TW201113323A - Acid anhydride cured thermal setting resin composition - Google Patents

Abstract

The invention provides a resin composition adapted for printed circuit boards. The resin composition includes one or more epoxy resin mixtures, curing agents, accelerating agents, and additives. The ratio of the curing agent and the epoxy resin is about 1.55 to 2.5, in which at least one epoxy resin a phenol-benzaldehyde multifunctional epoxy resin; at least one curing agent is a styrene-maleic anhydride copolymer. The resin composition has excellent electrical properties, high glass transition temperature and thermal durability after cured, can be used in the fields of printed circuit board such as lead-free process of printed circuit boards , high frequency and carrier board packaging.

Description

201113323 VI. Description of the invention: [Technical field of invention] j-ray and a kind of epoxy resin composition with high-transition temperature, excellent pair, field, sex Wu and excellent electrical characteristics' suitable for prepreg Materials, adhesive sheets, copper recording boards, can be applied to electronic components and high-flip printed circuit boards, or sealed materials. Heart [Prior Art] Epoxy resin has been applied to copper foil substrates and printed circuit boards for many years, such as epoxy __ such as __ cloth, glass, paper, etc., and the strength is good, and = = = ^ volatile , the molding shrinkage is small; the copper recording board produced has excellent mechanical strength

Si miscellaneous, dimensional accuracy and easy processing have been printed today

The main raw material of the road board. At present, the printed circuit board makes the editing substrate (C. ah cladLaminate, C on the quantity or technical level) is mainly based on FR_4, but the development of electric surface is ^, enter, the important part of the machine - Printed circuit boards must also keep pace with the times. In terms of system products, the products are light, thin, short, and power-saving. For electronic components, the operating frequency is constantly reduced with the size of the process. Improve, the continuous voltage drop of the servo voltage, the transistor consumption "-thief less" and the smaller the noise of the material, the original low frequency does not need to consider the issue is also emerging, for the only interconnected line (10) (10) brain (iv) The industrial printed circuit board has produced two main development directions; its high-density printed circuit board, its main technology, m small holes, blind holes, buried holes. Second, high-frequency f sub-component carrier and high-speed electronics The circuit board of the product: the main technology is low dielectric f·, low loss factor plate and thin dielectric layer plate and precision impedance control, etc. The 21st century will become the video generation, the application of high frequency and high speed is the future printed circuit board (pcB) Important development Trends - 'Although the traditional FR-4 substrate can still meet the needs of most of the current printed circuit board industry, and occupy the largest market share, but with the increasing demand, in the material performance and cost test it 'mu fresh πμ test ( Wei _ cloth grade) can meet the demand 'but for the products of the frequency transmission, the substrate material requirements are high, the low dielectric constant, low loss factor substrate is to cooperate with this information product to move toward high speed and high frequency and communication products. A large number of fast and fast transmission of voice, video data, etc. The copper foil substrate material is mainly composed of a reinforcing material and a resin composition, and the outer layer is then laminated with copper foil, so the resin combination meal is a major factor affecting the electrical properties of the substrate... The development of the resin composition is used to improve the electrical properties of the substrate. 201113323 物作脳27887 * ί It is mentioned that a Malay _ with stupid ethylene copolymerizes but this Weishuchi compound _岐_transfer temperature g) Low and resistant to New Zealand's make it unsuitable for the manufacture of patina and printing (4). No, 5 hard lysing and ring-researching greases are quick to react at room temperature with the addition of promotion, and are not suitable for use in the field of printed circuit boards. The quasi-paving substrate and the printed circuit board rouge system are epoxy tree-shaped, generally used standardized ring (four) atf 'red to be a material lion called "fine fat or raiga A made of desert agent, ΐΐΐϋ ΐΐΐϋ 树月1 ingredients 'The disadvantage of using diazodiamine as a hardener, adding a promoter and melting and melting the resin alpha is that the glass transition is too low (12 (M40 ° C), hetero (10) functional epoxy _ substitution Lion A Epoxy

, the degree of the six can improve the shortcomings of low glass transition temperature (Tg), but does not contribute much to the change of resistance to heat and electrical properties. °..., 2 patent US65G9414 reveals that the county s-wire riding (sma) as a hardener can make the epoxy resin improving material of the double-recording base (4) heat, then benefit, co-crosslinking _ method, For example, the phenolic benzene and the co-crosslinking agent are four'/odor bisphenol hydrazine (ΤΒΒΑ), and tetrabromo bis, A diglycidyl hydrazine (TBBADGE), which improves the glass transitional mobility (Tg) of the sheet. Towels;; 〖 巾 g 办 彡 彡 罐 罐 罐 罐 罐 罐 罐 罐 罐 罐 罐 罐 罐 罐 罐 罐 罐 罐 罐 罐 罐 罐 罐 罐 罐 罐 罐 罐 罐 罐 罐 罐 罐 罐 罐 罐 罐 罐 罐 罐 罐 罐 罐, DSC vitrification transfer temperature (lower illusion by 122β (: increased to 155 it, and then increased by 11 〇〇 /.), DSC vitrification transfer temperature (10) instead (5) decreased to 137 ° C. From this phenomenon, it is known that the equivalent ratio exceeds about 11%, and the degree of crosslinking agent increases the DSC_er shift temperature (Tg). ^ Today's copper box substrates and _ electric manufacturing trends are recorded by the line (transfer to age-resistant agents) TBBA) goes to a non-brominated system (mainly a phosphorus-based flame retardant) or even a halogen-free system; the modified maleic acid Sf recording of the present invention is hard-synthesized, and can be used in the system. Halogen System. SUMMARY OF THE INVENTION The present invention provides an anhydride cured thermosetting resin composition suitable for use in a printed circuit board, the composition comprising one or more epoxy resin mixtures, hardeners, accelerators, and additives. The ratio of the hardener to the epoxy resin is 155 to 25, wherein the epoxy resin is at least an age-old formic acid epoxy resin (at least one of the hardeners is a stupid ethylene-maleic anhydride copolymer. After curing, the resin composition has excellent electrical properties, high glass transition temperature and excellent heat resistance of 201113323, and can be applied to the field of lead-free brush circuit boards for printed circuit boards. Printing of A-frequency and package carrier boards [Embodiment] (4) Irr supply--seeing money with money (4) Resin composition with high-quality and excellent properties, which can be applied to the field of brushless circuit boards for printed circuit boards without conversion, high frequency and high-rise boards. Ingredients for the composition, including a mixture of fats, hardeners, accelerators and additives. More than one% of the lyophilized compound, at least _- trace of benzoic acid, used in benzoquinone The purpose of the epoxy resin is to have a high-density benzene ring structure and a suitable number of epoxy functional groups on the oxygen. Therefore, the Tg, the Weiwei New Ring structure of the 瞒 赖 赖 目 目 目 目 目 目 目 目 目 目 目 目 目 目 目 目 目 目The functional group 'double official' is 150~3〇〇〇g/eq, which is selected from double bismuth epoxy resin, double test F epoxy flammability, optional bromine epoxy resin, epoxy resin or nitrogen system. Epoxy resin, also used brominated resin with 3 phenol-benzaldehyde polyfunctional epoxy resin. In addition, improve electrical properties y add CyanateEster, ΡΡ0 resin, dicyclopentadiene (dcpd) ring Oxygen, fat, such as BA23® having a cyanate resin having a cyanate functional group produced by L〇nza, and the like.

Formula I / The above-mentioned phenol-cracked aldehyde polyfunctional epoxy resin is a phenolphthalein-ester obtained by the condensation reaction of phenol with benzaldehyde in the presence of an acidic catalyst, and continues with helium-2. 3_epoxychloropropane was synthesized in the presence of sodium hydroxide to form a ben-benzaldehyde polyfunctional epoxy resin. The synthesis reaction conditions are as follows: the general use of 2,3-epoxychloropropane epoxidation process, the synthesis of benzophenone polyfunctional epoxy resin with epoxy = 2JO~260g / eq, the average number of functional groups is 2 ~6, the average molecular weight Mw is 4〇〇~25〇〇. Brominated resin containing phenol-benzaldehyde polyfunctional epoxy resin, comprising (A) phenol-benzaldehyde polyfunctional ring 201113323 oxygen resin, content 10~70wt%, (B) bifunctional epoxy resin, content 〇~ 55wt%, ring volume is 170~500g/eq, (C) bromine-containing difunctional epoxy resin, content 〇~2〇m%, epoxy when ^ is 300~500g/eq 'Bromide content 30~55% (D) tetrabromobisphenol a, content 15~40wt%, ϋ 544, reacting (D) with at least one epoxy resin of (A), (Β), (C) to form oxygen The tree is sputum, and then the remaining parts of (A), (B), and (C) are added. The uniformity of the kiln is uniform, and the average molecular weight Mw is 1500-4000, and the molecular weight distribution index (the ratio of Mw/Mn) is 丨5. ~4 〇, equivalent weight 300~500g/eq. The selection of the epoxy resin mixture may be carried out by selecting one or more of the above resins depending on processability, physical properties and the like. 〃 The hardener described above uses at least one styrene-maleic anhydride copolymer. The purpose of the anhydride hardener is that the anhydride compound has excellent thermal properties, low hygroscopicity, and an anhydride compound having a styrene-like compound is added because The dilute compound has excellent electrical properties, and in addition to improving the heat of the resin composition, it can also enhance the electrical properties of the resin composition. The acid sulphur hardener selected in the present invention is a styrene-maleic anhydride polymer having the present ethylene structure, and has the following structure. The stearic ethylene-maleic anhydride polymer having a styrene structure may be selected from commercially available products. Smai〇(8), SMA2000, SMA3000, ΕΗ0, EF2〇, EF3〇, 〇, 〇, etc. One, the upper acid-epoxy equivalent ratio is L55~2·5, preferably L55~23, this resin combination After hardening, it has excellent electrical properties, high Tg & excellent sturdiness. ,

m, n is a positive integer, which can be the same or different

The added projection tree assay _ sexual needs,

201113323 Rubber, etc., such as the addition of PKHS high molecular weight phenoxy resin (4) _y Na) can be used in the formulation system to improve the impact strength; for example, adding curry (four) N 1300x8 rubber can improve the bonding strength between copper and flute. The use of a flame retardant, such as the addition of tetrabromobisphenol A (TBBA), or Da Ba Industrial PX2 〇〇 flame retardant, can increase the non-flammable properties of the sheet, etc. The object of the present invention is to provide a thermosetting property of an acid anhydride hardening at a reasonable price. Resin composition 'The composition can be completely dissolved with a solvent at normal temperature, and is formulated into a stable homogeneous varnish. 'Prepreg substrate (4) (4) made of it), _ substrate material, can be used for printed circuit boards.

The prepreg substrate is prepared by blending the resin composition of the present invention into a varnish, using a reinforcing material through a composition impregnated with an epoxy resin, and then evaporating the solvent by a heating oven while the resin composition is subjected to a portion. The reaction showed a semi-cured film (B_stage). The reinforcing material may be glass fiber, carbon fiber, kelvar, paper fiber, such as aromatic polyimide paper, etc.; the prepreg substrate (Prepreg) may be further pressed into a copper foil substrate, One or more prepreg substrates are combined to form a copper foil on the upper and lower sides thereof, and then the composition is heated under pressure to finally obtain a composite material of the copper foil substrate. The resin composition of the present invention has a high glass transition temperature (Tg), good heat resistance and excellent electrical properties after being cured, and can be applied to a printed circuit board in a general or high frequency field. The following examples are further described in the following examples. [Example 1] Using an age-benzaldehyde polyfunctional epoxy resin (Nan Ya NPPN-433) 100 g of a copolymer of styrene and maleic anhydride (EF30) 104 g, pre-dissolved in mercaptoethyl The ketone (MEK) forms a 60% solution, and the promoter 2MI is 0.04 grams. The anhydride to epoxy equivalent ratio is 1.2 relative to the overall resin solids content. After stirring the resin composition for 3 hours, the gelation time was tested on a hot plate at 170 ° C for 270 seconds; the solution was sent to an impregnation tank and continuously impregnated with a glass fiber cloth (Model 7628) via a heating oven. The solvent is volatilized while the resin composition is partially reacted to form a semi-cured film (B-stage). After the oven is cooled to room temperature, the semi-cured film is cut into sheets; 8 sheets of thin semi-solid film are placed above and below. Stack a piece of copper foil (specification loz), then use a hot press to increase the temperature of 2.5eC / min, rise to 195 ° C for 60 to 120 minutes, use a pressure of 20 ~ 30kg / cm2, press the resin composition through a hot press The reaction was continued until the completion of the hardening (C-stage), and the physical property test data having a glass transition temperature (Tg) of 175 ° C and excellent heat resistance were confirmed by the physical property test. [Example 2] According to the resin composition of Example 1, the ratio of the anhydride to the epoxy resin was increased to 1.75, and the resin composition cured according to the above production method was confirmed by the physical property test except for the original 201113323. The physical property test data is listed in Table 2. In addition to the characteristics, it is helpful for Tg lifting and electrical properties. [Embodiment 3] According to the resin composition ratio of the second embodiment, 20% of the flame retardant PX2 is contained with respect to the entire resin solid. . 'With 1G% hydrazine. Dioxin, and then according to the above-mentioned method of hardening the tree shroud's through the product, _ test. The original special material low heat • expansion coefficient and flame retardant help. The physical property test data is listed in Table 2. T; lower [Example 4] Using brominated epoxy resin curry · 487 Α 80) 1 gram containing 酴 · 笨 路 多 multi-functional epoxy resin, this solution added 7 〇 9 grams of stupid ethylene and Malay Acid wildergic polymer (EF30) is pre-dissolved in methyl [ketone] (形成) to form a 6〇% solution and accelerator 0.04g 'acid if and Wei resin equivalent ratio is 165 ^ according to the embodiment __ Manufacturing method

The sex test proved to have a Tg of 1 WC and excellent heat resistance and the like. The physical property test data is listed in Table 2. [Example 5] - According to Cao, the resin composition of Example 4, the ratio of the anhydride to the epoxy resin was increased to 22 Å, and the molecular weight phenoxy resin (Phenoxy resin 'INCHEMREZ PKHS) was 18.9 g, manufactured according to Example 1. The method and the secret test prove that it has 195t; ^Tg& excellent heat resistance; etc.; and the physical property test data is listed in Table 2. [Comparative example 1] A brominated epoxy resin made of 100 grams of bisphenol A epoxy resin and tetrabromobisphenol A is used as the main resin component. The dicyandiamide is used as a hardener and firstly dimethyl. The indoleamine (DMF) is pre-dissolved, and the equivalent ratio of epoxy resin to hardener is 〇·5 relative to the overall resin solid content, and then the accelerator 2ΜΙ is added to adjust the solid content by methyl ethyl ketone (μεκ). 65% of the resin composition. According to the manufacturing method of the first embodiment, the physical properties of the Tgl 40 ° C and 288 ° C tin furnace heat resistance were 2 to 3 minutes. Physical property test data is listed in Table 2. [Comparative Example 2] Based on Comparative Example 1, a brominated epoxy resin made of bisphenol A epoxy resin and tetrabromobisphenol A was changed to a brominated resin containing a phenol-benzaldehyde polyfunctional epoxy resin. ^Nan Ya company NPEfe-487A80). According to the manufacturing method of the first embodiment, the physical property test Tgl7〇〇c & 288 ° C tin furnace heat for 2-3 minutes. The physical property test data is listed in Table 2. 201113323 _ Table 1, resin composition equivalent ratio of each of the examples and the comparative examples. Comparative Example_1_2_3_4_5__!_ Equivalent ratio 1.2 1.75 1.75 1.65 2.20 〇.5 1 Table 2, substrate characteristics examples of the respective examples and comparative examples 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Glass transition temperature (DSC), °C 175 189 176 188 195 140 170 Copper foil tear strength, lb/in 6.4 6.0 6.0 6.5 6.2 12 10 Solder heat test a (288 ° C), min > 10 > 10 > 10 > 10 > 10 2-3 2-3 Cracking temperature (Td), °C 362 369 361 367 371 310 315 T288 (TMA), min >30 >30 >30 >30 >30 2~3 2~3 CTE,ppm/〇C - 50/280 45/250 - - - - Dielectric constant (1 GHz) 3.91 3.80 3.79 3.82 3.76 4.6 4.3 Loss factor (1 GHz) 0.010 0.010 0.009 0.010 0.009 0.025 0.015 a: after pressure cooker for 30 mins

A resin composition containing a styrene-phenylene chain polyfunctional epoxy resin and a styrene-maleic anhydride hardener is selected to have a high Tg, excellent thermal and electrical properties after hardening. Increasing the acid equivalent ratio 'in addition to increasing the Tg, the f constant 盥 loss for reducing electrical properties is significantly improved; the ratio of acid needle to epoxy resin equivalent is K55~2.5, and the optimum ratio is i 55~23. High Tg, excellent electrical properties of resin composition, can be applied to printed circuit boards.

Claims (1)

201113323 VII. Patent application scope: 1. A thermosetting resin composition with anhydride hardening, comprising: one or more epoxy resin mixtures 'hardeners, accelerators and additives, ratio of hardener to epoxy resin It is 1.55~2.5; wherein at least one epoxy resin mixture contains a phenol-benzaldehyde polyfunctional epoxy resin, and at least one styrene-maleic anhydride copolymer is used as the hardener. 2. The resin composition according to claim 1, wherein the optimum ratio of the anhydride to the epoxy resin is 1.55 to 2.3. 3. A thermosetting resin composition having acid needle hardening as described in claim 1 of the patent application, The epoxy equivalent of the oxygen-based resin of the present invention is 21 〇 26 〇 g / eq, the average functional group number is 2 to 6, and the average molecular weight is Vlw 400 to 2500. 4. If you apply for the patent scope! An acid anhydride-cured thermosetting resin composition containing a brominated resin of an age-formaldehyde polyfunctional epoxy resin, comprising a phthalocyanine multifunctional epoxy resin 10 to 70%, and an epoxy resin thereof The equivalent weight is 3〇〇_5〇〇g/eq, and the average molecular weight Mw 15〇〇~4 is a distribution index of 1.5 to 4.0. 5. If you apply for the _ hardened lysate as described in the special item, the accelerator ^ uses a tertiary amine and its salts, a quaternary amine compound, a microphone, a single or multiple compounds. And one or more of a complex of boron difluoride and an organic substance thereof, phosphoric acid or triphenyl phosphite. Preferred are tertiary amines and their faces, sittings or mixtures thereof. 6. If you apply for a patent scope! The thermosetting resin composition having acid needle hardening according to the above item is selected from the group consisting of inorganic powder, flame retardant or booster depending on the characteristics of the resin composition.夂 7. The fine resin composition having a brittle hardening according to item 1 of the patent scope, /X or coated on the reinforcing material to obtain a prepreg. 8. The thermosetting resin composition having acid needle hardening according to item 1 of the invention, which is modified or coated on a reinforcing material to obtain an adhesive sheet. 4 Ji 9 · Such as Shen Qing Patent Fan '7 item of the thief material, after the New Zealand made copper _ laminated board. 10.ΐ1=The copper-layer plate described in Items 8 to 9 of the patent range is printed by hot pressing and wet process. 10 201113323 IV. Designation of representative drawings: (1) The representative figure of the case is: ( ). (2) A brief description of the component symbols of this representative figure·· 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: