Resin composition and article made therefrom

Abstract

The present disclosure provides a resin composition which comprises: 90 parts by weight of vinyl-containing polyphenylene oxide resin; 35 to 70 parts by weight of chemically synthetic silica; and 10 to 30 parts by weight of spherical inorganic fillers, wherein the spherical inorganic fillers include spherical boron nitride, spherical hollow boron silicate or a combination thereof. The present disclosure also provides an article made from the resin composition, wherein the article includes a prepreg, a resin film, a laminate or a printed circuit board. The resin composition of the invention can make the article made therefrom achieve better peeling strength, dielectric constant, dissipation factor, no weave exposure produced and no stripes of branch-like pattern produced at the laminate edge.

Claims

1. A resin composition, comprising: 90 parts by weight of vinyl-containing polyphenylene oxide resin; 35 to 70 parts by weight of chemically synthetic silica; and 10 to 30 parts by weight of spherical inorganic fillers, wherein the spherical inorganic fillers comprise spherical boron nitride, spherical hollow boron silicate or a combination thereof.

2. The resin composition according to claim 1, wherein the vinyl-containing polyphenylene oxide resin comprises vinylbenzyl polyphenylene oxide resin, methacrylate polyphenylene oxide resin, allyl polyphenylene oxide resin, vinylbenzyl-modified bisphenol A polyphenylene oxide, vinyl chain-extended polyphenylene oxide or a combination thereof.

3. The resin composition according to claim 1, wherein the chemically synthetic silica comprises silica synthesized by chemical method, having a median particle diameter (D50) of 0.01 to 9 micrometer.

4. The resin composition according to claim 1, wherein the chemically synthetic silica is selected from silica synthesized by chemical method, made by microemulsion.

5. The resin composition according to claim 1, wherein the spherical boron nitride comprises spherical boron nitride with an aspect ratio of 1 to 2.

6. The resin composition according to claim 1, wherein the spherical boron nitride comprises spherical boron nitride agglomerates by agglomerating hexagonal boron nitride sheets.

7. The resin composition according to claim 1, wherein the spherical hollow boron silicate comprises spherical hollow boron silicate with a density of 0.12 to 0.6 g/cm.sup.3.

8. The resin composition according to claim 1, further comprising maleimide resin, small molecular vinyl compound, acrylate, polyolefin, epoxy resin, cyanate ester resin, phenolic resin, benzoxazine resin, styrene maleic anhydride, polyester resin, amine curing agent, polyamide resin, polyimide resin or a combination thereof.

9. The resin composition according to claim 1, further comprising flame retardant, inorganic fillers other than the spherical boron nitride and the spherical hollow boron silicate, curing accelerator, solvent, silane coupling agent, coloring agent, toughening agent or a combination thereof.

10. An article, which is made from the resin composition according to claim 1, wherein the article comprises a prepreg, a resin film, a laminate or a printed circuit board.

11. The article according to claim 10, which has one, more or all of the following properties: a peel strength as measured by reference to the method of IPC-TM-650 2.4.8 is greater than or equal to 3.00 lb/in; a dissipation factor at a frequency of 10 GHz as measured by reference to the method of JIS C2565 is less than or equal to 0.0030; a dielectric constant at a frequency of 10 GHz as measured by reference to the method of JIS C2565 is less than or equal to 3.40; a surface of laminate appearance is flat and smooth without producing a weave exposure; no branch-like pattern is produced at a laminate edge after lamination.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a schematic view of a copper-free laminate having weave exposure.

(2) FIG. 2 is a schematic view of a copper-free laminate having a branch-like pattern.

(3) FIG. 3 is a schematic view of a normal copper-free laminate having no branch-like pattern.

DETAILED DESCRIPTION OF THE INVENTION

(4) To facilitate understanding of the object, characteristics and effects of this present disclosure, the following embodiments for the detailed description of the present disclosure are provided.

(5) Raw Materials

(6) SA-9000: methacrylate polyphenylene oxide resin, available from SABIC.

(7) OPE-2st: OPE-2st 2200, vinylbenzyl polyphenylene oxide resin, available from Mitsubishi Gas corporation.

(8) Ricon 257: styrene-butadiene-divinyl benzene terpolymer, available from Cray Valley.

(9) PQ-60: p-xylylene-bis-diphenylphosphine oxide, available from Chin Yee Chemical Industries Co., Ltd.

(10) Chemically synthetic spherical silica A: having a median particle diameter about 1.5±0.5 micrometer, made by microemulsion, chemically synthetic spherical silica with a surface treating by silane coupling agents, available from Ginet new material technology Co., Ltd.

(11) Chemically synthetic spherical silica B: having a median particle diameter about 1.5±0.5 micrometer, chemically synthetic spherical silica made by microemulsion, available from Ginet new material technology Co., Ltd.

(12) PTX60: spherical boron nitride agglomerate with an aspect ratio of 1.0 to 1.5, available from MOMENTIVE company.

(13) iM16K: spherical hollow boron silicate with a density of about 0.46 g/cm.sup.3, available from 3M.

(14) 525ARI: fused silica with an irregular shape, available from Sibelco.

(15) UHP-2: boron nitride sheets, available from Showa Denko corporation.

(16) Kamin 2000C: kaolin, available from KaMin company.

(17) 25B: 2,5-dimethyl-2,5-di(t-butyl peroxy)hexyne-3) peroxide, available from NOF corporation.

(18) Toluene: available from Chambeco Group.

(19) Methyl ethyl ketone: the sources are not limited.

(20) The specimens (samples) are prepared by referring to the methods as follows, and then the characteristics are analyzed according to the specific conditions.

(21) 1. Prepregs: the resin compositions of Examples E1-E6 shown as the following Table 1, the resin compositions of Examples E7-E12 shown as the following Table 2, the resin compositions of Comparative Examples C1-C7 shown as the following Table 3 and the resin compositions of Comparative Examples C8-C14 shown as the following Table 4 are selected respectively. Each of the resin compositions is added into a stirring tank and well-mixed to form a varnish, which is loaded to an impregnation tank and then a fiberglass fabric (e.g., style 2116 and 1080 L-glass fiber fabric, available from Asahi company) is impregnated into the impregnation tank to adhere the resin composition onto the fiberglass fabric, followed by heating and baking at 140° C. for 4 minutes to obtain a prepreg.

(22) TABLE-US-00001 TABLE 1 E1 E2 E3 E4 E5 E6 vinyl- SA-9000 60 60 60 60 60 60 containing OPE-2st 2200 30 30 30 30 30 30 polyphenylene oxide resin polyolefin Ricon 257 10 10 10 10 10 10 flame retardant PQ-60 30 30 30 30 30 30 chemically chemically synthetic 45 45 45 45 45 30 synthetic silica spherical silica A chemically synthetic 15 spherical silica B spherical PTX60 15 10 30 10 15 inorganic filler iM16K 15 5 fused silica 525ARI non-spherical UHP-2 inorganic filler Kamin 2000C curing 25B 0.2 0.2 0.2 0.2 0.2 0.2 accelerator solvent toluene 70 70 70 70 70 70 methyl ethyl ketone 10 10 10 10 10 10

(23) TABLE-US-00002 TABLE 2 E7 E8 E9 E10 E11 E12 vinyl- SA-9000 60 60 60 60 60 55 containing OPE-2st 2200 30 30 30 30 30 35 polyphenylene oxide resin polyolefin Ricon 257 10 10 8 15 10 10 flame retardant PQ-60 30 30 30 30 35 25 chemically chemically synthetic 35 70 45 45 45 40 synthetic silica spherical silica A chemically synthetic spherical silica B spherical PTX60 15 15 15 15 15 15 inorganic filler iM16K fused silica 525ARI non-spherical UHP-2 inorganic filler Kamin 2000C curing 25B 0.2 0.2 0.2 0.2 0.2 0.1 accelerator solvent toluene 70 70 70 70 70 55 methyl ethyl ketone 10 10 10 10 10 25

(24) TABLE-US-00003 TABLE 3 C1 C2 C3 C4 C5 C6 C7 vinyl- SA-9000 60 60 60 60 60 60 60 containing OPE-2st 2200 30 30 30 30 30 30 30 polyphenylene oxide resin polyolefin Ricon 257 10 10 10 10 10 10 10 flame retardant PQ-60 30 30 30 30 30 30 30 chemically chemically synthetic 45 45 45 45 synthetic silica spherical silica A chemically synthetic spherical silica B spherical PTX60 15 40 inorganic filler iM16K fused silica 525ARI 45 15 45 45 non-spherical UHP-2 15 15 inorganic filler Kamin 2000C 15 15 curing 25B 0.2 0.2 0.2 0.2 0.2 0.2 0.2 accelerator solvent toluene 70 70 70 70 70 70 70 methyl ethyl ketone 10 10 10 10 10 10 10

(25) TABLE-US-00004 TABLE 4 C8 C9 C10 C11 C12 C13 C14 vinyl- SA-9000 60 60 60 60 60 60 60 containing OPE-2st 2200 30 30 30 30 30 30 30 polyphenylene oxide resin polyolefin Ricon 257 10 10 10 10 10 10 10 flame retardant PQ-60 30 30 30 30 30 30 30 chemically chemically synthetic 60 0 0 0 45 45 45 synthetic silica spherical silica A chemically synthetic spherical silica B spherical PTX60 0 60 5 inorganic filler iM16K 60 40 5 fused silica 525ARI 60 non-spherical UHP-2 inorganic filler Kamin 2000C curing 25B 0.2 0.2 0.2 0.2 0.2 0.2 0.2 accelerator solvent toluene 70 70 70 70 70 70 70 methyl ethyl ketone 10 10 10 10 10 10 10

(26) All examples E1-E12 of Table 1 and Table 2 comprise polyolefin (Ricon 257) as crosslinking agent, but the invention is not limited thereto. In an embodiment, the resin composition of the invention comprises polyolefin or other crosslinking agent. In an embodiment, the resin composition of the invention fails to comprise polyolefin or other crosslinking agent. In an implementation, polyolefin or other crosslinking agent is added in the step of “each of the resin compositions is added into a stirring tank and well-mixed to form a varnish”.

(27) All examples E1-E12 of Table 1 and Table 2 comprise p-xylylene-bis-diphenylphosphine oxide (PQ-60) as flame retardant, but the invention is not limited thereto. In an embodiment, the resin composition of the invention comprises p-xylylene-bis-diphenylphosphine oxide or other flame retardant. In an embodiment, the resin composition of the invention fails to comprise p-xylylene-bis-diphenylphosphine oxide or other flame retardant. In an implementation, p-xylylene-bis-diphenylphosphine oxide or other flame retardant is added in the step of “each of the resin compositions is added into a stirring tank and well-mixed to form a varnish”.

(28) All examples E1-E12 of Table 1 and Table 2 comprise initiator (25B) as curing accelerator, but the invention is not limited thereto. In an embodiment, the resin composition of the invention comprises 25B or other curing accelerator. In an embodiment, the resin composition of the invention fails to comprise 25B or other curing accelerator. In an implementation, 25B or other curing accelerator is added in the step of “each of the resin compositions is added into a stirring tank and well-mixed to form a varnish”.

(29) All examples E1-E12 of Table 1 and Table 2 comprise toluene and methyl ethyl ketone (MEK) as solvent, but the invention is not limited thereto. In an embodiment, the resin composition of the invention comprises toluene or methyl ethyl ketone. In an embodiment, the resin composition of the invention fails to comprise toluene or methyl ethyl ketone, and is changed to use other solvents. In an implementation, toluene and methyl ethyl ketone or other solvents are simultaneously added in the step of “each of the resin compositions is added into a stirring tank and well-mixed to form a varnish”.

(30) 2. Copper-containing laminate (it is also called copper clad laminate, 8-ply, formed by lamination of eight prepregs): Two 18 μm HVLP (Hyper Very Low Profile) copper foils and eight prepregs obtained from 2116 L-fiberglass fabrics impregnated with each specimen (each Example or Comparative Example) and having a resin content of about 55% were prepared and stacked in the order of copper foil, eight prepregs and copper foil, followed by lamination under vacuum at 30 kgf/cm.sup.2 pressure and 200° C. temperature for 120 minutes to form a copper-containing laminate. Insulation layers were formed by laminating eight sheets of prepreg between the two copper foils, and the resin content of the insulation layers is about 55%.

(31) 3. Copper-containing laminate (it is also called copper clad laminate, 2-ply, formed by lamination of two prepregs): Two 18 μm HVLP (Hyper Very Low Profile) copper foils and two prepregs obtained from 1080 L-fiberglass fabrics impregnated with each specimen (each Example or Comparative Example) and having a resin content of about 70% were prepared and stacked in the order of copper foil, two prepregs and copper foil, followed by lamination under vacuum at 30 kgf/cm.sup.2 pressure and 200° C. temperature for 120 minutes to form a copper-containing laminate. Insulation layers were formed by laminating two sheets of prepreg between the two copper foils, and the resin content of the insulation layers is about 70%.

(32) 4. Copper-free laminate (8-ply, formed by lamination of eight prepregs): Each aforesaid copper-containing laminate (8-ply) was etched to remove the two copper foils to obtain a copper-free laminate (8-ply) formed by laminating eight sheets of prepreg and having a resin content of about 55%.

(33) 5. Copper-free laminate (2-ply, formed by lamination of two prepregs): Each aforesaid copper-containing laminate (2-ply) was etched to remove the two copper foils to obtain a copper-free laminate (2-ply) formed by laminating two sheets of prepreg and having a resin content of about 70%.

(34) Peeling Strength (P/S)

(35) The copper-containing laminate (formed by lamination of eight prepregs) was selected and cut into a rectangle specimen with a width of 24 mm and a length of greater than 60 mm, and the surface copper foil was etched and only a strip of copper foil with a width of 3.18 mm and a length of greater than 60 mm was left, and tested by using a universal tensile strength tester by reference to the method of IPC-TM-650 2.4.8 at room temperature (about 25° C.), the specimen was tested to measure the force, unit being lb/in, required to separate the copper foil from a surface of the insulation layer of the laminate. In the present field, the larger peeling strength, the better a copper-containing laminate is. For a copper clad laminate having a measured value of dissipation factor of less than 0.0040 at a frequency of 10 GHz, a difference in peeling strength of greater than 0.1 lb/in represents a significant difference.

(36) Dissipation Factor (Df)

(37) In dissipation factor measurement, the copper-free laminate (formed by lamination of two prepregs, and having a resin content of about 70%) was selected as a specimen. Each specimen is tested by using a microwave dielectrometer available from AET Corp. by reference to the method of JIS C2565 at a frequency of 10 GHz, at room temperature (about 25° C.). Lower dissipation factor represents better dielectric properties of the specimen. For a copper clad laminate having a measured value of dissipation factor of less than 0.0040 at a frequency of 10 GHz, a difference in Df of less than 0.0001 represents there is no significant difference in dissipation factor of laminates (no significant difference represents that there is no significant technical difficulty), a difference in Df of greater than or equal to 0.0001 represents a significant difference in dissipation factor of different laminates.

(38) Dielectric Constant (Dk)

(39) In dielectric constant measurement, the copper-free laminate (formed by lamination of two prepregs, and having a resin content of about 70%) was selected as a specimen. Each specimen is tested by using a microwave dielectrometer available from AET Corp. by reference to the method of JIS C2565 at a frequency of 10 GHz, at room temperature (about 25° C.). Lower dielectric constant represents better dielectric properties of the specimen. For a copper clad laminate having a measured value of dissipation factor of less than 0.0040 at a frequency of 10 GHz, a difference in Dk of less than 0.01 represents there is no significant difference in dissipation factor of laminates (no significant difference represents that there is no significant technical difficulty), a difference in Dk of greater than or equal to 0.01 represents a significant difference in dissipation factor of different laminates.

(40) Laminate Appearance Inspection

(41) Visually inspect, with naked eyes, the surface of each copper-free laminate (formed by lamination of eight prepregs) to determine whether it is flat and smooth or having weave exposure. The planar size of the copper-free laminate is 9×12 inch. If at least one weave exposure greater than 1×1 cm.sup.2 on the copper-free laminate is found, it is determined as weave exposure. In other words, a laminate with flat and smooth surface is not designated as weave exposure. Weave exposure is as known by a skilled person in the art, for example FIG. 1. Laminates having weave exposure cannot be subject to subsequent processes for producing multi-layer boards or circuit boards.

(42) Branch-Like Pattern Formation at Laminate Edge After Lamination (Branch-like Pattern)

(43) The surface of the insulation layer of the copper-free laminate (formed by lamination of eight prepregs) was examined with naked eyes to determine whether branch-like pattern was formed at the laminate edge, which represents poor compatibility of the resin composition or high flowability variation that causes inhomogeneity. A schematic view of a copper-free laminate having branch-like pattern is shown as FIG. 2, calculating the number of stripes in branch-like pattern, the more number of stripes represents the more serious the branch-like pattern, and a schematic view of a normal copper-free laminate having no branch-like pattern is shown as FIG. 3. Presence of branch-like pattern will cause several drawbacks including inconsistent properties (poor reliability) of circuit boards made therefrom and significantly lowered yield, such as poor dielectric properties, low thermal resistance, inconsistent thermal expansion or poor interlayer adhesion. Therefore, laminates having branch-like pattern must be scrapped directly.

(44) The evaluation of the results of Examples E1 to E12 and Comparative Examples C1 to C14 is shown in Table 5 to Table 8 below.

(45) TABLE-US-00005 TABLE 5 properties unit E1 E2 E3 E4 E5 E6 HVLP P/S lb/in 3.15 3.25 3.26 3.04 3.21 3.10 (Hoz) Df@10 GHz, none 0.0027 0.0029 0.0028 0.0026 0.0028 0.0027 L-glass RC = 70% Dk@10 GHz, none 3.15 3.05 3.13 3.26 3.11 3.05 L-glass RC = 70% laminate none none none none none none none appearance (weave exposure) branch-like stripes 0 0 0 0 0 0 patterns formed at the laminate edge (branch- like pattern)

(46) TABLE-US-00006 TABLE 6 properties unit E7 E8 E9 E10 E11 E12 HVLP P/S lb/in 3.22 3.02 3.16 3.09 3.08 3.25 (Hoz) Df@10 GHz, none 0.0027 0.0027 0.0029 0.0026 0.0027 0.0028 L-glass RC = 70% Dk@10 GHz, none 3.09 3.35 3.17 3.10 3.18 3.16 L-glass RC = 70% laminate none none none none none none none appearance (weave exposure) branch-like stripes 0 0 0 0 0 0 patterns formed at the laminate edge (branch- like pattern)

(47) TABLE-US-00007 TABLE 7 properties unit C1 C2 C3 C4 C5 C6 C7 HVLP P/S lb/in 3.11 2.81 3.29 2.96 3.25 3.15 3.27 (Hoz) Df@10 GHz, none 0.0048 0.0026 0.0049 0.0027 0.0046 0.0049 0.0058 L-glass RC = 70% Dk@10 GHz, none 3.21 3.41 3.35 3.16 3.45 3.28 3.52 L-glass RC = 70% laminate none none weave none none none none none appearance exposure (weave exposure) branch-like stripes 5 0 0 12 6 12 27 patterns formed at the laminate edge (branch- like pattern)

(48) TABLE-US-00008 TABLE 8 properties unit C8 C9 C10 C11 C12 C13 C14 HVLP P/S lb/in 2.89 2.70 3.22 3.21 2.95 3.36 3.37 (Hoz) Df@10 GHz, none 0.0028 0.0026 0.0034 0.0056 0.0031 0.0026 0.0026 L-glass RC = 70% Dk@10 GHz, none 3.28 3.37 3.02 3.17 3.12 3.39 3.41 L-glass RC = 70% laminate none none weave weave none weave none none appearance exposure exposure exposure (weave exposure) branch-like stripes 0 0 0 6 0 0 0 patterns formed at the laminate edge (branch- like pattern)

(49) The Evaluation of the Results of Examples and Comparative Examples

(50) It can be known from the comparison of Examples E1 to E12 and Comparative Examples C1 to C14 that Comparative Example C1 uses fused silica with an irregular shape instead of spherical chemically synthetic silica so as to demonstrate poor dissipation factor (Df@10 GHz=0.0048), and produce 5 stripes of branch-like patterns at the laminate edge;

(51) Comparative Example C2 uses excessive spherical boron nitride (the amount of spherical boron nitride being 40 parts by weight) so as to demonstrate poor peeling strength (P/S=2.81 lb/in), poor dielectric constant (Dk@10 GHz=3.41) and produce weave exposure; Comparative Example C12 uses excessive spherical hollow boron silicate (the amount of spherical hollow boron silicate being 40 parts by weight) so as to produce weave exposure; Comparative Example C13 uses less spherical boron nitride (the amount of spherical boron nitride being 5 parts by weight) so as to demonstrate poor dielectric constant (Dk@10 GHz=3.39); C14 uses less spherical hollow boron silicate (the amount of spherical hollow boron silicate being 5 parts by weight) so as to demonstrate poor dielectric constant (Dk@10 GHz=3.41);

(52) Comparative Example C3 uses fused silica with an irregular shape instead of spherical boron nitride, Comparative Example C4 uses boron nitride sheets instead of spherical boron nitride, and Comparative Example C5 uses kaolin instead of spherical boron nitride, so that C3 demonstrates poor dissipation factor (Df@10 GHz=0.0049) and dielectric constant (Dk@10 GHz=3.35); C4 produces 12 stripes of branch-like patterns at the laminate edge; C5 demonstrates poor dissipation factor (Df@10 GHz=0.0046), dielectric constant (Dk@10 GHz=3.45) and produces 6 stripes of branch-like patterns at the laminate edge;

(53) Comparative Example C8 only uses chemically synthetic silica and fails to use spherical boron nitride so that C8 demonstrates poor peeling strength (P/S=2.89 lb/in); Comparative Example C9 only uses spherical boron nitride and fails to use chemically synthetic silica so that C9 demonstrates poor peeling strength (P/S=2.70 lb/in), dielectric constant (Dk@10 GHz=3.37) and produces weave exposure;

(54) Comparative Example C10 only uses spherical hollow boron silicate and fails to use chemically synthetic silica so that C10 produces weave exposure.

(55) It can be known from Table 5 to Table 8 and the above description that Examples E1 to E12 can simultaneously achieve better peeling strength (P/S>3.00 lb/in), for example between 3.02 lb/in and 3.26 lb/in (including two ends of 3.02 lb/in and 3.26 lb/in), dissipation factor (Df@10 GHz<0.0030), for example between 0.0026 and 0.0029 (including two ends of 0.0026 and 0.0029), dielectric constant (Dk@10 GHz<3.40), for example between 3.05 and 3.35 (including two ends of 3.05 and 3.35), no weave exposure produced, and no stripes of branch-like patterns produced at the laminate edge (branch-like patterns formed at the laminate edge=0). Conversely, one or more of the above properties of Comparative Examples C1 to C14 cannot achieve the above effect.

(56) While the present disclosure has been described by means of specific embodiments, numerous modifications and variations could be made thereto by those skilled in the art without departing from the scope and spirit of the present disclosure set forth in the claims. Therefore, the scope of the invention is indicated by the appended claims.