CN114456574A

CN114456574A - Prepreg and product thereof

Info

Publication number: CN114456574A
Application number: CN202210137166.2A
Authority: CN
Inventors: 张书豪
Original assignee: Elite Material Co Ltd
Current assignee: Elite Material Co Ltd
Priority date: 2022-02-10
Filing date: 2022-02-15
Publication date: 2022-05-10
Anticipated expiration: 2042-02-15
Also published as: TW202222981A; CN114456574B; TWI809707B

Abstract

The invention discloses a prepreg, which comprises a quartz non-woven fabric and a resin composition, wherein the resin composition comprises: (A)40 to 115 parts by weight of an unsaturated carbon-carbon double bond-containing resin; and (B)30 to 120 parts by weight of spherical silica, wherein the resin containing unsaturated carbon-carbon double bonds comprises 50 to 100 parts by weight of vinyl-containing polyphenylene ether resin or 5 to 40 parts by weight of vinyl-containing polyolefin or a combination thereof, and the total weight of the vinyl-containing polyphenylene ether resin and the vinyl-containing polyolefin in the resin containing unsaturated carbon-carbon double bonds is between 40 and 115 parts by weight. In addition, the invention also discloses a product made of the prepreg, and the product comprises a laminated plate or a printed circuit board.

Description

Prepreg and product thereof

Technical Field

The present disclosure relates to prepregs and products thereof, and particularly to a prepreg for manufacturing a laminate or a printed circuit board.

Background

With the rapid development of the fifth generation mobile communication technology (5G), low dielectric substrate materials suitable for high-frequency and high-speed information transmission also become the main development direction of printed circuit boards, and the technical requirements include that the substrate has an extremely low dielectric constant and an extremely low dielectric loss at high frequency, so that the manufactured printed circuit board can be used for high-frequency and high-speed 5G communication transmission. For example, the dielectric constant of the low dielectric substrate material measured at 10GHz frequency is less than or equal to 3.2, and the dielectric loss measured at 10GHz frequency is less than or equal to 0.0020, which is a technological direction for active development in the field. Therefore, how to develop a suitable material for the high performance substrate is a goal of active efforts in the industry. In addition, the prepreg manufactured by using the conventional woven fabric is prone to defects such as weak interlayer peeling strength of the laminated substrate, insufficient flow in the laminated substrate, and vacuoles generated in the laminated substrate, and is also a target to be improved.

Disclosure of Invention

In view of the problems encountered in the prior art, and in particular the inability of the existing materials to meet one or more of the above-mentioned requirements, a primary object of the present invention is to provide a prepreg that achieves at least one or more of excellent properties such as a very low dielectric constant, a very low dielectric loss, a high inter-substrate peel strength, a suitable flow in the substrate board, and no voids in the substrate board after lamination.

In order to achieve the above object, the present invention discloses a prepreg comprising a quartz nonwoven fabric and a resin composition, the resin composition comprising:

(A)40 to 115 parts by weight of a resin containing an unsaturated carbon-carbon double bond; and

(B)30 to 120 parts by weight of a spherical silica,

wherein the resin containing unsaturated carbon-carbon double bonds comprises 50 to 100 parts by weight of vinyl-containing polyphenylene ether resin or 5 to 40 parts by weight of vinyl-containing polyolefin or a combination thereof, and the total weight of the vinyl-containing polyphenylene ether resin and the vinyl-containing polyolefin in the resin containing unsaturated carbon-carbon double bonds is between 40 to 115 parts by weight.

For example, in one embodiment, the vinyl-containing polyphenylene ether resin comprises a vinylbenzylbiphenyl-containing polyphenylene ether resin, a methacrylate-containing polyphenylene ether resin, a vinylbenzylbisphenol a-containing polyphenylene ether resin, a vinyl-extended polyphenylene ether resin, or a combination thereof.

For example, in one embodiment, the vinyl-containing polyolefin comprises polybutadiene, polyisoprene, styrene-butadiene copolymers, styrene-isoprene copolymers, styrene-butadiene-divinylbenzene terpolymers, styrene-butadiene-maleic anhydride terpolymers, vinyl-polybutadiene-urethane oligomers, maleic anhydride-butadiene copolymers, or combinations thereof.

For example, in one embodiment, the aforementioned resin composition further comprises 5 to 25 parts by weight of a hydrogenated polyolefin, 20 to 40 parts by weight of a maleimide resin, 20 to 35 parts by weight of a triallyl isocyanurate, 0.1 to 0.5 parts by weight of a hardening initiator, 0.1 to 0.5 parts by weight of an inhibitor, 45 to 70 parts by weight of a flame retardant, or a combination thereof.

For example, in one embodiment, the resin composition further includes an inorganic filler different from the spherical silica, a solvent, a silane coupling agent, a colorant, a toughening agent, a core-shell rubber, or a combination thereof. For example, in one embodiment, the inorganic filler other than the spherical silica may be 5 to 50 parts by weight compared to 40 to 115 parts by weight of the unsaturated carbon-carbon double bond-containing resin. For example, but not limited to, the inorganic filler may be 5 to 10 parts by weight, compared to 55 parts by weight of the unsaturated carbon-carbon double bond-containing resin. For example, in one embodiment, the amount of the solvent is not particularly limited, and the amount of the solvent may be adjusted according to the viscosity of the resin composition. For example, in one embodiment, the respective content of the silane coupling agent, the coloring agent, the toughening agent, or the core shell rubber in the disclosed resin composition may be 0.01 to 20 parts by weight, such as but not limited to 0.01 to 5 parts by weight, 0.05 to 20 parts by weight, or 0.03 to 10 parts by weight, compared to 40 to 115 parts by weight of the unsaturated carbon-carbon double bond-containing resin.

For example, in one embodiment, the aforementioned resin composition does not include an epoxy resin.

Another main object of the present invention is to provide an article made of the aforementioned prepreg, which includes a laminate or a printed circuit board.

For example, in one embodiment, the article of manufacture described above has one, more, or all of the following characteristics:

the copper-containing substrate has an interlayer peel strength greater than 6 lb/in as measured by the method described with reference to IPC-TM-6502.4.8;

the edge of the plate without the copper substrate has no stripes;

the surface does not contain a copper substrate and has no vacuole;

a dielectric constant of 3.2 or less as measured at a frequency of 10GHz according to the method described in JIS C2565; and

a dielectric loss of 0.0017 or less as measured at a frequency of 10GHz according to the method described in JIS C2565.

Drawings

FIG. 1 is a schematic diagram of the appearance of a substrate with a plate edge stripe.

Fig. 2 is a schematic view of the appearance of a normal substrate.

FIG. 3 is a schematic illustration of in-board flow-through-gel sample plate measurement points.

Detailed Description

To enable those skilled in the art to understand the features and effects of the present invention, the general description and definitions of the terms and words used in the specification and claims are set forth below. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

The theory or mechanism described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, i.e., the present disclosure may be practiced without limitation to any particular theory or mechanism.

The use of "a," "an," "the," or similar language herein to describe elements and features of the invention is made merely for convenience and to provide a general sense of the scope of the invention. Thus, the description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise.

In this context, "or a combination thereof" means "or any combination thereof", "any", or "any" means "any", or "any".

In this document, the terms "comprising," "including," "having," "containing," or any other similar term, are intended to refer to an open-ended franslational phrase (open-ended franslational phrase) that is intended to cover non-exclusive inclusions. For example, a composition or article comprising a plurality of elements is not limited to only those elements recited herein, but may include other elements not expressly listed but generally inherent to such composition or article. In addition, unless expressly stated to the contrary, the term "or" is intended to mean an inclusive "or" rather than an exclusive "or". For example, the condition "a or B" is satisfied in any of the following cases: a is true (or present) and B is false (or not present), a is false (or not present) and B is true (or present), both a and B are true (or present). Furthermore, in this document, the terms "comprising," "including," "having," "containing," and "containing" are to be construed as specifically disclosed and also to cover both the conjunctions of "consisting of …," "consisting of," "the balance being," and conjunctions of "consisting essentially of …," "consisting essentially of …," "consisting essentially of …," "consisting essentially of," and the like.

All features or conditions, such as values, amounts and concentrations, defined herein as numerical ranges or percentage ranges are for brevity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to cover and specifically disclose all possible subranges and individual values (including integers and fractions) within the range, particularly integer values. For example, a description of a range of "1.0 to 8.0", "between 1.0 to 8.0", or "between 1.0 and 8.0" should be considered to have been specifically disclosed as all subranges from 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 so forth, and should be considered to encompass the endpoints, particularly the subranges bounded by integer values, and should be considered to have specifically disclosed individual values within the range such as 1.0, 2.0, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, and so forth. Unless otherwise indicated, the foregoing explanatory methods apply to all matters contained in the entire disclosure, whether broad or not.

If an amount, concentration, or other value or parameter is expressed as a range, preferred range, or a list of upper and lower limits, then it is understood that all ranges subsumed therein by any pair of the upper or preferred value of that range and the lower or preferred value of that range, regardless of whether ranges are separately disclosed. Further, when a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range.

Numerical values herein are to be understood as having the precision of the numerical significance given the number of significant digits in question, provided that the resulting improved visual performance is achieved. For example, the number 40.0 should be understood to cover a range from 39.50 to 40.49.

In this context, forWhere Markush groups (Markush groups) or pick-type language is used to describe features or examples of the invention, it will be understood by those skilled in the art that subgroups of all members of the Markush group or pick-list or any individual member may also be used to describe the invention. For example, if X is described as "selected from the group consisting of₁、X₂And X₃The group "also indicates that X has been fully described as X₁Is claimed with X₁And/or X₂And/or X₃Claim (5). Furthermore, to the extent that markush group or option language is used to describe features or examples of the invention, those skilled in the art will recognize that subgroups of all members or any combination of individual members of the markush group or option list may also be used to describe the invention. Accordingly, for example, if X is described as "selected from the group consisting of₁、X₂And X₃Group consisting of "and Y is described as" selected from Y₁、Y₂And Y₃The group "formed indicates that X has been fully described as X₁Or X₂Or X₃And Y is Y₁Or Y₂Or Y₃Claim (5).

Unless otherwise specified, in the present invention, the compound refers to a chemical substance formed by two or more elements connected by chemical bonds, including a small molecule compound and a high molecule compound, and is not limited thereto. The compounds herein are not limited to a single chemical species when read, but are to be construed as having the same composition or class of chemical species with the same properties.

Unless otherwise specified, in the present invention, a polymer refers to a product formed by polymerization of a monomer, and often includes an aggregate of a plurality of macromolecules, each macromolecule being formed by repeating connection of a plurality of simple structural units by covalent bonds, the monomer being a compound for synthesizing the polymer. The polymer may include, but is not limited to, a homopolymer (also referred to as an autopolymer), a copolymer, a prepolymer, and the like. Prepolymer refers to a chemical species resulting from the polymerization of two or more compounds at a conversion rate of between 10% and 90%. The polymer of course includes oligomers, and is not limited thereto. The oligomer is also called oligomer, and is a polymer composed of 2-20 repeating units, usually 2-5 repeating units. For example, diene polymers, when read, include diene homopolymers, diene copolymers, diene prepolymers, and of course diene oligomers, and the like.

Unless otherwise specified, in the present invention, a copolymer refers to a product formed by polymerization of two or more different monomers, and includes, but is not limited to, a random copolymer, an alternating copolymer, a graft copolymer, or a block copolymer. For example, a styrene-butadiene copolymer is a product formed by polymerization of only two monomers, i.e., styrene and butadiene, such as, but not limited to, styrene-butadiene copolymers including styrene-butadiene random copolymers, styrene-butadiene alternating copolymers, styrene-butadiene graft copolymers, or styrene-butadiene block copolymers. Styrene-butadiene block copolymers include, for example, but are not limited to, polymerized molecular structures of styrene-butadiene. Styrene-butadiene block copolymers include, for example, but are not limited to, styrene-butadiene-styrene block copolymers. Styrene-butadiene-styrene block copolymers include, for example, but are not limited to, polymerized molecular structures of styrene-butadiene-styrene. Similarly, the hydrogenated styrene-butadiene copolymer includes a hydrogenated styrene-butadiene random copolymer, a hydrogenated styrene-butadiene alternating copolymer, a hydrogenated styrene-butadiene graft copolymer or a hydrogenated styrene-butadiene block copolymer. The hydrogenated styrene-butadiene block copolymer includes, for example, but is not limited to, a hydrogenated styrene-butadiene-styrene block copolymer.

Unless otherwise specified, "resin" may be generally a conventional name of a synthetic polymer, but in the present invention, "resin" may include a monomer, a polymer thereof, a combination of monomers, a combination of polymers thereof, or a combination of a monomer and a polymer thereof, and the like, when read, and is not limited thereto. For example, in the present invention, "maleimide resin" is read to include maleimide monomers, maleimide polymers, combinations of maleimide monomers, combinations of maleimide polymers, or combinations of maleimide monomers and maleimide polymers.

For example, in the present invention, "vinyl-containing" when read includes vinyl, vinylene, allyl, (meth) acrylate, or combinations thereof. Wherein the vinyl group comprises a vinylbenzyl group.

In the present invention, unless otherwise specified, the modified product (also referred to as "modified product") includes: a product obtained by modifying a reactive functional group of each resin, a product obtained by pre-polymerization of each resin with other resins, a product obtained by cross-linking each resin with other resins, a product obtained by homopolymerization of each resin, a product obtained by copolymerization of each resin with other resins, and the like. For example, but not limited to, the modification may be to replace the original hydroxyl group with a vinyl group through a chemical reaction, or to obtain a terminal hydroxyl group through a chemical reaction between the original terminal vinyl group and p-aminophenol.

Unless otherwise specified, the unsaturated bond in the present invention refers to a reactive unsaturated bond, such as but not limited to an unsaturated double bond capable of undergoing a crosslinking reaction with other functional groups, such as but not limited to an unsaturated carbon-carbon double bond capable of undergoing a crosslinking reaction with other functional groups.

Unless otherwise specified, in the present invention, specific examples of acrylate compounds are written in the form "(meth)" which, when read, is to be understood to include both the case where methyl is contained and the case where methyl is not contained, for example, cyclohexanedimethanol di (meth) acrylate is read to include cyclohexanedimethanol diacrylate and cyclohexanedimethanol dimethacrylate.

Unless otherwise specified, alkyl groups recited herein are to be read as including the various isomers thereof, e.g., propyl is to be read as including n-propyl and isopropyl.

It should be understood that the features disclosed in the embodiments herein can be combined in any combination to form the technical solution of the present application, as long as the combination of the features is not contradictory.

Unless otherwise specified, parts by weight, as used herein, refers to parts by weight, which may be in any weight unit, such as, but not limited to, kilograms, grams, pounds, and the like. For example, 100 parts by weight of maleimide resin, which may represent 100 kilograms of maleimide resin or 100 pounds of maleimide resin. If the resin solution comprises a solvent and a resin, the parts by weight of the (solid or liquid) resin generally refers to the weight units of the (solid or liquid) resin and does not include the weight units of the solvent in the solution. And parts by weight of the solvent means the unit by weight of the solvent.

The following detailed description is merely exemplary in nature and is not intended to limit the invention or the application thereof. Furthermore, there is no intention to be bound by any theory presented in the preceding prior art or the summary of the invention or the following detailed description or examples. The methods, reagents and conditions employed in the examples are, unless otherwise indicated, those conventional in the art.

In summary, the present invention mainly discloses a prepreg, which includes a quartz non-woven fabric and a resin composition, wherein the resin composition includes:

(B)30 to 120 parts by weight of a spherical silica,

wherein the resin containing unsaturated carbon-carbon double bonds comprises 50 to 100 parts by weight of vinyl-containing polyphenylene ether resin or 5 to 40 parts by weight of vinyl-containing polyolefin or a combination thereof, and the total weight of the vinyl-containing polyphenylene ether resin and the vinyl-containing polyolefin in the resin containing unsaturated carbon-carbon double bonds is between 40 and 115 parts by weight.

For example, in one embodiment, unless otherwise specified, the quartz non-woven fabric (which may also be referred to as a quartz fiber mat) mentioned in the embodiments of the present invention is made of quartz fibers having a silica content of 99.9 weight percent or more. Wherein the quartz fibers in the quartz non-woven fabric present a fiber mesh structure. For example, but not limited to, silica fibers may be formed into a fiber network of silica nonwoven fabric using conventional binder (binder) techniques. Therefore, the quartz nonwoven fabric is not produced by a conventional weaving method, compared to the quartz woven fabric.

For example, in one embodiment, unless otherwise specified, the vinyl-containing polyphenylene ether resins mentioned in the various embodiments of the present invention may include various polyphenylene ether resins end-modified with vinyl groups or allyl groups, such as vinylbenzylpolyphenylene ether resins. Or the vinyl-containing polyphenylene ether resin may be a (meth) acrylate-containing polyphenylene ether resin. For example, the vinyl-containing polyphenylene ether resin includes a vinylbenzylbiphenyl-containing polyphenylene ether resin, a methacrylate-containing polyphenylene ether resin, a vinylbenzylbisphenol a-containing polyphenylene ether resin, a vinyl-chain-extended polyphenylene ether resin, or a combination thereof, and is not limited thereto.

For example, in one embodiment, the vinyl-containing polyphenylene ether resin may comprise various types of vinyl-containing polyphenylene ether resins known in the art. The vinyl-containing polyphenylene ether resin suitable for use in the present invention is not particularly limited, and may be any one or more of commercially available products, self-made products, or a combination thereof. In certain embodiments, any one or more of the following vinyl-containing polyphenylene ether resins may be used: vinylbenzylbiphenyl-containing polyphenylene ether resins (e.g., OPE-2st, available from mitsubishi gas chemical company), methacrylate-containing polyphenylene ether resins (e.g., SA9000, available from Sabic company), vinylbenzylbisphenol a-containing polyphenylene ether resins, vinyl chain extended polyphenylene ether resins, or combinations thereof. The aforementioned vinyl-extended polyphenylene ether resins may include the various polyphenylene ether resins of U.S. patent application publication No. 2016/0185904a1, which is incorporated herein by reference in its entirety.

For example, in one embodiment, such as but not limited to, the foregoing resin composition includes 100 parts by weight of a vinylbenzylbiphenyl-containing polyphenylene ether resin. For another example, the resin composition includes 50 parts by weight of a vinylbenzylbiphenyl-containing polyphenylene ether resin and 50 parts by weight of a methacrylate-containing polyphenylene ether resin. For another example, the resin composition includes 20 parts by weight of an vinylbenzylbiphenyl-containing polyphenylene ether resin, 20 parts by weight of a methacrylate-containing polyphenylene ether resin, 5 parts by weight of an vinylbenzylbisphenol a-containing polyphenylene ether resin, and 5 parts by weight of a vinyl-chain-extended polyphenylene ether resin.

For example, in one embodiment, the foregoing vinyl-containing polyolefins are not limited in kind and may include various vinyl-containing olefin polymers known in the art, such as, but not limited to, vinyl-containing polyolefins including polybutadiene, polyisoprene, styrene-butadiene copolymers, styrene-isoprene copolymers, styrene-butadiene-divinylbenzene terpolymers, styrene-butadiene-maleic anhydride terpolymers, vinyl-polybutadiene-urea ester oligomers, maleic anhydride-butadiene copolymers, or combinations thereof. If not specifically indicated, the amount of the vinyl-containing polyolefin used in the present invention may be adjusted as needed, for example, but not limited to, 5 to 40 parts by weight, such as, but not limited to, 5 parts by weight, 10 parts by weight, 15 parts by weight, 18 parts by weight, 25 parts by weight, 35 parts by weight or 40 parts by weight, as compared to 50 parts by weight to 100 parts by weight of the vinyl-containing polyphenylene ether resin.

For example, the spherical silica is contained in the resin composition in an amount of 30 to 120 parts by weight, such as, but not limited to, 30 parts by weight, 35 parts by weight, 40 parts by weight, 50 parts by weight, 60 parts by weight, 70 parts by weight, 100 parts by weight, or 120 parts by weight, compared to 40 to 115 parts by weight of the resin containing unsaturated carbon-carbon double bonds. For another example, the resin composition includes 40 parts by weight of an unsaturated carbon-carbon double bond-containing resin and 60 parts by weight of a spherical silica. For another example, the resin composition includes 115 parts by weight of a resin containing unsaturated carbon-carbon double bonds and 120 parts by weight of spherical silica, but not limited thereto.

For example, in one embodiment, the spherical silica can comprise various types of spherical silica known in the art, which can have a particle size distribution D50 of, for example, less than or equal to 2.0 micrometers (μm). For example, the preferred particle size distribution D50 may be between 0.2 microns and 2.0 microns. Such as, but not limited to, 0.2 microns, 0.3 microns, 0.4 microns, 0.6 microns, 0.8 microns, 1.2 microns, 1.3 microns, 2.0 microns. Unless otherwise indicated, the particle size distribution D50 refers to the particle size corresponding to 50% of the cumulative volume distribution of the filler (such as, but not limited to, spherical silica) as determined by laser scattering. The spherical silica suitable for use in the present invention is not particularly limited and may be any one or more of commercially available products, such as, but not limited to, spherical silica from Admatechs corporation or spherical silica from Denka corporation.

For example, in one embodiment, the spherical silica may optionally be pretreated with a silane coupling agent, such as, but not limited to, an amino silane coupling agent, an epoxy silane coupling agent, a vinyl silane coupling agent, or an acrylate silane coupling agent. The content of the silane coupling agent pretreatment may be 0.005 to 0.5 parts by weight, compared to 100 parts by weight of the spherical silica, and is not limited thereto.

For example, in one embodiment, the aforementioned resin composition may further optionally include 5 to 25 parts by weight of hydrogenated polyolefin, 20 to 40 parts by weight of maleimide resin, 20 to 35 parts by weight of triallyl isocyanurate, 0.1 to 0.5 parts by weight of a hardening initiator, 0.1 to 0.5 parts by weight of an inhibitor, 45 to 70 parts by weight of a flame retardant, or a combination thereof.

For example, in one embodiment, the hydrogenated polyolefin can include various types of hydrogenated styrene-butadiene-styrene triblock copolymers (also known as styrene-ethylene/butylene-styrene copolymers) known in the art. The hydrogenated polyolefin suitable for use in the present invention is not particularly limited and may be any one or more of commercially available products, self-made products, or a combination thereof. For example, in one embodiment, the hydrogenated polyolefin comprises a hydrogenated styrene-butadiene-styrene triblock copolymer, a maleic anhydride substituted hydrogenated styrene-butadiene-styrene triblock copolymer, or a combination thereof. That is, the hydrogenated polyolefin comprises an unsubstituted hydrogenated styrene-butadiene-styrene triblock copolymer, a maleic anhydride substituted hydrogenated styrene-butadiene-styrene triblock copolymer, or a combination thereof. For example, in one embodiment, the hydrogenated polyolefin may be a hydrogenated polyolefin produced by Asahi KASEI corporation under the tradenames H1221, H1062, H1521, H1052, H1041, H1053, H1051, H1517, H1043, N504, H1272, M1943, M1911, M1913, etc., or a hydrogenated polyolefin produced by KRATON corporation under the tradenames G1650, G1651, G1652, G1654, G1657, G1726, FG1901, FG1924, etc., or a hydrogenated polyolefin produced by Kuraray corporation under the tradenames 8004, 8006, 8007L, etc.

If not specifically indicated, the content of the hydrogenated styrene-butadiene-styrene triblock copolymer is 5 to 25 parts by weight, compared to 40 to 115 parts by weight of the unsaturated carbon-carbon double bond-containing resin, and is not limited thereto. Such as, but not limited to, 5 parts by weight, 8 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, or 25 parts by weight. For another example, the resin containing unsaturated carbon-carbon double bonds includes 100 parts by weight of a vinyl-containing polyphenylene ether resin, 15 parts by weight of a vinyl-containing polyolefin, and 5 parts by weight of a hydrogenated polyolefin. For another example, the resin containing unsaturated carbon-carbon double bonds includes 50 parts by weight of a vinyl-containing polyphenylene ether resin, 5 parts by weight of a vinyl-containing polyolefin, and 15 parts by weight of a hydrogenated polyolefin, and is not limited thereto.

For example, in one embodiment, unless otherwise specified, the maleimide resin of the present invention refers to a compound or mixture having more than one maleimide functional group in the molecule. The maleimide resin employed in the present invention is not particularly limited, and may be any one or more maleimide resins suitable for the production of prepregs, laminates or printed wiring boards. Specific examples include, but are not limited to, 4' -diphenylmethane bismaleimide (4, 4' -diphenylmethanmaleimide), polyphenylmethane maleimide (or phenylmethane maleimide oligomer), bisphenol A diphenylether bismaleimide (bisphenone A diphenylether bismaleimide), 3 ' -dimethyl-5,5 ' -diethyl-4, 4' -diphenylmethane bismaleimide (3,3 ' -dimethyl-5,5 ' -diethyl-4, 4' -diphenylmethanbismaleimide), 3 ' -dimethyl-5,5 ' -dipropyl-4, 4' -diphenylmethanbismaleimide (3,3 ' -dimethyl-5,5 ' -diphenylmethanimide), M-phenylene bismaleimide (m-phenylene bismaleimide), 4-methyl-1,3-phenylene bismaleimide (4-methyl-1,3-phenylene bismaleimide), 1,6-bismaleimide- (2,2,4-trimethyl) hexane (1,6-bismaleimide- (2,2,4-trimethyl) hexane), N-2, 3-dimethylphenylmaleimide (N-2, 3-xylmaleimide), N-2, 6-dimethylphenylmaleimide (N-2, 6-xylmaleimide), N-phenylmaleimide (N-phenylmaleimide), vinylbenzylmaleimide (vinyl benzylimide, VBM), linked maleimide containing a biphenyl structure, a maleimide containing a long structure, a maleimide resin containing a diene structure, a prepolymer of a diene propyl compound and a maleimide resin, and a maleimide resin, A prepolymer of a diamine and a maleimide resin, a prepolymer of a polyfunctional amine and a maleimide resin, a prepolymer of an acidic phenol compound and a maleimide resin, or a combination thereof. Modifications of these ingredients are also included when read.

For example, the maleimide resin may be, for example, but not limited to, maleimide resins produced by Daiwakasei Industry under the trade names BMI-1000, BMI-1000H, BMI-1100, BMI-1100H, BMI-2000, BMI-2300, BMI-3000H, BMI-4000, BMI-5000, BMI-5100, BMI-TMH, BMI-7000 and BMI-7000H, or maleimide resins produced by K.I chemical company under the trade names BMI-70, BMI-80 and the like, maleimide resins produced by Nippon chemical company under the trade names MIR-3000 or MIR-5000 and the like.

For example, maleimide resins containing aliphatic long chain structures, such as, but not limited to, maleimide resins produced by designer molecular companies under the trade names BMI-689, BMI-1400, BMI-1500, BMI-1700, BMI-2500, BMI-3000, BMI-5000, and BMI-6000.

Examples of commercially available maleimide resins containing aliphatic long chain structures are as follows, for example:

BMI-3000, BMI-5000, BMI-6000: (formula 6)

If not specifically indicated, the maleimide resin is contained in an amount of 20 to 40 parts by weight, compared to 40 to 115 parts by weight of the unsaturated carbon-carbon double bond-containing resin, and is not limited thereto. Such as, but not limited to, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, or 40 parts by weight. For another example, the resin containing unsaturated carbon-carbon double bonds includes 100 parts by weight of a vinyl-containing polyphenylene ether resin, 15 parts by weight of a vinyl-containing polyolefin, and 20 parts by weight of a maleimide resin. For another example, the resin containing unsaturated carbon-carbon double bonds includes 40 parts by weight of vinyl-containing polyolefin and 30 parts by weight of maleimide resin, and is not limited thereto.

For example, in one embodiment, the amount of triallyl isocyanurate used is not particularly limited. For example, in one embodiment, the triallyl isocyanurate may be used in an amount of, for example, 20 parts by weight to 35 parts by weight, compared to 40 parts by weight to 115 parts by weight of the unsaturated carbon-carbon double bond-containing resin, and not limited thereto. For another example, the resin containing unsaturated carbon-carbon double bonds includes 100 parts by weight of a vinyl-containing polyphenylene ether resin, 15 parts by weight of a vinyl-containing polyolefin, and 20 parts by weight of triallyl isocyanurate. For another example, the unsaturated carbon-carbon double bond-containing resin includes 40 parts by weight of vinyl-containing polyolefin and 30 parts by weight of triallyl isocyanurate, and the invention is not limited thereto.

If not specifically indicated, the hardening accelerator used in the present invention may be any one or more of hardening initiators suitable for prepreg, laminate or printed circuit board fabrication, which may be a peroxide, azo initiator, carbon initiator or a combination thereof. Peroxides include, but are not limited to: dibenzoyl peroxide (BPO), dicumyl peroxide, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, 2, 5-dimethyl-2, 5-di (t-butylperoxy) -3-hexyne (25B), di-t-butyl peroxide, di (t-butylperoxyisopropyl) benzene, di (t-butylperoxy) phthalate, di (t-butylperoxy) isophthalate, t-butyl peroxybenzoate, 2-bis (t-butylperoxy) butane, 2-bis (t-butylperoxy) octane, 2, 5-dimethyl-2, 5-di (benzoylperoxy) hexane, lauroyl peroxide, t-hexyl peroxypivalate, dibutylperoxyisopropylbenzene, and bis (4-t-butylcyclohexyl) peroxydicarbonate, or a combination thereof. The amount of the curing initiator may be adjusted as necessary. For example, the amount of the curing initiator is not particularly limited, and may be, for example, 0.1 to 0.5 parts by weight, such as 0.1, 0.2, 0.3, 0.45, 0.5 parts by weight, compared to 40 to 115 parts by weight of the unsaturated carbon-carbon double bond-containing resin in the resin composition of the present invention.

The inhibitor used in the present invention may be any one or more of those suitable for prepreg, laminate or printed wiring board production, unless otherwise specified. The inhibitor includes various molecular type polymerization inhibitors, stable free radical type polymerization inhibitors or combinations thereof known in the art. For example, molecular polymerization inhibitors include, but are not limited to, phenolic compounds, quinone compounds, aromatic amine compounds, aromatic nitro compounds, sulfur-containing compounds, variable valence metal chlorides, or combinations thereof. More specifically, molecular type polymerization inhibitors include, but are not limited to, phenol, hydroquinone, 4-t-butylcatechol, benzoquinone, chloranil, l, 4-naphthoquinone, trimethylquinone, aniline, nitrobenzene, Na₂S、FeCl₃、CuCl₂Or a combination thereof. For example, stable free radical type polymerization inhibitors include, but are not limited to, 1-diphenyl-2-trinitrophenylhydrazine (DPPH), triphenylmethyl, 2,6, 6-tetramethylpiperidine-1-oxide, derivatives of 2,2,6, 6-tetramethylpiperidine-1-oxide, or derivatives thereofAnd (4) combining. For example, the amount of the inhibitor is not particularly limited, and may be, for example, 0.1 to 0.5 parts by weight, such as 0.1, 0.2, 0.3, 0.45, 0.5 parts by weight, compared to 40 to 115 parts by weight of the resin containing unsaturated carbon-carbon double bonds in the resin composition of the present invention.

If not otherwise specified, the flame retardant suitable for use in the present invention may be any one or more flame retardants suitable for use in prepreg, laminate or printed circuit board manufacture, such as, but not limited to, phosphorus-containing flame retardants, preferably including: ammonium polyphosphate (ammonium polyphosphate), hydroquinone-bis- (diphenylphosphate) (hydroquino bis- (diphenylphosphate)), bisphenol-A bis- (diphenylphosphate) (biphenol A bis- (diphenylphosphate)), tris (2-carboxyethyl) phosphine (tri (2-carboxyethyl) phosphine, TCEP), tris (chloroisopropyl) phosphate, trimethyl phosphate (TMP), dimethyl methylphosphonate (dimethylmethyl phosphonate, DMMP), resorcinol bis- (dimethylphenyl phosphate) (resorcinol bis (dihydroxyphenyl phosphate), RDXP (commercially available products such as PX-200, PX-201, PX-202), phosphazene compounds (phosphazene, commercially available products such as SPB-100, SPH-100, SPV-100, melamine polyphosphate (polyphosphate), 9-10-phosphophenanthrene phosphate (DOP-10) and derivatives thereof such as phosphophenanthrene-10-O-10-dihydrogenphosphate (DOP-10-O) and derivatives thereof Products) or resins, diphenylphosphine oxide (DPPO) and its derivatives (e.g., bis-DPPO compounds) or resins, melamine cyanurate (melamine cyanurate), tris-hydroxyisocyanurate (tri-hydroxyisocyanurate), aluminum phosphinates (e.g., products such as OP-930, OP-935, etc.), or combinations thereof. The amount of the above flame retardant is not particularly limited, unless otherwise specified.

For example, the flame retardant may be DPPO compound (e.g., double DPPO compound), DOPO compound (e.g., double DOPO compound), DOPO resin (e.g., DOPO-HQ, DOPO-NQ, DOPO-PN, DOPO-BPN), DOPO-bonded epoxy resin, etc., wherein the DOPO-PN is DOPO phenol novolac resin, and the DOPO-BPN may be DOPO-BPAN (DOPO-bisphenol A novolac), DOPO-BPFN (DOPO-bisphenol F novolac), or DOPO-BPSN (DOPO-bisphenol S novolac), etc., bisphenol-based novolac resin. The amount of the above flame retardant is not particularly limited, unless otherwise specified.

For example, in one embodiment, the amount of the flame retardant may be, for example, 45 parts by weight to 70 parts by weight, compared to 40 parts by weight to 115 parts by weight of the resin containing unsaturated carbon-carbon double bonds, and is not limited thereto.

In addition to the foregoing ingredients, for example, in one embodiment, the resin composition of the present invention may optionally further comprise a polysiloxane, such as, but not limited to, those commercially available from shin corporation under the trade names X-22-161A, X-22-161B, X-22-163A, X-22-163B, X-22-164, and the like. For example, in one embodiment, the amount of the aforementioned polysiloxane is not particularly limited. For example, in one embodiment, the polysiloxane can be used in an amount of, for example, 5 parts by weight to 30 parts by weight, such as 5 parts by weight to 15 parts by weight, compared to 40 parts by weight to 115 parts by weight of the unsaturated carbon-carbon double bond-containing resin, and is not limited thereto.

In addition to the foregoing ingredients, for example, in one embodiment, the resin composition of the present invention may optionally further comprise the following compounds or mixtures: divinylbenzene, bis (vinylbenzyl) ether, bis (vinylphenyl) ethane, bis (vinylphenyl) dimethylene benzene, bis (vinylphenyl) dimethylene ether, bis (vinylphenyl) diethylene benzene, divinylnaphthalene, divinylbiphenyl, self-polymers of divinylbenzene, copolymers of divinylbenzene with other vinyl-containing compounds, styrene, polystyrene, triallyl cyanurate, 1,2, 4-trivinylcyclohexane, multifunctional acrylates, dicyclopentadiene, norbornene, acenaphthylene, or combinations thereof. For example, in one embodiment, the respective amounts of the above compounds or mixtures may be, for example, 1 to 50 parts by weight, preferably 5 to 40 parts by weight, compared to 40 to 115 parts by weight of the unsaturated carbon-carbon double bond-containing resin, and not limited thereto.

In addition to the foregoing ingredients, for example, in one embodiment, the resin composition of the present invention may further include an inorganic filler other than the spherical silica, a hardening accelerator, a solvent, a flame retardant, a silane coupling agent, a coloring agent, a toughening agent, a core shell rubber, or a combination thereof, as desired.

For example, in one embodiment, the inorganic filler other than spherical silica can be any one or more of inorganic fillers other than spherical silica suitable for prepreg, laminate or printed circuit board fabrication, and specific examples include but are not limited to: non-spherical silica (i.e., conventional irregular type, irregular type not spherical), alumina, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, aluminum silicon carbide, titanium dioxide, barium titanate, lead titanate, strontium titanate, calcium titanate, magnesium titanate, barium zirconate, lead zirconate, magnesium zirconate, lead zirconate titanate, zinc molybdate, calcium molybdate, magnesium molybdate, ammonium molybdate, zinc molybdate-modified talc, zinc oxide, zirconium oxide, mica, boehmite (AlOOH), calcined talc, silicon nitride, or calcined kaolin. In addition, the inorganic filler may be in the form of spheres, fibers, plates, granules, flakes or whiskers, in addition to the non-spherical silica. The inorganic filler other than the spherical silica may be optionally pretreated with a silane coupling agent.

If not specifically indicated, the amount of the inorganic filler other than the spherical silica used in the resin composition of the present invention is not particularly limited, and may be, for example, 5 parts by weight to 100 parts by weight, compared to 40 parts by weight to 115 parts by weight of the unsaturated carbon-carbon double bond-containing resin. Preferably, it is 10 to 80 parts by weight.

The main functions of the solvent are to dissolve the components in the resin composition, change the solid content of the resin composition and adjust the viscosity of the resin composition. For example, the solvent may include, but is not limited to, methanol, ethanol, ethylene glycol monomethyl ether, acetone, methyl ethyl ketone (also known as methyl ethyl ketone), methyl isobutyl ketone, cyclohexanone, toluene, xylene, methoxyethyl acetate, ethoxyethyl acetate, propoxyethyl acetate, ethyl acetate, propylene glycol methyl ether, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone, or a mixture thereof. The amount of the solvent is not particularly limited, and the amount of the solvent to be added may be adjusted depending on the viscosity required for the resin composition.

For example, in one embodiment, the respective amounts of the silane coupling agent, the colorant, the toughening agent, or the core shell rubber in the resin composition disclosed herein may be 0.01 to 100 parts by weight, such as but not limited to 0.01 to 3 parts by weight, 30 to 80 parts by weight, or 50 to 100 parts by weight.

Unless otherwise specified, the silane coupling agent suitable for use in the present invention may include silane compounds (silanes, such as, but not limited to, siloxane compounds (siloxane)), which may be further classified into amino silane compounds (amino silanes), epoxy silane compounds (epoxy silanes), vinyl silane compounds, ester silane compounds, hydroxyl silane compounds, isocyanate silane compounds, methacryloxy silane compounds, and acryloxy silane compounds, depending on the kind of the functional group. The amount of the silane coupling agent is not particularly limited, and the amount of the silane coupling agent added may be adjusted depending on the dispersibility of the inorganic filler in the resin composition.

Dyes suitable for use in the present invention may include, but are not limited to, dyes (dye) or pigments (pigment), unless otherwise specified.

The main function of the toughening agent is to improve the toughness of the resin composition. If not otherwise specified, suitable toughening agents for use in the present invention may include, but are not limited to, rubbers such as carboxyl-terminated butadiene nitrile rubber (CTBN).

Core shell rubbers suitable for use in the present invention may include various core shell rubbers that are commercially available, unless otherwise specified.

The resin composition of the embodiments of the present invention can be manufactured into various products by various processing methods, including but not limited to prepregs, laminates, or printed circuit boards.

For example, the resin composition of the present invention can be prepared into a prepreg.

For example, in one embodiment, the prepreg of the present invention has a reinforcing material and a layer disposed on the reinforcing material, wherein the layer is formed by heating the resin composition to a semi-cured state (B-stage) at a high temperature. The baking temperature for producing the prepreg is, for example, 130 ℃ to 180 ℃. The reinforcing material is quartz non-woven fabric. In a preferred embodiment, the reinforcing material may also optionally be pretreated with a silane coupling agent. The insulating layer is formed after the prepreg is subsequently heated and cured (C-stage).

For example, in one embodiment, the resin composition may be uniformly mixed to form a glue solution (varnish), the glue solution is placed in an impregnation tank, the quartz nonwoven fabric is immersed in the impregnation tank, the resin composition is attached to the quartz nonwoven fabric, and the resin composition is heated and baked at a suitable temperature to be converted into a semi-cured state, so as to obtain a prepreg.

For example, the resin composition of the present invention can be formed into a laminate.

For example, in one embodiment, the laminate of the present invention comprises at least two metal foils and at least one insulating layer disposed between the two metal foils, and the insulating layer can be formed by pressing and curing the resin composition at high temperature and high pressure (C-stage), wherein the curing temperature is, for example, between 190 ℃ and 235 ℃, preferably between 200 ℃ and 230 ℃, the curing time is 60 to 240 minutes, preferably between 90 and 180 minutes, and the curing pressure is 350 to 800psi, preferably between 400 and 650 psi. The insulating layer can be obtained by curing the prepreg. The metal foil may be made of copper, aluminum, nickel, platinum, silver, gold, or an alloy thereof, such as copper foil. In a preferred embodiment, the laminate is a copper foil substrate (also called copper clad laminate).

For example, in one embodiment, the laminate of the present invention may be formed by laminating the following layers in sequence, and then pressing and curing the laminated layers at high temperature and high pressure. The stack comprises: (A) one copper foil, at least one prepreg and one copper foil; (B) a copper foil, a prepreg, a quartz nonwoven fabric, a prepreg, and a copper foil; (C) a copper foil, a resin film, the quartz nonwoven fabric, a resin film, and a copper foil; or (D) one copper-clad resin film, one quartz nonwoven fabric, and one copper-clad resin film.

For example, in one embodiment, the resin film is formed by baking and heating the resin composition to a semi-cured state. For example, the resin composition may be selectively coated on a liquid crystal resin film, a polyethylene terephthalate film (PET film), or a polyimide film (polyimide film), and then heated and baked at a suitable heating temperature to a semi-cured state to form a resin film. For example, the resin composition of each embodiment of the present invention may be coated on a copper foil to uniformly adhere the resin composition, and then baked at an appropriate temperature to a semi-cured state to obtain a copper clad resin film.

For example, in one embodiment, the laminate may be further processed to form a printed circuit board, and the printed circuit board may be manufactured by any conventional method.

One way of fabricating the printed circuit board of the present invention may be to use a double-sided copper foil substrate (e.g., product EM-891, available from optoelectronics materials inc.) having a thickness of 28 mils (mil) and having a 0.5 ounce (ounce) hvlp (super low profile) copper foil, and to drill holes and then electroplate the holes to form electrical continuity between the upper and lower copper foils. And etching the upper layer copper foil and the bottom layer copper foil to form an inner layer circuit. And then performing brown coarsening treatment on the inner layer circuit, so that a concave-convex structure is formed on the surface to increase the roughness. And then, stacking a copper foil, at least one prepreg, the inner layer circuit, at least one prepreg and a copper foil in sequence, and heating the copper foil, the prepreg and the copper foil for 60 to 240 minutes at the temperature of between 190 and 235 ℃ by using a vacuum laminating device to cure the insulating layer material of the semi-cured sheet. 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.

In one embodiment, the prepreg provided by the invention can improve at least one of the characteristics of an interlayer peeling strength of a copper-containing substrate of an article, no stripe at the edge of the copper-containing substrate, no void on the surface of the copper-containing substrate, low dielectric constant, low dielectric loss and the like.

In one embodiment, the prepreg provided by the invention has no node of the traditional woven fabric because the quartz non-woven fabric has no node, so that the prepreg has no problem of directionality of signal transmission derived from the traditional node, and a circuit substrate made of the prepreg is not easy to generate signal delay.

For example, articles made from the resin compositions provided herein may satisfy one, more, or all of the following characteristics:

the copper-containing substrate has an interlayer peel strength greater than 6 lb/in, for example between 6 lb/in and 7 lb/in, as measured by the method described in IPC-TM-6502.4.8;

the edge of the plate without the copper substrate has no stripes;

the surface does not contain a copper substrate and has no vacuole;

a dielectric constant of 3.2 or less, for example, a dielectric constant of 2.7 to 3.2, measured at a frequency of 10GHz according to the method described in JIS C2565; and

the dielectric loss measured at a frequency of 10GHz according to JIS C2565 is less than or equal to 0.0017, for example, the dielectric loss is between 0.0013 and 0.0017.

Resin compositions of examples of the present invention and comparative examples of the present invention were prepared from the following raw materials in the amounts shown in tables 1 and 4, respectively, and further prepared into various test samples.

The chemical raw materials used in the examples of the present invention and the comparative examples are as follows:

SA 9000: methacrylate-containing polyphenylene ether resins, available from Sabic.

Ricon 100: styrene-butadiene copolymer available from Cray Valley.

H1052: hydrogenated styrene-butadiene-styrene triblock copolymer, available from Asahi KASEI.

HLBH-P2000: hydroxyl-terminated hydrogenated polybutadiene, available from Cray Valley.

BMI-5100: bis (3-ethyl-5-methyl-4-maleimidobenzene) methane, purchased from Dazawa.

BMI-3000: the maleimide resin of formula 6, was purchased from designer molecules.

TAIC: triallyl isocyanurate, commercially available.

X-22-164: both terminal methacrylate-based polysiloxanes are available from Beacon.

MX-136: core shell rubber, available from Kaneka.

25B: 2, 5-dimethyl-2, 5-di (t-butylperoxy) -3-hexyne, available from Nippon grease.

BB: yoshinox BB, 4,4' -butylidenebis (6-tert-butyl-3-methylphenol), commercially available.

SC2050 SVJ: spherical silica, available from Admatechs.

911C: zinc molybdate modified talc, commercially available.

iM 16K: hollow inorganic filler (borosilicate) available from 3M.

EA 2000: fluorine-containing filler, available from AGC.

KBM-573: silane coupling agents, available from Ann.

PX-202: phosphorus containing flame retardants available from Daba Chemicals.

Toluene and butanone: are commercially available.

NC-3000: biphenyl-containing epoxy resins, available from japan chemicals.

HP-7200: dicyclopentadiene-containing epoxy resins, available from DIC.

HP-9900: naphthalene containing epoxy resins, available from DIC.

LZ8290 and LZ 8280: benzoxazine resins, available from Huntsman.

C500 and C900: styrene-maleic anhydride, available from Polyscope.

HPC-8000 and HPC-8150: polyester, available from DIC.

BA-230S: cyanate ester, available from Lonza.

2E4 MI: imidazole, purchased from four nations.

525: non-spherical fused silica, available from Silicocco.

XZ 92741: phosphorus containing flame retardants available from Dow Chemical.

Q nonwoven (i.e. quartz nonwoven): about 0.004 inches thick prior to lamination, and is commercially available (e.g., from technical fiber products, inc.).

Weaving Q fiber: the woven fabric type is 2116, commercially available.

L glass fiber weaving: the woven fabric type is 2116, commercially available.

E, glass fiber weaving: the woven fabric type is 2116, commercially available.

The compositions (units are parts by weight) and the results of the property test of the resin compositions of the examples and comparative examples are shown in the following table:

TABLE 1 compositions (unit: parts by weight) of resin compositions of examples and comparative examples

TABLE 2 reinforcing materials and characteristic test results of the resin compositions of examples

TABLE 3 Reinforcement and characteristic test results for comparative resin compositions

TABLE 4 composition of resin compositions of comparative examples (unit: parts by weight)

TABLE 5 reinforcing materials and characteristic test results of the resin compositions of comparative examples

Reinforcement material	Weaving pattern	C5	C6	C7
					Quartz non-woven fabric	Non-woven fabric	Use of
Q fiber woven cloth	2116
					L-shaped glass fiber woven cloth	2116		Use of
E glass fiber woven cloth	2116			Use of
					Characteristics of	Unit	C5	C6	C7
Dielectric constant	Without unit	3.4～3.6	3.4～3.6	>3.7
					Dielectric loss	Without unit	>0.005	>0.005	>0.005

The aforementioned characteristics are obtained by preparing a sample to be tested in the following manner and then performing characteristic analysis according to specific conditions.

1. Prepreg preparation: the resin compositions of the examples and comparative examples (listed in tables 1 and 4) and the corresponding reinforcing materials (listed in tables 2,3 and 5) were selected, and the respective chemicals in the resin compositions were uniformly mixed to form a varnish (varnish) in which all the soluble solid chemicals were dissolved. And (3) putting the glue solution into an impregnation tank, then immersing the Q non-woven fabric, the Q fiber woven fabric, the L glass fiber woven fabric or the E glass fiber woven fabric which are correspondingly used into the impregnation tank, so that the resin composition is attached to the reinforcing material, and heating the reinforcing material to be in a semi-solidified state (B-Stage) at 130-180 ℃ to respectively obtain the prepregs of each group of examples or comparative examples.

2. Copper-containing substrate 1 (or called copper foil substrate 1, formed by laminating two prepregs): two pieces of ultra low surface roughness (HVLP) copper foil having a thickness of 18 μm and two pieces of the aforementioned prepreg (each set of examples or each set of comparative examples) were prepared, laminated in this order, and laminated under vacuum at a lamination pressure of 450psi and 225 ℃ for 120 minutes to form the copper-containing substrate 1.

3. A copper-containing substrate 2 (or called copper foil substrate 2, formed by pressing eight prepregs): two pieces of ultra low surface roughness (HVLP) copper foil having a thickness of 18 μm and eight pieces of the aforementioned prepreg (each set of examples or each set of comparative examples) were prepared, and the copper foil, eight pieces of the prepreg, and the copper foil were laminated in this order, and were pressed under vacuum conditions at a pressing pressure of 450psi and at 225 ℃ for 120 minutes to form the copper-containing substrate 2.

4. No copper substrate 1 (formed by laminating two prepregs): and etching the copper-containing substrate 1 to remove the copper foils on the two sides to obtain the copper-free substrate 1 which is formed by laminating two prepregs.

5. Copper-free substrate 2 (formed by pressing eight prepregs): and etching the copper-containing substrate 2 to remove the copper foils on the two sides to obtain the copper-free substrate 2 which is formed by pressing eight prepregs.

For the sample to be tested, the test methods and the analysis items of the characteristics are as follows:

interlayer peel strength of substrate

A copper-containing substrate 2 (formed by pressing eight prepregs) was cut into a rectangle having a width of 12.7 mm and a length of more than 60 mm, and measured using a universal tensile strength tester by referring to the method described in IPC-TM-6502.4.8, except that no surface copper foil was etched, and the test position was the bonding surface between the 2 nd layer prepreg and the 3 rd layer prepreg, and the force (in pounds per inch) required to separate the two layers of the cured insulating substrate was measured at room temperature (about 25 ℃) to obtain the interlayer peel strength of the substrate. Generally, there is a significant difference in the peel strength between the layers of the substrate of greater than 0.10 lb/in. If the substrate interlaminar peel strength is greater than 6.00 pounds per inch, a score of >6.00 pounds per inch indicates that the substrates are difficult to delaminate.

After lamination, the appearance of the base plate has plate edge stripes (the stripe is called as plate edge stripe for short)

The surface condition of the insulating layer without the copper substrate 2 (formed by laminating eight prepregs) is determined by visual observation of personnel, and if the dendritic distribution appears on the edge of the board, the compatibility in the resin composition is not good or the phenomenon of non-uniformity is caused by large fluidity difference. The schematic diagram of the dendritic striations is shown in fig. 1, the more the number of the dendritic phenomena is calculated, the more the number of the dendritic phenomena is, the more the dendritic phenomena are, and the schematic diagram of the normal copper-free substrate without dendritic distribution is shown in fig. 2. The test results set forth the number of dendritic stripes and the length of a single stripe, the length of the stripe representing the perpendicular maximum distance (in mm) of the end of the stripe compared to the board edge, and the presence of a board edge stripe is recorded by a human eye of a stripe greater than or equal to 1 mm. The dendritic distribution of the substrate may cause non-uniform characteristics (poor reliability) and greatly reduced yield of the circuit board to be manufactured, such as poor dielectric properties, low heat resistance, non-uniform thermal expansion, or poor interlayer adhesion, and the substrate with dendritic distribution is directly scrapped.

Inner glue flow of substrate plate

First, an EM-827 copper-containing substrate having a thickness of 28 mils (mil) was prepared as a copper-containing core substrate (available from Taiwan optoelectronic materials Co., Ltd., 7628E-glass fiber cloth and 1 oz HTE copper foil). The surface copper foil of the copper-containing core plate is processed by the conventional browning treatment process to obtain a browned core plate.

A prepreg prepared in the above examples (E1 to E3) and comparative examples (C1 to C4) and a browned core board having a thickness of 28 mils and a length and width of 18 inches and 16 inches, respectively, were prepared in batches, wherein the prepreg had a diamond-shaped opening in the center thereof, the diamond-shaped opening having a length and width of 4 inches (a 4-inch diamond-shaped space was punched out in the center of the prepreg using a conventional punching machine).

And laminating a 0.5 ounce HTE copper foil (back pressure, namely that the bright side of the copper foil contacts the prepreg), the prepreg and the brown core plate in sequence, and then pressing and curing for 2 hours under the conditions of vacuum, high temperature (200 ℃) and high pressure (360psi) to obtain the copper-containing multilayer plate. And removing the surface back pressure copper foil of the copper-containing multilayer board to obtain an in-board flow template. Taking the in-plate flow sample plate, taking each side of a 4 inch by 4 inch diamond as a base line, dividing each side into 4 equal parts (as shown in fig. 3), measuring the flow of glue at 12 points (i.e. the respective vertical direction flow distance at 12 points) from a to l in fig. 3, and calculating the average value of the flow of glue at 12 points to obtain the in-plate flow (average value) with unit being millimeter (mm). Generally speaking, the in-board flow is preferably between 5 and 10 mm, a flow amount is insufficient when the in-board flow is less than 5 mm, and a hole cannot be filled effectively when a subsequent prepreg is used for layer increasing, which is likely to cause board explosion of a circuit board.

Cavitation (inner layer circuit substrate without copper surface test whether cavitation exists)

A copper-containing substrate with a thickness of 2.5 mils is processed into a brown oxidation circuit board as an inner layer by a conventional brown oxidation process, and the ability of the resin flowing and filling the empty region between the circuits during the lamination of the prepreg is evaluated. Prepregs were prepared with each set of examples or comparative examples, respectively. And (3) respectively laminating one prepreg on each of two sides of the brown oxidation circuit board with the thickness of 2.5 mils, and respectively laminating one ultra-low surface roughness copper foil (with the thickness of 18 microns) on the outer layer. Pressing in a vacuum press for 2 hours at the pressure of 450psi and the temperature of 200 ℃ to form the inner layer circuit substrate with copper on the surface, and removing the outer copper foil by etching to obtain the inner layer circuit substrate without copper on the surface. Whether bubbles exist in the board (which is semitransparent) of the insulating layer without the copper surface of the inner layer circuit substrate without copper on the surface is observed in a visual mode by personnel, one bubble with the diameter larger than or equal to 1 millimeter is marked as one bubble by the visual observation of personnel, and the total number of the bubbles is counted. If the substrate is laminated, the subsequent circuit board is scrapped due to the existence of the vacuole inside the substrate.

Dielectric constant (Dk)

In the measurement of the dielectric constant, the copper-free substrate 1 (formed by laminating two prepregs) is selected as a sample to be measured. Each sample to be measured was measured at room temperature (about 25 ℃ C.) and at a frequency of 10GHz with a microwave dielectric analyzer (microwave dielectrometer, available from AET of Japan) in accordance with the method described in JIS C2565, to obtain a dielectric constant Dk. Lower dielectric constant indicates better dielectric properties of the sample to be tested. A Dk value less than 0.1 indicates no significant difference in dielectric loss for the substrates (no significant difference indicates no significant technical difficulty), and a Df value greater than or equal to 0.1 indicates a significant difference in dielectric loss between different substrates (indicating significant technical difficulty).

Dielectric loss (Df)

In the measurement of dielectric loss, the copper-free substrate 1 (formed by laminating two prepregs) is selected as a sample to be measured. Each sample to be measured was measured at room temperature (about 25 ℃ C.) and at a frequency of 10GHz using a microwave dielectric analyzer (available from AET, Japan) in accordance with the method described in JIS C2565, and the dielectric loss Df was obtained, the lower the dielectric loss, the better the dielectric characteristics of the sample to be measured. In the range of 10GHz measurement frequency and Df less than 0.0040, a difference in Df less than 0.0001 indicates no significant difference in dielectric loss of the substrates (no significant difference indicates no significant technical difficulty), and a difference in Df greater than or equal to 0.0001 indicates a significant difference between dielectric losses of different substrates (indicates significant technical difficulty). In the range of 10GHz measurement frequency and Df value greater than 0.0040 or more, a difference of Df less than 0.0005 represents no significant difference in dielectric loss of the substrates, and a difference of Df greater than or equal to 0.0005 represents significant difference in dielectric loss of different substrates.

From the above test results, the following phenomenon can be observed.

Examples E1 to E3 of the prepreg of the present invention using the resin composition all achieved peel strength between substrate layers of greater than 6 lb/in, no dendrite streaks on the substrate edges, no voids in the substrate, a dielectric constant of less than or equal to 3.2 measured at 10GHz, and a dielectric loss of less than or equal to 0.0017 measured at 10 GHz.

Compared with the embodiment E1, the resin compositions of the comparative examples C1 to C3 are completely the same as the resin composition of the embodiment E1, but the quartz non-woven fabric is used in the embodiment E1, the quartz non-woven fabric is not used in the comparative examples C1 to C3, and the characteristics of the comparative examples C1 to C3, such as the peeling strength between the substrate layers, no dendritic streaks on the substrate edges, no bubbles on the substrate, and the like, can not achieve the effects of the previous embodiments.

The resin composition of comparative example C4 was identical to the resin composition of example E3 in comparison with example E3, but the resin composition of example E1 used a quartz nonwoven fabric, the resin composition of comparative example C4 used no quartz nonwoven fabric, and the resin composition of comparative example C4 could not achieve the effects of the foregoing examples in terms of the properties such as the peel strength between the substrate layers, the absence of dendritic streaks on the substrate edges, and the absence of voids in the substrate.

In comparison with examples E1 to E3, comparative examples C5 to C7 do not use the resin composition used in the present invention, comparative examples C5 to C7 use the resin composition containing an epoxy resin, comparative examples C5 to C7 have a dielectric constant of 3.4 or more measured at 10GHz and a dielectric loss of 0.0050 or more measured at 10GHz, and prepregs of comparative examples C5 to C7 do not meet the requirements of low dielectric constant and low dielectric loss required for the low dielectric substrate material.

In addition, the 16-layer circuit substrates (16-layer PCBs) manufactured in the embodiments E1 to E3 and the 16-layer circuit substrates manufactured in the comparative examples C1 to C4 respectively, and the network analyzer (including TDR time domain module) is used to measure the circuit substrates of the respective sets of embodiments and comparative examples, so that the circuit substrates of the embodiments E1 to E3 have almost no signal delay, the circuit substrates of the comparative examples C1 and C4 have relatively small signal delay, and the circuit substrates of the comparative examples C2 and C3 have relatively large signal delay. The 16-layer circuit board can be manufactured by using a conventional 16-layer circuit board manufacturing method, but each set of examples and comparative examples are manufactured by using the same manufacturing method to obtain a 16-layer circuit board (the differences are only the variables in each set of examples and comparative examples, and the other manufacturing methods are the same). The measurement of the signal delay using the network analyzer (including the TDR time domain module) can be obtained by using the conventional measurement method.

The above embodiments are merely exemplary in nature and are not intended to limit the claimed embodiments or the application or uses of such embodiments. In this document, the term "exemplary" represents "as an example, instance, or illustration. Any exemplary embodiment herein is not necessarily to be construed as preferred or advantageous over other embodiments.

In addition, while at least one exemplary embodiment or comparative example has been presented in the foregoing detailed description, it should be appreciated that a vast number of variations are possible. It should also be appreciated that the embodiments described herein are not intended to limit the scope, applicability, or configuration of the claimed subject matter in any way. Rather, the foregoing implementations will provide those skilled in the art with a convenient road map for implementing the described embodiment or embodiments. Rather, various changes may be made in the function and arrangement of elements without departing from the scope defined in the claims, which includes known equivalents and all foreseeable equivalents at the time of filing this patent application.

Claims

1. A prepreg comprising a quartz nonwoven fabric and a resin composition, the resin composition comprising:

(A)40 to 115 parts by weight of an unsaturated carbon-carbon double bond-containing resin; and

(B)30 to 120 parts by weight of a spherical silica,

2. The prepreg according to claim 1, wherein the vinyl-containing polyphenylene ether resin comprises an ethylene benzyl biphenyl-containing polyphenylene ether resin, a methacrylate-containing polyphenylene ether resin, an ethylene benzyl bisphenol a-containing polyphenylene ether resin, a vinyl chain-extended polyphenylene ether resin, or a combination thereof.

3. The prepreg of claim 1, wherein the vinyl-containing polyolefin comprises polybutadiene, polyisoprene, styrene-butadiene copolymers, styrene-isoprene copolymers, styrene-butadiene-divinylbenzene terpolymers, styrene-butadiene-maleic anhydride terpolymers, vinyl-polybutadiene-urethane oligomers, maleic anhydride-butadiene copolymers, or combinations thereof.

4. The prepreg of claim 1, wherein the resin composition further comprises 5 to 25 parts by weight of a hydrogenated polyolefin, 20 to 40 parts by weight of a maleimide resin, 20 to 35 parts by weight of triallyl isocyanurate, 0.1 to 0.5 parts by weight of a hardening initiator, 0.1 to 0.5 parts by weight of an inhibitor, 45 to 70 parts by weight of a flame retardant, or a combination thereof.

5. The prepreg according to claim 4, wherein the resin composition comprises 5 to 25 parts by weight of a hydrogenated polyolefin, wherein the hydrogenated polyolefin comprises an unsubstituted hydrogenated styrene-butadiene-styrene triblock copolymer, a maleic anhydride substituted hydrogenated styrene-butadiene-styrene triblock copolymer, or a combination thereof.

6. The prepreg according to claim 4, wherein the resin composition comprises 20 to 40 parts by weight of a maleimide resin, wherein the maleimide resin comprises 4,4' -diphenylmethane bismaleimide, phenylmethane maleimide oligomer, bisphenol A diphenylether bismaleimide, 3 ' -dimethyl-5,5 ' -diethyl-4, 4' -diphenylmethane bismaleimide, 3 ' -dimethyl-5,5 ' -dipropyl-4, 4' -diphenylmethane bismaleimide, m-phenylene bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6-bismaleimide- (2,2,4-trimethyl) hexane, a, 2, 3-dimethylbenzylmaleimide, 2, 6-dimethylbenzylmaleimide, N-phenylmaleimide, vinylbenzylmaleimide, a maleimide resin containing an aliphatic long chain structure, a prepolymer of a diallyl compound and a maleimide resin, a prepolymer of a diamine and a maleimide resin, a prepolymer of a polyfunctional amine and a maleimide resin, a prepolymer of an acidic phenol compound and a maleimide resin, or a combination thereof.

7. Prepreg according to claim 1, characterized in that the resin composition does not comprise an epoxy resin.

8. The prepreg according to claim 1, wherein the resin composition further comprises an inorganic filler other than the spherical silica, a solvent, a silane coupling agent, a coloring agent, a toughening agent, a core shell rubber, or a combination thereof.

9. An article made from the prepreg of claim 1, wherein the article comprises a laminate or a printed circuit board.

10. The article of claim 9 wherein the copper-containing substrate has an interlayer peel strength of greater than 6 lb/in as measured by the method of IPC-TM-6502.4.8.

11. The article of claim 9, wherein the article is free of striations at plate edges of the copper substrate.

12. The article of claim 9, wherein the surface of the article is void-free of copper-free inner layer circuit substrate surfaces.

13. The article according to claim 9, wherein the article has a dielectric constant of 3.2 or less as measured at a frequency of 10GHz according to the method of JIS C2565.

14. The article according to claim 9, wherein the article has a dielectric loss of 0.0017 or less as measured at a frequency of 10GHz according to the method of JIS C2565.