Thermosetting epoxy resin composition and prepreg, laminated board and printed circuit board using thermosetting epoxy resin composition

Abstract

Provided are a thermosetting epoxy resin composition and a prepreg, laminated board and printed circuit board using the thermosetting epoxy resin composition. The thermosetting epoxy resin composition comprises the following components in parts by weight: 2-10 parts of a phosphorus-containing anhydride, 5-40 parts of a phosphorus-free anhydride, 5-45 parts of an epoxy resin, 40-70 parts of a filler, and 0-15 parts of a phosphorus-containing flame retardant, with the total part by weight of all these components being 100 parts, wherein the phosphorus-containing anhydride has a structure as represented by formula I or II, and the epoxy resin is selected from one of or a combination of at least two of a bisphenol A epoxy resin, a bisphenol F epoxy resin and a biphenyl epoxy resin. The thermosetting epoxy resin composition also has good heat resistance, discoloration resistance and dimensional stability after curing while ensuring V-0 grade flame resistance, and can be used for the preparation of printed circuit board substrates in the field of LEDs.

Claims

1. A thermosetting epoxy resin composition, comprising the following components in part by weight: Component A: 2-10 parts of a phosphorus-containing anhydride, Component B: 5-40 parts of a phosphorus-free anhydride, Component C: 5-45 parts of an epoxy resin, Component D: 40-70 parts of a filler, and Component E: 0-15 parts of a phosphorus-containing flame retardant; the total part by weight of the Component A, Component B, Component C, Component D and Component E is 100 parts; the phosphorus-containing anhydride has a structure represented by Formula I or Formula II as follows: ##STR00019## wherein R.sup.1 and R.sub.2 are each independently selected from any one of hydrogen, C1-C5 alkyl, substituted phenyl, unsubstituted phenyl, substituted naphthyl, and unsubstituted naphthyl; R.sub.3 is selected from any one of hydrogen, C1-C5 alkyl, siloxy and siloxyalkyl; X.sub.1 and X.sub.2 are each independently selected from any one of ##STR00020## wherein * represents a linkage site of the group; R.sub.11 and R.sub.12 are each independently selected from any one of C1-C5 alkyl, benzoxazinyl, substituted phenyl, unsubstituted phenyl, substituted naphthyl, and unsubstituted naphthyl; when the above group contains a substituent, the substituent is a halogen atom or a C1-C5 linear or branched alkyl group; wherein the epoxy resin is selected from a bisphenol A epoxy resin, a bisphenol F epoxy resin, a biphenyl epoxy resin, and combinations thereof; wherein the epoxy resin of Component C is the only epoxy resin present in the composition; and wherein the filler is titanium dioxide.

2. The thermosetting epoxy resin composition according to claim 1, wherein R.sup.3 in Formula I is siloxy or siloxyalkyl.

3. The thermosetting epoxy resin composition according to claim 2, wherein R.sup.3 in Formula I is selected from any one of ##STR00021## wherein n is an integer of 1-3, and * represents a linkage site of the group.

4. The thermosetting epoxy resin composition according to claim 2, wherein the phosphorus-free anhydride is selected from methyltetrahydrophthalic anhydride, methylnadic anhydride, styrene-maleic anhydride, and combinations thereof.

5. The thermosetting epoxy resin composition according to claim 4, wherein the styrene-maleic anhydride has a structure represented by Formula III as follows: ##STR00022## wherein n.sub.1:n.sub.2=0.8-19:1.

6. The thermosetting epoxy resin composition according to claim 4, wherein a number average molecular mass of the styrene-maleic anhydride is 1000-50000.

7. The thermosetting epoxy resin composition according to claim 2, wherein a median particle size of the filler is 0.1-10 mm.

8. The thermosetting epoxy resin composition according to claim 1, wherein the phosphorus-containing flame retardant is an aluminum phosphate salt and/or a high-melting-point phosphorus-containing flame retardant, and the high-melting-point phosphorus-containing flame retardant has a melting point of more than or equal to 260 C.; the high-melting-point phosphorus-containing flame retardant has a structure represented by Formula (1) or Formula (2) as follows: ##STR00023## wherein Y is selected from any one of a directly-linking bond, aryl, alkyl, substituted cycloalkyl, unsubstituted cycloalkyl, substituted cycloalkenyl, and unsubstituted cycloalkenyl, and when the group contains a substituent, the substituent is C1-C6 alkyl; R.sub.6, R.sub.7, R.sub.8 and R.sub.9 are each independently selected from any one of hydrogen, C1-C6 alkyl, C6-C12 aryl, and C7-C15 aralkyl; or R.sub.6, R.sub.7, R.sub.8 and R.sub.9 are bonded to form a saturated or unsaturated ring, and the saturated or unsaturated ring is optionally substituted with C1-C6 alkyl; m.sub.1, m.sub.2, m.sub.3 and m.sub.4 are each independently 1, 2, 3 or 4; R.sub.4, R.sub.4, R.sup.5 and R.sub.5 are each independently hydrogen or C1-C6 alkyl; a and b are each independently 0, 1, 2, 3, 4 or 5, and when Y is aryl or a directly-linking bond, a and b are not 0.

9. The thermosetting epoxy resin composition according to claim 1, wherein the thermosetting epoxy resin composition further comprises 0.001-5 parts by weight of a catalyst, based on the total 100 parts by weight of the Component A, Component B, Component C, Component D and Component E.

10. The thermosetting epoxy resin composition according to claim 4, wherein the catalyst is selected from a tertiary amine, a tertiary phosphine, a quaternary ammonium salt, a quaternary phosphonium salt, an organometallic complex, an imidazole compound, and combinations thereof.

11. A resin film, which is prepared by semi-curing the thermosetting epoxy resin composition according to claim 1 through baking and heating.

12. A resin-coated copper foil, which is prepared by coating the thermosetting epoxy resin composition according to claim 1 on a copper foil, and heating the same for a semi-cured state.

13. A prepreg, comprising a reinforcing material, and the thermosetting epoxy resin composition according to claim 1 which is adhered to the reinforcing material after impregnating and drying.

14. A laminate, comprising one or at least two stacked prepregs according to claim 13.

15. A metal foil-clad laminate, comprising one or at least two stacked prepregs according to claim 13, and a metal foil covering on one or two sides of the one prepreg or the stacked prepregs.

16. A printed circuit board, which is prepared through a method of removing part of the metal foil on the surface of the metal foil-clad laminate according to claim 15 to form a circuit.

Description

DETAILED DESCRIPTION

(1) Technical solutions of the present application are further described below in conjunction with specific embodiments. Those skilled in the art should understand that the embodiments described herein are merely used for a better understanding of the present application and should not be construed as specific limitations to the present application.

Synthesis Example 1: Synthesis of Phosphorus-Containing Anhydride 1

(2) Nadic anhydride

(3) ##STR00007##
and a phosphorus compound

(4) ##STR00008##
reacted in the presence of benzoyl peroxide as an initiator at a reaction temperature of 135 C., and the carbon-carbon double bond in nadic anhydride reacted with the active hydrogen group in the phosphorus compound, so as to obtain the phosphorus-containing anhydride 1.

(5) Phosphorus-containing anhydride 1:

(6) ##STR00009##

Synthesis Example 2: Synthesis of Phosphorus-Containing Anhydride 2

(7) Endomethyl nadic anhydride

(8) ##STR00010##
and a phosphorus compound

(9) ##STR00011##
reacted in the presence of benzoyl peroxide as an initiator at a reaction temperature of 135 C., and the carbon-carbon double bond in nadic anhydride reacted with the active hydrogen group in the phosphorus compound, so as to obtain the phosphorus-containing anhydride 2.

(10) Phosphorus-containing anhydride 2:

(11) ##STR00012##

Synthesis Example 3: Synthesis of Phosphorus-Containing Anhydride 3

(12) Nadic anhydride

(13) ##STR00013##
and a phosphorus compound

(14) ##STR00014##
reacted in the presence of benzoyl peroxide as an initiator at a reaction temperature of 135 C., and the carbon-carbon double bond in nadic anhydride reacted with the active hydrogen group in the phosphorus compound, so as to obtain the phosphorus-containing anhydride 3.

(15) Phosphorus-containing anhydride 3:

(16) ##STR00015##

Synthesis Example 4: Synthesis of Phosphorus-Containing Anhydride 4

(17) A siloxy-containing nadic anhydride

(18) ##STR00016##

(19) and a phosphorus compound

(20) ##STR00017##
reacted in the presence of benzoyl peroxide as an initiator at a reaction temperature of 135 C., and the carbon-carbon double bond in nadic anhydride reacted with the active hydrogen group in the phosphorus compound, so as to obtain the phosphorus-containing anhydride 4.

(21) Phosphorus-containing anhydride 4:

(22) ##STR00018##

(23) The sources of raw materials used in examples and comparative examples of the present application are shown in Table 1 as follows.

(24) TABLE-US-00001 TABLE 1 Component Type Brand Supplier A Phosphorus-containing Prepared in Synthesis / anhydride 1 Example 1 Phosphorus-containing Prepared in Synthesis / anhydride 2 Example 2 Phosphorus-containing Prepared in Synthesis / anhydride 3 Example 3 Phosphorus-containing Prepared in Synthesis / anhydride 4 Example 4 Phosphorus-containing XZ92741 DOW phenolic B Styrene-maleic EF40 Cray Valley anhydride Styrene-maleic EF60 Cray Valley anhydride Methyltetrahydrophthalic / Aladdin anhydride C Bisphenol A epoxy resin GELR128E Hongchang Bisphenol A epoxy resin GESN901A80 Hongchang Bisphenol F epoxy resin GEFR170 Hongchang Biphenyl epoxy resin NC3000H Nippon Kayaku Dicyclopentadiene 7200H DIC novolac epoxy resin Phosphorus-containing BEP310A75 Changchun resin epoxy resin Phosphorus-containing BEP330A70 Changchun resin epoxy resin D Titanium dioxide TA-300 Fuji, Japan Boehmite BG601 Anhui Estone Aluminum hydroxide C303 Sumitomo, Japan Silica E Aluminum phosphate OP935 Clariant salt High-melting-point (Formula 5) Reference phosphorus-containing CN20108002202.6 flame retardant High-melting-point (Formula 6) Reference phosphorus-containing CN20108002202.6 flame retardant DOPO HCA Sanko Catalyst 2-ethyl 24MI 4-methylimidazole

Examples 1-7

(25) Examples 1-7 each provide a copper foil-clad laminate, of which the preparation method is as follows.

(26) (1) Preparation of Resin Adhesive Solution

(27) Component A of a phosphorus-containing anhydride, Component B of a phosphorus-free anhydride, Component C of an epoxy resin, Component D of a filler, and Component E of a phosphorus-containing flame retardant, a catalyst, were added to a solvent in proportion, and mixed uniformly, so as to obtain the resin adhesive solution;

(28) (2) Preparation of Prepreg

(29) A glass fabric was impregnated with the resin adhesive solution, and then baked in an oven at 155 C. to remove the solvent, so as to obtain the prepreg;

(30) (3) Preparation of Copper Foil-Clad Laminate

(31) The obtained prepreg was stacked according to a certain number, added with an 18-micron copper foil on both sides, respectively, and cured in a press at 200 C. for 90 minutes, so as to obtain the copper foil-clad laminate.

(32) The types and usage amounts (parts by weight) of the raw materials used in Examples 1-7 and the performance data of the obtained copper clad laminates are shown in Table 2 as follows.

(33) TABLE-US-00002 TABLE 2 Example Example Example Example Example Example Example Raw material 1 2 3 4 5 6 7 A Phosphorus- 5 containing anhydride 1 Phosphorus- 10 5 containing anhydride 2 Phosphorus- 3 3 3 3 containing anhydride 3 Phosphorus- containing anhydride 4 B EF40 10 5 20 20 EF60 20 35 17 C NC3000H 15 GELR128E 22 17 5 GESN901A80 35 30 20 D Titanium dioxide 50 50 55 50 50 40 65 E OP935 0 5 5 5 5 5 10 Solvent Butanone 50 50 50 50 50 50 50 Catalyst 24MI 0.03 0.03 0.03 0.03 0.03 0.03 0.03 Performance Dimensional 200 200 180 200 230 270 180 of copper stability (ppm) clad Heat discoloration laminate resistance Flame retardancy V0 V0 V0 V0 V0 V0 V0 Water absorption 0.23 0.31 0.17 0.23 0.3 0.27 0.23 rate (%)

Examples 8-18

(34) Examples 8-18 each provide a copper foil-clad laminate, which differs from Example 1 only in the types and usage amounts of the raw materials used. The types and usage amounts (parts by weight) of the raw materials used in Example 8-18 and the performance data of the obtained copper clad laminate are shown in Table 3 and Table 4 as follows.

(35) TABLE-US-00003 TABLE 3 Example Example Example Example Example Example Example Raw material 8 9 10 11 12 13 14 A Phosphorus-containing anhydride 1 Phosphorus-containing 5 5 5 5 5 5 anhydride 2 Phosphorus-containing anhydride 3 Phosphorus-containing 2 anhydride 4 B EF40 20 20 20 20 20 Methyltetra- 5 10 hydrophthalic anhydride C NC3000H GELR128E 15 15 15 10 25 GESN901A80 15 GEFR170 15 5 D Titanium dioxide 70 55 55 55 55 55 50 E OP935 8 10 High-melting-point 5 5 5 5 phosphorus-containing flame retardant (Formula 5) High-melting-point 5 phosphorus-containing flame retardant (Formula 6) Solvent Butanone 50 50 50 50 50 50 50 Catalyst 24MI 0.03 0.03 0.03 0.03 0.03 0.03 0.03 Performance Dimensional 290 230 230 220 220 220 280 of copper stability (ppm) clad Heat discoloration laminate resistance Flame retardancy V0 V0 V0 V0 V0 V0 V0 Water absorption 0.10 0.31 0.17 0.23 0.3 0.27 0.23 rate (%)

(36) TABLE-US-00004 TABLE 4 Example Example Example Example Raw material 15 16 17 18 A Phosphorus-containing 5 5 5 5 anhydride 1 Phosphorus-containing anhydride 2 Phosphorus-containing anhydride 3 Phosphorus-containing anhydride 4 B EF40 10 10 10 10 Methyltetrahydrophthalic anhydride C NC3000H GELR128E GESN901A80 35 35 35 35 GEFR170 D Titanium dioxide 30 50 50 Boehmite 50 10 Aluminum hydroxide 20 Silica 10 E OP935 High-melting-point phosphorus-containing flame retardant (Formula 5) High-melting-point phosphorus-containing flame retardant (Formula 6) Solvent Butanone 50 50 50 50 Catalyst 24MI 0.03 0.03 0.03 0.03 Performance Dimensional stability (ppm) 275 280 280 280 of Heat discoloration resistance copper Flame retardancy V0 V0 V0 V0 clad Water absorption rate (%) 0.23 0.23 0.23 0.20 laminate

Comparative Example 1

(37) This comparative example provides a copper foil-clad laminate, which differs from Example 1 in that Component A of phosphorus-containing anhydride 1 was replaced with a non-reactive flame retardant of aluminum phosphate salt with an equivalent amount.

Comparative Example 2

(38) This comparative example provides a copper foil-clad laminate, which differs from Example 2 in that a usage amount of Component A of phosphorus-containing anhydride 2 was 15 parts by weight.

Comparative Example 3

(39) This comparative example provides a copper foil-clad laminate, which differs from Example 1 in that Component A of phosphorus-containing anhydride 1 was replaced with a flame-retardant curing agent of phosphorus-containing phenolic with an equivalent amount.

Comparative Example 4

(40) This comparative example provides a copper foil-clad laminate, which differs from Example 1 in that Component A of phosphorus-containing anhydride 1 was replaced with a flame-retardant curing agent of phosphorus-containing phenolic, and a phosphorus content of the resin composition was kept the same as that in Example 1.

Comparative Examples 5-7

(41) These comparative examples each provide a copper foil-clad laminate, which differs from Example 3 in the type of Component C.

(42) The types and usage amounts (parts by weight) of the raw materials used in Comparative Examples 1-7 and the performance data of the obtained copper foil-clad laminates are shown in Table 5 as follows.

(43) TABLE-US-00005 TABLE 5 Comparative Comparative Comparative Comparative Comparative Comparative Comparative Example Example Example Example Example Example Example Raw material 1 2 3 4 5 6 7 A Phosphorus- containing anhydride 1 Phosphorus- 15 5 5 5 containing anhydride 2 Phosphorus- containing anhydride 3 Phosphorus- containing anhydride 4 XZ92741 5 5.6 B EF40 10 5 10 10 20 20 20 EF60 C NC3000H 10 GELR128E 10 GESN901A80 35 30 35 35 GEFR170 7200H 15 BEP330A70 5 BEP310A75 5 D Titanium dioxide 50 50 50 50 55 55 55 E OP935 5 5 5 5 5 HCA Solvent Butanone 50 50 50 50 50 50 50 Catalyst 24MI 0.03 0.03 0.03 0.03 0.03 0.03 0.03 Performance Dimensional 290 400 280 280 280 270 270 of copper stability (ppm) clad Heat discoloration X X X X X X laminate resistance Flame retardancy fail V0 fail V0 V0 V0 V0 Water absorption 0.27 0.55 0.23 0.25 0.27 0.27 0.30 rate (%)

(44) The test methods for the above performance are described below. 1. Dimensional stability: The dimensional change rate of a laminate of 300 mm300 mm in size was measured by image observation, and the method refers to IPC-TM650-2.4.39. 2. Heat discoloration resistance:

(45) A laminate of 50 mm50 mm was prepared, processed at a high temperature of 200 C. for 4 hours, and then inspected whether discoloration occurred. represented almost no discoloration; represented slight discoloration; and X represented yellowing. 3. Flame retardancy: This performance was tested according to the flammability method specified in UL94. 4. Water absorption rate: A laminate of 100 mm100 mm was prepared, processed in a pressure cooker at 103 kPa and 121 C. for 2 hours, and measured for the weight change rate, namely, the water absorption rate.

(46) It can be seen from the Tables 2-4 that the copper foil-clad laminate prepared by using the thermosetting epoxy resin composition provided in the present application has excellent dimensional stability, flame retardancy and heat discoloration resistance, and low water absorption rate as well. Its flame retardant grade reached V0 grade, the dimensional change rate was 180-290 ppm in IPC-TM650-2.4.39 test, the color had no obvious change after high temperature treatment at 200 C., and the water absorption rate was 0.17-0.31%.

(47) It can be seen from the test results in Table 5 that compared with Example 1, Comparative Example 1 used the same amount of aluminum phosphate flame retardant to replace the phosphorus-containing anhydride 1, obtained the copper foil-clad laminate with deteriorated dimensional stability, and also failed to reach V0 grade flame retardancy.

(48) Compared with Example 2, Comparative Example 2 added an excessive amount of Component A of phosphorus-containing anhydride, and thus the dimensional stability, heat discoloration resistance and water absorption performance of the obtained copper foil-clad laminate obviously deteriorated.

(49) Compared with Example 1, Comparative Example 3 used the same amount of flame-retardant curing agent of phosphorus-containing phenolic to replace the phosphorus-containing anhydride 1, and the obtained copper foil-clad laminate which could not reach V0 grade flame retardancy and also had the significantly deteriorated heat discoloration resistance.

(50) Compared with Example 1, Comparative Example 4 used the flame-retardant curing agent of phosphorus-containing phenolic to replace the phosphorus-containing anhydride 1, and kept the phosphorus content unchanged in the resin composition: although the obtained copper foil-clad laminate reached V0 grade flame retardancy, the heat discoloration resistance and dimensional stability significantly deteriorated.

(51) Compared with Example 3, Comparative Example 5 did not use epoxy resins of the type defined in the present application, and Comparative Examples 6-7 added other types of epoxy resins, and thus the obtained copper foil-clad laminates had significantly deteriorated heat discoloration resistant.

(52) The applicant has stated that although the specific embodiments of the present application is described above, the protection scope of the present application is not limited to the embodiments, and it should be apparent to those skilled in the art that variations or replacements, which are obvious for those skilled in the art without departing from the technical scope disclosed in the present application, all fall within the protection scope and the disclosure scope of the present application.