TW574246B - High Tg brominated epoxy resin for glass fiber laminate - Google Patents

Abstract

This invention discloses a novel brominated epoxy resin, which is synthesized from the following components: 10 to 70 weight % of (A) phenol-benzyl formaldehyde multi-functional epoxy resin (formula I), 0 to 55 weight % of (B) di-functional epoxy resin, 0 to 20 weight % of (C) romine-containing di-functional epoxy resin, and 15 to 40 weight % of (D) tetra-bromo bisphenol A. During the synthesis, (D) tetra-bromo bisphenol A is used to first react with at least one of the three epoxy resins (A), (B) and (C) then adding the rest and the components are well mixed to obtain the novel brominated epoxy resin; the novel epoxy resin can be used for glass fiber laminates, shows adequate reactivity and has broad lamination working window, in which the laminated glass fiber laminates exhibit high glass transition temperature (Tg), show excellent heat resistance and can be applied for high performance electronic material.

Description

574246 V. Description of the invention (1) (Field of invention) The present invention relates to a kind of process with good operability in the process of # g A & σσ 3 is a novel brominated epoxy resin with excellent processing and heat resistance. The substrate has a high glass transition temperature (Tg), and it is suitable for use as an electronic material. (Background of the invention) Performance: = Light, thin, small and complicated, so -Hf is urgent for high-performance fingers. Usually material. Value system-a very high temperature ... ΐ'Λ 不 Λ Poor dynamic stress at operating temperature and: Dipole, if the material temperature is higher than Tg, it often results in high interlayer bonding. It is one of the most important issues that cause the material to deteriorate. Hezhu P is a glass fiber laminate currently available on the market for FR-4 substrates. It is made of bifunctional resin and has a Tg value between 130 and 140. Usually, a square coat is used to remove it. Polyfunctional epoxy resins such as o-cresol formaldehyde novolac epoxy resin, o-cresol formaldehyde novalac epoxy resin, tetra functional epoxy, novolac epoxy resin ~ The use of the above-mentioned polyfunctional epoxy resins, such as phenol novolac epoxy, etc. ^ Although it can improve T g and has excellent heat resistance, when it is hardened with a commonly used hardener dicyandiamide, it causes gelation time (Gel time) is too fast and the working window is too narrow.

574246 5. Description of the invention (2) Precisely control the processing process to avoid the occurrence of defective products, which often affects the production yield and capacity. i 1_ 画 _ Page 7 574246 V. Description of the invention (3) (Advantages of the invention) To solve the above-mentioned use of multifunctional epoxy resins such as o-cresol cresol novolac epoxy resin, tetrafunctional epoxy resin, novolac Type epoxy resin, etc., caused the problem of poor processability of glass fiber laminates. The object of the present invention is to provide a novel brominated epoxy resin with suitable reactivity, wide lamination processing interval, and good processability. , And high Tg with excellent heat resistance, electrical properties, and flammability, as well as low water absorption.

The novel brominated epoxy resin related to the present invention comprises (A). A phenol-phenylbenzoaldehyde polyfunctional epoxy resin (formula I) (B), a bifunctional epoxy resin (C), and a brominated bifunctional epoxy resin. Epoxy resin (D). Tetrabromobisphenol A

Obtained through synthesis. Synthesized with (D) tetrabromobisphenol A and

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The first step is to mix (A), (B), (C) at least one of the two epoxy resins (including-after the reaction, and then add (ALCBh cc) the three epoxy resins after the remaining sentences are combined. A novel brominated epoxy resin is obtained. (Detailed description of the present invention) The most significant feature of the novel brominated epoxy resin of the present invention is a benzyl multifunctional epoxy resin, which has a high chemical structure; ^ 出 二-Structure and appropriate number of epoxy functional groups, so it has excellent two: high Tg, at the same time the appropriate number of epoxy functional groups and benzene ring ^

Restriction makes it have the appropriate reactivity to make Fen Yigu look like I from the # 7 Hansaki people, and the relatively high resin melt viscosity, so it has a wide processing range, which can provide high performance Broken fiber laminate. Σ In the process of substrate hot pressing, how to control the resin flow (resln ηο is appropriate, the surrounding system is extremely important, because the resin flow is too large, it will cause white edges, white angles, etc .; otherwise, if the resin flow is partial If it is small, weaves are prone to be exposed ... and other problems occur. 1 In 978, Barlett and Blochle proposed that the resin flow glue amount formula in the pressure rheological behavior of the resin is: F (t) = (c / 12) x ( p / A) Sdt / n (t) where C is a constant, p is the pressure, a is the area of the substrate, and dt / n (t) is the flow integral. It can be understood from the formula that when the pressure and the area of the substrate are fixed, Resin flow is related to (1) resin viscosity and (2) gel time of prepreg, that is, resin flow is affected by (1) resin viscosity and (?) Gel time of prepreg, That is, the minimum melt viscosity of the resin and the gelation time of the pre-crushed woven fabric need to be properly controlled within its range to enable easy lamination.

574246 V. Description of the invention (5) 200 ~ 100. The minimum melt viscosity of the resin in the hot-pressing rheological behavior is maintained at the product. The applicability is better than that of the material: it can be used for processes with different hot-pressing heating rates, and the uniformity of the production of Yin and Yang on the same day is also better. Shuguang: A new desertification compound synthesized from diformate polyglycerin epoxy resin. Γ-Λbenzyl multifunctional epoxy resin, the content is W ~ 70. The content is 0 to 55% by weight. The purpose is to first react St to advanced bromide epoxy resin (EP-0), and then add the _, ^ and the remaining parts, mix well to obtain a new brominated epoxy tree called "month", "chemical oxygen resin ( EP — 0). The reaction method is to dissolve the reactant between 90 ° and 120 ° C. After the solution is fully dissolved, the catalyst is added. The temperature of the catalyst is 1 0 0 · 1 3 0 C '11 5 ~ 1 3 〇 ° C is most suitable. The catalyst can be used with quaternary phosphorous salts or imidazoles. The quaternary phosphorous salt can be used to obtain a better hue catalyst. · 〇6 ~ 〇 · 1%, the reaction temperature is 150 ~ 200 ° C, more suitable reaction temperature is 160 ~ 180 ° C, the reaction time A is 60 ~ 180 minutes. The (A) phenol-benzaldehyde polyfunctional epoxy resin system is a benzene-phenanthrene acid resin obtained by conducting a condensation reaction with stearic acid in the presence of an acidic catalyst. Epichlorohydrin synthesizes phenol in the presence of sodium hydroxide (Na0H) ~

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V. Description of the invention (6) Synthetic reaction of acetaldehyde polyfunctional epoxy resin, the general reaction conditions are the same as those used in the process of gas-epoxy-2,3-epoxypropylene epoxidation, and the synthesized phenol-benzaldehyde polyguandiyl group The epoxy resin has an epoxy equivalent weight (EEW) = 210 to 26 0 g / eq, an average function / number of two to 2 to 6, and an average molecular weight Mw = 4 0 0 to 2 5 0. (B) Bifunctional epoxy tree ^: Contains diglycidyl ether of 2, 2-bis (4-hydroxypheny 1) propane), bisphenolρ epoxy resin (diglycidy1 ether of

The range of epoxy equivalent weight (EEW) of 2,2-bis (4-hydroxyphenyl) methanembisphenolF epoxy), (B) is 170 ~ 500g / eq. (C) The bromine-containing bifunctional epoxy resin is a tetrabromobisphenol A epoxy resin (diglycidyl ether of epoxy equivalent (EEW) = 3 0 0 to 5 0 0 g / eq, and the bromine content = 30 to 55% (D) tetra-bromo bisphenol A (TBBA for short), molecular weight Mw = 544 〇 This novel brominated epoxy resin composition, whose Mw = 150 0 ~ 40 0 0, dispersibility of molecular weight distribution Index (Mw / Mn ratio) = 1. 5 ~ 4. 0, EEW = 3 0 0 ~ 500 g / ed, hardeners such as dicyandiamide, bisphenol A, tetrabromobisphenol A, multifunctional 4 Multifunctional novolac is used to prepare laminate varnish composition. When dicyandiamide is used as the hardener, the amount of dicyandiamide is 2 ~ 8phr, most preferably 2 ~ 4phr, and polyhydr ic phenol is used. ic) When the hardener is used, the amount of polyhydric phenol is a ratio of phenolic OH groups to epoxy equivalents = 0. 5 to 1.5. The most appropriate amount ratio is 0.9 to 1.1.

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The varnish composition prepared from the novel brominated resin also needs to be added with an accelerator, and suitable accelerators are imidazoles (benzyldimethylamine) and benzyldimethylamine. Most preferably 2-phenyl imidazole (2-phenyl imidazole) and 2-methyl imidazole (2iethy; l imidaz〇ie), the amount of accelerator added is 0. (Η ~ 0. 15phr. The following examples illustrate the invention , But does not limit the scope of the present invention. In the examples, parts " and each means "parts by weight" and "wt%", the novel brominated epoxy resin of the present invention can be made into copper by methods known in the industry Foil epoxy laminates, such as children's compositions, commonly use di Cyd i am i de as a hardener, imidazole (tertiary amine) or tertiary amines as accelerators, and solvents (appropriate The solvent is N, N dimethylformamide (DMF), acetone, butanone. After adjusting the viscosity, the glass fiber cloth is heated to dry the impregnated glass fiber cloth into a pre-impregnated body. A copper foil is placed on one or both sides of the prepreg, and one or more prepregs are laminated, and finally the laminate is heated under pressure to produce a copper foil substrate. Example 1: φ will 9. 5 parts of Pan-benzaldehyde-type polyfunctional epoxy resin (EEW = 24〇, Nanya Plastics Co., Ltd., NPPN-433), 53. 7 Bipana-type epoxy resin with an epoxy equivalent of iggg / eq (Nanya Plastic Company, product name: NPEL-128E), 27.2 parts) tetrabromobisphenol A (TBBA), 4 · 8 parts ring Oxygen equivalent (EEW) of 390 gram / eq of quaternary bisphenol A epoxy resin (Nanya Plastic Company, product name: npeb-40 0), 4 · 8 parts

574246

Guanxi-based epoxy resin (EEW = 220 g / eq, (Nanya Plastics Co., Ltd., name: NPPN: 431)) These five chemical substances were reacted at 170 ° C for 12 minutes to obtain a brominated% oxygen resin "EP -1π, and the brominated epoxy resin "Ep — 丨” was dissolved in 20% acetone and formulated into an 80% solution. The epoxy resin thus obtained “Ep — 丨” has an epoxy equivalent (EEW) = 390 g / eq, weight average molecular weight = 2300, bromine content = 18 2%.

The ingredients used in the copper foil substrate of the present invention are that 〇00part brominated epoxy resin EP-1, 2.5 parts dicyandiamide, and 〇07 parts 2-phenylimide σ are dissolved in n, n, Dimethy methoxamine and a resin solution adjusted to 65%. The glass fiber cloth (brand: Nanya Plastic Glass Fiber Cloth, cloth type 7628) containing / fork the above resin solution, and then dried at 170 ° C (impregnation machine) for several minutes. The drying time can be adjusted by adjusting and controlling the drying time. The minimum melting degree of the post-pre-impregnated body is between 40,000 and 1000 poise. Finally, 8 pieces of pre-impregnated body are stacked on top of each other between 3 and 5 um thick copper foils at a pressure of 25 kg / cm2. Under the control of temperature rise program: '85 ° C-85 ° C-185 ° C-> 185 ° C-i3〇 ° c 2 in 3 0m in 1 2 0m in slowly cooling to obtain a copper foil of 1.6mm thickness Substrate. Example 2: 40 parts of a bisphenol A epoxy resin (Nanya Plastic Company, product name: NPEL-128E) with an epoxy equivalent weight (EEW) of 186 g / eq and 13 parts of a phenol-benzyl type multi-agent

574246 V. Description of the invention (9) Moon dagger epoxy resin, 28 parts of Si Mo Bi A (TBBA), and 2 parts of tetrafunctional epoxy tree Yue Yue (Nanya Plastic Company, product name: NPPN-431), 4 170 kinds of chemicals. After reacting for 120 minutes at 0 ° C, cool to 130 ° C and add 12 parts of bisphenol A epoxy resin (Nanya Plastic Company, product name: NPEL-128E) with an epoxy equivalent weight (EEW) of 186 g / eq and 5 parts of ring. Tetrabromobisphenol a epoxy resin (Nanya Plastics Co., Ltd., name: NPEB-4 0 0) with an oxygen equivalent of 390 g / eq. Brominated epoxy resin "EP-2II dissolved in 20% acetone and formulated into an 80% solution. The epoxy resin thus obtained" EP-2, has epoxy equivalent EEW = 394g / eq, weight average molecular weight = 2138 , Bromine content = 18 8%. Φ A resin solution was prepared from the epoxy resin EP-2Π, and a copper rhenium substrate was prepared from the resin solution. The basic method used above was the same as that in Example 1. The varnish formulation used 2.5 parts of dicyandiamide and 〇.〇 7 parts of 2-phenyl flavor, dissolved in Ν, Ν'dimethylmethdonamine, adjusted to 65% resin solution, and controlled in the impregnation machine for drying time, adjusted the minimum melt viscosity of the pre-impregnated body after drying It is between 40 0 0 to 1 0 0 0 poise. Example 3: 20. 2 parts of a bisphenol a epoxy resin (Nanya Plastics Corporation, product name: NPEL-128E) with an epoxy equivalent weight (EEW) of 186 g / eq and 49.5 parts of Pan-Stupid Functional epoxy resin, 2 1 · 2 parts of tetrabromobisphenol A (TBBA), 3 chemical substances react at 170 ° C for 120 minutes, then cool to 130 ° C and add 7 parts of epoxy Tetrabromobisphenol A epoxy resin (Nanya Plastics Co., Ltd., product name: NPEB-400) with an equivalent weight (EEW) of 390 g / eq and 2 parts of tetrafunctional epoxy resin (Nanya Plastics Co., Ltd. product name: NPPN-43 1), the brominated epoxy resin "Ep — was prepared after homogeneous mixing, and

Page 14 574246 V. Description of the invention (10) The odorant epoxy resin EP-3Π is dissolved in 20% acetone and formulated into an 80% solution. The epoxy resin thus obtained has epoxide equivalent (EEW ) = 378, weight average molecular weight = 3 36 6, bromine content = 5 · 8%. A resin solution was prepared from epoxy resin, EP-3, and a copper foil substrate was prepared from the resin solution. The basic method used above was the same as that in Example 1, except that 2.5 parts of dicyandiamide and 〇5. 2-Phenyl salicylic acid, dissolved in N, N 'dimethylformamide, adjusted to 6 5% of the resin solution, and controlled in the impregnation machine drying time, adjusted the minimum pre-impregnated body after drying The melt viscosity is between 4000 and 1000 pSe. Comparative Example 1: m 9.5 parts of o-cresol-type phenolic polyfunctional epoxy resin (EEW = 2 10 g / eq, average number of functional groups = 12 to 13, Nanya Plastics Corporation, product name: NPCN-704), 532 parts of bisphenol A epoxy resin with bad oxygen equivalent (EEW) of 186 g / eq (Nanya Plastics, Division, product name: NPEL-128E), 27.2 parts of tetrabromobisphenol a (tBBA), 4 · 8 Parts of tetrabromobisphenol A epoxy resin with an epoxy equivalent of 390 g / eq (Nanya Plastics Company, product name: NPEB-40 0), 4 · 8 parts of a tetrafunctional epoxy resin (EEW = 22〇g / eq , Nanya Plastics Co., Ltd., Product Name: NPPN-431) These five chemical substances were reacted at 17 (rc for 120 minutes to obtain the desertified epoxy resin "Ep-4", and the brominated epoxy resin "EP-4" It was dissolved in m and formulated into an 80% solution. The epoxy resin ❿ EP-4 thus obtained had% oxygen when: E = 372 g / eq, weight average molecular weight = 3500, and bromine content = 18.2%. 100 parts of the above-mentioned desertified epoxy resin " Ep_4 ", 2.5 parts of dicyandiamide and 0.03 parts of 2-phenyl flavor saliva were dissolved in N, N 'diamidinofluoramine to adjust to 65%

574246

The resin solution is controlled in the impregnating machine drying time, and the minimum melt viscosity of the pre-impregnated body after drying is adjusted to be between 4,000 and 10,000 pise. Comparative Example 2: 37 parts of a bisphenol a epoxy resin (Nanya Plastic Company, product name: NPEL-1 2 8 E) having an epoxy equivalent weight (EEW) of 186 g / eci and 10 parts of an o-phenol phenolic acid ring Oxygen resin (EEW = 210g / eq, Nanya Plastics Co., Ltd., NPCN — 704), 26 parts of Si Mo ^ A (TBBA), and 5 parts of tetrafunctional epoxy resin (Nanya Plastics Co., Ltd., NPPN- 431). After reacting the four chemicals at 170 ° C for 120 minutes, cool to 130 ° C and add 15 parts of bisphenol A cycloepoxy resin (South Asia) with an epoxy equivalent weight (EEW) of 186 g / eq. Plastic company, product name: NPEL-128E), 7 parts of epoxy equivalent, tetrabromobisphenol A epoxy resin (EEW) of 390 g / eq (Nanya Plastics Company, product name: NPEB-4 0 0), After homogeneous mixing, a brominated epoxy resin "£ p — & " and a brominated epoxy resin π EP-5" was dissolved in 20% acetone and formulated into an 80% solution. The epoxy resin thus obtained 1 'ΕΡ-5 " has epoxy equivalent weight (EEW) = 354 g / eq, weight average molecular weight = 2800, and bromine content = 18.7%. A resin liquid was prepared from the above-mentioned epoxy resin "EP-5", and a copper foil substrate was prepared from the resin liquid. The basic method used above was the same as that of Example 1 except that 2.5 parts of dicyandiamide and 0.02 parts of 2-phenyl 17-meter saliva was dissolved in n, n, difluorenylamine, adjusted to 65% of the resin solution, and controlled by the impregnation machine drying time, and the minimum melt viscosity of the pre-impregnated body after drying was adjusted to 4000 ~ 10000poise room.

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P.16 574246 V. Description of the invention (12) Comparative example 3: π parts of epoxy equivalent (EEW) of 186 g / eq of Shuangweng a-type epoxy resin C Nanya Plastic Company, product name: NPEL-128E) and 35 Parts of phenolic polyfunctional epoxy resin (EEW = 178g / eq, Nanya Plastics Co., Ltd., NPPN-638), 19 parts of Si Mo Shuangpan A (TBBA), and 5 parts of tetrafunctional epoxy resin (Nanya Plastics Co., Product name: NPPN-43 1). After 4 kinds of chemical substances react at 170 ° C for 120 minutes, cool to 130 ° C and add 9 parts of epoxy equivalent (EEW) of 49.0 g / eq. Type A epoxy resin (Nanya Plastics Co., Ltd., NpEB—400), and 5 parts of O-Pan, and hope to build a multi-functional epoxy resin (EEW = 21〇g / eq). Epoxy resin "EP-6", and brominated epoxy resin "Ep-6" was dissolved in 25% acetone to prepare a 75% solution. a " and ^ t * (EEW) = 370, t * ^ Γ *! ΐ5: ^ 0 / η A resin liquid was prepared from the above-mentioned epoxy resin "EP-6", and the resin liquid was prepared from the resin liquid. Copper foil substrate, the basic method used above Same as in Example 丨, 2.5 parts of dicyandiamide and 0.02 parts of 2-phenylimidazole were used in different places, dissolved in N, N dimethylformamide, adjusted to 65% resin solution and Controlled in the impregnating machine drying time, adjusted the minimum melt viscosity of the pre-impregnated body after drying to be between 4000 and 1000 poise. Comparative Example 4: A commercially available standard bifunctional brominated epoxy resin was used, EEW = 420 g / eq, Bromine content = 19.3%, weight average fraction = 26〇〇 (南

574246, Description of the invention (13) Asia Plastics Corporation, product name NPEB-45 0), adding 95 parts of the above-mentioned difunctional epoxy resin to 5 parts of tetrafunctional epoxy resin (EEW = 220 g / eq) to obtain bromine Resin π EP-7π, and brominated resin π EP-7π was dissolved in 20% acetone to prepare an 80% solution. " The epoxy resin "EP-7" obtained above is used to prepare a resin solution, and a copper foil substrate is prepared from the resin solution. The basic method used above is the same as that in Example 5 except that it is used 2 · 5 parts of dicyandiamide and 0.05 parts of 2-methylimidazole, dissolved in Ν, Ν-methyl methylamine, adjusted to 65% of the resin solution and controlled in the impregnation machine drying time, adjusted for pre-impregnation after drying The minimum melt viscosity of the body is between $ 4000 ~ 1000pse. Table 1 and Table 2 are the formulation tables of all examples and comparisons and the physical properties of the prepreg copper foil substrate. 2 It can be known (1) When adjusting the gelatinization time of the varnish = 3,000 seconds + seconds, the amount of accelerator used can be increased, and the reaction speed of the desertified epoxy resin can be known. Therefore, the example is shown: phenol-benzaldehyde polyfunctional group Epoxy Epoxy (" EP-Γ ,, " EP-2 ", " E " ") Comparative Example: O-Phenylphenol: Polyfunctional epoxy resin and multifunctional epoxy resin All the companies (" EP-4 ", "Ep_5 ", " Ep_6 ") have a slow reactivity. ⑺Control the tree M ’s low dynamic viscosity ^ _P〇1Se left Example ": Brominated resin (" EP_ 丨 ,, (, Ep 2 ", polyfunctional epoxy resin) whose pre-impregnated gelation time is longer than that of the comparative example: o-formamidine light 574246 5. Description of the invention (14) A brominated resin (π EP-4Π, π EP-5Π, π EP-6Π) synthesized from a multifunctional epoxy resin, and a basic bifunctional epoxy resin (brominated resin '' EP) —7 ") are close to each other, showing that the brominated resin synthesized by the hope of a benzyl polyfunctional epoxy resin has a wide compression processing range. (3) Synthetic from a phenol-benzaldehyde polyfunctional epoxy resin Brominated resin with high Tg and excellent heat resistance.

Page 19 574246 V. Description of the invention (15) Table 1 Examples and Comparative Examples Formula Unit: Gram item list 1 Potential example 2 Miscellaneous example 3 Financial transaction example 4 thl Transportation example 5 Transportation example 6 Financial transaction example 7 EP-1 (Solid state) 100 — — — — — — EP-2 (Solid state) — 100 — — — — One BP · 3 (Solid state) — — 100 — — — — ΗΜ (Solid state) — — — 100 — — — ΒΡ-5 (Solid state) — — — — 100 — — Β-6 (Solid state) — — — — — 100 — EP · 7 (Solid state) — — One — — — 100 Acetone 25 25 25 25 25 33.3 25 Double test 2.5 2.5 2.5 2.5 2.5 25 2.5 2-methylimidazole — — — — — — 0.05 2-phenylimidazole 0.07 0.07 0.05 0.03 0.02 0.02 — Ν, Ν-dimethylformamide 30 30 30 30 30 30 30 Table 2 Examples and Comparative Example Physical Property Comparison Table iiiii Page 20 574246

V. Description of the invention (16) Item Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Lacquer gelling time (not) 292 seconds 310 seconds 315 seconds 304 seconds 285 seconds 170 seconds 286 Prepreg gelation time in seconds (170 °, 133s, 130s, 134s, 100s, 95s, 80s, 136s, minimum melt viscosity of prepreg * 1 4200 6000 5200 5000 5300 5200 4800 Glass transition temperature (° C, DSC) * 2 150 150 170 151 152 174 140 Water absorption ° /. (After half-hour pressure cooker treatment) * 3 0.2% 0.2% 0.18% 0.2% 0.2% 0.18% 0.23% 288 ° C Solder heat resistance (half After hours pressure cooker treatment) * 4 5 minutes 5 minutes 5 minutes 5 minutes 5 minutes 5 minutes 3 minutes 40 seconds Peel strength of copper foil (lb / inch) 11.5 11.5 9 11 11 8 12 Flame resistance (UL-94) V0 V0 V0 V0 V0 V0 V0 Note: * 1 · Use Shimadzu sh i mazuCFT-1 0 0 F 1 owme ter to test the minimum melt viscosity, heating rate = 1.75 ° C / min. * 2. Use a micro scanning thermal analyzer ( DSC). Wood 3. The sample is heated in a 120 ° C and 2 atm pressure cooker for 30 minutes. Wood 4. The sample is heated in a 120 C and 2 atm pressure steel for 30 minutes and then immersed in a 288 m ° C soldering furnace. Record Delamination time required for burst-like. (Measured Description) 1. varnish gel time (V a r n i s h g e 1 t i m e) The test for reactivity of novolac epoxy resin solution with a dicyandiamide curing agent solution

574246 V. Description of the invention (17) Liquid (> Gu Yuluo DMF, > Valley liquid> Chen degree = 1 3 · 3%), Accelerant 2 —Phenyl sigma or 2-methyl taste saliva Liquid (> Valley > Valley DMF, solution concentration = 1 4 · 2 8%) g of a varnish mixture, the varnish mixture drips about 0 · 3 m 1 on a hot plate, the hot plate temperature = 17 〇 ° C, record the time required to gel. 2. The gelation time of the impregnated body (Prepreg gei timy test method is to weigh the pre-impregnated body powder 0.2mg on a hot plate, the hot plate temperature = 170 ° C, record to gel The required time 3. The minimum melt viscosity of the prepreg body The test method of the minimum dynamic viscosity of the prepreg body is the Shimadzu CFT-1 00 flowmeter using the instrument brand, and 丨 · 8g of prepreg powder is formed into a cylindrical shape ， Temperature test range = 80 ~ 130 ° C, Heating rate =; [· 7 5 / m 丄 n. 4. Water absorption test The water absorption test method is to cut the etched substrate into 5 cm2 square test pieces' After supplying in the box for 2 hr at 105 C, place the test piece in the pressure cooker. The condition of the pressure cooker is 2 atm X, 1 2 QC. After passing through the pressure steel 3 ◦ m ^ n, record the test piece in the pressure cooker. The difference in reset is divided by the initial weight of the test piece, which is the water absorption rate. 5 · 2 8 8 ° C The test method for solder heat resistance is to dip the test piece that passed the pressure cooker into a 288 ° C soldering furnace and record the burst of the test piece. Required time.

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Claims (1)

574246 This new glass brominated laminated board is made of high-glass Koreans + Japanese dagger # 丄 η, and a novel brominated epoxy tree moon-day shift (Tg), based on (A) phenol-benzaldehyde Contained content &% by weight 旎 chen rolled resin (formula π, 10 ~ 70 li. ") Bi-B This base% oxygen resin, 0 ~ 55% by weight; (〇 functional group containing epoxy resin, 0 ~ 20% by weight ， Self-working 3 shoulders again. / ^, Liri / g, (D) Tetrabromopropanol, 15 ~ 40 reset / ;; First, (D) and (A), (B), (C) At least one of the three kinds of ΐ = line reaction '. Then add ⑴, ⑻, ⑹ the rest of the &> It is evenly balanced to get a flat weight, said that the number of ten to 77 (MW) is 1500 to 4000, and the molecular weight is / Dispersion index (ratio of Mw / Mn) of knife cloth is 15 ~ 4 0 denier (EEW) is 30 0 ~ 45 0g / ea Brominated irregularities such as dagger # 丄 ·, Tanari ^, gQ / Wuhua鳅 Milk resin has a glass transition temperature (Tg) of 150 ~ 190 ° C. 2. A novel brominated epoxy resin with a high glass temperature (T g) for glass fiber laminates as described in item 1 of the scope of patent application, where the epoxy equivalent (EEW) of (a) is 210 ~ 2 60 g / eq , The average number of functional groups is 2 to 6, and the average stomach fraction (Mw) is 40 0 to 2 5 0 0 Page 23 574246 6. Scope of patent application 3. If a novel temperature-brominated epoxy resin (Tg) of item 1 of the scope of patent application is used, it is used for s-board and the glass-breaking transfer resin contains bisphenol A epoxy resin. 5⑻ is a bifunctional epoxy resin with a range of 170 ~ 50 0 § / called "^% oxygen resin, (β) epoxy when 4. as the scope of patent application! One of the novel desertification epoxy resins with the ancient temperature (Tg) of glass fiber layer, the mouthpiece ^ glass transfer epoxy resin is tetrabromobisphenol A if f （() is the epoxy of 3 bromine bis s energy-based resin Equivalent ⑽ is ... Mo Shuangguan ... ^)) is 300 ~ 500g / ec [, bromine content = 30 ~ 55%. 5 · As in the scope of the patent application, the first process g + _ ^ ^ e. Λ temperature σ g k novel desertification Λ plywood with high glass transfer 544 of the four desert double A. Yixueshuyue said ‘where (D) is the molecular weight ⑽ is Page 24