TW201114853A - Novelty composition of low dielectric laminated board and manufacturing method thereof - Google Patents

Abstract

This invention can be applied to laminated boards with low dielectric constant (Low Dk and Low Df) properties. The composition includes (A) Dicyclo-pentadiene-Phenolic Novolac (DCPD-PN) resin; or (B) at least one kind of epoxy resin(s)(DCPD-PNE); or (C) a novel Dicyclopentadiene- Dihydrobenzoxazine (DCPD-BX) resin; or the mixture of (B) and (C), with (D) Flame retardant agent(s). Because of thermosetting resin compound DCPD-BX and DCPD-PN contain the backbone of dicyclopentadiene that is saturated multi-cyclic structure. That will decrease the dipole of the resin to lower the dielectric constant of the composition of vanish. The vanish in this invention possesses excellent electric properties and lower moisture-absorption. And that will be having an excellent high thermal stability by using the brominated or phosphorus flame retardant agents. Laminated boards can be made from this composition and reached the level of Low Dk (< 4.0@1GHz) and Low Df (< 0.009@1GHz). That can be applied to high performance electronic materials widely.

Description

[Technical Field] The present invention is a sheet which is pressed by a resin varnish composition for a novel laminate in a laminate process, and has a low dielectric constant and high heat stability. Properties and low moisture absorption properties. It can be tested for flame-resistant UL94V-0 and can be used for high-performance circuit boards. — [Prior Art] With the rapid development of technology, many computer information industries, communications and consumer electronics products are changing very fast. Looking at the development of the entire electronics industry has several characteristics: 1. The frequency of use is getting higher and higher. 2. The level of manufacturing technology is getting higher and higher. Therefore, the printed circuit board will be low dielectric, low thermal expansion, multi-layer, high heat resistance. Φ to the development (five) time to meet the requirements of the friendly environment, to meet the needs of electronic and communication products tend to be light and thin, high-key, multi-functional, environmental protection. With the high frequency of wireless networks and communication products, the high-frequency substrate is bound to become a future development trend. Basically, the material requirements of the 焉 轨 基板 基板 四 四 四 四 四 四 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料 材料Basic characteristics: L dielectric constant is small and stable 2' dielectric consumption factor must be small 3. Low water absorption rate 201114853 4. Good chemical resistance 5. Good heat resistance Printed circuit board material electrical properties can be composed of the main three kinds of composite materials of the substrate (1) Resin, (2) filler (3) The type of reinforcing material is determined. For the resin system, the FR_4 (Tgl4〇C) substrate with a combination of epoxy resin (such as South Asia NPEB454A80) and glass fiber (e glass) has a dielectric constant (Dk) value of only 4.6. Unable to meet the high-frequency transmission field, although the land is turned out to emit different resin systems (such as Βτ, shouting ester, PTFE, etc.). However, in general, the newly developed resin system has a large difference between the processing conditions and the existing substrate processing conditions, and thus cannot be widely applied. [Summary of the Invention] [Technical Problem to Be Solved] The development of laminated boards for printed circuits is moving toward light, thin, small, precise, and high-frequency applications, avoiding data loss and interference during transmission. The material must further have excellent electrical properties', but the newly developed low dielectric resin materials need to maintain the existing processing and processing conditions and equipment operating requirements, while meeting the requirements of environmental friendliness' has become an important issue that this technology industry must overcome. [Technical means for solving the problem] In view of the above problems, the present invention is a novel saturated cyclic structure resin which is used in a resin varnish formulation + to obtain excellent electrical properties (low dielectric constant Dk and low dielectric loss) The characteristic of the coefficient Df). Due to the saturated cyclic structure of the resin, the chemical structure has a cyclical rotation of 201114853, which can effectively reduce the _ swell, reduce the dielectric constant of the substrate and dielectric loss storage; and at the same time, under the existing curing process Various types of hardeners achieve substrate properties of different needs. The main purpose of this study was to develop circuit board substrates with low dielectric constants. The research method is based on the use of dicyclopentadiene (DCPD), a cheap by-product of light oil cracking, to make novel low dielectric circuit board substrates. The resin having a DCPD structure and the BX resin are synthesized by the rigid ring structure of the raw material itself to form a copper ruthenium substrate having low dielectric, high thermal stability, low moisture absorption and easy processing. The varnish composition prepared from the novel low dielectric resin comprises: (A) a desired resin; (B) a novel low dielectric resin, a low dielectric BX resin; (one or more Epoxy resin; and (D) flame retardant, etc., after mixing (A), (B), (c) and (D) in a certain ratio, the resin varnish formulation for laminates can be obtained. The raw material DCPD-PN was added to the propylene oxide (Epichlorohydrin) in a fixed equivalent ratio to synthesize the DCPD epoxy resin in the presence of NaOH. The other part of the BX resin was DCPD-PN as the raw material, and then the fixed ratio of polyoxymethylene and aniline was used. Synthetic: Hardener: NPEH-710S and 710H are the main hardeners in South Asia; in order to increase DCPD content, DCPD-PN is used as a hardener. Dynamite: The current use of flame retardants is divided into three categories. Traditional bromine-based flame retardants (such as: TBBA), two are phosphorus-based flame retardants (such as phosphate compounds, D〇P〇), and three are inorganic-added flame retardants (such as Al2〇3, ATH). It is also possible to choose not to add any flame retardant. 201114853 The slab-like lining composition of the present invention has a saturated multi-ring structure. It has better chemical and physical properties than ordinary epoxy resin. The resin is introduced into the varnish formulation and cured by hot pressing to obtain excellent electrical properties, high thermal stability and low absorption of the beach. [Detailed Description of the Invention] The present invention is a low dielectric resin varnish (Varnish) formulation composition for a laminate. The resin composition includes: Dicyclopentadiene-Phenolic Novolac (DCPD-PN); (B) A new type of 'Dicyclopenta-diene-Dihydrobenzoxazine (DCPD_BX) thermosetting resin (〇 at least one epoxy resin; and (9) flame retardant, etc. wherein component (A) dicyclopentadiene-phenolic resin (DCPD-PN), the structural formula is as follows, using (a) dicyclopentane The diene; and (b) the phenolic compound are obtained by reacting two kinds of reactants. After the modification or conversion of the reactants, various types can be used, and the synthesis examples thereof are described below:

201114853 z: is represented by the following chemical formulas -ch3, -C2H5, -C(CH3)3, -H η : 0.5~1.5. Preparation of dcpd-pn, placed in a heating bag, temperature controller, electric mixer, condensation, 5 B four-neck glass reaction tank, placed 940 grams of hope and 2 plus / 0 of Lewis acid catalyst ( AICI3), the temperature was raised to ho c stirring 'heating to i2 〇 ° c reaction'. 132 g of DCPD was added dropwise to the reaction and allowed to react for 4 hours. Finally, after adding the sodium hydroxide neutralization solution, the reaction solution is extracted with water to remove the salt and the catalyst, and finally the excess reactant is removed by the pressure of tor(6) under 70 torr to obtain the dcpd-PN product. Preparation of (b) phenolic compounds of DCPD-PN, generally using phenol, o-nonylphenol, propylene glycol (Bisphenol-A), 4,4'-diphenol decane (Bisphenol_F), 4,4,-two A phenolic sulfone (Bisphenol-S) or a phenolic resin, etc., is preferably a propylene glycol or a phenolic resin. The solvent is not particularly limited as long as it can dissolve each reactant. A hydrocarbon solvent such as toluene or xylene is preferred. In order to increase the DCPD content, the hardener is mainly DCPD-PN. The following resin hardeners may also be used, including phenolic resin hardeners, such as polyvalent amines, polyvalent carboxylic acids, Dicyanodiamide, Anhydrides, and Pana Resin (PhenolNovolac, PN for short), carboxylic acid (CresolNovolac, CN for short), Melamine Phenol Novolac (MPN), BPA Phenol Novolac (BPA-PN for short) ), Siyi B-burning resin (Tetra-Phenol 201114853

Novolac (referred to as TPN) and Dicyclopentadiene-Phenolic Novolac (DCPD-PN). The component (B) is a novel dicyclopentadiene-Dihydro-benzoxazine (DCPD-BX) thermosetting resin which is formed by reacting the following four compounds. (a) dicyclopentadiene-phenolic resin (DCPD-PN); (b) monofunctional and difunctional mixed monoamine compounds; and (c) formaldehyde or polyfurfural compounds. After the modification, it can be various types, and the synthesis examples are detailed below:

Z: is represented by the following chemical formula

CH3, -C2H5, -C(CH3)3, -Hn · 〇~1 〇 R: may be an alkyl group or an aromatic group. Preparation of DCPD-BX, in a 5L four-neck glass reaction tank equipped with a heating pack, a temperature controller, an electric mixer, and a condenser tube, put 480 g of DCPD-PN, 486 g of polyformic acid, and then add 500 g of 曱Mix and dissolve, and slowly add 279 g of Aniline into the above solution, the temperature is controlled between 6 〇 and 11 (rc, reaction for 4 to 6 hours, and then use 180 ° C under 70t 〇rrs pressure, The solvent and the unreacted material are removed to obtain a solid cyclopentadienyl dihydro cumene thermosetting resin, hereinafter referred to as DCpD_Bx. 201114853 Preparation of DCPD-ΒΧ(b)-monofunctional and difunctional mixed one-stage The amine compound is generally methylamine, ethylamine, aniline, T〇luidine, orniidine, etc. It can also be an aliphatic or aromatic amine compound, most Preferably, it is aniline or diaminodiphenyl fluorene. Preparation of DCPD-ΒΧ (c) formaldehyde or polyfurfural compound, generally using formaldehyde, polyoxymethylene or formaldehyde vapor, etc., and polyoxymethylene is the best. The solvent of DCPD-ΒΧ is not particularly limited as long as it can dissolve each reactant. It is preferably a hydrocarbon solvent such as methyl benzoate or diphenyl benzene. The component (c) at least one epoxy resin of the resin varnish formulation of the present invention is prepared by reacting DCPD-PN resin with epoxidized gas propane. Epoxy resin DCPD-PNE. The structure is as follows:

Z: is represented by the following chemical formula: -CH3 ' -C2H5 ^ -C(CH3)3 -Η η : 0.5 to 1.5. The preparation of DCPD-PNE is carried out in a 5L four-neck glass reaction tank equipped with a heating pack, a temperature controller, an electric feeder, and a condensation officer, and placed in a 5 gram g DCpD_pN, π" 2 g t s. 201114853 Epoxy propane 'heated to 55 ΐ pre-dissolved, added 281g of sodium hydroxide in 4~6 hours in low-addition mode, then heated to 78 ° C for 1 hour at llOTorrs pressure, and finally at 180 ° C at 70torrs pressure The product DCPD-PNE can be obtained by removing excess reactants. The epoxy resin can also be BPA type epoxy resin, brominated BPA type epoxy resin, novolac type epoxy resin, phosphate ester type epoxy resin. Inventive resin varnish formulation composition (D), flame retardant is mainly bromine and phosphorus resin. 'Inorganic filler flame retardant can also be used. Bromine based flame retardant mainly includes: tetrabromopropanediol (TBBA), NPEB-485A80 (trade name, produced by Nanya Plastics Co., Ltd., bromine content 18~21%), ΝΡΕΒ·454Α80 (trade name, produced by Nanya Plastics Co., Ltd., bromine content 18~21%). Phosphorus-based flame retardant: 〇〇?〇(9,10-〇吻咖〇-9-€^-10_

Phosphaphenanthrene-10-Oxide) 'DOPO-HQ &gt; DOPO-Phenol Novolac Epoxy Resin (DOPO-PNE) 'DOPO-Hydroquinone-Phenol Novolac Epoxy Resin (DOPO-HQ-PNE). Inorganic fillers are mainly flame retardants: hydrogen hydride, sulphur dioxide, sulfuric acid, oxidized, and nitriding. A hardening accelerator is also used, and the hardening accelerator includes a tertiary phosphine, a tertiary amine, a quaternary phosphonium salt, a quaternary ammonium salt, an Imidazole compound, wherein the tertiary phosphine includes: triphenylphosphine, etc.; The amine includes: trimethylaniline, triethylamine, tributylamine, dimethylamine ethanol, etc.; quaternary phosphonium salt includes: tetrabutyl bromide scale, tetraphenyl bromide scale, ethyl triphenyl a quaternary salt containing a dentate such as a brominated scale, a propyltriphenyl chloride scale, or a butyltriphenyl brominated scale; the quaternary ammonium salt includes tetramethyl bromide, tetraethylammonium bromide, and tetrabutyl a quaternary ammonium salt containing a bromine, a triethylbenzylammonium bromide, a diethylphenylethylammonium bromide or the like; an imidazole [S 1 201114853 compound includes: 2-methylimidazole, 2-ethyl Imidazole, 2-dodecylimidazole, 2-phenylimidazole, 4-mercaptoimidazole, 4-ethylmethane, 4-dodecylimidazole, 2-ethyl-4-mercaptoimidazole, 2-Ethyl-4-pyridylpyridine V»Sit, etc., most suitable for 2-mercapto-based π sitting or 2·ethyl_4_曱基咪° sitting. The accelerator may be used singly or in combination of two or more kinds, and the amount thereof is 相对1 〜1 PHR with respect to the total amount of the resin, and the optimum amount is 〇.〇4 to 0.15 PHR. The composition of the novel environment-friendly resin composed of a synthetic resin having a ring structure comprises (A) a DCPD-PN content of 1 to 50% by weight; (B) a DCPD-BX content of 30 to 50% by weight and ' ( C) DCPD-PNE content is 13~60wt ° / 〇; (D) total content of flame retardant is 22~32wt%; additional hardening accelerator with 〇〇1~lpHR relative to the total amount of resin; The varnish is shouted as 'Lai' is an ageing fine solvent, protic solvent, ketone solvent, ether solvent and ester solvent (the appropriate solvent is benzene, n, n• dimethyl decylamine, acetone, methyl Ethyl hydrazine, μ methoxy _2 • propanol, acetic acid (five), etc.). When used in a laminate, 'this composition is immersed in a _ _ cloth, and then heat up, so that the impregnated glass fiber thieves smashed ah g), placed Xie I ' on one or both sides of the job The stack of the prepreg is laminated, and finally the mannequin is applied under pressure to obtain a copper plate. The resin varnish formulation is cured to 30 CTC, preferably 150 to 210. MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail by way of preferred embodiments, the examples and the symbols and their compositions are as follows:

Resin A: represents homemade DQ &gt; D_pNE 270~230g/eq. Wei·'s _ equivalents 201114853 Resin B: represents the homemade DCPD-indene resin. Resin C: Represents the brominated resin produced by Nanya Plastics. The trade name is Ν^ρΕΒ_485Α80. Resin D: represents the phosphorus resin (DOPa638) produced by Nanya Plastics, trade name 210A70. Resin E: represents the phosphorus resin (DOP〇_Hq_638) produced by Nanya Plastics, trade name 220A70. Hardener A: Represents the phenolic resin produced by Nanya Plastics, trade name 71〇HA65. Hardener B: Represents the phenolic resin produced by Nanya Plastics, trade name 71〇SA65. Hardener C: stands for homemade DCPD-PN. Flame Retardant A: bromine-containing flame retardant, TBBA. Flame Retardant B: Contains a flame retardant, ρχ_2〇〇. Flame retardant C: filler, aluminum hydroxide ATH. Flame retardant D: filler, cerium oxide Si〇2. Promoter 2MI; represents 2-methylimidazole, 14.2% is soluble in DMF. [Examples 1 to 15] A new resin was used in combination with different hardeners. The composition of the composition was detailed in Table 1, and acetone was used to adjust the varnish resin composition having a solid content of 65%; a laminate was prepared by a conventional method. The method is to impregnate the 7628 glass fiber cloth with the varnish resin liquid, and then dry it for 1 minute in a machine (the temperature of the impregnation machine), adjust the drying time to adjust the drying time, and then reduce the pre-impregnation body to be reduced to 8 pieces. The film layer is stacked on two pieces of 35·thick copper, and under the pressure of 25kg/em2, its temperature rises 201114853

130 ° C

The program is as follows, after hot pressing, the laminate can be obtained. 85 ° C - 85 ° C - 200 ° c - 200 ° C Slowly cooled 20 min 30 min i2 〇 min to obtain a 1.6 mm thick copper foil substrate. [Comparative Examples 1 to 3] Using a general-purpose brominated epoxy resin (South Asian brominated epoxy resin, trade name: NPEB-485A80) with different hardeners, the formulation of which is detailed in Table 1, using acetone to adjust A varnish resin composition having a solid content of 65%; and a laminated laminate was prepared in the same manner as in the production of a laminate of Example 丨9. [Measurement Description] Dielectric constant test: The test method is to cut the etched substrate into 5 em2 square test pieces, at 丨〇5. After drying in the oven for 2 hr, the thickness of the test piece was taken out at three places. Then, the test piece is clamped into the dielectric measuring instrument, and the data of three points is measured and averaged. ] 15 201114853

Example 9 2 I 1 1 15.5 I 1 15.5 | in d 361 1 167.2 | | 94V-0 I 0.08 I 1 3.92 j 0.009 0 Ss OH Satin 0 - s? Zhao · Your peak 〇 Φ4 4 1 ^ f ^ ε t Machinery. 〇 W. $ m ^ 3 Ii ^ ^ ° ^ d £ ^ f ^ f ^ ^ -3⁄4 ΓΛ ^ A ; -5- p|ll^ ^ ^ 1 5 ^ c ^ ν 鹄 Lithium G ^ ^ # ο 〇^ Shoulder喵π ..d K ^ ^ g! &lt; _ _ _ _ i&amp;J *—i (N cn ^t· +3⁄4 * * * * * 1 Example 8| 2 d 1 355 I | 173.5 | | 94V -0 I 0.07 1 3.89 0.009 Example 7 2 Γ so VC — d 365 163.5 | 94V-0 | 0.09 r3 | 0.008 | Example 6 9 rq 0.28 368 | 165.5 | | 94V-1 | 0.08 1 418 1 | 0.012 | Example 5 !75 00 &lt;s 0.24 370 1 171 1 | 94V-0 | 1 0.07 1 1 421 1 0.016 Example 4 »Λ jH 00 fS 0.28 375 1 157 1 | 94V-0 | 0.08 0.014 Example 3 25.7 223 | 031 372 1 164 1 | 94V-1 | 0.07 1 418 0.012 Example 2 0.25 0.25 364 rj 94V-0 j 0.07 &lt;s | 0.012 | Example 1 | Upper 2 380 1 159 1 j 94V-0 1 0.08 1 4·22 1 | 0.014 Resin A Resin B Resin C Resin D Resin E Hardener A Hardener B Hardener C Flame Retardant A Flame Retardant B Flame Retardant c Flame Retardant D Accelerator 2MI (PHR) Varnish Gel Time sec *1 (N^ l· h. i Water absorption %*4 Dielectric constant (1GHz) Electric loss factor (1GHz)*5 201114853

Comparative Example 3 00 s 324 &lt;s 94V-0 I 1 0.08 I 0.025 I 0 5? Satin 〇 H € . - 牛飨 皤 _ _ .黎妒S» ^ £ ^ C ^ S i V s ® W ^ (N 3 ^ ^ ^ p7 3 2 痴 - - garlic Ϊ 二 - + 接 g Q ^ . &amp; f ^ 15 ^ C 馊 Lithium ^.寒碱砵: H: ..&lt;=&gt; w ^ ^ ^ — rvi 〆·〆* * * * * Comparative Example 2 | 00 &lt;s &lt;sd 1 Training I so fH | 94V-0 | | 0.08 I | 0.028 | Comparative Example 1 6C o 320 m (4) | 94V-0 | | 0.07 I 卜 | 0.03 | Example 15 | 15.5 15.5 | 0.28 350 00 VO 94V-1 | 0.08 1 415 1 0.012 Example 141 &lt;s Tn | 0.24 | 1 345 1 | 94V-0 | 0.07 L^·20! 0.014 Example 13 η ΙΛ 0.28 335 | 94V-0 | 0.08 | 4.35 | 0.015 Example 12 2 VC | 15.5 | 1 15.5 | 0.26 1 345 1 § 1 94V-1 | 0.07 1 416 1 0.012 Example 11 fS • Λ 53 0.21 355 p 1 94V-0 | | 0.07 | 1 418 0.013 | Example 10 η 2 η VC — 0.25 | 360 00 tn | 94V- 0 | 0.08 1 ^ | 0.014 Resin A Resin 树脂 Resin C Resin D Resin 硬化 Hardener A Hardener B Hardener c Flame Retardant A Flame Retardant B Flame Retardant c Flame Retardant D Accelerator 2MI (PHR) Varnish Gel Time sec* 1 glass transfer temperature °c*2 Km Water absorption % *4 Dielectric constant (1 GHz) Dielectric loss factor (1 GHz)*5 201114853 It is proved by the above experiment that the resin of the winter squid DCPD structure has a low absorption /.", low; Hang number and low dielectric loss. The resin is matched with Han ^_pN as hardener, and the pressed substrate can effectively reduce the dielectric constant and dielectric loss; if DCPD-BX is added, the content of g DCpD structure Increase, the number of (four) can be further reduced, and by adding the flame retardant Filler, up to 94v_ igniting standard and good thermal stability. Resistant

Claims (1)

201114853 X. Patent Application Range: 1. The present invention is a low dielectric resin varnish (Vamish) formulation composed of a laminate. The resin composition thereof includes: (A) dicyclopentadiene age-receiving resin. ^1 (^血脱116-PhenolicNovolac; DCPD-PN); (B) a new type of dicyclopentadiene-Dihydrobenzoxazine (DCPD-BX) thermosetting resin; (C) one or more Epoxy resin; and (D) flame retardant. Among them, the composition of (A) dicyclopentadiene ♦ resin (DCPD_PN) resin, which has the following structure: Z: is represented by the following chemical formula: -CH3 &gt; -C2H5 ' -C(CH3)3«-Η η : 0.5 to 1.5. A novel dicyclopentadiene-dihydrobenzo (DcpD de-heating resin) composed of (Β) having the following structure: 19 201114853 z: Represented by the following chemical formulas _CH3, -C2H5, _C(CH3)3, -Η R. may be a burnt group or an aromatic group. η · 0~1 〇2. As claimed in the first paragraph of the patent scope, the cyclopentadiene-phenolic resin (DCpD_pN) is a cyclopentadiene; and (b) a compound, The two reactants are reacted. Among them, phenolic compounds are phenol, o-nonylphenol, Bisphen〇i_A, 4,4'-diphenol decane (Bisphenol-F), 4,4,-diphenol sulfone (Bisphenol-S). ) or phenolic resin. 3. If the new dicyclopentadiene-phenolic resin (DCPD-PN) resin of the composition (A) of the scope of claim 1 is used as a hardener, 1. If it is claim 3, it may be another resin hardener. For example, phenolic resins, amines, hardeners of organic acids and acid anhydrides, such as polyvalent amines, polyvalent carboxylic acids, Dicyanodiamide, anhydrides, phenols Formaldehyde resin (Phenol Novolac, PN for short), cresol novolac (CN) melamine Phenol Novolac 'MPN, propylene glycol formaldehyde resin (BPA Phenol Novolac, ΒΡΑ-ΡΝ), four TetraPhenol Novolac (TPN) and Dicyclopentadiene-Phenolic Novolac (DCPD-PN). 2. The novel Dicyclopentadiene-Dihydro-benzoxazine (DCPD-BX) thermosetting tree of claim 1 contains: (8) dicyclopentadiene phenolic resin (DCPD) - PN); (b) a monofunctional m 201114853-based and difunctional mixed mono-amine compound; and (c) a furfural or polyfurfural compound. 3. As claimed in item 5, (a) dicyclopentadiene phenolic resin (DcpD_pN), which is the DCPD-PN structure of claim 1, and n = (M. 4. as requested in item 5 '(b) monofunctional A primary amine compound mixed with a difunctional group, using a primary amine such as mercaptoamine, aniline, t〇luidine, anisidine, etc., may also be aliphatic or aromatic. Amine compounds 5. As in claim 5, (c) furfural or polyoxymethylene compounds, formaldehyde, polyacetal or furfural vapor, etc. are used. 6. According to claim 1, one or more of the components (C) Epoxy resin The DCPD-PNE structure is as follows: Z: is represented by the following chemical formulas CH3, -C2H5, -C(CH3)3, -H 7. For example, an oxygen resin. 8. As requested in item 1, The composition of (〇) is the resin containing the material surface, and it can also make 21 201114853 an inorganic filler flame retardant. 9. In the case of claim 11, the bromine-based flame retardants are mainly: tetrabromopropanediol (τΒΒΑ) or tetradecylphenol type epoxy resin. 10. In the case of claim 11, the flame retardant is DOPO, DOPO-HQ, and its acid epoxy resin. 11. According to claim 11 'Inorganic filler flame retardants are mainly: ATH, cerium oxide, cerium sulphate, aluminum oxide, boron nitride, and the like. I2. Further, it is necessary to add a promoter to the formulation, and the accelerator may be used singly or in combination of two or more kinds thereof, and the amount thereof is from 0 4 to 015 phr based on the total amount of the resin. 13. As claimed in claim 15, the hardening accelerator comprises a tertiary phosphine, a tertiary amine, a quaternary phosphonium salt, a quaternary ammonium salt, an imidazole compound, etc., wherein 2-methylimidazole (2me%1 imidazole, 2MI) and 2-ethyl-4-methylimidazole (2E4MZ) 〇14. The composition ratio of the resin composition of the novel cyclic structure obtained by synthesis, including DCPD-PN content of 1~5〇wt〇/0; (8) DcpD_BX content of 3 〇~fine % and; (C) DCPD-PNE content is 13~6_%; (D) total flame retardant content is 22~32wt%; and a hardening accelerator of _~〇15pHR relative to the total amount of the resin is added. Is as claimed in claim 1 and η', which have a resin composition containing a novel cyclic structure, have low enthalpy electric reading, low dielectric loss factor, high heat stability and low hygroscopicity after hardening and can achieve flame resistance. Shen 94 ν, 〇 test. It can be applied to a wide range of high performance circuit boards such as multi-layer laminates, composites, printed circuit boards, inks or packaging materials. 22 201114853 VII. Designation of representative drawings: (1) The representative representative of the case is: ( ). (2) A brief description of the symbol of the representative figure: None 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: 201114853 f) Instruction manual #年丨月1日正 (The format, sequence and bold characters of this manual, please - do not change any more, please do not fill in the ※ part) ※Application number: and ※Application deadline: Thick 1?&lt ;: Classification: I. Name of the invention: (Chinese / English) Composition of low dielectric resin varnish for novel laminates and its preparation method II. Abstract of the invention: The invention is a kind of _ brush circuit laminate board dielectric dielectric f number The resin varnish (Varnish) composition and the preparation method thereof, the resin composition thereof comprises: (8) Dicyclopentadiene-Phenolic Novolacjh^DCPD-PN; 4(B) a novel one-ring pentylene- DiCycl〇penta_diene-Dihydmbenzoxazine (DCPMX) thermosetting resin; or (8) a mixture with (9) and (C) at least - or a variety of flavors; and (9) difficult to fine, and hardening accelerator Composition. The composition of the varnish composition (A) DcpD_pN and the component (B) DCpD_Bx contain a saturated &gt; ring-shaped bicyclopentadiene 纟 structure, which can reduce the dipole moment of the varnish (dlP〇le) ), dielectric constant (Dk), dielectric loss (Df) and hygroscopicity; the resin varnish is added with the indifference and the meal, it is difficult to make the group rich and hot. According to the steel foil substrate of the month of the month, not only can the low dielectric constant (Dk&lt;4.0@lGHz) and low; the loss factor (Df&lt;〇〇〇9@1GHz) can be achieved. High heat stability and low moisture absorption characteristics are widely used in neon's electronic materials. 201114853 Manli patent specification (this manual format, shunma β Α ι— --- Bei & and bold, please do not change, ※ Do not fill in the mark) ※Application number·· η名(&gt;Sr&gt;]iy ※Application date · Correct PC classification: 1. Name of the invention: (Chinese / English) Novel laminate (4) Low dielectric resin varnish composition II. Abstract of Chinese invention: The present invention relates to a low dielectric constant resin varnish for a printed circuit laminate (Vam 组成 组成 composition, and includes: (VIII) _ cyclopentadiene 酴 resin (DiCyCi〇 pentadiene_phen〇 Iic N_lac '1 is called lion's marriage; (8) one or more dicyclopentadiene Phenolic Novolac Epoxy (DCPD-PNE)^i|#^| 1 ; new type of pentylene-monohydrobenzene And resin (Dicyd〇pen secret coffee · Shi ydr〇benz〇xaz ^ ^ DCPD-BX) is also known as resin 2, or mixed resin of (8) and (c) and (9) flame retardant, hardener and solubilizing turtle杰. And the composition of the ingredients (A) DCPD_PN, composition (B) DC]? D_PNE and the composition d丨ΓΖΪί rich and pure-grained two-ring red riding structure, reducing the dipole moment dielectric loss and suction Adding ageing, flame retardant, έ正正&quot;Supplement is still the same as the hot * fixed and low rhyme chicks, extensive _ in the energy of electronic materials. 201114853 VI. Description of the Invention: [Technical Field] The present invention is characterized by low dielectric constant, high thermal stability and low hygroscopicity, and can achieve a flame-resistant UL94V-0 test, which is suitable for use in high-performance circuit boards. A resin varnish composition for a novel integrated screen panel. [Prior Art] With the rapid development of technology, many computer information industries, communications, and consumer electronics products are changing very fast. Looking at the development of the entire electronics industry has several characteristics: 1. The frequency of use is getting higher and higher. 2. The level of manufacturing technology is getting higher and higher. In the case of printed circuit boards, it will be low dielectric, low thermal expansion, multi-layer, high heat resistance. The development of chemical materials is also in line with the requirements of Wei Youshan, and the electronic and rail products tend to be fortunate to the second, the fourth, the small, the reliability, the multi-functionality and the environmental protection. With the high frequency of wireless networks and communication equipment, the demand for high-frequency substrates is bound to become a future development trend. The material requirements for the 'Southern Frequency' communication board are nothing more than the ability to transmit the material quickly, and the data transmission process will not cause loss of data or plagiarism. Therefore, the following must be made when selecting high frequency communication equipment. Several basic characteristics: (1) The dielectric constant is small and stable (2) The dielectric consumption factor must be small (3) Low water absorption rate (4) Good chemical resistance (5) Good heat resistance 4 201114853 VI. Invention description: TECHNICAL FIELD The present invention is a novel resin varnish group Z for laminates which has low dielectric constant, high thermal stability and low hygroscopicity and can be tested for UL94V-0 and is suitable for high performance circuit boards. . ..., warfare Previous technology With the rapid development of technology, many computer information industries, communications and consumer electronics products are very fast. Looking at the entire electronics industry, its development characteristics have; °σ 1. The frequency of use is getting higher and higher. 2. The level of manufacturing technology is getting higher and higher. In the case of printed circuit boards, it will develop toward low dielectric, low thermal expansion, multi-layer, high heat resistance, and at the same time, in order to meet the requirements of environmental friendliness, electronic and communication products tend to be light, thin, short, and reliable. , multi-functional and environmental protection needs. With the high frequency of wireless networks and communication equipment, the demand for two-frequency substrates is bound to become a future development trend. In short, the materials used in the high-frequency communication substrate must not be able to transmit data at a speed, and the transmission process will not cause damage to the dragon. Therefore, the following must be available when selecting high-frequency communication equipment. Basic characteristics: 1. The dielectric constant is small and stable. 2. The dielectric consumption factor must be small. 3. Low water absorption rate 4. Good chemical resistance 5. Good heat resistance The electrical properties of the material can be composed of the main three kinds of composite materials of the substrate (1) resin, (2) Aw The type of soil reinforcement is determined. As far as the resin system is concerned, the currently widely used epoxy tree ^ 屮 Μ Μ 夂 无法 无法 无法 无法 无法 无法 无法 无法 无法 无法 无法 无法 无法 无法 无法 无法 无法 无法 无法 无法 无法 无法 无法 无法 无法 无法 无法 无法 无法 无法 无法 无法 无法 无法 无法 无法 无法 无法The benzene resin (9) is still the same as the top - = m,), the cyanate ester resin, and the polytetrafluoroethylene resin. The components are very different, and the current equipment cannot be used. Therefore, it cannot be widely used. 4 201114853 The electrical characteristics of the printed circuit board material can be determined by the types of the three main composite materials (1), resin, (9) filler, and (iv) reinforcing material. For the resin system, the FR-4 (TgH0°C) substrate specification of the currently used epoxy resin (such as the South Asian shame 4 fan) and the surface (E surface) is 'the dielectric constant (Dk) The level of μ cannot meet the requirements of high-frequency transmission. 'Although different resin systems (such as BT resin (Bismaleimide Triazine resin), cyanate resin (Cyanate City (7), polytetrafluoroethylene (PTFE), etc.) have been developed. However, the newly developed resin system is inconsistent with the manufacturing process and the reinforced substrate and the gambling substrate plus the king's miscellaneous pieces. The township cannot use the existing equipment, so it cannot be widely used. [Summary of the invention]颞 Small, precise and high-frequency development of printed circuit laminates, towards the trend of light and thin 〇 applications, in order to avoid transmission of wealth caused by _ loss and interference, the resin materials used not only must be prepared At the same time, the composition of the syllabus rouge varnish also needs to be transferred to the existing plus I system to turn the interesting pieces and operate under the control, and meet the requirements of the people's environment, has this skill _ 贱 H H 赖 、 、 、 、 、 、 、 、 、 The technical means are in the above lessons. The inventor--~π艽畀 test found that it has saturation: a general structure, and its chemical series has a 姊Wei series (4), which can effectively lower the thermal expansion coefficient, dielectric constant and dielectric loss factor of the substrate; In the resin varnish, excellent low dielectric constant Dk and low dielectric loss coefficient Df electrical characteristics 201114853 [Invention content] The technical problem to be solved is toward the development of printed circuit laminates towards light, thin, and ancient介 脂 清 清 喊 减 城 城 城 城 城 城 城 城 城 城 ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' 崎 崎 崎 崎 崎 崎 崎 崎 崎 崎 崎 崎 崎 崎 崎 崎 崎 崎 崎Years of research and experimentation have found that there is a heterogeneous structure with a saturated ring-shaped tree red with yarn, which can have the coefficient of expansion of the Shanban board, Ο The electric loss factor; the low dielectric constant / residual Di f secretness of the fine lacquer formula towel. (4) It is possible to use various hardeners in the current equipment plus jade_ to achieve the properties of substrates with different requirements. According to the present invention, the main object of the present invention is to provide a wire plate having a low dielectric constant, a low dielectric loss, a low moisture absorption, and a (four) mosquito. The substrate is a cheap (four) solution for the cheaper service. The diene (D1Cyd〇pentadiene; DCPD) is composed of a rigid aliphatic cyclic steric structure of the raw material itself. The combination of '' and _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ iicNov〇iac 'DCPD tearing, and then reacting with dcpd resin 盥dihydrobenzene f (^Henzoxazine 'BX) resin or reacting with epoxy resin to form dicyclopentadiene-Dihydrobenzoxazine , DCPD-BX); or generate 〇0?0 epoxy resin _1] ^ 〇化£? (^, 00? 0-;? division), to produce low dielectric, high heat stability, low moisture absorption The circuit board and the copper enamel substrate can be easily processed by the current equipment and processing conditions. The varnish composition made of the novel low dielectric resin is: (a) *DCPD age-old resin (DCPD) (B)—or more than one epoxy resin or epoxy tree with dCPD(DCPD-PNE); (Q with DCPDD) CPD_BX resin; and (9) flame retardant, hardener and accelerator, which are mixed with (8), (9), (C) or (B) + (C) and (D) mixed with a certain proportion of solvent, then It can be used in the resin varnish formulation for laminates of the present invention; Π main agent: DCPD-PN raw material is mixed with Epichlorohydrin (ECH) in a fixed equivalent ratio in the presence of NaOH to synthesize DCPD epoxy resin. (dcpd-PNE). Another BX resin is also synthesized from DCPD-PN as a raw material, and then reacted with aniline in a fixed equivalent ratio. Hardener: South Asian hardener]^1&gt;] £11_71〇3 or 710H Mainly; in order to increase the DCPD content, another 201114853 ί - at the same time can be used in the current equipment plus reading process with a variety of hardeners to achieve different substrate properties. According to the invention 'the main purpose is to provide a circuit substrate having a low dielectric constant, a low dielectric loss A, a low moisture absorption and a high thermal stability, and the substrate is a raw material for the production of a new low-dielectric circuit substrate. With the rigid fat ring of the original 枓The stereostructure is synthesized by synthesizing DCPD_PN with DCPD structure and Dihydmbenzoxazine (BX) resin and PNE (Phen〇1 N〇v〇Iac Ερ〇χ force to obtain L low dielectric, high age qualitative Low-lying and woven and reinforced conditions can also be easily processed copper foil substrates. The varnish composition prepared from the novel low dielectric resin described above is composed of: (A) a phenolic resin having DCpD; (B) a low dielectric BX resin having DCPD; (a) or a plurality of epoxy resins; And (D) a flame retardant, a hardening accelerator, and (A), (B), (c), and (d) are mixed with a uniform, which can be used in the lion-resin varnish of the present invention. Formulation, the main agent, the DCPD-PN is prepared in a fixed equivalent ratio in the presence of NaOH, and is added with propylene oxide (Epichlorohydrin) to synthesize DCPD epoxy; ^DC (DCPD-PNE). The other BX resin is DCPD- PN is the raw material, and then reacted with polyanisaldehyde and aniline in a fixed equivalent ratio. Hardener: NPEH-710S and 710H are the main hardeners of South Asia; in order to increase the content of DcpD, DCPD-P; N can be used as a hardener. Flame retardant: At present, conventional flame retardants are classified into three categories, one is a traditional bromine-based flame retardant, such as four 6 201114853. DCPD-PN is used as a hardener. Flame retardant: At present, the conventional fuel is divided into three categories. , for traditional injection, flame retardant, such as tetrabromopropane (TBBA); two for phosphorus-based flame retardants, such as phosphate compounds (D〇p〇); Inorganic additive type flame retardant, such as Al2〇3, ATH, may also be added without any flame retardant. The resin composition for the novel laminate of the present invention is prepared by the following steps: 1. The light oil lysate dicyclopentadiene of the aliphatic cyclic solid skeleton is reacted with a compound to prepare (A) dicyclopentadiene phenolic resin (DCPD_PN); then 2. ^ with DCPD_PN and ring with KPD component Oxygen-acrylic (ECH) epoxidation to form dicyclopentadiene phenolic epoxy resin (DCPD-PNE, otherwise known as Resin 1); or 3. Mixing DCPD-PN with monofunctional and difunctional amines The compound is reacted with formaldehyde or polyoxymethylene compound to obtain dicyclopentadiene-dihydrobenzo(〇(^13_3:^) resin, otherwise known as resin 2. The resin composition of the novel laminated board invented by the class &quot;f, because of its saturated multi-ring structure, has better chemical and physical properties than the general epoxy resin, and the glass fiber cloth is introduced into the resin varnish formulation. 'The circuit board which has the characteristics of excellent electric strength, high-filament property and low-absorbing beach through hot press hardening is suitable for general circuit boards or high-frequency, high-function laminated boards. DETAILED DESCRIPTION OF THE INVENTION θ The present invention is a low dielectric resin varnish composition for a laminate, the resin composition of which is: (A) dicyclopentadiene-phenolic resin (DCPD_pN); B) one or more epoxy resins (DCPD-PNE) or (a new type of dicyclopentadiene _ dibenzobenzo (DcpD_BX) resin; or (9) + (c) resin and (D) flame retardant, A curing accelerator is mixed, etc. Among them, a (4) dicyclopentadiene-phenolic resin (DCpD pN) having a DCPD component is obtained by reacting (4) dicyclopentadiene with (b) a phenol compound. The formula is as follows: Wherein Z: is -CH3, η: 0_5~1.5 can be converted into various types after the modification or transformation reaction, and the synthesis examples thereof are as follows: Preparation of DCPD-PN: provided with heating pack, temperature controller, electric scale a few four-neck glass reaction tanks for the machine and the condenser. 940 g of a phenolic compound and 2 wt% of a Lewis acid catalyst (AlCl3) were added, and the temperature was raised to 11 ° C to stir the reaction to "not: after" to add m g of DCPD in a dropwise manner. And holding the temperature anti-201114853 4 C-test (TBBA); the second is the dish-based flame retardant, such as phosphate vinegar compound (ΟΡΟ), the second is the inorganic added flame retardant, such as A丨2〇3, ATH, or not added Any flame retardant. Ben Maoming's _ layered fine tree chisel, because of the saturated multi-ring knot, so that ^, compared to the general epoxy resin has better chemical and physical properties, the fiber-breaking cloth V into the tree 曰 varnish formula After impregnation, it can obtain circuit boards with excellent electrical properties, high thermal stability and low hygroscopicity through heat hardening. It is suitable for general circuit boards or thin and sturdy functional riding boards. DETAILED DESCRIPTION OF THE INVENTION The present invention is a low dielectric resin varnish composition for laminated sheets, the resin composition of which is: (A) dicyclopentadiene-phenolic resin (Dicycl〇pentadiene_phen〇lic) Novolac; abbreviated as DCPD_PN); or (9) a novel dicyclopenta-diene-dihydrobenzoxazine (DCPD-BX) thermosetting resin; or a mixture of (A) and (B) 〇 at least one or more epoxy resins; and (D) a flame retardant' and a hardening accelerator, etc. Ο wherein, component (A) dicyclopentadiene-president resin (DCPD-PN), its structure The formula (I) is obtained by reacting (a) dicyclopentadiene and (b) a phenol compound. Where Z · is -ch3, -c2h5, -c(ch3)3, -h 201114853 crystallization neutralization solution 'extracting the reaction solution with water to remove salt and touch, and removing excess reactant under the pressure of 't〇rrS , the DCPD-PN product can be obtained. (8) Dicyclopentadiene is a light oil cracking (4) product, which (b)_Chemicals·,., Neighboring, Bisphenol-A, 4,4,-Ethylene (=^n〇1-F), 二盼基卿 iSPhen〇1_S) or secret resin, etc., the best is propylene or acid test resin. The solvent used for the preparation of DCPD-PN is not particularly limited as long as it can dissolve the respective reactants, and a solvent such as toluene or xylene is preferred. In order to increase the DCPD content, the invention can add DCPD_PN as a hardener, and can also 5 if ^(Polyvalent amines) ' ^ if ^St.(Polyvalent carboxylic aeids), Dicyan〇diamide, Anhydrides, Phenol Novolac 'PN, 曱 曱 曱Acid resin (cres〇i Novolac, referred to as CN), melamine Phenol Novolac (MPN), propylene glycol formaldehyde resin (BPAPhenol Novolac 'BPA-PN), tetraphenol ethane resin (Tetra-PhenoINovolac, abbreviation TPN) and so on. The composition of the present invention (B) one or more epoxy resins, of which dicyclopentadiene epoxy resin (DCPD_PNE) with dcpd is also called resin 1, which will be (DCPD-PN) Epoxy resin prepared by reacting with epoxy propylene. Its structural formula is as shown in the following formula (n): °\&gt;1&gt;?&gt; Wherein Z: is -ch3, -c2h5 ' -c(ch3)3, -h η . 0.5 〜1 · 5 〇DCPD-PNE (resin 1) preparation: with heating pack, temperature controller, electric mixer, In the 5L four-neck glass reaction tank of the condenser, 500g of DCPD-PN and 2927.2g of epichlorohydrin were placed, and the temperature was raised to 55Ό to be pre-dissolved. 281g of sodium aroxide was added dropwise in 4~6 hours, and then heated. The reaction was carried out at 78 ° C under a pressure of 11 OTorrs for 1 hour, and finally the excess reactant was removed at 180 ° C under a pressure of 70 torr to obtain a DCPD-PNE product. 7 201114853 η : 〇·5~1.5. • It can be used in various types after upgrading or changing the reactants. The synthesis examples are detailed below: Preparation of DCPD-PN, 5L four-neck glass reaction tank equipped with heating pack, temperature controller, electric mixer and condenser Medium, 940 g of phenolic compound and 2 wt% of phenolic weight of Lewis acid catalyst (AICI3) 'heated to 1 HTC stirring' to raise temperature to 12 (rc reaction, add 132 g of DCPD to the reaction by dropwise addition And react with the temperature for 4 hours, then add the sodium hydroxide neutralization solution, extract the reaction solution with water to remove the salt and the catalyst. After taking off the excess reactant under the pressure of 180C '70torrs, the DCPD can be obtained. -PN product. The above (b) phenolic compounds for the preparation of DCPD-PN are generally based on phenol, o-nonylphenol, Bisphenol-A, 4,4'-bis-bis-carbazide (Bisphenol-F). 4, 4'-two Bisphenol-S or phenolic resin, etc., preferably propylene glycol or phenolic resin. The solvent used for preparing DCPD-PN is not particularly limited as long as it can dissolve each reaction. The material is preferably a hydrocarbon solvent such as toluene or diphenylbenzene. The present invention is to improve DCPD. The content is added with DCPD-PN as a hardener. The following can also be used as a resin hardener. For example, Polyvalent amines, Polyvalent carboxylic acids, Dicyanodiamide ), Anhydrides, Phenol Novolae (PN), Cresol Novolac (CN), Melamine Phenol Novolac (MPN), propylene glycol furfural Resin (BPAPhenolNovolac, referred to as "&quot;?&gt;1), Siyiyizhuo resin (Dingla-like: 11611〇1]^〇^〇^, abbreviated as 1?&gt;1) and dicyclopentadiene- Dirt resin (0 notes>^1〇卩61^出61^-?116110 this]^0¥0, abbreviated as 201114853 This so-called epoxy resin can also be propylene (纷) type epoxy resin, Evolution of bismuth epoxy resin, phenolic epoxy resin, phosphate ester epoxy resin. DCPD component (〇 dicyclopentadiene _ dihydrobenzo resin (DcpD_Bx), otherwise known as resin 2, is composed of the following '( 1) Dicyclopentane bismuth thinning (DCPD marriage) and upper thief A; (2) monofunctional and dibasic compounds; The compound is obtained by a reaction, and its structural formula is as follows: Z: is -CH3, -C2H5, -C(CH3)3, -H η · 0 〜1. (III) wherein Ο R: may be an alkyl group or an aromatic group. After modification, it can be of various types, and its synthesis example is described in detail below: Preparation of DCPD-BX (resin 2): Storage in heat pack, temperature control, electric mixer and condensation f , ^, 486 wire cap, plus human fine μ benzene guess, and 279 grams of round (Anilme) slowly drip into the above solution, the temperature is controlled under the pressure of _ Ο, remove solvent and unreacted matter, ie (1) is available as a lion component (octa) dicyclopentadiene phenolic resin =, or an aliphatic or aromatic amine compound, preferably aniline or bismuth bismuth resin 2 (3) Cap wire cap compound, - 撼 帽 、, poly 甲 戍 戍 戍 戍 戍 , , , , , , , , , , , , , 聚The solvent = the solvent for preparing the dcpmx resin 2 is not particularly limited as long as it can dissolve the respective reactants, such as toluene and diterpene. The component (d) in the fresh flammable agent comprises a flame retardant and a hardening accelerator. It is difficult to use shoulder and disc-based resins as well as inorganic fillers. Fill in the flame retardant 8 201114853 dcpd-pn) and so on. Ingredient (9) Bicyclic fluorene di-dihydrobenzo (DCPD-BX) thermosetting resin having the formula: (II) ' is obtained by reacting the following three compounds. (a) Dicyclopentadiene-phenolic resin (DCPD-PN); (b) Monofunctional and difunctional mixed primary amine compounds; formaldehyde or polyfurfural compounds. ❹ Z : is • ch3, -c2h5, -c(ch3)3.-h n . 0 〜1 〇 R· can be a leuco group or an aryl group. After modification, it can be of various types. The synthesis examples are detailed below: Preparation of DCPD-BX, placed in a 5L four-neck glass reaction tank equipped with a heating pack, a temperature controller, an electric mixer, and a condenser tube, and placed in 480克DCPD-PN, 486g polydecanoic acid·' add 500g of benzene to dissolve and dissolve, and 279g of aniline (Aniline) slowly drip into the above solution, the temperature is controlled between 60~ll〇°C, The reaction is carried out for 4 to 6 hours, and then the solvent and the unreacted material are removed by a pressure of 180 ° C and 70 torr to obtain a solid dicyclopenta-dihydrobenzothermic thermosetting resin. The above preparation of DCPD-BX (b) - a monofunctional and difunctional mixed monoamine compound, generally using mercaptoamine, ethylamine, aniline, toluidine, o-methoxy Anisidine, also known as aliphatic or aromatic amines 9 201114853 There are: tetrabromopropane (ΤΒΒΑ), ΝΡΕΒ-485Α80 (trade name, produced by Nanya Plastics Co., Ltd., bromine content '18~21%), ΝΡΕΒ_454Α80 (trade name, produced by South Asia Plastics Co., Ltd., bromine content 18~21%). ^ The flame retardant is DOPO (9,10-Dihydro-9-Oxa-10-Phosphaphenanthrene -10-Oxide), DOPO-HQ, DOPO-Phenol Novolac Epoxy Resin (DOPO-PNE), DOPO-Hydroquinone-Phenol Novolac Epoxy Resin (DOPO-HQ-PNE). The inorganic fillers are mainly composed of aluminum hydroxide, cerium oxide, barium sulfate, aluminum oxide, boron nitride and the like. Further used as the hardening accelerator of the present invention are; a tertiary phosphine, a tertiary amine, a quaternary phosphonium salt, a quaternary ammonium salt, and an Imidazole compound. The tertiary phosphine includes triphenylphosphine, etc.; the tertiary amine includes trimethylbenzene 'amine, triethylamine, tributylamine, dimethylamine ethanol, etc.; the quaternary phosphonium salt includes tetrabutyl bromide. Chlorinated, tetraphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium chloride, butyltriphenylphosphonium bromide, etc., containing halogenated, quaternary scale salts; Quaternary ammonium salt, such as ammonium chloride, tetraethylammonium chloride, tetrabutylammonium desert, triethylenesulfonyl methyl/smelly sulphate, diethyl ether, ammonium sulphate, etc. The compound includes 2-methylimidazole, 2-ethylimidazole, 2-dodecylimidazole, 2-phenylimidazole, 4-mercaptoimidazole, 4-ethylimidazole, 4-dodecylimidazole, 2 _Ethyl_4_methylimidazole, 2-ethylidene via methyl sulphur, etc., most suitable for 2-methyl odor or 2-ethyl _4_ fluorene. The above hardening accelerator may be used alone or in combination of two or more kinds. The amount used is 0.H pHR relative to the total amount of the resin, and the optimum amount is 0.04 to 0.15 PHR. The present invention is composed of a resin having a cyclic structure. The novel low dielectric resin composition has a Ht^PN content of 1~5〇Wt% of the total amount of the resin; (8) DCPD-PNE (resin) content is 13~6_% of the tree; (C) DCPD sister (resin 2) the content is 3〇~5〇wt% of the total red of the resin; Li~ is 22~32wt% of the total amount of the resin; the hardening accelerator is added with respect to the total amount of the resin; and the solvent varnish is used to reduce the mixing Composition, among which is a solvent, a solvent, a solvent, a hydrazine solvent, a solvent, and a solvent (suitable for di-n-methyl, methyl ketone, _, methyl ethyl ketone, S methoxy -2- propyl Alcohol, , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , Cohering into a prepreg, one of the prepreg bodies is laminated or laminated with a plurality of prepregs, and the laminate is heated and pressurized. Copper slab The hardening temperature of the lacquer composition ranges from 3 〇 to .c, preferably from 15 〇 to (10). [Embodiment] Hereinafter, the invention will be described in detail by way of example. Each code and composition of the towel is as 201114853 compound, preferably aniline or diaminodiphenyl decane. Preparation of DCPD-ΒΧ (e) formic acid or polyoxymethylene compound, generally using formazan, polyacetal or hydrazine The aldehyde vapor is preferred as the polyoxymethylene. The solvent used for the preparation of the DCPD-BX is not particularly limited as long as it can dissolve the respective reactants, and a hydrocarbon solvent such as toluene or xylene is preferred. Inventive resin varnish composition (c) at least one or more epoxy resins, the DCPD-PN resin is reacted with epichlorohydrin, and the epoxy resin obtained is abbreviated as DCPD-PNE resin. As shown in the formula (ΙΠ)·· Ζ : Preparation of (III) -ch3, -c2h5, -c(ch3)3, -h η · 0 _ 5 ~1.5 〇DCPD-PNE, equipped with heating pack, temperature controller, electric mixer, 500 g of DCPD-PN and 2927.2 g of epichlorohydrin were placed in a 5 L four-neck glass reaction vessel of a cold condenser. The temperature was raised to 55 ° C to pre-dissolve, and 281 g of hydroxide was added dropwise in 4 to 6 hours. The sodium was further heated to 78 ° C, reacted for 1 hour at a pressure of 11 OTorrs, and finally the excess reactant was removed at a pressure of 180 ° C '70 torr to obtain a DCPD-PNE product. The so-called epoxy resin may be a propylene glycol (BPA) type epoxy resin, a brominated BPA type epoxy resin, a novolac type epoxy resin, or a phosphate ester type epoxy resin. 10 201114853 Ο Bottom: Resin 1 · Component of the present invention (B) DCPD_PNE resin having an epoxy equivalent of 270 to 230 g/eq. Resin 2: The component of the present invention (C) DCPD-BX resin, the nitrogen content of which is 6.2wi% Resin 3 · The desert resin produced by Nanya Plastics Co., Ltd., the trade name is Zhong ^^ He Gossip. Resin 4 · The structure resin (D〇p〇_638) produced by Nanya Plastics Co., Ltd., trade name: 21〇8〇. Resin 5. The structural resin (D〇p〇_HQ_638) produced by Nanya Plastics Co., Ltd., trade name 22〇A7〇. Hardener 1 ·Previous - Hardener 2 Hardener 3 Fuels 1 Flame Retardant 2 Flame Resistant 3 and Fuel 4 G phenolic resin produced by Nanya Plastics Co., Ltd., trade name 71〇HA65 Phenolic resin produced by Nanya Plastics Co., Ltd. The trade name is 71〇SA65. The DCPD-PN of the present invention. Contains bromine-resistant flame retardant, tetrabromopropanediol (TBBA). The phosphorus-containing flame retardant produced by Sakamoto Daiba Chemical Co., Ltd. is sold under the trade name ρχ_2〇〇. Aluminium hydroxide (ΑΤΗ) filler. A oxidized (Si〇2) filler. Hardening accelerator 2MI: 2-mercapto miso, I4.2wt% dissolved in DMF. Fiberglass cloth 7628: Glass fiber cloth produced by Nanya Plastics Co., Ltd. Example 1 DCPD_PNE was used as a refining fat-reducing hardener 71GHA65, which was resistant to TBBA, and its formula group cake was on the table--, which was used as a 65% varnish tree test substance. Solvent, adjusted to 65% of the resin varnish composition, the glass fiber cloth was modified to the above varnish resin liquid, and then the temperature of the impregnation machine was 17 Torr. 〇, take out the drying for a few minutes, by adjusting the control Lin _, so that the dry test 溃 _ _ 麟 side ~ face between the coffee, and finally 8 layers of film layered on two pieces of 35 · thick copper pig room In the control as follows: 85 ° C - 85 ° C 20min 30min 2 ° ° C 200 ° C 120min slowly cooled after hot pressing 'can be made 1.6mm thick auxiliary substrate. The composition of this composition is detailed in Table 1. Example 2 The procedure was repeated except that the hardener was changed to 71 〇 SA65, and the obtained composition was obtained. Example 3 - The killing of Example 1 was repeated, but the hardener was changed to DCPD_PN, and the function of the obtained composition was detailed. Example 4 μ = main tree month 1 'with hardener 710HA65, flame retardant changed to PX-200 C'U, formula composition is shown in the table - 'Repeat Example i to manufacture copper box substrate step, the resulting 130 ° C 10 201114853 ' The component (D) in the resin varnish composition of the present invention is a flame retardant and a hardening accelerator, and the flame retardant is mainly a bromine-based or phosphorus-based resin, and an inorganic filler-based flame retardant can also be used. Brominated flame retardants include · tetrabromopropanediol (TBBA), NPEB-485A80 (trade name, produced by Nanya Plastics Co., Ltd., bromine content 18~21%), NPEB-454A80 (trade name, produced by South Asia Plastics Co., Ltd., bromine Content 18~21%). Phosphorus-based flame retardants are D〇p〇 (9,10-Dihydro-9-Oxa-1 〇-Ph〇sphaphenanthrene -10-Oxide), DOPO-HQ, DOPO-Phenol Novolac Epoxy Resin (DOPO-PNE) ' ❸ DOPO-Hydroquinone-Phenol Novolac Epoxy Resin (DOPO-HQ-PNE). The inorganic fillers are mainly composed of cerium oxide, cerium oxide, cerium sulfate, aluminum oxide, boron nitride and the like. Further used as the hardening accelerator of the present invention are; a tertiary phosphine, a tertiary amine, a quaternary phosphonium salt, a quaternary ammonium salt, and an imidazole compound. The tertiary phosphine includes triphenylphosphine, etc.; the tertiary amine includes dimethyl sulfamine, triethylamine, tributylamine, dinonylamine ethanol, etc.; the quaternary salt includes tetrabutyl bromide, a tetraphenyl bromide scale, an ethyl triphenyl bromide scale, a propyl triphenyl weathering scale, a butyl diphenyl bromide scale, etc., containing a halide quaternary salt; , tetraethylammonium evolution, tetrabutyl evolution, triethylbenzyl evolution, diethylaminoethylammonium bromide and other halide-containing quaternary salt; jmidaz〇ie compound including 2-曱Imidazole, 2-ethylimidazole, 2-dodecylimidazole, 2-phenylimidazole, 4-methylimidazole, 4-ethylimidazole, 4-dodecylimidazole, 2-ethyl-4- Mercaptoimidazole, 2-ethyl-4-methylol imidazole, etc., most preferably 2-methylimidazole or 2-ethyl-4-methylimidazole. The above hardening accelerator may be used singly or in combination of two or more kinds, and is used in an amount of 0.01 to 1 PHR based on the total amount of the resin, and the optimum amount is 〇.〇4 to 0.15 PHR. 201114853 The function of the object is detailed in Table 1. Example 5 The actual thin 4 was implemented, but the hard can be changed to 7 legs 65, and the resulting city was applied to the table. Example 4 was carried out, but the hard butterfly was changed to DCPD_PN, and the composition of the obtained composition is shown in Table 1. Use DCPD-BX as the main connection [Moon 匕, agent 710 dirty, and touch H 吏 with hydrogen 曰 加 ^ PD PD_PNE resin to adjust the equivalent, with hardening, Example 1 to make the substrate step, repeat the example 8 Ο Ο Implement 'but the paste is changed to 7_5' to get her composition _ in Table 1. The implementation of Ϊ 实 实 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 The function of the composition of the fibrosis 710 is shown in Table 2. The 'Table-' repeats the procedure of making a copper wire plate in the first example, and the obtained Example 11 was carried out 1G' but the hardener was changed to 71GSA65, and the obtained city was as shown in Table 1. The rif is turned off 12' but the hardener is changed to dcpd_pn, and the functions of the obtained composition are detailed in Table 1. The composition of the composition 71 〇 _ composition is detailed in Table 2. Table 1 shows the steps of fabricating the substrate, and the obtained example 14 is carried out, but the obtained material of the hardener is changed to 71GSA65. Example 13 was repeated, but the hardener was changed to (4), and the functions of the obtained composition were detailed in Table--. Comparative Example 1 ΝΡΕΒ-485Α80)^^^, 屺 砰 砰 表 表 , , , , , , , , , , , , 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 The (D) DCPD-PN content is set to 1% to 5 〇% of the total amount of the resin; (8) dcpd_BX, the content is 3G~5〇wt% of the total amount; and (C) the DCPD_PNE content is the total resin 13~60wt%; (D) the flame retardant content is 22~32wt% of the total amount of the resin; the hardening accelerator is added with respect to the total amount of the resin; 〇1~1PHR; and the viscosity of the varnish is adjusted by using the solvent. The solvent may be an organic aromatic solvent, a protic solvent, a ketone solvent, an ether solvent, or an ester solvent (suitable solvents are toluene, N,N-dimethylformamide, acetone, methyl ethyl) Ketone, 1-methoxy-2-propanol, ethyl acetate, etc.). In the manufacture of the printed circuit laminate, the glass fiber cloth is impregnated into the composition of the composition, and then heated to dry the impregnated fiberglass cloth into a prepreg, on one side of the prepreg or A copper foil is placed on both sides to laminate one or more prepreg layers, and the laminate is heated and pressed to obtain a copper foil substrate. The resin varnish composition has a hardening temperature in the range of 3 Torr to 3 ° C, preferably 150 to 210. EXAMPLES Hereinafter, the present invention will be described in detail by way of preferred examples. The respective symbols and components in the examples and comparative examples are as follows: Resin 1: The DCPD-PNE resin of the present invention has an epoxy equivalent of 27 〇. 23〇g/eq. Resin 2: The DCPD-BX resin of the present invention has a nitrogen content of 6.2% by weight. Resin 3: Brominated resin produced by Nanya Plastics Co., Ltd., trade name. Resin 4: Filling resin (D〇p〇_638) produced by Nanya Plastics Co., Ltd., trade name 12 201114853 ίί:; The functions of the obtained composition are detailed in Table 2. Comparison = Comparative Example 1, but the hardener was changed to 讥 &amp; The function of the resulting conjugate was detailed in Table--. The measurement was compared with the example 1 ', but the hardener was changed to lion·ΡΝ, and the function of the obtained composition was. 1. Varnish gel time (sec): Boots plus group, amount of time. 3. And the heating rate = 2 〇 ° C / mM _ Miao thermal analyzer (DSC) test. Ο :====:: Do 峨 1 细 second fine, 4. Water absorption: The sample is heated at I20 ° C and 2 atni pressure cooker for 3 〇 minutes. 5. Dielectric loss (1 GHz): (2) Take the 3 points of the board and measure the thickness of the board and then clamp it into the dielectric analysis instrument. 6. The dielectric constant (1 GHz): The word has been side = the board is cut into W square test pieces. ., in the supply box for the addition and then take out, the thickness of the thick gauge to make three corrections. Then, the test piece is clipped to the data and averaged. 〇 12 201114853 210A70 Resin 5: Phosphorus resin produced by Nanya Plastics Co., Ltd. φ〇ρ〇_Η(^_638), trade name 220Α70 ° Hardener 1: Phenolic resin produced by Nanya Plastics Co., Ltd., trade name 710ΗΑ65. Hardener 2: Phenolic resin produced by Nanya Plastics Co., Ltd., trade name 71〇SA65. Hardener 3: DCPD-PN of the present invention. Flame Retardant 1: Brominated flame retardant 'Tetrabromopropanediol (TBBA).耐 Flame Retardant 2: A scaly flame retardant produced by Japan's Daeba Chemical Co., Ltd., trade name ρχ_2〇〇. Flame Retardant 3: Aluminium hydroxide (ΑΤΗ) filler. Flame retardant 4 ··cerium dioxide (si〇2) filler. Hardening accelerator 2MI: 2-mercaptopurine, i4.2wt% dissolved in DMF. Fiberglass cloth 7628. Glass fiber cloth produced by South Asia Plastics Co., Ltd. Example 1 DC DCPD-PNE was used as the main tree, with hardener 71〇HA65, and TBBA was used for the flame retardant. The formula is detailed in Table 1. The varnish resin group with 65% solid content adjusted by acetone This formula is finely assisted, which is adjusted to be the hot resin clearing 』, and the product is immersed in the varnish resin liquid in the mud 8 glass fiber cloth, and then dried at the temperature of the impregnation machine at 17G ° C (4) Minutes, borrowing _ whole (four) Lin _, so that the pre-impregnated k-body melt viscosity after drying is between 4GG0~i_GpGise, and finally 8 layers of film layer are enriched between two pieces of 35·thick copper, at 25kg/em2M force The temperature control is as follows: 85〇C - 85〇C 20min 30min 130°C 200°C — 200°C 120min Slowly cool 201114853 1 Example 9 fO VD 15.5 15.5 | in o Ό 167.2 94V-0 0.08 3.92 0.009 Example 8 ro &lt;s ITi fO 〇355 173.5 ! [94V-0 j 0.07 3.89 0.009 Example 7 fO is tn o 365 163.5 j 94V-0 0.09 0.008 ! 1 Example 6 m (S 0.28 368 | 165.5 I | 94V-1 | 0.08 1 4.18 | Γ 0.012 | Example 5 In 00 fS 0.24 370 — 94V-0 0.07 , l 4.21 [0.016 | Example 4 υη CO 0.28 1 375 1 1 157 I 94V-0 1 0.08 1 0.014 Example 3 &lt;s tn | 25.7 | 1 22.3 j 0.31 372 164 | 94V-1 0.07 4.18 0.012 Example 2 g tn &lt;s 0.25 364 fS 94V-0 0.07 j &lt;s 0.012 | Example 1 s (S 2 380 1—159 —| 1 94V-0 0.08 I 4.22 1 | 0.014 j Resin 1 DCPD-PNE Resin 2 DCPD-BX Resin 3 NPEB- 485A80 resin 4 210A70 resin 5 220A70 hardener 1 710HA70 hardener 2 710SA70 hardener 3 DCPD-PN flame retardant 1 TBBA flame retardant 2 PX-200 flame retardant 3 ATH flame retardant 4 Si〇2 accelerator 2MI (PHR) varnish gel Time sec glass transition temperature °c flammability water absorption % dielectric constant (1 GHz) Electric loss factor (1 GHz) 201114853 After hot pressing, a 1.6 mm thick steel box substrate was obtained. Example 2 The same procedure as in Example 1, except that the hardener was changed to 710 SA65. Example 3 The same method as in Example 1, except that the hardening was changed. The agent is DCPD-PN. Example 4 Ο DCPD-PNE is used as the main resin, with the hardener 71〇HA65, and the flame retardant is PX-2(8)Phosphorus (four) face, and its formula is scaled on the table. 65% of the varnish resin composition, the formulation is a propionate solvent, and the solid content is adjusted to the resin varnish composition of (4). The 7628 glass fiber cloth is immersed in the varnish resin liquid, and then the temperature of the impregnation machine is not; After a few minutes of drying, the pre-impregnation viscosity after drying is adjusted to be between 4_~deleted (8)pGise, and finally the layer of film is stacked on two pieces of 35-um thick steel. 25kg/em2 pressure, temperature is as follows: Work G B5°C 2〇min 85°C — 200°c 3〇min 120min After hot pressing, thick steel foil substrate can be obtained. Example 5 200°C — Slow The method of slow cooling at 130 ° C was the same as in Example 4 except that the hardener was changed to 71 〇 SA65. Example 6 The same procedure as in Example 4 except that the hardener was changed to DcpD_pN. Example 7 14 201114853 Comparative Example 3 90 V·© ro o 324 1 162 1 | 94V-0 1 1 0.08 1 0.025 1 Comparative Example 2 00 cs (N o 318 1 167 η 94V-0) 0.08 i — 0.028^ ; Comparative Example 1 00 o 320 153 94V-0 0.07 , 0.03 i Example 15 rn | 15.5 1 15.5 | 0.28 I 350 Γ 168 1 | 94V-1 1 0.08 1 "WI f 0.012 1 Example 14 &lt;s Xti n 0.24 345 175 | 94V- 0 1 0.07 1 1 4.20 I 0.014 | Example 13 in 2 VO 0.28 335 &lt;s VO — 94V-0 ! 0.08 4.35 0.015 Example 12 沄f〇| 15.5 I 15.5 | 0.26 345 | 94V-1 | 1 0.07 1 4-16 | Γ 0.012 Example 11 fS in 0.21 355 1 1*731 | 94V-0 1 1 0.07 1 4.18 1 | 0.013 | |Example ίο IT) ΓΟ ro 0.25 360 00 ΙΛ | 94V-0 1 0.08 丨4.32 0.014 Resin 1 DCPD-PNE I Resin 2 DCPD-BX Resin 3NPEB-485A80 Resin 4 210A70 Resin 5 220A70 Hardener 1 710HA70 Hardener 2 710SA70 Hardener 3 DCPD_PN Flame Retardant 1 TBBA Flame Retardant 2 PX-200 Flame Retardant 3 ATH Flame Resistant Agent 4 Si〇2 accelerator 2MI (PHR) varnish gelation time sec glass transfer temperature °C flame resistance Water absorption% dielectric constant (1GHz) dielectric loss factor (1GHz) 201114853 Use DC Lion X as the main resin, add DcpD_pNE resin to replace the equivalent, with hardener 7H)HA65 'Miscellaneous Wei she and Diox, the formula is detailed in the table -, adjust it to 65% The varnish tree remains, the formula is called the agent, the adjustment is _ part of the 65% reading paint group, the fine glass fiber cloth is immersed on the silk, and the _ is at the temperature of the aging, take out the drying for a few minutes. By adjusting the balance _ between, so that the post-money smelting melt viscosity is between 4000~10_poise, and finally stacking 8 film layers between two pieces of 35·thick copper foil, at 25kg/cm2 pressure, temperature The control was as follows: 85 ° C 20 min After hot pressing Example 8 130 ° C 85 C 4 200 ° C 200 ° C 30 min 120 min Slowly cooled to obtain a 1.6 mm thick copper foil substrate. The procedure was the same as in Example 7 except that the hardener was changed to 710SA65. Example 9 The procedure was the same as in Example 7, except that the hardener was changed to DCPD-PN. Example 10 A DC-free substrate was prepared by using DCPD-BX as a main resin and a phosphorus-based resin 210A70 in combination with a curing agent 710HA65. The composition of the formula is detailed in Table 2, which is adjusted to a 65% varnish resin composition with a solid content of acetone. The formulation is adjusted to a 65% resin varnish composition with a propylene solvent, and 7628 glass fiber is used. The cloth was dipped in the above varnish resin liquid 'and then at the impregnation machine temperature 170. (:, take out and dry for a few minutes, adjust the drying time to make the pre-impregnated body melt viscosity after drying to be between 4000~10000poise, 15 201114853 Inventive efficacy example = 6 formula, using DCPMNE household The substrate has a dielectric constant of 4 and 4.2 and a dielectric loss factor of 0.012 to 6; the substrate of the embodiment ι〇~ΐ5 with DCPD-BX has a dielectric constant of 41(4)2 and a dielectric loss factor. Characteristics of 〇.016; In the formulations of Examples 7 to 9, the simultaneous use of DCPD_PNE and DCPD-BX f? 'has a low dielectric constant of 3.89 to 3.92 and a low dielectric loss factor _~〇·_ number ^4 ^ is superior to other substrates without DCPD and structural resin, and has a dielectric constant of 4. 4 to 4.7 and a dielectric loss factor of 0.025 to 0.03. 上 It is known that 'containing dcpd is __ in glass fiber The distribution of DCPD PN has a low moisture absorption, low dielectric constant and low dielectric loss factor, and the resin is used as a substrate for the hardener to reduce the dielectric constant and dielectric. Loss due to the varnish resin's due to the increased resin content of the structure, and by the tree The resistance of the 1 mesh ligament &quot; filler material' its dielectric constant can be further reduced, step can also reach 94V-〇, knowing that it has good thermal stability. 〇15 201114853 Finally, 8 layers of film layer Stacked between two 35-um thick copper boxes, at 25kg/cm2, the temperature is controlled as follows: 85〇C 2〇min 85 C — 200°C —&gt; 200. 3〇min 120min Slowly After cooling at 130 ° C, a 1.6 mm thick copper foil substrate was obtained after hot pressing. Example 11 was the same as Example 10 except that the hardener was changed to 710 SA65. Example 12 The method was the same as in Example 12 except that the hardener was changed to DCPD-PN. Example 13 DCPD-BX was used as a main resin, and a phosphorus resin 22〇A7〇 was added, and a hardener 710HA65 was used to prepare a toothless substrate. The formulation composition thereof is shown in Table 2, and the varnish resin having a solid content of 65% adjusted with acetone was used. The composition is adjusted to a resin varnish composition having a solid content of 65% in an acetone solvent, and 7628 glass fiber cloth is immersed in the varnish resin liquid, and then dried at a temperature of 17 (TC), and dried for several minutes. Adjusting the drying time by adjustment, so that the pre-impregnated body melt viscosity after drying is between 4000~i〇〇〇〇p〇ise, and finally stacking 8 film layers between two 35-um thick copper foils At 25kg/cm2 pressure, the temperature is controlled as follows: 85〇C 85〇C 200°C 200°C ^ 13〇°q 20min 30min 120min After slowly cooling, a 1.6mm thick copper foil substrate can be obtained. Example 14 16 201114853 The procedure was the same as in Example 13, except that the hardener was changed to 71 〇 SA 65. Example 15 The same procedure as in Example 13 'The hardener was changed to dcpD-PN. Comparative Example 1 , use / stinky epoxy resin (South Asia &gt; stinky epoxy grease, the product name is fierce and tender) f ball month, with hardener 710 delete 5, its formula is detailed in Table 1, Adjust the shape of acetone (10) 65% of the fine silk test 'to listen to the solvent, adjust the solid part ^ 65% of the resin varnish composition, the glass fiber cloth is dipped in the above varnish resin liquid, and then at the impregnation machine temperature 17 ( Rc, take out and dry for a few minutes, by adjusting the control of the dry coffee, so that the view of the clothes will be reduced to gamma ~ face coffee &amp; between the last 8 layers of film layered in two pieces of 35 tons of copper In the box, in the pressure & temperature, the temperature control is as follows: 〇B5°C 2〇min 85〇C 200°c —&gt; 200°C —&gt; 130°C 30min 12〇min Slowly cooled after hot pressing A 1.6 mm thick steel foil substrate was obtained. Comparative Example 2 The same procedure as in Comparative Example 1 except that the hardener was changed to 7i〇SA65. Comparative Example 3 The method was the same as Comparative Example 1, except that the hardener was changed to DCPD-PN. 201114853 1·Cream gelation time (sec): Take 0.3ml resin varnish on a hot plate at 170°C and measure the gelation time. Shift temperature (°〇: Tested using a heating rate=20°C/min differential scanning thermal analyzer (DSC). 3. Flame resistance: The test piece is cut into 〇5in x4.7in rectangle, with a flame height of 2cm. After the color flame is burned for 10 seconds, it is removed. After a total of two burnings, the self-extinguishing time after the flame is removed is recorded. 4. Water absorption rate (%): The sample was heated in 120 ° C and 2 atm pressure steel for 30 minutes. 5. Dielectric loss (1 GHz): The test piece is cut into 5x5 squares, and the plate is measured at 3 points and then clamped into the dielectric analysis instrument for measurement. After the completion, the average value is taken. 6. Dielectric constant (1 GHz): The etched substrate was cut into 5 cm2 square test pieces at 1〇5. 〇In the oven, the back is taken out to measure the plate thickness of the plate thickness tester ^: test piece. Then, the test piece is cooled into a dielectric meter, and the data of three points is measured and averaged. 201114853 ο 实施 Example 9| rn 15.5 15.5 &lt;r&gt; o | 361 167.2 94V-0 0.08 3.92 0.009 Example 8 ro &lt;s in i/J o 355 173.5 1 94V-0 0.07 3.89 0.009 Example 7 rn fS In iS o 365 163.5 94V-0 0.09 0.008 Example 6 rn fO fS 0.28 368 165.5 94V-1 0.08 4.18 0.012 Example 5 CO fS 0.24 o fO i 94V-0 0.07 4.21 0.016 Example 4 Cn μ 00 | 0.28 375 ΙΛ 94V-0 0.08 0.014 Example 3 I 25.7 1 1 22.3 1 0.31 I 372 164 , 94V-1 | 0.07 4.18 0.012 Example 2 § IT) 0.25 | 364 fS , 94V-0 1 0.07 τί 0.012 Example 1 § (Λ tn accelerator 2MI(PHR) | 0.3 varnish gelation time sec S 380 159 Γ 94V-0 | 0.08 1 4,22 0.014 Resin 1 DCPD-PNE Resin 2 DCPD-BX Resin 3 NPEB-485A80 Resin 4 210A70 Resin 5 220A70 Hardener 1 710ΗΑ70 Hardener 2 710SA70 Hardener 3 DCPD-PN Flame Retardant 1 TBBA Flame Retardant 2 PX-200 Flame Retardant 3ATH and Fuel 4 Si〇2 Glass Transfer Temperature °c Flame Resistance Water Absorption φ% Dielectric Constant ( 1 GHz) i dielectric loss due to (1 GHz) 201114853 Comparative Example 3 I 00 SO TH 〇 324 ns 〇 vH 94V-0 I j 0.08 0.025 | Comparative Example 2 00 o 318 \o | 94V-0 0.08 1____ Tf 0.028 Comparative Example 1 00 (N fS o 320 1 153 | 94V- 0 0.07 l_ .. .... — 0.03 Example 15i f〇Ό 15.5 15.5 0.28 350 00 \o 94V-1 0.08 4.15 0.012 Example 14 in 2 ΓΟ 0.24 345 in 94V-0 0.07 4.20 0.014 Example 13 &lt; N tn f〇0.28 335 94V-0 0.08 4.35 0.015 Example 12, _1 Pan fO | 15.5 1 15.5 | | 0.26 | 345 I s 94V-1 | 0.07 1_ 4.16 | 0.012 Example 11 rs ΙΛ ΓΟ PO 0.21 355 173 94V -0 0.07 4.18 0.013 | Example Μ in | 0.25 I 00 \n | 94V-0 | 0.08 1 4.32 | I 0.014 1 Resin 1 DCPD-PNE Tree Moon 2 DCPD-BX Resin 3NPEB-485A80 Resin 4 210A70 Resin 5 220A70 Hardener 1 710HA70 Hardener 2 710SA70 Hardener 3 DCPD-PN Flame Retardant 1 TBBA Flame Retardant 2 PX-200 Flame Retardant 3ATH Flame Retardant 4 Si02 Accelerator 2MI (PHR) Varnish Gel Time sec Glass Transfer Temperature °c Flame Resistant Water Absorption Rate ° / 〇 dielectric constant (1 GHz) dielectric loss Loss factor (1 GHz) 201114853 'Examples> ~6, the substrate prepared using dcpd-pne, having dielectric characteristics: coefficient 4.18~4·21 and dielectric loss factor ~0.016; Example 1 〇~= In the formulation, the substrate prepared by using DCPD-BX has a dielectric constant of ~4.s2 and a dielectric loss factor of _2~G.G16; in the formulation of Examples 7~9, _ The substrate prepared by DCPD-PNE and DCPD-BX has the characteristics of low dielectric constant 3 89~3 and low dielectric loss factor~; it is significantly better than other formulations without DCPD and structural resin. The substrate has a dielectric constant ο~ο and a dielectric loss factor of 0.025 to 0.03. 〇 It is known from the examples (Tables - and Table 2) that the varnish resin containing the DCPD structure is impregnated on the fiberglass cloth, and the age-dependent electric constant loss factor. In the resin, the substrate with DCPD_PN as the curing agent can also effectively reduce the dielectric dip and dielectric enthalpy; if the county adds DCPD_BX age, the DCPD increases by 3 1 and borrows the 峨 漆 漆 物 物It is difficult to paste the filler, the age electric constant can be further reduced, the step can be reduced, and the standard can have good thermal stability. Ο 21 201114853 f) Instruction manual #年丨月1日正 (The format, order and bold characters of this manual, please - do not change any more, please do not fill in the ※ part) ※Application number: and ※Application deadline: 1 ?&lt;:Classification: I. Name of the invention: (Chinese/English) Low dielectric resin varnish composition for novel laminated board and its preparation method II. Abstract: The present invention is a kind of brush circuit laminated board dielectric The resin varnish composition of f number and the preparation method thereof, the resin composition thereof comprises: (8) Dicyclopentadiene-Phenolic Novolacjh^DCPD-PN; 4(B) novel one-ring one DiCycl〇penta_diene-Dihydmbenzoxazine (DCPMX) thermosetting resin; or (8) a mixture with (9) and (C) at least - or a variety of races; and (9) difficult to fine, and hardening promotion Composition of the agent. The composition of the varnish composition (A) DcpD_pN and the component (B) DCpD_Bx contain a saturated &gt; ring-shaped bicyclopentadiene 纟 structure, which can reduce the dipole moment of the varnish (dlP〇le) ), dielectric constant (Dk), dielectric loss (Df) and hygroscopicity; the resin varnish is added with the indifference and the meal, it is difficult to make the group rich and hot. According to the steel foil substrate of the month of the month, not only can the low dielectric constant (Dk&lt;4.0@lGHz) and low; the loss factor (Df&lt;〇〇〇9@1GHz) can be achieved. High heat stability and low moisture absorption characteristics are widely used in neon's electronic materials. 201114853 Mandala · Lee manual (this manual format, order and bold characters, please do not change anymore, ※ mark department one ^ ※ application case number · · ※ application date: ※ [卩仁分类: First, the name of the invention · ( Chinese, / English) Low dielectric resin varnish composition for novel laminates II. Abstract: The present invention relates to a low dielectric constant resin varnish (Vamish) composition for a printed circuit laminate, the resin composition of which includes : (A) Dicyclopentadiene_phen〇lic Novolac 'DCPD-PN for short; (B) - or a variety of dicyclopentadiene Phenolic Novolac Epoxy (DCPD-PNE) Resin 1; or (C) a new type of dicyclopentadiene-dihydrobenzo resin (Dicyd〇pentadiene_Dihydr〇benz〇xazine; abbreviated as DCPD-BX), otherwise known as resin 2, or mixed resin of (8) and (c) And (9) a flame retardant, a hardener and a promoter solvent. The components of the resin varnish composition (A) DCPD_PN, component (B) DcpD_pNE and component (C) DCPD_BX both contain a saturated heterocyclic red ring Structure, reduce the dipole of the lion Moment (mail ole), dielectric constant (Dk), dielectric loss (four) and hygroscopicity; added flame retardant, or the filling of the system, so that the composition has a high thermal bond The mineral substrate can not only be low-level electricity, number (Dk &lt; 4.0@iGHz) and low dielectric loss coefficient (Df &lt; 〇.〇〇9 @! GHz) demand, still ask hot female 疋 and low moisture absorption Characteristics, widely used in high-performance electronic materials. 201114853 III. Abstract: This invention can be applied to laminated boards with low dielectric constant (Low Dk and Low Df) properties. The composition includes (A) Dicyclo- pentadiene-Phenolic Novolac (DCPD-PN) resin; or (B) a novel Dicyclopentadiene-Dihydrobenzoxazine (DCPD-BX) resin; or the mixture of (A) and (B), and (C) at least one kind of epoxy resin(s) ; and (D) Flame retardant agent(s). Because of thermosetting resin compound DCPD-BX and DCPD-PN contain the backbone of dicyclopentadiene that is saturated multi-cyclic structure. That will decrease the dipole of the resin to lower the dielectric constant of the composition of vanish. The vanish in this invention possesses And that will be having an excellent high thermal stability by using the brominated or phosphorus flame retardant agents. Laminated boards can be made from this composition and reached the level of Low Dk (&lt;4.0@lGHz And low Df (&lt;0.009@lGHz). That can be applied to high performance electronic materials widely. 201114853 III, English invention summary: This invention can be applied to laminated boards with low dielectric constant (Low Dk and Low Df) properties The composition includes (A) Dicyclo-pentadiene-Phenolic Novolac (DCPD-PN) resin; or (B) at least one kind of epoxy resin(s)(DCPD-PNE); or (C) a novel Dicyclopentadiene- Dihydrobenz Oxazine (DCPD-BX) resin: or the mixture of (B) and (C), with (D) Flame retardant agent(s). Because of thermosetting resin compound DCPD-BX and DCPD-PN contain the backbone of dicyclopentadiene that is saturated multi-cyclic structure. That will decrease the dipole of the resin to lower the dielectric constant of the composition of vanish. The vanish in this invention possesses And that will be having an excellent high thermal stability by using the brominated or phosphorus flame retardant agents. Laminated boards can be made from this composition and reached the level of Low Dk (&lt;4.0@lGHz And Low Df (&lt;0.009@lGHz). That can be applied to high performance electronic materials widely. 201114853 VII. Patent application scope: • 1. A low dielectric resin varnish (Varnish) composition for laminates, its resin Compositions include: (A) Dicyclopentadiene-Phenolic Novolac (DCPD-PN); or (B) a new type of Dicyclopentadiene-Dihydrobenzoxazine (DCPD-) BX) thermosetting resin; or a mixture of (A) and (B) and (at least one or more epoxy resins; and (D) a flame retardant, a hardening accelerator and a solvent; wherein 'component (A) is a bicyclononadiene- Phenolic resin (DCPD-PN) resin, cookware structure: The novel dicyclopentadiene-dihydrobenzo (DCPD-BX) thermosetting resin of the component (9) has the following structure: -CH3 '-C2H5 ' -C(CH3)3 -Η is an alkyl group or an aromatic group. η : 〇~卜 2. Low dielectric resin for laminates as described in claim 1 of the patent scope 22 201114853 VII. Patent scope: 〇~fo new tree = lacquer composition' resin composition consists of: resin (9) one by weight of the total weight of the resin (DCP just); or the total amount of the resin of 13 to 60% by weight (0 - = _CPD - Bay resin 1; or the total amount of resin known ~ 5 〇., day 厶Also this new species of decadiene-dihydrobenzo (DCPI > BX) resin 2; or (B) and (C) this. '』 〃 (D) miscellaneous agent, Wei agent New aux and dissolved age Composition The rt, and the '(4) dicyclopentadiene-divalent resin (DCPD-PN) are obtained by reacting dicyclopentadiene/phenol compounds, and the structural formula is as follows Ϊ ' (B)—or more than one epoxy resin (DCPD_PNE) resin crucible, made by reacting DCPD_pN resin with epoxy gas. Its structural formula is as follows: 2 : is -ch3, -C2H5, -C(CH3)3, -H η . 0~2 〇 (C) New dicyclopentadiene-dihydrobenzo resin 2 (DCPD-BX), mixed and stirred reaction (1) dicyclopentadiene-phenolic resin, (2) monofunctional and difunctional The base is mixed with the amine compound and (3) the furfural or polyfurfural compound, and its structural formula is as follows: Z. is -CH3, -^23⁄4, -C(CH3)3, -H R· is a leukoyl group or an aromatic group. η · 〇~1 〇16 201114853 - Paint composition, (A) dicyclopentadiene resin (DCPD-PN), with (a), dicyclopentadiene; and (b) terpenoids , the reaction is made. Among them, dicyclopentadiene is a by-product of light oil cracking; phenolic compounds are selected from the group consisting of phenol, o-nonylphenol, Bisphenol-A, and 4,4'-bis-bismuth (Bisphenol- F), 4, 4'-two Bisphenol-S or a combination of resins. 3. The low dielectric resin varnish composition for laminated sheets according to claim 1, wherein the component (A) dicyclopentadiene-phenolic resin (DCPD-PN) can be used as a hardening to increase DCPD content. Use of 剂 ^ 4. The low dielectric resin varnish composition for laminates as described in claims 1 and 3 'The DCPD-PN resin hardener can be used with other resin hardeners; such as phenolic resin, amine Hardeners of the class, organic acids and anhydrides, such as polyvalent amines, polyvalent carboxylic acids, Dicyanodiamide, Anhydrides, phenol formaldehyde resins Novolac 'PN for short), o-cresol formaldehyde resin (cres〇l Novolac, referred to as CN) Melamine Phenol Novolac (MPN), BPA Phenol Novolac (ΒΡΑ-ΡΝ), four Phenol ethane resin (TetraPhenol Novolac, ΤΡΝ) and dicyclopentadiene-Phenolic Novolac (DCPD~PN). 5. The low dielectric resin varnish composition for laminated sheets according to claim 1, wherein (8) dicyclopentadiene-dihydrobenzo (DCPD-BX) thermosetting resin is (8) two-ring A pentane-p-preparative resin (DCPD-PN); (b) a monofunctional amine compound in which a monofunctional group and a difunctional group are mixed; and (c) a furfural or a polyoxymethylene compound, which are obtained by reaction synthesis. 23 201114853 2. A novel low dielectric resin varnish composition for laminates according to claim 1, which is used for the manufacture of (di) dicyclopentadiene-phenolic resin (DCPD-PN) Dicyclopentadiene is a by-product of light oil cracking; phenolic compounds are selected from the group consisting of phenol, o-nonylphenol, propylene glycol (Bisphenol-A), 4,4'-diphenolmethane (Bisphenol-F), 4,4'-diphenol sulfone (Bisphenol-S) or older resin. 3. A low dielectric resin varnish composition for a novel laminate as described in claim 1 'to increase the DCPD content of the component (A) dicyclopentadiene-phenolic resin (DCPD-PN) can be used as Hardener used. 4. A low dielectric resin varnish composition for a novel laminate according to the scope of the application of the invention, wherein the resin hardener may be selected from other resin hardeners such as a resin, an amine, an organic acid and an acid anhydride. Hardeners; such as Polyvalent amines, carboxylic acids, Dicyanodiamide, Anhydrides, Phenol Novolac (PN), neighbors Cresol Novolac (CN) melamine Phenol Novolac (MPN), propylene diene resin and Dicyclopentadiene-Phenolic Novolac (DCPD-) PN) 5. A novel low dielectric resin varnish group for a laminate according to claim 1, wherein the material (B) or a plurality of epoxy resin (DCPD-PNE) resin 1; (C) Dicyclopentadienyl dihydrobenzo (DCPD-BX) resin 2 can be used singly or in combination or in combination with other epoxy resins. 6. A low dielectric resin clear composition for a novel laminate according to claims 1 and 5, which is used for producing (c) dicyclopentadiene-dihydrobenzo resin 2 (DCPD_BX). Single official a mercapto and a difunctional mixed primary amine compound using a primary amine such as mercaptoamine, aniline, toluidine, anisidine, or an aliphatic or aromatic amine compound . A novel low-dielectric resin clearing composition for use in the manufacture of (c) dicyclopentadiene-dihydrobenzoic resin 2 (DcpD) according to the first and fifth aspects of the patent. _ Formaldehyde or polyformic acid compound, selected from furfural, polyacetal or furfural. = A low dielectric resin for a new laminate as described in items i and 5 of the patent application 9 - nl f # ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ° A novel laminate for the use of the low-dielectric tree lf (D) is difficult to burn, and the resin is filled or filled with resin. , or an inorganic filler _ agent...., K) · A low-dielectric varnish for a new laminated board as described in the scope of claim i 2011 2011-85 - 6. The laminate described in 5 consists of a low dielectric resin varnish. The substance 'a (a) dicyclopentadiene oxime resin (DCPD-PN) is (4) dicyclopentadiene; and 0) phenolic compound 'Reaction made. Among them, dicyclopentadiene is a by-product of light oil cracking; g classified compound is selected from the group consisting of bismuth, o-tolan, biSphenol-A, and 4,4'-diphenolmethane (Bispheno丨- F), 4,4,-diphenol sulfone (Bisphenol-S) or phenolic resin. 7. For the application of the laminated resin dielectric varnish composition described in Sections 1-5 and 5, the (b) monofunctional and difunctional mixed amine compounds are used as primary amines: The base amine, aniline, o-anilide, and anisidine may also be aliphatic or aromatic amine compounds. 8. The composition of the low dielectric resin varnish for laminates according to claims 1 and 5, wherein the (C) methyl or polyformic acid compound is selected from the group consisting of formic acid, polyformic acid or formic acid vapor. 9. For example, the low-pass varnish composition for laminates, 2% MC) or more than 100% epoxy resin, is made by reacting DcpD_pN resin with epoxidized propane. |DcpD_pNE. The structure is as follows: The epoxy resin according to item 9 may also be a composition of brominated epoxy 24 201114853 m, and the bromine-based flame retardant mainly has tetrabromopropanediol (TBBA) or tetrabromopropene. .Lin. · 5 Secrets 11_ A low-dielectric paint composition for a novel laminate according to the scope of the patent application, and the phosphorus-based flame retardant is DOPO, DOPO-HQ and its phenolic epoxy tree.曰巧12. A low dielectric varnish composition for a novel laminate according to claims 1 and 9, wherein the inorganic filler flame retardant is mainly aluminum hydroxide, cerium oxide, aluminum sulfate. Boron nitride.瓜瓜 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ In the total amount of resin, 〇 4 〇, ΐ 5 ΡΗΙΙ. 14. A low dielectric resin varnish 0 composition for a novel laminate according to claim 1, wherein the hardening accelerator is selected from the group consisting of 2-methylimidazole (2-methyl) in an imidazole compound. Imidazole, 2MI) with 2-ethyl-4-mercaptoimidazole (2E4MZ). 18 201114853 Resin or phosphorus epoxy resin. u. For the first part of the patent application, the component (D) is a flame retardant. The composition of the lining oil low-density varnish as described in the item is filled or contained with a resin, or the inorganic filler is not difficult to burn side of the 丨 丨 η η η 板 板 板 板 η η η η η 八 八 八 八 八 八 八 八 八 八 八 八 八) or four fine two epoxy resin. ❹ 13. The laminate resin dielectric varnish condensate according to the above-mentioned items 1-3, and the phosphorus-based flame retardant is D0P0, DOPO-HQ, and its phenolic epoxy tree. For example, the low-dielectric fine-grained material for the laminated board described in the scope of the application of the patent scopes i and u, the inorganic filler is difficult, mainly: hydrogen hydroxide, dioxo, barium sulfate, alumina, Nitriding side, etc. 15·If you want to apply for the lacquer lacquer composition of the first job, the hardening accelerator of (D) may be used alone or in combination of two or more kinds, and the amount used is relative to the total amount of the resin. After 4~〇15pHR. 16. The low dielectric resin varnish composition for laminated sheets according to the scope of claims 1 and 1S, the hardening accelerator comprising tertiary phosphine, tertiary amine, quaternary salt, quaternary ammonium salt, ♦ sitting Imidazole) compounds such as 2-mercaptoimidazole (2_methyUmidaz〇ie, 2MI) and 2-ethyl-4-indolyl "sit (2E4MZ). 17. The low dielectric resin varnish composition for laminates according to claim 1, wherein the composition of the resin composition having a novel ring structure is synthesized, and (A) DCPD-PN accounts for the total amount of the resin. Run % ; &lt;B) DCpD_BX accounted for the total amount of resin 25 201114853 • 30~50wt% and; (C) DCPD-PNE accounted for 13~60wt% of the total resin; (D) flame retardant accounted for 22% of the total resin ~32wt% and hardening accelerator account for 0.04~0.15PHR of total resin 〇