TWI274773B - The printed circuit board composition of polybutadiene thermosetting resin and its manufacture - Google Patents

Abstract

This invention is about a composition for high performance printed circuit board. Which includes 20 to 35 wt% of high molecular weight of polybutadiene with high vinyl groups, low molecular weight of polybutadiene, cyclic olefin copolymer with two or above vinyl groups, and/or thermosetting polymer resin which was polymerized from acrylic acid, acrylonitrile and butadiene; 10 to 30 wt% glass fiber cloth; 25 to 50 wt% inorganic particulate filler; 1 to 10 wt% metallic coagents; 10 to 30 wt% bromine-containing fire retardant. Using solvents to dilute the composition to the suitable viscosity. After the prepreg had been made by impregnation, the electric circuit board composition with excellent properties can be obtained by laminating at 170 to 220 DEG C with 20 to 50 kg/cm<2>.

Description

1274773 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a printed circuit board carrier material, which is based on a thermosetting resin of polybutylene nieni)

Lij's inorganic particle filler (such as buckle) and metal copolymerization = general heat _ operation. Among them, the fat produced by the fortune is r = medium rim viscosity does not cause sliding when pressed. The resin group i of the present invention;: rilc〇coagent 5 j [Prior Art] Conventionally, a polybutadiene resin is used as a main material, and a non-woven reinforcing material, a particle filler, a hardening initiator, a bromine-containing flame retardant, and the like are added. The circuit board is, for example, the circuit/carrier board composition mentioned in U.S. Patent No. 4,241,132, including polybutadiene ^^^(Ricon 150?70wt% 1,2-addition polybutadiene er, Sart〇mer) and fiber reinforcement Materials, such as fibers composed of Polypropylene (4) chat (4). In this insulation composition, the dielectric constant or loss factor of the resin is matched with the fiber reinforcement. The disadvantages are: 1. The polybutadiene used has insufficient Vinyl base and the substrate strength is poor. 2. No flame retardancy. · The composition of the circuit carrier mentioned in U.S. Patent No. 4,997,702, which includes an inorganic filler or a fiber reinforcing material in addition to the epoxy resin, is 2 to 7 wt% of the total composition. The 1 medium fiber comprises glass or polymeric fibers, and the filler comprises clay or mineral (such as vermiculite /) 'particle filler. There are also obvious disadvantages: 1. Using epoxy resin to make the substrate, its electrical properties (Dk, Df) are poor, and the rate of thirst is ancient. 2. Using non-woven fabric, the strength of the substrate is poor. ... sheep back to the thermosetting composition of the circuit board described in U.S. Patent No. 5,223, 568, including · 5 1274773 a · Polybutadiene or polyisoprene having a molecular weight of less than 5 at room temperature. Resin b. Butadiene or isoprene solid polymer cross-polymerized with polybutadiene or p〇iyis〇prene resin c. When the temperature is hardened, the temperature is greater than 250 ° C, and low The composition of the thermal cracking temperature. Although the physical properties of the circuit carrier materials mentioned in this invention are good, they still have the following disadvantages:

1. High temperature hardening (hot pressing temperature &gt; 25 (TC) is required. Because the conventional circuit board manufacturing equipment is limited by the temperature of 180 C, and the bromine-containing flame retardant cannot withstand the high temperature of 25 ° C, here Decomposition or chemical cracking under high temperature will damage the physical properties of the material. 2. The film made of polybutadiene or p〇lyiSOprene resin has a large viscosity, and the pressing operation of the continuous automatic circuit carrier is difficult. US Patent 6,048, 807 The substrate composition comprises: a·10~75 vol·% thermosetting resin composition, which comprises a polybutadiene or p〇lyisoprene resin having a molecular weight of less than 5, 〇〇(), and an unsaturated di-block polymer containing bmadiene, b · Less than 14 vol·% of vinyl propylene (ethyiene pr〇pyiene MW&lt;5〇, leak) liquid rubber' can be ethylenepropylene copolymer (c〇p〇lymer) or ethiylene propylene diene ( Such a (10) ah - or ethylidenenorbomene) terpolymer or a combination thereof; c. particle filler; and ^ mouth 'd. The shortcomings of weaving are:

1. The circuit carrier board must be obtained by high temperature and high pressure (10) c, finely applied. The bromine-containing flame retardant will decompose or chemically crack at this high temperature, no more than X cases or even as much as 70% by weight. As far as most of the current settings are set, the drilling of the drills is very large, and the processing difficulties of the process are increased. U.S. Patent No. 6,071,836 has several circuit board sets as follows: 1274773 ΐϊΓ, ϊ 填料 Filling range, so that the film has almost no viscosity and is easy to operate, and the damage is good and has good performance. Thermal expansion coefficient in the direction of 2 axes; •..., the temperature of the pressing process is lower than 25 °C, to avoid cracking; and by adding; ^ burning, increasing the bonding strength of resin and copper foil and weaving b such as = Ξ; Although the properties of the plate composition are quite excellent, 'there is still a good peeling strength, even if it is added with the stone oxide, it is lower than 5 legs nch; ^ Regardless of the moisture absorption rate of water or p-benzene, it is high; , Yue fill, the proportion of 50Wt 〇 / 〇 or more, even as much as 70wt%, the current majority of f and Lu, not only difficult to handle during impregnation, and the drilling of the drill hole in the PCB drilling process is very large, processing is difficult. Other technical literature does not mention the use of polybutadiene on circuit carrier materials. For example, NSawatari et al, Ieee Transacti〇ns such as Electrical 1 Cong 1 also, Pei £1_18, price 2, ¥ 1983 publication, which related to the new fire-resistant material 1,2-polybutadiene substrate mentioned l,2-p〇lybutadiene It is difficult to operate in a semi-hardened stage. It is difficult to be non-sticky, and it is very flammable and has poor adhesion to copper. Although this document proposes a solution to these problems, in addition to using a large amount of high molecular weight p〇lybutadiene to eliminate the viscosity of the B stage, a small amount of low molecular weight modified polybutadiene resin is used to assist the bonding and pressing of the copper foil. Liquidity during the period. However, there is no mention of the use of any type of filler. In European Patent No. 0202488 A2, there is also a circuit board containing polybutadiene as a main resin, in which a ruthenium molecular weight prepolymer (Prep〇lymer) is added to reduce the viscosity and flammability of the polybutadiene film. Further, Japanese Patent No. 4,258,658 incorporates a high molecular weight compound to control viscosity, and this compound mainly provides flame retardancy, and preferably copper foil adhesion and heat resistance. There is no mention of the use of other fillers, but 7 1274773 This circuit carrier has a disadvantage of a relatively high loss factor. In the "Electronic Industry's l,2_p〇1ybutadiene high-performance resin (re C 84pp.73G·733, 1984)" mentioned (10) PQ Café City (4) tree day supply; circuit board use, and explicitly mentioned that there are (4) Reactive monomer reported for the common hardening of coffee. =· Patent APPl〇cati〇n Νο·2172892 The general circuit carrier is a thermoplastic resin pedestal composed of styrene and an unsaturated double bond and p〇lybutadiene. Person [Technical Problem to be Solved] In view of the related literature reports of the prior art mentioned above, the present invention mainly replaces the electrical, chemical and enthalpy resistance of the conventional circuit carrier board with polybmadiene as the main material. Including its flame resistance, thermal expansion coefficient, dielectric constant, loss factor, viscosity, and access to a new polybutadiene fine-density circuit; the first purpose of the cleverness is to provide a large amount of unsaturated vinyl A cross-linking reaction is carried out to produce a circuit carrier composition having excellent high temperature physical properties. μ if=The second purpose is to provide proper filler dosage and surface selection to produce a film with very low viscosity. It is easy to press and process, and has excellent dielectric constant and loss of electrical properties. . The first purpose of this month is to provide a circuit carrier that uses a general copper foil and a peel strength of 4 to 51 bf/ind^ or more. In violation of the cost, the fourth purpose of the Ming is to provide a circuit board that has a lower moisture rate than the current one. The fifth object of the present invention and the fifth object of the present invention is to provide a low-resistance (17 〇 22 22 〇 板 板 板 板 板 板 避免 避免 避免 避免 避免 避免 避免 避免 避免 避免 8 8 8 8 8 8 8 8 8 8 8 8 8 8 SUMMARY OF THE INVENTION According to the present invention, a novel polybutadiene thermosetting resin circuit carrier is provided, comprising:

20 to 35 wt% of a resin polymer comprising a high molecular weight polybutadiene resin (MW 200,000 g/mol or more) and a low molecular weight polybutadiene (MW = 5,000 to 10,000 g/mol) having a high vinyl content (7% by weight or more), And a cyclic olefin compound having two or more vinyl double bonds, and/or a high molecular polymer obtained by polymerization of acrylic add, acryl〇ntrile and butadiene; a glass fiber cloth of 1% to 3% Reinforcing material; 25~50wt ° / 〇 particle filler, the composition of which is best with sintered cerium oxide; 10~3 〇 wt% bromine flame retardant (added to increase flame resistance), 1~10wt% Metallic coagents ( Used to increase the peel strength of resin and metal); and contain a peroxide hardening initiator. [Technical means of the invention] The present invention contains a high-vinyl content polybutadiene thermosetting resin in the above composition. Such a resin contains 1,2-addi=(m, a group) which provides a large amount of unsaturated vinyl groups for cross-linking reaction, and can form the highest crosslink density after hardening. Excellent. High temperature resistance. 另一 Another technical feature of the present invention is that the formulation composition is selected by a suitable filler, and the filler type is selected so that the arnis_ degree is not high immersed after hardening 3, and the film layer and the layer are almost No reduction, not only easy to press, dielectric properties (such as loss factor), lowering the temperature of the process into the hot pressing process of the substrate, and can be applied to lower rtf = 敫, the present invention The most important technical feature is that .J 1 Metallic coagents increase the peeling strength of resin to metal. The temperature of the bell is usually in the range of no~22 (TC range 9 1274773.) Low temperature hardening can not only avoid the inclusion of The bromine flame retardant is cracked and can be used in general circuit board process equipment. At the same time, an appropriate amount of organic peroxide such as dicumyl peroxide (DCP) and t-butyl perbenzoate peroxide (TBPB) can be used at a lower hardening temperature. [ The following is a detailed description of the resin substrate, the filler, the Metallic coagents, the crosslinking agent, the glass fiber cloth, the flame retardant and the peroxide hardening initiator, and the source thereof. , Resin substrate: ® The resin substrate used in the circuit carrier material of the present invention is composed of a thermosetting resin composed of '1 (poly)adibutadiene resin; and (2) one having two or more vinyl pairs The cyclic cycloolefin compound and/or (3) a polymer obtained by polymerizing acrylic acid, acrylonitrile, butadiene, and participating in a crosslinking reaction during hardening. # * &quot (1) Folybutadiene resin may be solid or liquid at room temperature, but must be a high molecular weight solid resin (Mw = 1 〇〇, 〇〇〇g / m 〇 1 or more). Low molecular weight liquid resin (MW = 5,000) ~l〇, 〇〇〇g/m〇l) mixed φ admixture' and its Addition vinyl content is above 70wt%, more preferably above 90wt%. Its high vinyl content polybutadiene resin can provide _ hardening A lot of insufficient time Vinyl, which increases the bridging density when cross-linked' provides a circuit board with an excellent high temperature resistance. The best - high molecular weight resin is RB based resins such as RB810, RB820 and RB830, ~ more than 90% by weight of 1 , 2 addition polybutadiene solid resin. RB series resin is commercially available from Japan Synthetic Rubber Company. Low-molecular-weight liquid resins such as Ricon 153 and Riconl 54 resins (products of Sartomer Co., Ltd.) or resins such as B30 and B1000 (products of Nippon Soda Co., Ltd.) are preferred. 10 Another thermosetting resin (2) is a polymer having two or more ethyl double-bonded cyclic olefin compounds and/or having acrylic acid, acrylonitrile, and &gt; Utadien = polymerization. The cyclic olefin compound having two or more vinyl double bonds can be crosslinked by a vinyl double bond, and the cyclic olefin compound on the molecular chain can also lower the moisture absorption rate, dielectric constant and dielectric. Loss, such a cyclic olefin compound is synthesized by a metal locene metal catalyst from a monomer such as ethylene, borneol and vinyl bornerene: (a) a cyclic olefin copolymer (coc-A) Synthesis: In the purity of the norbornene (norb〇mene) 4 〇lkg, ENB (5_Ethylidene-2-norbomene) 2.27kg and 2.59kg of benzene were placed in the south pressure reaction tank 'heated to 1 〇〇. After injecting 2kg of l〇wt% helper catalyst (MAO/曱本) and 6x10 5 kg of metallocene catalyst, a mixture of ethylene (800ml/min) and gas (5〇ml/min) is introduced. 'The polymerization was started under a pressure of 18 kg/cm2. After completion of the reaction, the toluene is diluted to a solid content of 10% by weight or less, neutralized with hydrochloric acid, and then filtered, and the filtrate is added to a large amount of acetone, and the solid which precipitates and precipitates is dried to obtain a cyclic olefin copolymer (C〇C_A) having a molecular weight Mw. = 41,000 g/mol, Tg = 125 °C. (b) Synthesis of cyclic olefin copolymer (COC_b) · Addition by DCPD; reaction of UHexene at high temperature, available

Butyl-NB, high purity Butyl-NB 2kg, NB (norbomene) lkg, ENB (5-etheylidene-2-norbomene) 2kg and lkg are placed in the high pressure reaction tank, and heated to l〇〇 °C to inject a After 8 kg of 10 wt% of the catalyst (MAO/ transcript) and 2x10_5 kg of metallocene catalyst, a mixture of ethylene (800 ml/min) and hydrogen (50 ml/min) was introduced, and polymerization was started under a pressure of 10 kg/cm 2 . . After the completion of the reaction, the terpene was diluted to a solid content of 10% by weight or less, neutralized with hydrochloric acid, and filtered, and the filtrate was added to a large amount of propylene, and the precipitated solid was dried to obtain a cyclic olefin copolymer (C0C_B). Its molecular weight Mw is 26,000 g/mol and Tg = 123 °C. 1274773 (c) Synthesis of cyclic olefin copolymer (COC-C): added by DCPD; Uoctene synthesizes long-chain Hexyl-NB in high purity

Hexyl-NB 2.2kg, ENB (5_etheylidene-2-norbomme) 2.8kg and lkg toluene were placed in a high-pressure reaction tank, heated to 100 ° C, and then injected into 10 kg of 10 wt% of the catalyst (MAO / benzene) and After 2xl (T5kg of metallocene catalyst, a mixture of ethylene (800ml/min) and hydrogen (50ml/min) was introduced, and polymerization was started under the pressure of 10kg/cm2. After the reaction was completed, the mixture was diluted to a solid part. After wt% or less, it is neutralized with hydrochloric acid, filtered, and the filtrate is added to a large amount of acetone, and the precipitated solid is dried to obtain a cyclic olefin copolymer (COC-C). Its molecular weight Mw=70,500 g/mol , Tg = l 〇 7 ° C. Another polymer (3) acrylic acid, acrylonitrile and butadiene polymerized polymer can increase the bonding strength of resin and copper foil. For example, Carboxyl terminated butadiene acrylonitrile rubber series ( Such as CTBN130〇x8, CTBN130〇xl3, CTBN130〇x31 - etc., commercially available from Noveon. II. Particle Filling Materials The particle filler used in the present invention includes titanium dioxide, barium titanate, total acid, and chopped stone. (including amorphous Xi Shi and the stone treated after sintering treatment account for 25~50wt% of the total composition, and the best ratio is between 30~45wt%. They can be used alone or in combination in the process. The best filler is none. Shaped vermiculite 'as far as possible to choose a high surface area, such as the stone stone after sintering. Because of the high surface. The area is more effective in reducing the viscosity than the standard amorphous vermiculite (generally ΙΟμιη). The vermiculite is a sintered stone AEROSIL200' which can be obtained from Degussa, which is characterized by a surface area of about 200 m2/g and a particle size of 12 nm. Others. CE44I (10 micron amorphous Silica, CE Minerals), FB_35 (Fused) Silica 'Denka), Minsil 5 (Fused Silica, Minco), Min-sil 20 (Fused Slica, Minco), Novacite 325 (Natural crystalline silica, Minerals), GP7I (Fused Silica, Harbison 12 1274773

Walker) and other fillers. 2. Metallic coagent The metallic coagent used in the present invention is a wrong compound formed by the reaction of a gold tester, a soil tester or a zinc element with an acrylic acid. Such a reagent is usually a metallic diacrylate (such as SR63). 3, SR636, SR63 8, SR705, SR706), and metallic dimethacrylate (such as SR634, SR708), and metallic monomethacrylate (SR709), etc. by Sartomer

Company production. During the thermal hardening of Process 4, due to the higher reaction of Metallic coagent, it will react with the peroxide hardening initiator to form a free Radical compound, and then with p〇iybutadiene resin or other double bond resin. The cross-linking reaction is carried out so that each molecular chain contains acrylate, so that the strength of the resin and the copper foil can be enhanced. 4. Crosslinking Agent The crosslinking agent of the present invention is a crosslinking agent of the present invention, including triallyl cyanurate &gt; triallyl isocyanurate ^ diallyl phthalate r divinylbenzene or a combination thereof. V. Fiberglass cloth The fiberglass cloth used in the invention accounts for about 1〇~3〇wt% of the assembly. The fiberglass cloth produced by Nanya Plastics Co., Ltd. is used as the reinforcing material, and the glass fiber of different thickness is used according to the substrate requirements. Cloth type, the specifications are as follows: · cloth type basis weight thick tissue (吋) (g / m) (mm) Jing Shao" weft yarn ^ 7628 208 0.18 -------- _44_ 33 — 2116 105 0.19 one ~~60~ ------ —58 1080 48 0.055 —48 106 24 0.04 ~56~ __56 VI. Flame Retardant — The flame retardant used in the present invention is mainly bromine-based flame retardant, and the dosage is 10 ~30wt%. Preferred bromine-containing flame retardants are as follows:

Saytex BT 93 W (ethylene bistetrabromophthalimide), 13 1274773

Saytex 120 (tetradec^bromodiphenoxy benzene) or

Saytex 102 (decabromo diphenoxy oxide) VII. Hardening initiator Adding a radical hardening initiator can accelerate the crosslinking reaction. When the composition of the invention is heated, the initiator decomposes to form a radical, and then starts to crosslink. Polymerization. Preferred free radical hardening initiators, such as organic peroxides, dicumyl peroxide (DCP) ^ t-butylperbenzoate (TBPB) and • hexyne-3, are commonly used hardeners, generally _ θ·2~ Between 3wt%. [Examples] The materials used in the prototype circuit carrier mentioned in the examples of the present invention are the following materials in addition to the three cyclic olefin copolymers synthesized above: Circuit board group - material specifications and source manufacturers Commercial Name Material Content JSR RB810 1,2-addition Polybutadiene Rubber Mn=140,000g/mol,vinyl=90% SART0MER Riconl54 1,2-addition Polybutadiene Rubber Mn=5,200g/mol,vinyl=90% SART0MER Riconl53 1,2- Addition Polybutadiene Rubber Mn=4,700g/mol,vinyl=85% DENKA FB-35 Fused Silica ALBEMARLE SAYTEX8010 Bromine-based flame retardant, Br=82% ACR0S TAIC Triallyl isocyanurate LAP0RTE DCP Dicumyl peroxide SART0MER SARET633 Zinc diacrylate South Asia 1080woven glass Thickness 0.05mm , basis weight = 48 g / m2 Example 1 taken 104.3 parts by weight of high molecular weight polybutadiene rubber RB81 〇, g; 3 14 1274773 parts by weight of low molecular polybutadiene rubber Ricon 154, and 85. 9 parts by weight The ring fine fe copolymer (COC-A) and 12·5 parts by weight of CTBN130〇x8 are mixed and stirred uniformly; then, 13.3 parts by weight of SARET 633 is added, and 429.5 weight is added. a portion of the ceria filler (fb-35), and then uniformly mixed with 163.2 parts by weight of a bromine-based flame retardant (SAYTEX 8010), 8 parts by weight of a crosslinking agent (TAIC), and an 8-fold visbreaking starter (DCP). Immersed in 111 · 7 parts by weight of 1080 woven glass. After hardening at 130 ° C for film, it was stacked with 8 sheets of film, coated with copper foil of South Asia i〇z, and hot-pressed at 30 kg/cm 2 (426 psi) at 195 ° C for 3 hours to form a circuit board. The material composition, its physical property measurement data are listed in Table 1. Example 2 To increase the COC-A amount of the substituted portion of RB810, that is, 61. 3 parts by weight of RB810, 63. 6 parts by weight of Riconl54, and 128. 9 parts by weight of COC, A and 12. 5 parts by weight of CTBN130 〇x8 mixed and stirred evenly; then blended with 13.3 parts by weight of SARET 633 and added 429.5 parts by weight of FB-35 filler, and then mixed with 163.2 parts by weight of SAYTEX8010, 8 parts by weight of TAIC, and 8 parts by weight of DCP. , impregnated with 1 Π. 7 parts by weight of 1080woven glass. After semi-hardening to film at 130 ° C, it is stacked with 8 sheets of film, coated with South Asian loz copper foil, and hot-pressed at 30 kg/cm 2 (426 psi) at 195 ° C for 3 hours to form a circuit board material. The physical property measurement data are listed in Table 1. Example 3 The amount of COC-A was reduced and replaced by the addition of RB810, that is, 147.2 parts by weight of RB810, 63. 6 parts by weight of Riconl54, and 43.0 parts by weight of COC-A and 12.5 parts by weight of CTBN130〇x8 were mixed and stirred. Uniform; then blended with 13.3 parts by weight of SARET 633 and added 429. 5 parts by weight of FB-35 filler, and then mixed with 163.2 parts by weight of SAYTEX 8010, 8 weights of 15 1274773 parts of TAIC, 8 parts by weight of dcp, and evenly mixed. , impregnated with ln.7 parts by weight of 1080wovenglass. After semi-hardening to film at 130 ° C, it is stacked with 8 sheets of film, which is covered with South Asian 〇ζ 〇ζ copper foil, and is hot-pressed at 30 kg/cm 2 (426 psi) at 195 ° C for 3 hours to form a circuit board. The material composition, its physical property measurement data are listed in Table 1. - Example 4 Riconl54 resin was substituted with Riconl53, ie, 104. 3 parts by weight of RB810, 63.6 parts by weight of Riconl53, and 85. 9 parts by weight of _COC-A and 12.5 parts by weight of CTBN130 〇x8 were mixed and stirred. Uniform; then blended with 13.3 parts by weight of SARET 633 and added 429.5 parts by weight of FB-35 filler, and then mixed with 163.2 parts by weight of SAYTEX 8010, 8 parts by weight of Ding 8 10 8 parts by weight 00? 111.7 parts by weight of 1080woven glass impregnated. After semi-hardening to film at 130 ° C, it is stacked with 8 sheets of film, which is covered with a copper sheet of South Asia loz, and is heat-pressed for β hours at 195 ° C at 30 kg/cm 2 (426 psi) to form a circuit board. The material composition, its physical property measurement data are listed in Table 1. Comparative Example 1 • No SARET 633 is added. Take 105·7 parts by weight of RB810, 64·5 parts by weight of Riconl54 and 87·1 parts by weight of COC-A and 12·6 parts by weight. CTBN1300&gt;&lt;8 mixing and stirring; mixing evenly; adding 435·3 parts by weight The fb-35 filler was further mixed with 165. 4 parts by weight of SAYTEX 8010, 8.1 parts by weight of TAIC, and 8.1 parts by weight of DCP, and then impregnated with 113. 2 parts by weight of 1080 woven glass. After 13CTC is semi-hardened into film, it is stacked with 8 sheets of film, coated with South Asian loz copper foil, and heat-pressed at 3Gkg/em2 (426psi) at 195°C for 3 hours to form circuit board material composition. The physical property measurement data is listed in Table 1. 6重量份的。 The 1 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。

Riconl53 was mixed with 85. 9 parts by weight of coc-A and 12.5 parts by weight of CTBN130〇x8; then, 1 part by weight of SAfET 633' was added and 429. 5 parts by weight of FB-35 filler was added, followed by 163. 2 parts by weight of SAYTEX 8010, 8 parts by weight of TAIC, and 8 parts by weight of dCp were mixed and stirred, and then uniformly impregnated with 11.7 parts by weight of 丨_独·glass. After semi-hardening into film, it is stacked with 8 sheets of film, which is covered with South Asia l〇z, pois c, at 30 kg/cm2 (426 psi), 195. Under the conditions of 〇, the composition of the material of the circuit board was rolled for 3 hours, and the physical property measurement data is listed in Table 1. also

Composition Weight RB810 Riconl54 Riconl53 COC-A CTBN1300x8 FB-35 1080woven glass SAYTEX8010 TAIC SARET633 DCP 1043 63.6 〇·0 85.9 12.5 429.5 111.7 163.2 8.0 13.3 8.0 Table 1Τ 61~ 63.6 0.0 128.9 12.5 429.5 111.7 163.2 8.0 13.3 8.0 Test Data 4.65 2.91 0.0009 0.21 300 or more V-0

1 147.5&quot; 63.6 0.0 43.0 12.5 429.5 111.7 163.2 8.0 13.3 8.0 1 104 0.0 63.6 85.9 12.5 429.5 111.7 163.2 8.0 13.3 8.0 Specific pain 丄105J 64.5 0.0 87.1 12.6 435.3 113.2 165.4 8.1 0.0 8.1 2 0.0 63.6 104.3 85.9 12.5 429.5 111.7 163.2 8.0 13.3 8,0

Item/data peel strength (Μ/inch) Dielectric constant Dk Loss factor Df Moisture absorption rate (wt%) Solder heat resistance (seconds) Flame retardancy UL-94 I 4.34 2.95 0.0011 0.24 300 or more V-0 3 4.02 2.99 0.0011 0.26 300 or more V-0 4 4.21 2.93 0.0010 0.25 250.0 V-0 1.41 2.65 2.97 3.01 0.0011 0.0015 0.25 0.23 3〇〇 or more 15 V-0 V-0 17 1274773 Physical property analysis: Increasing the amount of COC-Α can slightly improve the peeling degree. And reduce the moisture absorption rate; the low molecular weight polybutadiene rubber Ricon153 (molecular weight Mn &lt; 5000) in the formulation has little effect on the replacement of Riconl54 resin, but if it is substituted (molecular weight Mn &gt; 5000), the peel strength will be deteriorated, and the weld bead will be deteriorated. Heat resistance is obviously insufficient. As can be seen from Table 1, the incorporation of SARET 633 (5 phr in the amount of thermosetting resin) can improve the peel strength, and the peel strength is deteriorated without adding it. , Example 5 Reduce the amount of filler. Take 141.5 parts by weight of RB810, 75·9 parts by weight of 1^〇11154, and 85.4 parts by weight of (^0 (^8 and 14.9 parts by weight of CTBN1300X8 mixed and stirred evenly, and then incorporated into 1.9 weight) SARET 633 and added 341. 6 parts by weight of FB-35 filler, and then mixed with 194.7 parts by weight of SAYTEX, 9.5 parts by weight of TAIC, and 9.5 parts by weight of DCP. The 1080woven glass is impregnated. After semi-hardening to film at 130 ° C, it is stacked with 8 sheets of film, which is coated with copper foil in the south and south, and is hot-pressed at 30 kg/cm 2 (426 psi) at 195 ° C. The circuit board material composition is made in hours, and the physical property measurement data is listed in Table 2. Clothes φ Example 6 The RB810 is replaced by the COC-A amount, that is, the energy is 8 parts by weight of RB810, 75·9 weight. Riconl54, mixed with 128. 1 part by weight of COC-A and 14.9 parts by weight of CTBN130〇x8; then - then replaced with 5.9 parts by weight of SARET 633 and added 341.6 parts by weight - FB- 35 filler, and then with 194. 7 parts by weight of SAYTEX8010, 9.5 parts by weight, immersed in 10 9.5 parts by weight of 00? mixed and stirred evenly, with 111 () weight ^: 1080wov En glass impregnation. After 130T: semi-hardened into film, it is stacked with 8 sheets of film. It is covered with southerly loz matte, and is hot-pressed at 30kg/cm2 (426psi) at 195°C for 3 hours. The material composition measurement data of Table 18 is listed in Table 2. Example 7 Reduce the amount of COC-A and replace it with RB810, ie, 184 2 parts by weight of RB810, 75·9 parts by weight of Riconl54, and 42 7 parts by weight of (3) C-A and 14.9 parts by weight of CTBN130〇x8 mixed with the same sentence; then incorporated with 9.9 parts by weight of SARET 633 and added 341.6 parts by weight of FB-35 filler, and then with 194 · 7 parts by weight of SAYTEX 8010, 9.5 parts by weight of TAIC, 9.5 parts by weight of DCP, mixed and stirred, and then impregnated with 111.0 parts by weight of 1080woven glass. After semi-hardening at 130 ° C for film, use 8 sheets of film stack $ ' The upper and lower layers are covered with South Asian loz copper foil, and are subjected to hot pressing at 30 kg/cm 2 (426 psi) at 195 ° C for 3 hours to prepare a circuit board material composition, and the physical property measurement data is listed in Table 2. Replacing Riconl53 resin with Riconl54 tree, ie, taking 141.5 parts by weight of RB810 '75.9 parts by weight of Ric〇nl53, and 85.4 The COC-A and the 14.9 parts by weight of CTBN130〇x8 were mixed and mixed uniformly; then, 15.9 parts by weight of SARET 633 was added and 341.6 parts by weight of FB-35 filler was added, and then with 947·7 parts by weight of SAYTEX8010, 9· 5 parts by weight of TAIC and 9.5 parts by weight of DCP were mixed and stirred uniformly, and then impregnated with 111 Å by weight of 1080 woven glass. At 13 〇. After the semi-hardening is film, it is coated with 8 sheets of film. The upper and lower sides are covered with 1 〇Ζ copper foil of South Asia, and then heat-pressed at 30 kg/cm 2 (426 psi) at 195 ° C for 3 hours to form a circuit board material composition. The physical property measurement data is listed in Table 2. Comparative Example 3 does not add SARET 633. 143. 8 parts by weight of RB810, 77.1 parts by weight of Riconl54 and 86. 8 parts by weight of COC-A and 15.1 parts by weight of 1274773 CTBN130〇x8 were mixed and stirred uniformly; 347·1 part by weight of FB-35 was added. The filler was further mixed with 197·9 parts by weight of SAYTEX 8010, 7.9 parts by weight of TAIC, and 7.9 parts by weight of DCP, and then impregnated with 112 parts of 1080w〇ven glass. At 13 〇. After the semi-hardening is film, it is coated with 8 sheets of film stack, which is covered with a copper foil of South Asia, and is hot-pressed for 3 hours at 30kg/cm2 (426Psi) and 195t to form a circuit board material composition. The physical property measurement data is listed in Table 2. Comparative example 4

The RB810 resin was replaced with Ric〇nl53, and the remaining steps were the same as in Example 5. Comparative Example 5 The ratio of the filler was reduced to 25 wt%, and the amount of the bromine-based flame retardant was increased to make the substrate of the circuit board reach the flame retardant requirement. 1 重量份 of SARET 633 and then blended with 94.1 parts by weight of RB810, 88. 1 parts by weight of Riconl54, and 99.0 parts by weight of COC_A&amp; 16.6 parts by weight of CTBN130〇x8; 254·7 parts by weight of FB-35 filler, and then 225·9 parts by weight of SAYTEX8010, 11.1 parts by weight of TAIC, 11.1

After the DCP was mixed and stirred uniformly, it was impregnated with in. 〇 by weight of i〇8〇 woven glass. After semi-hardening to film at 130 ° C, it is stacked with 8 sheets of film, which is covered with South Asian loz copper foil, and is hot-pressed at 3 〇kg/cm 2 (426 psi) at 195 ° C for 3 hours to form a circuit board. The material composition, its physical property measurement data are listed in Table 2. 20 1274773 Table 1 Composition of the guest example Comparative material / part by weight 5 6 7 8 3 4 5 RB810 141.5 98.8 184.2 141.5 143.8 0.0 164.1 Riconl54 75.9, 75.9 75.9 0.0 77.1 75.9 88.1 Riconl53 0.0 0.0 0.0 75.9 0.0 141.5 0.0 COC-A 85.4 128.1 42.7 85.4 86.8 85.4 99.0 CTBN1300x8 14.9 14.9 14.9 14.9 15.1 14.9 16.6 FB-35 341.6 341.6 341.6 341.6 347.1 341.6 254.7 1080woven glass 111.0 111.0 111.0 111.0 197.9 111.0 111.0 SAYTEX8010 194.7 194.7 194.7 194.7 197.9 194.7 225.9 TAIC 9.5 9.5 9.5 9.5 9.7 9.5 11.1 SARET 633 15.9 15.9 15.9 15.9 0.0 15.9 18.4 DCP 9.5 9.5 9.5 9.5 9.7 9.5 11.1 Test data item / data 5 6 7 8 3 4 5 Peel strength (Μ/inch) 5.46 5.87 5.18 5.33 1.65 4.87 6.18 Dielectric constant DK 2.82 2.78 2.81 2.83 2.84 2.85 2.80 Loss factor Df 0.0007 0.0007 0.0008 0.0008 0.0009 0.0010 _08 Moisture absorption rate (wt%) 0.27 0.24 0.28 0.28 0.27 0.26 0.20 Solder heat resistance (seconds) 300 or more 300 or more 300 or more 220 300 or more 10 10 Flame retardant UL-94 V-0 V-0 V-0 V-0 V-0 V-0 V-1

Physical property analysis: Increasing the amount of thermosetting resin and increasing the ratio of SARET 633 (5 hr of thermosetting resin) can improve the peel strength and lower the dielectric constant; however, if the filler content is less than 30% by weight of the total composition, heat resistance and flame retardancy Sex will deteriorate.' I. 7 21 1274773 Poor application 9~16 With the same method of step 8 , only the C〇CA in the composition is replaced by c〇CB. The physical property test data of the material of the % carrier board is shown in Table 3 and Table 4. Listed. Comparative Examples 6 to 10 The same procedure as Comparative Examples 1 to 5 except that the COC-Α in the composition was changed to COC-B, and the physical property measurement data of the circuit board material composition are listed in Tables 3 and 4.

Two components 15 parts by weight RB810 Riconl54 Riconl53 COC-B CTBN1300x8 FB-35 1080woven glass SAYTEX8010 TAIC SARET633 DCP on 104 63.6 0.0 85.9 12.5 429.5 111.7 163.2 8.0 13.3 8.0 I ^10 6U 63.6 0.0 128.9 12.5 429.5 111.7 163.2 8.0 13.3 ^8.0 147T 63.6 0.0 43.0 12.5 429.5 111.7 163.2 8.0 13.3 8.0 12_ 1043 0.0 63.6 85.9 12.5 429.5 111.7 163.2 8.0 13.3 8.0

2 ^4 4.06 2.94 0.0011 0.30 Comparative Example 6 105.7 0.0 64.5 63.6 0.0 104.3 87.1 85.9 12.6 12.5 435.3 429.5 113.2 111.7 165.4 163.2 8.1 8.0 0.0 13.3 8.1 8.0 2 Item/Data Peel Strength (lbf/inch) Dielectric Constant Dk Loss Factor Df Moisture absorption rate (wt%) Solder heat resistance (seconds) Flame retardancy UL-94 2 4.14 2.96 0.0010 0.27 300 or more V-0 3.δΤ 2.97 0.0011 0.29 3〇〇 or more 3〇〇 or more V-0 4.46 2.93 0.0009 0.25 1.18 2.28 2.98 3.01 0.0010 0.0014 0.28 0.27 270.0 300 or more 25 V-0 V-0 V-0 22 1274773 Table 4 Composition Example Comparative Example Material/Part by Weight 13 14 15 16 8 9 10 RB810 141.5 98.8 184.2 141.5 143.8 0.0 164.1 Riconl54 75.9 75.9 75.9 0.0 77.1 75.9 88.1 Riconl53 0.0 0.0 0.0 75.9 0.0 141.5 0.0 COC-B 85.4 128.1 42.7 85.4 86.8 85.4 99.0 CTBN1300x8 14.9 14.9 14.9 14.9 15.1 14.9 16.6 FB-35 341.6 341.6 341.6 341.6 347.1 341.6 254.7 lOSOwoven glass 111.0 111.0 111.0 111.0 197.9 111.0 111.0 SAYTEX8010 194.7 194.7 194.7 194.7 197.9 194.7 225.9 TAIC 9.5 9.5 9.5 9.5 9.7 9·5 11.1 SARET 633 15.9 15. 9 15.9 15.9 0.0 15.9 18.4 DCP 9.5 9.5 9.5 9.5 9.7 9.5 11.1 Test data/data 5 6 7 8 3 4 5 Peel strength (lbf/inch) 5.39 5.72 5.01 5.12 1.48 4.59 5.88 Dielectric constant Dk 2.84 2.80 2.82 2.83 2.85 2.87 2.81 Loss factor Df 0.0008 0.0007 0.0009 0.0008 0.0010 0.0011 0.0009 Moisture absorption rate (wt%) 0.31 0.28 0.32 0.33 0.32 0.30 0.37 Solder heat resistance (seconds) 300 or more 300 or more 300 or more 235 300 or more 40 30 flammability UL-94 V- 0 V-0 V-0 V-0 V-0 V-0 V-1 Example 17~24 Steps are the same as Example 8 except that c〇CA in the composition is replaced by c〇c_c, /, stroke The physical property test data of the carrier material composition are listed in Tables 5 and 6. Comparative Examples 11 to 15 The steps of the complex were the same as those of the comparative examples 1 to 5, except that the composition of the C0C-A was replaced by c〇c_c, and the physical property test data of the composition of the pen carrier material was as listed in Tables 5 and 6. 23 1274773

Table 5 Composition Example Comparative Example Material/Part by Weight 17 18 19 20 11 12 RB810 104.3 61.3 147.2 104.3 105.7 0.0 Riconl54 63.6 63.6 63.6 0.0 64.5 63.6 Riconl53 0.0 0.0 0.0 63.6 0.0 104.3 COC-C 85.9 128.9 43.0 85.9 87.1 85.9 CTBN1300x8 12.5 12.5 12.5 12.5 12.6 12.5 FB-35 429.5 429.5 429.5 429.5 435.3 429.5 1080woven glass 111.7 111.7 111.7 111.7 113.2 111.7 SAYTRX8010 163.2 163.2 163.2 163.2 165.4 163.2 TAIC 8.0 8.0 8.0 8.0 8.1 8.0 SARET633 13.3 13.3 13.3 13.3 0.0 13.3 DCP 8.0 8.0 8.0 8.0 8.1 8.0 Test Data item/data 1 2 3 4 1 2 Peel strength (lbf/mch) 4.08 4.25 3.81 3.92 1.05 2.16 Dielectric constant DK 2.94 2.91 2.95 2.93 2.96 3.02 Loss factor Df 0.0011 0.0010 0.0012 0.0011 0.0010 0.0013 Moisture absorption rate (wt%) 0.30 0.28 0.31 0.32 0.30 0.31 Solder heat resistance (sec) 300 or more 300 or more 300 or more 285.0 300 or more 40 Flame retardant UL-94 V-0 V-0 V-0 V-0 V-0 V-0

24 1274773 Composition Material/Part by Part 21 Example RB810 Riconl54 Riconl53 COC-C CTBN1300x8 FB-35 1080woven glass SAYTEX8010 TAIC SARET 633 DCP Surface/data fil^S(ibf/inch) Dielectric constant Dk Loss factor Df Moisture absorption rate (wt %) Solder heat resistance (seconds) Flame retardancy UL-94 141.5 75.9 0.0 85.4 14.9 341.6 111.0 194.7 9.5 15.9 9.5 98.8 75.9 0.0 128.1 14.9 341.6 111.0 194.7 9.5 15.9 9.5 Comparative example 22 A 23 24 13 14 , 15 184.2 141.5 143.8 0.0 164.1 75.9 0.0 77.1 75.9 88.1 0.0 75.9 0.0 141.5 0.0 42.7 85.4 86.8 85.4 99.0 14.9 14.9 15.1 14.9 16.6 341.6 341.6 347.1 341.6 254.7 111.0 111.0 112.8 111.0 111.0 194.7 194.7 197.9 194.7 225.9 9.5 9.5 9.7 9.5 11.1 15.9 15.9 0.0 15.9 18.4 9.5 9.5 9.7 9.5 11.1 _ 23 13 14 15 4.96 5.01 1.35 4.46 5.75 2.81 2.82 2.83 2.86 2.79 0.0009 0.0100 0.0008 0.0010 0.0009 0.34 0.34 0.35 0.33 0.40 300 or more 250 300 or more 70, 5〇_ V-0 V-0 V-0 V-0 V- 1 Physical property analysis: and the damage 彡 = the purpose of % = hydrocarbon lion species 'on the dielectric constant L. Solder heat-resistant chicks without side chains (10) C-A ^ The lower the side chain on the low-twisted silk, the easier it is to absorb water, and the strength is also 25 1274773 [Effect of the invention] The degree of measurement: d. (2) Dielectric properties, milk is thermosetting resin and the higher the proportion of tf thermosetting resin, the heavier the heavier, the increased the amount of _ smoke copolymer can reduce the moisture absorption of the ancient (4) solder heat resistance and thermosetting resin composition in the flood control The ratio of the Γ 知 知 (molecular weight Mn &gt; 5,000) and the amount of the filler are -T:-s 〇 35 wt%. (5) The flame retardancy should meet the standard of UL_94 v_〇, ^ related, because the invention will be inferior _ quantity control ΐ planted into 3 ^. / (without filler and W〇VenglaSS), so if the filler ratio is lower than ίίΪΞ, the flame retardancy will be poor, and the film will have a large viscosity, which is unfavorable. (4) Substrate comparison, the circuit carrier of the present invention is composed of inflammation [, 々 Electrical properties, that is, a lower dielectric constant and loss factor ίί rate. In terms of peel strength, the use of general copper can achieve a change in properties, and the general copper is better than the B. At the same time, it hardens after processing, and the circuit board is extremely excellent in physical properties. Although the present invention has been disclosed above in the preferred embodiments, it is not intended to cover the application of the invention and the scope of the invention.

Claims (1)

1274773 First, the scope of application for patents: 1. Kind of south of this circuit carrier material composition, including: (1) thermosetting resin substrate, accounting for 20~35wt% of the assembly, which contains: (a) high vinyl (70wt% The above polybutadiene thermosetting resin has a molecular weight of MW of not more than 100,000 g/m〇l and a molecular weight range of MW=5 〇〇〇~1〇〇〇〇g/m〇1. And (b) a cyclic olefin compound having two or more vinyl double bonds, and/or a high molecular polymer obtained by polymerizing acrylic add, aCryl〇ntrile and butadiene. (2) 10~30wt°/〇 glass fiber cloth reinforcement; (3) 25~50wt°/〇 inorganic particle filler; (4) 1~10wt% Metallic coagents; and (5) 10~30%% bromine Flame retardant. Composition. 2. The circuit board material composition according to claim 1, wherein the thermosetting resin substrate preferably has a ratio of 25 to 32% by weight. 3. If you apply for the circuit test material composition described in item 2, the ratio of the polybutadiene thermosetting resin to the thermosetting resin substrate is 4〇~9〇wt% f. 4. =Application·Scope The material composition of the above-mentioned circuit, a cyclic olefin compound having one or more vinyl double bonds, and/or a high molecular polymer of h: aC1d, aCryl〇ntrile and butadiene The ratio of the /solid resin substrate is 10 to 60% by weight. 5. If you apply for the remaining material composition of the circuit described in item 2, and the U-ethyl group content of the polydiene thermosetting resin is more than 80% by weight. s 6· Wei Zhiwei her _ domain, which is polybutan..., October, its Mw==100,000g/mol and above 7. The power as stated in the application __ 1 to 27 1274773 ϊίΐΐStrength Preferred ratio 4 10~20 composition of Qin 丄 丄 , , , , , 无机 无机 无机 无机 无机 无机 无机 无机 无机 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ 电路 电路 电路The circuit carrier material composition is preferably m_lc diactylate or a circuit of the remainder of the circuit described in the claw-slit item, and the inorganic one is made of titanium oxide, barium titanate, barium titanate or vermiculite. 13 Du Rushen 1 The composition of the circuit carrier material according to Item 12 of the patent scope, wherein the machine particle filler is selected from the group consisting of amorphous stone or sintered stone stone. • The composition of the circuit carrier material as described in claim 1 is preferably 15 to 25 wt% of the bromine flame retardant. 15. The composition of the circuit board material as described in claim 14 of the patent application, which is selected from the price of the earth/smell and the odorant is selected from the price of the gamma (10) coffee, and the tetradecabromodiphenoxy becon ^ oxide 〇16· Manufacture of a high-performance circuit carrier material composition, taking: (1) Thermosetting resin substrate, accounting for 2〇~35wt% of the assembly, including: (a) Southern vinyl content (7〇wt%) The polybutadiene thermosetting resin of the above) is obtained by mixing two molecular weight ranges of MW = 100,000 g/mol or more and MW = 5,000 to 10,000 g/mol. And (b) a polymeric compound having one or more "one or more ethylenic double bonds" and/or a polymer obtained by polymerization of acrylic acid, acrylontrile and butadiene. (2) 10~30wt% glass fiber cloth reinforcement; 28? 1274773 (3) 25~50wt% inorganic particle filler; (4) 1~10wt%Metallic co agents; and (5)10~30~〖% Desert fire retardant. The above ingredients are diluted with a solvent to an appropriate viscosity, and the dust board is generated in a circuit board at a temperature of 17 Torr to 22 Torr and a dust force of 2 Torr to 5 Torr/cm 2 .如 If the patent application method of the 16th circuit is made, the glass is semi-hardened to stack 5 to 8 pieces of the thorns and the upper and lower layers are coated _ to be carried out = at a temperature of 195 ° C and a pressure of 30 kg / cm 2 at the optimum temperature.