TW201235401A - High thermal resistance epoxy resin composition, prepreg, metal-clad laminate, and printed circuit board - Google Patents

Abstract

To provide an epoxy resin composition which is capable of maintaining flame resistance without the inclusion of a halogen flame retardant, has heat resistance sufficient for lead-free solder, and can provide a substrate that maintains excellent plate adhesion, a prepreg obtained from this composition, and a metal-clad laminate and printed circuit board on which a resin insulating layer of this composition is formed. The epoxy resin composition contains a phosphorus-modified phenol curing agent and an epoxy compound, wherein the phosphorus-modified phenol curing agent contains a phosphorus compound and a compound represented by the formula (I) (where R is a hydroxyl group or an O-methyl group, and n is an integer of 2 or greater), and the phosphorus compound is bonded to an aliphatic carbon in a compound represented by formula (I).

Description

201235401 VI. Description of the Invention: [Technical Field of the Invention] [0001] The present invention relates to a material which is substantially free of teeth and is suitable for use as a printed circuit board or the like. In addition, the present invention is inferior to the use of a five-ply type such as two, and an integrated, gold-plated 4-layer board and a printed circuit board. Pre-dip of the composition of the composition of the prior art [Prior Art] [0002] The electrically insulating and resistant epoxy resin composition 'is widely used for printed circuit board materials because of its good adhesive properties and the like. [0003] ^, because epoxy resin is relatively lacking in difficulty, the % oxygen resin composition used in printed circuit materials is generally blended with a flammable flame retardant or other elemental flame retardant' or blended with four deserts. A P-type epoxy resin or the like contains a relatively high epoxy resin, etc., and has a high effect of flame retardancy! | A system of flame retardants. However, the cured product of such a resin-containing epoxy resin composition has a drawback in that it is likely to cause harmful substances such as hydrogen and hydrogen, which may have a bad influence on the human body or the natural environment. In order to eliminate the aforementioned disadvantages, it is known that, for example, an epoxy resin blended with a phosphorus compound can be used instead of a halogen-based flame retardant (for example, Patent Document). <[0005] Further, a compound which can be blended with a resin composition as a flame-retardant method of such a halogen-free material is known, and an additive type and a reaction type are known. For example, a resin composition using phenoxyphosphazene as an additive type scaly compound has been reported (for example, Patent Document 2). Further, a resin composition using a reactive phosphine compound as a reactive ram compound has also been reported (for example, Patent Document 3). [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. JP-A-2002-36736 SUMMARY OF THE INVENTION [0007] However, the glass transition temperature (Tg) generated by the resin composition using the added Wei compound is lowered and the moisture absorption and heat retention are not good. Further, a problem with the resin composition using the counter compound is that the flame retardancy is high. Heart [0008] In recent years, there has been an increase in the demand for higher quality of material resins, and there is a need for a material-free material that can be used to compare Tg and moisture absorption. [0009] The purpose of the present invention is to provide a prepreg which is free of bismuth, has a high Tg, can be composed of an epoxy resin composed of a substrate having high heat resistance and high reliability; and has a resin formed of the foregoing composition. Absolute, 'genus along the laminate; and printed circuit boards. [0010] Using ίΐίϊ, the results of the above-mentioned problem to be solved have been found to solve the above problems. [0011] and the ring g on the person = invention is an epoxy resin composition, comprising a phenolic phenolic hardener ϋ below, 1, and characterized in that the phosphorus-modified phenolic hardener comprises a phosphating compound (I) the compound represented,

5 201235401 Formula (i) Prepreg; and 'can provide the printed circuit board 〇'" ',:,,, _a_ 曰, [Embodiment] [0013] The composition basically comprises a phosphorus-modified age. First, the epoxy resin composition of the present invention and an epoxy compound. The filled hardening curing agent used in the present invention contains a compound and a compound represented by the following formula (I).

R

Ch2 Formula (I) (wherein R represents a hydroxyl group or a 0-fluorenyl group, and n represents an integer of 2 or more), and the above hydrazine compound is bonded to the aliphatic carbon of the compound represented by the above formula (I). The phosphorus compound used in the phosphorus-modified phenol curing agent according to the present invention is a lipid 6 201235401 aliphatic carbon which has a skeleton containing a lining and which can be bonded to the compound represented by the above formula (I). Yes, there is no particular limitation. Specifically, it is exemplified by 9, m _ 10 ' 粦 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 A phosphorus phenanthrene or the like is preferable, and hca represented by the following formula (11) is preferably used as the phosphorus compound.

°~P° 式 Formula (II) [0016] The epoxy resin of the present invention can be suitably used for various substrates by using such a scaly sclerosing hardener, and is prepared for burning smoldering, south ig and Good moisture absorption for heat, materials. [0017] In the modified sclerosing agent of the present invention, it is bonded to the following simple carbon of the conjugate, but it is preferred that it has a bond and can be adiposely carbon. As described above, the dish is present in the scoop of the compound skeleton. For example, the general reactive phosphorus compound has a low flame retardancy, and it does not cause a high flame retardancy. % [0018] In addition to the bismuth compound in the phosphorus modified stone enamel modified phenol hardener, the ratio of the phosphorus compound in the 戟 bond of all the bonds of the 戟 (!) _^b 3 mass% or less. Or, it is preferable that the aliphatic 201235401 which is bonded to the compound represented by the above formula (1) is .1 mass% or less. Preferably, the hydroxyl group of the phosphorus-modified phenol curing agent used in the present invention has an equivalent weight of about 150 to 300. The better case is in the range of 150 to 250. [0020] The phosphorus-modified phenol curing agent as described above can be obtained as a commercially available product, for example, EXB9000, EXB9005, etc., manufactured by DIC Corporation. [0021] Preferably, the content ratio of the phosphorus-modified hardener in the epoxy resin composition of the present invention is 0.1 to 90% by mass based on the total mass of the epoxy resin composition, and more preferably 〇 1 ~ mass%. [0022] Secondly, the epoxy compound in the epoxy resin of the present invention is as long as it is; the effect of the invention is not contained in the inside of the invention, and the [0023] can be made more effective, for example, with an epoxy resin. Η :· FI%, Oxygen Tree, and phenolic novolac type epoxy resin: Epoxy resin, Equivalent ring, Resin, or two or more types of fine people. It is better to use the f__face oxygen, ^' in the resins [0024] money milk day 4 __ epoxy resin. The average is the epoxy equivalent of the epoxy compound in the resin, and the epoxy resin composition of the present invention is the total mass of the epoxy resin composition, preferably the ratio of the knives, to 20 to 90 mass. %. 1 9 〇夤 % % ' is more preferably 8 201235401 [0026] In addition to the above-mentioned essential components, the use of the above-mentioned epoxy tree can be promoted. The hardening accelerator is not limited to a compound, and there is no such thing as a methyl hydrazine or a cyanoethyl ketone which is a hardening reaction of a sizing agent; for example, a metal fertilizer such as 2-acid can be cited; : phenylphosphine heart!;, acid, ring-burning acid copper, ring compound; 1,8. hinder the amine in the ring of the amine == amount [0028] Berry / 〇you right. Filling material. The rigidity of the epoxy resin composition may include a powder of a metal hydrate such as sputum in the east, and a servant; and a second embodiment, an inorganic filler such as a oxidized earth; It is preferred to use only one of the fillers alone, preferably. The above filler is blended [0029]; the total mass of the latex resin composition is 〇·1 to 250 mass. %. Effect ring composition 'Do not detract from the leveling agent of the present invention as necessary (leveling ag^3 with a coloring agent' such as flame retardant (4) [0030] to #^: epoxy resin composition, usually can be modulated In the form of lacquer (face), add [cutting; use the following method to prepare the aforementioned lacquer. The components of the epoxy resin composition (Ler) ===f and f are ball mill, bead mill, J 抨 抨 ;; (blender) 4, uniformly dispersed, mixed, that can be modulated by 201235401 [0032] The fox is defined by the system, and can be used for the meaning of only H, E, and the like; eelbsolve, etc. ssr makes these organic solvents, or can be used in combination with 2 _. Prepreg) 质 ΪΙ ΪΙ ΪΙ 是 是 是 是 是 是 是 是 是 是 是 是 是 前 前 含 含 含 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 ___ post, 涂丁々. The impregnation procedure can be repeated several times according to the necessary conditions, and the impregnation procedure is repeated using a plurality of solutions of different compositions and concentrations, and adjusted to the final desired composition and amount of resin. 0035] Η (4) The substrate is not made to ship. It is better to use ί substrate, for example, you can give money, such as _ cloth (secret) cloth aramid cloth (aramidcIoth), polyester cloth and paper. The thickness of the substrate is generally a substrate of G.G2 to G.2 mm. [0036] , 'With the required heating conditions (for example, 100 to 18) 0 ° C for 3 to 10 minutes), the substrate with the varnish-like epoxy resin composition is heated and dried, and the solvent is removed while half-listening (stage B), and the body is made. The amount of the resin in the prepreg is in the total amount of the suspension, preferably 3G to 8 [0037] (metal foil laminate). The prepreg prepared above is used to manufacture a metal foil laminate. The method is as follows. One or more sheets of the aforementioned prepreg are overlapped, and the upper and lower layers of 201235401 or press forming are used so that the superimposed pressure condition is a 4-layer body which can be made according to the stack thickness = J. The heating force 5 is again 1 to 5 Pa, and the time is set to 30 to 240 minutes. L Pressure [0038] (Multilayer Printed Circuit Board) A circuit board formed on the surface of the laminate obtained as described above is formed into a circuit, and a printed circuit board can be obtained from the stacked office. Secret ~ Lai surface. There is also a conductor pattern as a circuit [0039] • If the board is used, it has excellent resistance to lead-free solder, and it is not suitable for flame retardant. Sex. . It is to be understood that the following detailed description of the present invention is by way of example only. EXAMPLES [0041] First, the raw material 硬化 (hardener) used in the present example was prepared and listed. Phosphorus-modified phenol hardener 1: DIC (manufacturing) ΕΧΒ 9000 (the equivalent of hydroxyl group 2 〇 7 phosphorus reform) Phenol hardener 2 : DIC 5 5 5 ΕΧΒ ΕΧΒ ( ΕΧΒ ΕΧΒ ΕΧΒ ΕΧΒ ΕΧΒ ΕΧΒ ΕΧΒ ΕΧΒ ΕΧΒ ΕΧΒ ΕΧΒ ΕΧΒ 167 167 167 167 TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD Phenoxy phosphazene (additional dish compound): "SPB-100" manufactured by Chemical Co., Ltd. Heterophenanthrene (HCA): "HCA" manufactured by Sanguang Co., Ltd. Reactive phosphonium nitrogen: Otsuka Chemical Co., Ltd. "SPH-100" (hydroxyl equivalent 25m (epoxy compound)) nonylphenol phenolic epoxy: DIC (share) "N-690" (nonanol phenolic epoxy resin, ring 201235401 oxygen equivalent 215) Phenol hardener: "FX289" manufactured by Tohto Kasei Co., Ltd. (equivalent to 318 of epoxy) (filler) Aluminum hydroxide: "CL-303" manufactured by Sumitomo Chemical Co., Ltd. Melting 矽: "SC" manufactured by Admatechs Co., Ltd. -2500-SEJ" (hardening accelerator) "2E4MZ" manufactured by Shimadzu Chemical Co., Ltd. (Examples 1 to 4 and Comparative Examples 1 to 5) The mixing shown in Table 1 was added. The epoxy resin varnish of Examples 1 to 4 and Comparative Examples 1 to 5 in which the composition (mass portion) was further added with ethyl ketone as a solvent to prepare a solid content of 50 to 70% by mass. [0043] Mainly followed by 'glass The cloth (2116 manufactured by Asahi Kasei Materials (Essence Chemicals) was immersed in various resin varnishes, and the resin varnish was impregnated into the glass cloth, and then dried by heating at 150 to 170 C for 3 to 5 minutes. The solvent is semi-hardened (staged) at the same time to obtain a prepreg. At this time, the amount of the resin in the prepreg is 45 to 55 mass% with respect to the total amount of the prepreg. 0044] » Next, a prepreg prepared by stacking 8 sheets was placed on both sides of a copper alloy metal company CTPZ) having a thickness of 12 μm to form a pressed body at a temperature of 3 MPa/pressure The condition of /Cm2 was 'heated and pressurized for 240 minutes, and the copper was pressed on both sides of the pressed body to obtain a copper laminated plate having a thickness of 8 mm.

<>», using the prepreg and copper-clad laminates prepared as described above, as the evaluation method below to evaluate the glass transition temperature (Tg), PCT solder resistance and flame retardant Sex. The results are shown in Table 1. [Glass transfer temperature (Tg) j using a viscoelastic optical meter (spe bloody meter) manufactured by Seiko Instruments Co., Ltd. 12 201235401

(—"^ ' I /ML/JU /Jo. 2i$u (J, do Tg. 1) The bending module sets the frequency to 5 degrees per minute at a temperature increase rate and displays a great temperature at tan5 [0047] [ PCT solder heat-resistant] After removing the copper box on the surface of the copper-clad laminate, cut into test pieces with a length of 5 feet and a width of 50 mm. Place the test piece at (2) c, 2 atm, humidity 〇 (1) The Pressure Cooker Test (PCT) machine was used for 4 hours and 6 hours. The test piece after the injection was immersed in a 26 〇t solder bath for 20 seconds, and all the samples were 3 No white spots (measling) and swelling (swelling) were evaluated as sputum; 2 of the 3 samples had no white spots and swelling, and the remaining samples had white spots and swelling, and the evaluation was eight; the number of samples was 3 When two or more of them had white spots and swelling, they were evaluated as X. [Vaan flame resistance] After removing the copper foil of the copper-clad laminate, the test piece was cut into a length of 127 mm and a width of 12 and 7 minutes. Thereafter, the test piece was subjected to the "Test for Flammability of Plastic Materials UL 94" combustion test method of Underwriters Labor atories. The test was conducted by the firing test. [0049] 13 201235401 [Table i] Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Indophenol novolac type epoxy resin 50.95 56.28 60.73 50.95 67.19 67.19 67.19 59.23 Phosphorus modified epoxy tree month 1 75.18 Phosphorus modified phenol hardener 1 49.05 19.635 49.05 Phosphorus modified phenol hardener 2 43.72 Phenol hardener 19.635 32.81 24.82 32.81 32.81 20.38 Aluminum hydroxide 45 45 45 45 45 45 45 45 45 cerium oxide 75 75 75 75 75 75 75 75 75 phenoxy azo phosphate 20 10 HCA 1.1 15 reactive azo phosphate 20.38 p m 嗤 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Resin in resin Content ratio (%) 2.2 1.5 0.9 2.4 1.8 1.7 1.9 1.1 2.4 Tg (°C) 210 221 228 207 190 185 200 212 217 PCT solder heat resistance 〇〇0 Δ 〇0 X 0 0 Flame retardancy (UL-94) V -0 V-0 V-0 V-0 V-0 V-0 V-0 V-1 All Burning 14 201235401 [Results] From the results of Table 1, it is known that Embodiments 1 to 4 according to the present invention Any of the laminates has a high Tg And even if a halogen-based flame retardant is not used, it exhibits excellent flame retardancy. Moreover, the multilayer printed circuit board of any of the embodiments also exhibits good PCT solder heat resistance. Further, in Example 4, in Example 1, phosphaphenanthrene (HCA) was further added. However, since the content of the phosphorus compound which is not bonded is 1% by mass or more based on the organic component of the resin composition, the PCT solder heat resistance is slightly inferior to those of Examples 1 to 3. On the other hand, in place of the phosphorus-modified phenol hardener of the present invention, the laminate of Comparative Example 1 was observed using a phenolic hardener and 20 parts by mass of phenoxyphosphorus nitrogen (additional phosphorus compound). The Tg thereof was lowered, and the laminate of Comparative Example 2 did not contain a curing agent, and a chemically modified epoxy resin was used as the epoxy resin, and a decrease in Tg was observed. Regarding this point, the amount of phenoxyphosphorus nitrogen added in Comparative Example 4 was half that of Comparative Example, and although the Tg was increased, the flame retardancy was lowered. Further, in place of the modified g-based hardener of the present invention, in Comparative Example 3, a hardener and a phosphaphene (HCA) 15 mass portion were used, and the pcT solder was poor in resistance. [0054] Further, in place of the filled hydrazine hardener of the present invention, in Comparative Example 5, a phenol hardener and a reactive phosphine (reactive phosphorus compound) were used, and the test piece was completely burned in the combustion test. . [0055] It can be seen from the results of π, that the epoxy resin composition of the present invention can be used as a prepreg having good properties such as high Tg, moisture absorption heat resistance and flame retardancy; Laminated board; and printed circuit board. [0056] 15 201235401 'As explained above, an epoxy resin composition according to an embodiment of the present invention comprises a phosphorus-modified phenol hardener and an epoxy compound, characterized in that the phosphorus-modified phenol hard & contains phosphorus a compound and a compound represented by the following formula (I), ch2 Λ Formula (I) (wherein R represents a hydroxyl group or a thiol group, and n represents an aliphatic carbon 1 of 2 or more compounds represented by the above formula (1) The use of the secrets of the stolen goods can touch the shortcomings of the current or reactive bismuth compounds and provide a substrate with high moisture resistance and flame retardancy and high reliability. The situation is that the former _ compound is represented by Machi (10)

式 Formula (II) has a high Tg, and a substrate formed by using the above-mentioned structured Wei resin, has good moisture absorption heat resistance and hardenability. [0058] ", 201235401 In the phosphorus-modified phenolic hardener, the ratio of the phosphorus compound not bonded to the compound represented by the formula (1) is preferably 3% by mass or less. A high flame retardancy and moisture absorption and heat resistance are obtained in the field. [0059] The proportion of the phosphorus compound bonded to the compound represented by Formula 1 is preferably not i relative to the organic component in the epoxy resin composition. According to such a structure, it is possible to surely obtain high flame retardancy and moisture absorption heat resistance. [0060] In the case of phosphorus reforming, the phosphorus compound is bonded to the formula (1). When the compound represented by the compound has an aliphatic carbon at the molecular end thereof, it is possible to ensure a high degree of difficulty. [0061], and the prepreg according to another embodiment of the invention is characterized in that the composition of the pre-tree is composed of The material is impregnated with the woven base material, and then dried to make the metal-clad laminated board and the printed circuit board which are made by the method. The reliability of the material is sufficient. [0062] According to another embodiment of the present invention, the layer is applied to the prepreg, and the addition is performed. The shape is divided into two ===,=, the circuit board' is characterized in that it is made by the part, and belongs to the metal box on the surface of the laminate to form a circuit, and the simple description is added. [Main component symbol description] 17

Claims (1)

201235401 VII. Applicable scope of the patent: 1. An epoxy resin composition comprising a modified hardening 彳 彳 and an epoxy compound, wherein the phosphorus modified phenol curing agent comprises a phosphorus compound and is represented by the following formula (1) Compound represented, (wherein R represents a hydroxyl group or a fluorenyl group, η represents an integer of 2 or more), and the phosphorus compound is bonded to an aliphatic carbon of the compound represented by the formula (I). 2. The epoxy resin composition according to claim 1, wherein the phosphorus compound is a phosphorus compound represented by the following formula (Π); Η (I I). The example ' is 3% by mass or less. (4) 3. An epoxy resin composition as in the first application of the patent scope, wherein the epoxy resin has a ratio of a compound which is not bonded to a compound of a compound represented by the formula (Ϊ). a composition in which, in relation to the component, the ratio of the phosphorus compound which is not bonded to the compound represented by the formula (I), such as the organic component 18 201235401 in the 5 9% oxygen resin composition of the first application of the patent scope, is 1% by mass or less. 5. The epoxy resin composition of claim 1, wherein in the dish-modified phenol hardener, the phosphorus compound is bonded to the aliphatic carbon at the molecular end of the compound represented by the formula (I). A prepreg of 6 is prepared by impregnating a woven polyolefin substrate as in the first aspect of the patent application.曰, ', 7, a metal foil laminated board obtained by laminating a metal foil to the prepreg according to item 6 and performing heat and pressure forming. H 8. A printed circuit board which is partially obtained by removing the metal falling from the surface of a patented smectite laminate to form an electric circuit. Item VIII. Schema: None. 19