Method for preparing benzoxazine-containing resin composition, and prepreg and laminate made therefrom

Abstract

The present invention relates to a method for preparing a benzoxazine-containing resin composition and a prepreg and a laminate made therefrom. The method for preparing a benzoxazine-containing resin composition is adding an acidic filler to a benzoxazine-containing resin composition. By adding an acidic filler to the benzoxazine-containing resin composition, the present invention promotes greatly the polymerization reaction of benzoxazine and epoxy resin, reduces the curing temperature required for polymerization of benzoxazine and epoxy resin. The laminate prepared from the benzoxazine-containing resin composition, to which an acidic filler is added, has high anti-stripping stability, high glass transition temperature, low water absorption, high heat resistance, high bending strength and good processability, and can achieve low coefficient of thermal expansion.

Claims

1. A method for preparing a benzoxazine-containing resin composition, wherein the method comprises the steps of: adding an acidic filler to a benzoxazine-containing resin composition, wherein the pH value of the acidic filler is between 2 and 6, wherein the benzoxazine is diamine benzoxazine; wherein the diamine benzoxazine resin monomer has a structure of formula (II) ##STR00013## wherein R.sub.3 is any one selected from the group consisting of ##STR00014## wherein the addition amount of the acidic filler is 5 to 200 parts by weight, based on 100 parts by weight of organic solids in the benzoxazine-containing resin composition.

2. The method of claim 1, wherein the acidic filler is any one selected from the group consisting of silica powder, quartz powder, mica powder, clay, calcium oxalate and carbon black, or a mixture of at least two of them.

3. The method of claim 1, wherein the particle size of the acidic filler is between 50 nm and 50 μm.

4. The method of claim 1, wherein the amount of the benzoxazine resin is 10 to 100 parts by weight, based on 100 parts by weight of organic solids in the benzoxazine-containing resin composition.

5. The method of claim 1, wherein the benzoxazine-containing resin composition comprises an epoxy resin; wherein the epoxy resin is in an amount greater than 0 to 75 parts by weight or less, based on 100 parts by weight of organic solids; the epoxy resin is any one selected from the group consisting of bisphenol A epoxy resin, bisphenol F epoxy resin, o-cresol phenolic epoxy resin, bisphenol A phenolic epoxy resin, trisphenol phenolic epoxy resin, dicyclopentadiene phenolic epoxy resin, biphenyl phenolic epoxy resin, alkylbenzene phenolic epoxy resin, and naphthol phenolic epoxy resin, or a mixture of at least two of them.

6. The method of claim 5, wherein the benzoxazine-containing resin composition comprises a curing accelerator; the curing accelerator is in an amount greater than 0, to 1 part by weight or less, based on 100 parts by weight of the total addition amounts of acidic filler, benzoxazine and epoxy resin; the curing accelerator is any one selected from the group consisting of an imidazole compound, a derivative of an imidazole compound, a piperidine compound, Lewis acid and triphenylphosphine, or a mixture of at least two of them.

7. The method of claim 5, wherein the benzoxazine-containing resin composition comprises a non-acidic filler; the non-acidic filler is any one selected from the group consisting of calcium carbonate, calcium sulfate, alumina, barium sulfate, ceramic powder, talcum powder and hydrotalcite, or a mixture of at least two of them; and the non-acidic filler is in an amount greater than 0 to 100 parts by weight or less, based on 100 parts by weight of the total addition amounts of acidic filler, benzoxazine and epoxy resin.

8. The method of claim 5, wherein the epoxy resin is selected from epoxy resins having the following structure: ##STR00015## wherein X.sub.1, X.sub.2 and X.sub.3 are each independently selected from ##STR00016## R.sub.4 is any one selected from the group consisting of substituted or unsubstituted C1-C5 linear alkyl and substituted or unsubstituted C1-05 branched alkyl; Y.sub.1 and Y.sub.2 are each independently any one selected from the group consisting of —CH.sub.2—, ##STR00017## R.sub.5 is any one selected from the group consisting of hydrogen atom, substituted or unsubstituted C1-C5 linear alkyl and substituted or unsubstituted C1-05 branched alkyl; and m is any integer of 1 to 10.

9. The method of claim 1, characterized in that the benzoxazine-containing resin composition comprises a phenolic resin; the amount of the phenolic resin is 0 to 40 parts by weight, based on 100 parts by weight of organic solids; the phenolic resin is any one selected from the group consisting of linear phenolic resin, bisphenol A phenolic resin, o-cresol phenolic resin, phosphorus-containing phenolic resin, and trifunctional phenolic resin, or a mixture of at least two of them.

10. The method of claim 1, characterized in that the benzoxazine-containing resin composition comprises a cyanate ester; the amount of the cyanate ester is 0 to 50 parts by weight, based on 100 parts by weight of organic solids; the cyanate ester is any one selected from the group consisting of bisphenol A cyanate ester, phenolic cyanate ester and dicyclopentadiene phenolic resin, or a mixture of at least two of them.

11. The method of claim 1, characterized in that the benzoxazine-containing resin composition comprises a thermosetting polyphenylene ether; the amount of the thermosetting polyphenylene ether is 0 to 40 parts by weight, based on 100 parts by weight of organic solids.

12. The method of claim 1, characterized in that the benzoxazine-containing resin composition comprises an active ester; the amount of the active ester is 0 to 40 parts by weight, based on 100 parts by weight of organic solids.

13. The method of claim 1, characterized in that the benzoxazine-containing resin composition comprises a styrene maleic anhydride copolymer; the amount of the styrene maleic anhydride copolymer is 0 to 40 parts by weight, based on 100 parts by weight of organic solids; the mass ratio of styrene to maleic anhydride in the styrene maleic anhydride copolymer is 9:1 to 6:4.

14. The method of claim 1, wherein the benzoxazine-containing resin composition comprises a flame retardant; the flame retardant is any one selected from the group consisting of decabromodiphenyl ether, octabromoether, hexabromocyclododecane, tetrabromobisphenol A, decabromodiphenyl ethane, triphenyl phosphate, tricresyl phosphate, trioctyl phosphate, diphenyl octyl phosphate, diphenyl isodecyl phosphate, tri(xylene) phosphate, diphenyl tert-butylphenyl phosphate, diphenyl isopropylphenyl phosphate, resorcinol bis[di(2,6-dimethylphenyl) phosphate], diphenyl isooctyl phosphate, aluminum methylethylphosphinate, aluminum diethylphosphinate, aluminum hydroxymethylphenylphosphinate, 3-hydroxyphenylphosphinyl-propanoic acid, hydroxyphenylphosphoryl propanoic acid, hydroxypropionyloxy phenylphosphonoyl, 2-carboxyethyl(phenyl)phosphinic acid, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and poly[nitrilo(diphenoxyphosphoranylidyne)], or a mixture of at least two of them.

15. A benzoxazine-containing resin composition, characterized in that it comprises a benzoxazine resin and an acidic filler, wherein the acidic filler is added in an amount of 5 to 200 parts by weight based on 100 parts by weight of organic solids in the benzoxazine-containing resin composition, wherein the benzoxazine is diamine benzoxazine; wherein the diamine benzoxazine resin monomer has a structure of formula (II) ##STR00018## wherein R.sub.3 is any one selected from the group consisting of ##STR00019##

16. The benzoxazine-containing resin composition of claim 15, characterized in that the acidic filler has a pH value between 2 and 6.

17. A prepreg comprising a resin composition of claim 15.

18. A laminate comprising at least one sheet of the prepreg of claim 17.

19. A printed circuit board comprising at least one sheet of the prepreg of claim 17.

Description

EMBODIMENTS

(1) The technical solutions of the present invention are further described by the following examples.

(2) The following descriptions are specific examples of the embodiments of the present invention, and it should be noted that those skilled in the art can make a number of improvements and modifications without departing from the principles of the examples of the present invention, and these improvements and modifications are also considered to fall within the protection scope of the present invention.

(3) The examples of the present invention will be described in further details with reference to the following examples. The embodiments of the present invention are not limited to the following specific examples. It is possible to appropriately change the examples without changing the scope of the claims.

(4) In the following, the “parts” represents “parts by weight” and “%” represents “% by weight”, unless otherwise specified.

(5) The materials and their trademark informations of the examples and comparative examples are as follows.

(6) (A) Acidic Fillers

(7) A-1: acidic filler, spherical silicon powder, pH: 4, purchased from Jiangsu Lianrui, model: DQ1030;

(8) A-2: acidic filler, quartz powder, pH: 3, purchased from Wuzhou Yingfeng Mining Company, model: 3000 mesh air flow quartz powder;

(9) A-3: acidic filler, mica powder, pH: 5, purchased from Anhui GeRui, model: GD-2;

(10) A-4: acidic filler, carbon black, pH: 3, purchased from Tianjin Xinglongtai Chemical Products Technology Co., Ltd.

(11) (B) Benzoxazine

(12) B-1: diphenol-type benzoxazine, bisphenol A benzoxazine, purchased from HUNSTMAN, model: LZ8290;

(13) B-2: diamine-type benzoxazine, 4,4′-diaminodiphenyl ether benzoxazine, purchased from Sichuan EM Technology Co., Ltd., model: D125;

(14) (C) Epoxy Resin

(15) C-1: DCPD epoxy resin, purchased from Japan DIC, model: HP-7200;

(16) C-2: biphenyl type epoxy resin: purchased from NIPPON KAYAKU, model: NC-3000H;

(17) D: linear phenolic, purchased from KOLON in Korea, model: KGH-3300;

(18) E: cyanate ester, purchased from LONZA, model: BA-3000S;

(19) F: thermosetting polyphenylene ether, purchased from SABIC, model: SA-90;

(20) G: active ester, purchased from SHINA in Korea, model: SHC-4314;

(21) H: styrene maleic anhydride copolymer, purchased from the Sartomer, model: EF-40;

(22) I: flame retardant, purchased from Otsuka Chemical Co., Ltd., model: SPB-100;

(23) J: accelerator, purchased from SHIKOKU, model: 2-MI.

(24) (K) Non-Acidic Filler

(25) K-1: non-acidic filler, spherical silicon powder, pH: 8, purchased from admatechs in Japan, model: SC2500-SEJ;

(26) K-2: non-acidic filler, alumina, pH: 9, purchased from Bengbu Xinyuan Materials Technology Co., Ltd., model: SJA-0051;

(27) K-3: non-acidic filler, calcium carbonate, pH: 9, purchased from Guangdong Zhongqi, model: 1500 mesh light calcium carbonate;

(28) K-4: non-acidic filler, talcum powder, pH: 8, purchased from Specialty Minerals Inc. in America, model: AG-609.

(29) The resin compositions of examples and comparative examples were used to prepare laminates for printed circuit according to the following method, and the properties of the prepared laminates were tested.

(30) The method for preparing a laminate for printed circuit includes: Preparing a laminate by bonding at least one sheet of the prepreg by heating and pressing; Bonding metal foils at one side or both sides of the laminate obtained in step {circle around (1)}; Laminating the resultant of step {circle around (2)} in a laminator.

(31) In step {circle around (2)}, eight prepregs and two sheets of metal foils in an amount of 1 ounce (having a thickness of 35 μm) were superimposed together.

(32) In step {circle around (3)}, the operating conditions for laminating are: heating rate is controlled to be 1.5-2.5° C./min when the material temperature is 80-140° C.; full pressure, which is about 350 psi, is applied when the temperature of the outer material layer is 80-100° C.; when curing, the material temperature is 195° C. and is kept for more than 60 min.

(33) Formulations and test results of properties of resin compositions provided in examples and comparative examples are shown in the following tables.

(34) TABLE-US-00001 TABLE 1 Comp. Comp. Comp. Comp. Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 1 Ex. 2 Ex. 3 Ex. 4 A-1 50 100 — — — 50 — — — — A-2 — — 50 — — — — — — — A-3 — — — 50 — — — — — — A-4 — — — — 50 — — — — — K-1 — — — — — — 50 — — — K-2 — — — — — — — 50 — — K-3 — — — — — — — — 50 — K-4 — — — — — — — — — 50 B-1 — — — — — 100 — — — — B-2 100 100 100 100 100 — 100 100 100 100 J Appro- Appro- Appro- Appropriate Appropriate Appropriate Appropriate Appropriate Appropriate Appropriate priate priate priate amount amount amount amount amount amount amount amount amount amount DSC 198 190 196 201 194 199 215 217 213 219 initial reaction temperature ° C. DSC 233 236 237 238 235 234 260 251 254 258 peak temperature ° C. Glass 215 219 216 215 210 209 206 205 209 202 transition temperature (DSC)° C. Bending 492 486 502 486 475 476 473 456 446 462 strength, MPa CTE 1.7 1.6 1.7 1.7 1.8 1.8 1.9 1.8 2 1.9 (50-260) Peeling 1.15-1.21 1.16-1.22 1.13-1.19 1.14-1.20 1.17-1.21 1.14-1.19 1.02-1.18 1.04-1.17 1.09-1.20 1.01-1.12 strength

(35) TABLE-US-00002 TABLE 2 Ex. 7 Ex. 8 Ex. 9 Ex. 10 Ex. 11 Ex. 12 A-1 30 30 30 30 30 30 B-2 50 50 50 50 50 50 C-1 50 — 30 30 30 — C-2 — 50 — — — — D — — 20 — — — E — — — 20 — — F — — — — 20 — G — — — — — 50 H — — — — — — I 10 10 10 10 10 10 J Appropriate Appropriate Appropriate Appropriate Appropriate Appropriate amount amount amount amount amount amount K-1 — — — — — — DSC initial 152 163 166 162 155 152 reaction temperature ° C. DSC peak 234 232 238 236 237 233 temperature ° C. Glass 196 194 199 213 209 190 transition temperature (DSC)° C. Bending 482 479 489 493 488 465 strength, MPa CTE 1.8 1.9 2 1.8 1.8 2 (50-260) Peeling 1.14-1.20 1.16-1.21 1.18-1.22 1.16-1.22 1.17-1.19 1.16-1.23 strength Comp. Comp. Comp. Comp. Ex. 13 Ex. 14 Ex. 5 Ex. 6 Ex. 7 Ex. 8 A-1 30 15 — — — — B-2 50 50 50 50 50 50 C-1 30 50 50 30 — 30 C-2 — — — — — — D — — — — — — E — — — 20 — — F — — — — — — G 10 — — — 50 10 H 10 — — — — 10 I 10 10 10 10 10 10 J Appropriate Appropriate Appropriate Appropriate Appropriate Appropriate amount amount amount amount amount amount K-1 — 15 30 30 30 30 DSC initial 160 178 209 206 207 203 reaction temperature ° C. DSC peak 237 243 254 256 260 257 temperature ° C. Glass 196 195 191 182 182 189 transition temperature (DSC)° C. Bending 475 462 465 476 462 446 strength, MPa CTE 2 1.9 2 2.1 2.4 2.2 (50-260) Peeling 1.14-1.18 1.08-1.17 1.02-1.13 1.03-1.12 1.02-1.14 1.01-1.10 strength

(36) Tested items of properties and specific methods thereof are as follows:

(37) (a) Initial Reaction Temperature

(38) The initial reaction temperature was tested according to differential scanning calorimetry (DSC) under nitrogen atmosphere with a heating rate of 10° C./min.

(39) (b) Glass Transition Temperature

(40) The glass transition temperature was tested according to differential scanning calorimetry (DSC) method as specified in IPC-TM-650 2.4.25.

(41) (c) Bending Strength

(42) The bending strength was tested according to IPC-TM-650 2.4.4 B method.

(43) (d) CTE

(44) The coefficient of thermal expansion was tested according to IPC-TM-650 2.4.41 method.

(45) (e) Peeling Strength (PS)

(46) The peeling strength of the metal overlayer was tested under the conditions of “after thermal stress” in the IPC-TM-650 2.4.8 method.

(47) From the performance data of each of the examples and comparative examples in Table 1, it can be seen that:

(48) for the test results of examples 1-6 and comparative examples 1-4, examples 1-6 with the addition of acidic filler can remarkably reduce the reaction temperature of the resin composition compared with comparative examples 1-4 with the addition of ordinary non-acidic filler, and the initial reaction temperature in examples 1-6 is only 194-201° C. while it is at least 213° C. in comparative examples 1-4;
in addition, laminates obtained in examples 1-6 have higher peeling strength stability, and the difference in peeling strength was only 0.06 to 0.08, while it can be 0.11 or more in comparative examples 1-4 showing a deteriorated peeling strength stability;
furthermore, laminates obtained in examples 1-6 have higher glass transition temperature, and also lower coefficient of thermal expansion and high bending strength;
moreover, from the comparison of example 1 and example 2, it can be seen that the addition of more acidic fillers further can improve glass transition temperature, reduce curing temperature and coefficient of thermal expansion of the resin composition.

(49) From the performance data of each of the examples and comparative examples in Table 2, it can be seen that: for examples 7-14 and comparative examples 5-8, the addition of phenolic resin, cyanate ester, thermosetting polyphenylene ether, active ester and styrene maleic anhydride copolymer in the benzoxazine systems containing acidic filler can also reduce curing reaction temperature, improve peeling strength stability, improve glass transition temperature of the resin composition, and reduce coefficient of thermal expansion of the resin composition.

(50) As described above, the laminate prepared by the resin composition into which an acidic filler is added of the present invention has more stable peeling strength, higher glass transition temperature, high bending strength, lower coefficient of thermal expansion, and is suitable for use in the fields which requires a thermosetting resin with high modulus, high strength, low thermal expansion and others.

(51) The applicant states that: the present application illustrates the detailed method of the present invention by the above examples, but the present invention is not limited to the detailed method, that is, it does not mean that the present invention must be conducted relying on the above detailed method. Those skilled in the art should understand that any modifications to the present invention, any equivalent replacements of each raw material of the present invention and the additions of auxiliary ingredients, the selections of specific embodiments and the like all fall into the protection scope and the disclosure scope of the present invention.