TW200804516A - Syntheses of novel dihydrobenzoxazine thermosetting resins and its applications - Google Patents

Abstract

This invention is composition of an epoxy vanish with high Tg applied to laminated boards. The composition includes (A) a novel dihydrobenzoxazine thermosetting resin, which is generated from the reaction of the following compounds: (i) a phenolic product generated from difunctional or multifunctional epoxy resin react with difunctional phenolic compound; (ii) mixed primary amine compound with monofunction and difunction; (iii) a difunctional phenolic compound; and (iv) a formaldehyde or paraformaldehyde compound; (B) one or various kinds of epoxy resin(s); (C) novolac-curing agent; and (D) the curing accelerator. Because of the thermosetting resin compound "modified dihydrobenzoxazine" is multifunctional in the epoxy resin varnish composition, that can increase the crosslinking with resins to improve the mechanical intensity and heat resistance of base plates obviously. And resolve the bad solubility of dihydrobenzoxazine in the solution to increase the production efficiency sharply. Moreover, using the novolac-curing agent can reduce the curing temperature for dihydrobenzoxazine compound and epoxy resin, and advance the crosslinking completely with epoxy resin. This epoxy resin composition in this invention can improve the high Tg, low water absorption, outstanding heat resistance and pass the UL94 V-0 flame resistance test. That can be applied to high performance electronic materials widely.

Description

200804516 IX. Description of the invention: [Technical field to which the invention pertains] The present invention is a high-glass transition temperature ring I resin which is excellent in reactivity and wide window in a laminate process. And ^ ^ ^ nn is good, and its pressed sheet has a high glass transition temperature (Tg), low water absorption, a heat resistance and pass the flame resistance UL94V»0 job. It can effectively reduce the enthalpy or bromine to make 2 = . demand and save costs. Connected to flame-resistant [Prior Art] Epoxy resin due to its own chemical structure, in reactivity and ageing, transmission ± f-like verification; · Du New = face = Bo t phase 1 more 'hard to lose The fat $ is still only read in the county, the cake and chemical shells are more barrier- ing and have the advantages of low quality and low cost, so that the epoxy makes the sub-boards secret, light, ^, and (4) County-end printing at the end of the year [Invention content]: [Technical subject to be solved] The name of the mouth, printed: 1^, the laminate board, with the promotion of environmental awareness 'current international standards require no error 1 (ea free ), so the processing requirements of the substrate are particularly strict, especially for the glass of the material, the temperature (Tg) and the base of the cloth, the _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The technical means of the subject] ~ ί ίΐίίΐϊ 'This Γ 经 经 经 经 经 Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂Sex, low water absorption and New Wei, _ two scales willow hydrcbe job azi β χ two f if seeking characteristics. * The diazonium benzoate thermosetting resin has excellent heat resistance, high Tg and flame resistance in its chemical structure: y, and has a stereoscopic restriction on the functional group of each gas resin and the structure of the benzene ring.苴 亘 亘 亘 亘 亘 亘 亘 亘 亘 亘 亘 亘 亘 亘 亘 亘 亘 亘 亘 亘 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 A small amount of phosphorus is introduced into the resin, and a resin material for a flame-retardant laminate can be obtained by a synergistic effect. The object of the present invention is to provide a high glass transition temperature epoxy resin varnish composition for a laminate, comprising: (A) a novel dihydrobenzo (10) thermosetting resin which is obtained by reacting the following compounds; The composition comprises: (8) a difunctional or difunctional epoxy resin and a difunctional compound obtained by reacting a variety of products; (b) a monofunctional and difunctional mixed monoamine compound (c) a difunctional phenolic compound; and (formaldehyde or polyoxymethylene compound. (B) or a compound of the above epoxy resin, (C) a resin hardener; 1) a hardening accelerator. ^ This epoxy resin varnish formulation can effectively improve the glass transition temperature (Tg) of the material after hardening to reduce the water absorption of the substrate and improve the heat resistance, and can effectively reduce the cost and excellent processing. · This, the continuous hard layer (4) glass ray varnish temperature epoxy resin varnish domain, because of the new mixed bismuth benzo (NPBX) thermosetting resin, so that it has better mechanical and chemical than ordinary epoxy resin This and physical Wu, such as low moisture absorption, high glass transition temperature, dimensional stability and good electrical properties; under the South temperature (2 thieves) technology can not promote the self-opening polymerization of its own energy, and its opening The ring polymerization has no volatile matter (by-product) and does not affect the physical properties of the substrate (4), but the hardening reaction rate & at high temperature is not easy to control. If a proper amount of the phenolic structural compound is added during the hardening process, not only the curing speed and the hardening temperature are promoted, but also the ring-opening polymerization is promoted, so that the substrate has better physical properties. The novel dihydrobenzo (NPBX) thermosetting resin to which the present invention is incorporated is disclosed in U.S. Patent No. 4,607,091, which is incorporated herein by reference to U.S. Patent No. 4,607,091, and U.S. Patent No. 6, (9) :〗 64 No. 64 is prepared by using phenolic resin, aniline and formaldehyde. However, the hydrogen benzo (NPBX) resin prepared by the above-mentioned U.S. patent, due to poor solubility, is liable to be supersaturated due to storage at room temperature, which causes crystallization of large solids, which is inconvenient for subsequent use. In order to avoid crystal precipitation, the novel dihydrobenzo (NPBX) resin synthesized by reforming has a modified chemical structure, and does not cause a large amount of crystal precipitation when it exists, and is applicable to a large number of industrial products. produce. Another U.S. Patent No. 5, No. 21,484 is the use of Benzoxazine for direct high temperature hardening and the addition of α1(〇η)3 flame retardant, i.e., 2逹 to UL94 V-0 rating. U.S. Patent No. 5,443,911 utilizes Benz〇xazii^, brominated epoxy resin and hardener to reduce the amount of bromine used, and the laminate can also be graded after hardening. The Republic of China Patent No. 091125399, which uses an aromatic diamine compound, a phenolic compound aniline and an aldehyde compound, proposes a method for preparing a Dihydrobenzoxazine thermosetting resin, but uses a compound of Fangxiangzhi, which is expensive and not suitable for industrial use. produce. 200804516 [Detailed Description of the Invention] The present invention is composed of Ifl-provided Weishu County mixed two main and inflammatory formulas, and its composition includes ··(8)-species new (10) Xin) heat _ 曰 月 漆 lacquer hardening t (D a hardening accelerator, etc.; (4), (8), =Lii= & 4, a duck-laminated plate-like plate containing _solid or dibenzoxan x), the structural formula is as follows, a paste (8) - a difunctional LI 2 The surface product obtained by the reaction of a difunctional group with a difunctional group; (b) a first-order amine compound mixed with #7 earlier; (C) a difunctional group. The compound 'and ()m or polysulfonate compound, and is obtained by reacting in a hydrocarbon solvent. After the modification, it can be various types, and the synthesis examples are detailed below:

Among them, A can be represented by the following chemical formula

And C can be -CH2 - and D can be I -c - ! -Q- 53ιί-0Η3 ηϊφο?η2ίη2ο-

2 Η 2 Η Η Η > -οάά-clo- H2HH2Η 0-CC-C0-^ )-cl^ ^ —ο 200804516 R1 and R2 can be respectively: H, CH3, Br where 'B can be amine (amine) or diamine compound. (A-1) NPBX-610 is placed in a four-neck glass reaction tank equipped with a heating pack, a temperature controller, an electric mixer and a condenser. 1710 g of bisphenol (Bispheol A, BPA) and 558 g of liquid ring are placed. Oxygen resin (NPEL-128E), adding a quaternary phosphorus salt catalyst to a 15 (y > c reaction for 2 hours in a small amount of solvent, and then adding 782 g of paraformaldehyde and 1000 g of toluene to dissolve and dissolve, and then 16 g of aniline was slowly dropped into the above solution, the temperature was controlled between 60 and 11 (rc, the reaction was carried out for 4 to 6 hours, and then the vacuum and the unreacted matter were extracted by vacuum), and then 900 g of propylene was taken. Adding to dissolve, you can get 80% of the modified dihydrobenzo compound, hereinafter referred to as NPBX-610. (A-2) NPBX-620 is equipped with heating package, temperature controller, electric mixer, condenser In a 5L four-neck glass reaction tank, put 171 grams of propylene glycol (Bispheol A, BPA), 279 grams of liquid epoxy resin * qing -128] £), add a four-stage salt-filling catalyst in a small amount of solvent. The reaction was carried out at 150 ° C for 2 hours, and after cooling, 880 g of paraformaldehyde and 148 g of diaminodiphenyl metha were added. Ne) and 1 gram of benzene benzene were dissolved and dissolved, and 1116 g of aniline (aniUne) was slowly dropped into the above solution, the temperature was controlled between 60 and 110 ° C, the reaction was carried out for 4 to 6 hours, and then the bath was vacuumed. The agent and the unreacted material are extracted, and 900 g of acetone is added to dissolve, and the modified dihydrobenzo compound of the solid content of go% is obtained, hereinafter referred to as NPBX-620. (A-3) NPBX-630 is provided with Heating bag, temperature controller, electric mixer; I four-neck glass reaction tank of condensing tube, put 1710 g of bisphenol (Bispheol A, BPA), 600 g of tetrafunctional cyclic oxime resin (NPPN-431). Add a quaternary salt catalyst to 15 in a small amount of solvent (rc reaction for 2 hours, add 782 g of paraformaldehyde and 1000 g of toluene to dissolve and dissolve, and slowly drop 1116 g of aniline into the above. In the solution, the temperature is controlled between 60 〇 〇 〇 ° C, the reaction is 4 to 6 hours, and then the solvent and the unreacted materials are extracted by vacuum, and then 9 gram of acetone is added to dissolve, thereby obtaining a solid portion 80. % modified dihydrobenzo compound, hereinafter referred to as npbX-630. (A-4) NPBX-640 is equipped with heating package, control 1710 g of propylene glycol (BiSpheol A, BPA), 300 g of tetrafunctional epoxy resin (NPPN-431), and a four-stage epoxy resin (NPPN-431) were placed in a four-neck glass reaction tank of a mixer, electric mixer and condenser. The phosphorus salt catalyst was reacted at 15 ° C for 2 hours. After cooling, 880 g of paraformaldehyde, 148 g of melamine diphenyl oxime (Mamiiiodipheiiyl methane) and 1000 g of toluene were stirred and dissolved, and 1116 was added. Acetanilide (tnmne) is slowly, into the above solution, the temperature is controlled between 60~11 (rc, reaction for 4~6 hours, then the solvent and unreacted materials are extracted by vacuum, and then 9 gram of acetone is added to dissolve The modified dihydrobenzo compound, hereinafter referred to as NPBX-640, can be obtained. In the above synthesis examples of A-1, A-2, A-3 and A-4, the preparation of the dihydrobenzo compound (a) -9 200804516 decano-functional epoxy resin and trifunctional group Reaction of a compound

.*, New Zealand uses liquid epoxy resin and Cyan II compound, and the desired product obtained after the reaction. Xing, nickname is the following chemical formula:

Among them, F can be represented by the following chemical formulas·· CH〇

E can be represented by the following chemical formula: R3, R4 can be H, CH3, Br, respectively.

犏Preparation of 5-chloro benzoate compound (b) A monofunctional and difunctional mixed mono-amine compound. Generally, a primary amine such as methylamine, aniline, t〇luidine, decyl aniline is used. (^msidme), etc. 'may be a thief aromatic compound, preferably aniline or diaminodiphenyl preparation = hydrogen benzo compound (c) a difunctional phenolic compound, generally using o-- Pan-propion® 7 A-propanoid F, propylene-dissolved s, melamine or expectant resin, etc., the best is propylene or sulphuric acid. To prepare (6) citric acid or polymethyl compound, generally using methacrylate, polyoxymethylene or formaldehyde oxime, etc., preferably polyfurfural, because polyoxymethylene will slowly dissolve as the primary amine is added dropwise. To promote the formation of a dihydro benzo (ru) resin ring. The solvent for preparing the dihydro benzo compound compound is not particularly limited as long as it can dissolve each reaction 10 200804516. For example: alcohols, ketones, ethers, esters or hydrocarbon solvents, hydrocarbon solvents such as toluene, mono-toluene, etc., because water molecules are produced after polymerization, and the reaction water is not compatible with toluene. , can be re-used after distillation and reused. x The component (B) of the resin varnish formulation of the present invention, the epoxy resin of which may be an organic phosphine compound (for example, 9,10-dihydro-9-oxa-10-phosphphenyrene) -10氡 compound (abbreviated as ^〇^〇)θ) reacts with o-cresol formaldehyde novolac epoxy (NPCN-703) epoxy resin to form a phosphine-containing epoxy resin (filled in an amount of 2 to 5% by weight); or bromine The epoxy resin is prepared by reacting tetraclidine with liquid epoxy resin (NPEL-12) and blending a polyfunctional epoxy resin to produce a resin (bromine content of 14 to 21% by weight). . The component (C) of the resin varnish formulation of the present invention, the resin hardener comprises a hardening agent such as polyvalent amines, polyvalent carboxylic acid (p〇lyvaient carboxylic), Dicyano diamide, anhydrides, phenolic furfural resin (Phen〇1 N〇VQlae Ερ^ PN for short), Melamine Phenol Novolac (MPN), BPA Phenli

Novolac (abbreviated as BPA-PN) and tetraphenol ethane resin (abbreviated as τγρν, produced by South Asia Plastics), etc., which is a tetraphenol ethane resin. And /, take 1 part of the resin varnish formulation composition of the invention (D), the hardening accelerator includes a tertiary shell, a tertiary amine, a quaternary salt, a quaternary ammonium salt, an imidazole compound, of which three Phosphine includes ···3·; tertiary amines include: trimethylaniline, triethylamine, tributylamine, dimethylamine ethanol, g salt, including: tetrabutyl desertification scale, tetraphenyl desertification镌, ethyl triphenyl brominated scales, propyl triphenyl squamous scales, butyl diphenyl-based desert scales and the like containing quaternary salt; quaternary salt includes: tetramethylammonium bromide, tetraethyl a quaternary ammonium salt of ammonium methoxide, tetrabutylammonium bromide, triethyl benzoyl ammonium bromide, triethyl stupid ethyl desertification, etc.; imidazole compounds include: 2-methylimidazole, 2-ethylimidazole, indoledecyl imidazole, 2-phenylimidazole, 4-methylcarbazole, 4-ethylimidazole, 4-dodecylimidazole, 2-ethylaminopyrene, 2 - Ethyl ice light methyl coffee sitting, etc., most suitable for 2_ methyl ipsi or 2 seven base fighting arm ^ wow. The accelerator can be used alone to mix the thief with two or more secrets. The amount of use is 0.01~1PHR of the total amount of fat, and the optimum amount is 0.04~〇.15PHRq, and the epoxy resin varnish of the south glass transition temperature of the laminated board of the present invention is used. Formula composition, is a new type of dihydrobenzo (peng x lion, 62G, (10) or (10)), containing 2g ~ 7g wt% β oxygen resin (10) EP, material * 2 ~ 5%) or containing _ oxygen axis (peng B, the age is 14~'2 hearts), 200804516 s is 30~70 wt%, (〇 hardener, content is added% and (D) hardening accelerator, its usage is Ϊΐ in Shulin 4 reading ~ 1PHR; and can add money to fill (dioxane, aluminum hydroxide, etc.) ' = other agents (plasticizer, light stabilizer, thermal stabilizer and UV absorber, etc.), using solvent wrap to make a square solvent , protic solvent, duck solvent, ether solvent solvent (suitable solvent is stupid, N, N-dimethylformamide, acetone, methyl ethyl ketone, μ methoxy 2-propanol, acetic acid Ethyl ester 1) Adjusting the viscosity of varnish. When used in laminates, this formula is composed of impregnated glass fiber cloth, and it is heated to make the fiberglass cloth of the shell dry. Ulcer body ②repreg), in one of the prepreg collapse thereof, or the copper surface is placed '_ and allowed to collapse or more prepreg layers folded body, and finally heating the sheet under pressure, to obtain a copper foil substrate. • The curing temperature of this oxyresin varnish formulation can range from 3 〇 to 3 (10). c, preferably 15〇 to j〇C ', = hardening $ is too low, the hardening rate is too slow, the hardening time needs to be extended, and the production efficiency is not met; the Hz dish is too low, which tends to promote the inferior solution of the resin, and the hardening reaction rate The shortcomings of being too fast to control, the addition of dihydrobenzo (NPBX) to the epoxy paint formula can reduce the cost; adding a hardener substance, the low reaction temperature of σ cattle and promoting the hardening cross-linking completely, improving the Tg and other characteristics of the substrate. EXAMPLES: DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The preferred embodiments of the present invention, the examples and the codes used in the comparative examples, and the phosphorous epoxy resin produced by the plastics of South Asia, have the trade name -〇〇LA70' The epoxy equivalent is between 340 and 380 g/eq and the phosphorus content is 26.6%. The tree ΐ Γ represents the two oxygen products produced by South Yana, trade name NLEP-204A70, two ', § 1 between 440~480g/eq, and the dish content is 4%. Represents the epoxy resin produced by Nanya Plastics Co., Ltd. under the trade name NPEB-454A80, ϊ between 420~455g/eq and bromine content of 19%. Representing the epoxy resin produced by Nanya Plastics Co., Ltd., the trade name is NPEB-485A80, , and the %虱 is set at 385~405g/eq, and the bromine content is 19〇/〇. Hardener A; represents dicyandiamide (DICY), 14.7% dissolved in DMF. Stone Chemical Agent B; represents the secret resin produced by South Asia Plastics Co., Ltd., the trade name is Nen·ρΝ.

It?1. ; represents the tetraphenol ethane resin produced by South Asia Plastics Co., Ltd., the trade name is ΤΡΝ. Scratch 2MI, representing 2-methyl methane, 14.2% dissolved in DMF. 12 200804516 [Scheme 1 to 8] Use different proportions of phosphorus-containing epoxy resin, new dihydrobenzo (see >] 8:?<:) and hardener, and add inorganic filler (Α1 ( ΟΗ) 3 and Si 〇 2) and a hardening accelerator, the formulation composition of which is detailed in Table 1, using acetone to adjust the varnish resin composition having a solid content of 65%; a laminate is prepared by a conventional method. The 7628 glass fiber cloth is impregnated with the varnish resin liquid, and then dried at 17 (rc (immersion machine temperature) for several minutes, and the melt viscosity of the prepreg after drying is adjusted to 4000~10 by adjusting the drying time. ^) 00poise room 'The last 8 layers of film are layered between two pieces of 35-um thick copper foil. Under the pressure of 25kg/cm, the temperature control program is as follows. After hot pressing, the laminate can be obtained.

85 〇 C ^ 85 〇 C - ^ 200 ° C - 20 min 30 min 120 min to obtain a 1.6 mm thick copper foil substrate. 200 ° C - slowly cooled

130 ° C than the rut example 1 to 2] 帛 not (five) proportion of the scaled epoxy and hardener, and add inorganic filler (A ^ OH) 3 and Si 〇 2) and hardening accelerator, but not Dihydrobenzo (4) was added, and it was used to adjust the viscosity of the 5% varnish tree; and the laminate was prepared in the same manner as the preparation of the laminate. [Beiyan 9~16] use different proportions of evolution epoxy resin, new dihydrobenzo (10) Xin) and hardening and add hardening accelerator. The varnish formula is detailed in Table 2, and it is adjusted by acetone.

The varnish resin composition having a shape of 65 Å/〇 was prepared by the method of preparing a laminate by the example W. [Compared to the parent's example 3~4] One piece uses a different proportion of the stinky epoxy resin and hardener, and adds a hardening accelerator, but does not add: lactic acid open (NPBX), which uses C- to adjust the solid shape A varnish resin composition of 65% was prepared; and a laminate was prepared in the same manner as in the preparation of a laminate of Example 1.8. [Measurement] 1. Varnish gel time (VGT) = paint reactivity test is to prepare epoxy resin solution with various hardeners and accelerators, and to prepare varnish. 3ml was dropped on a hot plate, the temperature of the hot plate was i7〇〇c, recorded to 200804516 2. 3· The time required for gelation, called VGT. The water absorption rate test 为 is to make the side back domain into a 5 cm2 square test piece, after the 105 °C container heat 3 〇 2, the test piece is placed in the house steel, the pressure steel condition is 2atmxl20 °c, After the sugar-coated steel was dried, the test piece was recorded at the pressure error, and the over-pressure 288 〇C resistance to solder heat resistance showed that the initial weight of the seven-piece piece was the water absorption rate. Law, the above-mentioned manual steel test piece, dip 288 <1: welding fresh towel, record the time required for layering 1 μ plate. Kiss version γ record martial arts explosion 200804516 Table 1; percentage table of phosphorus-containing epoxy resin varnish prepared by stirring at room temperature

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Comparative Example 1 Comparative Example 2 Epoxy Resin A 58 54 57 58 97 Epoxy Resin B 41 39 37 38 79 NPBX- 610 26 47 NPBX-620 30 47 NPBX-630 26 50 NPBX-640 28 45 Hardener A 3 Hardener B 16 17 13 21 Hardener C 16 14 12 14 17 Filler Si02/ATH 30 30 30 30 30 3❶ 30 30 30 30 Accelerator 2MI(PHR). 0.11 0.08 0.06 0.1 0.1 0.08 ❹.07 0.07 0.05 0.08

15 200804516 Table 2; Percentage of composition of bromine-containing epoxy resin varnish prepared by stirring at room temperature

Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Comparative Example 3 Comparative Example 4 Epoxy resin C 53 5❹ 49 50 97 Epoxy resin D 46 44 45 47 78 NPBX- 610 31 38 NPBX-620 33 44 NPBX-630 37 42 NPBX-640 35 39 Hardener A 3 Hardener B 16 14 12 22 Hardener C 17 15 16 13 14 Accelerator 2MI(PHR) ❹.06 0.07 0.05 0.06 0.09 0.05 0.04 0.06 0.08 0.1

16 200804516 Table 3; Substrate characteristic evaluation analysis item Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 ^ Example 7 Example 8 Comparative Example 1 Comparative Example 2 Varnishing time sec*1 320 .330 350 300 380 290 330 340 310 340 Glass transfer temperature °c*2 170 182 173 186 192 189 182 . 195 150 153 Water absorption % *3 0.21 0.19 0.15 0.20 0.21 0.18 0.17 0.16 0.3❹ 0.28 Solder heat resistance sec* 4 40Q 600 ---__ -——--- 450 500 400 460 480 590 380 390 Flammability (UL-94) V-0 V-0 V-0 V-0 V-0 . V-0 v- 0 V-0 V-0 V-0 Description: ---__ --·~·_ -- *1· Take 0.3ml of resin varnish on a hot plate at 170 ° C and measure the gel time. *2. Using a differential scanning thermal analyzer (DSC), the heating rate = 20 ° C / min. *3. The sample was heated in 120 ° C and 2 atm pressure steel for 3 minutes. *4. The sample was heated in a 120 ° C and 2 atm pressure cooker for 30 minutes and then immersed in 288 ° C. - Tin furnace, when recording the sample blasting layer is required. 17 200804516 Table of substrate characteristics evaluation analysis item Example 9 Example 11 Example 12 ----- Example 13 Example 14 Example 15 Implementation Example 16 t 龄 4 4 4 4 4 4 4 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 - 177 182 180 179 149 151 Water absorption % 氺3 0.20 0.21 0.19 0.22 ----- 0.16 0.17 0.19 0.19 0.28 0.30 Solder 4 thermal sec*4 600 560 500 600 500 600 520 590 400 500 Flame resistance (UL-94) V-0 V-0 V-V-0 V-0 V-0 V-0 V-0 V-0 V-0 Description: *1· Take 0.3ml of resin varnish on a 170°C heating plate and measure Its gelation time. *2· Using a differential scanning thermal analyzer (DSC), the heating rate = 2 〇 / 111 丨 11. *3. The sample was heated in a 12 ° ° C and 2 atm pressure pin for 3 minutes. *4. After the sample was heated in a thief and 2 atm pressure steel for 3 minutes, it was immersed in a 288 〇c soldering furnace to record the time required for the blasting of the sample. According to the test results of the substrate of Table 3, the halogen-free resin formula composition of the present invention does not need to add a halogenated substance, and can reduce the content, thereby achieving the UL94V-〇 flame resistance standard and improving other physical properties of the substrate. The halogen resin formulation of Table 4 can also reduce the bromine content to achieve V-0 flame resistance standard and other physical properties of the substrate. Therefore, the invention adds a new dihydrobenzo (NPBX) thermosetting resin in a resin varnish formulation, which not only can reduce the cost, but also can be combined with a phenolic resin hardener, can further reduce the reaction hardening temperature, increase the crosslink density of the resin, and improve the physical properties of the substrate. 18

Claims (1)

200804516 X. Patent application scope: 1. A laminate containing a high glass transition temperature epoxy resin blended with a dihydrobenzoxazine thermosetting resin varnish formulation composition comprising: (A) a novel dihydrobenzene (Dihydrobenzoxazine) thermosetting resin, the content of 2 〇 ~ 70wt%; (B) one or more of 5 clothing Μ Μ 曰 (including epoxy resin or bromine containing epoxy resin), content 30~70wt%; (c) The aged acid resin hardener, the content is 1 to 2% by weight; and (D) the hardening accelerator, which is used in an amount of 0.1 PHR relative to the total amount of the resin. 2. A high-glass transfer temperature epoxy resin varnish formulation composition for a laminate of the first application of the scope of the patent application, (A) a novel dihydrobenzoxazine thermosetting resin in an amount of 20 to 70 wt. %, the structure is as follows Among them, A is the following chemical formula: And D is: R1 and R2 are respectively: H, CH3, Br · wherein B is an amine or a diamine compound. 19 200804516 3. A high-glass transfer temperature epoxy resin varnish formulation for laminates in the first and second sections of the patent application, (Α) a new type of dihydrobenzoxazine thermosetting tree The following compounds are used: a phenolic product obtained by reacting a difunctional or difunctional epoxy resin with a difunctional phenolic compound; (b) a monofunctional and difunctional mixed primary amine compound; (C) a compound obtained by reacting a difunctional phenolic compound; and (d) a formaldehyde or a polyoxymethylene compound. 4. The composition of claim 3, (a) is a phenolic product obtained by reacting a difunctional or difunctional epoxy resin with a difunctional phenolic compound in a ratio of 5 ~40wt%, the structural formula is as follows. Η2 Η Η2 -c-c-c- OH - where F is the following chemical formula: E is the following chemical formula: —ch2—113,114 are 0«3,61* respectively. 5. The composition of claim 3, wherein (b) is a monoamine-based compound in which a monofunctional group and a difunctional group are mixed in a ratio of 20 to 40% by weight. 6. The composition of claim 3, (c) is a difunctional phenolic compound in a ratio of 15 to 70 wt/hr. 20 200804516 7· The composition of claim 3, (d) is a meth or polycarboxylic acid compound, and the pot is 10 to 30% by weight. , 夕 J Bureau 8 · If you apply for the composition of the third paragraph of the patent scope, the organic solvent is such as: alcohol, freshman, stern, ester or hydrocarbon solvent, with a hydrocarbon solvent such as toluene and the like. , 9. If the laminate of the patent application scope 帛i is made of epoxy resin varnish with high glass transfer temperature, (8) is one or more epoxy resins, which may be Moist epoxy resin. , ι〇· ^ application 'patent scope s 9 items containing oxygen resin, is a phosphorus compound (such as m oxa-10- phenanthrene-10 oxygen compound, referred to as D〇p〇 for the adjacent __ 襄 襄 resin ( 〇__〇! j=naldeltyde ^〇volac epoxy) prepared by the reaction, the epoxy equivalent range is 350~48〇g/eq, the resin phosphorus content is 2~5 wt〇/〇, and the formula content is 3〇~ 〇················································································· Age methoxy resin (4) = 〇xy reaction, the epoxy equivalent range of 34 〇 ~ 46 〇 g / eq, resin scale content of 2 ~ 5 s / 〇, the formula content of 30 ~ 70 wt%. For example, the bromine-containing epoxy tree of the ninth application of the patent scope is prepared by the reaction of tb Wei resin, and its epoxy equivalent range is over 1 = Wt %, and its formulation content is 30. ~7〇wt%., Fruit δ 14 13. t Shenli turned the first item of the board with high glass _ shift temperature Wei resin varnish, and medium (c) phenolic resin hardener can be phenol formaldehyde resin ( Phen〇l (4) PN: Melaxmne Phenol Novolac (.xTS MPN) . BPAphen〇1 Ν〇ν〇^(α = Qiao BPA-PN), donated to the job fat (hereinafter referred to as τρΝ), etc., the best is the secret B-burning resin, the formula content is 5~30 wt %. 14· ft, ΐSpecial H 帛 帛 1 layer of laminated board with high glass transfer temperature epoxy varnish formula, /, medium (D) hardening accelerator is imidazole (imidazole) and benzyl Mercaptoamine b=dimethyl _ne). It is most suitable for 2·Methyl-flavored clothes, and the blood is also reduced. 2-Phenyl iidazole or 2-ethyl-Hejimi is deleted. For the total amount of fat, 0.01~0.15phr. ', 15.=ΐSpecial range of the first layer of the laminate board with high glass transfer temperature epoxy resin varnish formula, its additives (10) inorganic filler such as hydroxide _ 3), dioxide egg 102) ^ soil (day), titanium dioxide, barium titanate, titanium acid error, etc., the content of which is added 3 〇 ~ 5 〇 wt%. I6·For example, the epoxy resin varnish formula with high glass transfer temperature for the laminate of the first layer of the Shenqing patent dry circumference 21 200804516 The composition, wherein the medium viscosity is selected from the group consisting of acetone (heart kaolin methyl ethyl ketone (MEK), 17 oxy 1 propanol (PM), isopropyl alcohol (IPA) or N, N _ Methylformamide (DMF). As for the high-strength glass-turning and w-composition of the laminated board of the first application of the patent scope, it can be applied to the multi-laminated plywood and the composite material. Monthly paint formula, etc. Material, printed circuit board, ink or packaging material 22 200804516 VII. Designated representative diagram · (1) The representative representative figure of this case is: ( ) (II) The symbol of the representative figure is simple Description: 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: