Prepolymers, resin compositions comprising the same, and articles

Abstract

This invention discloses a prepolymer, a resin composition comprising the prepolymer, and an article thereof. The prepolymer is obtained by a prepolymerization reaction of a mixture comprising the following components: (a) a maleimide resin, (b) an epoxy-modified cyclic siloxane, and (c) a compound containing active hydrogen, including aminosiloxane, diallyl bisphenol, or a combination thereof. The prepolymer and the resin composition comprising the prepolymer of this invention can significantly improve one or more of the following: X-CTE uniformity of the article, copper foil peel strength after copper plating, dimensional stability after tinning, and heterogeneous flow length.

Description

Technical Field

[0001] This invention relates primarily to a prepolymer, a resin composition comprising the prepolymer, and articles thereof, particularly to a prepolymer and a resin composition comprising the prepolymer applicable to prepregs, resin films, laminates (e.g., copper foil substrates, or copper clad laminates) and printed circuit boards. Background Technology

[0002] In recent years, electronic devices such as mobile phones and personal computers have been developing towards higher performance and smaller size. This trend has been driving the upgrading of semiconductor packaging technology and has also put forward increasingly stringent characteristic requirements for printed circuit boards used in semiconductor packaging.

[0003] Maleimide resin possesses excellent heat resistance, electrical insulation, flame retardancy, and dimensional stability, making it a commonly used base resin for manufacturing IC packaging substrates and similar substrates. However, it also suffers from drawbacks such as poor solubility and easy precipitation, resulting in uneven copper-clad laminates with high brittleness, which greatly limits its application development. To meet the increasingly strong demand in the current substrate market, the modification research of maleimide resin has become a new hot topic. However, products made with maleimide resin currently on the market still have defects such as poor uniformity of X-axis thermal expansion coefficient, low copper foil peel strength after copper plating, low dimensional stability after tinning, and large heterogeneous resin flow length. Summary of the Invention

[0004] In view of the aforementioned technical problems in the prior art, particularly the inability of existing materials to meet one or more of the aforementioned performance requirements, the main objective of this invention is to provide a prepolymer, a resin composition comprising the prepolymer, and articles made from the resin composition. The prepolymer of this invention possesses an extremely high glass transition temperature and can solve at least one of the aforementioned technical problems.

[0005] A first aspect of the present invention provides a prepolymer obtained by a prepolymerization reaction of a mixture comprising the following components:

[0006] (a) Maleimide resin.

[0007] (b) Epoxy-modified cyclic siloxanes, and

[0008] (c) Compounds containing active hydrogen,

[0009] The compounds containing active hydrogen include aminosiloxanes, diallyl bisphenols, or combinations thereof.

[0010] In one embodiment, the amount of the epoxy-modified cyclic siloxane is 3 to 30 parts by weight relative to 100 parts by weight of maleimide resin, and the amount of the compound containing active hydrogen is 5 to 45 parts by weight.

[0011] In one embodiment, the amount of the epoxy-modified cyclic siloxane is 3 to 25 parts by weight relative to 100 parts by weight of maleimide resin, and the amount of the compound containing active hydrogen is 5 to 40 parts by weight.

[0012] In one embodiment, the weight-average molecular weight of the prepolymer is 3000-5000.

[0013] In one embodiment, the conversion rate of the prepolymerization reaction is 1-99%, preferably 10-90%.

[0014] In one embodiment, the maleimide resin includes oligomeric maleimide resin, non-oligomeric maleimide resin, or a combination thereof.

[0015] In one embodiment, the maleimide resin comprises 70-100 wt% non-oligomeric maleimide resin and 0-30 wt% oligomeric maleimide resin.

[0016] In one embodiment, the oligomeric maleimide resin includes polyphenylene maleimide, maleimide containing an indane structure, maleimide containing isopropyl and meta-arylene structures, maleimide containing a biphenylene alkylene structure, maleimide containing an aliphatic structure with 10 to 50 carbon atoms, or combinations thereof.

[0017] In one embodiment, the non-oligomeric maleimide resin comprises 4,4'-diphenylmethane bismaleimide, 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-dimethylphenylmaleimide, N-2,6-dimethylphenylmaleimide, N-phenylmaleimide, vinylbenzylmaleimide, or combinations thereof.

[0018] In one embodiment, the epoxy-modified cyclic siloxane comprises the structure shown in formula (1):

[0019]

[0020] In formula (1), n1 is an integer from 3 to 6, multiple R1s can be the same or different, and at least one of R1s is a group containing an epoxy group. Each R1 independently represents a C1 to C3 alkyl group.

[0021]

[0022]

[0023] R2 is a C1 to C3 alkyl group.

[0024] In one embodiment, the epoxy-modified cyclic siloxane comprises any one or a combination of the structures shown in formulas (1-1) to (1-3):

[0025]

[0026]

[0027] In one embodiment, the aminosiloxane comprises the structure shown in formula (2):

[0028]

[0029] In formula (2), multiple R3s may be the same or different, each of which is independently alkyl, phenyl or alkoxy, and multiple R4s may be the same or different, each of which is independently alkylene, alkenylene, alkynylene, arylene or -O-, and m is an integer from 1 to 100.

[0030] In one embodiment, the diallyl bisphenol includes diallyl bisphenol A, diallyl bisphenol F, diallyl biphenol, or a combination thereof.

[0031] Another aspect of the present invention provides a resin composition comprising the prepolymer described above.

[0032] In one embodiment, the resin composition further includes a crosslinking agent, a silicone resin, an epoxy resin, a maleimide resin, or a combination thereof.

[0033] In one embodiment, the resin composition further includes polyphenylene ether resin, polyolefin resin, benzoxazine resin, polyester resin, phenolic resin, amine curing agent, polyamide, polyimide, cyanate ester resin, maleimide triazine resin, or a combination thereof.

[0034] In one embodiment, the resin composition further includes a curing accelerator, a polymerization inhibitor, a flame retardant, an inorganic filler, a surface treatment agent, a dye, a toughening agent, a solvent, or a combination thereof.

[0035] Another aspect of the present invention provides an article made of the above-described resin composition, the article comprising a prepreg, a resin film, a laminate, or a printed circuit board.

[0036] In one embodiment, the article has one or more of the following characteristics:

[0037] According to the method of IPC-TM-650 2.4.24.5, the X-CTE in the board is less than or equal to 3.8 ppm / ℃.

[0038] The X-CTE at the plate edge, obtained by testing and calculation according to the method described in IPC-TM-650 2.4.24.5, is less than or equal to 4.0 ppm / ℃;

[0039] The difference between the X-CTE values ​​between the board center and the board edge, obtained by testing and calculation according to the method described in IPC-TM-650 2.4.24.5, is less than or equal to 0.3 ppm / ℃;

[0040] The peel strength of the copper foil after copper plating, as tested according to the method described in IPC-TM-650 2.4.8, is greater than or equal to 5.0 lb / in;

[0041] According to the method described in IPC-TM-650 2.4.39, the dimensional change Cpk of the substrate after tin bleaching treatment is greater than or equal to 1.35.

[0042] The glass transition temperature obtained by the method described in IPC-TM-650 2.4.24.4 is greater than or equal to 330°C. Detailed Implementation

[0043] To enable those skilled in the art to clearly and correctly understand the technical content of this invention, the terms and symbols mentioned in this invention are explained and defined in general below. Unless otherwise defined or implied in this specification, all terms and symbols used in this invention (including scientific terms, technical terms, and general symbols, wherein general symbols include general mathematical symbols, general physical symbols, general chemical symbols, etc.) have the same meaning as commonly understood by those skilled in the art, and should not be interpreted in an idealized or overly formalized sense.

[0044] In this invention, "any one or a combination thereof" should be interpreted as "using any one of the listed elements alone" or "using any two of the listed elements in combination" or "using any three or more of the listed elements in combination".

[0045] In this invention, the numerical ranges represented by "equal to", "=", "greater than or equal to", "≥", "less than or equal to", "≤", "to", "~", "-", "above", or "below" should be interpreted as including the endpoint values, and should cover all possible subranges and individual numerical values ​​within the range (numerical types include, but are not limited to, integers, decimals, and fractions). For example, the numerical ranges represented by "equal to 3.0", "= 3.0", "greater than or equal to 3.0", "≥ 3.0", "less than or equal to 3.0", "≤ 3.0", "above 3.0", or "below 3.0" all include the endpoint value "3.0"; the numerical ranges represented by "3.0 to 6.0", "3.0 to 6.0", and "3.0 to 6.0" all include the endpoint values ​​"3.0" and "6.0", and should be understood to include, but are not limited to, subranges such as 3.0-5.0, 4.0-6.0, and 5.0-6.0, as well as individual numerical values ​​such as 3.0, 4.0, 5.0, 5.5, and 6.0.

[0046] In this invention, the numerical ranges represented by "greater than", ">", "less than", and "<" should be interpreted as excluding endpoint values. For example, the numerical ranges represented by "greater than 3.0", ">3.0", "less than 3.0", and "<3.0" all exclude the endpoint value "3.0".

[0047] In this invention, the numerical value has a precision, which is achieved by rounding up to the nearest whole number.

[0048] In this invention, "containing unsaturated carbon-carbon double bonds" means "containing unsaturated C=C double bond groups," such as, but not limited to, vinyl, vinylbenzyl, (meth)acryloyl, allyl, etc. Wherein, "vinyl" should be interpreted to include both vinyl and vinylidene, and "(meth)acryloyl" should be interpreted to include both acryloyl and methacryloyl.

[0049] In this invention, the functional groups such as alkyl and alkenyl should be interpreted to include their various isomers. For example, "alkyl" means a group derived from aliphatic hydrocarbons and includes straight-chain, branched or cyclic groups. Furthermore, propyl should be interpreted to include n-propyl and isopropyl.

[0050] In this invention, the term "monomer" or "compound" should be interpreted to include its various isomers, such as, but not limited to, structural isomers, stereoisomers, etc.

[0051] In this invention, "parts by weight" should be interpreted as a relative number of parts by weight, which can be any unit of weight, such as, but not limited to, kilograms, grams, pounds, etc.

[0052] In this invention, wt% represents weight (or mass) percentage.

[0053] In this invention, mil is a unit of thickness, and 1 mil is approximately 25.4 micrometers; ounce is also a unit of thickness, and 1 ounce is approximately 35 micrometers.

[0054] In this invention, the polymer includes copolymers and homopolymers (self-polymers). Unless otherwise specified, the degree of polymerization (conversion rate) of the polymer is not limited; for example, it can be a fully polymerized polymer (conversion rate of 100%) or a partially polymerized polymer (conversion rate, for example, but not limited to, between 1% and 99%, which may also be referred to as a "prepolymer" in this invention). The molecular weight of the polymer is not limited; for example, polymers composed of 2 to 20 repeating units are called oligomers (also known as low-molecular-weight polymers), and typically oligomers are polymers composed of 2 to 5 repeating units.

[0055] In this invention, the molecular weight of the prepolymer refers to the product when the monomer undergoes partial polymerization and reaches an intermediate molecular weight state. The molecular weight of this product is greater than the molecular weight of the monomer before the reaction, but less than the molecular weight of the final polymer obtained after complete reaction. Furthermore, the prepolymer contains reactive functional groups that can undergo further polymerization to obtain a fully cross-linked or hardened high molecular weight product.

[0056] In this invention, different compounds are first partially polymerized to obtain prepolymers, which are then added to the resin composition. This results in different resin compositions compared to adding these compounds directly to the resin composition without prior partial polymerization. For example, resin composition 1 is obtained by adding prepolymers of compounds A, B, and C, while resin composition 2 is obtained by adding compounds A, B, and C separately without prior partial polymerization. Resin composition 1 and resin composition 2 are different resin compositions, and their products and properties also differ.

[0057] In this invention, oligomeric maleimide resin refers to a maleimide resin having repeating units and an average degree of polymerization of 0.5 to 20, which is usually a mixture of two or more maleimides with different degrees of polymerization. Non-oligomeric maleimide resin refers to a maleimide resin that does not contain repeating units and has a defined molecular structure.

[0058] The present invention will be described below with reference to specific embodiments and examples. These embodiments are merely illustrative examples of preferred implementations and do not limit the scope of protection of the present invention.

[0059] As described above, this invention discloses a prepolymer obtained by a prepolymerization reaction of a mixture, the mixture comprising the following components:

[0060] (a) Maleimide resin.

[0061] (b) Epoxy-modified cyclic siloxanes, and

[0062] (c) Compounds containing active hydrogen,

[0063] The compounds containing active hydrogen include aminosiloxanes, diallyl bisphenols, or combinations thereof.

[0064] In one embodiment, the weight-average molecular weight of the prepolymer of the present invention is 3000 to 5000.

[0065] The amounts of epoxy-modified cyclic siloxane and active hydrogen-containing compounds are calculated based on a total amount of maleimide resin of 100 parts by weight. For example, but not limited to, relative to 100 parts by weight of maleimide resin, the amount of epoxy-modified cyclic siloxane is 3 to 30 parts by weight, preferably 3 to 25 parts by weight, for example, including but not limited to 3 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 28 parts by weight, and 30 parts by weight; relative to 100 parts by weight of maleimide resin, the amount of active hydrogen-containing compounds is 5 to 45 parts by weight, preferably 5 to 40 parts by weight, for example, including but not limited to 5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 42 parts by weight, and 45 parts by weight.

[0066] Prepolymerization is a process in which one or more monomers undergo partial polymerization to obtain a prepolymer, wherein the monomer conversion rate is between 0% and 100% (excluding 0% and 100%). A small amount of unreacted (unconverted) monomer can increase the compatibility and crosslinking degree of the prepolymer resin in the resin composition. Specifically, a monomer conversion rate of 0% means that the monomer has not reacted at all and cannot form a prepolymer. Similarly, a monomer conversion rate of 100% means that the monomer has reacted completely and therefore cannot form a prepolymer. Preferably, the monomer conversion rate of the prepolymer of the present invention is between 1% and 99%, and more preferably, the monomer conversion rate is, for example, but not limited to, between 10% and 90%. The method for determining the monomer conversion rate of the present invention is not particularly limited and can be tested by various methods known in the art, such as, but not limited to, using gas chromatography to analyze the monomer conversion rate.

[0067] In one embodiment, the maleimide resin includes oligomeric maleimide resin, non-oligomeric maleimide resin, or a combination thereof.

[0068] In one embodiment, the maleimide resin comprises 70-100 wt% non-oligomeric maleimide resin and 0-30 wt% oligomeric maleimide resin.

[0069] In one embodiment, the oligomeric maleimide resin includes polyphenylene maleimide, maleimide containing an indane structure, maleimide containing isopropyl and meta-arylene structures, maleimide containing a biphenylene alkylene structure, maleimide containing an aliphatic structure with 10 to 50 carbon atoms, or combinations thereof.

[0070] Oligomeric maleimide resins include maleimide resins manufactured by Daiwakasei Industry Co., Ltd. under the trade names BMI-2000 and BMI-2300, maleimide resins manufactured by Nippon Kayaku Co., Ltd. under the trade names MIR-3000 or MIR-5000, and maleimide resins containing indane structures manufactured by DIC. Maleimide resins containing aliphatic structures with 10 to 50 carbon atoms, or imide-elongated maleimide resins, may include various imide-elongated maleimide resins disclosed in Taiwan Patent Application Publication No. TW200508284A, all of which are incorporated herein by reference. The aliphatic maleimide resins containing 10 to 50 carbon atoms suitable for use in this invention may include, for example, but not limited to, maleimide resins manufactured by Designer Molecules Inc. under trade names such as BMI-1400, BMI-1500, BMI-1700, BMI-2500, BMI-3000, BMI-5000, and BMI-6000.

[0071] In one embodiment, the non-oligomeric maleimide resin comprises 4,4'-diphenylmethane bismaleimide, 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-dimethylphenylmaleimide, N-2,6-dimethylphenylmaleimide, N-phenylmaleimide, vinylbenzylmaleimide, or combinations thereof.

[0072] Non-oligomeric maleimide resins include, for example, but not limited to, maleimide resins produced by Daiwakasei Industry Co., Ltd. under trade names such as BMI-1000, BMI-1000H, BMI-1100, BMI-1100H, BMI-3000, BMI-3000H, BMI-4000, BMI-5000, BMI-5100, BMI-TMH, BMI-7000 and BMI-7000H, or maleimide resins produced by KI Chemical Industry Co., Ltd. under trade names such as BMI-70 and BMI-80.

[0073] In one embodiment, the epoxy-modified cyclic siloxane comprises the structure shown in formula (1):

[0074]

[0075] In formula (1), n1 is an integer from 3 to 6, multiple R1s can be the same or different, and at least one of R1s is a group containing an epoxy group. Each R1 independently represents a C1 to C3 alkyl group.

[0076]

[0077] R2 is a C1 to C3 alkyl group.

[0078] In one embodiment, the epoxy-modified cyclic siloxane comprises any one or a combination of the structures shown in formulas (1-1) to (1-3):

[0079]

[0080]

[0081] In one embodiment, the aminosiloxane comprises the structure shown in formula (2):

[0082]

[0083] In formula (2), multiple R3s may be the same or different, each of which is independently alkyl, phenyl or alkoxy, and multiple R4s may be the same or different, each of which is independently alkylene, alkenylene, alkynylene, arylene or -O-, and m is an integer from 1 to 100.

[0084] The aminosiloxanes applicable to this application include, but are not limited to, aminosiloxanes manufactured by Shin-Etsu Chemical Industry Co., Ltd. under trade names such as PAM-E, KF-8010, X-22-161A, X-22-161B, KF-8012, KF-8008, X-22-9409, X-22-1660B-3, etc., and aminosiloxanes manufactured by Toray-Dow Corning Co., Ltd. under trade names such as BY-16-853U, BY-16-853, BY-16-853B, etc., or combinations thereof.

[0085] In one embodiment, the diallyl bisphenol includes diallyl bisphenol A, diallyl bisphenol F, diallyl biphenol, or a combination thereof.

[0086] On the other hand, the present invention also provides a resin composition comprising the aforementioned prepolymer.

[0087] In one embodiment, the resin composition further includes a crosslinking agent, a silicone resin, an epoxy resin, a maleimide resin, or a combination thereof.

[0088] The crosslinking agent includes bis(vinylphenyl)ethane (BVPE), divinylbenzene (DVB), divinylnaphthalene, divinylbiphenyl, triallyl isocyanurate (TAIC), triallyl cyanurate (TAC), vinylbenzocyclobutene (VBCB), di(vinylbenzyl)ether (BVBE), diallyl bisphenol A, diallyl bisphenol F, diallyl biphenyl, trivinylcyclohexane (TVCH), difunctional or higher acrylates, butadiene, decadiene, octadiene, or combinations thereof. The crosslinking agent content is 0 to 30 parts by weight relative to 100 parts by weight of the prepolymer of the present invention.

[0089] The difunctional or higher-functional acrylates include, but are not limited to, difunctional, trifunctional, or tetrafunctional or higher-functional acrylates, and may be purchased from Shin-Nakamura Chemical Industry Co., Ltd., Kyoeisha Chemical Co., Ltd., Nippon Kayaku Co., Ltd., or Sartomer Co., Ltd. The difunctional acrylates include, but are not limited to, diallyl isophthalate (DAIP), dioxanediol diacrylate, tricyclodecanediethanol diacrylate, tricyclodecanediethanol dimethacrylate, or combinations thereof.

[0090] The silicone resins include, but are not limited to, polyalkyl silicone resins, polyaryl silicone resins, polyalkylaryl silicone resins, modified silicone resins, or combinations thereof. Modified silicone resins include, but are not limited to, methacrylamide-modified silicone resins, hydroxyl-modified silicone resins, carboxyl-modified silicone resins, amino-modified silicone resins (including the aforementioned aminosiloxanes), epoxy-modified silicone resins, or combinations thereof. The silicone resin content is 0 to 20 parts by weight relative to 100 parts by weight of the prepolymer of the present invention.

[0091] The epoxy resin may be any type of epoxy resin known in the art. From the perspective of improving the heat resistance of the resin composition, the epoxy resin includes, but is not limited to, any one or a combination of, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AD ​​epoxy resin, phenolic (novolac) epoxy resin, trifunctional epoxy resin, tetrafunctional epoxy resin, multifunctional phenolic epoxy resin, dicyclopentadiene (DCPD) epoxy resin, phosphorus-containing epoxy resin, p-xylene epoxy resin, naphthalene-type epoxy resin (e.g., naphthol-type epoxy resin), benzofuran-type epoxy resin, and isocyanate-modified epoxy resin. In this invention, the phenolic epoxy resin may be phenol novolac epoxy resin, bisphenol A novolac epoxy resin, bisphenol F novolac epoxy resin, biphenyl novolac epoxy resin, phenol benzaldehyde epoxy resin, phenol aralkylnovolac epoxy resin, or o-cresol novolac epoxy resin. In this invention, the phosphorus-containing epoxy resin may be DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) epoxy resin, DOPO-HQ epoxy resin, or a combination thereof.The aforementioned DOPO epoxy resin may be selected from one or more of the following: DOPO-containing phenol novolac epoxy resin, DOPO-containing o-cresol novolac epoxy resin, and DOPO-containing bisphenol-A novolac epoxy resin; the aforementioned DOPO-HQ epoxy resin may be selected from one or more of the following: DOPO-HQ-containing phenolnovolac epoxy resin, DOPO-HQ-containing o-cresol novolac epoxy resin, and DOPO-HQ-containing bisphenol-A novolac epoxy resin, and is not limited thereto. The epoxy resin content is 0 to 20 parts by weight relative to 100 parts by weight of the prepolymer of the present invention.

[0092] The maleimide resin applicable to this invention is as described above, including various oligomeric maleimide resins, non-oligomeric maleimide resins, or combinations thereof, wherein the content of maleimide resin is 0 to 70 parts by weight relative to 100 parts by weight of the prepolymer of this invention.

[0093] In one embodiment, the resin composition further includes polyphenylene ether resin, polyolefin resin, benzoxazine resin, polyester resin, phenolic resin, amine curing agent, polyamide, polyimide, cyanate ester resin, maleimide triazine resin, or a combination thereof.

[0094] Unless otherwise specified, in the resin composition of the present invention, the amount of each component added is calculated based on a total amount of 100 parts by weight of the prepolymer of the present invention. For example, relative to 100 parts by weight of the prepolymer of the present invention, the amounts of polyphenylene ether resin, polyolefin resin, benzoxazine resin, polyester resin, phenolic resin, polyamide, polyimide, cyanate ester resin, and maleimide triazine resin are not particularly limited and can be adjusted as needed. Each component can be independently 1 part by weight to 100 parts by weight, for example, but not limited to 1 part by weight, 5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 50 parts by weight, or 100 parts by weight. Relative to 100 parts by weight of the prepolymer of the present invention, the amount of amine curing agent is not particularly limited and can be adjusted as needed. The amount of amine curing agent can be 1 part by weight to 30 parts by weight.

[0095] There are no particular limitations on the polyphenylene ether resins applicable to this invention. They can be any type of polyphenylene ether resin known in the art, and can be any one or more commercially available products, homemade products, or combinations thereof. For example, they include, but are not limited to, hydroxyl-containing polyphenylene ether resins (e.g., SA90, SA120, which can be purchased from Sabic), polyphenylene ether resins containing unsaturated carbon-carbon double bonds, or combinations thereof. The polyphenylene ether resins containing unsaturated carbon-carbon double bonds include any one or a combination of vinyl benzyl polyphenylene ether resin, (meth)acryloyl polyphenylene ether resin, vinyl polyphenylene ether resin, and allyl polyphenylene ether resin.

[0096] The polyphenylene ether resin containing unsaturated carbon-carbon double bonds of the present invention has unsaturated carbon-carbon double bonds and a phenylene ether backbone, wherein the unsaturated carbon-carbon double bonds are reactive functional groups, which can self-polymerize upon heating, or undergo free radical polymerization with other components containing unsaturated bonds in the resin composition and ultimately crosslink and cure. Preferably, the polyphenylene ether resin containing unsaturated carbon-carbon double bonds includes a polyphenylene ether resin containing unsaturated carbon-carbon double bonds in which the phenylene ether backbone is substituted with 2,6-dimethyl groups. After substitution, the methyl groups form steric barriers, making it difficult for the oxygen atoms on the ether to form hydrogen bonds or van der Waals forces, thus preventing moisture absorption.

[0097] Polyphenylene ether resins containing unsaturated carbon-carbon double bonds include, but are not limited to, vinyl benzyl polyphenylene ether resins with a number average molecular weight of about 1200 (e.g., OPE-2st 1200, available from Mitsubishi Gas Chemical Company), vinyl benzyl polyphenylene ether resins with a number average molecular weight of about 2200 (e.g., OPE-2st 2200, available from Mitsubishi Gas Chemical Company), vinyl benzyl polyphenylene ether resins with a number average molecular weight of about 2400 to 2800 (e.g., vinyl benzyl bisphenol A polyphenylene ether resin), (meth)acryloyl polyphenylene ether resins with a number average molecular weight of about 1900 to 2300 (e.g., SA9000, available from Sabic Company), vinyl polyphenylene ether resins with a number average molecular weight of about 2200 to 3000, or combinations thereof. The vinyl polyphenylene ether resins may include all types of polyphenylene ether resins disclosed in U.S. Patent Application US20160185904A1, all of which are incorporated herein by reference. Vinyl benzyl polyphenylene ether resin includes, but is not limited to, vinyl benzyl biphenyl polyphenylene ether resin, vinyl benzyl bisphenol A polyphenylene ether resin, or combinations thereof.

[0098] The polyolefin resin includes, but is not limited to, any one or a combination of polybutadiene, polyisoprene, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-butadiene-divinylbenzene polymer, vinyl-polybutadiene-urea polymer, polymethylstyrene, hydrogenated polybutadiene, hydrogenated polyisoprene, hydrogenated styrene-butadiene-divinylbenzene polymer, hydrogenated styrene-butadiene copolymer, hydrogenated styrene-isoprene copolymer, styrene-ethylene-divinylbenzene polymer, and styrene-ethylvinylbenzene-divinylbenzene polymer.

[0099] The styrene-ethylvinylbenzene-divinylbenzene polymers used in this invention may include various styrene-ethylvinylbenzene-divinylbenzene polymers disclosed in U.S. Patent US20070129502A1, all of which are incorporated herein by reference.

[0100] The benzoxazine resins include, but are not limited to, bisphenol A type benzoxazine resins, bisphenol F type benzoxazine resins, phenolphthalein type benzoxazine resins, dicyclopentadiene type benzoxazine resins, phosphorus-containing benzoxazine resins, diamine type benzoxazine resins, and phenyl, vinyl, or allyl modified benzoxazine resins. Applicable commercially available products include, for example, those sold by Huntsman under the trade names LZ-8270 (phenolphthalein type benzoxazine resin), LZ-8298 (modified benzoxazine resin), LZ-82818 (bisphenol F type benzoxazine resin), and LZ-82919 (bisphenol A type benzoxazine resin), or those sold by Kolon Industries, Inc. under the trade names KZH-5031 (allyl modified benzoxazine resin) and KZH-5032 (phenyl modified benzoxazine resin). The diamine-type benzoxazine resin may be a diaminodiphenylmethane benzoxazine resin, a diaminodiphenyl ether type benzoxazine resin, a diaminodiphenyl sulfone benzoxazine resin, a diaminodiphenyl sulfide benzoxazine resin, or a combination thereof, and is not limited thereto.

[0101] The polyester resin may be any type of polyester resin known in the art. Specific examples include, but are not limited to, polyester resins containing a dicyclopentadiene structure, polyester resins containing a biphenyl structure, and polyester resins containing a naphthalene ring structure. Specific examples include, but are not limited to, the trade names HPC-8000-65T, HPC-8800, or HPC-8150-62T sold by DIC Corporation.

[0102] The phenolic resin may be any type of phenolic resin known in the art. Specific examples include, but are not limited to, phenolic resins or phenoxy resins, wherein phenolic resins include, but are not limited to, phenolic resins, o-methylphenolic resins, bisphenol A phenolic resins, naphthol phenolic resins, biphenyl phenolic resins, and dicyclopentadienol resins.

[0103] The amine curing agent may be any type of amine curing agent known in the art. Specific examples include, but are not limited to, diaminodiphenyl sulfone, diaminodiphenylmethane, diaminodiphenyl ether, diaminodiphenyl sulfide, and dicyandiamide.

[0104] The polyamide can be any type of polyamide known in the art. Specific examples include, but are not limited to, various commercially available polyamide resin products.

[0105] The polyimide can be any type of polyimide known in the art. Specific examples include, but are not limited to, various commercially available polyimide resin products.

[0106] The cyanate ester resin can be any type of cyanate ester resin known in the art, such as compounds having an Ar-OC≡N structure, wherein Ar can be a substituted or unsubstituted aromatic group. From the perspective of improving the heat resistance of the resin composition, specific examples include, but are not limited to, phenolic cyanate ester resins, bisphenol A cyanate ester resins, bisphenol F cyanate ester resins, cyanate ester resins containing a dicyclopentadiene structure, cyanate ester resins containing a naphthalene ring structure, phenolphthalein cyanate ester resins, adamantane cyanate ester resins, fluorene cyanate ester resins, or combinations thereof. Among these, the phenolic cyanate ester resin can be bisphenol A phenolic cyanate ester resin, bisphenol F phenolic cyanate ester resin, or combinations thereof. Cyanate ester resins can be those produced by Arxada AG under trade names such as Primaset PT-15, PT-30, PT-30S, PT-60, PT-60S, BA-200, BA-230S, BA-3000, BA-3000S, BA-4000, BA-4000S, DT-4000, DT-7000, ULL950S, HTL-300, LVT-50, LVT-100, and LeCy.

[0107] The maleimide triazine resin may be any type of maleimide triazine resin known in the art. Specific examples include, but are not limited to: maleimide triazine resin obtained by polymerizing maleimide resin with bisphenol A type cyanate resin; maleimide triazine resin obtained by polymerizing maleimide resin with bisphenol F type cyanate resin; maleimide triazine resin obtained by polymerizing maleimide resin with phenolic phenolic cyanate resin; and maleimide triazine resin obtained by polymerizing maleimide resin with cyanate resin containing a dicyclopentadiene structure. In one embodiment, the maleimide triazine resin may be obtained by polymerizing the aforementioned maleimide resin and the aforementioned cyanate resin in any molar ratio; the molar ratio of maleimide resin to cyanate resin may be 1:1 to 10, for example, but not limited to 1:1, 1:2, 1:4, 1:6, 1:8, and 1:10.

[0108] In one embodiment, the resin composition further includes a curing accelerator, a polymerization inhibitor, a flame retardant, an inorganic filler, a surface treatment agent, a dye, a toughening agent, a solvent, or a combination thereof.

[0109] The curing accelerator may include catalysts such as Lewis bases or Lewis acids. Lewis bases may include one or more of the following: imidazole, boron trifluoride amine complex, ethyltriphenyl phosphonium chloride, 2-methylimidazole (2MI), 2-phenyl-1H-imidazole (2PZ), 2-ethyl-4-methylimidazole (2E4MZ), triphenylphosphine (TPP), and 4-dimethylaminopyridine (DMAP). Lewis acids may include metal salt compounds, such as manganese, iron, cobalt, nickel, copper, zinc, etc., and metal catalysts such as zinc octanoate and cobalt octanoate. The curing accelerator also includes curing initiators, such as peroxides that can generate free radicals. Curing initiators include, but are not limited to, diisopropylbenzene peroxide (DCP), tert-butyl peroxybenzoate, dibenzoyl peroxide (BPO), 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne (DYBP), di-tert-butyl peroxide (DTBP), and bis(tert-butylperoxyisopropyl)benzene or combinations thereof. In one embodiment, the resin composition of the present invention may further comprise 0.01 to 5.0 parts by weight of curing accelerator, preferably 0.1 to 4.0 parts by weight, more preferably 0.1 to 1.0 parts by weight, but not limited thereto, compared to 100 parts by weight of the prepolymer of the present invention.

[0110] The polymerization inhibitor may include, but is not limited to, 1,1-diphenyl-2-trinitrophenylhydrazine, methacrylonitrile, nitroxide-stabilized free radicals, triphenylmethyl free radicals, metal ion free radicals, sulfur free radicals (e.g., including but not limited to dithioesters), hydroquinone, p-methoxyphenol, p-benzoquinone, phenthiazide, β-phenylnaphthylamine, p-tert-butylcatechol, methylene blue, 4,4'-butylenebis(6-tert-butyl-3-methylphenol), and 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), or combinations thereof. The aforementioned nitroxide-stabilized free radicals may include, but are not limited to, 2,2,6,6-substituted-1-piperidinoxy free radicals or 2,2,5,5-substituted-1-pyrrolidineoxy free radicals derived from cyclic hydroxylamines. As substituents, preferably alkyl groups with four or fewer carbon atoms, such as methyl or ethyl. The specific nitroxide free radical compounds are not limited, and examples include, but are not limited to, 2,2,6,6-tetramethyl-1-piperidineoxy radical, 2,2,6,6-tetraethyl-1-piperidineoxy radical, 2,2,6,6-tetramethyl-4-oxo-1-piperidineoxy radical, 2,2,5,5-tetramethyl-1-pyrrolidineoxy radical, 1,1,3,3-tetramethyl-2-isodihydroindoleoxy radical, N,N-di-tert-butylamineoxy radical, etc. Stable free radicals such as galvinoxyl radicals can also be used instead of nitroxide free radicals. The polymerization inhibitors suitable for the resin compositions of the present invention can also be products derived from the substitution of hydrogen atoms or groups in the inhibitor by other atoms or groups. For example, products derived from the substitution of hydrogen atoms in the inhibitor by groups such as amino, hydroxyl, or ketone carbonyl groups. In one embodiment, the resin composition of the present invention may further comprise, but is not limited thereto, 0.001 to 20 parts by weight of a polymerization inhibitor, preferably 0.01 to 10 parts by weight of a polymerization inhibitor, compared to 100 parts by weight of the prepolymer of the present invention.

[0111] The flame retardants include, but are not limited to, phosphorus-containing or bromine-containing flame retardants. Bromine-containing flame retardants preferably include decabromodiphenyl ethane. Phosphorus-containing flame retardants preferably include: hydroquinone bis-(diphenyl phosphate), bisphenol A bis-(diphenyl phosphate), tri(2-carboxyethyl)phosphine (TCEP), trichloroisopropyl phosphate, trimethyl phosphate (TMP), dimethyl methylphosphonate (DMMP), resorcinol bis(dixylenyl phosphate), RDX (such as commercially available products like PX-200, PX-201, PX-202, etc.), ammonium polyphosphate, and melamine phosphate. Polyphosphate, phosphazene compounds (such as commercially available products like SPB-100, SPH-100, SPV-100), 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) compounds and their derivatives or resins (e.g., bisDOPO compounds), diphenylphosphine oxide (DPPO) compounds and their derivatives or resins (e.g., bisDPPO compounds), melamine cyanurate and trishydroxyethyl isocyanurate, aluminum phosphonates (e.g., OP-930, OP-935, etc.), or combinations thereof.

[0112] The flame retardant may be a flame retardant sold by Katayama Chemical Industry Co., Ltd., such as, but not limited to, V1, V2, V3, V4, V5, V7, S-2, S-4, E-4c, E-7c, E-8g, E-9g, E-10g, E-100, B-3, W-1o, W-2h, W-2o, W-3o, W-4o, OX-1, OX-2, OX-4, OX-6, OX-6+, OX-7, OX-7+, OX-13, BPE-1, BPE-3, HyP-2, API-9, CMPO, ME-20, C-1R, C-1S, C-3R, C-3S, or C-11R. The flame retardant of the present invention may include one or more of the above. Compared to 100 parts by weight of the prepolymer of the present invention, the resin composition of the present invention may further include 1 to 100 parts by weight of a flame retardant, preferably 5 to 50 parts by weight of a flame retardant.

[0113] The inorganic fillers include, but are not limited to: silica (molten, non-molten, porous, or hollow), alumina, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, silicon aluminum 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 (AlOOH), calcined talc, talc, silicon nitride, zirconium tungstate, litharge, calcined kaolin, or combinations thereof. Furthermore, the inorganic fillers can be spherical (including solid or hollow spheres), fibrous, plate-like, granular, flake-like, or needle-like, and may be selectively pretreated with a silane coupling agent. Furthermore, the inorganic filler can be prepared by various methods, such as melt processing, deflagration, and chemical synthesis. The particle size of the inorganic filler is not particularly limited, but the median particle size D50 can be 1 to 45 micrometers, preferably 1 to 15 micrometers, and more preferably 1 to 10 micrometers. The inorganic filler can be a powder or a slurry. In one embodiment, the resin composition of the present invention may further comprise 10 to 450 parts by weight of inorganic filler, preferably 100 to 400 parts by weight, but not limited thereto, compared to 100 parts by weight of the prepolymer of the present invention.

[0114] The surface treatment agents include, but are not limited to, silane coupling agents (such as siloxane compounds), which can be further classified according to the type of functional group as amino silane coupling agents, epoxy silane coupling agents, vinyl silane coupling agents, hydroxy silane coupling agents, isocyanate silane coupling agents, methacryloxy silane coupling agents, and acryloyloxy silane coupling agents. The main function of adding surface treatment agents in this invention is to ensure that the inorganic filler is uniformly dispersed in the resin composition. In one embodiment, compared to 100 parts by weight of the prepolymer of this invention, the resin composition of this invention may further include 0.001 parts by weight to 20 parts by weight of surface treatment agent, preferably 0.01 parts by weight to 10 parts by weight of surface treatment agent, but not limited thereto.

[0115] The dyeing agent may include, but is not limited to, dyes or pigments. In one embodiment, the resin composition of the present invention may further include 0.001 to 10 parts by weight of dyeing agent, preferably 0.01 to 5 parts by weight of dyeing agent, but not limited thereto, compared to 100 parts by weight of the prepolymer of the present invention.

[0116] The toughening agent may include, but is not limited to, carboxyl-terminated butadiene acrylonitrile rubber (CTBN), core-shell rubber, ethylene propylene rubber, and other compounds or combinations thereof. In one embodiment, the resin composition of the present invention may further include 1 to 20 parts by weight of toughening agent, preferably 3 to 10 parts by weight of toughening agent, but not limited thereto, compared to 100 parts by weight of the prepolymer of the present invention.

[0117] The solvents include, but are not limited to: methanol, ethanol, ethylene glycol monomethyl ether, acetone, butanone (also known as methyl ethyl ketone), methyl isobutyl ketone, cyclohexanone, N-methylpyrrolidone, toluene, xylene, methoxyethyl acetate, ethoxyethyl acetate, propoxyethyl acetate, ethyl acetate, dimethylformamide, dimethylacetamide, propylene glycol methyl ether acetate, and other solvents or mixtures thereof. The amount of solvent added is intended to completely dissolve the resin and adjust it to a specific total solids content of the resin composition. In one embodiment, the amount of solvent added is adjusted to a total solids content of 50% to 85% (by weight) of the resin composition, but is not limited thereto.

[0118] In addition to the aforementioned resin composition, the present invention also provides an article made from the above-mentioned resin composition, such as a component suitable for use in various electronic products, including but not limited to: prepreg, resin film, laminate, or printed circuit board.

[0119] The resin composition of the present invention can be made into a prepreg, which includes a reinforcing material and a layer disposed on the reinforcing material. The layer is obtained by heating the aforementioned resin composition at a high temperature to form a semi-cured state (B-stage). The baking temperature for making the prepreg is between 100°C and 180°C, preferably between 120°C and 160°C. The reinforcing material can be any of a fiber material, woven fabric, or nonwoven fabric, and the woven fabric preferably includes glass fiber cloth. There is no particular limitation on the type of glass fiber cloth; it can be any type of glass fiber cloth suitable for printed circuit boards, such as E-type glass fiber cloth, D-type glass fiber cloth, S-type glass fiber cloth, T-type glass fiber cloth, L-type glass fiber cloth, Q-type glass fiber cloth, or QL-type glass fiber cloth (a glass fiber cloth with a mixed structure made of Q glass and L glass). The types of glass fibers include yarn and roving, and the form includes open or closed fibers, with end face shapes including round or flat shapes. The aforementioned nonwoven fabric preferably includes liquid crystal resin nonwoven fabric, such as polyester nonwoven fabric, polyurethane nonwoven fabric, etc., but is not limited thereto. The aforementioned fabric may also include liquid crystal resin fabric, such as polyester fabric or polyurethane fabric, and is not limited thereto. This reinforcing material can increase the mechanical strength of the prepreg. In a preferred embodiment, the reinforcing material may also be selectively pretreated with a silane coupling agent. The prepreg subsequently undergoes heating and curing (C-stage) to form an insulating layer.

[0120] The resin composition of the present invention can be made into a resin film, which is obtained by baking and heating the aforementioned resin composition to form a semi-cured state. The resin composition can be selectively coated onto a support material, including but not limited to liquid crystal resin film, polytetrafluoroethylene film, polyethylene terephthalate film (PET film), polyimide film (PI film), metal foil or resin-coated copper (RCC) foil, and then baked and heated to form a semi-cured state, so that the resin composition forms a resin film.

[0121] The resin composition of this invention can be used to form various laminates comprising at least two metal foils and at least one insulating layer disposed between the two metal foils. The insulating layer can be formed by curing the aforementioned resin composition under high temperature and high pressure (C-stage). Applicable curing temperatures are, for example, between 190°C and 250°C, preferably between 200°C and 240°C, with a curing time of 90 to 180 minutes, preferably 120 to 150 minutes. Applicable pressing pressures are, for example, between 300 psi and 550 psi, preferably between 400 psi and 550 psi. The aforementioned insulating layer can be obtained by curing the aforementioned prepreg or resin film. The aforementioned metal foils can be made of copper, aluminum, nickel, platinum, silver, gold, or alloys thereof, such as copper foil. In a preferred embodiment, the laminate is a copper foil substrate.

[0122] The aforementioned multilayer board can be further processed into a printed circuit board. One method of manufacturing the printed circuit board of this invention involves using a double-sided copper-clad laminate (e.g., product EM-827, available from Taiguang Electronic Materials (Kunshan) Co., Ltd.) with a thickness of 28 mils and 1 ounce HTE (High Temperature Elongation) copper foil. After drilling, electroplating is performed to create electrical conductivity between the upper and lower copper foil layers. The upper and lower copper foil layers are then etched to form the inner layer circuitry. Next, the inner layer circuitry undergoes a browning and roughening treatment to create a surface texture. Then, the copper foil, the aforementioned prepreg, the aforementioned inner layer circuit board, the aforementioned prepreg, and the copper foil are stacked sequentially, and then heated in a vacuum lamination apparatus at a temperature of 190°C–240°C for 90–180 minutes to cure the insulating material of the prepreg. Next, various circuit board processes known in the art, such as blackening, drilling, and copper plating, are performed on the outermost copper foil to obtain a printed circuit board.

[0123] Articles made from the resin compositions of the foregoing embodiments contain reinforcing or supporting materials and semi-cured or cured products obtained by heating and chemically cross-linking the resin compositions.

[0124] In one embodiment, the article has one, more, or all of the following characteristics:

[0125] The X-CTE in the board, as determined by testing and calculation according to the method in IPC-TM-650 2.4.24.5, is less than or equal to 3.8 ppm / ℃, for example, between 3.2 ppm / ℃ and 3.8 ppm / ℃.

[0126] The X-CTE at the board edge, obtained by testing and calculation according to the method described in IPC-TM-650 2.4.24.5, is less than or equal to 4.0 ppm / ℃, for example, between 3.3 ppm / ℃ and 4.0 ppm / ℃;

[0127] The difference between the X-CTE values ​​at the center and the edge of the board, obtained by testing and calculation according to the method described in IPC-TM-650 2.4.24.5, is less than or equal to 0.3 ppm / ℃, for example, between 0 ppm / ℃ and 0.3 ppm / ℃;

[0128] The peel strength of the copper foil after copper plating, as tested according to the method described in IPC-TM-650 2.4.8, is greater than or equal to 5.0 lb / in, for example, between 5.0 lb / in and 6.4 lb / in;

[0129] The length of the heterogeneous flow is less than or equal to 2 mm, for example, between 1 mm and 2 mm, or even 0 mm;

[0130] According to the method described in IPC-TM-650 2.4.39, the dimensional change Cpk of the substrate after tin bleaching treatment is greater than or equal to 1.35, for example, between 1.35 and 1.85.

[0131] The glass transition temperature obtained by the method described in IPC-TM-650 2.4.24.4 is greater than or equal to 330°C, for example, between 330°C and 350°C, or even greater than 350°C.

[0132] Examples and comparative examples of the present invention, which use various raw materials from the following sources and prepare prepolymers 1 to 16 and comparative prepolymers 1 to 6 according to the amounts in Tables 1 to 4, and formulate resin compositions according to the amounts in Tables 5 to 9, are further made into test samples or articles.

[0133] MI 1: Maleimide containing isopropyl and meta-aryl structures, with the following structural formula, where n = 1 to 10, commercially available.

[0134]

[0135] MI 2: Maleimide containing a biphenyl structure, with the following structural formula, where n = 1 to 10, commercially available.

[0136]

[0137] Indane MI: The structural formula is as follows, where n = 0.5~20, and it is commercially available.

[0138]

[0139] BMI-2300: Polyphenylene maleimide, with the following structural formula, where n = 0.5–20, purchased from Daiwa Chemical Industry Co., Ltd.

[0140]

[0141] BMI-3000: A maleimide resin with an aliphatic structure containing 10 to 50 carbon atoms, with the following structural formula, where n = 1 to 10. Purchased from the designer's molecular company.

[0142]

[0143] BMI-5100: 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, purchased from Daiwa Chemical Industry Co., Ltd.

[0144] BMI-4000: Bisphenol A diphenyl ether bismaleimide, purchased from Yamato Chemical Co., Ltd.

[0145] BMI-1000: 4,4'-diphenylmethane bismaleimide, purchased from Daiwa Chemical Industries, Ltd.

[0146] X-40-2670, purchased from Shin-Etsu Chemical Industry Co., Ltd., has the following structural formula:

[0147]

[0148] X-40-2678, purchased from Shin-Etsu Silicone Co., Ltd., structural formula as follows:

[0149]

[0150] YL9029, purchased from Mitsubishi Chemical, has the following structural formula:

[0151]

[0152] X-22-161A: Aminosiloxane, amino equivalent of 800 g / eq, purchased from Shin-Etsu Chemical Industry Co., Ltd.

[0153] X-22-161B: Aminosiloxane, amino equivalent of 1500 g / eq, purchased from Shin-Etsu Chemical Industry Co., Ltd.

[0154] KF-8012: Aminosiloxane, amino equivalent of 2200 g / eq, purchased from Shin-Etsu Chemical Industry Co., Ltd.

[0155] DABPA: Diallyl Bisphenol A, commercially available.

[0156] DABPD: diallyl biphenol, commercially available.

[0157] NC-3000: Biphenyl-type epoxy resin, purchased from Nippon Kayaku Co., Ltd.

[0158] SA90: Hydroxyl polyphenylene ether resin, purchased from Saudi Basic Industries Corporation (SABIC).

[0159] Ricon 100: Styrene-butadiene copolymer, purchased from Cray Valley SA.

[0160] Momentive coatosil MP200 is obtained by hydrolysis and condensation of the following structure, wherein R5 to R7 are each independently a saturated alkane group with 1 to 5 carbon atoms, and R8 is an alkoxy group or a saturated alkane group with 1 to 5 carbon atoms.

[0161]

[0162] TPP: Triphenyl phosphate, purchased from Shanghai McLean Biochemical Technology Co., Ltd.

[0163] Synthetic spherical silica slurry: The median particle size D50 of the spherical silica is about 2.5±2 micrometers. It is produced by microemulsification and is chemically synthesized spherical silica with a surface treated with silane coupling agent. It is commercially available and has a solid content of about 70%.

[0164] Solvent: Dimethylacetamide (DMAC) and butanone in a weight ratio of 2:1. Both DMAC and butanone are commercially available. The solvent content is expressed as "appropriate amount," meaning that the solvent content is adjusted to a total solid content (S / C = 60% to 68%) of the resin composition.

[0165] Manufacturing Example 1: Preparation of Prepolymer 1

[0166] In a reaction vessel, 100 parts by weight of propylene glycol methyl ether acetate (PMA) solvent and 100 parts by weight of maleimide resin (BMI-4000) are added. The mixture is heated to 110°C and stirred for 15 minutes to dissolve the maleimide resin. Then, 30 parts by weight of a compound containing active hydrogen (amino-modified siloxane X-22-161B) are added dropwise. The mixture is heated to 120°C and stirred for 2 hours. Then, the mixture is cooled to 70°C, and 3 parts by weight of epoxy-modified cyclic siloxane (X-40-2670) are added. The mixture is stirred for another 2 hours. After cooling, a solution of prepolymer 1 is obtained. The conversion rate of each monomer is between 10% and 90%.

[0167] Manufacturing Examples 2 to 16: Preparation of Prepolymer 2 to Prepolymer 16

[0168] Referring to the prepolymer preparation method of Manufacturing Example 1 above, using the amounts in Tables 1 to 3, maleimide resin was added to 100 parts by weight of PMA, stirred at 110°C for 15 minutes to dissolve the maleimide resin, then a compound containing active hydrogen was added dropwise, the temperature was raised to 120°C and stirred for 2 hours, then the temperature was lowered to 70°C, epoxy-modified cyclic siloxane was added, and the reaction was continued for 2 hours to obtain solutions of prepolymers 2 to 16, with the conversion rate of each monomer ranging from 10% to 90%.

[0169] Comparative Manufacturing Example 1: Preparation of Comparative Prepolymer 1

[0170] Using the dosages in Table 4, maleimide resin was added to 100 parts by weight of PMA and stirred at 110°C for 15 minutes to dissolve the maleimide resin. Then, the temperature was lowered to 70°C, epoxy-modified cyclic siloxane was added, and the mixture was stirred for 2 hours to obtain a solution of the comparative prepolymer 1. The conversion rate of each monomer was between 10% and 90%.

[0171] Comparative Manufacturing Examples 2 to 4: Preparation of Comparative Prepolymer 2 to Comparative Prepolymer 4

[0172] Using the dosages in Table 4, maleimide resin was added to 100 parts by weight of PMA and stirred at 110°C for 15 minutes to dissolve the maleimide resin. Then, a compound containing active hydrogen was added dropwise, and the temperature was raised to 120°C and stirred for 2 hours to obtain solutions of comparative prepolymer 2 to comparative prepolymer 4. The conversion rate of each monomer is between 10% and 90%.

[0173] Comparative Manufacturing Example 5: Preparation of Comparative Prepolymer 5

[0174] Using the dosages in Table 4, add 100 parts by weight of PMA and a compound containing active hydrogen, heat to 120°C and stir for 2 hours, then cool to 70°C, add epoxy-modified cyclic siloxane, and continue the reaction for 2 hours to obtain a solution of the comparative prepolymer 5, with the conversion rate of each monomer ranging from 10% to 90%.

[0175] Comparative Manufacturing Example 6: Preparation of Comparative Prepolymer 6

[0176] Using the amounts in Table 4, maleimide resin was added to 100 parts by weight of PMA and stirred at 110°C for 15 minutes to dissolve the maleimide resin. Then, a compound containing active hydrogen was added dropwise, and the temperature was raised to 120°C and stirred for 2 hours. The temperature was then lowered to 70°C, and Momentive coatosil MP200 was added. The reaction was continued for 2 hours to obtain a solution of the comparative prepolymer 6. The conversion rates of each monomer were between 10% and 90%.

[0177] Table 1: Composition of prepolymer raw materials in manufacturing examples 1-6

[0178]

[0179] Table 2: Composition of prepolymer raw materials in manufacturing examples 7-12

[0180]

[0181] Table 3: Composition of prepolymer raw materials in manufacturing examples 13-16

[0182]

[0183] Table 4: Comparative Prepolymer Raw Material Composition of Comparative Manufacturing Examples 1-6

[0184]

[0185] Table 5. Composition and property test results of the resin compositions in Examples E1 to E6

[0186]

[0187]

[0188] Table 6. Composition and property test results of the resin compositions in Examples E7 to E12

[0189]

[0190]

[0191] Table 7. Composition and property test results of the resin compositions in Examples E13 to E16

[0192]

[0193]

[0194] Table 8. Composition and property test results of the resin compositions of comparative examples C1 to C6.

[0195]

[0196] Table 9. Composition and property test results of the resin compositions of comparative examples C7 to C9

[0197]

[0198] The characteristic tests of the embodiments and comparative examples of the present invention are performed by preparing the test sample in the following manner and then according to the specific test conditions.

[0199] (1) Prepreg (PP): The resin compositions from the examples or comparative examples were selected respectively. The resin compositions were uniformly mixed to form a varnish. The varnish was injected into an impregnation tank, and then glass fiber cloth (e.g., L-glass fiber fabric of specification 2116 or 1080, both purchased from Asahi Corporation) was immersed in the impregnation tank to allow the resin composition to adhere to the glass fiber cloth. The mixture was heated at 150°C to 170°C to form a semi-cured state (B-Stage) to obtain a prepreg. The resin content of the prepreg made using 1080 L-glass fiber cloth was approximately 70%; the resin content of the prepreg made using 2116 L-glass fiber cloth was approximately 55%.

[0200] (2) Copper Foil Substrate I (8-ply, formed by laminating 8 prepreg sheets): Two 18-micron thick ultra-low surface roughness (HVLP) copper foils and eight 2116 L-glass fiber cloths were prepared to impregnate the prepreg sheets prepared from each test sample (each set of examples or comparative examples). The resin content of each prepreg sheet was approximately 55%. The copper foil, eight prepreg sheets and one copper foil were stacked in sequence and laminated under vacuum conditions, pressure of 500 psi and 240°C for 2 hours to form copper foil substrate I (8-ply).

[0201] (3) Copper-free substrate I (8-ply, formed by laminating 8 prepreg sheets): The copper foil on both sides of the above copper foil substrate I (8-ply) is etched to obtain copper-free substrate I (8-ply).

[0202] (4) Copper Foil Substrate II (8-ply, formed by laminating 8 prepreg sheets): Prepare 2 carrier copper foils (model MT18-EX, purchased from Mitsui Copper Foil Co., Ltd.) and 8 sheets of 2116 L-glass fiber cloth impregnated with the prepregs prepared from each test sample (each set of examples or comparative examples). The resin content of each prepreg is approximately 55%. The prepregs are stacked in the order of 1 copper foil, 8 prepreg sheets, and 1 copper foil, and then laminated under vacuum conditions, a pressure of 500 psi, and 240°C for 2 hours to form copper foil substrate II (8-ply).

[0203] (5) Copper-free substrate III (1-ply, formed by laminating one prepreg): Prepare two ultra-low profile (VLP) copper foils with a thickness of 12 micrometers and one 2116 L-glass fiber cloth impregnated with the prepregs prepared for each test sample (each set of examples or comparative examples). Lay them together in the order of one copper foil, one prepreg and one copper foil, and press them together under vacuum conditions, pressure of 500 psi and 240°C for 2 hours to form copper foil substrate III (1-ply). The copper foil substrate III (1-ply) is etched to remove the copper foil on both sides to obtain copper-free substrate III (1-ply).

[0204] The characteristic testing methods and characteristic analysis items of the embodiments and comparative examples of the present invention are as follows:

[0205] 1. The uniformity of the coefficient of thermal expansion (X-axis, X-CTE) and the uniformity of the coefficient of thermal expansion (X-CTE) along the X-axis of the plate and at its edges.

[0206] Three 3mm x 24mm samples were cut from the edge and center regions of the aforementioned copper-free substrate I (8-ply). Thermal mechanical analysis (TMA) was performed according to IPC-TM-650 2.4.24.5. The temperature was increased from 35℃ to 330℃ at a rate of 10℃ / min. The X-axis thermal expansion coefficient (in ppm / ℃) of each sample was measured within the temperature range of 40℃ to 125℃. The average X-axis thermal expansion coefficient of the three samples cut from the center region was recorded as A1, which is the X-axis thermal expansion coefficient of the board center. The average X-axis thermal expansion coefficient of the three samples cut from the edge region was recorded as A2, which is the X-axis thermal expansion coefficient of the board edge. The difference between the X-axis thermal expansion coefficient of the board center and the X-axis thermal expansion coefficient of the board edge is equal to the absolute value of A1 - A2. A smaller difference indicates better uniformity of the X-axis thermal expansion coefficient.

[0207] 2. Peeling strength (P / S) of copper foil after copper plating

[0208] The protective copper foil on the surface of the aforementioned copper-containing substrate II (8-ply) was peeled off, and the bottom copper of the inner layer was electroplated until the thickness of the surface copper foil increased to 35 micrometers to form evaluation substrate I. Evaluation substrate I was cut into rectangular samples with a width of 24 mm and a length greater than 60 mm, and the surface copper foil was etched, leaving only a strip of copper foil with a width of 3.18 mm and a length greater than 60 mm. Using a universal tensile testing machine, at room temperature (about 25°C), the force required to pull the copper foil away from the surface of the insulating layer was measured according to the method described in IPC-TM-650 2.4.8, and the unit was lb / in.

[0209] 3. Heterogeneous flow length

[0210] The aforementioned copper-containing substrate I (8-ply) was selected as the inner layer substrate. Its surface was browned. Four 10 cm * 10 cm squares were cut out at equal intervals from the aforementioned 1080 prepreg. One of the cut prepregs was stacked on the browned inner layer substrate. A 12-micron thick HVLP copper foil was then covered on the surface of the prepreg. The substrate was then pressed under vacuum conditions, pressure of 500 psi, and temperature of 240°C for 2 hours. The three-layer board was then etched. The presence of heterogeneous adhesive flow (irregular color or streaks at the heterogeneous adhesive flow points) was visually inspected within the squares. The length of the heterogeneous adhesive flow was measured and recorded in millimeters.

[0211] 4. Dimensional stability after solder floating

[0212] The aforementioned copper-free substrate III (1-ply) was selected as the test sample, with 20 pieces per group. Nine holes were drilled evenly in a 3x3 grid pattern on the substrate, and the distance 'a' between the holes was measured using an X-ray measuring machine. The substrate was then subjected to tin bleaching (the substrate was placed horizontally on the surface of molten solder in a tin bath at a constant temperature of 288°C, floating on the solder for 10 seconds each time, then being removed and cooled for 30 seconds; this was repeated 20 times). The distance 'b' between the holes was measured again. The shrinkage rate was calculated as (ab) / a*100%. The shrinkage rate after tin bleaching was statistically analyzed, and the complex process capability index (Cpk) was calculated. A higher Cpk indicates better dimensional stability control after tin bleaching.

[0213] 5. Glass transition temperature (Tg)

[0214] The aforementioned copper-free substrate I (8-ply) was selected as the test sample. A dynamic mechanical analyzer (DMA) was used to measure the glass transition temperature (Tg) of each sample, in °C, according to the method described in IPC-TM-650 2.4.24.4. The measurement temperature range was 50 °C to 400 °C, with a temperature rise rate of 2 °C / min. If the measured Tg is less than 330 °C, it is considered unqualified and recorded as X; if the measured Tg is between 330 °C and 350 °C, it is considered qualified and recorded as △; if the measured Tg is greater than 350 °C, it is considered excellent and recorded as O.

[0215] Based on the comprehensive reference to the characteristic test results in Tables 5 to 9, the following phenomena can be clearly observed:

[0216] From Examples E1 to E16, it can be determined that the resin composition and articles thereof of the present invention can be improved in one or more aspects, such as X-CTE in the board, X-CTE at the board edge, X-CTE uniformity, P / S after copper plating, heterogeneous flow length, dimensional stability after tinning, and glass transition temperature.

[0217] The amount of active hydrogen compound used in the prepolymers contained in Examples E1 to E7 and Examples E9 to E16 was 5 to 40 parts by weight, and the amount of active hydrogen compound used in the prepolymer contained in Example E8 was 45 parts by weight. Compared with the amount of active hydrogen compound used in the prepolymer being 45 parts by weight, when the amount of active hydrogen compound used in the prepolymer is 5 to 40 parts by weight, the resin composition and its products have achieved significant improvements in at least the aspects of X-CTE uniformity, P / S after copper plating, heterogeneous flow length and glass transition temperature.

[0218] The amount of epoxy-modified cyclic siloxane used in the prepolymers contained in Examples E1-E3 and Examples E5-E16 was 3-25 parts by weight, and the amount of epoxy-modified cyclic siloxane used in the prepolymer contained in Example E4 was 30 parts by weight. Compared with the amount of epoxy-modified cyclic siloxane used in the prepolymer being 30 parts by weight, when the amount of epoxy-modified cyclic siloxane used in the prepolymer was 3-25 parts by weight, the resin composition and its articles achieved a significant improvement in at least the dimensional stability after tin bleaching.

[0219] Although the resin compositions of Comparative Examples C6 to C8 contain maleimide resin, epoxy-modified cyclic siloxane, and active hydrogen compounds, these three components are not prepolymerized. The prepolymer contained in the resin compositions of Comparative Examples C1 to C5 is formed by prepolymerizing any two of the three components: maleimide resin, epoxy-modified cyclic siloxane, and active hydrogen compounds. Comparing Examples E1 to E16 with Comparative Examples C1 to C5 and Comparative Examples C6 to C8, it can be seen that, compared with the case where the three components of maleimide resin, epoxy-modified cyclic siloxane, and active hydrogen compounds are not prepolymerized or partially prepolymerized, the resin compositions containing the prepolymer of the present invention are improved in at least the aspects of X-CTE uniformity, heterogeneous flow length, and dimensional stability after tinning.

[0220] The prepolymer contained in the resin composition of Comparative Example C9 is obtained by prepolymerizing maleimide resin with other epoxy-modified siloxanes (Momentive coatosil MP200) and compounds containing active hydrogen. Comparing Examples E1 to E16 with Comparative Example C9, it can be seen that, compared with the prepolymer obtained by replacing the epoxy-modified cyclic siloxane in the prepolymer component with other epoxy-modified siloxanes, the resin composition containing the prepolymer of the present invention is improved in at least the aspects of X-CTE in the board, X-CTE uniformity, heterogeneous flow length, dimensional stability after tinning, and glass transition temperature.

[0221] The above embodiments are merely illustrative in nature and are not intended to limit the embodiments of this application or the application or use of such embodiments. In this application, terms such as "example" mean "as an example, illustration, or description." Any exemplary embodiment herein is not necessarily to be interpreted as preferred or more advantageous than other embodiments, unless otherwise indicated.

[0222] Furthermore, although at least one exemplary embodiment or comparative example has been presented in the foregoing embodiments, it should be understood that numerous variations are still possible in this application. It should also be understood that the embodiments described herein are not intended to limit the scope, use, or configuration of the claimed technical solution in any way. Rather, the foregoing embodiments will provide a simple guide for those skilled in the art to implement one or more of the described embodiments and their equivalents. Moreover, the claims include known equivalents and all foreseeable equivalents at the time of filing of this patent application.

Claims

1. A prepolymer, characterized by, The prepolymer is obtained from a mixture via a prepolymerization reaction, the mixture comprising the following components: (a) Maleimide resin. (b) Epoxy-modified cyclic siloxanes, and (c) Compounds containing active hydrogen, The compounds containing active hydrogen include aminosiloxanes, diallyl bisphenols, or combinations thereof.

2. The prepolymer as described in claim 1, characterized in that, The amount of the epoxy-modified cyclic siloxane is 3 to 30 parts by weight relative to 100 parts by weight of maleimide resin, and the amount of the compound containing active hydrogen is 5 to 45 parts by weight.

3. The prepolymer as described in claim 1, characterized in that, The amount of the epoxy-modified cyclic siloxane is 3 to 25 parts by weight relative to 100 parts by weight of maleimide resin, and the amount of the compound containing active hydrogen is 5 to 40 parts by weight.

4. The prepolymer as described in claim 1, characterized in that, The conversion rate of the prepolymer reaction is 1 to 99%; and / or the weight-average molecular weight of the prepolymer is 3,000 to 5,000.

5. The prepolymer as described in claim 1, characterized in that, The maleimide resin includes oligomeric maleimide resin, non-oligomeric maleimide resin, or a combination thereof.

6. The prepolymer as described in claim 5, characterized in that, The maleimide resin comprises 70-100 wt% non-oligomeric maleimide resin and 0-30 wt% oligomeric maleimide resin.

7. The prepolymer as described in claim 5, characterized in that, The oligomeric maleimide resin includes polyphenylene maleimide, maleimide containing an indane structure, maleimide containing isopropyl and meta-arylene structures, maleimide containing a biphenylene alkylene structure, maleimide containing an aliphatic structure with 10 to 50 carbon atoms, or combinations thereof.

8. The prepolymer as described in claim 5, characterized in that, The non-oligomeric maleimide resins include 4,4'-diphenylmethane bismaleimide, 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-dimethylphenylmaleimide, N-2,6-dimethylphenylmaleimide, N-phenylmaleimide, vinylbenzylmaleimide, or combinations thereof.

9. The prepolymer as claimed in claim 1, characterized in that, The epoxy-modified cyclic siloxane includes the structure shown in formula (1): In formula (1), n1 is an integer from 3 to 6, multiple R1s can be the same or different, and at least one of R1s is a group containing an epoxy group. Each R1 independently represents a C1 to C3 alkyl group. R2 is a C1 to C3 alkyl group.

10. The prepolymer as claimed in claim 1, characterized in that, The epoxy-modified cyclic siloxane includes any one or a combination of the structures shown in formulas (1-1) to (1-3):

11. The prepolymer as claimed in claim 1, characterized in that, The aminosiloxane includes the structure shown in formula (2): In formula (2), multiple R3s may be the same or different, each of which is independently alkyl, phenyl or alkoxy, and multiple R4s may be the same or different, each of which is independently alkylene, alkenylene, alkynylene, arylene or -O-, and m is an integer from 1 to 100.

12. The prepolymer as claimed in claim 1, characterized in that, The diallyl bisphenol includes diallyl bisphenol A, diallyl bisphenol F, diallyl biphenol, or combinations thereof.

13. A resin composition, characterized in that, The resin composition comprises the prepolymer according to any one of claims 1-12.

14. The resin composition according to claim 13, characterized in that, The resin composition further includes a crosslinking agent, an organosilicon resin, an epoxy resin, a maleimide resin, or a combination thereof.

15. The resin composition according to claim 13, characterized in that, The resin composition further includes polyphenylene ether resin, polyolefin resin, benzoxazine resin, polyester resin, phenolic resin, amine curing agent, polyamide, polyimide, cyanate ester resin, maleimide triazine resin, or combinations thereof.

16. The resin composition according to claim 13, characterized in that, The resin composition further includes a curing accelerator, a polymerization inhibitor, a flame retardant, an inorganic filler, a surface treatment agent, a dye, a toughening agent, a solvent, or a combination thereof.

17. An article made from the resin composition of claim 13, characterized in that, The products include prepregs, resin films, laminates, or printed circuit boards.

18. The article of claim 17, characterized in that, The article has one or more of the following characteristics: According to the method of IPC-TM-650 2.4.24.5, the X-CTE in the board is less than or equal to 3.8 ppm / ℃. The X-CTE at the plate edge, obtained by testing and calculation according to the method described in IPC-TM-650 2.4.24.5, is less than or equal to 4.0 ppm / ℃; The difference between the X-CTE values ​​between the board center and the board edge, obtained by testing and calculation according to the method described in IPC-TM-650 2.4.24.5, is less than or equal to 0.3 ppm / ℃; The peel strength of the copper foil after copper plating, as tested according to the method described in IPC-TM-650 2.4.8, is greater than or equal to 5.0 lb / in; According to the method described in IPC-TM-650 2.4.39, the dimensional change Cpk of the substrate after tin bleaching treatment is greater than or equal to 1.

35. The glass transition temperature obtained by the method described in IPC-TM-650 2.4.24.4 is greater than or equal to 330°C.

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