TW201100488A - Thermosetting resin composition and copper clad laminate - Google Patents

Abstract

A thermosetting resin including Dicyclopentadiene epoxy resin, Benzoxazine, Bismaleimide, Styrene-Maleic Anhydride Copolymer, Filler, a flame retardant, and Imidazole catalyst, is provided. The thermosetting resin is applied to a circuit board of high speed transmission, has the dielectric property of low permittivity and low dissipation coefficient, to be applied to copper clad laminate for high speed signal transmission. In addition, the composition thereof does not include halogen such that less contamination is done to the environment.

Description

201100488 VI. Description of the Invention: [Technical Field] The present invention relates to a thermosetting resin composition, in particular to a low dielectric constant and a low dissipation coefficient, and is used for producing high-speed signals with copper foil laminates. Thermosetting resin composition. [Previous technology] Ο With the advancement of technology, people are more concerned with the deepest electronic products such as personal computers, personal computers, personal assistants (PDAs) and mobile phones. In the case of the brain, the inside of the product, the height of the circuit board of the electronic product can be stratified and miniaturized. The formation, multi-_Ik? integrated body cutting and the development of Xiaowei, the signal between the circuit 'and therefore the signal delay and the transmission loss problem is proportional to the square root of the dielectric constant of the insulator, and the transfer board =: In order to solve the above problem with the material of low-consumption _ characteristics, the second method of Japan 2__23949 and the second ring = _2 with low dielectric constant and dissipation coefficient to reduce the dielectric constant and the dissipation coefficient. characteristic. It is not possible to provide an electric (200) electric high-capacity transmission circuit board. The invention discloses a method for mixing a phenol-modified cyanate oligomer with a polyphenylene ether to reduce the dielectric constant. U.S. Patent No. 6,162,876 and U.S. Patent No. 6,245,841. And the method of dissipation factor. However, the circuit board manufactured by this method is inferior in heat resistance after absorbing moisture. In order to solve the problems of the above various conventional techniques, the Republic of China Patent No. 1297346 discloses a thermosetting resin mixed with a cyanate ester-based resin, a dicyclopentadienyl epoxy resin, a smoked vermiculite, and a thermoplastic resin.组成 Composition, the composition of such a thermosetting resin has a low dielectric constant and a low dissipation coefficient. However, this manufacturing method must use a flame retardant containing _ 素 (especially Mo; BKnnine; Br), such as four molybdenum, six molybdenum, and (10)-wang (three) odor phenoxy Azabenzenes, which are resistant to indifferent components, are susceptible to environmental pollution when manufactured, recycled, or discarded. In view of the above, in the technique of the conventional system for supplying Γ + ^ i 隹 袈 袈 袈 电路 电路 , , 若 若 若 若 若 若 若 若 若 若 若 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热After the thermosetting resin garment is made into a circuit board, the circuit board cannot be smashed. &>, a m built into the UL94-V0 safety fire resistance test* - called, 〇 enough halogen-containing damper' agent, will i# if &amp Cheng, loss

dye. Therefore, it is impossible to simultaneously solve the problem of the present invention by the above description. ^ B ^ ^ know the technology of making circuit boards, no

Na Na does not add enough U T in the thermosetting resin. The tooth-containing flame retardant can not effectively solve the problem of poor flame resistance and environmental pollution at the same time; therefore, the main object of the present invention is to provide a composition of a thermosetting resin having a low dielectric constant and a low dissipation property. In the production process, a halogen-free flame retardant flame retardant is used to replace the ij-containing flame retardant in the prior art, thereby solving the above two problems at the same time. The technical means for solving the problem of the invention: a thermosetting resin composition comprising dicyclopentadiene epoxy resin, benzoxazine, maleimide, styrene/maleic anhydride copolymer, filler, flame retardant and imidazole Promoter. The thermosetting resin is composed of an excellent dielectric property having a low dielectric constant and a low dissipation coefficient, and can be used for a copper foil laminate for high-speed signal transmission. In the embodiment of the invention, the use of a Phosphorous Content Resin as a halogen-free flame retardant flame retardant is used to replace the south-containing resistance in the prior art. Burning agent. Further, a copper foil laminate of the present invention is used for high-speed signal transmission, and the copper foil laminate comprises the above-mentioned thermosetting resin. The present invention compares the efficacy of the prior art: In the technique of adding a halogen-containing flame retardant, since the present invention adds sufficient non-fluorinated flame retardant to the thermosetting resin composition; therefore, the thermosetting property of the present invention can be utilized. The circuit board made of the resin composition has sufficient flame resistance and the thermal cracking temperature is as high as 36 〇t: or more, and can be applied to a lead-free reflow process. Compared with the conventional technique of adding sufficient halogen-containing flame retardant, the composition of the thermosetting resin of the invention of 201100488 is not known. (4) The resin is made of the characteristics of the present invention and the low dissipation coefficient. And has an effective viscosity;: genus! The dielectric constant is used in the production of copper foil laminates for high-speed transmission applications. The specific embodiments employed in the present invention are effectively overcome and will be further described by the following formula. The present invention relates to a composition of a thermosetting resin for a high-speed transmission circuit board, and particularly to a solid resin having a low dielectric constant and a low dissipation coefficient. composition. In the following, a preferred embodiment will be described to illustrate the invention, which is known to those skilled in the art and is not intended to limit the invention itself. The contents of this preferred embodiment are detailed below. The composition of the thermosetting resin of the present invention comprises Dicyclopentadiene epoxy resin (DCPD epoxy resin), Benzoxazine (BZ), maleimide (Bismaleimide; BMI), benzene. Styrene-Maleic Anhydride Copolymer (SMA), Filler, flame retardant, and Imidazole catalyst. In a preferred embodiment of the present invention, the composition of the thermosetting resin of the present invention comprises: (a) 100 parts by weight of a dicyclopentadiene epoxy resin; (b) 20 to 70 parts by weight of a benzoic acid Qin; 7 201100488 (c) 30 to 90 parts by weight of one type of maleated imidate. (d) 40 to 120 parts by weight of a stupid ethylene/maleic acid mound (e) 40 to 16 parts by weight Filler;--"container" (f) 60 to 120 parts by weight of a flame retardant; 'to' and (g) 0_1 to 1.0 part by weight of a stilbene promoter

Wherein, the dicyclopentadiene ring in (a) is between 45 and 105 ° C, and in (8). The species is represented by the following chemical structural formula: s milk softening point Between the pentadiene epoxy resin system

〇-&

The weight average molecular weights (Mw) of the benzoxoxine in (b) is between 200 and 2000, and the chemical structure of the genus Expressed by:

Wherein 'R1 is a group of alkyl groups, ketone groups and C(CH3)2 having a carbon number of 1 to 15; R2 and R3 are a group of a 7-membered carbon group, a phenyl group and a cyclophenyl group. The maleic imide melting point in (c) is between 60 and 180 ° C, 8 201100488 and the maleidamide in (C) is represented by the following chemical structural formula By:

Among them, R is a group of CH2, C2H5, phenyl or maleimide. In the stupid ethylene/maleic anhydride copolymer of (d), the chemical structure ratio of styrene to maleic anhydride is 1 to 6, and the styrene/maleic anhydride co-type system in (d) For a representation of the following chemical structural formula, m and η are both positive integers:

Further, the filler in (e) may be a molten cerium oxide (Fused Silica), and the diameter of the molten cerium oxide is less than 4 Å/zm. Alternatively, the filler may be a type of dehydroxylated Kaolin, and the straight lanthanide of the kaolin is less than 4 〇 #m. Further, the flame retardant in (1) is a scaly hardening resin (4) (10) rushing (four) (10), and the phosphorus content of the phosphorus-containing hardened cerium is between 3% and 15%, and Flame retardants containing _ (especially bromine) components are used in non-known techniques. The present invention also provides a copper-on-layer laminate for the high-speed signal transmission comprising the composition of the thermosetting resin 9 201100488 of the present invention described above by dissolving or dispersing the composition of the thermosetting resin in a solvent, and then the fiber. The cloth is dipped in this composition. The fiber cloth is then dried at a temperature of 110 to 195 tons for a predetermined period of time to prepare a prepreg for a printed circuit board having a B stage. Then, the adhesive sheet is laminated on at least one layer, and then covered with a copper sheet on the upper and lower sides of the bonded adhesive sheet, and heated and pressed by a vacuum press to prepare a copper pig laminate for the transmission of the south speed signal. Ο 〇 where 'this fiber cloth can be made into a woven or non-woven fabric. In addition, the fiber cloth (10) may be made of inorganic fibers such as glass, oxygen, asbestos, (four) glass, stone glass, carbon cut, and nitrogen cut, or aromatic polyamine, poly-, poly-, And organic fibers such as cellulose. Preferably, in the embodiment, the fiber cloth is a woven fiber. Because of the invention patent No. 346 of the Republic of China (hereinafter referred to as "346, the technical documents disclosed in the article also use four different thermosetting trees respectively" to make four f-plates (ie, the following comparison: τ = anti-respect Carrying out the glass transition temperature, the absorption of water and heat = % constant, the dissipation coefficient, and the __ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ In the above-mentioned (4) project order, Wang "46 諕 patent equivalent results, the following specifically provides four different material ratio / ·] made of (four) laminates of the embodiment (ie, the following example 46 patent for the above five Alignment detection of item detection items. The second 胄 '----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------- For comparison of comparative examples made of four different material ratios disclosed in No. 1297346, refer to the second drawing, which is a thermosetting resin group material ratio table used in four comparative examples of the prior art. Example 1 The composition of the thermosetting resin contains 1 part by weight of dicyclopentadiene epoxy resin, (10) parts by weight of a Weiwei resin as a flame retardant agent, 65 parts by weight of a stupid ethylene/maleic anhydride copolymer, 4〇 Parts by weight of benzotrifene 50 parts by weight of maleic diamine, 0.12 parts by weight of u-salt catalyst and 90 parts by weight of molten cerium oxide as a filler. ^The fiber cloth is impregnated with the thermosetting resin In the solution of the composition, the fiber cloth is dried at a temperature of no to 195 ° C to prepare an adhesive sheet for a printed circuit board having a B state. Then, the adhesive sheet is covered with a 35 mm thick steel foil. The vacuum press was heated and pressed to prepare a copper crucible laminate for the transfer of the Example: V. The second embodiment is different from the first embodiment in the composition of the thermosetting resin. Change from 50 parts by weight to 35 parts by weight, and the filler is changed to 7 〇 曰 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 Foil laminate. 眭 Example 3 Unlike Example 1, heat The composition of the resin is stupid ethylene/Malay 201100488. The content of the anhydride copolymer is changed from 65 parts by weight to 8 parts by weight, and the content of benzophenone is changed from 40 parts by weight to 30 parts by weight 'melted dioxide II' < Spear H: changed from 90 parts by weight to 70 parts by weight. The rest of the composition of the thermosetting resin and the steel foil laminate for high-speed signal transmission were carried out in the same manner as in Example 1. & Example 4 was different from Example 1. The content of the benzoic acid in the composition of the thermosetting resin is changed from 40 parts by weight to 35 parts by weight, and the content of maleimide is changed from "% by weight to 65 parts by weight of the content of the molten cerium oxide. 9 parts by weight of 1 part was changed to 70 parts by weight, and the composition of the thermosetting resin was prepared in the same manner as in Example i and the copper laminate for transmission at the two speeds. Comparative Example 1 The composition of the thermosetting resin used in Comparative Example 1 contained 40 parts by weight of polyphenylene ether (HPP820) as a thermoplastic resin, 7 parts by weight of smoked stone, and 2 parts by weight of 4,4,6- Tris(tribromophenoxy)-1,3,5-triazabenzene as flame retardant, 20 parts by weight of a phenolic compound, 1 part by weight of 2,2_bis(4-cyanophenyl) Propylene-based prepolymer (BA230S) as cyanate-based resin, part by weight of dicyclopentadienyl epoxy resin, 0.01 part by weight of cobalt acetylacetonate as curing accelerator for cyanate-based resin, 0.5 weight Epoxy resin curing accelerator. The fiber cloth is impregnated into a solution containing the composition of the thermosetting resin. The fiber cloth was then dried at a temperature of 80 to 200 ° C to prepare an adhesive sheet for a printed circuit board having a b state. Then, the adhesive sheet was covered with a 35 μm thick copper foil sheet and heated and pressed with a vacuum press to prepare a copper foil 12 201100488 laminate of Comparative Example 1. Comparative Example 2 Four weights of hidden weight parts The base is stupid? The dicyanic acid prepolymer ( ) is prepared as the (four) from the base resin. The rest are prepared in the same manner as the shame embodiment - a kind of heat-based resin and a kind of (four) laminate. Comparative examples... 80 parts by weight of 2,2-bis(4-cyanophenyl)propane-fired prepolymer as cyanate resin '(3) heavy part of dicyclopentadienyl epoxy resin, 1 part by weight of smoked sputum A thermosetting resin and a resin were prepared in the same manner as in Example 1 except that stone, 0.008 parts by weight of a cyanate resin curing accelerator, 0.6 parts by weight of an epoxy resin curing accelerator, and 15 parts by weight of a first phenolic compound. Copper foil laminate for high speed signal transmission. Comparative Example 4 0 The same procedure as in Example 1 was carried out except that 40 parts by weight of polystyrene (15 NFI) was used instead of polyphenylene ether, and 1 part by weight of the smoked vermiculite was used. To prepare a thermosetting resin and a copper for high-speed signal transmission Foil laminates. For each of the copper foil laminates prepared in Examples 1 to 4 and Comparative Example 1 to Comparative Example 4, the glass transition temperature, heat resistance after absorption of water, dielectric constant, and Dissipation coefficient and adhesion to copper foil. Please refer to the third figure, the third figure is the test comparison table of Examples 1 to 4 and Comparative Examples 1 to 4. 13 201100488 oJ by the first no matter in the glass track It is a secret that the composition of the thermal shutdown resin of the present invention can be expressed in terms of adhesion, and the composition of the present invention is a comprehensive flame retardant, but can be low to the environment. The degree of pollution. Number and low-consumption materials (4) (4) Sexually unpredictable with low dielectric constant temperature, H t ' while maintaining good vitrification, and used for the preparation of multi-layer and south speed signal transmission Steel box laminating environment (4) degree of dyeing, to enhance the degree of environmental protection. More " to reduce the details of the preferred embodiment by X, the characteristics and spirit, and not the above-mentioned disclosure of the scope of the invention , to limit it. On the contrary, 'the purpose: the Greek t' function And the equivalents are arranged within the scope of the present invention. Patent target [Simplified description of the drawings] The first figure is a thermosetting resin group material ratio table used in the four embodiments of the present invention; The figure is a thermosetting resin group material ratio table used in the four comparative examples of the prior art; and the third figure is the test comparison table of Examples 1 to 4 and Comparative Examples 1 to 4. Table 0 14 201100488 [Main components Symbol Description】

15

Claims (1)

201100488 VII. Patent application scope: 1. A thermosetting resin composition for making a high-performance circuit board comprising: (a) 100 parts by weight of a dicyclopentadiene epoxy resin (Dicyclopentadiene) Epoxy; DCPD epoxy); • (b) 20 to 70 parts by weight of a Benzoxazine (BZ); (c) 30 to 90 parts by weight of a maleimine (Bismaleimide; 〇BMI); d) 40 to 120 parts by weight of a Styrene-Maleic Anhydride Copolymer (SMA); (e) 40 to 160 parts by weight of a filler (Filler); (f) 60 to 120 parts by weight a flame retardant; and (g) 0.1 to 1.0 part by weight of an imidazole catalyst. The thermosetting resin composition according to claim 1, wherein the (a) The dicyclopentadiene epoxy resin of the present invention is represented by the following chemical structural formula, and has a softening point of 45 to 1〇5. (: between. 16 201100488 3. The composition of the thermosetting resin according to claim 1, wherein the stupid and dioxin in the item (b) is a weight average molecular weight (Weight average molecular weights) expressed by the following chemical structural formula. ; Mw) is between 200 and 2000. R3 〇 4. The composition of the thermosetting resin according to claim 3, wherein the core is a group having an alkyl group having 1 to 15 carbon atoms, a ketone group, and C(Ch3)2. 5. The composition of the thermosetting resin according to item 3 of the patent application, wherein R3 is a group of a base group, a stupid group and an epoxy group of carbon number 20. 6. The composition of the heat/resin according to the scope of the patent application, wherein the maleidene imine in the item (4) is one of the following chemical structural formulas, shown in Table 17 201100488, the melting point of which is Between 60 and 180 ° C. 7. The thermosetting resin composition according to claim 6, wherein R is a group of any one of CH2, C2H5, phenyl and maleimine. 8. The composition of the thermosetting resin according to claim 1, wherein the styrene/maleic anhydride copolymer of the item (d) is one represented by the following chemical structural formula, in the copolymer, m and η are both positive integers, and the ratio of m/n is 1 to 6. c2-Mg 9. The composition of the thermosetting resin according to claim 1, wherein the filler in the item (e) is a molten cerium oxide (Fused Silica). 10. The thermosetting resin composition of claim 7, wherein the molten cerium oxide has a diameter of less than 40/zm. 18 201100488 n. The composition of the thermosetting resin according to claim 1, wherein the filler in the () page is a dehydroxylated Kaolin ° 12. as claimed in claim 9 The thermosetting resin composition, wherein the diameter of the Dehydroxylated Kaolin is less than 40/m. 〇 13. The composition of the thermosetting resin according to claim 1, wherein the flame retardant in the item (f) is a resin containing a hardening resin (Ph〇Sph〇r〇us Content Resin). 14. The composition of the thermosetting resin according to claim 13, wherein the phosphorus-containing hardening resin has a phosphorus content of from 3% to 15% by weight. 〇 15. A copper foil laminate for use in high-speed signal transmission, the copper foil laminate comprising the thermosetting resin composition as described in claim 1. 19