TW201028434A - Thermosetting resin composition and applications thereof - Google Patents

Abstract

This invention discloses a thermosetting resin composition, including the following components: bi-functional or multi-functional epoxy resins, polystyrene-maleic acid anhydride copolymer (SMA) as a curing agent, diallyl biphenolA based allyl phenol as a co-curing agent and a toughness enhancing agent, low-bromo or high-bromo BPA type epoxy resin or tetrabromobiphenol A (TBBPA or TBBA) as a flame retardant, a proper promoting agent and a solvent. The resin composition of this invention after curing has a lower dielectric performance and a better thermal reliability and toughness, having a lower dielectric constant ( abbreviated as Dk) and an electric loss tangent (abbreviated as Df), a high Tg, a high thermal decomposing temperature (abbreviated as Td), a better toughness and a good PCB processing feature of the copper clad plate produced with enhancing materials such as glass fabric, suitable for producing copper clad plate for PCB and semicured plate, and may also be applied in common purposes of epoxy resins, such as molding resins and composite materials for construction, cars and aviation.

Description

201028434 VI. Description of the Invention: [Technical Field] The present invention relates to a thermosetting resin composition suitable for the production of pCB sheets, and to a common use of epoxy resins. Such as molding resin and the like on the composite material. ~ [Prior Art] % Oxygen Resin has been widely used in various t-substrate materials. Mainly because S has good heat, chemical, good insulation and dielectric properties, commonly used curing agents are amines. 'Acid needles and _ or _ _ ' Especially in the application of copper clad laminates, dicyandiamide (amines) and secret resins (frequently used as a curing agent) are used as curing agents for epoxy resins. Properties, heat resistance, chemical resistance and insulation properties, but its dielectric properties cannot meet the requirements of high-frequency signal transmission integrity because of its high dielectric constant and dielectric loss factor. The use of styrene-maleic anhydride copolymer (abbreviated as) as an epoxy resin curing agent is described in the BE 627 887 patent, but this epoxy resin composition has the following disadvantages after curing cross-linking: glass transition temperature (Tg) ) low, poor thermal stability and poor processability. Such compositions are also proposed in the EP 413 386 and the use of inexpensive difunctional epoxy resins in place of relatively expensive polyfunctional epoxy resins, as well as the same level of thermal performance. However, this article is about the application of IPN polymerization. The curing agent of epoxy resin is an example of polybromination. In fact, the specific example of acid needle curing agent proves that it is not satisfactory, especially the Tg after curing crosslinking. Too low and electrical properties and prepreg stability also need to be improved. The use of styrene-maleic anhydride copolymer (SMA) is proposed in the patent DE 3 839 105, in which the co-crosslinking agent dicyanodiamine is the basic composition of the resin composition, but the dicyanodiamide is only soluble. There are disadvantages in toxic and expensive solvents, so it is preferred to find a suitable co-crosslinking agent which avoids the disadvantages of dicyandiamide. An epoxy resin composition comprising a low molecular weight copolymer of methyl styrene and maleic anhydride is described in the U.S. Patent No. 4,045,550, but such a composition is not suitable for the manufacture of a PCB. Styrene-maleic anhydride copolymer (SMA) as a curing agent for epoxy resin, the cured product of which is relatively brittle 3 201028434 'prep used for making printed circuit boards (PCB), when prepreg edges are cut The resin part is scattered like a mushroom spore, sometimes called the "mushroom effect", and is not suitable for making a prepreg. σ Just because the epoxy resin composition which simply uses styrene-maleic anhydride copolymer (SMA) as a curing agent is relatively brittle, in order to enable such a resin composition to be applied to a prepreg for PCB, an improvement is disclosed in the patent W09818845. The brittle method uses tetrabromobis (abbreviated as ΤΒΒΡΑ4ΤββΑ), tetrabromobisphenol A diglycidyl ether (TBBAPDGE) or a mixture thereof as a co-crosslinking agent, and styrene maleic anhydride copolymer (SMA) as a crosslinking agent. FR-4 epoxy resin is cured to achieve the purpose of improving toughness and stability. However, although the brittleness of the composition after curing is improved, the peel strength is low, and the peel strength φ of 1 低于 is lower than 7 · Olb/ιη, not suitable for making fine lines, and still brittle, and its poor pCB drilling process results in poor PCB reliability. The application of SMA-cured epoxy resin is also proposed in CN1935896A, CN1955217A, CN1955219A. This application also simply introduces the low dielectric properties of SMA into the polymer structure to achieve better heat resistance and dielectric properties, but As with the aforementioned patents, there is no disadvantage of overcoming the brittleness of the cured product. The allyl structure is commonly used to improve the toughness of the epoxy resin composition after curing, mainly by introducing an allyl-added fat flexible chain by IpN polymerization, as described in US Pat. No. 27,7177, DE 352 15 〇 6, 郃 994 484 and EP 417 837. An allyl epoxy resin composition using an acid anhydride as an epoxy resin curing agent, but such an acid anhydride belongs to an ethylenically unsaturated acid anhydride such as maleic anhydride, and this acid anhydride not only cures the unsaturated double on the acid anhydride of the epoxy resin The bond also participates in the formation of an allyl network. Another type is described in the WO 09607683 patent; [pn polymer resin composition, the resin composition is different from the above IPN polymer in that the ethylenically unsaturated acid anhydride forms a copolymer with maleic anhydride, and the anhydride on the copolymer becomes The functional group reacted by the epoxy resin, since the alkenyl group on the ethylenically unsaturated acid anhydride has been polymerized with the double bond on the maleic anhydride, and there is no double bond involved in the allyl network, only the allyl group is present. The double bond addition reaction is carried out, and the crosslinked structure of the anhydride-cured epoxy resin forms an IpN structure. However, since the allyl compound in this patent is a triethyl propyl cyanate (TAC) or a triallyl isocyanuric acid 8 曰 (TAIC), the molecular structure is The water absorption rate is high, and there are many CN groups in the molecular structure, which leads to the disadvantages of high water absorption, dielectric properties and thermal cracking temperature, which are resistant to heat reduction of 201028434 after curing. In the new resin group, the dilute propionate such as diallyl Wei A contains not only its oxy-oxygen, but also the ΓΑ/epoxy resin network to form 1PN, ❿ and propyl The bribe base is involved in the ring turtle to cure, so as to ensure that the heat resistance is not lowered, and at the same time, the curing and the real money production rate of the resin composition can be improved, and the present invention aims at Providing a fine tree test compound, the remuneration age is not reduced, and the tree compound can be improved at the same time. __Miscellaneous, real (four) financial rate, _ can guarantee lower dielectric properties. In order to achieve the above object, the solution of the present invention is: - a thermal SI tree complex comprising the following components: a difunctional or polyfunctional epoxy resin, a styrene-maleic acid if copolymer (SMA) A curing agent, a dipropyl group such as diallyl is expected to be a co-curing agent, and an increase or decrease, a low-moisture or high-performance BPA type epoxy resin or a four-part anti-binder A (TBBpA or τ touch-type flame retardant, Suitable accelerators and solvents. The epoxy resin is bismuth, BPF, bisphenol S (abbreviated as BPS) or alkyl substituted bisphenol diglycidyl ether, phenol-phenolic epoxy (pNE) ), o-cresol-phenolic epoxy type (abbreviated as (3) illusion, ❿ double-sided A-secret epoxy type (abbreviated as 臓), m-benzodiazepine _ oxygen thin, diaminobiphenyl or isocyanide Hydric acid, etc., miscellaneous reaction, heteroglycidylamine, phenolic alkyl glycidyl ether epoxy resin, tricyclopentadiene or cyclopentadiene and surface polycondensation resin Epoxy resin 'isocyanate modified epoxy resin, epoxy resin with naphthalene ring, hydanti〇n epoxy resin, terpene modified epoxy resin 9,10_Dihydro-9-oxa-1〇_filled phenanthrene-1-indole (abbreviated as D0P0) or 9,10-dihydrogen+oxy-1〇-(2',5,-dihydroxyl Phenyl)phosphonium phenanthrene-oxide (referred to as DOPO-HQ) modified lining epoxy resin, the above epoxy resins may be used singly or in combination. The styrene-maleic anhydride copolymer (SMA) In the resin system as a curing agent for epoxy resin, the styrene structure with good dielectric properties is introduced into the crosslinked structure to achieve low dielectric constant and dielectric loss. The SMA with very high molecular weight (Mw is generally high) At 60,000), it has poor compatibility with epoxy, and its acid 5 201028434 needle has a low weight percentage (generally less than 3%), which is not suitable as a curing agent for epoxy resin, so it is not suitable for SMA/epoxy printing. Circuit board application. Experiments have shown that SM with a molecular weight (Mw) in the range of about 3 〇〇〇 to 6 、 and an acid anhydride weight percentage of about 3% or more can be cured as an epoxy resin. The agent is applied in a printed circuit board, in particular, the molecular weight (Mw) is in the range of about 5 〇〇〇 to 12 ,, and the molar ratio of styrene (S): maleic anhydride (MA) In:! L 2: Shu, 3: i and 4: j 3 of comfort and mixtures thereof such as

Sartomer's SMA1000, SMA2000, SMA3000 (or SMA EF-30) and SMA4000C or SMA EF 40) 'has good thermal reliability and low dielectric properties when used in printed circuit boards, and good = printed circuits Board processability. SMA is used as a curing agent for epoxy resin in printed circuit boards. The equivalent ratio (SMA anhydride and ugly base: epoxy resin) is suitable in the range of 〇6:1 to 16:1. 0.9:1 to 1.1:1). Bisphenolphthalein (abbreviated as 〇8-8?), 2,4,6-triallylphenol, etc., the allyl- acyl group is substituted in the phenyl ring ortho, the genus (10) row _, such as di-propyl The chemical structure of the base is as follows:

R1, R2, R3: -Η, -CH2-CH=CH: CH3 (Rl, R2, R3 at least one is -ch2-CH=CH2)

R5 , ^2, R3, R4, R5: ~H, -CH2~CH=CHz, -CH2-CH=CH2) > CH3 (R2, R3, R4, R5 at least one is R1 structural formula such as 201028434

The phenolic hydroxyl group of allyl phenol can react with the epoxy group of the epoxy resin to form a crosslinked structure, and the dilute propyl group can spontaneously form a crosslinked structure at a certain initiator and high temperature, and the crosslinked structure and The crosslinked structure of the reaction of the propyl phenolic hydroxyl group, the SMA anhydride and the epoxy group forms an interpenetrating network (IPN), so that the final polymer has better toughness due to the addition of the allyl polymerization network, and Dilyl is itself involved in chemical cross-linking to maintain the polymer with other excellent properties such as thermal reliability.阻燃The flame retardant includes a low bromine BPA type epoxy resin, such as a general-purpose FR-4 epoxy resin (such as BET-535), a high bromine BPA type epoxy resin, such as BET_4 〇〇, or a higher bromine content of four Bromobis A (abbreviated as TBBPA or TBBA) 'They can react with SMA or epoxy resin to form a crosslinked structure, which achieves better flame retardancy and does not affect the thermal reliability of the polymer after curing. Trustworthiness. Another part of the addition of odor / odor flame retardant can also achieve better flame retardant effect, such as e gamma (trade name SAYTEX BT-93), the chemical structure is as follows: 201028434

Ethane-l, 2-bis (pentabromophenyl) (trade name SAYTEX8010), the chemical structure is as follows:

Commonly used imidazole accelerators are the accelerators used in the present invention, especially alkyl-substituted imidazoles, such as hydrazine 2-methylimidazole, 2-ethyl-4-mercaptoimidazole, 2-phenylimidazole, 2-ethyl -4-Phenyl imidazole and the like; accelerators suitable for the present invention also include various primary, secondary and quaternary amines, quaternary ammonium salts or phosphonium salts such as benzyldimethylamine, bromobutyltriphenyl salt, 4, 4'- and 3,3,-diaminodiphenyl hydrazine; other promoters suitable for the present invention also include peroxygen initiators (such as t-butyl peroxybenzoate), azo initiators (such as azobisisobutyronitrile) and organic metal salts or complexes (such as zinc acetate); Lewis acid can also be used in combination with the above accelerators to accelerate the curing reaction rate, the use ratio of the accelerator is 〇. 〇〇1 ~5%, the usual ratio is 〇. 〇1 ～2% is better. The solvent for use in the present invention may be a mixture of one or more of a ketone (e.g., propylene, butadiene, cyclohexanone), an aromatic (e.g., toluene), an alcoholic (e.g., propanol) solvent. © In order to further increase the glass transition temperature (Tg) of the resin composition of the present invention, a partial cyanate (such as a bisphenol A type cyanate BA-230S) or a bismaleimide or the like Amine resins are also often added to the resin compositions of the present invention to form higher crosslink densities and achieve higher Tg (up to about 200 ° C above). Rubber or rubbery compounds such as benzene (tetra) / butyl (10), copolymer of dilute / benzene 6-methyl methacrylate or other ethylene compound, polymethyl methacrylate / butyl Two women / styrene rubber core shell particles? Or its miscellaneous series Oxygen lining _ fat, poly two? Silk sister minus particles or its modified ring thief secret age, eTBN 彳 rubber, _ Wei _, can be combined with the thorn base into: step 増 plus tree 敝 _ sex. The ether of the duck's test compound is formed by the propyl group (IV) propyl test, such as diallyl bisphenol A ether. 8 201028434 The invention of the invention tree towel can also be added to the appropriate He, the simple printed circuit of the printed circuit, the expansion coefficient 'this filler can be a dioxide dioxide (including crystalline, dazzling, hollow Type and globular dioxide #), oxygen, mica, talc, nitriding, nitrogen, carbonization dream, diamond, smoldering dry soil, oxygen tilting, nitriding! g fiber or glass _ towel Or a mixture of. The resin composition of the present invention may further contain other additives such as a dough, a coupling agent, a leveling agent, a dye, a pigment, and the like. The present invention employs a copolymer of an unsaturated acid liver and an ethylene compound having a dilute double bond (e.g., a styrene-maleic anhydride copolymer) as a curing agent, which can effectively improve heat resistance and dielectric properties. The invention has a lower dielectric impurity and better thermal reliability and affinity after curing, and a copper-clad laminate made of a reinforcing material such as glass fiber cloth has a lower dielectric constant (abbreviation (8) and electricity). Loss tangent (referred to as Df), high Tg, high thermal cracking temperature (Td for short) and good bouncing property and good pcB processing I1. Therefore, the present invention is suitable for making copper clad laminates and prepregs for peg. In addition, due to its low dielectric properties, high thermal reliability and good properties, it can also be applied to composite materials such as surface resins and architectural, automotive and aerospace applications. Method: Implementation method: firstly mix the components such as resin and solvent into a uniform resin glue, immerse it in a uniform glue with 2116 glass cloth, and dry the solvent for 5 minutes at 17 形成 to form a prepreg. Zhang 2116 prepreg with upper and lower two 1〇2 _ copper swell in a vacuum hot press high temperature curing 'curing conditions to ensure that the high pressure is 350 PSI when curing at 19 〇 U for more than 1 ,, then The physical properties and electrical properties of the copper clad laminate are tested according to the test method of the ipC-TM-65 standard. This embodiment is used in the following examples. The following examples are used to describe the present invention in detail, but not in the present invention. The scope of the invention is defined. Embodiments 1 to 5, when the acidity equivalent and the _ base equivalent are different from the epoxy equivalent, the Tg of the resin composition prepared by the above method may have properties such as Tg. The corresponding change is specifically changed as shown in the negative table of the table. The ratio of § is 9:1 Q~i 1:1, which is the highest corresponding to the coated steel plate. 201028434 Example No. 1 2 3 4 5 Anhydride Equivalent + phenol base equivalent 1.6 1.3 1.1 0.9 0.6 Epoxy equivalent 1 1 1 1 1 Tg(DSC)rc) 162 165 185 175 138 Note: The ratio of each component in the above table is calculated as solid. Example 6 (Comparative Example) A resin composition was prepared according to the following formulation: 192 g of methyl ketone (MEK) solvent was first used to dissolve 156 g of SMA3000 and 4 g of TBBA, and then 185 g of BET-535A80C was added at a solid content of 80%. 20% is C-solvent) and 93.3 g of BET-400T60C solid content is 60%, 40% is toluene solvent), and then 0.12 g of 2-ethyl-4-methylimidazole (abbreviation 2E4Mz) is added, stirring 2 After the hour, the mixture was uniformly mixed, and a copper clad laminate was prepared according to the method described above and tested for physical properties and electrical properties. In this embodiment, the ratio of the anhydride equivalent plus the phenolic hydroxyl equivalent to the epoxy equivalent is 丨.U. Example 7 (Comparative Example) A resin composition was prepared according to the following formulation: firstly dissolving i4〇g of SMA3000 and 36g of TBBA with 2〇〇g of methyl ethyl ketone solvent, and then adding 165g of BET-535A80C with a solid content of 80%, 20 % is propylene-solvent), 86.7 g of BET-400T60C has a solid content of 60%, 40% is a toluene solvent) and 4 〇g of TAC, and further added 〇4 g of t-butyl peroxybenzoate and hydrazine. I2g of 2E4Mz, mixed for 2 hours and then uniformly mixed. A copper clad laminate was prepared according to the method described above and tested for physical and electrical properties. In this example, the ratio of the anhydride equivalent to the phenolic hydroxyl equivalent to the epoxy equivalent was 11:1. Example 8 A resin composition was prepared according to the following formulation: first, 16 g of SMA4000 and 20 g of TBBA were dissolved in 192 g of methyl ethyl ketone solvent, and then 130 g of BET-535A80C solid content of 80%, 20% of acetone solvent), 160 g was added. BET-400T60C solid content is 60%, 40% is toluene solvent) and 2 〇g of DABPA, then add 2 g of tert-butyl peroxybenzoate and 〇. i2g of 2E4Mz, stir for 2 hours and mix well. The copper clad laminate was fabricated in accordance with the method described above and tested for physical and electrical properties. In the example of 201028434, the ratio of the anhydride equivalent plus the phenolic hydroxyl equivalent to the epoxy equivalent is i.1:1. Example 9 A resin composition was prepared according to the following formulation: First, 176 g of a methyl ethyl ketone solvent was used to dissolve I56 g of SMA3000 and 12 g of TBBA, and then 145 g of BET-535A80C solid content of 80%, 20% of acetone solvent), 160 g of BET was added. -400T60C 60% solids, 40% toluene solvent) and 2 〇g of DABPA, then add 2 g of tert-butyl peroxybenzoate and 〇. I2g of 2E4Mz, stir for 2 hours and mix evenly. The method of manufacture produced a copper clad laminate and tested its physical and electrical properties. In this embodiment, the ratio of the anhydride equivalent to the phenolic hydroxyl equivalent to the epoxy equivalent is 丨. Example: 树脂 The resin composition was prepared according to the following formula: firstly, 168 g of a butyl ketone solvent was used to dissolve 10 g of SMA 1000, and then 255 g of BET-535A80C solid content was 80%, 20% was acetone solvent), and 113. 3 g was added. BET-400T60C solid content of 60%, 40% of toluene solvent) and 20g of DABPA, and then added 0. 2g of tert-butyl peroxybenzoate and 〇. I2g of 2E4Mz, stirred for 2 hours, mixed evenly, according to the previous article The method of the invention is to produce a copper clad laminate and test its physical properties and electrical properties. In this embodiment, the ratio of the acid anhydride equivalent to the phenolic hydroxyl equivalent and the epoxy equivalent is 1. 〇:1. Example 11 A resin composition was prepared according to the following formulation: First, 16 g of a butyl ketone solvent was used to dissolve i24 g of SMA3000 and 12 g of TBBA, and then 165 g of BET-535A80C was added in an amount of 80%, and 2% by weight was an acetone solvent. , 160g of BET-400T60C solid content of 60%, 40% of toluene solvent), 2i.3g of BA-230S (solid content of 75%, 25% of methyl ethyl ketone solvent) and 20g of DABPA, and then added 〇. 2g The tert-butyl peroxybenzoate and 0.12 g of 2E4Mz were mixed for 2 hours, mixed uniformly, and a copper clad laminate was prepared according to the method described above and tested for physical properties and electrical properties. In this example, the acid field equivalent plus the ratio of the desired hydroxyl equivalent to the epoxy equivalent was 1.1:1. Example 12 A resin composition was prepared according to the following formulation: first, 160 g of methyl ethyl ketone solvent was used to dissolve U4g of SMA3000 and 12 g of TBBA, then 165 g of BET-535A80C solid content of 8% by weight, 2% by weight of acetone solvent), 160 g. BET-400T60C has a solid content of 60%, 40% is a toluene solvent), 21 3g of BA-230S (solid content is 75%, 25% is methyl ethyl ketone solvent) and 20g of DABPA, and then added 〇. 2g of over 11 201028434 Oxidized benzoic acid tert-butylate, please g zinc acetate and strontium. 12g of 2E4Mz, Q. Q. 5 hours, finally add 100g of melt-oxygen cut, and the lion is mixed evenly after 2 hours, according to the method described above. The production of copper clad laminates and the technical and electrical properties. The ratio of the amount of bribes to the amount of bribes and the equivalent of epoxy equivalents is M:1. Example 13 A resin composition was prepared according to the following formulation: first, 14 g of SMA3000 and 12 g of TBBA were dissolved using 184 g of methyl ethyl ketone solvent, and then 145 g of BET-535A80C solid content of 80%, 20% of acetone solvent), 140 g of BET-400T60 (solid content is _, which is benzene solvent), 2〇g 腑a and 20g polymethyl methacrylate methyl vinegar / butyl bismuth / styrene core-shell particles and then added 〇. The tert-butyl carboxylic acid and 0.12 g of 2E4MZ were mixed for 2 hours, and then uniformly mixed. 1:1。 The ratio of the ratio of the amount of the base and the equivalent of the epoxy equivalent of 1. 1:1. The blending ratio of the resin compositions of Examples 6 to 13 and the characteristics of the copper clad laminate produced by using the resin composition are shown in Table 2. Compared with Comparative Example 6, 'Examples 9 and 13 added 腑a or / and polymethyl propyl acrylate, sulphuric acid vinegar / dibutyl benzene / styrene core shell particles, etc., can significantly improve the flexibility of the composition Therefore, the peel strength is improved while the heat resistance is not lowered; compared with Comparative Example 7, the Dk of Examples 9 and 13 is relatively low - some 'heat is also good, and the DABpA or / and the poly Compared with the dilute propyl vinegar such as TAC, the core-shell particle mobilization of methyl acetoacetate/butadiene/styrene can maintain a lower Dk and better W heat; The addition of cyanic acid vinegar to u and 12 can significantly increase the Tg of the composition. Meanwhile, the addition of an inorganic filler to the towel of Example 12 can reduce the expansion coefficient of the resin composition and improve the reliability of the resin composition in PCB application. The S:MA molar ratio of the legs in Examples 8 to 1 was 4:1, 3:1 and 1:1, and the copper clad laminates produced had lower dielectric properties, better heat resistance and better. Off' However, as the proportion of stupid ethylene in the SMA increases, the Tg will decrease, but the sink will decrease. Example number BET-535

12 201028434 ΤΒΒΑ 10 9 5 3 / 3 3 3 BET-400 14 13 24 24 17 24 24 21 SMA4000 / / 40 / / / / / SMA3000 (or EF-30) 39 35 / 39 / 31 31 37 SMA1000 / / / / 27 / / / TAC / 10 / / / / / / DABPA / / 5 5 5 5 5 5 Polymethyl methacrylate / butyl diene / styrene core shell particles / / / / / / / 5 BA-230S / / / / / 4 4 / 'Molten cerium oxide / / / / / / / 25 / 2E4Mz 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 tert-butyl peroxybenzoate / 0.1 0.05 0.05 0. 05 0.05 0.05 0.05 Zinc Acetate / / / / / 0.02 0.02 / Tg (DSC) (°C) 178 182 180 188 198 201 199 182 Td (5% weight loss) (.C) 365 361 368 365 361 351 349 366 Peel strength (lb/ In) 6.55 6.81 6.93 7.28 7. 98 7.44 7.24 7.54 Dk (lOOMHz) 3.76 3.71 3.65 3. 73 3.89 3.75 3.85 3.70 13 201028434

Df(lOOMHz) 0.0090 0. 0081 0. 0078 0. 0087 0.0129 0.0099 0.0088 0.0087 al(ppm/°C ) 76 70 78 72 74 68 50 85 • Flexural modulus (GPa) 48.8 41.9 42.4 43.3 45.4 44.6 48.2 41.3 Note The ratio of each component in the above table is calculated as solid; αΐ is the expansion coefficient before Tg. [Simple description of the diagram] None [Main component symbol description]

Claims (1)

201028434 VII. Patent application scope: 1. A thermosetting resin composition characterized by comprising the following components: a difunctional or polyfunctional epoxy resin, a styrene-maleic anhydride copolymer SMA as a curing agent, allyl phenol As co-curing agent and toughening agent, low bromine or high desert BPA type epoxy resin or tetrabromobisphenol a as flame retardant, accelerator and solvent. 2. A thermosetting resin composition according to claim 1, wherein the epoxy resin is a BPA type, a BPF type, a bisphenol S type or an alkyl substituted bisphenol diglycidyl ether, phenol _phenol epoxy type, o-methyl-phenolic epoxy type, bisphenol A-phenolic epoxy type, m-benzenediol furfural epoxy resin, diamine biphenyl decane or isocyanuric acid polyamine Glycidylamine epoxy g-ester reactive with epigas alcohol, phenolic alkyl glycidyl ether epoxy resin such as trisphenol methane tricondensate, dicyclopentadiene or cyclopentadiene and phenolic polycondensation resin Epoxy resin, isocyanate modified epoxy resin, epoxy resin with naphthalene® ring, hydantoin epoxy resin, terpene modified epoxy resin, 9,10-dihydro-9-oxa: 10-disc phenanthrene-10-oxide or 9,1()_dihydro-9-oxo (2,5'-di-diphenyl) phenanthrene oxide modified phosphorus-containing epoxy resin The above epoxy resins are used singly or in combination. 3. For example, if you apply for a supplement (4), the 1st secret - sex tree test compound, wherein the molecular weight of the methylated maleic anhydride copolymer is in the range of 3 〇〇〇 to 〇〇, and its acid liver weight is 100. About 3% or more. 4. A thermosetting resin composition according to claim 3, wherein the styrene maleic anhydride copolymer has a molecular weight in the range of from _ to 12,000, and the molar ratio of styrene: maleic anhydride is 1 to 4:1. 5. A thermosetting resin composition as described in the fourth aspect of the invention, wherein the equivalent ratio of the lining and the achieving: epoxy resin is in the range of from 0.6:1 to 1.6:1. 6. As stated in the article i of the t-th item, the heat of the tree is a compound of the tree, and the propyl group of the towel is expected to be a propyl group in the phenyl group, and the opposite position is substituted for the lining, and its chemical structure As follows: OH R1 , Rl, R2, R3: ~H,_CHH:H=CH2,.(R1, R2, R3 at least one is n(f), 15 201028434 R2 R4 h Μ' OH——<)R1>——OH \ — —/ \_:/ / \ R3 R5 , R2, R3, R4, R5: -H,-CH2-CH=CH2, -CH3 (R2, R3, R4, R5 at least one is -CH2-CH=CH2) , R1 structure is as follows: 7. The thermosetting resin composition according to claim 1, wherein the flame retardant is one of BET-535, BET-400, ruthenium or osmium, and a partially added bromine flame retardant is added. The chemical structural formula is as follows: 201028434 or 8. The thermosetting resin composition according to claim 1, wherein the accelerator is an oxime promoter: 2-methylimidazole, 2-ethyl-4-methylimidazole, 2- Phenyl imidazole and 2-ethyl-4-phenylmeridene; or primary, secondary and quaternary amines, quaternary ammonium salts and phosphonium salts: benzyldimethylamine, bromobutyltriphenyl phosphate and 4, 4'- and 3,3'-diaminodiphenyl barrier; or peroxygen initiator, azo initiator and organometallic salt or complex; or Lewis acid; the above accelerators are used alone or in combination The ratio of the accelerator to the epoxy resin is 〇. 〇〇1~5%. 9. The thermosetting resin composition of claim 1, wherein the solvent is a mixture of one or more of a ketone, an aromatic, and an alcohol ether solvent. 10. A thermosetting resin composition according to claim 1, wherein a polyamidene resin such as cyanate or bismaleimide is further added to the resin composition. 11. A thermosetting resin composition according to claim 1, wherein a rubber or rubber modified compound is further added to the resin composition: styrene/butadiene copolymer, butadiene/ Copolymer of styrene with methyl methacrylate or other vinyl compound, polymethyl methacrylate / butyl styrene / styrene rubber core-shell particles or modified epoxy resin or phenolic resin, poly 2 A ruthenium-based oxynuclear core particle or a modified epoxy resin or phenolic resin or a rubber modified epoxy resin such as CTBN. 12. A thermosetting resin composition according to claim 1, wherein the resin composition further comprises a filler: crystalline, molten, hollow and spherical ceria, alumina mica, A mixture of one or more of talc, nitriding, nitriding, carbonized, diamond, calcined clay, oxidized, nitrided or fiberglass. 13. The thermosetting resin composition according to claim 2, wherein the resin composition further comprises an additive: one or more of an antifoaming agent, a coupling agent, a leveling agent, a dye or a pigment. 17 201028434 Mixed _. 14. The use of a thermosetting resin composition according to claim 1 in a copper clad laminate or a prepreg for a PCB. 18 201028434 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: