Thermosetting resin composition, prepreg containing same, metal foil-clad laminate and printed circuit board

Abstract

The thermosetting resin composition, a prepreg containing same, a metal foil-clad laminate and a printed circuit board; the resin composition comprises the following components: a combination of a bismaleimide resin and a benzoxazine resin or a prepolymer of a bismaleimide resin and a benzoxazine resin, an epoxy resin and an active ester. A metal foil-clad laminate prepared by using the resin composition provided by the present invention has a high glass transition temperature, a low thermal expansion coefficient, a high high-temperature modulus, a high peel strength, a low dielectric constant, a low dielectric loss factor, as well as good heat resistance and good processability.

Claims

1. A thermosetting resin composition, comprising the following components: a combination of a bismaleimide resin and a benzoxazine resin, an epoxy resin and an active ester; wherein a monomer of the bismaleimide resin has a structure shown in Formula I: ##STR00008## wherein R.sub.1 is a substituted or unsubstituted C3-C4 alkyl group; R2 is an alkyl group C3 or more; the active ester comprises an active ester having a structure as shown in Formula III: ##STR00009## wherein La is a phenyl group or a naphthyl group; Y in (Y)q is selected from a methyl group and an ester group; q is 1, 2 or 3; j is an integer of 1-10; m is an integer of 1-10.

2. The thermosetting resin composition claimed in claim 1, wherein the thermosetting resin composition further comprises a phosphorous-containing flame retardant.

3. The thermosetting resin composition claimed in claim 2, wherein the phosphorus-containing flame retardant is any one or more selected from the group consisting of tris(2,6-dimethylphenyl)phosphine, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-pho sphinophenanthrene-10-oxide, 2,6-bis(2,6-dimethylphenyl)-phosphinobenzene, 10-phenyl-9,10-dihydro-9-oxa-10-phosphinophenanthrene-10-oxide and phosphazene.

4. The thermosetting resin composition claimed in claim 1, wherein the thermosetting resin composition comprises, in parts by weight, the following components: the bismaleimide resin 15-50 parts by weight; the benzoxazine resin 15-30 parts by weight; the epoxy resin 15-30 parts by weight; the active ester 2-20 parts by weight; a phosphorous-containing flame retardant 0-10 parts by weight.

5. The thermosetting resin composition claimed in claim 1, wherein the benzoxazine resin is an allyl-containing benzoxazine resin.

6. The thermosetting resin composition claimed in claim 1, wherein the epoxy resin is a halogen-free and phosphorus-free epoxy resin, which is any one selected from a biphenyl epoxy resin, a naphthol epoxy resin, a phenolic epoxy resin, a dicyclopentadiene epoxy resin, an aralkyl epoxy resin, a multifunctional epoxy resin, and a mixture of at least two selected therefrom.

7. The thermosetting resin composition claimed in claim 1, wherein the thermosetting resin composition further comprises 0.01-1 part by weight of a curing accelerator.

8. The thermosetting resin composition claimed in claim 7, wherein the curing accelerator is any one or more selected from the group consisting of an imidazole, 4-dimethylaminopyridine, triphenylphosphine, boron trifluoride monoethylamine and zinc octoate.

9. The thermosetting resin composition claimed in claim 1, wherein the thermosetting resin composition further comprises 5 to 300 parts by weight of a filler.

10. The thermosetting resin composition claimed in claim 9, wherein the median particle size of the filler is 0.01-50 ?m.

11. The thermosetting resin composition claimed in claim 9, wherein the filler is selected from an organic filler and an inorganic filler.

12. The thermosetting resin composition claimed in claim 11, wherein the inorganic filler is any one or more selected from the group consisting of a non-metal oxide, a metal nitride, a non-metal nitride, an inorganic hydrate and an inorganic salt; and wherein the organic filler is any one or more selected from the group consisting of polytetrafluoroethylene, polyphenylene sulfide and polyethersulfone.

13. The thermosetting resin composition claimed in claim 11, wherein the inorganic filler is a surface-treated inorganic filler; a surface treatment agent for surface treatment is any one or more selected from the group consisting of a silane coupling agent, an organo silicon oligomer and a titanate coupling agent.

14. The thermosetting resin composition claimed in claim 11, wherein the inorganic filler is any one or more selected from the group consisting of fused silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, aluminum oxide, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, boehmite, calcium carbonate, calcium silicate and mica.

15. A prepreg comprising a reinforcing material and the thermosetting resin composition claimed in claim 1 attached to the reinforcing material after impregnation and drying.

16. A metal foil-clad laminate comprising one or at least two laminated prepregs claimed in claim 15 and metal foil covered on one or both sides of the outer side of the prepregs.

17. A printed circuit board comprising at least one prepreg as claimed in claim 15.

Description

EMBODIMENTS

(1) The technical solution of the present invention will be further explained through examples below. Those skilled in the art shall know that the examples are merely to help understand the present invention, and should not be regarded as specific limitations to the present invention.

(2) The materials and brand information involved in the following examples and comparative examples are as follows: (A) Bismaleimide resin A-1: 3,3-dimethyl-4,4-diamino-5,5-diisopropyldiphenylmethane bismaleimide, D937, EM Technology, having a specific structure as follows,

(3) ##STR00004## A-2: 4,4-diamino-3,3,5,5-tetraisopropyldiphenylmethane bismaleimide, EM Technology, having a specific structure as follows,

(4) ##STR00005## A-3: 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, BMI-80, KI Chemical, Japan, having a specific structure as follows,

(5) ##STR00006## A-4: diphenylmethane-type bismaleimide, BMI-01, Hubei Province Honghu Bismaleimide Resin Factory, having a specific structure as follows,

(6) ##STR00007## (B) Benzoxazine resin B-1: Allyl-containing benzoxazine resin, D148, EM Technology; B-2: Allyl-containing benzoxazine resin, 5031, Kolon; B-3: Non-allyl benzoxazine, DCPD-type benzoxazine resin 8260, Huntsman; (C) Epoxy resin C-1: DCPD-type epoxy resin, HP-7200H, DIC, Japan; C-2: Biphenyl-type epoxy resin, NC-3000L, Nippon Kayaku; C-3: Naphthalene-containing epoxy resin, NC-7300L, Nippon Kayaku; (D) Active ester D-1: DCPD-type active ester, 8000, DIC, Japan; D-2: DCPD modified active ester, 8000L, DIC, Japan; D-3: Naphthalene-containing active ester, 8150, DIC, Japan; (E) Phosphorus-containing flame retardant E-1: allyl-containing phosphazene, SPV-100, Otsuka Chemical, Japan; E-2: Additive phosphorus-containing flame retardant, OP930, Clariant, Germany; E-3: Phosphorus-containing phenolic aldehyde, XZ-92741, Olin, USA; (F) Curing accelerator: dimethylimidazole, 2-MI, Shikoku Chemicals, Japan; (G) Filler G-1: Spherical silica, SC2050, Admateches, Japan; G-2: Angular silica, 525, Sibelco.

Examples 1-4

(7) The thermosetting resin composition was prepared according to the components shown in Table 1 (the amounts of raw materials were in parts by weight), and the metal foil-clad laminate sample was prepared according to the following production method for laminates. (1) Reacting the bismaleimide resin and the benzoxazine resin in a DMF solution at 130-160? C. for 0.5-8 h to obtain a prepolymer of the bismaleimide resin and the benzoxazine resin, then adding other components and evenly mixing to obtain a resin varnish; (2) Infiltrating 2116 electronic-grade glass fiber cloth with the resin varnish, baking off the solvent and baking to a semi-cured state to obtain a prepreg having a suitable resin content, then stacking a certain amount of prepregs, placing a piece of electrolytic copper foil dedicated for copper clad laminate on top and bottom, respectively, curing and laminating with a high temperature press at 220? C./90 min to obtain a copper clad laminate.

Examples 5-10

(8) The thermosetting resin composition was prepared according to the components shown in Table 1 (the amounts of raw materials were in parts by weight), and the copper clad laminate sample was prepared according to the following production method for laminates. (1) Evenly mixing the bismaleimide resin, benzoxazine resin, epoxy resin and active ester in a formula amount in a DMF solution to obtain a resin varnish; (2) Infiltrating 2116 electronic-grade glass fiber cloth with the resin varnish, baking off the solvent and baking to a semi-cured state to obtain a prepreg having a suitable resin content, then stacking a certain amount of prepregs, placing a piece of electrolytic copper foil dedicated for copper clad laminate on top and bottom, respectively, curing and laminating with a high temperature press at 220? C./90 min to obtain a copper clad laminate.

Comparative Examples 1-14

(9) The thermosetting resin composition was prepared according to the components shown in Table 2 and Table 3 (the amounts of each raw material were in parts by weight), and the copper clad laminate sample was prepared according to the production method for laminates in Examples 5-10.

(10) TABLE-US-00001 TABLE 1 Example Example Example Example Example Example Example Example Example Example Samples 1 2 3 4 5 6 7 8 9 10 A-1 17 A-2 20 50 17 20 50 15 20 A-3 20 A-4 20 B-1 17 20 17 20 20 B-2 30 30 15 B-3 20 20 C-1 16 16 30 C-2 16 16 16 16 16 C-3 15 15 D-1 6 6 20 D-2 10 10 10 10 10 D-3 2 2 E-1 4 4 1 E-2 6 6 6 6 6 E-3 1 1 F 0.05 0.05 0.05 0.05 0.05 0.05 1 0.05 0.05 0.05 G-1 40 2 40 2 19 G-2 28 28 28 28 28

(11) TABLE-US-00002 TABLE 2 Comparative Comparative Comparative Comparative Comparative Comparative Comparative Samples Example1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 A-1 33.3 A-2 50 25 A-3 10 A-4 B-1 50 25 33.3 B-2 15 B-3 C-1 30 C-2 16 16 16 16 16 16 C-3 D-1 20 D-2 50 16.7 16.7 D-3 E-1 1 E-2 6 6 6 6 6 6 E-3 F 0.05 0.05 0.05 0.05 0.05 0.05 1 G-1 24 G-2 28 28 28 28 28 28

(12) TABLE-US-00003 TABLE 3 Comparative Comparative Comparative Comparative Comparative Comparative Comparative Samples Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 A-1 A-2 52 50 20 50 A-3 15 15 15 A-4 B-1 20 B-2 30 10 32 15 30 15 B-3 C-1 30 35 30 C-2 10 C-3 15 15 15 D-1 20 20 25 D-2 10 D-3 2 2 0 E-1 1 1 1 E-2 6 E-3 1 1 1 F 0.05 0.05 0.05 0.05 0.05 0.05 0.05 G-1 24 14 4 14 G-2 34
Performance Tests

(13) Performance tests were carried out for the copper clad laminates provided in Examples 1-10 and Comparative Examples 1-14. The test methods are as follows. (1) Glass transition temperature (T.sub.g): measured by using a DMA test according to the DMA test method specified in IPC-TM-650 2.4.24; (2) Modulus: measured by using a DMA test according to the DMA test method specified in IPC-TM-650 2.4.24; (3) Coefficient of thermal expansion (CTE): measured in accordance with the CTE test method specified in IPC-TM-650 2.4.24 C; (4) Dielectric constant (Dk) and dielectric loss factor (Df): the dielectric constant and dielectric loss factor at 1 GHz were measured according to IPC-TM-650 2.5.5.9 using a plate capacitor method; (5) Anti-peel strength: measured according to the test method for anti-peel strength specified in IPC-TM-650 2.4.8; (6) Thermal cracking resistance time (T-288): measured by using a TMA instrument in accordance with the T-288 test method specified in IPC-TM-650 2.4.24.1; (7) PCT: in accordance with the IPC standard method, under the test conditions of 105 KPa/60 min, 288? C. limit; (8) 2116 sizing process: observing the appearance of the prepreg, sampling and weighing to obtain the weight per unit area, and comparing and evaluating whether the appearance and unit weight of the prepreg is easy to control, wherein Excellent: The unit weight being within the standard?4 g/m.sup.2; the appearance being flat and smooth; and no visible defects; General: The unit weight being within the standard?4 g/m.sup.2, the appearance being relatively flat; no visible defects; Poor: The unit weight being not within the standard?4 g/m.sup.2; visible defects such as sagging or bubbles.

(14) Tables 4-7 show the test results of the laminates provided in Examples 1-8 and Comparative Examples 1-14.

(15) TABLE-US-00004 TABLE 4 Example Example Example Example Example Example Items 1 2 3 4 5 6 T.sub.g(? C.) 230 230 237 231 231 232 Modulus 19/8 18/5 17/1 19/8 18/5 17/1 (50? C./260? C., GPa) Z-CTE(%) 1.8 2.6 3.6 1.8 2.6 3.5 Dk(1 GHz) 3.95 3.90 3.81 3.90 3.95 3.86 Df(1 GHz) 0.0048 0.0058 0.0086 0.0045 0.0062 0.0090 PS(1/2 OZ, N/mm) 0.95 1.05 0.98 0.94 0.97 0.92 T-288? C.(min) >30 >30 >30 >30 30 29 PCT(1 h) pass pass pass pass pass pass 2116 sizing process Excellent Excellent Excellent Excellent General General

(16) TABLE-US-00005 TABLE 5 Example Example Example Example Comparative Comparative Items 7 8 9 10 Example 1 Example 2 T.sub.g(? C.) 195 225 208 180 170 168 Modulus 17/2 18/5 18/6 17/0.2 13/0.1 16/0.3 (50? C./260? C., GPa) Z-CTE(%) 3.2 2.6 2.6 3.6 2.9 2.8 Dk(1 GHz) 3.85 4.08 4.15 4.0 3.95 4.15 Df(1 GHz) 0.0050 0.0060 0.0075 0.0085 0.0045 0.0095 PS(1/2 OZ, N/mm) 0.95 0.93 0.98 1.00 0.3 1.0 T-288? C.(min) 20 28 25 16 2 30 PCT(1 h) pass pass failed failed failed pass 2116 sizing process General General General General Poor General

(17) TABLE-US-00006 TABLE 6 Comparative Comparative Comparative Comparative Comparative Comparative Items Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 T.sub.g(? C.) 170 225 176 170 180 240 Modulus 17/0.2 18/5 13/0.6 16/0.3 16/0.6 16/0.5 (50? C./260? C., GPa) Z-CTE(%) 2.8 2.5 2.9 2.8 3.0 3.6 Dk(1 GHz) 4.1 4.1 4.1 4.05 3.98 3.8 Df(1 GHz) 0.0086 0.0092 0.0055 0.0065 0.0072 0.0100 PS(1/2 OZ, N/mm) 0.72 0.98 0.5 0.85 0.93 0.98 T-288? C.(min) 18 30 5 28 30 9 PCT(1 h) pass pass failed pass pass failed 2116 sizing process General General Poor General General General

(18) TABLE-US-00007 TABLE 7 Comparative Comparative Comparative Comparative Comparative Comparative Items Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 T.sub.g(? C.) 174 230 220 168 236 167 Modulus 16/0.3 16/0.3 16/1.5 16/0.4 17/1 16/0.3 (50? C./260? C., GPa) Z-CTE(%) 2.9 3.6 2.9 3.1 3.6 3.1 Dk(1 GHz) 3.95 3.81 3.96 3.88 3.85 3.87 Df(1 GHz) 0.009 0.0099 0.0091 0.009 0.0098 0.0088 PS(1/2 OZ, N/mm) 1.05 0.99 0.98 0.94 0.95 0.93 T-288? C.(min) 16 8 26 15 23 13 PCT(1 h) pass failed failed failed failed failed 2116 sizing process General General General General General General

(19) It can be seen from the examples and performance tests that the copper clad laminate prepared by the resin composition in the present invention has a high glass transition temperature, a low coefficient of thermal expansion, a higher high-temperature modulus, a relatively higher peel strength, and a relatively lower dielectric constant and dielectric loss factor, as well as good heat resistance and good processability. The glass transition temperature may reach 230? C. or higher; the lowest coefficient of thermal expansion may reach 1.8%; the lowest dielectric constant (1 GHz) may reach 3.81; and the lowest dielectric loss (1 GHz) may reach 0.0045.

(20) It can be seen from the comparison between Example 1 and Example 4 that, when R.sub.1 in the structure of Formula I is a substituted or unsubstituted C3-C4 alkyl group, the finally-obtained copper clad laminate has a higher glass transition temperature and may achieve relatively lower dielectric constant and dielectric loss factor.

(21) In Example 2, the resin composition was prepared by firstly forming a prepolymer by using the bismaleimide resin and the benzoxazine resin, and then mixing with other components to prepare a prepreg. In Example 5, the bismaleimide resin and the benzoxazine resin were directly mixed with other components. From the comparison between Examples 2 and 5, it can be seen that the prepolymer of a bismaleimide resin and a benzoxazine resin in the present invention can make the finally-obtained copper clad laminate have a lower coefficient of thermal expansion and better sizing process.

(22) From the comparison between Example 2 and Examples 8-10, it can be seen that the present invention discloses preferably using a bismaleimide resin having the structure of Formula I in conjunction with an allyl-containing benzoxazine resin. At this time, the finally-obtained copper clad laminate has better overall performance.

(23) From the comparison between Example 5 and Comparative Examples 1-6, it can be seen that the combined action and synergistic interaction of the bismaleimide resin, benzoxazine resin and active ester in the present invention make the finally-obtained copper clad laminate have a high glass transition temperature, a low dielectric constant and a low dielectric loss factor, and other excellent properties. All three components are indispensable.

(24) From the comparison between Examples 5-7 and Comparative Examples 7-14, it can be seen that the addition amounts of the bismaleimide resin, benzoxazine resin, epoxy resin and active ester in the present invention need to be within the ranges defined in the present invention. Above or below the ranges, the beneficial effects of the present invention cannot be obtained.

(25) The applicant declares that the present invention discloses the above-mentioned examples to illustrate the thermosetting resin composition, prepreg, metal foil-clad laminate and printed circuit board containing the same of the present invention. The present invention, however, is not limited to the above detailed methods. That is to say, it does not mean that the present invention must rely on the above detailed methods to be implemented. Those skilled in the art should understand that any improvement to the present invention, equivalent replacement of each raw material in the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection and disclosure scope of the present invention.