Cycloolefin copolymer, resin composition and product prepared from resin composition

Abstract

The invention relates to a cycloolefin copolymer, a resin composition and a product prepared from the resin composition. The cycloolefin copolymer and the resin composition have good storage stability and are especially suitable for preparing prepregs, resin films, laminated boards and / or printed circuit boards and other products, and the products have excellent adhesive filling performance, T288 heat resistance, glass transition temperature and high copper foil peel strength, and are suitable for being used in the fields of electronic devices, electronic devices and the like. And the Z-axis thermal expansion rate, the dielectric loss and the water absorption rate are low.

Description

Technical Field

[0001] The present invention relates to a cycloolefin copolymer, a resin composition and products made thereof, in particular to a cycloolefin copolymer and a resin composition suitable for preparing a prepreg, a resin film, a laminate and / or a printed circuit board. Background Art

[0002] As the information processing of electronic products continues to develop towards high-frequency signal transmission and high-speed digitalization, the market's performance requirements for printed circuit boards are becoming increasingly higher. Copper clad laminates and prepregs are the basic materials for printed circuit boards, and their dielectric properties, heat resistance and other properties have an important impact on the performance of printed circuit boards.

[0003] In recent years, a series of low dielectric materials for making copper clad laminates and prepregs have been continuously developed, such as polyphenylene ether, polyolefin, etc. Among them, cycloolefin copolymer (Cyclic-Olefin Copolymer) has attracted much attention because it not only has a lower dielectric constant, but also has a higher modulus and is moisture-proof. However, conventional cycloolefin copolymers still have many performance disadvantages in industrial applications, such as ethylene-norbornene copolymers. When applied to resin compositions, they have poor compatibility with the system, and the glue is stored and easily crystallized. The prepreg produced has a filler shadow, and the product T288 has poor heat resistance, low glass transition temperature, high thermal expansion coefficient, and poor heat resistance after moisture absorption. Summary of the invention

[0004] In view of the above-mentioned deficiencies of conventional cycloolefin copolymers and resin compositions in the art, the present application aims to develop a new cycloolefin copolymer and its resin composition with good storage stability, and the products made therefrom also have excellent filling properties, high T288 heat resistance, glass transition temperature and copper foil peeling strength, and low Z-axis thermal expansion coefficient, dielectric loss and water absorption.

[0005] In a first aspect, the present application discloses a cycloolefin copolymer, which includes a structural unit a formed by a monomer a', a structural unit b formed by a monomer b' and a structural unit c formed by a monomer c', wherein the monomer a' includes any one of ethylene, propylene, acetylene, and propyne or a combination thereof, the monomer b' includes any one of norbornene, cyclopentene, cyclopentadiene, dicyclopentadiene, and tricyclopentadiene or a combination thereof, and the monomer c' includes a monomer represented by formula (1),

[0006]

[0007] In one embodiment, the molar ratio of structural unit c to structural unit b in the cycloolefin copolymer is 0.01 to 0.25: 1. In a preferred embodiment, the molar ratio of structural unit c to structural unit b in the cycloolefin copolymer is 0.03 to 0.2:1.

[0008] In one embodiment, the number average molecular weight of the cyclic olefin copolymer is 3000 to 15000. In a preferred embodiment, the number average molecular weight of the cyclic olefin copolymer is 4000 to 10000.

[0009] In one embodiment, the cycloolefin copolymer includes any one of the cycloolefin copolymers represented by formula (2), the cycloolefin copolymers represented by formula (3), the cycloolefin copolymers represented by formula (4), the cycloolefin copolymers represented by formula (5), and the cycloolefin copolymers represented by formula (6), or a combination thereof.

[0010]

[0011]

[0012] In formula (2) to formula (6), n1 is an integer between 1 and 500, n2 is an integer between 1 and 150, and n3 is an integer between 1 and 50.

[0013] In a second aspect, the present application discloses a resin composition comprising the following components:

[0014] - the cyclic olefin copolymer according to the first aspect; and

[0015] -Polyphenylene ether resin containing unsaturated carbon-carbon double bonds.

[0016] In one embodiment, in the resin composition, the cycloolefin copolymer is 5 to 60 parts by weight based on 100 parts by weight of the polyphenylene ether resin containing unsaturated carbon-carbon double bonds. In a preferred embodiment, in the resin composition, the cycloolefin copolymer is 5 to 50 parts by weight based on 100 parts by weight of the polyphenylene ether resin containing unsaturated carbon-carbon double bonds.

[0017] In one embodiment, the polyphenylene ether resin containing unsaturated carbon-carbon double bonds includes any one of (meth)acryloyl polyphenylene ether resin, vinylbenzyl polyphenylene ether resin, vinyl polyphenylene ether resin, or a combination thereof.

[0018] In one embodiment, the resin composition further comprises an additive, wherein the additive comprises any one of a cross-linking agent containing unsaturated carbon-carbon double bonds, a polyolefin, a silicone resin, a benzoxazine resin, an epoxy resin, a polyester resin, a phenolic resin, an amine curing agent, a polyamide, a polyimide, styrene maleic anhydride, a maleimide resin, a cyanate resin, and a maleimide triazine resin, or a combination thereof.

[0019] In one embodiment, the resin composition further comprises any one of a hardening accelerator, a polymerization inhibitor, a flame retardant, an inorganic filler, a surface treatment agent, a coloring agent, a toughening agent, and a solvent, or a combination thereof.

[0020] In a third aspect, the present application discloses an article made from the resin composition of the second aspect, wherein the article includes a prepreg, a resin film, a laminate or a printed circuit board.

[0021] In one embodiment, the articles disclosed herein have one or more of the following characteristics:

[0022] -T288 heat resistance measured according to IPC-TM-650 2.4.24.1 method is more than 70 minutes;

[0023] - The glass transition temperature measured according to IPC-TM-650 2.4.24.4 is above 197°C;

[0024] - The Z-axis thermal expansion rate measured according to IPC-TM-650 2.4.24.5 is less than 2.0%;

[0025] - Water absorption of 0.18% or less as measured by IPC-TM-650 2.6.2.1 and IPC-TM-650 2.6.16.1;

[0026] - Copper foil peel strength of 3.4 lb / in or greater as measured by IPC-TM-650 2.4.8; and / or

[0027] - The dielectric loss measured at a frequency of 10 GHz according to the method of JIS C2565 is 0.00185 or less.

[0028] In a fourth aspect, the present application discloses a method for preparing a cycloolefin copolymer, comprising: mixing a monomer a', a monomer b' and a monomer c' in a reaction container and performing a polymerization reaction in the presence of a catalyst to obtain a cycloolefin copolymer; wherein the monomer a' comprises any one of ethylene, propylene, acetylene and propyne or a combination thereof, the monomer b' comprises any one of norbornene, cyclopentene, cyclopentadiene, dicyclopentadiene and tricyclopentadiene or a combination thereof, and the monomer c' comprises a monomer represented by formula (1).

[0029]

[0030] In one embodiment, the molar ratio of structural unit c to structural unit b in the cycloolefin copolymer is 0.01 to 0.25: 1. In a preferred embodiment, the molar ratio of structural unit c to structural unit b in the cycloolefin copolymer is 0.03 to 0.2:1.

[0031] In one embodiment, the number average molecular weight of the cyclic olefin copolymer is 3000 to 15000. In a preferred embodiment, the number average molecular weight of the cyclic olefin copolymer is 4000 to 10000.

[0032] In one embodiment, the cycloolefin copolymer includes any one of the cycloolefin copolymers represented by formula (2), the cycloolefin copolymers represented by formula (3), the cycloolefin copolymers represented by formula (4), the cycloolefin copolymers represented by formula (5), and the cycloolefin copolymers represented by formula (6), or a combination thereof.

[0033]

[0034]

[0035] In formula (2) to formula (6), n1 is an integer between 1 and 500, n2 is an integer between 1 and 150, and n3 is an integer between 1 and 50.

[0036] In one embodiment, the preparation method disclosed in the present application satisfies one or more of the following conditions:

[0037] - The catalyst comprises any one of a metallocene catalyst and an aluminoxane catalyst or a combination thereof;

[0038] - Mixing is carried out in an organic solvent;

[0039] - The polymerization reaction is carried out at a temperature of 30 to 80°C and the reaction time is 2 to 15 hours;

[0040] - Mixing is achieved by: introducing monomer a' gas into a reaction container, then adding a catalyst, an organic solvent, and monomer b' to obtain an intermediate product, continuing to introduce monomer a' gas into the reaction container containing the intermediate product until saturation, and adding monomer c'; or introducing monomer a' gas into a reaction container, then adding a catalyst, an organic solvent, monomer b' and monomer c', and continuing to introduce monomer a' gas until saturation. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Figure 1 The example shows that a shadow exists on the copper-free surface of the inner layer circuit substrate that does not contain copper in the glue filling test.

[0042] Figure 2 The example shows that there is no shadow on the copper-free surface of the inner circuit substrate that does not contain copper in the glue filling test.

[0043] Figure 3 The GPC chart of the cycloolefin copolymer (P1) is shown. DETAILED DESCRIPTION

[0044] In order to enable those skilled in the art to understand the characteristics and effects of the present application, the following is a general description and definition of the terms and expressions mentioned in the specification and claims. Unless otherwise specified, all technical and scientific terms used herein have the common meanings understood by those skilled in the art for the present application. In case of conflict, the definitions in this specification shall prevail.

[0045] The theories or mechanisms described and disclosed herein, whether completely accurate or not, should not limit the scope of the present application in any way, that is, the content of the present application can be implemented without being limited by any specific theory or mechanism.

[0046] The use of "one", "an", "a" or similar expressions to describe the components and technical features described herein is merely for the convenience of expression and to provide a general meaning to the scope of the present application. Therefore, such description should be understood to include one or at least one, and the singular also includes the plural, unless it is obvious that it refers to another meaning.

[0047] As used herein, the terms "comprises," "includes," "has," "contains," or any other similar terms are open-ended transitional phrases, which are intended to cover non-exclusive inclusions. For example, a composition or article comprising a plurality of elements encompasses any one or any one of the listed elements, and is not limited to the elements listed herein, but may also include other elements that are not explicitly listed but are generally inherent to the composition or article. In addition, unless expressly stated to the contrary, the term "or" refers to an inclusive "or" rather than an exclusive "or." For example, any of the following situations satisfies the condition "A or B": A is true (or exists) and B is false (or does not exist), A is false (or does not exist) and B is true (or exists), and both A and B are true (or exist). In addition, in this article, the terms "comprising", "including", "having", and "containing" should be interpreted as being specifically disclosed and simultaneously covering closed conjunctions such as "consisting of", "consisting of", "the remainder of", and conjunctions such as "consisting essentially of", "mainly consisting of", "mainly consisting of", "basically containing", "essentially consisting of", "essentially consisting of", and "essentially containing".

[0048] As used herein, “or a combination thereof” means “or any combination thereof”, covering any combination of more than two of the listed elements; “any one”, “any one”, “any one” means “any one”, “any one”, “any one”. For example, “a composition or its product includes A, B, C, or a combination thereof”, when interpreted, covers the following situations: A is true (or exists) and B and C are false (or do not exist), B is true (or exists) and A and C are false (or do not exist), C is true (or exists) and A and B are false (or do not exist), A and B are true (or exist) and C is false (or do not exist), A and C are true (or exist) and B is false (or do not exist), B and C are true (or exist) and A is false (or do not exist), A, B and C are all true (or exist), and other elements not explicitly listed but generally inherent to the composition or its product.

[0049] In this article, all features or conditions defined in the form of numerical ranges or percentage ranges, such as numerical values, quantities, contents and concentrations, are only for simplicity and convenience. Accordingly, the description of numerical ranges or percentage ranges should be deemed to have covered and specifically disclosed all possible sub-ranges and individual values ​​within the range (including integers and fractions), especially integer values. For example, the range description of "1.0 to 8.0" or "between 1.0 and 8.0" should be deemed to have 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 should be deemed to cover endpoint values, especially sub-ranges defined by integer values, and should be deemed to have specifically disclosed individual values ​​such as 1.0, 2.0, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, etc. Unless otherwise specified, the above-mentioned interpretation method is applicable to all contents of the full text of this application, regardless of whether the scope is extensive or not.

[0050] If the quantity, concentration or other numerical value or parameter is expressed as a range, a preferred range (or a better range) or a series of upper and lower limits, it should be understood that all ranges consisting of any pair of the upper limit or preferred value (or a better value) of the range and the lower limit or preferred value (or a better value) of the range have been specifically disclosed herein, regardless of whether these ranges are disclosed separately. In addition, if a numerical range is mentioned herein, unless otherwise specified, the range should include its endpoints and all integers and fractions within the range.

[0051] In this document, numerical values ​​should be understood to have the accuracy of the number of significant digits of the numerical value, provided that the purpose of the invention can be achieved. For example, the number 40.0 should be understood to cover the range of 39.50 to 40.49.

[0052] In this article, for the use of Markush groups or optional terms to describe the features or examples of the present application, those skilled in the art should understand that all subgroups or any individual elements in the Markush group or option list can also be used to describe the present application. For example, if X is described as "selected from the group consisting of X1, X2 and X3", it also means that the claim that X is X1 and the claim that X is X1 and / or X2 and / or X3 have been fully described. Furthermore, for the use of Markush groups or optional terms to describe the features or examples of the present application, those skilled in the art should understand that any combination of subgroups or individual members of all elements in the Markush group or option list can also be used to describe the present application. Accordingly, for example, if X is described as "selected from the group consisting of X1, X2 and X3", and Y is described as "selected from the group consisting of Y1, Y2 and Y3", it means that the claim that X is X1 and / or X2 and / or X3 and Y is Y1 and / or Y2 and / or Y3 has been fully described.

[0053] Unless otherwise specified, in this application, a compound refers to a chemical substance formed by two or more elements connected by chemical bonds, including small molecule compounds and polymer compounds, but not limited thereto. The interpretation of a compound in this article is not limited to a single chemical substance, but can also be interpreted as the same type of chemical substances with the same composition or the same properties.

[0054] If not otherwise specified, in this application, polymer refers to the product formed by the polymerization reaction of monomers, and monomers are compounds that synthesize polymers. "Structural unit" can be called a repeating unit (Repeating unit) or a chain (Chainelement). The structural unit has the same elemental composition as the monomer, but the electronic structure is changed. Polymers often include aggregates of many macromolecules, each of which is formed by repeated connection of many simple structural units by covalent bonds. Polymers can include homopolymers, copolymers, prepolymers, etc., and are not limited to this. Homopolymers refer to polymers polymerized from one monomer. Copolymers refer to polymers polymerized from two or more monomers. The process of polymerizing monomers into copolymers is called copolymerization. Copolymers include random copolymers (structures such as -AABABBBAAABBA-), alternating copolymers (structures such as -ABABABAB-), graft copolymers (structures such as -AA(A-BBBB)AA(A-BBBB)AAA-) and block copolymers (structures such as -AAAAA-BBBBBB-AAAAA-), etc. For example, the styrene-butadiene copolymer of the present application should be interpreted as including styrene-butadiene random copolymer, styrene-butadiene alternating copolymer, styrene-butadiene graft copolymer, styrene-butadiene block copolymer or a combination thereof. A prepolymer refers to a polymer with a molecular weight between that of a monomer and a final polymer, and the prepolymer contains reactive functional groups that can be further polymerized to obtain a fully cross-linked or hardened product with a higher molecular weight. Polymers of course include oligomers, but are not limited thereto. Oligomers, also known as oligomers, are polymers composed of 2 to 20 repeating units, usually 2 to 5 repeating units.

[0055] Unless otherwise specified, the "resin" in this application is a customary name for a synthetic polymer, which may include monomers, polymers thereof, combinations of monomers, combinations of polymers thereof, or combinations of monomers and polymers thereof, etc., and is not limited thereto.

[0056] If not otherwise specified, in the present application, modified products include products after modification of reactive functional groups of each resin, products after prepolymerization of each resin with other resins, products after crosslinking of each resin with other resins, products after copolymerization of each resin with other resins, etc.

[0057] If not otherwise specified, the unsaturated bonds described herein refer to reactive unsaturated bonds, such as but not limited to unsaturated double bonds that can undergo cross-linking reactions with other functional groups, such as but not limited to unsaturated carbon-carbon double bonds that can undergo cross-linking reactions with other functional groups.

[0058] The unsaturated carbon-carbon double bonds described herein preferably include vinyl, vinylbenzyl, (meth)acryloyl, allyl or a combination thereof. Vinyl should be interpreted to include vinyl and vinylidene. (Meth)acryloyl should be interpreted to include acryloyl and methacryloyl.

[0059] Unless otherwise specified, the alkyl, alkenyl, and monomer described herein include their various isomers when interpreted. For example, propyl should be interpreted as including n-propyl and isopropyl.

[0060] Unless otherwise specified, in this application, parts by weight represent relative parts by weight in the composition, which may be any weight unit, such as but not limited to kilograms, kilograms, grams, pounds, etc. For example, 100 parts by weight of polyphenylene ether resin containing unsaturated carbon-carbon double bonds may represent 100 kilograms of polyphenylene ether resin containing unsaturated carbon-carbon double bonds or 100 pounds of polyphenylene ether resin containing unsaturated carbon-carbon double bonds.

[0061] It should be understood that the features in each embodiment of this document may be arbitrarily combined to form the technical solution of this application, as long as there is no contradiction in the combination of these features.

[0062] The present application will be described below with specific embodiments and examples. It should be understood that these specific embodiments and examples are merely exemplary and are not intended to limit the scope of the present application and its use. Unless otherwise stated, the methods, reagents and conditions used in the examples are methods, reagents and conditions conventional in the art.

[0063] The present application relates to a cycloolefin copolymer, which comprises a structural unit a formed by a monomer a', a structural unit b formed by a monomer b' and a structural unit c formed by a monomer c', wherein the monomer a' comprises any one of ethylene, propylene, acetylene and propyne or a combination thereof, the monomer b' comprises any one of norbornene, cyclopentene, cyclopentadiene, dicyclopentadiene and tricyclopentadiene or a combination thereof, and the monomer c' comprises a monomer represented by formula (1),

[0064]

[0065] In one embodiment, the molar ratio of structural unit c to structural unit b in the cycloolefin copolymer is 0.01-0.25:1, preferably 0.03-0.2:1, and the molar ratio of structural unit a to structural unit b in the cycloolefin copolymer is 0.01-1:1, preferably 0.5-1:1.

[0066] In one embodiment, the number average molecular weight of the cycloolefin copolymer is 3,000 to 15,000, preferably 4,000 to 10,000.

[0067] In one embodiment, the cycloolefin copolymer includes any one of the cycloolefin copolymers represented by formula (2), the cycloolefin copolymers represented by formula (3), the cycloolefin copolymers represented by formula (4), the cycloolefin copolymers represented by formula (5), and the cycloolefin copolymers represented by formula (6), or a combination thereof.

[0068]

[0069]

[0070] In formula (2) to formula (6), n1 is an integer between 1 and 500, n2 is an integer between 1 and 150, and n3 is an integer between 1 and 50.

[0071] In the present application, when the cycloolefin copolymer contains two or more structural units, the bonding order of the structural units is not particularly limited, for example, it can be random bonding (structure such as -abbbaaabba-), alternating bonding (structure such as -abababab-) or block bonding (structure such as -aaaaa-bbbbbb-aaaaa-). For example, when the cycloolefin copolymer contains three structural units of ethylene (represented by a1), norbornene (represented by b1), and formula (1) (represented by c1), the structural formula -a1b1c1- is used to represent it (for example, formula (2)). This is only an exemplary representation that the cycloolefin copolymer contains three structural units of a1, b1, and c1, and does not limit the bonding order of the three structural units. In other words, the structural formula -a1b1c1- should be interpreted as a cycloolefin copolymer in which the three structural units a1, b1, and c1 are randomly bonded, a cycloolefin copolymer in which the three structural units a1, b1, and c1 are alternately bonded, and a cycloolefin copolymer in which the three structural units a1, b1, and c1 are block bonded.

[0072] The cyclic olefin copolymers described herein can be prepared by various conventional methods known to those skilled in the art.

[0073] For example, a cycloolefin copolymer can be prepared by the following method: introducing monomer a' gas into a reaction container, then adding a catalyst, an organic solvent, monomer b' and monomer c', continuing to introduce monomer a' gas until saturation, and allowing the mixture to react at a suitable temperature for a certain period of time, thereby preparing the cycloolefin copolymer of the present application.

[0074] The catalyst of the above reaction process includes a metallocene catalyst and / or an aluminoxane catalyst; wherein the metallocene catalyst includes but is not limited to dicyclopentadienyl zirconium dichloride (Cp2ZrCl2), and the aluminoxane catalyst includes but is not limited to methylaluminoxane, ethylaluminoxane, isobutylaluminoxane or a combination thereof.

[0075] The organic solvent used in the above reaction process includes but is not limited to toluene.

[0076] The reaction temperature of the above reaction process is 30°C to 80°C.

[0077] The reaction time of the above reaction process is 2 to 15 hours.

[0078] For example, a cycloolefin copolymer can be prepared by the following method: step (1), introducing monomer a' gas into a reaction vessel, and then adding a catalyst, an organic solvent, and monomer b' to obtain an intermediate product; step (2), continuing to introduce monomer a' gas into the reaction vessel containing the intermediate product until saturation, and adding monomer c', and allowing the mixture to react at a suitable temperature for a certain period of time, thereby preparing the cycloolefin copolymer of the present application.

[0079] The catalyst of the above reaction process includes a metallocene catalyst and / or an aluminoxane catalyst; wherein the metallocene catalyst includes but is not limited to dicyclopentadienyl zirconium dichloride (Cp2ZrCl2), and the aluminoxane catalyst includes but is not limited to methylaluminoxane, ethylaluminoxane, isobutylaluminoxane or a combination thereof.

[0080] The organic solvent used in the above reaction process includes but is not limited to toluene.

[0081] The reaction temperature of the above reaction process is 30°C to 80°C.

[0082] The reaction time of the above reaction process is 2 to 15 hours.

[0083] The present application also relates to a resin composition comprising the following components:

[0084] a cycloolefin copolymer comprising a structural unit a formed from a monomer a', a structural unit b formed from a monomer b' and a structural unit c formed from a monomer c', and

[0085] - polyphenylene ether resin containing unsaturated carbon-carbon double bonds,

[0086] Wherein, monomer a' includes any one of ethylene, propylene, acetylene, propyne or a combination thereof, monomer b' includes any one of norbornene, cyclopentene, cyclopentadiene, dicyclopentadiene, tricyclopentadiene or a combination thereof, and monomer c' includes the monomer represented by formula (1).

[0087]

[0088] In one embodiment, in the resin composition, the cycloolefin copolymer is 5 to 60 parts by weight based on 100 parts by weight of the polyphenylene ether resin containing unsaturated carbon-carbon double bonds. For example, compared to 100 parts by weight of the polyphenylene ether resin containing unsaturated carbon-carbon double bonds, the total amount of the cycloolefin copolymer added may be 5, 15, 25, 35, 50 or 60 parts by weight, and is not limited thereto. Preferably, in the resin composition, the cycloolefin copolymer is 5 to 50 parts by weight based on 100 parts by weight of the polyphenylene ether resin containing unsaturated carbon-carbon double bonds.

[0089] In one embodiment, in the resin composition, the molar ratio of structural unit c to structural unit b in the cycloolefin copolymer is 0.01 to 0.25:1, preferably 0.03 to 0.2:1, and the molar ratio of structural unit a to structural unit b in the cycloolefin copolymer is 0.01 to 1:1, preferably 0.5 to 1:1.

[0090] In one embodiment, in the resin composition, the number average molecular weight of the cycloolefin copolymer is 3,000 to 15,000, preferably 4,000 to 10,000.

[0091] In one embodiment, in the resin composition, the cycloolefin copolymer includes any one of the cycloolefin copolymers represented by formula (2), the cycloolefin copolymers represented by formula (3), the cycloolefin copolymers represented by formula (4), the cycloolefin copolymers represented by formula (5), and the cycloolefin copolymers represented by formula (6), or a combination thereof.

[0092]

[0093]

[0094] In formula (2) to formula (6), n1 is an integer between 1 and 500, n2 is an integer between 1 and 150, and n3 is an integer between 1 and 50.

[0095] The polyphenylene ether resin containing unsaturated carbon-carbon double bonds applicable to the present application is not particularly limited, and may be any one or more polyphenylene ether resin containing unsaturated carbon-carbon double bonds applicable to the production of prepregs, resin films, laminates or printed circuit boards, and may be any one or more commercially available products, homemade products or combinations thereof, such as (meth)acryloyl polyphenylene ether resin, vinylbenzyl polyphenylene ether resin, vinyl polyphenylene ether resin or combinations thereof.

[0096] The polyphenylene ether resin containing unsaturated carbon-carbon double bonds used in the present application all have unsaturated carbon-carbon double bonds and a phenylene ether skeleton, wherein the unsaturated carbon-carbon double bonds are reactive functional groups, which can self-polymerize after being heated, and can also undergo free radical polymerization with other unsaturated bond-containing components in the resin composition and finally cross-link and cure. The cured product has the characteristics of high heat resistance and low dielectric. Preferably, the polyphenylene ether resin containing unsaturated carbon-carbon double bonds includes a polyphenylene ether resin containing unsaturated carbon-carbon double bonds substituted with 2,6-dimethyl on the phenylene ether skeleton, and the methyl groups after substitution form a steric hindrance so that the oxygen atoms on the ether are not easy to produce hydrogen bonds or van der Waals forces and absorb moisture, thereby having lower dielectric properties.

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

[0098] In one embodiment, the resin composition of the present application may further include additives as needed, and the additives include cross-linking agents containing unsaturated carbon-carbon double bonds, polyolefins, silicone resins, benzoxazine resins, epoxy resins, polyester resins, phenolic resins, amine curing agents, polyamides, polyimides, styrene maleic anhydride, maleimide resins, cyanate esters, maleimide triazine resins, or combinations thereof.

[0099] If not otherwise specified, in the resin composition of the present application, the amount of the additive is not particularly limited and can be adjusted as needed. For example, relative to 100 parts by weight of the polyphenylene ether resin containing unsaturated carbon-carbon double bonds, the amount of the cross-linking agent containing unsaturated carbon-carbon double bonds, polyolefins, silicone resins, benzoxazine resins, epoxy resins, polyester resins, phenolic resins, amine curing agents, polyamides, polyimides, styrene maleic anhydride, maleimide resins, cyanate esters, and maleimide triazine resins is not particularly limited, and each component can independently be 1 part by weight to 100 parts by weight, for example but not limited to 1 part 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. The amount of the amine curing agent used relative to 100 parts by weight of the polyphenylene ether resin containing unsaturated carbon-carbon double bonds is not particularly limited, and can be, for example, 1 to 15 parts by weight, such as but not limited to 1 part by weight, 4 parts by weight, 7.5 parts by weight, 12 parts by weight or 15 parts by weight.

[0100] In the present application, for example, the cross-linking agent containing unsaturated carbon-carbon double bonds may be any cross-linking agent containing unsaturated carbon-carbon double bonds known in the art, and specific examples include bis(vinylphenyl)ethane, bisvinylbenzyl ether, divinylbenzene, divinylnaphthalene, divinylbiphenyl, triallyl isocyanurate, triallyl cyanurate, vinylbenzocyclobutene, trivinylcyclohexane, diallylbisphenol A, butadiene, decadiene, octadiene, difunctional or higher acrylates, or combinations thereof.

[0101] The difunctional or higher acrylate includes various difunctional acrylates, trifunctional acrylates or tetrafunctional or higher acrylates commonly used in the art, and can be purchased from Shin-Nakamura Chemical Industry Co., Ltd., Kyoeisha Chemical Co., Ltd., Nippon Kayaku Co., Ltd. or Sartomer Co., Ltd. Specific examples include but are not limited to diallyl isophthalate (DAIP), dioxanediol diacrylate, tricyclodecane dimethanol diacrylate, tricyclodecane dimethanol dimethacrylate or a combination thereof.

[0102] In the present application, for example, the polyolefin resin can be various types of polyolefin resins known in the art. Specific examples include, but are not limited to, polybutadiene, polyisoprene, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-butadiene-divinylbenzene terpolymer, maleic anhydride-added styrene-butadiene copolymer, vinyl-polybutadiene-urea polymer, maleic anhydride-added polybutadiene, polymethylstyrene, hydrogenated polybutadiene, hydrogenated polyisoprene, hydrogenated styrene-butadiene-divinylbenzene terpolymer, hydrogenated maleic anhydride-added styrene-butadiene copolymer, hydrogenated styrene-butadiene copolymer, hydrogenated styrene-isoprene copolymer, multifunctional vinyl aromatic copolymer or combinations thereof.

[0103] If not specifically stated, the multifunctional vinyl aromatic copolymer used in the present application may include various types of multifunctional vinyl aromatic copolymers disclosed in US Pat. No. 20070129502A1, which are all incorporated herein by reference.

[0104] In the present application, for example, the silicone resin may be any type of silicone resin known in the art, and specific examples include but are not limited to polyalkyl silicone resin, polyaryl silicone resin, polyalkylaryl silicone resin, modified silicone resin, or a combination thereof. Preferably, the silicone resin suitable for the present application is an amino-modified silicone resin, for example, amino-modified silicone resins produced by Shin-Etsu Chemical Co., Ltd. under the trade names KF-8010, X-22-161A, X-22-161B, KF-8012, KF-8008, X-22-9409, X-22-1660B-3, etc., amino-modified silicone resins produced by Toray-Dow Corning Co., Ltd. under the trade names BY-16-853U, BY-16-853, BY-16-853B, etc., amino-modified silicone resins produced by Momentive Performance Materials JAPAN under the trade names XF42-C5742, XF42-C6252, XF42-C5379, etc., or combinations thereof.

[0105] In the present application, the benzoxazine resin may be any type of benzoxazine resin known in the art. Specific examples include, but are not limited to, bisphenol A benzoxazine resin, bisphenol F benzoxazine resin, phenolphthalein benzoxazine resin, dicyclopentadiene benzoxazine resin, phosphorus-containing benzoxazine resin, diamino benzoxazine resin, and phenyl, vinyl or allyl modified benzoxazine resin. Suitable commercially available products include, for example, Huntsman sells under the trade names LZ-8270 (phenolphthalein benzoxazine resin), LZ-8298 (phenolphthalein benzoxazine resin), LZ-8280 (bisphenol F benzoxazine resin), LZ-8290 (bisphenol A benzoxazine resin), or, for example, Kolon Industries sells under the trade names KZH-5031 (vinyl modified benzoxazine resin), KZH-5032 (phenyl modified benzoxazine resin). The diaminobenzoxazine resin may be a diaminodiphenylmethane benzoxazine resin, a diaminodiphenyl ether benzoxazine resin, a diaminodiphenyl sulfone benzoxazine resin, a diaminodiphenyl sulfide benzoxazine resin, or a combination thereof, and is not limited thereto.

[0106] In the present application, 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, for example, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AD ​​epoxy resin, novolac epoxy resin, trifunctional epoxy resin, tetrafunctional epoxy resin, multifunctional novolac epoxy resin, dicyclopentadiene (DCPD) epoxy resin, phosphorus-containing epoxy resin, p-xylene epoxy resin, naphthalene epoxy resin (e.g., naphthol epoxy resin), benzofuran epoxy resin, isocyanate-modified epoxy resin, or a combination thereof. Among them, the novolac epoxy resin can be phenol novolac epoxy resin, bisphenol A novolac epoxy resin, bisphenol F novolac epoxy resin, biphenyl novolac epoxy resin, phenol benzaldehyde epoxy resin, phenolaralkyl novolac epoxy resin or o-cresol novolac epoxy resin; among them, the phosphorus-containing epoxy resin can be DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) epoxy resin, DOPO-HQ epoxy resin or a combination thereof.The DOPO epoxy resin may be selected from one or more of DOPO-containing phenol novolac epoxy resin, DOPO-containing o-cresol novolac epoxy resin and DOPO-containing bisphenol-A novolac epoxy resin; the DOPO-HQ epoxy resin may be selected from one or more of DOPO-HQ-containing phenol novolac epoxy resin, DOPO-HQ-containing o-cresol novolacepoxy resin and DOPO-HQ-containing bisphenol-A novolac epoxy resin, and is not limited thereto.

[0107] In the present application, for example, the polyester resin may be any polyester resin known in the art. Specific examples include, but are not limited to, polyester resins containing a dicyclopentadiene structure and polyester resins containing a naphthalene ring structure. Specific examples include, but are not limited to, the trade names HPC-8000 or HPC-8150 sold by Dainippon Ink Chemicals.

[0108] In the present application, for example, the phenolic resin may be any type of phenolic resin known in the art, specific examples include but are not limited to phenolic resin or phenoxy resin, wherein the phenolic resin includes phenol phenolic resin, o-cresol phenolic resin, bisphenol A phenolic resin, naphthol phenolic resin, biphenyl phenolic resin and dicyclopentadiene phenol resin, and is not limited thereto.

[0109] In the present application, for example, the amine curing agent may be any amine curing agent known in the art, and specific examples include but are not limited to at least one of diaminodiphenyl sulfone, diaminodiphenylmethane, diaminodiphenyl ether, diaminodiphenyl sulfide and dicyandiamide, or a combination thereof.

[0110] In the present application, for example, the polyamide may be various polyamides known in the art, including but not limited to various commercially available polyamide resin products.

[0111] In the present application, for example, the polyimide may be various polyimides known in the art, including but not limited to various commercially available polyimide resin products.

[0112] In the present application, for example, the styrene maleic anhydride may be any type of styrene maleic anhydride known in the art, wherein the ratio of styrene (St) to maleic anhydride (MA) may be 1 / 1, 2 / 1, 3 / 1, 4 / 1, 6 / 1, 8 / 1 or 12 / 1. Specific examples include, but are not limited to, styrene maleic anhydride copolymers sold by Cray Valley under the trade names SMA-1000, SMA-2000, SMA-3000, EF-30, EF-40, EF-60 and EF-80, or styrene maleic anhydride copolymers sold by Polyscope under the trade names C400, C500, C700, C900, and the like, and are not limited thereto.

[0113] In the present application, for example, the maleimide resin may be various maleimide resins known in the art. Specific examples include, but are not limited to, 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'-diethyl-4,4'-diphenylmethane bismaleimide, m-phenylene bismaleimide, and bisphenol A diphenyl ether bismaleimide. 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 The invention relates to maleimide, VBM, maleimide containing meta-arylene structure, maleimide containing biphenyl alkylene structure, maleimide containing indane structure, maleimide containing biphenyl structure, maleimide resin containing aliphatic structure of 10 to 50 carbon atoms, prepolymer of diallyl compound and maleimide resin, prepolymer of diamine and maleimide resin, prepolymer of multifunctional amine and maleimide resin, prepolymer of acidic phenol compound and maleimide resin or their combination, and also includes modified products of these components. Among them, maleimide containing meta-arylene structure refers to maleimide resin produced by Nippon Kayaku Co., Ltd. under the trade name of MIR-5000.

[0114] For example, the maleimide resin is, for example, but not limited to, a maleimide resin produced by Daiwakasei Industry with 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, or a maleimide resin produced by KI Chemical Co., Ltd. with the trade names of BMI-70, BMI-80, or a maleimide resin produced by Nippon Kayaku Co., Ltd. with the trade names of MIR-3000 or MIR-5000.

[0115] For example, maleimide resins with aliphatic structures containing 10 to 50 carbon atoms, or maleimide resins with imide extension, may include various maleimide resins with imide extension disclosed in Taiwan Patent Application Publication No. TW200508284A, which is incorporated herein by reference in its entirety. Maleimide resins with aliphatic structures containing 10 to 50 carbon atoms suitable for the present application are, for example but not limited to, maleimide resins with trade names of BMI-689, BMI-1400, BMI-1500, BMI-1700, BMI-2500, BMI-3000, BMI-5000 and BMI-6000, etc., produced by Designer Molecular Co., Ltd.

[0116] In the present application, for example, the cyanate resin may be various types of cyanate resins known in the art. For example, a compound having an Ar-OC≡N structure, wherein Ar may 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 resins, bisphenol A cyanate resins, bisphenol F cyanate resins, cyanate resins containing dicyclopentadiene structures, cyanate resins containing naphthalene ring structures, phenolphthalein cyanate resins, adamantane cyanate resins, fluorene cyanate resins, or combinations thereof. Among them, the phenolic cyanate resin may be a bisphenol A phenolic cyanate resin, a bisphenol F phenolic cyanate resin, or a combination thereof. For example, the cyanate resin may be a cyanate resin produced by Lonza under the trade names of Primaset PT-15, PT-30S, PT-60S, BA-200, BA-230S, BA-3000S, BTP-2500, BTP-6020S, DT-4000, DT-7000, ULL950S, HTL-300, CE-320, LVT-50, LeCy, etc.

[0117] For example, if not specifically specified, the maleimide triazine resin used in the present application is not particularly limited, and can be any one or more maleimide triazine resins suitable for the production of prepregs, resin films, laminates or printed circuit boards. For example, the maleimide triazine resin can be obtained by polymerizing the aforementioned cyanate resin and the aforementioned maleimide resin. The maleimide triazine resin can be, for example but not limited to, a bisphenol A type cyanate resin and a maleimide resin polymerized, a bisphenol F type cyanate resin and a maleimide resin polymerized, a phenol novolac type cyanate resin and a maleimide resin polymerized, or a cyanate resin containing a dicyclopentadiene structure and a maleimide resin polymerized. For example, the maleimide triazine resin can be obtained by polymerizing a cyanate resin and a maleimide resin in any molar ratio. For example, relative to 1 mole of maleimide resin, the cyanate resin can be 1 to 10 moles. For example, but not limited to, the amount of the cyanate resin is 1, 2, 4 or 6 moles relative to 1 mole of the maleimide resin.

[0118] In addition to the aforementioned components, the resin composition of the present application may further include any one of a hardening accelerator, a polymerization inhibitor, a flame retardant, an inorganic filler, a surface treatment agent, a colorant, a toughening agent, and a solvent, or a combination thereof, as required.

[0119] For example, the hardening accelerator (including the hardening initiator) may include a catalyst such as a Lewis base or a Lewis acid. The Lewis base may 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), triphenylphosphine (TPP) and 4-dimethylaminopyridine (DMAP). The Lewis acid may include a metal salt compound such as a metal salt compound of manganese, iron, cobalt, nickel, copper, zinc, etc., such as a metal catalyst such as zinc octoate and cobalt octoate. The hardening accelerator also includes a hardening initiator, such as a peroxide that can generate free radicals, and the hardening initiator includes but is not limited to: diisopropylbenzene peroxide, tert-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, in one embodiment, compared to 100 parts by weight of the polyphenylene ether resin containing unsaturated carbon-carbon double bonds, the resin composition of the present application may further include 0.01 to 5.0 parts by weight of the hardening accelerator, preferably 0.01 to 4.0 parts by weight of the hardening accelerator, and more preferably 0.1 to 3.0 parts by weight of the hardening accelerator, but is not limited thereto.

[0120] For example, the above-mentioned inhibitor may include, but is not limited to, 1,1-diphenyl-2-trinitrophenylhydrazine, methacrylonitrile, 2,2,6,6-tetramethyl-1-oxy-piperidine, dithioester, nitrogen oxide stable free radical, triphenylmethyl free radical, metal ion free radical, sulfur free radical, hydroquinone, p-methoxyphenol, p-benzoquinone, phenothiazine, 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 a combination thereof. For example, the above-mentioned nitrogen oxide stable free radical may include, but is not limited to, nitrogen oxide free radicals from cyclic hydroxylamines such as 2,2,6,6-substituted-1-piperidinyloxy free radical or 2,2,5,5-substituted-1-pyrrolidinyloxy free radical. As a substituent, an alkyl group with a carbon number of less than four, such as a methyl group or an ethyl group, is preferred. Specific nitrogen oxide free radical compounds are not limited, and examples include but are not limited to 2,2,6,6-tetramethyl-1-piperidinyloxy free radicals, 2,2,6,6-tetraethyl-1-piperidinyloxy free radicals, 2,2,6,6-tetramethyl-4-oxo-1-piperidinyloxy free radicals, 2,2,5,5-tetramethyl-1-pyrrolidinyloxy free radicals, 1,1,3,3-tetramethyl-2-isoindolinyloxy free radicals, N,N-di-tert-butylamineoxy free radicals, etc. Stable free radicals such as galvinoxyl free radicals can also be used to replace nitrogen oxide free radicals. The inhibitor suitable for the resin composition of the present application can also be a product derived from the hydrogen atom or atomic group in the inhibitor being replaced by other atoms or atomic groups. For example, the hydrogen atom in the inhibitor is replaced by an atomic group such as an amino group, a hydroxyl group, a ketocarbonyl group, etc. For example, in one embodiment, based on 100 parts by weight of the polyphenylene ether resin containing unsaturated carbon-carbon double bonds, the resin composition of the present application may further include 0.001 to 20 parts by weight of a polymerization inhibitor, preferably 0.01 to 10 parts by weight of a polymerization inhibitor, but is not limited thereto.

[0121] For example, the flame retardant may be any one or more flame retardants suitable for the production of prepregs, resin films, laminates or printed circuit boards, including but not limited to phosphorus-containing flame retardants or bromine-containing flame retardants. The bromine-containing flame retardant preferably includes decabromodiphenylethane, and the phosphorus-containing flame retardant preferably includes: hydroquinone bis-(diphenyl phosphate), bisphenol A bis-(diphenyl phosphate), tri(2-carboxyethyl)phosphine (TCEP), tri(chloroisopropyl) phosphate, trimethyl phosphate (TMP), dimethyl methylphosphonate (DMMP), resorcinol bis(dixylenylphosphate), RDXP (such as commercial products such as PX-200, PX-201, PX-202), ammonium polyphosphate, melamine polyphosphate, etc. polyphosphate), DPPO (diphenylphosphineoxide) and its derivatives (such as bis-DPPO compounds) or resins, melamine cyanurate and tri-hydroxy ethyl isocyanurate, aluminum phosphinate (such as OP-930, OP-935 and other products) or combinations thereof.

[0122] For example, in one embodiment, the flame retardant may also 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.

[0123] For example, in one embodiment, compared to 100 parts by weight of the polyphenylene ether resin containing unsaturated carbon-carbon double bonds, the resin composition of the present invention may further include 1 to 100 parts by weight of a flame retardant, preferably 5 to 80 parts by weight of a flame retardant, but is not limited thereto.

[0124] For example, the inorganic filler can be any one or more inorganic fillers suitable for the production of prepregs, resin films, laminates or printed circuit boards, and specific examples include but are not limited to: silicon dioxide (molten, non-molten, porous or hollow), aluminum oxide, 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 (boehmite, AlOOH), calcined talc, talc, silicon nitride, zirconium tungstate, petalite, calcined kaolin or a combination thereof. In addition, the inorganic filler can be spherical, fibrous, plate-like, granular, flaky or needle-like, and can be selectively pretreated with a silane coupling agent. In addition, the inorganic filler can be prepared by a variety of methods, such as deflagration method, chemical synthesis method. For example, in one embodiment, based on 100 parts by weight of the polyphenylene ether resin containing unsaturated carbon-carbon double bonds, the resin composition of the present application can further include 10 to 300 parts by weight of inorganic filler, preferably 30 to 250 parts by weight of inorganic filler, more preferably 60 to 200 parts by weight of inorganic filler, but not limited thereto.

[0125] For example, the type of the above-mentioned surface treatment agent is not particularly limited. For example, the surface treatment agent may include but is not limited to silane compounds (silane, such as siloxane compounds), which can be divided into aminosilane compounds, epoxysilane compounds, vinylsilane compounds, hydroxysilane compounds, isocyanatesilane compounds, methacryloxysilane compounds and acryloxysilane compounds according to the type of functional group. The main function of adding the surface treatment agent in the present application is to make the inorganic filler uniformly dispersed in the resin composition.

[0126] For example, the coloring agent may include but is not limited to dye or pigment.

[0127] For example, 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. For example, in one embodiment, based on 100 parts by weight of the polyphenylene ether resin containing unsaturated carbon-carbon double bonds, the resin composition of the present invention may further include 1 to 20 parts by weight of a toughening agent, preferably 3 to 10 parts by weight of a toughening agent, but not limited thereto. The main function of adding a toughening agent in the application is to improve the toughness of the resin composition.

[0128] For example, the solvent suitable for the resin composition of the present application is not particularly limited, and can be any solvent suitable for dissolving the resin composition of the present application, including but 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, dimethylformamide, dimethylacetamide, propylene glycol methyl ether acetate and the like solvents or their mixed solvents. The amount of solvent added is for the purpose of adjusting the overall solid content of the resin composition. For example, in one embodiment, the amount of solvent added is such that the overall solid content of the resin composition is adjusted to 50-85%, but is not limited thereto.

[0129] The resin composition of each of the aforementioned embodiments can be made into various products, for example, components suitable for use in various electronic products, including prepregs, resin films, laminates or printed circuit boards.

[0130] For example, the resin composition of each embodiment of the present application can be made into a semi-cured sheet, which includes a reinforcing material and a layered object arranged on the reinforcing material. The layered object 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 semi-cured sheet is between 120°C and 180°C, preferably between 120°C and 160°C. The reinforcing material can be any one of a fiber material, a woven fabric, and a non-woven fabric, and the woven fabric preferably includes a glass fiber cloth. The type of glass fiber cloth is not particularly limited, and can be various glass fiber cloths that can be used for printed circuit boards, such as E-type glass cloth, D-type glass cloth, S-type glass cloth, T-type glass cloth, L-type glass cloth, Q-type glass cloth or QL-type glass cloth (a glass cloth of a mixed structure made of Q glass and L glass); the types of glass fibers include yarns and rovings, etc., and the forms include open fiber or unopen fiber, and the end face shapes include round or flat shapes. The aforementioned non-woven fabric preferably includes a liquid crystal resin non-woven fabric, such as a polyester non-woven fabric, a polyurethane non-woven fabric, etc., and is not limited thereto. The aforementioned woven fabric may also include a liquid crystal resin woven fabric, such as a polyester woven fabric or a polyurethane woven fabric, etc., and is not limited thereto. This reinforcing material can increase the mechanical strength of the prepreg. In a preferred embodiment, the reinforcing material can also be selectively pretreated with a silane coupling agent. The prepreg is subsequently heated and cured (C-stage) to form an insulating layer.

[0131] For example, the resin composition of each embodiment of the present application can be made into a resin film, which is obtained by semi-curing the aforementioned resin composition after baking and heating. The resin composition can be selectively coated on a liquid crystal resin film, a polytetrafluoroethylene film, a polyethylene terephthalate film (PET film), a polyimide film (PI film), a copper foil or a copper foil with adhesive, and then formed into a semi-cured state after baking and heating, so that the resin composition forms a resin film.

[0132] For example, the resin composition described herein can be made into various laminates, which include at least two metal foils and at least one insulating layer, wherein the insulating layer is disposed between the two metal foils, and the insulating layer can be formed by curing the aforementioned resin composition under high temperature and high pressure (C-stage), and the applicable curing temperature is, for example, between 190°C and 220°C, preferably between 200°C and 210°C, and the curing time is 90 to 180 minutes, preferably 120 to 150 minutes. The aforementioned insulating layer can be obtained by curing the aforementioned semi-cured sheet or resin film. The material of the aforementioned metal foil can be copper, aluminum, nickel, platinum, silver, gold or their alloys, such as copper foil. In a preferred embodiment, the laminate is a copper foil substrate.

[0133] In one embodiment, the aforementioned laminate can be further processed into a printed circuit board.

[0134] One of the methods for making the printed circuit board of the present application can be to use a double-sided copper foil substrate (for example, product EM-827, which can be purchased from Taiwan Optoelectronics Materials) with a thickness of 28 mils and 1 ounce of HTE (High Temperature Elongation) copper foil, and then electroplating after drilling to form electrical conduction between the upper copper foil and the bottom copper foil. Then etch the upper copper foil and the bottom copper foil to form an inner layer circuit. Then the inner layer circuit is browned and roughened to form a concave-convex structure on the surface to increase the roughness. Then, the copper foil, the aforementioned prepreg, the aforementioned inner layer circuit board, the aforementioned prepreg, and the copper foil are stacked in sequence, and then a vacuum laminating device is used to heat for 90 to 180 minutes at a temperature of 190°C to 220°C to cure the insulating layer material of the prepreg. Then, various circuit board processes known in the art such as blackening, drilling, and copper plating are performed on the copper foil on the outermost surface to obtain a printed circuit board.

[0135] In one or more embodiments, the resin composition of the present application and various products prepared therefrom have one or more of the following characteristics, preferably all of them:

[0136] (1) The storage period of the resin composition glue solution is more than 30 days, for example, 30 to 35 days, or 30 to 45 days;

[0137] (2) There is no shadow on the copper-free surface of the inner circuit substrate that does not contain copper;

[0138] (3) T288 heat resistance measured according to the method of IPC-TM-650 2.4.24.1 is 70 minutes or more, for example, 70 minutes to 150 minutes, or 130 minutes to 140 minutes;

[0139] (4) The glass transition temperature measured according to the method of IPC-TM-650 2.4.24.4 is 197°C or higher, for example, 197°C to 232°C;

[0140] (5) The Z-axis thermal expansion coefficient measured according to the method of IPC-TM-650 2.4.24.5 is less than 2.0%, for example, 0.8% to 2.0%;

[0141] (6) The water absorption measured according to the method of IPC-TM-650 2.6.2.1 and IPC-TM-650 2.6.16.1 is less than 0.18%, for example, 0.08% to 0.18%;

[0142] (7) A copper foil peel strength of 3.4 lb / in or greater, e.g., 3.4 lb / in to 4.6 lb / in, as measured in accordance with IPC-TM-650 2.4.8; and / or

[0143] (8) The dielectric loss (Df) measured at a frequency of 10 GHz according to the method of JIS C2565 is 0.00185 or less, for example, 0.00160 to 0.00185.

[0144] In the present application, the characteristic tests of the embodiments and comparative examples are performed by making the test objects (samples) by the following method and then performing the tests according to specific test conditions.

[0145] 1. Prepreg: The resin compositions in the embodiments or comparative examples are respectively selected and uniformly mixed to form a varnish, which is placed in an impregnation tank, and a glass fiber cloth (for example, an L-glass fiber cloth with a specification of 2116, or an L-glass fiber cloth with a specification of 1080, or an L-glass fiber cloth with a specification of 1078, all purchased from Asahi Co., Ltd.) is immersed in the impregnation tank to adhere the resin composition to the glass fiber cloth, and the varnish is heated at 150° C. to 170° C. to a semi-cured state (B-Stage), thereby obtaining a prepreg.

[0146] 2. Copper foil substrate (8-ply, formed by pressing 8 prepregs): 2 ultra-low surface roughness (HVLP) copper foils with a thickness of 18 microns and 8 2116 L-glass fiber cloths were prepared to impregnate the prepregs prepared by the samples to be tested (each group of embodiments or comparative examples). The resin content of each prepreg was about 53%. One HVLP copper foil, eight prepregs and one HVLP copper foil were stacked in the order of one HVLP copper foil, eight prepregs and one HVLP copper foil, and pressed for 2 hours under vacuum conditions, a pressure of 500 psi, and 200° C. to form a copper foil substrate. Among them, the 8 stacked prepregs were cured to form an insulating layer between the two copper foils, and the resin content of the insulating layer was about 53%.

[0147] 3. Copper-free substrate (8-ply, formed by pressing together 8 prepregs): The above copper foil substrate (8-ply) is etched to remove 2 copper foils to obtain a copper-free substrate (8-ply). The copper-free substrate is formed by pressing together 8 prepregs, and the resin content of the copper-free substrate is about 53%.

[0148] 4. Copper-free substrate (2-ply, formed by laminating two prepregs): prepare two 18-micron-thick ultra-low surface roughness (HVLP) copper foils and two 1080 L-glass fiber cloths impregnated with the prepregs made from each sample to be tested (each set of embodiments or comparative examples), and laminate them in the order of copper foil, two prepregs, and copper foil, and press them for 2 hours under vacuum conditions, pressure of 500 psi, and 200° C. to form a copper-containing substrate (2-ply, formed by laminating two prepregs). Next, the copper-containing substrate (2-ply) is etched to remove the copper foils on both sides to obtain a copper-free substrate (2-ply), which is formed by laminating two prepregs, and the resin content of the copper-free substrate (2-ply) is about 70%.

[0149] The descriptions of each test method and its characteristic analysis items are as follows:

[0150] 1. Precipitation of glue (i.e. storage period of glue)

[0151] The resin compositions of the embodiments and comparative examples in Tables 1 to 3 are formulated into glue (without adding inorganic fillers). The uniformly mixed and completely dissolved glue is allowed to stand at 25°C for 30 days. On the 30th day, the glue is observed with the naked eye to see if brown solid matter is precipitated. If there is no precipitation, it is marked as "none", which means that the storage period of the glue is greater than or equal to 30 days, for example, the storage period of the glue is 30 to 45 days, and for another example, the storage period of the glue is 30 to 35 days. If at least one precipitate of about 0.5 to 5 cm in length (usually brown) is observed, it is marked as "precipitation". If the glue produces precipitates, the subsequent substrate properties will deteriorate.

[0152] 2. Filling

[0153] A copper-containing substrate (e.g., product EM-827, available from Taiwan Optoelectronics Materials Co., Ltd.) with a thickness of 2.5 mils was processed into a browned circuit board as the inner layer through a browning process to evaluate the ability of the prepreg to flow and fill the empty areas between the circuits during lamination. The resin composition varnish of each group of embodiments or comparative examples was impregnated with 1017 L-glass fiber cloth, and baked at 140°C for 4 minutes to obtain a prepreg, and the resin content of the prepreg was about 79%. A prepreg (a prepreg obtained by impregnating each sample to be tested (each group of embodiments or comparative examples) with 1017 L-glass fiber cloth) was stacked on both sides of the browned circuit board with a thickness of 2.5 mils, and an ultra-low surface roughness copper foil (thickness of 18 microns) was stacked on the outer layer. In a vacuum press, it was pressed for 2 hours at a pressure of 450psi and a temperature of 210°C to form an inner circuit substrate with a copper surface, and the outer copper foil was removed by etching to obtain an inner circuit substrate without copper on the surface. Repeat the above steps to make 15 inner circuit substrates without copper. Use an optical microscope to observe whether there is a shadow on the copper-free surface of the inner circuit substrate without copper. If there is a shadow on the surface, it means that the filling is poor, which will cause the subsequent circuit board to be scrapped. If at least one of the 15 inner circuit substrate samples without copper has a shadow on the surface (such as Figure 1 If there is no shadow on the surface of the 15 inner circuit substrate samples without copper (such as Figure 2 As shown in the figure, it is marked as "Pass", which means excellent filling performance.

[0154] 3.T288 heat resistance

[0155] In the T288 heat resistance test, the above copper foil substrate (8-ply, 8 prepregs pressed together) is selected as the sample to be tested. Using a thermal mechanical analyzer (TMA), at a constant temperature of 288°C, measure each sample to be tested with reference to the method described in IPC-TM-650 2.4.24.1 (2012), and record the time it takes for the copper foil substrate to explode due to heat. The longer the explosion time, the higher the heat resistance of the copper foil substrate made using the resin composition. If the test time exceeds 130 minutes and there is still no explosion, it is marked as ">130".

[0156] 4. Glass transition temperature (Tg)

[0157] The aforementioned copper-free substrate (8-ply) was selected as the sample to be tested, and the glass transition temperature of each sample to be tested was measured by a dynamic mechanical analyzer (DMA) with reference to the method described in IPC-TM-650 2.4.24.4 (2012), in °C. The measuring temperature range was 50-400 °C, and the temperature rise rate was 2 °C / min.

[0158] 5. Percent thermal expansion, z-axis (Z-PTE)

[0159] The aforementioned copper-free substrate (8-ply) was selected as the sample to be tested for thermal mechanical analysis (TMA). The sample was heated at a temperature rise rate of 10°C / min from 50°C to 260°C, and the Z-axis thermal expansion coefficient (in %) of each sample to be tested within the temperature range of 50°C to 260°C was measured with reference to the method described in IPC-TM-6502.4.24.5 (2012).

[0160] 6. Pressure cooking test (PCT)

[0161] The aforementioned copper-free substrate (8-ply) was selected, and the pressure cooking test was performed for 3 hours of moisture absorption (test temperature 121°C and relative humidity 100%) according to the method described in IPC-TM-650 2.6.16.1 (2012), and then immersed in a tin furnace at a constant temperature of 288°C according to the method described in IPC-TM-6502.4.23 (2012), and taken out after immersion for 20 seconds to observe whether there was a burst board (a burst board means failure, and a non-blow board means passing the test, O means no burst board, and X means a burst board phenomenon in the test), and 3 samples were tested in each group. One X means that one sample burst board appeared in three PCT tests, two Xs mean that two samples burst board appeared in three PCT tests, and three Xs mean that three samples burst board appeared in three PCT tests. For example, interlayer delamination between insulating layers can be called a burst board. Interlayer delamination will cause blistering and separation between any layers of the substrate.

[0162] 7. Water absorption

[0163] Take the aforementioned copper-free substrate (8-ply) with a length and width of 2 inches * 2 inches as the sample to be tested, and refer to the method described in IPC-TM-6502.6.2.1 (2012), put it into a 105±10℃ oven for baking for 1 hour, then take it out, cool it at room temperature (about 25℃) for 10 minutes, and weigh the weight of the copper-free substrate as W1. Refer to the method described in IPC-TM-650 2.6.16.1, and perform a pressure cooking test (pressure cooking test, PCT) for 3 hours of moisture absorption test (test temperature 121℃, relative humidity 100%), take out the copper-free substrate, cool it and wipe off the moisture on the surface of the copper-free substrate, and weigh the weight of the copper-free substrate as W2. The water absorption rate is calculated by the following formula:

[0164] Water absorption rate (%) = ((W2-W1) / W1)*100%.

[0165] 8. Copper foil peeling strength (peeling strength, P / S)

[0166] The aforementioned copper foil substrate (8-ply) 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 to leave only a long strip of copper foil with a width of 3.18 mm and a length greater than 60 mm. The strength was measured using a universal tensile strength tester at room temperature (about 25°C) according to the method described in IPC-TM-650 2.4.8 (2012) to measure the force required to pull the copper foil away from the surface of the substrate insulation layer in lb / in.

[0167] 9. Dielectric loss (dissipation factor, Df)

[0168] The aforementioned copper-free substrate (2-ply) was selected as the sample to be tested, and a microwave dielectric analyzer (microwave dielectrometer, purchased from AET, Japan) was used to measure each sample at room temperature (about 25°C) and at a frequency of 10 GHz, referring to the method described in JIS C2565 (1992). The lower the dielectric loss, the better the dielectric properties of the sample to be tested. At a measurement frequency of 10 GHz and a Df value of less than 0.002, a difference in Df values ​​greater than or equal to 0.0001 indicates that there is a significant difference in dielectric loss between different substrates (there is a significant technical difficulty).

[0169] The resin compositions of the examples and comparative examples were prepared using various raw materials from the following sources in the amounts shown in Tables 1 to 3, and were further prepared into various test samples.

[0170] The chemical raw materials used in the embodiments and comparative examples are as follows:

[0171] Cyclic olefin copolymers P1 to P9: homemade, detailed description as follows.

[0172] Copolymers D1-D4: homemade, detailed as follows.

[0173] SA9000: (meth)acryl polyphenylene ether resin, available from Sabic.

[0174] OPE-2st 1200: vinyl benzyl polyphenylene ether resin, purchased from Mitsubishi Gas Chemical.

[0175] OPE-2st 2200: vinyl benzyl polyphenylene ether resin, purchased from Mitsubishi Gas Chemical.

[0176] NBEimide: structure shown in formula (1), homemade.

[0177] TOPAS 6017: COC, purchased from Polyplastics, Japan.

[0178] DVB: divinylbenzene, purchased from Shanghai MacLean Biochemical Technology Co., Ltd.

[0179] BVPE: bis(vinylphenyl)ethane, purchased from Linchuan Chemical.

[0180] TAIC: triallyl isocyanurate, commercially available.

[0181] B1000: polybutadiene, purchased from Japan Soda.

[0182] 985: The structural formula is shown below, n=0-8, R1 is a C6-C30 hydrocarbon group containing an aromatic ring structure, and is commercially available.

[0183]

[0184] 25B: 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne, purchased from NOF Corporation.

[0185] SC-2500SVJ: spherical silica with the surface treated with a silane coupling agent, purchased from Admatechs.

[0186] Toluene: purchased from Sinopec. The content is expressed as "appropriate amount", which means that the content of toluene is adjusted to the overall solid content of the resin composition of 60% to 68% (solid content, S / C = 60% to 68%).

[0187] Preparation Example 1: Cyclic Olefin Copolymer P1

[0188] First, evacuate the 500 ml polymerization kettle twice and pass nitrogen, evacuate it again, and then pass ethylene gas, and then add 8 ml (1.5 mmol / ml) of dicyclopentadienyl zirconium dichloride (Cp2ZrCl2) and 4 ml (1.5 mmol / ml) of methylaluminoxane toluene solution, 66 ml of toluene treated with anhydrous and oxygen-free treatment, 20 ml (2 mmol / ml) of norbornene toluene solution, and NBEimide monomer accounting for 20% of the molar ratio of norbornene. Under mechanical stirring, 3 atmospheres of ethylene are introduced to saturation. The pressure is controlled to 3 standard atmospheres by supplementing ethylene, and the reaction is carried out at 40°C for 5 hours under this pressure. After the reaction is completed, the reaction solution is post-treated to obtain cycloolefin copolymer P1, that is, NBEimide-modified ethylene-norbornene copolymer or NBEimide-ethylene-norbornene copolymer. The number average molecular weight is measured by gel permeation chromatography (GPC) to be about 6900. The GPC spectrum of cycloolefin copolymer P1 is shown as follows Figure 3 shown.

[0189] Preparation Example 2: Cyclic Olefin Copolymer P2

[0190] First, a 500 ml polymerization reactor was evacuated and nitrogen was passed twice, and then evacuated again, and then ethylene gas was passed in, and then 8 ml (1.5 mmol / ml) of dicyclopentadienyl zirconium dichloride (Cp2ZrCl2) and 4 ml (1.5 mmol / ml) of methylaluminoxane toluene solution, 66 ml of toluene treated with anhydrous and oxygen-free treatment, 20 ml (2 mmol / ml) of norbornene toluene solution, and NBEimide monomer accounting for 10% of the molar ratio of norbornene were added in sequence. Three atmospheres of ethylene were passed in under mechanical stirring until saturation. The pressure was controlled to 3 standard atmospheres by supplementing ethylene, and the reaction was carried out at 40°C for 9 hours under this pressure. After the reaction was completed, the reaction solution was post-treated to obtain a cycloolefin copolymer P2, that is, an NBEimide-modified ethylene-norbornene copolymer or an NBEimide-ethylene-norbornene copolymer. The number average molecular weight was measured by gel permeation chromatography to be about 10,000.

[0191] Preparation Example 3: Cyclic Olefin Copolymer P3

[0192] First, a 500 ml polymerization reactor was evacuated and nitrogen was passed twice, and then evacuated again, and then ethylene gas was passed in, and then 8 ml (1.5 mmol / ml) of dicyclopentadienyl zirconium dichloride (Cp2ZrCl2) and 4 ml (1.5 mmol / ml) of methylaluminoxane toluene solution, 66 ml of toluene treated with anhydrous and oxygen-free treatment, 20 ml (2 mmol / ml) of norbornene toluene solution, and NBEimide monomer accounting for 3% of the molar ratio of norbornene were added in sequence. Three atmospheres of ethylene were passed in under mechanical stirring until saturation. The pressure was controlled to 3 standard atmospheres by supplementing ethylene, and the reaction was carried out at 40°C for 4 hours under this pressure. After the reaction was completed, the reaction solution was post-treated to obtain a cycloolefin copolymer P3, that is, an NBEimide-modified ethylene-norbornene copolymer or an NBEimide-ethylene-norbornene copolymer. The number average molecular weight was measured by gel permeation chromatography to be about 4000.

[0193] Preparation Example 4: Cyclic Olefin Copolymer P4

[0194] First, a 500 ml polymerization reactor was evacuated and nitrogen was passed twice, and then evacuated again, and then ethylene gas was passed in, and then 8 ml (1.5 mmol / ml) of dicyclopentadienyl zirconium dichloride (Cp2ZrCl2) and 4 ml (1.5 mmol / ml) of methylaluminoxane toluene solution, 66 ml of toluene treated with anhydrous and oxygen-free treatment, 20 ml (2 mmol / ml) of norbornene toluene solution, and NBEimide monomer accounting for 1% of the molar ratio of norbornene were added in sequence. Three atmospheres of ethylene were passed in under mechanical stirring until saturation. The pressure was controlled to 3 standard atmospheres by supplementing ethylene, and the reaction was carried out at 40°C for 12 hours under this pressure. After the reaction was completed, the reaction solution was post-treated to obtain a cycloolefin copolymer P4, that is, an NBEimide-modified ethylene-norbornene copolymer or an NBEimide-ethylene-norbornene copolymer. The number average molecular weight was measured by gel permeation chromatography to be about 15,000.

[0195] Preparation Example 5: Cyclic Olefin Copolymer P5

[0196] First, a 500 ml polymerization reactor was evacuated and nitrogen was passed twice, and then evacuated again, and then ethylene gas was passed in, and then 8 ml (1.5 mmol / ml) of dicyclopentadienyl zirconium dichloride (Cp2ZrCl2) and 4 ml (1.5 mmol / ml) of methylaluminoxane toluene solution, 66 ml of toluene treated with anhydrous and oxygen-free treatment, 20 ml (2 mmol / ml) of norbornene toluene solution, and NBEimide monomer accounting for 25% of the molar ratio of norbornene were added in sequence. Three atmospheres of ethylene were passed in under mechanical stirring until saturation. The pressure was controlled to 3 standard atmospheres by supplementing ethylene, and the reaction was carried out at 40°C for 6 hours under this pressure. After the reaction was completed, the reaction solution was post-treated to obtain a cycloolefin copolymer P5, that is, an NBEimide-modified ethylene-norbornene copolymer or an NBEimide-ethylene-norbornene copolymer. The number average molecular weight was measured by gel permeation chromatography to be about 3000.

[0197] Preparation Example 6: Cyclic Olefin Copolymer P6

[0198] First, a 500 ml polymerization reactor was evacuated and nitrogen was passed twice, and then evacuated again, and then ethylene gas was passed in, and then 8 ml (1.5 mmol / ml) of dicyclopentadienyl zirconium dichloride (Cp2ZrCl2) and 4 ml (1.5 mmol / ml) of methylaluminoxane toluene solution, 66 ml of toluene treated with anhydrous and oxygen-free treatment, 20 ml (2 mmol / ml) of dicyclopentadiene toluene solution, and NBEimide monomer accounting for 10% of the molar ratio of dicyclopentadiene were added in sequence. Three atmospheres of ethylene were passed in under mechanical stirring until saturation. The pressure was controlled to 3 standard atmospheres by supplementing ethylene, and the reaction was carried out at 40°C for 3 hours under this pressure. After the reaction was completed, the reaction solution was post-treated to obtain a cycloolefin copolymer P6, that is, an NBEimide-modified ethylene-dicyclopentadiene copolymer or NBEimide-ethylene-dicyclopentadiene copolymer. The number average molecular weight was measured by gel permeation chromatography and was about 4000.

[0199] Preparation Example 7: Cyclic Olefin Copolymer P7

[0200] First, a 500 ml polymerization kettle was evacuated and nitrogen was passed twice, and then evacuated again, and then ethylene gas was passed in, and then 8 ml (1.5 mmol / ml) of dicyclopentadienyl zirconium dichloride (Cp2ZrCl2) and 4 ml (1.5 mmol / ml) of methylaluminoxane toluene solution, 66 ml of toluene treated with anhydrous and oxygen-free treatment, 20 ml (2 mmol / ml) of cyclopentadiene toluene solution, and NBEimide monomer accounting for 10% of the molar ratio of cyclopentadiene were added in sequence. Three atmospheres of ethylene were passed in under mechanical stirring until saturation. The pressure was controlled to 3 standard atmospheres by supplementing ethylene, and the reaction was carried out at 40°C for 7 hours under this pressure. After the reaction was completed, the reaction solution was post-treated to obtain a cycloolefin copolymer P7, that is, an NBEimide-modified ethylene-cyclopentadiene copolymer or an NBEimide-ethylene-cyclopentadiene copolymer. The number average molecular weight was measured by gel permeation chromatography and was about 8000.

[0201] Preparation Example 8: Cyclic Olefin Copolymer P8

[0202] First, a 500 ml polymerization reactor was evacuated and nitrogen was passed twice, and then evacuated again, and then propylene gas was introduced, and then 8 ml (1.5 mmol / ml) of dicyclopentadienyl zirconium dichloride (Cp2ZrCl2) and 4 ml (1.5 mmol / ml) of methylaluminoxane toluene solution, 66 ml of toluene treated with anhydrous and oxygen-free treatment, 20 ml (2 mmol / ml) of tricyclopentadiene toluene solution, and NBEimide monomer accounting for 10% of the molar ratio of tricyclopentadiene were added in sequence. Three atmospheres of propylene were introduced to saturation under mechanical stirring. The pressure was controlled to 3 standard atmospheres by supplementing propylene, and the reaction was carried out at 40°C for 4 hours under this pressure. After the reaction was completed, the reaction solution was post-treated to obtain a cycloolefin copolymer P8, that is, a NBEimide-modified propylene-tricyclopentadiene copolymer or a NBEimide-propylene-tricyclopentadiene copolymer. The number average molecular weight was measured by gel permeation chromatography and was about 5000.

[0203] Preparation Example 9: Cyclic Olefin Copolymer P9

[0204] First, a 500 ml polymerization reactor was evacuated and nitrogen was passed twice, and then evacuated again, and then acetylene gas was introduced, and then 8 ml (1.5 mmol / ml) of dicyclopentadienyl zirconium dichloride (Cp2ZrCl2) and 4 ml (1.5 mmol / ml) of methylaluminoxane toluene solution, 66 ml of toluene treated with anhydrous and oxygen-free treatment, 20 ml (2 mmol / ml) of cyclopentene toluene solution, and NBEimide monomer accounting for 20% of the molar ratio of cyclopentene were added in sequence. Three atmospheres of acetylene were introduced to saturation under mechanical stirring. The pressure was controlled to 3 standard atmospheres by supplementing acetylene, and the reaction was carried out at 40°C for 8 hours under this pressure. After the reaction was completed, the reaction solution was post-treated to obtain a cycloolefin copolymer P9, that is, an NBEimide-modified acetylene-cyclopentene copolymer or an NBEimide-acetylene-cyclopentene copolymer. The number average molecular weight was measured by gel permeation chromatography and was about 10,000.

[0205] Preparation Example 10: Copolymer D1

[0206] First, evacuate the 500 ml polymerization reactor twice with nitrogen, evacuate again, and then introduce ethylene gas, and then add 8 ml (1.5 mmol / ml) of dicyclopentadienyl zirconium dichloride (Cp2ZrCl2) and 4 ml (1.5 mmol / ml) of methylaluminoxane toluene solution, 66 ml of toluene treated with anhydrous and oxygen-free treatment, and 20 ml (2 mmol / ml) of norbornene toluene solution. Under mechanical stirring, 3 atmospheres of ethylene are introduced to saturation. The pressure is controlled to 3 standard atmospheres by supplementing ethylene, and the reaction is carried out at 40°C for 2 hours under this pressure. After the reaction is completed, the reaction solution is post-treated to obtain copolymer D1, that is, ethylene-norbornene copolymer.

[0207] Preparation Example 11: Copolymer D2

[0208] First, evacuate the 500 ml polymerization reactor twice with nitrogen, evacuate again, and then introduce ethylene gas, and then add 8 ml (1.5 mmol / ml) of dicyclopentadienyl zirconium dichloride (Cp2ZrCl2) and 4 ml (1.5 mmol / ml) of methylaluminoxane toluene solution, 66 ml of toluene treated with anhydrous and oxygen-free treatment, 20 ml (2 mmol / ml) of norbornene toluene solution, and maleic anhydride monomer accounting for 10% of the molar ratio of norbornene. Under mechanical stirring, 3 atmospheres of ethylene are introduced to saturation. The pressure is controlled to 3 standard atmospheres by supplementing ethylene, and the reaction is carried out at 40°C for 4 hours under this pressure. After the reaction is completed, the reaction solution is post-treated to obtain copolymer D2, that is, maleic anhydride-ethylene-norbornene copolymer.

[0209] Preparation Example 12: Copolymer D3

[0210] First, 500 ml of the polymerization reactor was evacuated and nitrogen was passed twice, and then evacuated again, and then ethylene gas was passed in, and then 8 ml (1.5 mmol / ml) of dicyclopentadienyl zirconium dichloride (Cp2ZrCl2) and 4 ml (1.5 mmol / ml) of methylaluminoxane toluene solution, 66 ml of toluene treated with anhydrous and oxygen-free treatment, 20 ml (2 mmol / ml) of norbornene toluene solution, and norbornene diacid anhydride monomer accounting for 10% of the molar ratio of norbornene were added in sequence. Three atmospheres of ethylene were passed in under mechanical stirring until saturation. The pressure was controlled to 3 standard atmospheres by supplementing ethylene, and the reaction was carried out at 40°C for 6 hours under this pressure. After the reaction was completed, the reaction solution was post-treated to obtain copolymer D3, that is, norbornene diacid anhydride-ethylene-norbornene copolymer.

[0211] Preparation Example 13: Copolymer D4

[0212] First, evacuate the 500 ml polymerization reactor twice with nitrogen, evacuate again, and then introduce ethylene gas, and then add 8 ml (1.5 mmol / ml) of dicyclopentadienyl zirconium dichloride (Cp2ZrCl2) and 4 ml (1.5 mmol / ml) of methylaluminoxane toluene solution, 66 ml of toluene treated with anhydrous and oxygen-free treatment, 20 ml (2 mmol / ml) of norbornene toluene solution, and acrylate monomer accounting for 10% of the molar ratio of norbornene. Under mechanical stirring, 3 atmospheres of ethylene are introduced to saturation. The pressure is controlled to 3 standard atmospheres by supplementing ethylene, and the reaction is carried out at 40°C for 5 hours under this pressure. After the reaction is completed, the reaction solution is post-treated to obtain copolymer D4, i.e., acrylate-ethylene-norbornene copolymer.

[0213] The resin composition compositions (unit: parts by weight) of Examples E1-E14 and Comparative Examples C1-C7 and the test results of sample properties are shown in Tables 1 to 3. Since monomer a' is a gas, it cannot be directly added to the resin composition without forming a copolymer with monomer b' and monomer c', and samples cannot be prepared for testing.

[0214] Table 1 Composition of the resin composition of Examples E1 to E7 (unit: parts by weight) and test results of properties of their products

[0215]

[0216] Table 2 Composition of the resin composition of Examples E8 to E14 (unit: parts by weight) and test results of properties of their products

[0217]

[0218] Table 3 Compositions of the resin compositions of Comparative Examples C1 to C7 (unit: parts by weight) and test results of properties of their products

[0219]

[0220] From Tables 1 to 3 above, we can see that:

[0221] 1. Compared with Comparative Example C1 which does not contain the cyclic olefin copolymer of the present application, the following properties of Examples E1 to E14 using the cyclic olefin copolymer of the present application have been significantly improved: water absorption, copper foil peel strength (P / S) and dielectric loss (Df). Among them, the water absorption of the samples of Examples E1 to E14 is less than 0.18%, while the water absorption of the sample of Comparative Example C1 is 0.25%; the P / S of the samples of Examples E1 to E14 is more than 3.4 lb / in, while the P / S of the sample of Comparative Example C1 is 3.0 lb / in; the Df of the samples of Examples E1 to E14 is less than 0.00185, while the Df of the sample of Comparative Example C1 is 0.00312.

[0222] 2. Compared with Comparative Example C2 using a mixture of NBEimide and ethylene-norbornene copolymer, Examples E1 to E14 using the cycloolefin copolymer of the present application have achieved significant improvements in the following properties: adhesive storage life (adhesive precipitation), filling properties, T288 heat resistance, glass transition temperature (Tg), Z-axis thermal expansion coefficient (Z-PTE) and copper foil peel strength (P / S). Among them, the glue storage of samples in Examples E1 to E14 is more than 30 days (no foreign matter precipitated), while the glue storage period of the sample in Comparative Example C2 is short, with solid matter precipitated within 30 days; there is no shadow when filling the glue of samples in Examples E1 to E14, while there is a shadow when filling the glue of the sample in Comparative Example C2; ​​the T288 heat resistance of samples in Examples E1 to E14 is more than 70 minutes, while the T288 of the sample in Comparative Example C2 is 35 minutes; the Tg of samples in Examples E1 to E14 is more than 197°C, while the Tg of the sample in Comparative Example C2 is 188°C; the Z-PTE of samples in Examples E1 to E14 is less than 2.0%, while the Z-PTE of the sample in Comparative Example C2 is 2.2%; the P / S of samples in Examples E1 to E14 is more than 3.4lb / in, while the P / S of the sample in Comparative Example C2 is 1.3lb / in.

[0223] 3. Compared with the comparative examples C3 to C7 using other cycloolefin copolymers, the following properties of the embodiments E1 to E14 using the cycloolefin copolymer of the present application have been significantly improved: filling, T288 heat resistance, glass transition temperature (Tg), Z-axis thermal expansion coefficient (Z-PTE). Among them, the filling of the samples of embodiments E1 to E14 has no shadow, while the filling of the samples of comparative examples C3 to C7 has shadow; the T288 heat resistance of the samples of embodiments E1 to E14 is more than 70 minutes, while the T288 heat resistance of the samples of comparative examples C3 to C7 is less than or equal to 45 minutes; the Tg of the samples of embodiments E1 to E14 is more than 197°C, while the Tg of the samples of comparative examples C3 to C7 is less than or equal to 187°C; the Z-PTE of the samples of embodiments E1 to E14 is less than 2.0%, while the Z-PTE of the samples of comparative examples C3 to C7 is greater than or equal to 2.4%.

[0224] The above embodiments are essentially only auxiliary explanations and are not intended to limit the embodiments of the present application or the application or use of these embodiments. In the present application, words similar to "example" represent "as an example, example or illustration". Any illustrative implementation form herein is not necessarily interpreted as being preferred or more advantageous relative to other implementation forms, unless otherwise specified.

[0225] In addition, although at least one exemplary embodiment or comparative example has been proposed in the aforementioned embodiment, it should be understood that there are still a large number of changes in the present application. It should also be understood that the embodiments described herein are not intended to limit the scope, use or configuration of the requested technical solution in any way. On the contrary, the aforementioned embodiment will provide a simple guide for those skilled in the art to implement one or more of the embodiments and their equivalents. Furthermore, the claims include known equivalents and all foreseeable equivalents when the present patent application is filed.

Claims

1. A cycloolefin copolymer, characterized in that The cycloolefin copolymer comprises a structural unit a formed by a monomer a', a structural unit b formed by a monomer b' and a structural unit c formed by a monomer c', wherein the monomer a' comprises any one of ethylene, propylene, acetylene and propyne or a combination thereof, the monomer b' comprises any one of norbornene, cyclopentene, cyclopentadiene, dicyclopentadiene and tricyclopentadiene or a combination thereof, and the monomer c' comprises a monomer represented by formula (1), 2. The cycloolefin copolymer according to claim 1, characterized in that The molar ratio of the structural unit c to the structural unit b in the cycloolefin copolymer is 0.01-0.25:

1.

3. The cycloolefin copolymer according to claim 1, characterized in that The number average molecular weight of the cycloolefin copolymer is 3,000 to 15,000.

4. The cycloolefin copolymer according to claim 1, characterized in that The cycloolefin copolymer includes any one of the cycloolefin copolymers represented by formula (2), the cycloolefin copolymers represented by formula (3), the cycloolefin copolymers represented by formula (4), the cycloolefin copolymers represented by formula (5), and the cycloolefin copolymers represented by formula (6), or a combination thereof. In formula (2) to formula (6), n1 is an integer between 1 and 500, n2 is an integer between 1 and 150, and n3 is an integer between 1 and 50.

5. A resin composition, characterized in that Contains the following ingredients: The cyclic olefin copolymer according to any one of claims 1 to 4; and Polyphenylene ether resin containing unsaturated carbon-carbon double bonds.

6. The resin composition according to claim 5, characterized in that In the resin composition, based on 100 parts by weight of the polyphenylene ether resin containing unsaturated carbon-carbon double bonds, the cycloolefin copolymer is 5 to 60 parts by weight.

7. The resin composition according to claim 5, characterized in that The polyphenylene ether resin containing unsaturated carbon-carbon double bonds includes any one of (meth)acryl polyphenylene ether resin, vinylbenzyl polyphenylene ether resin, vinyl polyphenylene ether resin, or a combination thereof.

8. The resin composition according to claim 5, characterized in that The resin composition also includes additives, which include any one of a cross-linking agent containing unsaturated carbon-carbon double bonds, polyolefins, silicone resins, benzoxazine resins, epoxy resins, polyester resins, phenolic resins, amine curing agents, polyamides, polyimides, styrene maleic anhydride, maleimide resins, cyanate resins, and maleimide triazine resins, or a combination thereof.

9. The resin composition according to claim 5, characterized in that The resin composition further comprises any one of a hardening accelerator, a polymerization inhibitor, a flame retardant, an inorganic filler, a surface treatment agent, a dye, a toughening agent, and a solvent, or a combination thereof.

10. An article made of the resin composition according to any one of claims 5 to 9, characterized in that: The product includes a prepreg, a resin film, a laminate or a printed circuit board.

11. The product according to claim 10, characterized in that The product has one or more of the following characteristics: The T288 heat resistance measured according to IPC-TM-650 2.4.24.1 is more than 70 minutes; The glass transition temperature measured according to IPC-TM-650 2.4.24.4 is above 197°C; The Z-axis thermal expansion rate measured according to IPC-TM-650 2.4.24.5 is less than 2.0%; The water absorption measured according to the methods of IPC-TM-650 2.6.2.1 and IPC-TM-650 2.6.16.1 is less than 0.18%; Copper foil peel strength of 3.4 lb / in or greater as measured by IPC-TM-650 2.4.8; and / or The dielectric loss measured at a frequency of 10 GHz according to the method of JIS C2565 is 0.00185 or less.

12. A method for preparing a cycloolefin copolymer, characterized in that: A monomer a', a monomer b' and a monomer c' are mixed in a reaction container and subjected to a polymerization reaction in the presence of a catalyst to obtain a cycloolefin copolymer; wherein the monomer a' comprises any one of ethylene, propylene, acetylene and propyne or a combination thereof, the monomer b' comprises any one of norbornene, cyclopentene, cyclopentadiene, dicyclopentadiene and tricyclopentadiene or a combination thereof, and the monomer c' comprises a monomer represented by formula (1).

13. The preparation method according to claim 12, characterized in that: The preparation method satisfies one or more of the following conditions: The catalyst comprises any one of a metallocene catalyst and an aluminoxane catalyst or a combination thereof; The mixing is carried out in an organic solvent; The polymerization reaction is carried out at a temperature of 30 to 80° C. and the reaction time is 2 to 15 hours; The mixing is achieved as follows: introducing monomer a' gas into a reaction container, then adding a catalyst, an organic solvent, and monomer b' to obtain an intermediate product, continuing to introduce monomer a' gas into the reaction container containing the intermediate product until saturation, and adding monomer c'; or introducing monomer a' gas into a reaction container, then adding a catalyst, an organic solvent, monomer b' and monomer c', and continuing to introduce monomer a' gas until saturation.

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