: 10 g of each of A resin, B resin, C resin, D resin, and E resin is baked at 150 ° C for 2 hours, and then degassed at 180 ° C for 2 hours, and finally 210. After curing at ° C for 2 hours, a cured product having a film thickness of 1.0 mm was obtained, and the glass transition temperature, dielectric constant, and dielectric loss were measured, and the data are shown in Table 1.
將市售雙酚F型苯并噁嗪(BPF-BZ)取10g在150℃下烘烤2小時，再180℃下脫氣壓鑄成形2小時，最後以210℃下固化2小時，得到膜厚1.0mm之固化物，測量其玻璃轉移溫度、介電常數、介電損失，其數據如表一所示。 10 g of commercially available bisphenol F benzoxazine (BPF-BZ) was baked at 150 ° C for 2 hours, then degassed at 180 ° C for 2 hours, and finally cured at 210 ° C for 2 hours to obtain a film thickness. A 1.0 mm cured product was measured for its glass transition temperature, dielectric constant, and dielectric loss, and the data is shown in Table 1.
實施例11~15依序為：將A樹脂、B樹脂、C樹脂、D樹脂、E樹脂各取10g與雙酚A型環氧樹脂(Epoxy)3g、促進劑2E4MZ(2-乙基-四甲基咪唑)0.01、溶劑甲苯10g混合均勻，在150℃下烘烤2小時，180℃烘烤2小時下，最後以210℃下固化2小時，得到膜厚1.0mm之固化物，測量其玻璃轉移溫度、介電常數、介電損失、可撓性，其數據如表二所示。 Examples 11 to 15 are: 10 g of each of A resin, B resin, C resin, D resin, and E resin, 3 g of bisphenol A type epoxy resin (Epoxy), and 2E4MZ (2-ethyl-four) Methylimidazole) 0.01, solvent toluene 10 g was uniformly mixed, baked at 150 ° C for 2 hours, baked at 180 ° C for 2 hours, and finally cured at 210 ° C for 2 hours to obtain a cured product having a film thickness of 1.0 mm, and the glass was measured. Transfer temperature, dielectric constant, dielectric loss, and flexibility are shown in Table 2.
將市售雙酚F型苯并噁嗪(BPF-BZ)取10g與雙酚A型環氧樹脂(Epoxy)3g、促進劑2E4MZ(2-乙基-四甲基咪唑)0.01、溶劑甲苯10g混合均勻，在150℃下烘烤2小時，180℃烘烤2小時下，最後以210℃下固化2小時，得到膜厚1.0mm之固化物，測量其玻璃轉移溫度、介電常數、介電損失、可撓性，其數據如表二所示。 10 g of commercially available bisphenol F benzoxazine (BPF-BZ) and 3 g of bisphenol A epoxy resin (Epoxy), accelerator 2E4MZ (2-ethyl-tetramethylimidazole) 0.01, solvent toluene 10 g The mixture was uniformly mixed, baked at 150 ° C for 2 hours, baked at 180 ° C for 2 hours, and finally cured at 210 ° C for 2 hours to obtain a cured product having a film thickness of 1.0 mm, and the glass transition temperature, dielectric constant, and dielectric were measured. Loss and flexibility, the data is shown in Table 2.
實施例16~20依序為：將A樹脂、B樹脂、C樹脂、D樹脂、E樹脂各取10g與1,3亞苯基雙噁唑啉(1,3PBO)3g、溶劑二異丁酮(DIBK)10g研磨分散均勻，在160℃下烘烤2小時，180℃烘烤2小時下，最後以210℃下固化2小時，得到膜厚1.0mm之固化物，測量其玻璃轉移溫度、介電常數、介電損失、可撓性，其數據如表三所示。 Examples 16 to 20 sequentially to: A resin, B resin, C resin, D resin, E from each resin and 10g 1,3-phenylene bisoxazoline (1,3PBO) 3g, diisobutyl ketone solvent (DIBK) 10g grinding and dispersing evenly, baking at 160 °C for 2 hours, baking at 180 °C for 2 hours, and finally curing at 210 °C for 2 hours to obtain a cured product with a film thickness of 1.0 mm, measuring the glass transition temperature, The electrical constant, dielectric loss, and flexibility are shown in Table 3.
將市售雙酚F型苯并噁嗪(BPF-BZ)取10g與1,3亞苯基雙噁唑啉(1,3PBO)3g、溶劑二異丁酮(DIBK)10g研磨分散均勻，在160℃下烘烤2小時，180℃烘烤2小時下，最後以210℃下固化2小時，得到膜厚1.0mm之固化物，測量其玻璃轉移溫度、介電常數、介電損失、可撓性，其數據如表三所示。 10 g of commercially available bisphenol F benzoxazine (BPF-BZ) was ground and dispersed with 10 g of 1,3 phenylenebisoxazoline ( 1,3PBO ) and 10 g of solvent diisobutyl ketone (DIBK). Bake at 160 °C for 2 hours, 180 °C for 2 hours, and finally at 210 °C for 2 hours to obtain a cured product with a film thickness of 1.0 mm. The glass transition temperature, dielectric constant, dielectric loss, and flexibility were measured. Sex, its data is shown in Table 3.
玻璃轉移溫度(Tg)：以TA公司製DSC測定。 Glass transition temperature ( Tg ): measured by DSC manufactured by TA Corporation.
介電常數(Dk)：以Agilent公司製LCR Meter在1GHz頻率下測定。 Dielectric constant ( Dk ): Measured at a frequency of 1 GHz using an LCR Meter manufactured by Agilent .
介電損失(Df)：以Agilent公司製共振腔在1GHz頻率下測定。 Dielectric loss ( Df ): Measured at a frequency of 1 GHz using a resonant cavity made by Agilent .
可撓性：將膜厚1.0mm之固化物對折後檢視外觀 Flexibility: Viewing the appearance of a cured product with a thickness of 1.0 mm
○ 表示無折痕 ○ indicates no crease
△ 表示有折痕 △ indicates crease
X 表示有裂痕 X indicates cracking
由表一可知實施例6~10之A樹脂、B樹脂、C樹脂、D樹脂、E樹脂固化物，相對與比較例1之BBF-BZ固化物，有較低之介電常數(Dk)、較低之介電損失(Df)、更佳之可撓性；由表二可知實施例11~15之A樹脂、B樹脂、C樹脂、D樹脂、E樹脂與雙酚A型環氧樹脂固化物，相對與比較例2之BBF-BZ與雙酚A型環氧樹脂固化物，有較低之介電常數(Dk)、較低之介電損失(Df)、更佳之可撓性；由表三可知實施例16~20之A樹脂、B樹脂、C樹脂、D樹脂、E樹脂與1,3亞苯基雙噁唑啉固化物，相對與比較例3之BBF-BZ與1,3亞苯基雙噁唑啉固化物，有較低之介電常數(Dk)、較低之介電損失(Df)、更佳之可撓性。 It can be seen from Table 1 that the A resin, the B resin, the C resin, the D resin, and the E resin cured product of Examples 6 to 10 have a lower dielectric constant ( Dk ) than the BBF-BZ cured product of Comparative Example 1. Lower dielectric loss ( Df ), better flexibility; Table 2 shows the resin of A, B resin, C resin, D resin, E resin and bisphenol A type epoxy resin of Examples 11-15 Compared with the BBF-BZ and bisphenol A type epoxy resin cured materials of Comparative Example 2, it has a lower dielectric constant ( Dk ), a lower dielectric loss ( Df ), and better flexibility; 3, A resin, B resin, C resin, D resin, E resin and 1,3 phenyl bisoxazoline cured product of Examples 16 to 20 , and BBF-BZ and 1,3 sub-comparison of Comparative Example 3, respectively. The phenylbisoxazoline cured product has a lower dielectric constant ( Dk ), a lower dielectric loss ( Df ), and better flexibility.
本發明在提供一種熱固性樹脂、熱固性樹脂組成物、環氧樹脂組成物比一般傳統苯并噁嗪及其組成物有更佳之低介電常數、低介電損失、可撓性，本發明之一種熱固性樹脂之用途，係於製造黏合片、積層板、增厚法之基板、銅箔用之接著劑、密封劑、預浸漬片、可撓性基板、半導體構裝材、FCCL、覆蓋膜、高頻基板等。 The present invention provides a thermosetting resin, a thermosetting resin composition, and an epoxy resin composition which have better low dielectric constant, low dielectric loss and flexibility than conventional benzoxazine and a composition thereof, and are one kind of the present invention. The use of thermosetting resin is used in the manufacture of adhesive sheets, laminates, substrates for thickening methods, adhesives for copper foils, sealants, prepregs, flexible substrates, semiconductor structures, FCCL, cover films, and high Frequency substrate, etc.
本發明已經配合上述具體實施例、比較例描述，熟悉本項技藝人士將可基於以上描述作出多種變化，不因此而限制本發明之申請專利範圍。 The present invention has been described in connection with the foregoing specific embodiments and comparative examples, and those skilled in the art can make various changes based on the above description, and do not limit the scope of the patent application of the present invention.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW102114286A TWI471358B (en) | 2013-04-23 | 2013-04-23 | A thermosetting resin, a composition thereof, a use thereof, and an epoxy resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW102114286A TWI471358B (en) | 2013-04-23 | 2013-04-23 | A thermosetting resin, a composition thereof, a use thereof, and an epoxy resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201441280A true TW201441280A (en) | 2014-11-01 |
| TWI471358B TWI471358B (en) | 2015-02-01 |
Family
ID=52422802
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW102114286A TWI471358B (en) | 2013-04-23 | 2013-04-23 | A thermosetting resin, a composition thereof, a use thereof, and an epoxy resin composition |
Country Status (1)
| Country | Link |
|---|---|
| TW (1) | TWI471358B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114710886A (en) * | 2022-06-02 | 2022-07-05 | 深圳市板明科技股份有限公司 | Ink hole plugging method for high-heat-conductivity PCB |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI748898B (en) | 2021-03-15 | 2021-12-01 | 晉一化工股份有限公司 | Thermosetting resin compositions, flame-retardant resin compositions, liquid packaging material and its use, and film and its use |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI313685B (en) * | 2002-10-03 | 2009-08-21 | Chang Chun Plastics Co Ltd | Method for prodcuing nitrogen-oxygen heterocyclic compound |
| CN101550235A (en) * | 2009-06-02 | 2009-10-07 | 北京化工大学 | Benzoxazine colophony based on renewable resources, its composition and preparing method thereof |
| EP2580261A1 (en) * | 2010-03-19 | 2013-04-17 | Momentive Specialty Chemicals Research S.A. | Main-chain benzoxazine oligomer compositions, and method for the preparation thereof |
| WO2013033955A1 (en) * | 2011-09-09 | 2013-03-14 | 复旦大学 | Benzoxazine monomer comprising benzocyclobutenyl functional group, synthetic method therefor and use thereof |
-
2013
- 2013-04-23 TW TW102114286A patent/TWI471358B/en active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114710886A (en) * | 2022-06-02 | 2022-07-05 | 深圳市板明科技股份有限公司 | Ink hole plugging method for high-heat-conductivity PCB |
| CN114710886B (en) * | 2022-06-02 | 2022-08-19 | 深圳市板明科技股份有限公司 | Ink hole plugging method for high-heat-conductivity PCB |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI471358B (en) | 2015-02-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6689475B1 (en) | Maleimide resin, curable resin composition and cured product thereof | |
| JP6429862B2 (en) | Aromatic amine resin, maleimide resin, curable resin composition and cured product thereof | |
| JP6752390B1 (en) | Maleimide resin, curable resin composition and cured product thereof | |
| EP2900726B1 (en) | Resin composition and composite structure containing resin | |
| JP2024063017A (en) | Phenol resin, epoxy resin, epoxy resin composition and cured product thereof | |
| KR102603395B1 (en) | Phosphorus-containing phenolic compound, phosphorus-containing epoxy resin, curable resin composition or epoxy resin composition, and cured product thereof | |
| JP6764470B2 (en) | Maleimide resin, curable resin composition and cured product thereof | |
| JPWO2009001658A1 (en) | One-component cyanate-epoxy composite resin composition | |
| CN104024337A (en) | Silane-containing composition, curable resin composition, and sealing material | |
| TWI438216B (en) | Modified liquid epoxy resin, epoxy resin composition by using modified liquid epoxy resin and cured product thereof | |
| TWI471358B (en) | A thermosetting resin, a composition thereof, a use thereof, and an epoxy resin composition | |
| JP6254475B2 (en) | Epoxy resin curing agent, production method, composition, cured product and use thereof | |
| JP6863679B2 (en) | Solution, its manufacturing method, epoxy resin composition and laminate | |
| WO2013080936A1 (en) | Phenol novolak resin and epoxy resin composition using same | |
| CN116670199A (en) | Epoxy resin, method for producing same, curable resin composition, and cured product thereof | |
| JP7034793B2 (en) | Oxazine compound having a fluorene skeleton and its production method | |
| US20230227603A1 (en) | Epoxy resin composition and cured product thereof | |
| US20230242753A1 (en) | Thermosetting resin composition and cured product thereof | |
| JP7464474B2 (en) | Maleimide resin, curable resin composition and cured product thereof | |
| US20230272155A1 (en) | Phenol resin, epoxy resin, methods for producing these, epoxy resin composition and cured product thereof | |
| US20230227601A1 (en) | Epoxy resin composition and cured product thereof | |
| KR102377780B1 (en) | Toughened epoxy adhesive composition | |
| KR101910134B1 (en) | Modified epoxy resin and the method thereof | |
| KR20170014277A (en) | Modified epoxy resin and the method thereof | |
| CN116410445A (en) | Epoxy resin composition and resin film |