Resin composition and article made using the same

Abstract

The invention provides a resin composition. The resin composition comprises the following components in parts by weight: 100 parts of maleimide resin with a structure as shown in a formula (1); 1.5 parts by weight to 20 parts by weight of hydrogenated polybutadiene; and 10 to 35 parts by weight of a vinyl-containing benzyl compound, in the formula (1), n is the average number of repeating units (based on the number-average molecular weight), and n is a number from 1 to 20, and R1 to R4 are each independently hydrogen or a C1-C3 alkyl group. The invention also provides an article made from the aforementioned resin composition.

Description

TECHNICAL FIELD

[0001] The present application relates to a resin composition and an article made using the same, in particular, to a resin composition with improved performance requirements and an article made using the same. BACKGROUND

[0002] The operation of electronic devices is achieved by connecting numerous electronic components by conductive lines on a circuit board for power supply and signal transmission. The circuit board (such as a printed circuit board) is generally composed of an insulating substrate and a conductive line pattern on the insulating substrate, and the build-up board is one of the key raw materials for making circuit boards.

[0003] With the rapid development of the fifth generation mobile communication technology (5G) and the high functionality and miniaturization of electronic devices, the circuit boards used are also developing in the direction of multilayer, high-density wiring and high-speed signal transmission. Correspondingly, in order to ensure the quality of electronic devices, there are higher requirements for the comprehensive performance of build-up boards. The resin composition is the basic raw material for making build-up boards, and the design process of the resin composition directly affects the performance of the build-up board and the circuit board.

[0004] Therefore, how to develop a resin composition suitable for high-performance circuit boards is the direction of active efforts in the industry. SUMMARY

[0005] In view of the problems encountered in the prior art, in particular, the existing materials cannot meet one or more of the above performance requirements, the main purpose of the present application is to provide a resin composition and an article made using the same, which can meet the above performance requirements.

[0006] The present application provides a resin composition, comprising: 100 parts by weight of a maleimide resin having a structure represented by formula (1); 1.5 parts by weight to 20 parts by weight of a hydrogenated polybutadiene; and 10 parts by weight to 35 parts by weight of an ethylbenzyl-containing compound,

[0007] Formula (1),

[0008] wherein n is the average number of repeating units (based on the number average molecular weight), and n is a number from 1 to 20, and R1 to R4 are each independently hydrogen or C1 to C3 alkyl.

[0009] In the present application, the ethylbenzyl-containing compound can include divinyl diphenyl ethane, an ethylbenzyl-containing compound having a structure represented by formula (2), or a combination thereof,

[0010] Formula (2),

[0011] wherein z is the average number of repeating units (based on the number average molecular weight), and z is a number from 1 to 20.

[0012] The present application also provides an article made from the aforementioned resin composition, wherein the article comprises a prepreg, a resin film, a laminate, or a printed circuit board.

[0013] An article made from the resin composition of the present application, such as a prepreg, a resin film, a laminate, or a printed circuit board, has excellent properties in at least one of the coefficient of thermal expansion in the X-axis direction, the presence or absence of crystallization on the surface of the prepreg, the presence or absence of elongated bubbles in the interior of a copper-free substrate, and the tensile force on a copper foil, and thus can be a high-performance substrate that satisfies comprehensive requirements. BRIEF DESCRIPTION OF DRAWINGS

[0014] Figure 1 is a schematic view of the presence of elongated bubbles in the interior of a copper-free substrate.

[0015] Figure 2 is a schematic view of the presence of elongated bubbles in the interior of a copper-free substrate indicated by an arrow.

[0016] Figure 3 is a schematic view of the absence of elongated bubbles in the interior of a copper-free substrate.

[0017] Figure 4 is a schematic view of the presence of crystallization on the surface of a prepreg.

[0018] Figure 5 is a schematic view of the absence of crystallization on the surface of a prepreg. DETAILED DESCRIPTION

[0019] In order to make the objects, technical solutions, and advantages of the present application clearer, the following further describes the present application in conjunction with specific embodiments and with reference to the drawings.

[0020] The detailed features and advantages of the present application are described in detail in the following embodiments, and the content is sufficient for those skilled in the art to understand the technical content of the present application and to implement it. Based on the content disclosed in the specification, claims, and drawings, those skilled in the art can easily understand the related objects and advantages of the present application. The following embodiments are further detailed to illustrate the ideas of the present application, but do not limit the scope of the present application in any way.

[0021] In order for those skilled in the art to understand the features and effects of the present application, the following only generally describes and defines the terms and phrases mentioned in the specification and claims. Unless otherwise specified, all technical and scientific terms used in the present application have their usual meanings understood by those skilled in the art in the present application. In case of conflict, the definition in the specification shall prevail.

[0022] In the present application, the terms "comprise", "include", "have", "contain", or any other similar term are open-ended transitional phrases, which are intended to encompass non-exclusive inclusion. For example, a composition or article that comprises a list of elements is not limited to only those elements recited but can also include other elements not expressly listed or inherent to such composition or article. In addition, unless expressly specified to the contrary, the term "or" refers to an inclusive "or" and not to an exclusive "or". For example, any of the following are satisfied by 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). Furthermore, in the present application, the terms "comprise", "include", "have", and "contain" are to be construed as if each of the terms is specifically recited and encompasses the closed transitional phrases "consist of", "consist essentially of", "consist in", and "consist substantially of", as well as the transitional phrases "consist essentially of", "consist primarily of", "consist in primarily", "consist in essentially", "consist substantially of", "consist in substantially", and "consist in essentially".

[0023] In the present application, the phrase "a composition comprises A, B, and C, wherein A comprises a1, a2, or a3" is equivalent to "a composition comprises A, B, and C, wherein A comprises a1, a2, a3, or a combination thereof", which means "a composition comprises A, B, and C, wherein A comprises a1, a2, a3, a combination of a1 and a2, a combination of a1 and a3, a combination of a2 and a3, or a combination of a1, a2, and a3".

[0024] In the present application, all features or conditions defined in the form of a numerical range or a percentage range, such as numerical values, amounts, contents, and concentrations, are for brevity and convenience only. Therefore, the description of a numerical range or a percentage range is to be considered as having specifically disclosed and encompassing all possible sub-ranges and individual numerical values within the range, including integer and fractional values, particularly integer numerical values. For example, the range description "1.0 to 8.0", "1.0~8.0", "between 1.0 and 8.0", or "between 1.0 and 8.0" is to be considered as having specifically disclosed all sub-ranges such as 1.0 to 8.0, 1.0 to 7.0, 2.0 to 8.0, 2.0 to 6.0, 3.0 to 6.0, 4.0 to 8.0, 3.0 to 8.0, and the like, and encompassing the end-point values, particularly sub-ranges defined by integer numerical values, and as having specifically disclosed individual numerical values within the range such as 1.0, 2.0, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, and the like.

[0025] In the present invention, numerical values should be understood as having the precision of the number of significant digits stated. For example, the number 40.0 should be understood to encompass the range from 39.50 to 40.49.

[0026] In the present invention, "compound" refers to a chemical substance formed by the connection of two or more elements through chemical bonds, including small molecule compounds and polymer compounds, and is not limited thereto. In the present invention, "compound" is not limited to a single chemical substance, but can also be interpreted as a same kind of chemical substance having the same component or having the same property.

[0027] In the present invention, "polymer" refers to a product formed by the polymerization of monomers, including many polymer aggregates, each of which is formed by the repeated connection of many simple structural units through covalent bonds. Monomers are compounds that synthesize polymers. Polymers can include homopolymers (also known as self-polymers), copolymers, prepolymers, and the like, and are not limited thereto. Prepolymers refer to chemical substances produced by a polymerization reaction of two or more compounds with a conversion rate of 10% to 90%. Polymers also include oligomers, and are not limited thereto. Oligomers, also known as low polymers, are polymers composed of 2 to 20 repeating units, and are usually polymers composed of 2 to 5 repeating units. For example, "diene polymer" includes diene homopolymers, diene copolymers, diene prepolymers, and of course diene oligomers, etc.

[0028] Unless otherwise specified, "copolymer" in the present invention refers to a product formed by polymerization of two or more different monomers, including but not limited to a hetero copolymer (also known as a random copolymer or random copolymer), an alternating copolymer, a graft copolymer, or a block copolymer. For example, a styrene-butadiene copolymer is a product formed by polymerization of only two monomers, styrene and butadiene. For example, a styrene-butadiene copolymer includes but is not limited to a styrene-butadiene hetero copolymer, a styrene-butadiene alternating copolymer, a styrene-butadiene graft copolymer, or a styrene-butadiene block copolymer. A styrene-butadiene block copolymer includes, for example but not limited to, a post-polymerization molecular structure of styrene-styrene-styrene-butadiene-butadiene-butadiene-butadiene. A styrene-butadiene block copolymer includes, for example but not limited to, a styrene-butadiene-styrene block copolymer. A styrene-butadiene-styrene block copolymer includes, for example but not limited to, a post-polymerization molecular structure of styrene-styrene-styrene-butadiene-butadiene-butadiene-butadiene-styrene-styrene-styrene. Similarly, a hydrogenated styrene-butadiene copolymer includes a hydrogenated styrene-butadiene hetero copolymer, a hydrogenated styrene-butadiene alternating copolymer, a hydrogenated styrene-butadiene graft copolymer, or a hydrogenated styrene-butadiene block copolymer. A hydrogenated styrene-butadiene block copolymer includes, for example but not limited to, a hydrogenated styrene-butadiene-styrene block copolymer.

[0029] Unless otherwise specified, "resin" can be a conventional designation of a synthetic polymer, but in the present invention, "resin" can include, upon interpretation, a monomer, a polymer thereof, a combination of monomers, a combination of polymers thereof, or a combination of monomers and polymers thereof, and is not limited thereto. For example, in the present invention, "maleimide resin" upon interpretation includes a maleimide monomer, a maleimide polymer, a combination of maleimide monomers, a combination of maleimide polymers, or a combination of maleimide monomers and maleimide polymers.

[0030] In the present invention, "vinyl group" upon interpretation includes a vinyl group, a stretch vinyl group, an allyl group, a (meth)acrylate group, or a vinylbenzyl group.

[0031] Unless otherwise specified, in the present invention, a modified product (also known as a modified substance) includes a product of modification of a reactive functional group of each resin, a product of prepolymerization of each resin with another resin, a product of crosslinking of each resin with another resin, a product of homopolymerization of each resin, a product of copolymerization of each resin with another resin, and the like. For example, modification can be replacement of an original terminal hydroxyl group with a terminal vinyl group by chemical reaction, or obtaining a terminal hydroxyl group from an original terminal vinyl group and p-aminophenol by chemical reaction.

[0032] Unless otherwise specified, in the present application, when a specific example of a compound is written in the form of "(substituent)", it should be interpreted as including both the case with the substituent and the case without the substituent, for example, cyclohexanedimethanol di(meth)acrylate should be interpreted as including cyclohexanedimethanol diacrylate and cyclohexanedimethanol dimethacrylate, and (meth)acrylate should be interpreted as including acrylate and methacrylate.

[0033] Unless otherwise specified, in the present application, the alkyl group described should be interpreted as including various isomers thereof, for example, propyl should be interpreted as including n-propyl and isopropyl.

[0034] It should be understood that the features disclosed in each embodiment of the present application can be combined to form the technical solutions of the present application, as long as there is no contradiction in the combination of the features.

[0035] Unless otherwise specified, in the present application, parts by weight represent parts by weight, which can be any unit of weight, for example, but not limited to, kilograms, grams, pounds, and other units of weight. For example, 100 parts by weight of maleimide resin represents 100 kilograms of maleimide resin or 100 pounds of maleimide resin. If the resin solution contains a solvent and a resin, the parts by weight of the (solid or liquid) resin generally refers to the unit of weight of the (solid or liquid) resin, and does not include the unit of weight of the solvent in the solution, and the parts by weight of the solvent refers to the unit of weight of the solvent.

[0036] The following detailed description is merely exemplary in nature and is not intended to limit the present application and its uses. Furthermore, the present application is not limited by any of the foregoing description or the following detailed description or examples. Methods, reagents and conditions employed in the examples are routine to the art unless otherwise stated.

[0037] An embodiment of the present application provides a resin composition, comprising: 100 parts by weight of a maleimide resin having a structure represented by formula (1); 1.5 parts by weight to 20 parts by weight of a hydrogenated polybutadiene; and 10 parts by weight to 35 parts by weight of an ethylbenzyl-containing compound, wherein the ethylbenzyl-containing compound comprises: a divinyl diphenylethane, an ethylbenzyl-containing compound having a structure represented by formula (2), or a combination thereof,

[0038] Formula (1)

[0039] Formula (2)

[0040] wherein n is the average number of repeating units (based on number average molecular weight) and n is a number from 1 to 20, each of R1to R4is independently hydrogen or a C1to C3alkyl group, and z is the average number of repeating units (based on number average molecular weight) and z is a number from 1 to 20.

[0041] In formula (1), n represents the average number of repeating units (based on number average molecular weight) of the structural unit within the parentheses, that is, the degree of polymerization n of the repeating unit of the maleimide resin having the structure shown in formula (1) is the average number of repeating units calculated from the measured value of the number average molecular weight of the maleimide resin having the structure shown in formula (1). Therefore, n is a number from 1 to 20, n can be a positive integer from 1 to 20, and n can also be a non-integer from 1 to 20. For example, in an embodiment, n can be 1, 1.2, 2, 3, 4.5, 5, 7, 8.75, 10, 15.3, 19, 20, or 20.3, for example but not limited to. For example, in an embodiment, the number average molecular weight of the maleimide resin having the structure shown in formula (1) is 1272, and the value of n is [(1272-718.94) / 158.24]+1=4.495, that is, n is 4.5.

[0042] For example, in an embodiment, the maleimide resin having the structure shown in formula (1) of the present application is a maleimide resin having the structure shown in formula (1.1):

[0043] Formula (1.1)

[0044] wherein n is the average number of repeating units (based on number average molecular weight) and n is a number from 1 to 20.

[0045] In formula (1.1), n represents the average number of repeating units (based on number average molecular weight) of the structural unit within the parentheses, and n is a number from 1 to 20. For example, in an embodiment, n can be 1, 2, 3, 3.5, 4, 4.5, 5, 7, 7.5, 8, 8.5, 10, 15, 19, or 20, for example but not limited to.

[0046] For example, in an embodiment, the maleimide resin having the structure shown in formula (1) of the present application is a maleimide resin having the structure shown in formula (1.1.1):

[0047] Formula (1.1.1)

[0048] wherein n is the average number of repeating units (based on number average molecular weight) and n is a number from 1 to 20.

[0049] In Formula (1.1.1), n represents the average number of repeating units of the structure within the parentheses (based on the number average molecular weight), and n is a number from 1 to 20. For example, in an embodiment, n can be 1, 2, 3, 3.5, 4, 4.5, 5, 7, 7.5, 8, 8.5, 10, 15, 19, or 20, for example, but not limited to.

[0050] For example, in the resin composition of the present application, the hydrogenated polybutadiene is obtained by hydrogenating polybutadiene, and the hydrogenated polybutadiene has no reactive vinyl group, or the residual vinyl group content in the hydrogenated polybutadiene is less than 7%. In an embodiment, the hydrogenated polybutadiene can have no reactive vinyl bond. In an embodiment, unless otherwise specified, the hydrogenated polybutadiene mentioned in each embodiment of the present application can be, for example, but not limited to, BI-1000, BI-2000 and BI-3000 available from Japan Zeon, wherein BI-1000 is a hydrogenated polybutadiene with a number average molecular weight of 1100 to 1300, BI-2000 is a hydrogenated polybutadiene with a number average molecular weight of 2200, and BI-3000 is a hydrogenated polybutadiene with a number average molecular weight of 3300.

[0051] For example, in the resin composition of the present application, the content of the hydrogenated polybutadiene is 1.5 parts by weight to 20 parts by weight, for example, but not limited to, 1.5 parts by weight, 2 parts by weight, 3 parts by weight, 5 parts by weight, 7 parts by weight, 10 parts by weight, 13 parts by weight, 15 parts by weight or 20 parts by weight, relative to 100 parts by weight of the maleimide resin having the structure shown in Formula (1).

[0052] For example, in an embodiment, the divinyl diphenylethane includes any one or more of p,p-divinyl-1,2-diphenylethane (p,p-BVPE, a divinyl diphenylethane having the structure shown in Formula (3)), p,m-divinyl-1,2-diphenylethane (p,m-BVPE, a divinyl diphenylethane having the structure shown in Formula (4)), and m,m-divinyl-1,2-diphenylethane (m,m-BVPE, a divinyl diphenylethane having the structure shown in Formula (5)), and the like. Wherein p represents para, m represents meta,

[0053] Formula (3)

[0054] Formula (4)

[0055] Formula (5).

[0056] In formula (2), z represents the average number of repeating units (based on the number average molecular weight) of the structure within the parentheses, and z is a number from 1 to 20. For example, in an embodiment, z can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20, but is not limited thereto. If not specifically mentioned, the ethylene benzyl-containing compound having the structure shown in formula (2) can be obtained from a commercially available product, or can be prepared according to a known method, for example, the ethylene benzyl-containing compound having the structure shown in formula (2) can be prepared according to the method disclosed in Taiwan Patent No. TWI822584.

[0057] For example, in an embodiment, the ethylene benzyl-containing compound having the structure shown in formula (2) of the present application has the structure of an ethylene benzyl-containing compound shown in formula (2.1):

[0058] Formula (2.1)

[0059] wherein z is the average number of repeating units (based on the number average molecular weight), and z is a number from 1 to 20.

[0060] For example, in the resin composition of the present application, the content of the ethylene benzyl-containing compound is 10 parts by weight to 35 parts by weight, for example, but not limited to, 10 parts by weight, 20 parts by weight, 30 parts by weight, or 35 parts by weight, relative to 100 parts by weight of the maleimide resin having the structure shown in formula (1).

[0061] In an embodiment, the resin composition can further contain, as needed, a maleimide resin other than the maleimide resin having the structure shown in formula (1) of the present application, and the content of the maleimide resin is not limited.

[0062] In one embodiment, the foregoing maleimide resin can comprise 4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide (or oligomer of phenylmethane maleimide), bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 3,3'-dimethyl-5,5'-dipropyl-4,4'-diphenylmethane bismaleimide, m-phenylene bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, N-2,3-xylylmaleimide, N-2,6-xylylmaleimide, N-phenylmaleimide, vinyl benzyl maleimide, maleimide containing a biphenyl structure, maleimide resin containing a structure of 10 to 50 aliphatic carbon atoms, pre-polymer of a di-allyl compound and a maleimide resin, pre-polymer of a polyfunctional amine (greater than or equal to two amine groups) and a maleimide resin, pre-polymer of an amine group phenol and a maleimide resin, or a combination thereof.

[0063] For example, specific examples of other types of maleimide resins can include, but are not limited to, maleimide resins produced by Daiwakasei Industry Co., Ltd. under the trade names of BMI-1000, BMI-1000H, BMI-1100, BMI-1100H, BMI-2000, BMI-2300, BMI-3000, BMI-3000H, BMI-4000, BMI-5000, BMI-5100, BMI-TMH, BMI-7000, and BMI-7000H; maleimide resins produced by K.I Chemical Co., Ltd. under the trade names of BMI-70, BMI-80; or maleimide resins produced by Japan Chemicals Co., Ltd. under the trade names of MIR-3000 or MIR-5000.

[0064] For example, specific examples of maleimide resins having a structure of 10 to 50 aliphatic carbon atoms can include, but are not limited to, maleimide resins produced by Designer Molecules Co., Ltd. under the trade names of BMI-689, BMI-1400, BMI-1500, BMI-1700, BMI-2500, BMI-3000, BMI-5000, and BMI-6000, or maleimide resins having a structure of 10 to 50 aliphatic carbon atoms sold by Shin-Etsu Chemical Co., Ltd. under the trade names of SLK-3000 series, SLK-1500 series, and SLK-2000 series. Among them, the structure of SLK-3000 of Shin-Etsu Chemical is the same as the structure of BMI-3000 of Designer Molecules.

[0065] For example, in one embodiment, with respect to 100 parts by weight of the maleimide resin having a structure represented by Formula (1) of the present application, the resin composition can further include 5 parts by weight to 15 parts by weight of the aforementioned maleimide resin having a structure of 10 to 50 aliphatic carbon atoms.

[0066] In one embodiment, the resin composition can further include a vinyl polyphenyl ether resin, a triallylisocyanurate, or a combination thereof.

[0067] For example, in one embodiment, the vinyl polyphenyl ether resin can include various polyphenyl ether resins modified at the terminal with a vinyl group or an allyl group. In addition, the vinyl polyphenyl ether resin can also be a polyphenyl ether resin modified at the terminal with a (meth)acrylate.

[0068] For example, in one embodiment, the aforementioned vinyl polyphenyl ether resin represents a polyphenyl ether resin containing a vinyl group, which can include, but is not limited to, a polyphenyl ether resin containing a vinyl group, an allyl group, a vinylbenzyl group, or a (meth)acrylate group.

[0069] For example, in an embodiment, the aforementioned vinyl group-containing polyphenylene ether resin includes an ethylene benzyl biphenyl polyphenylene ether resin, a (meth)acrylate polyphenylene ether resin (i.e., a (meth)acryl polyphenylene ether resin), an allyl polyphenylene ether resin, an ethylene benzyl-modified bisphenol A polyphenylene ether resin, a vinyl chain-extended polyphenylene ether resin, or a combination thereof. For example, the aforementioned vinyl group-containing polyphenylene ether resin can be an ethylene benzyl biphenyl polyphenylene ether resin having a number average molecular weight of about 1200 (e.g., OPE-2st 1200, available from Mitsubishi Gas Chemical Company), an ethylene benzyl biphenyl polyphenylene ether resin having a number average molecular weight of about 2200 (e.g., OPE-2st 2200, available from Mitsubishi Gas Chemical Company), a methacrylate polyphenylene ether resin having a number average molecular weight of about 1900 to 2300 (e.g., SA9000, available from Sabic Company). Among them, the aforementioned vinyl chain-extended polyphenylene ether resin can include various types of polyphenylene ether resins disclosed in U.S. Patent Application Publication No. 2016 / 0185904 Al, which is incorporated herein by reference in its entirety.

[0070] For example, in an embodiment, the resin composition can further include 5 parts by weight to 40 parts by weight of a vinyl group-containing polyphenylene ether resin, a triallyl isocyanurate, or a combination thereof, such as, but not limited to, 5 parts by weight to 40 parts by weight of a triallyl isocyanurate, or 5 parts by weight to 40 parts by weight of a vinyl group-containing polyphenylene ether resin, or 20 parts by weight of a triallyl isocyanurate and 20 parts by weight of a vinyl group-containing polyphenylene ether resin, with respect to 100 parts by weight of the maleimide resin having the structure shown in Formula (1).

[0071] In an embodiment, the resin composition can further include an inorganic filler, a hardening accelerator, an inhibitor, a flame retardant, a dyeing agent, a toughening agent, a core-shell rubber, a silane coupling agent, or a solvent. The aforementioned components can be used alone or in combination.

[0072] In an embodiment, the resin composition can further include an inorganic filler, and the content of the inorganic filler is not limited. In another embodiment, the resin composition can further include 20 parts by weight to 230 parts by weight of an inorganic filler, or 20 parts by weight to 210 parts by weight of an inorganic filler, or 20 parts by weight to 80 parts by weight of an inorganic filler, or 25 parts by weight to 135 parts by weight of an inorganic filler, or 30 parts by weight to 100 parts by weight of an inorganic filler, or 30 parts by weight to 150 parts by weight of an inorganic filler, with respect to 100 parts by weight of the maleimide resin having the structure shown in Formula (1). However, the present application is not limited thereto, and the content of the inorganic filler can be adjusted as needed.

[0073] In one embodiment, the inorganic filler can be silica. In one embodiment, the inorganic filler can be spherical silica. The spherical silica can include various types of spherical silica known in the art, and the particle size distribution D50 of the spherical silica can be, for example, less than or equal to 2.0 micrometers (pm). For example, the particle size distribution D50 can preferably be between 0.2 micrometers and 2.0 micrometers, such as, but not limited to, 0.2 micrometers, 0.3 micrometers, 0.4 micrometers, 0.6 micrometers, 0.8 micrometers, 1.2 micrometers, 1.3 micrometers, 2.0 micrometers. Unless otherwise specified, the particle size distribution D50 refers to the particle size corresponding to 50% of the cumulative volume distribution of the filler (such as, but not limited to, spherical silica) as determined by laser scattering. The spherical silica suitable for use in the present application is not particularly limited and can be any one or more of commercially available products, such as, but not limited to, spherical silica available from Admatechs Co., Ltd.

[0074] In one embodiment, the spherical silica can be optionally pretreated with a siloxane compound, including an amino silane, an epoxide silane, a vinyl silane, an ester silane, a hydroxyl silane, an isocyanate silane, a methacryloxy silane, or an acryloxy silane, as needed. The content of the siloxane compound pretreatment can be, for example, 0.005 parts by weight to 0.5 parts by weight, based on 100 parts by weight of the content of the spherical silica, and the like. The amount of the siloxane compound is not particularly limited and can be adjusted as needed depending on the dispersibility of the inorganic filler of the resin composition.

[0075] In one embodiment, the inorganic filler in the resin composition can be an inorganic filler other than spherical silica, and the content thereof can be adjusted as needed.

[0076] In one embodiment, the inorganic filler other than spherical silica can include non-spherical silica (i.e., existing irregular silica that is not spherical), alumina, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, aluminum silicon carbide, silicon carbide, titanium dioxide, barium titanate, lead titanate, strontium titanate, calcium titanate, magnesium titanate, barium zirconate, lead zirconate, magnesium zirconate, lead zirconate titanate, zinc molybdate, calcium molybdate, magnesium molybdate, ammonium molybdate, zinc molybdate modified talc, zinc oxide, zirconium oxide, mica, boehmite (AIOOH), calcined talc, talc, silicon nitride, or calcined kaolin. In addition, the remaining inorganic fillers other than the aforementioned non-spherical silica can be spherical, fibrous, platy, particulate, flaky, or acicular. The inorganic filler other than spherical silica can be optionally pretreated with a siloxane compound, as desired. Examples of the siloxane compound used to pretreat the inorganic filler and the amount used are as previously described and will not be repeated here.

[0077] For example, the above-mentioned hardening accelerator (including a hardening initiator) can include a catalyst such as a Lewis base or a Lewis acid. Among them, the Lewis base can include one or more of imidazole, boron trifluoride amine complex, ethyltriphenyl phosphonium chloride, 2-methylimidazole (2MI), 2-phenyl-1H-imidazole (2PZ), 2-ethyl-4-methylimidazole (2E4MI), 2-Undecyl-1H-imidazole (C11Z), triphenylphosphine (TPP), and 4-dimethylaminopyridine (DMAP). The Lewis acid can include metal salt compounds such as manganese, iron, cobalt, nickel, copper, zinc, and the like, such as zinc octoate, cobalt octoate, and the like metal catalysts. The hardening accelerator can also include a hardening initiator, for example, a peroxide that generates a free radical, and the hardening initiator includes, but is not limited to, diisopropylbenzene peroxide, t-butyl peroxybenzoate, dibenzoyl peroxide (BPO), 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne (25B), and bis(tert-butylperoxyisopropyl)benzene, or a combination thereof. For example, the amount of the hardening accelerator used in the present application is not particularly limited compared to 100 parts by weight of the maleimide resin having the structure shown in Formula (1), and can be, for example, 0.01 to 1.0 parts by weight, or 0.05 to 0.5 parts by weight, or 0.05 to 0.1 parts by weight, or 0.02 to 0.08 parts by weight, or 0.15 to 0.5 parts by weight, or 0.1 to 0.2 parts by weight.

[0078] In one embodiment, the resin composition can further include an inhibitor, and the content of the inhibitor is not limited.

[0079] Without particular mention, the inhibitor in the resin composition can be any one or more inhibitors suitable for manufacturing of prepreg, resin film, laminate, or printed circuit board. The inhibitor can include various molecular type or stable free radical type inhibitors known in the art. The molecular type inhibitor can include, but is not limited to, phenol compound, quinone compound, aromatic amine compound, aromatic hydrocarbon nitro compound, sulfur-containing compound, or variable valence metal chloride. Specifically, the molecular type inhibitor can include, but is not limited to, phenol, hydroquinone, 4-tert-butylcatechol, benzoquinone, chloranil, 1,4-naphthoquinone, trimethylquinone, aniline, nitrobenzene, Na2S, FeCl3, or CuCl2. The stable free radical type inhibitor can include, but is not limited to, 1,1-diphenyl-2-trinitrophenylhydrazine (DPPH), triphenylmethyl radical, 2,2,6,6-tetramethylpiperidine-1-oxide, or derivatives of 2,2,6,6-tetramethylpiperidine-1-oxide.

[0080] In one embodiment, the resin composition can further include a flame retardant. In another embodiment, the resin composition can not include a flame retardant, that is, the content of the flame retardant is 0 parts by weight, here, it means that the resin composition is not intentionally added with the flame retardant.

[0081] The flame retardant in the resin composition can be any one or more flame retardants suitable for use in the manufacture of prepreg, resin film, laminate, or printed circuit board, such as, but not limited to, phosphorus-containing flame retardants, unless otherwise specified. For example, the phosphorus-containing flame retardant can include ammonium polyphosphate, hydroquinone bis(diphenyl phosphate), bisphenol A bis(diphenylphosphate), tri(2-carboxyethyl) phosphine (TCEP), tris(chloroisopropyl) phosphate, trimethyl phosphate (TMP), dimethylmethyl phosphonate (DMMP), resorcinol bis(dixylenylphosphate), RDXP (such as commercially available products PX-200, PX-201, PX-202, etc.), phosphazene (such as commercially available products SPB-100, SPH-100, SPV-100, etc.), melamine polyphosphate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and its derivatives (such as bis-DOPO compounds) or resins (such as DOPO-HQ, DOPO-NQ, DOPO-PN, DOPO-BPN), DOPO-bonded epoxy resin, diphenylphosphine oxide (DPPO) and its derivatives (such as bis-DPPO compounds) or resins, melamine cyanurate, tri-hydroxyethylisocyanurate, or aluminum hypophosphite salt (such as products OP-930, OP-935, etc.). Among them, DOPO-PN is a DOPO phenol novolac resin, and DOPO-BPN can be a bisphenol novolac resin such as DOPO-bisphenol A novolac (DOPO-BPAN), DOPO-bisphenol F novolac (DOPO-BPFN), or DOPO-bisphenol S novolac (DOPO-BPSN).

[0082] In one embodiment, the content of the dyeing agent, toughening agent, or core-shell rubber in the resin composition is not limited and can be adjusted as needed.

[0083] Unless otherwise specified, the dyeing agent suitable for the present application can include, but is not limited to, a dye or a pigment.

[0084] The main role of the toughening agent is to improve the toughness of the resin composition. Unless otherwise specified, the toughening agent suitable for the present application can include, but is not limited to, a carboxyl-terminated butadiene acrylonitrile rubber (CTBN) or the like.

[0085] Unless otherwise specified, the core-shell rubber suitable for the present application can include various commercially available core-shell rubbers.

[0086] For example, the silane coupling agent described above can include a silane compound (e.g., but not limited to a siloxane compound), which can be classified into an amino silane compound, an epoxide silane compound, a vinyl silane compound, an acrylate silane compound, a methacrylate silane compound, a hydroxyl silane compound, an isocyanate silane compound, a methacryloyloxy silane compound, and an acryloyloxy silane compound, depending on the type of functional group.

[0087] The main role of the solvent is to dissolve each component in the resin composition, change the solid content of the resin composition, and adjust the viscosity of the resin composition. For example, the solvent can include, but is not limited to, methanol, ethanol, ethylene glycol monomethyl ether, acetone, butanone (also known as methyl ethyl ketone), methyl isobutyl ketone, cyclohexanone, toluene, xylene, methoxyethyl acetate, ethoxyethyl acetate, propoxyethyl acetate, ethyl acetate, propylene glycol methyl ether, dimethylformamide, dimethylacetamide, nitrogen methyl pyrrolidone, or a mixed solvent thereof. The amount of the aforementioned solvent added is not particularly limited, and the amount of the solvent added can be adjusted depending on the desired viscosity of the resin composition. If the resin composition is added with a solvent, the solvent is removed by volatilization when the resin composition is heated at a high temperature to form a semi-cured state, and thus there is no solvent in the semi-cured sheet or the resin film, or only a trace amount of solvent is present in the semi-cured sheet or the resin film. For example, in one embodiment, the amount of the solvent added can be, for example, 10 to 90 parts by weight, or 30 to 50 parts by weight, or 60 to 80 parts by weight, with respect to 100 parts by weight of the maleimide resin having the structure shown in Formula (1).

[0088] The resin composition of one embodiment of the present application can be processed into various articles by various processing methods, including but not limited to a semi-cured sheet, a resin film, a laminate, or a printed circuit board.

[0089] For example, the resin composition of an embodiment of the present application can be made into a resin film by baking and semi-curing the resin composition. The resin composition can be optionally coated on a polyethylene terephthalate film (PET film), a polyimide film (PI film), a copper foil, or an adhesive-backed copper foil, and then formed into a resin film by baking and semi-curing the resin composition.

[0090] For example, the resin composition of an embodiment of the present application can be made into a resin film by baking and semi-curing the resin composition. The resin composition can be optionally coated on a polyethylene terephthalate film (PET film), a polyimide film (PI film), a copper foil, or an adhesive-backed copper foil, and then formed into a resin film by baking and semi-curing the resin composition.

[0091] For example, the resin composition of an embodiment of the present application can be made into a laminate. For example, the laminate can include at least two metal foils and at least one insulating layer disposed between the two metal foils. The insulating layer can be formed by pressing and curing (C-stage) the resin composition described above at high temperature and high pressure. The suitable curing temperature can be between 200°C and 240°C, preferably between 210°C and 230°C. The curing time can be 120 to 200 minutes, preferably 140 to 180 minutes, and the suitable pressure can be between 400 and 600 psi, preferably between 450 and 550 psi. The insulating layer can be formed by curing at least one prepreg or at least one resin film. The metal foils can be copper, aluminum, nickel, platinum, silver, gold, or alloys thereof. The metal foils can be, for example, copper foils. In a preferred embodiment, the laminate is a copper clad laminate (also known as a copper clad plate).

[0092] For example, in one embodiment, the aforementioned build-up board can be further processed by a circuit process to form a printed circuit board. The method of manufacturing the printed circuit board can be any of the existing manufacturing methods.

[0093] For example, the article made from the resin composition of one embodiment of the present application can satisfy one, more, or all of the following properties:

[0094] The dielectric constant measured at a frequency of 10 GHz is less than or equal to 3.20, for example, the dielectric constant is less than or equal to 3.15, as measured by the method described in JIS C2565;

[0095] The dielectric loss measured at a frequency of 10 GHz is less than or equal to 0.00210, for example, the dielectric loss is less than or equal to 0.00203, as measured by the method described in JIS C2565;

[0096] By optical microscopy, no long bubble streaks are observed inside the copper-free substrate;

[0097] The X-axis thermal expansion coefficient is less than or equal to 10.0 ppm / °C, for example, the X-axis thermal expansion coefficient is less than or equal to 9.9 ppm / °C, as measured by the method described in IPC-TM-650 2.4.24.5;

[0098] By optical microscopy, no crystallization is observed on the appearance surface of the prepreg;

[0099] The interlayer adhesion strength is greater than or equal to 2.3 lb / in, as measured by the method described in IPC-TM-650 2.4.8;

[0100] The copper foil peel strength of the copper-containing substrate is greater than or equal to 2.7 lb / in, as measured by the method described in IPC-TM-650 2.4.8;

[0101] The copper-containing substrate has no blistering after immersion tin heat resistance testing, as measured by the method described in IPC-TM-650 2.4.23;

[0102] The multilayer board has no blistering after heat resistance testing, as measured by the method described in IPC-TM-650 2.4.13.1, and the number of times without blistering is greater than 20 times;

[0103] The high-temperature rigidity change rate is less than or equal to 40.0%, for example, the high-temperature rigidity change rate is less than or equal to 39.4%, as measured by the method described in IPC-TM-650 2.4.24.4 standard.

[0104] The chemical raw materials used in the embodiments and comparative examples of the present application are as follows:

[0105] Maleimide A: maleimide resin having the structure of Formula (1.1.1) and n is a number from 1 to 5, available from DIC Corporation.

[0106] Maleimide B: maleimide resin having the structure of Formula (1.1.1) and n is a number from 6 to 10, available from DIC Corporation.

[0107] BMI-2300: benzomethane maleimide oligomer, commercially available.

[0108] BMI-70: 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, commercially available.

[0109] BMI-80: bisphenol A diphenyl ether bismaleimide, commercially available.

[0110] BMI-3000: maleimide containing 10 to 50 aliphatic carbon atom structure, available from Designer Molecules.

[0111] BI-3000: hydrogenated polybutadiene, Mn 3300, available from JSR.

[0112] BI-1000: hydrogenated polybutadiene, Mn 1100 to 1300, available from JSR.

[0113] BVPE: divinyl diphenylethane, which is a mixture of p,p-BVPE and p,m-BVPE, commercially available.

[0114] Vinyl benzyl containing compound having the structure of Formula (2): z is a number from 1 to 20, commercially available.

[0115] Divinylbenzene copolymer: divinylbenzene-styrene-ethylstyrene terpolymer, as in Synthesis Example 1.

[0116] Divinylbenzene: p-divinylbenzene, commercially available.

[0117] B-3000: polybutadiene, Mn 3200, available from JSR.

[0118] B-1000: polybutadiene, Mn 1200, available from JSR.

[0119] Ricon 150: polybutadiene, Mn 3900, commercially available.

[0120] H1052: hydrogenated styrene-butadiene-styrene triblock copolymer, commercially available.

[0121] H1054: hydrogenated styrene-butadiene-styrene triblock copolymer, commercially available.

[0122] SA9000: methacrylate-containing polyphenylene ether resin, commercially available.

[0123] TAIC: triallyl isocyanurate, commercially available.

[0124] C11Z: 2-undecylimidazole, commercially available.

[0125] 2Pz: 2-phenylimidazole, commercially available.

[0126] 25B: 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne, commercially available.

[0127] TPP: triphenylphosphine, commercially available.

[0128] SC2050 SMJ: spherical silica treated with a silane coupling agent on the surface, commercially available.

[0129] SC2050 SVJ: spherical silica treated with a silane coupling agent on the surface, commercially available.

[0130] MEK: methyl ethyl ketone, commercially available.

[0131] Toluene: toluene, commercially available.

[0132] Synthesis Example 1: Preparation of divinylbenzene-styrene-ethylstyrene terpolymer

[0133] Into a reactor, 3.0 moles (390.6 g) of divinylbenzene, 1.8 moles (229.4 g) of ethylvinylbenzene, 10.2 moles (1066.3 g) of styrene, and 15.0 moles (1532.0 g) of n-propyl acetate were added to obtain a polymerization solution. The polymerization solution was mixed uniformly while being stirred, and the polymerization solution was warmed to 70°C, and 600 mmol of a boron trifluoride-diethyl ether complex was added to the polymerization solution, and the polymerization reaction was continued for 4 hours while being stirred, and then the polymerization reaction was terminated by adding an aqueous sodium bicarbonate solution. The oil layer was washed with pure water three times, and the volatile components were removed under reduced pressure at 60°C to obtain a divinylbenzene-styrene-ethylstyrene terpolymer.

[0134] The above-described various raw materials were respectively adjusted in amounts according to Tables 1 to 4 below to prepare resin compositions of Examples and Comparative Examples of the present application, and further various test samples were prepared.

[0135] Table 1: Composition of resin compositions of Examples E1 to E4 (unit: parts by weight)

[0136]

[0137]

[0138] Table 2: Composition of resin composition of Examples E5 to E8 (unit: parts by weight)

[0139]

[0140]

[0141] Table 3: Composition of resin composition of Comparative Examples C1 to C5 (unit: parts by weight)

[0142]

[0143]

[0144] Table 4: Composition of resin composition of Comparative Examples C6 to C10 (unit: parts by weight)

[0145]

[0146]

[0147] Varnish

[0148] Each of the examples (denoted as E, such as E1 to E8) or comparative examples (denoted as C, such as C1 to C10) is prepared by adding the components in the amounts listed in Tables 1 to 4 into a stirring tank for stirring, and the resin composition formed after uniform mixing is referred to as varnish.

[0149] For example, the varnish of Example E1 is prepared by adding 100 parts by weight of maleimide A, 3 parts by weight of BI-3000, and 10 parts by weight of BVPE into a stirrer containing 30 parts by weight of butanone solvent and 50 parts by weight of toluene solvent, stirring until the BVPE is completely dissolved and all components are uniformly mixed, then adding 100 parts by weight of SC-2050 SMJ, 30 parts by weight of SC-2050 SVJ, and 0.1 parts by weight of C11Z and continuing to stir until uniformly mixed.

[0150] In addition, the varnishes of Examples E2 to E8 and Comparative Examples C1 to C10 are prepared according to the amounts of the components listed in Tables 1 to 4 above, using the preparation method of the varnish of Example E1.

[0151] The varnishes of Examples E1 to E8 and Comparative Examples C1 to C10 are used to prepare test samples (prepregs, copper-containing substrates, and copper-free substrates, respectively) according to the following method, and the properties are analyzed according to the following specific conditions.

[0152] Prepreg 1 (using 1035 L-glass fiber fabric)

[0153] The resin compositions listed in the various examples (E1 to E8) and comparative examples (C1 to C10) in Tables 1 to 4 were placed in a tank in batches. The glass fiber fabric (e.g., L-glass fiber fabric of 1035 grade) was passed through the tank, and the resin composition was attached to the glass fiber fabric. The resin composition was heated at 130°C for 4 minutes to become a B-stage, and a prepreg 1 (resin content of about 70%) was obtained.

[0154] Prepreg 2 (using 2116 L-glass fiber fabric)

[0155] The resin compositions listed in the various examples (E1 to E8) and comparative examples (C1 to C10) in Tables 1 to 4 were placed in a tank in batches. The glass fiber fabric (e.g., L-glass fiber fabric of 2116 grade) was passed through the tank, and the resin composition was attached to the glass fiber fabric. The resin composition was heated at 130°C for 4 minutes to become a B-stage, and a prepreg 2 (resin content of about 53%) was obtained.

[0156] Prepreg 3 (using 1078 L-glass fiber fabric)

[0157] The resin compositions listed in the various examples (E1 to E8) and comparative examples (C1 to C10) in Tables 1 to 4 were placed in a tank in batches. The glass fiber fabric (e.g., L-glass fiber fabric of 1078 grade) was passed through the tank, and the resin composition was attached to the glass fiber fabric. The resin composition was heated at 130°C for 4 minutes to become a B-stage, and a prepreg 3 (resin content of about 70%) was obtained.

[0158] Copper-containing substrate 1 (or copper foil substrate 1, prepared by laminating two prepregs 1)

[0159] Two reverse treated copper foils (RTF copper foils) of 18 micrometers in thickness and two prepregs 1 described above were prepared. The copper foils, the two prepregs 1, and the copper foils were laminated in this order, and were laminated under vacuum at a pressure of 500 psi at 220°C for 150 minutes to obtain a copper-containing substrate 1.

[0160] Copper-free substrate 1 (prepared by laminating two prepregs 1)

[0161] The copper-containing substrate 1 described above was subjected to etching to remove the copper foils on both sides, and a copper-free substrate 1 (prepared by laminating two prepregs 1) was obtained.

[0162] Copper-containing substrate 2 (made by pressing one prepreg 2)

[0163] Preparation method is basically the same as copper-containing substrate 1, the difference is made by pressing two prepregs 2.

[0164] Copper-free substrate 2 (made by pressing one prepreg 2)

[0165] The copper-containing substrate 2 described above is etched to remove the copper foil on both sides to obtain a copper-free substrate 2 (made by pressing one prepreg 2).

[0166] Copper-containing substrate 3 (made by pressing two prepregs 2)

[0167] Preparation method is basically the same as copper-containing substrate 1, the difference is made by pressing two prepregs 2.

[0168] Copper-free substrate 3 (made by pressing two prepregs 2)

[0169] The copper-containing substrate 3 described above is etched to remove the copper foil on both sides to obtain a copper-free substrate 3 (made by pressing two prepregs 2).

[0170] Copper-containing substrate 4 (made by pressing four prepregs 2)

[0171] Preparation method is basically the same as copper-containing substrate 1, the difference is made by pressing four prepregs 2.

[0172] Copper-free substrate 4 (made by pressing four prepregs 2)

[0173] The copper-containing substrate 4 described above is etched to remove the copper foil on both sides to obtain a copper-free substrate 4 (made by pressing four prepregs 2).

[0174] Copper-containing substrate 5 (made by pressing eight prepregs 2)

[0175] Preparation method is basically the same as copper-containing substrate 1, the difference is made by pressing eight prepregs 2.

[0176] Copper-free substrate 5 (made by pressing eight prepregs 2)

[0177] The copper-containing substrate 5 described above is etched to remove the copper foil on both sides to obtain a copper-free substrate 5 (made by pressing eight prepregs 2).

[0178] For the aforementioned test samples, the test methods and their characteristic analysis items are described as follows.

[0179] Dielectric constant (Dk)

[0180] In the measurement of the dielectric constant, the above-described copper-free substrate 1 (two pieces of prepreg 1 were laminated) was selected as the sample to be measured. A microwave dielectrometer (purchased from AET Corporation, Japan) was used to measure each sample to be measured at room temperature (about 25°C) and at a frequency of 10 GHz, in accordance with the method described in JIS C2565. The lower the dielectric constant, the better the dielectric properties of the sample to be measured. At a measurement frequency of 10 GHz, and in the range where the Dk value is less than 3.40 or less, a difference in Dk value of less than 0.05 indicates that there is no significant difference in dielectric constant between different substrates, and a difference in Dk value of greater than or equal to 0.05 indicates that there is a significant difference in dielectric constant between different substrates (there is a significant degree of technical difficulty).

[0181] Dissipation factor (Df)

[0182] In the measurement of the dielectric loss, the above-described copper-free substrate 1 (two pieces of prepreg 1 were laminated) was selected as the sample to be measured. A microwave dielectrometer (purchased from AET Corporation, Japan) was used to measure each sample to be measured at room temperature (about 25°C) and at a frequency of 10 GHz, in accordance with the method described in JIS C2565. The lower the dielectric loss, the better the dielectric properties of the sample to be measured. At a measurement frequency of 10 GHz, and in the range where the Df value is less than 0.00250 or less, a difference in Df value of less than 0.00010 indicates that there is no significant difference in dielectric loss between different substrates, and a difference in Df value of greater than or equal to 0.00010 indicates that there is a significant difference in dielectric loss between different substrates (there is a significant degree of technical difficulty). At a measurement frequency of 10 GHz, and in the range where the Df value is greater than or equal to 0.00250 or more to less than 0.00600, a difference in Df value of less than 0.00050 indicates that there is no significant difference in dielectric loss between different substrates, and a difference in Df value of greater than or equal to 0.00050 indicates that there is a significant difference in dielectric loss between different substrates (there is a significant degree of technical difficulty).

[0183] Observation of copper-free substrate for the presence or absence of elongated bubble striations

[0184] In the measurement of the copper-free substrate for the presence or absence of elongated bubble striations (striation), the above-described copper-free substrate 2 (one piece of prepreg 2 was laminated) was selected as the sample to be measured for optical microscope observation. The tester observed whether there were elongated bubble striations inside the insulating layer of the copper-free substrate 2 through an optical microscope. If there were elongated bubble striations with a length of greater than or equal to 5 mils, it was judged as “yes”. If there were no elongated bubble striations with a length of greater than or equal to 5 mils, it was judged as “no”. Please refer to Figure 1 and Figure 2, Figure 1 There is a long bubble streak with a length greater than or equal to 5 mils (5 mils is equal to 127 microns) by Figure 2 The vertical long straight line indicated by the two arrows on the left side of the figure is a long bubble streak with a length greater than or equal to 5 mils. There is no long bubble streak with a length greater than or equal to 5 mils by Figure 3 There is no long bubble streak with a length greater than or equal to 5 mils. If there is a long bubble streak in the insulating layer of the copper foil substrate, the copper-free substrate, or the printed circuit board, it will cause a short circuit problem of conductive anodic filamentation (CAF) of conductive ions migration in the subsequent printed circuit board, resulting in failure of the printed circuit board and scrap.

[0185] X-axis coefficient of thermal expansion (X-CTE)

[0186] In the measurement of the X-axis coefficient of thermal expansion, the above-mentioned copper-free substrate 3 (two prepregs 2 are pressed together) is selected as the sample to be measured for thermal mechanical analysis (TMA). The above-mentioned copper-free substrate 3 is cut into a sample with a length of 24 mm and a width of 3 mm. The sample is heated at a rate of 10°C per minute from 35°C to 260°C, and the X-axis coefficient of thermal expansion (a1) of each sample to be measured is measured in the temperature range of 40°C to 125°C (unit: ppm / °C) according to the method described in IPC-TM-650 2.4.24.5. The X-axis coefficient of thermal expansion of the present application refers to the thermal expansion coefficient of the sample in the X-axis direction. The lower the X-axis coefficient of thermal expansion, the better the dimensional expansion and contraction characteristics. When the difference in the X-axis coefficient of thermal expansion between different substrates is greater than or equal to 0.5 ppm / °C, it means that there is a significant difference in the X-axis coefficient of thermal expansion between different substrates (there is a significant technical difficulty). For example, the X-axis coefficient of thermal expansion of the article made of the resin composition disclosed in the present application is less than or equal to 10.0 ppm / °C, for example, between 8.0 ppm / °C and 10.0 ppm / °C, measured according to the method described in IPC-TM-650 2.4.24.5.

[0187] Appearance of prepreg

[0188] The prepreg 1 made from each sample to be tested (each group of examples or comparative examples) is selected for immersion of the L-glass fiber cloth of the above-mentioned 1035, and the appearance of the prepreg 1 is observed by optical microscope to see if there is crystallization. If there is no crystallization, it is recorded as "none", and the schematic diagram of the prepreg 1 without crystallization is shown in Figure 5 If there is crystallization, it is recorded as "yes", and the schematic diagram of the prepreg 1 with crystallization is shown in Figure 4If there is crystallization on the prepreg appearance surface, it will cause the prepreg to be easy to fall off powder, and further cause the resin content of the prepreg to be wrong, so as to be scrapped.

[0189] Interlayer bonding strength (B / S)

[0190] The copper-containing substrate 4 (four prepregs 2 are pressed together) is cut into a rectangular sample with a width of 12.7 mm and a length greater than 60 mm, and is measured by using a universal tensile strength testing machine and referring to the method described in IPC-TM-650 2.4.8. The surface copper foil does not need to be etched during the process, and the test position is the bonding surface of the second layer of prepreg and the third layer of prepreg. The force required to separate the aforementioned two layers of the cured insulating substrate is tested at room temperature (about 25°C) and is expressed in lb / in. In the field, the higher the interlayer bonding strength, the better. The higher the interlayer bonding strength, the better, and the difference in interlayer bonding strength between different test samples is greater than or equal to 0.1 lb / in, which represents a significant difference and represents a significant technical difficulty.

[0191] Copper foil peel strength (P / S)

[0192] The copper-containing substrate 4 (four prepregs 2 are pressed together) is cut into a rectangular test sample with a width of 24 mm and a length greater than 60 mm, and the surface copper foil is etched to leave only a long strip of copper foil with a width of 3.18 mm and a length greater than 60 mm. A universal tensile strength testing machine is used to measure the force required to pull the copper foil away from the surface of the substrate at room temperature (about 25°C) according to the method described in IPC-TM-650 2.4.8. The higher the copper foil peel strength, the better, and the difference in copper foil peel strength between different test samples is greater than or equal to 0.1 lb / in, which represents a significant difference and represents a significant technical difficulty.

[0193] Solder dipping resistance (S / D)

[0194] The copper-containing substrate 5 (eight prepregs 2 are pressed together) is used as the test sample. The test sample is cut to a size of 20 cm long and 10 cm wide, and then immersed in a tin bath at a constant temperature of 288°C according to the method described in IPC-TM-650 2.4.23. After 20 seconds of immersion, the sample is taken out and observed for any blown boards. A blown board is a failure, indicating "failure", and a non-blown board passes the test, indicating "OK". For example, interlayer separation between insulating layers is a blown board, and interlayer separation is a phenomenon of blistering and separation between any layers of the substrate.

[0195] Multilayer board heat resistance

[0196] The core board was prepared as follows: one 2116 L-glass fiber cloth prepreg 2 (the resin content of each prepreg 2 was about 53%) impregnated with each sample (each group of examples or comparative examples) was prepared, one RTF copper foil (thickness of 18 microns) was laminated on both sides of the prepreg 2, and then the copper-containing core board was obtained by pressing and curing under vacuum, high temperature (220°C) and high pressure (500 psi) for 2.5 hours. Then, the copper-containing core board was etched to remove the copper foil on both sides to obtain a copper-free core board (thickness of 5 mils). Three copper-free core boards were prepared according to the above method. Then, two RTF copper foils (thickness of 18 microns) and eight 1078 L-glass fiber cloth prepregs 3 (the resin content of each prepreg 3 was about 70%) impregnated with each sample (each group of examples or comparative examples) were prepared, and the eight-layer board with copper-containing outer foils was formed by laminating the copper foil, two prepregs 3 (prepared using 1078 L-glass fiber cloth), a copper-free core board, two prepregs 3 (prepared using 1078 L-glass fiber cloth), a copper-free core board, two prepregs 3 (prepared using 1078 L-glass fiber cloth), a copper-free core board, two prepregs 3 (prepared using 1078 L-glass fiber cloth), and a copper foil in order, and then pressing and curing under vacuum, pressure of 500 psi, and 220°C for 2.5 hours. The eight-layer board was cut into a rectangular sample (length of 5.9 inches and width of 2.2 inches), and a total of 500 through holes with a diameter of 0.3 mm (20*25 through hole matrix, the vertical distance between the adjacent hole walls and the hole walls was 0.25 mm) were formed on the surface of the rectangular sample by using the circuit board drilling technology. Then, electroplated copper was formed on the hole walls to obtain a multilayer board heat resistance test sample.

[0197] In the multilayer board heat resistance test, using the above multilayer board heat resistance test sample, referring to the method described in IPC-TM-650 2.4.13.1, the sample is placed horizontally (i.e. in contact) on the surface of the tin liquid in the tin furnace at a constant temperature of 288°C. Each time the test is performed, one side of the sample is placed on the tin surface for a total of 10 seconds, after which the sample is removed from the tin surface and cooled at room temperature for 30 seconds. The same side of the sample is again placed on the tin surface for 10 seconds, after which it is again removed and cooled at room temperature for 30 seconds. One cycle consists of placing the sample on the tin surface for 10 seconds and cooling it at room temperature for 30 seconds. The above steps are repeated, and the total number of times each sample to be tested is tested for heat resistance without board explosion is tested. If the total number of tests exceeds 20 times without board explosion, it is marked as "OK". Otherwise, if the total number of tests is less than or equal to 20 times, the board explodes, and it is marked as "failure". In general, the more times each sample to be tested can be repeatedly subjected to tin immersion heat resistance testing without board explosion, the better the heat resistance of the product (such as a copper foil substrate) made from the resin composition. The above "board explosion" can be understood as delamination or blistering. Board explosion can occur between any layers of the substrate, such as delamination between insulating layers, or blistering between the copper foil and the insulating layer. The heat resistance test results of the multilayer board, which contains multiple layers of copper foil and has undergone circuit board drilling, can more truly reflect the heat resistance of the printed circuit board. The heat resistance test results of ordinary double-layer boards that have not undergone circuit board drilling cannot accurately predict the heat resistance of multilayer boards, i.e. cannot predict the heat resistance of printed circuit boards.

[0198] High temperature stiffness difference (indicated as Δ stiffness, or simply ΔS)

[0199] The stiffness at 50°C and 250°C of the copper-free substrate 4 (four half-impregnated sheets 2 pressed together) was measured using a DMA instrument, with the measurement method referring to the method described in IPC-TM-650 2.4.24.4, and the unit being N / m. The stiffness measured at 50°C is defined as S1, and the stiffness measured at 250°C is defined as S2. The high temperature stiffness difference (ΔS) is equal to [(S1-S2) / S1]*100%, with the unit being %. The lower the high temperature stiffness difference, the better. A difference in high temperature stiffness difference greater than or equal to 1% is considered to be a significant difference, and a difference in high temperature stiffness difference less than 1% is considered to be no significant difference.

[0200] Referring to the test results in Table 3, the appearance of the copper-free substrate 1 made by Comparative Example C1 and the copper-free substrate 3 is rough and uneven, and the interlayer adhesion of the copper-free substrate 1 to 5 made by Comparative Example C1 and the copper-containing substrate 1 to 5 is very poor, and the layers of the insulating layer are easily separated from each other. Therefore, Comparative Example C1 has multiple sets of data that cannot be measured for the above-mentioned multiple property analyses.

[0201] According to the above-described embodiments, an article, such as a prepreg, a resin film, a laminate, or a printed circuit board, made of the resin composition of the present application has excellent characteristics in at least one of the coefficient of thermal expansion in the X-axis, the appearance of the prepreg, the surface of the substrate, and the tension against a copper foil, and thus can be a high-performance substrate that satisfies comprehensive requirements.

[0202] The above-described specific embodiments further explain the purpose, technical solutions, and beneficial effects of the present application. It should be understood that the above-described embodiments are merely specific embodiments of the present application and are not intended to limit the present application. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A resin composition comprising: 100 parts by weight of a maleimide resin having the structure shown in formula (1); 1.5 to 20 parts by weight of hydrogenated polybutadiene; and 10 to 35 parts by weight of ethylene-containing benzyl compounds, Equation (1), in, n is the average number of repeating units (based on number average molecular weight), and n is a value from 1 to 20. R1 to R4 are each independently hydrogen or C1 to C3 alkyl groups.

2. The resin composition according to claim 1, wherein, The maleimide resin having the structure shown in formula (1) is the maleimide resin having the structure shown in formula (1.1): Equation (1.1), Where n is the average number of repeating units (based on number-average molecular weight), and n is a value from 1 to 20.

3. The resin composition according to claim 1, wherein, Vinyl benzyl compounds include: divinyl diphenyl ethane, vinyl benzyl compounds having the structure shown in formula (2), or combinations thereof. Equation (2), Where z is the average number of repeating units (based on number-average molecular weight), and z is a value from 1 to 20.

4. The resin composition according to claim 3, wherein, Divinyl diphenyl ethane includes p,p-divinyl-1,2-diphenyl ethane, p,m-divinyl-1,2-diphenyl ethane, and m,m-divinyl-1,2-diphenyl ethane, or combinations thereof.

5. An article made of a resin composition according to any one of claims 1 to 4, wherein the article comprises a prepreg, a resin film, a laminate, or a printed circuit board.

6. The article according to claim 5, having at least one of the following characteristics: Using an optical microscope, stripes without elongated bubbles were observed inside the copper-free substrate. Using an optical microscope, it was observed that the surface of the prepreg showed no crystallization.

7. The article according to claim 5, having at least one of the following characteristics: The dielectric loss measured at a frequency of 10 GHz according to the method described in JIS C2565 is less than or equal to 0.00210. The X-axis thermal expansion coefficient measured according to the method described in IPC-TM-650 2.4.24.5 is less than or equal to 10.0 ppm / ℃; The copper foil peel strength of the copper-containing substrate, measured according to the method described in IPC-TM-650 2.4.8, is greater than or equal to 2.7 psi. The high-temperature stiffness change rate measured with reference to IPC-TM-650 2.4.24.4 standard is less than or equal to 40.0%.

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