PROCESS FOR PREPARING RESIN COMPOSITION COMPRISING BENZOXAZINE, PREPREG AND LAMINATE PREPARED THEREFROM

Abstract

The present invention relates to a process for preparing a resin composition comprising benzoxazine, a prepreg and a laminate prepared therefrom. Said resin composition comprising benzoxazine is prepared by adding an acidic filler into the resin composition comprising benzoxazine, wherein said resin composition comprising benzoxazine comprises a benzoxazine resin, an epoxy resin A1 having an epoxy equivalent of 150-450, and an epoxy resin A2 having an epoxy equivalent of 451-1000. By adding an acidic filler into the resin composition, the present invention greatly promotes the polymerization of benzoxazine and epoxy resins, and decreases the curing temperature needed for the polymerization of benzoxazine and epoxy resins. The laminates prepared from the resin composition added with an acidic filler have a high anti-stripping stability, a high glass transition temperature, a low water absorption, a high heat resistance, a high bending strength and a better processability, and can achieve a low coefficient of thermal expansion.

Claims

1. A process for preparing a resin composition comprising benzoxazine, characterized in adding an acidic filler having a pH of 2-6 into the resin composition comprising benzoxazine, wherein said resin composition comprising benzoxazine comprises a benzoxazine resin and epoxy resins comprising an epoxy resin A1 having an epoxy equivalent of 150-450, and an epoxy resin A2 having an epoxy equivalent of 451-1000.

2. The process claimed in claim 1, wherein the acidic filler is added in an amount of 0.05-100 parts by weight, based on 100 parts by weight of organic solids in the resin composition comprising benzoxazine.

3. The process claimed in claim 1, wherein the resin composition comprising benzoxazine comprises the following components, based on 100 parts by weight of organic solids, (A) from 5 to 80 parts by weight of epoxy resins, (B) from 10 to 80 parts by weight of a benzoxazine resin, and (C) from 1 to 30 parts by weight of a flame retardant, wherein epoxy resins A1 and A2 in the epoxy resins have a weight ratio of 10:1-1:10, preferably.

4. The process claimed in claim 3, wherein said epoxy resin A1 is anyone selected from the group consisting of a biphenyl epoxy resin, a dicyclopentadiene epoxy resin, a phenolic type epoxy resin, a naphthalene-containing epoxy resin and an anthracene-containing epoxy resin, or a mixture of at least two selected therefrom, and has an epoxy equivalent of 150-450.

5. The process claimed in claim 3, wherein said benzoxazine resin is anyone selected from the group consisting of a bisphenol A type benzoxazine resin, a dicyclopentadiene benzoxazine resin, a bisphenol F type benzoxazine resin, a phenolphthalein benzoxazine resin and an MDA type benzoxazine resin, or a mixture of at least two selected therefrom.

6. The process claimed in claim 3, wherein said flame retardant is anyone selected from the group consisting of a resorcinol-bis(diphenyl phosphate), a bisphenol A-bis(diphenyl phosphate), resorcinol-bis(2,6-dimethylphenyl phosphate), a dimethyl methyl phosphonate and a phosphazene compounds, or a mixture of at least two selected therefrom.

7. The process claimed in claim 3, wherein the resin composition comprising benzoxazine further comprises an epoxy resin having an epoxy equivalent of greater than 1000.

8. A resin composition comprising benzoxazine prepared by the process claimed in claim 1, characterized in the resin composition comprising benzoxazine comprises epoxy resins, a benzoxazine resin and an acidic filler, wherein the acidic filler has a pH of 2-6; said epoxy resin comprises an epoxy resin A1 having an epoxy equivalent of 150-450, and an epoxy resin A2 having an epoxy equivalent of 451-1000.

9. A prepreg comprising the resin composition prepared by the process claimed in claim 1, or the resin composition according to claim 8.

10. A laminate or printed circuit board comprising at least one sheet of the prepreg claimed in claim 9.

11. The Process claimed in claim 1, wherein the acidic filler is anyone selected from the group consisting of a silica power, a quartz powder, a mica powder, a clay, a calcium oxalate and a carbon black, or a mixture of at least two selected therefrom.

12. The Process claimed in claim 1, wherein, the acidic filler has a particle size of 50 nm-50 m.

13. The process claimed in claim 3 wherein, said epoxy resin A2 is anyone selected from the group consisting of a bisphenol A epoxy resin, a bisphenol F epoxy resin, a carboxylated nitrile-butadiene rubber modified epoxy resin and an epoxy resin containing oxazolidinone ring, or a mixture of at least two selected therefrom, and has an epoxy equivalent of 451-1000.

14. The process claimed in claim 3, wherein the resin composition comprising benzoxazine further comprises a non-acidic filler.

15. The process claimed in claim 14, wherein said non-acidic filler is anyone selected from the group consisting of a calcium carbonate, a calcium sulfate, a alumina, a barium sulfate, a ceramic powder, a talc powder and an hydrotalcite, or a mixture of at least two selected therefrom.

16. The process claimed in claim 14, wherein, said non-acidic filler is added in an amount of 0-100 parts by weight, based on 100 parts by weight of organic solids.

17. The process claimed in claim 3, wherein said resin composition comprising benzoxazine further comprises (D) a curing accelerator.

18. The process claimed in claim 17, wherein said curing accelerator is added in an amount of 0.1-1 part by weight, based on 100 parts by weight of organic solids.

19. The process claimed in claim 17, wherein said curing accelerator is anyone selected from the group consisting of an imidazole accelerators and their derivatives, a pyridine accelerators and a Lewis acid accelerators, or a mixture of at least two selected therefrom.

Description

EMBODIMENTS

[0058] The technical solutions of the present invention are further explained by the following embodiments.

[0059] The following refers to the specific embodiments of the present invention. It should be pointed out that, without departing from the principles of the examples of the present invention, a number of amendments and improvements can also be made for those ordinarily skilled in the art. Moreover, such amendments and improvements are also deemed as the protection scopes of the examples of the present invention.

[0060] The examples of the present invention are further stated below. The examples of the present invention are not limited to the following specific examples, and could be properly amended and carried out without changing the scopes of the claims.

[0061] Unless otherwise stated hereinafter, said parts refers to weight parts, and said % refers to weight %.

[0062] The materials and brands involved in the examples and comparison examples are provided as follows.

[0063] (A) Epoxy Resin [0064] A1: Biphenyl epoxy resin purchased from Nippon Kayaku, having the model of NC-3000H and having an epoxy equivalent of 288; [0065] A2: phenolic epoxy resin purchased from Nippon Kayaku, having the model of EPPN-501H and having an epoxy equivalent of 166; [0066] A3: Bisphenol F type epoxy resin purchased from Shanghai Shiyue, having the model of KF21 and having an epoxy equivalent of 540; [0067] A4: Bisphenol A type epoxy resin purchased from Changchun Resin, having the model of BE504ELM65 and having an epoxy equivalent of 890; [0068] A5: Epoxy resin purchased from NIPPON STEEL CHEMICAL, having the model of YDF-2004 and having an epoxy equivalent of 1005;

[0069] (B) Benzoxazine Resin [0070] B1: a product having the model of LZ8290H62 and purchased from Huntsman; [0071] B2: a product having the model of D125 and purchased from EM Technology;

[0072] (C) Flame Retardant [0073] C1: a product having the model of SPB-100 and purchased from Otsuka Chemical; [0074] C2: a product having the model of PX-200 and purchased from Daihachi Chemical;

[0075] (D) Filler [0076] D1: Spherical silica DQ-1030 having a pH=4.0 and purchased from Novoray; [0077] D2:Spherical silica DQ-1028L having a pH=5.8 and purchased from Novoray; [0078] D3: Air flow quartz powder purchased from Wuzhou Yingfeng Mining, having the model of 3000 meshes and having a pH of 3.0; [0079] D4: mica powder GD-2 having a pH=5.0 and purchased from Gerui; [0080] D5: carbon black having a pH=3.0 and purchased from Tianjin Xinglongtai Chemical Products Technology Co., Ltd; [0081] D6: boehmite BG-615 having a pH=6.8 and purchased from Bengbu Xinyuan; [0082] D7: Silica MEGASIL525 having a pH=6.5 and purchased from Sibelco; [0083] D8: Spherical silica power SC2500-SEJ having a pH pH=8.0 and purchased from Admatechs; and

[0084] (E) Curing Accelerator

[0085] E1: 2-Phenylimidazole Purchased from Shikoku Chemicals.

[0086] The resin compositions provided in the examples and comparison examples were used to prepare laminates for printed circuit according to the following method, and the performance test was carried out for the prepared laminates.

[0087] The laminates for printed circuit are prepared by [0088] {circle around (1)} binding one or more prepregs together by heating and pressing to prepare a laminate; [0089] {circle around (2)} binding metal foils to one or both sides of the laminate prepared in step {circle around (1)}; [0090] {circle around (3)} laminating in a laminator; [0091] overlapping 8 sheets of prepregs and 2 sheets of metal foils in an amount of one ounce (having a thickness of 35 m) during the step {circle around (2)}; [0092] during the step {circle around (3)}, laminating at 80-140 C. which is the material temperature, a temperature rising rate of 1.5-2.5 C./min, applying a full pressure of about 350 psi when the outer material temperature is 80-100 C.; controlling the material temperature at 195 C. and maintaining the temperature for at least 60 min.

[0093] The formulations and performance test results of the resin compositions provided in the examples and comparison examples are stated in Tables 1-4.

TABLE-US-00001 TABLE 1 Example Example Example Example Example Example Example Example Example 1 2 3 4 5 6 7 8 9 A1 8 24 6 45 45 70 25 25 10 A2 A3 2 6 24 5 5 10 25 25 70 A4 A5 B1 80 50 50 30 30 80 80 80 80 B2 C1 10 20 20 20 0 30 10 10 30 C2 20 D1 30 10 5 30 5 60 2 65 60 D2 D3 D4 D5 D6 D7 D8 E1 q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. Glue GT 320 270 286 240 272 230 348 204 224 Resin DSC starting 122 119 120 116 114 114 132 112 114 temperature Resin DSC peak 210 212 214 208 210 202 228 204 216 temperature Glass transition 185 178 171 170 159 167 160 173 152 temperature (Tg, C.) Flame retardancy V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 (1.60 mm) Dip soldering- >5 min >5 min >5 min >5 min >5 min >5 min <5 min <5 min <5 min resistant time Water absorption (%) 0.08 0.1 0.1 0.12 0.12 0.06 0.11 0.07 0.14 Peeling strength (N/mm) 1.10-1.25 1.20-1.35 1.05-1.35 1.20-1.40 1.10-1.20 0.90-1.15 1.15-1.30 0.95-1.20 1.10-1.30 CTE (%) 2 2.3 2.5 2.5 2.5 2.2 2.5 2.2 2.6

TABLE-US-00002 TABLE 2 Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- ple 10 ple 11 ple 12 ple 13 ple 14 ple 15 ple 16 ple 17 ple 18 ple 19 A1 45 45 45 45 45 45 25 25 A2 45 45 A3 5 5 5 5 5 25 25 A4 5 5 5 A5 5 B1 30 30 30 30 30 30 30 30 80 80 B2 C1 20 20 20 20 20 20 20 20 10 10 C2 D1 30 30 30 30 30 45 D2 30 D3 30 D4 30 20 D5 30 D6 D7 35 D8 E1 q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. Glue GT 241 238 240 242 207 210 235 248 281 268 Resin DSC starting 117 116 117 117 112 117 116 119 115 114 temperature Resin DSC peak 209 208 207 209 210 209 208 212 212 208 temperature Glass transition 170 170 170 170 188 186 170 168 168 175 temperature (Tg, C.) Flame retardancy V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 (1.60 mm) Dip soldering- >5 min >5 min >5 min >5 min >5 min >5 min >5 min >5 min >5 min >5 min resistant time Water absorption (%) 0.12 0.12 0.12 0.12 0.13 0.13 0.12 0.12 0.08 0.07 Peeling strength (N/mm) 1.20-1.40 1.20-1.40 1.20-1.40 1.20-1.40 1.20-1.45 1.20-1.45 1.20-1.40 1.25-1.45 0.85-1.10 0.85-1.10 CTE (%) 2.5 2.5 2.5 2.5 2.2 2.2 2.5 2.5 2.1 2.1

TABLE-US-00003 TABLE 3 Comparison Comparison Comparison Comparison Comparison Comparison Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 A1 8 24 24 24 25 A2 25 A3 2 6 6 6 25 A4 25 A5 B1 80 50 50 50 30 30 B2 C1 10 20 20 20 20 20 C2 D1 0 30 30 D2 D3 D4 D5 D6 10 D7 10 10 D8 10 E1 q.s. q.s. q.s. q.s. q.s. q.s. Glue GT 347 296 298 298 218 240 Resin DSC starting 138 128 127 127 114 119 temperature Resin DSC peak 226 223 221 221 210 232 temperature Glass transition 178 168 171 172 185 153 temperature (Tg, C.) Flame retardancy V-0 V-0 V-0 V-0 V-0 V-0 (1.60 mm) Dip soldering- <5 min <5 min <5 min <5 min <5 min <5 min resistant time Water absorption (%) 0.1 0.1 0.1 0.1 0.1 0.15 Peeling strength (N/mm) 0.95-1.15 1.00-1.15 0.85-1.05 0.85-1.05 1.20-1.40 1.10-1.30 CTE (%) 2.3 2.3 2.3 2.3 2.1 2.6

TABLE-US-00004 TABLE 4 Comparison Comparison Comparison Comparison Comparison Comparison Comparison Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 A1 24 30 0 25 A2 30 A3 6 0 30 25 A4 A5 50 25 25 B1 50 50 50 50 80 80 80 B2 C1 20 20 20 20 10 10 10 C2 D1 0 10 10 10 65 65 65 D2 D3 D4 D5 D6 D7 10 D8 E1 q.s. q.s. q.s. q.s. q.s. q.s. q.s. Glue GT 290 262 299 223 331 302 328 Resin DSC starting 125 117 122 112 138 129 135 temperature Resin DSC peak 218 209 216 212 237 221 235 temperature Glass transition 173 183 153 192 142 162 149 temperature (Tg, C.) Flame retardancy V-0 V-0 V-1 V-0 V-1 V-0 V-1 (1.60 mm) Dip soldering- <5 min >5 min <5 min <5 min <5 min >5 min <5 min resistant time Water absorption (%) 0.12 0.09 0.14 0.09 0.15 0.12 0.14 Peeling strength (N/mm) 0.90-1.15 1.00-1.20 0.90-1.15 1.10-1.55 0.75-1.35 1.05-1.30 0.75-1.35 CTE (%) 2.5 2.3 2.8 2.1 2.6 2.4 2.6

[0094] The items and specific methods of the performance test are as follows. [0095] (a) Glass transition temperature (Tg): tested according to the DSC method as stipulated under IPC-TM-650 2.4.25 in accordance with Differential Scanning calorimetry; [0096] (b) Flame retardancy: tested according to the UL-94 standard; [0097] (c) Water absorption: tested according to the method as stipulated under IPC-TM-650 2.6.2.1; [0098] (d) Glue GT: tested at a temperature of 174 C.; [0099] (e) Resin DSC reaction curve test: instrument manufacturer: TA, US; having a temperature rising rate of 10 C./min under N2 environment; [0100] (f) Peeling strength: tested according to the method as stipulated under IPC-TM-650 2.4.8 [0101] (g) Coefficient of Thermal expansion: tested according to the method IPC-TM-650 2.4.24.

[0102] The followings are the physical property analysises.

[0103] (1) According to Tables 1-4, it can be seen by comparing Example 1 with Comparison Example 1 that the addition of the acidic filler in Example 1 could make the resin DSC starting temperature and peak temperature lower as compared to no addition of any acidic filler in Comparison Example 1. The prepared boards had a higher glass transition temperature, a longer dip-soldering resistant time, a lower water absorption and a higher peeling strength.

[0104] By comparing Example 2 with Comparison Examples 2-4, it can be seen that the addition of the acidic filler having a pH of 4.0 in Example 2 could make the resin DSC starting temperature and peak temperature lower as compared to the addition of the acidic filler having a pH of higher than 6.0 in Comparison Examples 2-3 and the addition of non-acidic filler in Comparison Example 4. The prepared boards had a higher glass transition temperature, a longer dip-soldering resistant time, and a higher peeling strength.

[0105] By comparing Example 2 with Comparison Example 7, it can be seen that the addition of the acidic filler in Example 2 could make the resin DSC starting temperature and peak temperature lower as compared to no addition of any acidic filler in Comparison Example 7. The prepared boards had a higher glass transition temperature, a longer dip-soldering resistant time, a lower water absorption and a higher peeling strength.

[0106] According to Examples 1-2 and Comparison Examples 1-4 and 7, it can be seen that the addition of the acidic filler having a pH of 2-6 in the present invention could make the resin DSC starting temperature and peak temperature lower and make the boards have more excellent performances as compared to the fillers within other pH ranges.

[0107] (2) According to Tables 1-4, it can be seen by comparing Example 2 with Comparison Examples 8-10 that the additions of an epoxy resin having an epoxy equivalent of 150-450 and an epoxy resin having an epoxy equivalent of 451-1000 in Example 2 could make lower water absorption and more excellent peeling strength than the addition of only an epoxy resin having an epoxy equivalent of 150-450 in Comparison Examples 8 and 10, and lower resin DSC starting temperature and peak temperature than the addition of only an epoxy resin having an epoxy equivalent of 451-1000 in Comparison Example 9. The prepared boards had a higher glass transition temperature, a flame retardancy of the V-0 level, a longer dip-soldering resistant time, a lower water absorption and more excellent peeling strength.

[0108] By comparing Example 4 with Comparison Examples 5-6, it can be seen that the addition of an epoxy resin having an epoxy equivalent of 150-450 and an epoxy resin having an epoxy equivalent of 451-1000 in Example 4 could make more excellent dip-soldering resistance, lower water absorption and higher peeling strength than the addition of two epoxy resins having an epoxy equivalent of 150-450 in Comparison Example 5, and lower resin DSC starting temperature and peak temperature than the addition of two epoxy resins having an epoxy equivalent of 451-1000 in Comparison Example 6. The prepared boards had a higher glass transition temperature, a longer dip-soldering resistant time, a lower water absorption and more excellent peeling strength.

[0109] By comparing Example 8 with Comparison Examples 11-13, it can be seen that the addition of an epoxy resin having an epoxy equivalent of 150-450 and an epoxy resin having an epoxy equivalent of 451-1000 in Example 8 could make lower resin DSC starting temperature and peak temperature than the addition of an epoxy resin having an epoxy equivalent of greater than 1000 in Comparison Example 11. The prepared boards had a higher glass transition temperature and a lower water absorption. The addition in Example 8 could make lower resin DSC starting temperature and peak temperature, a higher glass transition temperature and a lower water absorption than the addition of an epoxy resin having an epoxy equivalent of 150-450 and an epoxy resin having an epoxy equivalent of greater than 1000 in Comparison Example 12, and the addition of an epoxy resin having an epoxy equivalent of 451-1000 and an epoxy resin having an epoxy equivalent of greater than 1000 in Comparison Example 13.

[0110] According to Examples 2, 4 and 8, and Comparison Examples 5-6 and 8-13, it can be seen that the present invention discloses the addition of an epoxy resin having an epoxy equivalent of 150-450 and an epoxy resin having an epoxy equivalent of 451-1000. Said two epoxy resins have synergistic effects, and their combined action makes the boards have more excellent performances.

[0111] (3) By comparing Examples 1 and 3 with Examples 6 and 9, it can be seen that, when the weight ratio of the epoxy resins having an epoxy equivalent of 150-450 and having an epoxy equivalent of 451-1000 in Examples 1 and 3 was controlled with the range of 4:1-1:4, the prepared boards had a higher glass transition temperature, as compared to those beyond said range in Examples 6 and 9.

[0112] It can be seen from the examples above that, by adding an acidic filler into the resin composition, the present invention greatly promotes the polymerization of benzoxazine and epoxy resins, decreases the curing temperature needed for the polymerization of benzoxazine and epoxy resins, and makes complete reaction of benzoxazine and epoxy resins. The laminates prepared from the resin composition added with an acidic filler have a high anti-stripping stability, a high glass transition temperature, a low water absorption, a high heat resistance, a high bending strength and a better processability, and can achieve a low coefficient of thermal expansion. Meanwhile, by combining epoxy resins having different structures and epoxy equivalents together, the present invention improves the worse machinability of the resin composition, while ensuring that the resin composition has a higher glass transition temperature, a better mechanical performance and a lower water absorption. The selection of epoxy resins, and the addition of acidic filler will produce synergistic effects with each other, which is conducive to realizing more stable peeling strength and increasing the reliability of the resin composition.

[0113] It shall be noticed and understood that various amendments and improvements can be made to the present invention detailedly stated above, without departing from the spirit and scope of the present invention as set forth in the appended claims. Thus the scope of the claimed technical solution is not limited by any specific demonstration teaching provided therein.

[0114] The applicant claims that the present invention describes the detailed process of the present invention, but the present invention is not limited to the detailed process of the present invention. That is to say, it does not means that the present invention shall be carried out with respect to the above-described detailed process of the present invention. Those skilled in the art shall know that any improvements to the present invention, equivalent replacements of the raw materials of the present invention, additions of auxiliary components, selections of any specific ways all fall within the protection scope and disclosure scope of the present invention.