Vinyl-modified maleimide, composition and article made thereby

Abstract

The present invention discloses vinyl-modified maleimide, a resin composition using the same and a preparation thereof. The vinyl-modified maleimide has better solvent selectivity and solvent compatibility. The obtained preparation can satisfy the properties of no crack between multilayer boards and high frequency and low dielectric properties maintained after moisture absorption.

Claims

1. A vinyl-modified maleimide made from the reaction of 4-vinylbenzyl amine with aliphatic long chain maleimide, wherein the aliphatic long chain maleimide comprises an aliphatic long chain maleimide having a structure unit represented by one of the following formula (6) and formula (7) ##STR00010## wherein n=1 to 10; or ##STR00011## wherein n=1 to 10, and the reaction ratio (part by weight) of the 4-vinylbenzyl amine to the aliphatic long chain maleimide is 20:80 to 35:65.

2. A resin composition, comprising the vinyl-modified maleimide of claim 1 and at least one cross-linking agent.

3. The resin composition of claim 2, wherein the cross-linking agent comprises at least one of divinylbenzene, bis(vinylbenzyl) ether, 1,2-bis(vinylphenyl)ethane, triallyl isocyanurate, triallyl cyanurate, cyanate ester, isocyanate ester, 1,2,4-trivinylcyclohexane, styrene, acrylate, polyphenylene oxide resin, polyamide, polyimide, styrene maleic anhydride copolymer, polyester, an olefin polymer, an epoxy resin and an anhydride curing agent, a prepolymer or a combination thereof.

4. The resin composition of claim 2, further comprising a flame retardant, a curing accelerator, an inorganic filler, a surfactant, a toughener, a solvent or a combination thereof.

5. The resin composition of claim 2, wherein the resin composition comprises 100 parts by weight of the vinyl-modified maleimide and 1 to 500 parts by weight of the cross-linking agent.

6. An article made from the resin composition of claim 2, comprising a resin film, a prepreg, a resin coated copper, a laminate or a printed circuit board.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is the FTIR spectrogram comparing vinyl-modified maleimide product A of Preparation Example 1 with reactant BMI-3000, wherein T % represents transmittance, and cm.sup.−1 represents wave number.

DETAILED DESCRIPTION OF THE INVENTION

(2) To allow a person skilled in the art to understand the features and effects of the present invention, terms and phrases used in the specification and claims are illustrated and defined in the following. Unless otherwise indicated, all technical and scientific terms used herein should have common meanings known by a person skilled in the art while the definitions in the specification should be based when conflict occurs.

(3) In the present application, terms “comprising,” “including,” “having,” “containing” and other similar terms all belong to open-ended transitional phrases and intend to encompass other non-exclusive components. For example, one composition or preparation containing a plurality of elements should not be limited to the listed elements, but also can include other conventional elements that are not specifically listed. In addition, unless expressly indicated to the contrary, term “or” refers to inclusive “or” rather than exclusive “or.” For example, any one of the following situations satisfies the condition “A or B.” A is true (or present) and B is false (or not present); A is false (or not present) and B is true (or present); and both A and B are true (or present). In addition, in the present application, terms “comprising,” “including,” “having” and “containing” should be interpreted to specifically disclose and encompass “consisting of . . . ” (close-ended phrase) and “essentially consisting of . . . ” (semi-close ended phrase).

(4) In the present application, features or conditions defined by numeral ranges or percentage ranges are for concise and convenience. As such, the description of numeral ranges or percentage ranges should be treated to encompass and specifically disclose individual numbers in all possible sub-ranges and ranges, especially integer numbers. For example, the range description of “1 to 8” should be treated to specifically disclose all sub-ranges, such as 1 to 7, 2 to 8, 2 to 6, 3 to 6, 4 to 8, and 3 to 8, especially all sub-ranges defined by integer numbers, and should be treated to specifically disclose individual numbers in the range, such as 1, 2, 3, 4, 5, 6, 7 and 8. Unless otherwise indicated, the above definition applies to all content of the present application, regardless of the range.

(5) If numbers or other numeral values or parameters are presented in a range, a preferable range or a series of upper limits and lower limits, it should be interpreted that all ranges constituted by any pairs of the upper limit (or preferable value) of a range and the lower limit (or preferable value) of a range are specifically disclosed, despite of whether the ranges are respectively disclosed or not. In addition, when the range of the numeral numbers is referred to herein, unless otherwise indicated, the range shall include its endpoints and all integers and fractions within the range.

(6) In the present application, under the condition that the purposes of the present invention can be achieved, numeral values should be interpreted to have the accuracy of the significant digits of the numeral values. For example, number 40.0 should be interpreted to encompass the range of 39.50 to 40.49.

(7) In the present application, for the situation that a Markush group and optional terms are used to describe the features or examples of the present application, a person skilled in the art should understand that sub-groups or any individual members in the Markush group and option list can also be used to describe the present invention. For example, if X is described to be “selected from the group consisting of X1, X2 and X3,” and Y is described to be “selected from the group consisting of Y1, Y2 and Y3,” it should include the situations that X is X1, X is X1 and/or X2, and X is X1 or X2 or X3 while Y is Y1 or Y2 or Y3.

(8) The following embodiments are illustrative only, but are not intended to limit the present invention and uses thereof. In addition, the present application is not bounded by any theories described in the prior art, the summary of the present invention or the following embodiments.

Preparation Example: Synthesis of Vinyl-Modified Maleimide

Preparation Example 1-1. Synthesis of Vinyl-Modified Maleimide of the Present Invention

(9) 100 g of BMI-3000 light yellow solid powder was added to 100 g of a toluene solvent in a glass stirring reaction tank, heated to 50° C. and stirred until the solid powder was completely dissolved to form a brown clear solvent. 15 g of 4-vinylbenzyl amine (VBA) was further added to the reaction tank and stirred until VBA was completely mixed. The solution was heated to 95° C. under stirring for 4 hours. Then, the solution was cooled to room temperature to obtain a product, vinyl-modified maleimide solution. The solvent can be removed from this solution by using conventional techniques (for example vacuum distillation) to give a solid product A (Product A).

(10) Product A made from Preparation Example 1-1 and material BMI-3000 were analyzed by Fourier transform infrared spectroscopy (FTIR). The results shown in FIG. 1 reveal that the product of Preparation Example 1-1 has a vinyl characteristic peak from vinylbenzyl at 920.15 cm.sup.−1, suggesting that the obtained product is vinyl-modified maleimide.

Preparation Example 1-2. Synthesis of Vinyl-Modified Maleimide of the Present Invention

(11) The method for preparing vinyl-modified maleimide is the same as that in Preparation Example 1-1, except that 100 g of BMI-3000 and 15 g of 4-vinylbenzyl amine in Preparation Example 1-1 were replaced with 66.5 g of BMI-3000 and 33.5 g of 4-vinylbenzyl amine, respectively. The product made from Preparation Example 1-2 is Product B.

Preparation Example 1-3. Synthesis of Vinyl-Modified Maleimide of the Present Invention

(12) The method for preparing vinyl-modified maleimide is the same as that in Preparation Example 1-1, except that 100 g of BMI-3000 and 15 g of 4-vinylbenzyl amine in Preparation Example 1-1 were replaced with 80 g of BMI-3000 and 20 g of 4-vinylbenzyl amine, respectively. The product made from Preparation Example 1-3 is Product C.

Preparation Example 1-4. Synthesis of Vinyl-Modified Maleimide of the Present Invention

(13) The method for preparing vinyl-modified maleimide is the same as that in Preparation Example 1-1, except that 100 g of BMI-3000 and 15 g of 4-vinylbenzyl amine in Preparation Example 1-1 were replaced with 66.5 of BMI-1700 and 33.5 g of 4-vinylbenzyl amine, respectively. The product made from Preparation Example 1-4 is Product D.

Preparation Example 1-5. Synthesis of Vinyl-Modified Maleimide of the Present Invention

(14) The method for preparing vinyl-modified maleimide is the same as that in Preparation Example 1-1, except that 100 g of BMI-3000 and 15 g of 4-vinylbenzyl amine in Preparation Example 1-1 were replaced with 66.5 g of BMI-70 and 33.5 g of 4-vinylbenzyl amine. The product made from Preparation Example 1-4 is Product E.

Preparation Example 1-6. Synthesis of Terminal Hydroxyl-Modified Maleimide

(15) The method used in this Example is the same as that in Preparation Example 1-2, except that 33.5 g of 4-vinylbenzyl amine in Preparation Example 1-2 was replaced with 33.5 g of 2,2′-diallyl bisphenol A. The product made from Preparation Example 1-6 is Product F.

Preparation Example 1-7. Synthesis of Terminal Hydroxyl-Modified Maleimide

(16) The method used in this Example is the same as that in Preparation Example 1-2, except that 33.5 g of 4-vinylbenzyl amine in Preparation Example 1-2 was replaced with 33.5 g of p-aminophenol. The product made from Preparation Example 1-7 is Product G.

Preparation Example 1-8. Synthesis of Terminal Amino-Modified Maleimide

(17) The method used in this Example is the same as that in Preparation Example 1-2, except that 33.5 g of 4-vinylbenzyl amine in Preparation Example 1-2 was replaced with 33.5 g of 4,4′-oxydianiline(ODA). The product made from Preparation Example 1-8 is Product H.

(18) Product A, Product B, Product C and Product D from Preparation Examples 1-1 to 1-4 all can dissolve in toluene and butanone solvents, and would not precipitate even after being left for 48 hours. Product E from Preparation Example 1-5 cannot dissolve in toluene.

Example

(19) Raw materials are obtained from the following sources. The resin compositions of Examples and Comparative Examples of the present invention were formulated, respectively, based on the amounts listed in Tables 1-4, and were further prepared to become various test specimens or preparations.

(20) Vinylbenzyl polyphenylene oxide: Trade name OPE-2st, available from MITSUBISHI GAS CHEMICAL COMPANY, INC.

(21) Bis-(3-ethyl-5-methyl-4-maleimidephenyl)methane: Trade name: BMI-70, available from KI Chemical.

(22) Aliphatic long chain maleimide 1: Trade name: BMI-3000, available from Designer Molecules Inc.

(23) Aliphatic long chain maleimide 2: Trade name: BMI-1700, available from Designer Molecules Inc.

(24) 3,3′,4,4′-Biphenyltetracarboxylic dianhydride: Trade name: BPDA, available from Sigma-Aldrich Co., LLC.

(25) 4-vinylbenzyl amine (VBA), available from LINCHUAN CHEMICAL CO., LTD.

(26) 2,2′-diallylbisphenol A (DABPA), available from Sigma-Aldrich Co., LLC.

(27) P-aminophenol, available from Sigma-Aldrich Co., LLC.

(28) 4,4′-oxydianiline, available from Kingyorker Enterprise Co. Ltd.

(29) Peroxide: Trade name: 25B, available from NOF CORPORATION.

(30) Spherical silica: Trade name: 2500SMJ, available from Admatechs Company Limited.

(31) Preparation of Varnish

(32) As shown in the following Tables 1-4, for each Example (represented by E, such as E1 and E2) or Comparative Example (represented by C, such as C1 and C2), the components were added to a stirring tanks based on the amounts in Tables for stirring, and mixed well to form a resin composition, called a varnish. For solid substances, the addition amount for each component (except the solvent) of the resin compositions in Tables is calculated based on parts by weight. For liquid substances, the solvent is also calculated based on parts by weight.

(33) The products or test specimens made from the resin compositions of the present invention and the methods for manufacturing the same are illustrated in the following.

(34) Prepreg: Each of the resin compositions from Examples and Comparative Examples was placed in an impregnation tank. Glass fiber fabric (1080 or 2116 E-glass fiber fabric, or 1080 L-glass fiber fabric, available from Asahi CO., LTD) was impregnated in the above impregnation tank, such that the resin composition adhered to the glass fiber fabric. The thus-obtained glass fiber fabric was baked at 130° C. for about 2 minutes to obtain a prepreg.

(35) Copper clad laminate (5-ply, laminated by five prepregs): Two HVLP (Hyper Very Low Profile) copper foils with a thickness of 18 microns and five prepregs of each test specimen (2116 E-glass fiber fabric) were provided. The resin content of each prepreg was about 52%. One copper foil, five prepregs and one copper foil were laminated in order, and were laminated under vacuum at 200° C. for 2 hours to form a copper clad laminate. Five prepregs were cured to for an insulating layer between two copper foils. The resin content of the insulating layer is about 52%.

(36) Copper-free laminate (5-ply, laminated by five prepregs): The above copper clad laminates (5-ply) were etched to remove the copper foils on two sides, so as to obtain a copper-free laminate (5-ply). The copper-free laminate (5-ply) was formed by laminating five prepregs. The resin content of the insulating layer of the copper-free laminate (5-ply) was about 52%.

(37) Copper-free laminate (2-ply, laminated by two prepregs): Two HVLP copper foils with a thickness of 18 microns and two prepregs of each test specimen (1080 L-glass fiber fabric) were provided. The resin content of each prepreg was about 68%. One copper foil, two prepregs and one copper foil were laminated in order, and were laminated under vacuum at 200° C. for 2 hours to form a copper clad laminate (2-ply). Then, The above copper clad laminates were etched to remove the copper foils on two sides, so as to obtain a copper-free laminate (2-ply). An insulating laminate was formed by laminating two prepregs. The resin content of the copper-free laminate (2-ply) was about 68%.

(38) The test method for each property is illustrated as follows.

(39) PP (prepreg) formability (resin content (RC) value test):

(40) 4 sheets of 4 (inches)×4 (inches) 2116 E-glass fiber fabric were provided by a punch press. Such 4 sheets of glass fiber fabric were weighted (W1). 4 sheets of prepregs (4 (inches)×4 (inches) (prepared by a method using 2116 E-glass fiber fabric) were provided by a punch press. Such 4 sheets of prepreg were weighted (W2). Resin Content %=[(W2−W1)/W2]×100%. If the RC value of a prepreg prepared by a method using 2116 is 52%, it suggests that such prepreg conforms to normal specifications. If the RC value of a prepreg prepared by a method using 2116 is smaller than 30%, it suggests that the resin flows out and cannot cure on a prepreg.

(41) Resin Flow:

(42) Referring to IPC-TM-650 2.3.17 regulations, 4 sheets of (4.0±0.010 inches)×(4.0±0.010 inches) prepregs prepared by a method using 2116 E-glass fiber fabric were weighted (Wo). 4 sheets of prepregs were laminated in the order of a steel plate/a release film/4 sheets of prepregs/a release film/a steel plate, and then were placed in a press machine and heat pressed at a temperature of 171±3° C. and a pressure of 200±10 psi for 5 minutes. The specimen was taken out after heat press and cooled to room temperature. A circular specimen with a diameter of 3.192 in (81.1 mm) was provided by a circular punch press. The circular specimen was weighted (Wd). The resin flow (%) was calculated based on the following formula.
Resin flow %=[(Wo−2Wd)/Wo]×100%.

(43) If the resin flow is larger than 30%, it means that the resin flow is too large, such that the resin will flow out when a laminate is laminated, and a laminate with an appropriate thickness cannot be formed (an appropriate RC value cannot be obtained).

(44) Resin Filling Property:

(45) A prepreg was prepared by a method using 2 sheets of 2116 E-glass fiber fabric, sandwiched by two 2-ounce HTE (high temperature elongation) copper foils, and laminated to form a copper clad laminate. Conventional lithography was conducted on the copper foil on the surface to form a core laminate having surface wires. The surface wires were brown, and then each of two surfaces was laminated with 3 sheets of prepregs prepared by a method using 1080 E-glass fiber fabric and 2-Ounce HTE copper foils. A second copper clad laminate was formed after lamination. The copper clad laminate was sectioned by using conventional microsection and observed by optical microscope and scanning electron microscope (SEM) to check whether voids exist between wires. If voids exist, it means that the filling property is poor.

(46) Dense Hole Test (Crack Prevention):

(47) 26-layer plates (formed by prepregs prepared by a method using 1080 E-glass fiber fabric) of Examples and Comparative Examples were prepared by a conventional multi-layer lamination process. A specimen was prepared to have a diameter of 0.25 mm (millimeter) (by mechanical drilling), a pitch of 0.7 mm between holes, and total number of pitch holes was 1000 holes. Desmearing and electroplating were then conducted on the specimen. The specimen passed through a 260° C. Reflow for six times, and was sectioned by a conventional microsection process. The specimen was observed by optical microscope to confirm whether delamination in pitch holes occurred. If yes, such pitch hole should be counted as a poor hole. The pass rate of a dense hole test=[1−(poor hole number/total observation hole number)]*100%. 0.7 mm pitch between holes is more strict than 1.0 mm. Preferably, the pass rate is 100%.

(48) Thermal Resistance T288:

(49) A copper clad laminate (5-ply) with 6.5 mm×6.5 mm was used as a specimen. At a constant temperature of 288° C., a thermal mechanical analyzer (TMA) was used and based on the method described in IPC-TM-650 2.4.24.1, the time that no delamination occurred after the copper clad laminate was heated was measured. Generally, a longer time means that the thermal resistance of the copper clad laminate made from the resin composition is better.

(50) Solder Dipping Test (S/D):

(51) The method described in IPC-TM-650 2.4.23 to measure the above copper clad laminate (5-ply) was referred to. Each specimen was dipped in a solder pot with a constant temperature of 288° C. for 10 seconds, and then was taken out at room temperature for 10 seconds. The above steps were repeated and the repeat number was recorded until the laminate was delaminated. In general, the more the repeat number for each sample in solder dipping without delamination is, the better the thermal resistance of an article (such as copper clad laminate) made from the resin composition is.

(52) PCT (Pressure Cooking Test) of Copper-Free Laminate

(53) A copper-free laminate (5-ply) was placed in an environment at 121° C. with saturated vapor pressure for 3-hour moisture absorption and then dipped in a solder pot with a constant temperature of 288° C. for 20 seconds to observe whether delamination occurred. PCT is based on the method described in IPC-TM-650 2.6.16.1. Delamination means that the insulating layer of the laminate delaminates.

(54) Dielectric Constant (Dk):

(55) The above copper-free laminate (2-ply) was used as a specimen. A microwave dielectrometer (available from Japan AET Company) was used and based on the method described in JIS C2565 (Measuring methods for ferrite cores for microwave device), each specimen was measured at room temperature and a frequency of 10 GHz. Generally, the lower a dielectric constant is, the better the dielectric properties of a specimen are. The Dk value difference greater than 0.05 means that different laminates have a significant difference in dielectric constant.

(56) Dissipation Factor (Df):

(57) In the measurements of a dissipation factor, the above copper-free laminate (2-ply) was used as a specimen. A microwave dielectrometer (available from Japan AET Company) was used and based on the method described in JIS C2565 (Measuring methods for ferrite cores for microwave device), each specimen was measured at room temperature and a frequency of 10 GHz. Generally, the lower a dissipation factor is, the better the dielectric properties of a specimen are. The Df value difference smaller than 0.0005 means that laminates do not have a significant difference in dissipation factor while the Df value difference greater than 0.0005 means that different laminates has a significant difference in dissipation factor.

(58) Dissipation Factor Post-Moisture Absorption

(59) In the measure of a dissipation factor post-moisture absorption, the above copper-free laminate (2-ply) was used as a specimen. The specimen was placed in 121° C. saturated vapor pressure (referring to the PCT test of the above copper-free laminate) for 3-hour moisture absorption, and then a dissipation factor test was performed. The method for testing the dissipation factor is the same as that in the above.

(60) Interlayer Adhesion:

(61) A copper clad laminate (5-ply) was cut to become 12.7 mm (width)×larger than 60 mm (length), and then was tested by using a universal tensile strength testing machine based on the method described in IPC-TM-650 2.4.8, except that the surface copper foil was not etched and the test position was the joining surface between the 2.sup.nd prepreg-layer and the 3.sup.rd prepreg-layer. At room temperature (about 25° C.), the force (1b/in) needed to separate the 2.sup.nd prepreg-layer and the 3.sup.rd prepreg-layer in a cured insulating laminate was measured. Interlayer adhesion difference >0.1 (lb/in) represents significant difference.

(62) In view of the resin compositions of Examples and Comparative Examples in Tables 1 and 3 and property test results in Tables 3 and 4, the copper clad laminates E1-E4 made from the resin compositions of the present invention have a better dense hole thermal resistance test (pitch=0.7 mm) pass rate and interlayer adhesion, good PP formability, resin filling property, T288 thermal resistance, solder dipping and thermal resistance after moisture absorption, and a low dielectric constant and a low dissipation factor. In addition, the dissipation factor changes on the copper clad laminates E1-E4 made from the resin compositions of the present invention after PCT moisture absorption are also the smallest. Thus, the copper clad laminate made from the resin composition of the present invention can maintain the excellent low-dissipation factor property even after moisture absorption.

(63) TABLE-US-00001 TABLE 1 Constituent of resin compositions in Examples and Comparative Examples (Unit: parts by weight) Resin Constituent Component E1 E2 E3 E4 E5 Polyphenylene oxide Vinylbenzyl polyphenylene oxide OPE-2st 60 Maleimide Terminal vinyl maleimide Product B 100 40 90 (VBA:BMI-3000 = 33.5:66.5) Terminal vinyl maleimide Product C 100 (VBA:BMI-3000 = 20:80) Terminal vinyl maleimide Product D 100 (VBA:BMI-1700 = 33.5:66.5) Terminal vinyl maleimide Product E (VBA:BMI-70 = 33.5:66.5) Terminal hydroxyl maleimide Product F (DABPA/BMI-3000 = 33.5:66.5) Terminal hydroxyl maleimide Product G (aminophenol/BMI-3000 = 33.5:66.5) Terminal amino maleimide Product H (ODA/BMI-3000 = 33.5:66.5) Maleimide BMI-70 5 Aliphatic long chain maleimide BMI-3000 5 Aliphatic long chain maleimide BMI-1700 Cross-linking agent 3,3′,4,4'-Biphenyltetracarboxylic dianhydride BPDA Vinylbenzyl amine VBA 2,2′-diallyl bisphenol A DABPA P-aminophenol 4,4′-oxydianiline ODA Peroxide Peroxide 25B 1 1 1 1 1 Inorganic filler Spherical silica SC2500SMJ 50 50 50 50 50 Solvent Toluene Toluene 100 100 100 100 100 Resin Constituent Component C1 C2 C3 C4 C5 C6 Polyphenylene oxide Vinylbenzyl polyphenylene oxide Maleimide Terminal vinyl maleimide (VBA:BMI-3000 = 33.5:66.5) Terminal vinyl maleimide (VBA:BMI-3000 = 20:80) Terminal vinyl maleimide (VBA:BMI-1700 = 33.5:66.5) Terminal vinyl maleimide 100 (VBA:BMI-70 = 33.5:66.5) Terminal hydroxyl maleimide 100 (DABPA/BMI-3000 = 33.5:66.5) Terminal hydroxyl maleimide 100 (aminophenol/BMI-3000 = 33.5:66.5) Terminal amino maleimide 100 (ODA/BMI-3000 = 33.5:66.5) Maleimide 100 Aliphatic long chain maleimide 100 Aliphatic long chain maleimide Cross-linking agent 3,3′,4,4'-Biphenyltetracarboxylic dianhydride Vinylbenzyl amine 2,2′-diallyl bisphenol A P-aminophenol 4,4′-oxydianiline Peroxide Peroxide 1 1 1 1 1 1 Inorganic filler Spherical silica 50 50 50 50 50 50 Solvent Toluene 100 100 100 100 100 100

(64) TABLE-US-00002 TABLE 2 Constituent of resin compositions in Examples and Comparative Examples (Unit: parts by weight) Resin Constituent Component C7 C8 C9 C10 C11 Polyphenylene oxide Vinylbenzyl polyphenylene oxide OPE-2st Maleimide Terminal vinyl maleimide Product B (VBA:BMI-3000 = 33.5:66.5) Terminal vinyl maleimide Product C (VBA:BMI-3000 = 20:80) Terminal vinyl maleimide Product D (VBA:BMI-1700 = 33.5:66.5) Terminal vinyl maleimide Product E (VBA:BMI-70 = 33.5:66.5) Terminal hydroxyl maleimide Product F (DABPA/BMI-3000 = 33.5:66.5) Terminal hydroxyl maleimide Product G (aminophenol/BMI-3000 = 33.5:66.5) Terminal amino maleimide Product H (ODA/BMI-3000 = 33.5:66.5) Maleimide BMI-70 Aliphatic long chain maleimide BMI-3000 66.5 80 Aliphatic long chain maleimide BMI-1700 100 66.5 Cross-linking agent 3,3′,4,4'-Biphenyltetracarboxylic dianhydride BPDA 66.5 Vinylbenzyl amine VBA 33.5 33.5 33.5 20 2,2′-dialIyl bisphenol A DABPA P-aminophenol 4,4′-oxydianiline ODA Peroxide Peroxide 25B 1 1 .1 1 1 Inorganic filler Spherical silica SC2500SMJ 50 50 50 50 50 Solvent Toluene Toluene 100 100 100 100 100 Resin Constituent Component C12 C13 C14 C15 C16 C17 C18 Polyphenylene oxide Vinylbenzyl polyphenylene oxide 60 100 60 Maleimide Terminal vinyl maleimide (VBA:BMI-3000 = 33.5:66.5) Terminal vinyl maleimide (VBA:BMI-3000 = 20:80) Terminal vinyl maleimide (VBA:BMI-1700 = 33.5:66.5) Terminal vinyl maleimide 40 (VBA:BMI-70 = 33.5:66.5) Terminal hydroxyl maleimide (DABPA/BMI-3000 = 33.5:66.5) Terminal hydroxyl maleimide (aminophenol/BMI-3000 = 33.5:66.5) Terminal amino maleimide (ODA/BMI-3000 = 33.5:66.5) Maleimide 66.5 Aliphatic long chain maleimide 66.5 66.5 66.5 26.7 Aliphatic long chain maleimide Cross-linking agent 3,3′,4,4'-Biphenyltetracarboxylic dianhydride Vinylbenzyl amine 33.5 13.3 2,2′-dialIyl bisphenol A 33.5 P-aminophenol 33.5 4,4′-oxydianiline 33.5 Peroxide Peroxide 1 1 1 1. 1 1 1 Inorganic filler Spherical silica 50 50 50 50 50 50 50 Solvent Toluene 100 100 100 100 100 100 100

(65) TABLE-US-00003 TABLE 3 Test results for Examples and Comparative Examples Test item Property (method) Unit E1 E2 E3 E4 E5 Resin flow Resin flow % 21 28 27 18 15 Resin filling property void exists No unit No No No No No observed by SEM Compatibility While precipitant occurs at the No unit No No No No No bottom of the varnish PP formability RC value (2116*4 sheets) % 52 52 52 52 52 Dense hole test Pass rate of dense % 100 100 100 100 100 hole thermal resistance test (a pitch of 1.0 mm between holes) Dense hole test Pass rate of dense % 100 100 100 100 100 hole thermal resistance test (a pitch of 0.7 mm between holes) T288 thermal T288 (TMA) Minute >70 >70 >70 >70 >70 resistance Solder dipping S/D Times >20 >20 >20 >20 >20 Thermal resistance after PCT (3 hr) No unit No No No No No moisture absorption delami- delami- delami- delami- delami- nation nation nation nation nation Dielectric constant Dk@10 GHz No unit 2.85 2.75 2.9 2.98 2.91 (1080*2 sheets) Df after moisture Df@10 GHz No unit 0.0026 0.0025 0.0028 0.0029 0.0034 absorption (1080*2 sheets) Dissipation Df@10 GHz No unit 0.0024 0.0023 0.0026 0.0026 0.0029 factor (1080*2 sheets) Interlayer Interlayer lb/in 4.05 4.15 3.95 3.55 3.75 adhesion adhesion force (ply to ply) Property C1 C2 C3 C4 C5 C6 Resin flow 10 10 12 11 >30 26 Resin filling property Yes Yes Yes Yes — No Compatibility Yes No No No Yes No PP 52 52 52 52 <30 52 formability Dense hole test 95 100 100 90 — 98 Dense hole test 90 95 97 85 — 89 T288 thermal >70 >70 30 24 — >70 resistance Solder dipping >20 >20 15 15 — >20 Thermal resistance after No No Delami- Delami- — No moisture absorption delami- delami- nation nation delami- nation nation nation Dielectric constant 3.41 3.41 3.48 3.51 — 2.78 Df after 0.0055 0.0063 0.0075 0.0058 — 0.0023 moisture absorption Dissipation 0.0046 0.0046 0.0057 0.0068 — 0.0021 factor Interlayer 3.35 3.45 3.49 3.49 — 3.86 adhesion “—” means that such item is not tested

(66) TABLE-US-00004 TABLE 4 Test results for Examples and Comparative Examples Property Test item (method) Unit C7 C8 C9 C10 C11 Resin flow Resin flow % >30 21 19 12 16 Resin filling property void exists No unit No Yes Yes Yes Yes observed by SEM Compatibility White precipitant occurs at the No unit No No No No No bottom of the varnish PP RC value (2116*4 sheets) % 52 52 52 52 52 formability Dense hole test Pass rate of dense % 99 96 96 89 97 hole thermal resistance test (a pitch of 1.0 mm between holes) Dense hole test Pass rate of dense % 91 91 91 75 94 hole thermal resistance test (a pitch of 0.7 mm between holes) T288 thermal T288 (TMA) Minute >70 31 33 30 32 resistance Solder dipping S/D Times >20 >20 18 16 17 Thermal PCT (3 hr) No unit No No No Delami- No resistance delami- delami- delami- nation delami- after moisture nation nation nation nation absorption Dielectric Dk@10 GHz No unit 2.68 2.88 2.83 3.56 2.87 constant (1080*2 sheets) Df after moisture Df@10 GHz No unit 0.0029 0.0042 0.0045 0.0053 0.0031 absorption (1080*2 sheets) Dissipation Df@10 GHz No unit 0.0023 0.0037 0.0038 0.0042 0.0024 factor (1080*2 sheets) Interlayer Interlayer lb/in 3.16 3.56 3.47 2.98 3.91 adhesion adhesion force (ply to ply) Property C12 C13 C14 C15 C16 C17 C18 Resin flow 21 19 20 23 23 5 19 Resin filling property Yes Yes Yes Yes Yes Yes Yes Compatibility No No No Yes No No No PP 52 52 52 52 52 52 52 formability Dense hole test 93 92 91 98 100 100 100 Dense hole test 91 89 84 94 96 98 97 T288 thermal 33 31 32 >70 24 60 15 resistance Solder dipping 14 15 15 >20 12 >20 12 Thermal No No No No No No Delami- resistance delami- delami- delami- delami- delami- delami- nation after moisture nation nation nation nation nation nation absorption Dielectric 3.13 3.41 3.49 3.55 3.35 3.05 3.56 constant Df after moisture 0.0052 0.0053 0.0057 — — — — absorption Dissipation 0.0034 0.0041 0.0042 0.0035 0.0038 0.0038 0.0067 factor Interlayer 3.88 3.86 3.89 3.12 3.06 2.65 3.18 adhesion “—” means that such item is not tested