TWI857885B - Resin compositions and articles made therefrom - Google Patents

Abstract

The present invention provides a resin composition, which includes: 100 parts by weight of a thermosetting resin, which includes a vinyl polyphenylene ether resin, a maleimide resin or a combination thereof; 10 to 20 parts by weight of a phosphine oxide having a structure shown in formula (1); and 10 to 20 parts by weight of an isocyanurate having a structure shown in formula (2), wherein m is an integer from 2 to 18. In addition, the present invention also provides an article made of the above resin composition, which includes a backing copper foil, a laminate or a printed circuit board, and which has improved properties in one or more aspects.

Description

Resin compositions and articles made therefrom

The present invention relates to a resin composition, in particular to a resin composition that can be used for backing copper foil, laminated boards or printed circuit boards.

As electronic products continue to develop towards high density and high precision, higher-level printed circuit board technologies such as high-density interconnect (HDI) have been widely used. Copper foil with adhesive backing is a way to add layers in the manufacturing process of printed circuit boards. It is to stack the resin layer of copper foil with adhesive backing on the core board and then press it to achieve the purpose of adding layers. The advantages of using copper foil with adhesive backing for adding layers include reducing the thickness of the insulation layer of the printed circuit board, and reducing the line width and line spacing of the printed circuit board lines, thereby achieving overall thinning of the printed circuit board.

However, when using adhesive copper foil for layering, it is necessary to consider the fold resistance of the adhesive copper foil and the tree-like stripes on the board edge after the circuit substrate is pressed. Therefore, how to develop an adhesive copper foil that can effectively solve the above problems is the direction of efforts in this field.

In view of the problems encountered in the prior art, especially the inability of existing materials to meet one or more of the above-mentioned technical problems, the main purpose of the present invention is to provide a resin composition that can overcome at least one of the above-mentioned technical problems, and an article made using the resin composition.

In order to achieve the above object, the present invention discloses a resin composition, which comprises: 100 parts by weight of a thermosetting resin, wherein the thermosetting resin comprises a vinyl polyphenylene ether resin, a maleimide resin or a combination thereof; 10 to 20 parts by weight of a phosphine oxide having a structure shown in formula (1); and 10 to 20 parts by weight of an isocyanurate having a structure shown in formula (2), wherein m is an integer from 2 to 18; Formula (1) Formula (2).

For example, in one embodiment, the vinyl-containing polyphenylene ether resin includes vinyl benzyl biphenyl-containing polyphenylene ether resin, methacrylate-containing polyphenylene ether resin or a combination thereof.

For example, in one embodiment, the maleimide resin includes 4,4'-diphenylmethane dimaleimide, polyphenylmethane maleimide, bisphenol A diphenyl ether dimaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane dimaleimide, 3,3'-dimethyl-5,5'-dipropyl-4,4'-diphenylmethane dimaleimide, Phenylenebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, N-2,3-dimethylphenylmaleimide, N-2,6-dimethylphenylmaleimide, N-phenylmaleimide, vinylbenzylmaleimide, maleimide containing a biphenyl structure, maleimide containing an indane structure, maleimide containing a _C10 to _C50 aliphatic long chain structure, or a combination thereof.

For example, in one embodiment, the resin composition further comprises 10 to 30 parts by weight of a polyolefin resin.

For example, in one embodiment, the polyolefin resin includes vinyl-containing polyolefin, hydrogenated polyolefin or a combination thereof.

For example, in one embodiment, the resin composition further includes an inorganic filler, a silane coupling agent, a hardening accelerator, an inhibitor, a flame retardant, a dye, a toughening agent, a solvent or a combination thereof.

In order to achieve the above object, the present invention also provides an article made of the above resin composition, which includes a backing copper foil, a laminate or a printed circuit board.

Articles made of the resin composition of the present invention, such as backing copper foil, laminate or printed circuit board, can have excellent properties in at least one of the following: adhesive filling property of circuit substrate, dendritic stripes on the board edge after circuit substrate pressing, evaluation of dendritic stripes on the board edge after circuit substrate pressing, X/Y axis thermal expansion coefficient, copper foil peeling strength, dead bending resistance and flame retardancy, and thus can become a high-performance substrate that meets comprehensive requirements.

In order to enable a person with ordinary knowledge in the field to understand the features and effects of the present invention, the following is a general explanation and definition of the terms and expressions mentioned in the specification and patent application. Unless otherwise specified, all technical and scientific terms used in the text have the usual meanings understood by a person with ordinary knowledge in the field regarding the present invention. In the event of a conflict, the definition in this specification shall prevail.

As used herein, the terms "include," "including," "have," "contain," or any similar terms are open-ended transitional phrases that are intended to cover a non-exclusive inclusion. For example, a composition or article containing multiple elements is not limited to those elements listed herein but may also include other elements not expressly listed but generally inherent to the composition or article. In addition, unless expressly stated to the contrary, the term "or" refers to an inclusive "or" and not to 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 document, the interpretation of the terms "comprising", "including", "having", and "containing" should be regarded as having specifically disclosed and covering at the same time closed conjunctions such as "consisting of", "consisting of", and "the remainder of", as well as semi-open conjunctions such as "consisting essentially of", "mainly consisting of", "mainly consisting of", "substantially containing", "consisting essentially of", "essentially consisting of", and "essentially containing".

In this document, all characteristics or conditions, such as numerical values, quantities, contents and concentrations, defined in the form of numerical ranges or percentage ranges are for simplicity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be deemed to have included and specifically disclosed all possible sub-ranges and individual numerical values (including integers and fractions) within the range, especially integer values. For example, a range description such as “1.0 to 8.0”, “1.0～8.0”, “between 1.0 and 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, etc., and cover endpoint values, especially sub-ranges defined by integer values, and should be deemed 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, etc.

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

Unless otherwise specified, in this article, polymer refers to the product formed by the polymerization reaction of monomers, including aggregates of many macromolecules, each of which is composed of many simple structural units repeatedly connected by covalent bonds. Monomers are compounds that synthesize polymers. Polymers can include homopolymers (also known as self-polymers), copolymers, prepolymers, etc., but are not limited to them. Prepolymers refer to chemicals produced by the polymerization reaction of two or more compounds with a conversion rate between 10% and 90%. Polymers also include oligomers, but are not limited to them. Oligomers, also known as low polymers, are polymers composed of 2 to 20 repeating units, usually 2 to 5 repeating units. For example, when interpreting diene polymers, they include diene homopolymers, diene copolymers, diene prepolymers, and of course diene oligomers, etc.

If not otherwise specified, in this article, copolymer refers to a product formed by polymerization of two or more different monomers, including but not limited to a random copolymer (also known as 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, styrene and butadiene. For example, a styrene-butadiene copolymer includes but is not limited to a styrene-butadiene random copolymer, a styrene-butadiene alternating copolymer, a styrene-butadiene graft copolymer or a styrene-butadiene block copolymer. A styrene-butadiene block copolymer includes, for example but not limited to, a molecular structure after polymerization of styrene-styrene-styrene-butadiene-butadiene-butadiene. A styrene-butadiene block copolymer includes, for example but not limited to, a styrene-butadiene-styrene block copolymer. Styrene-butadiene-styrene block copolymers include, for example, but not limited to, molecular structures of styrene-styrene-styrene-butadiene-butadiene-butadiene-butadiene-styrene-styrene after polymerization. Similarly, hydrogenated styrene-butadiene copolymers include hydrogenated styrene-butadiene random copolymers, hydrogenated styrene-butadiene alternating copolymers, hydrogenated styrene-butadiene graft copolymers or hydrogenated styrene-butadiene block copolymers. Hydrogenated styrene-butadiene block copolymers include, for example, but not limited to, hydrogenated styrene-butadiene-styrene block copolymers.

If not otherwise specified, "resin" is generally a customary name for a synthetic polymer, but in this article, "resin" can be interpreted to include monomers, polymers thereof, combinations of monomers, combinations of polymers thereof, or combinations of monomers and polymers thereof, and is not limited thereto. For example, in this article, "maleimide resin" can be interpreted to include maleimide monomers, maleimide polymers, combinations of maleimide monomers, combinations of maleimide polymers, or combinations of maleimide monomers and maleimide polymers.

As used herein, "containing a vinyl group" is to be interpreted as including a group containing a vinyl group, a vinylbenzyl group, a vinylene group, an allyl group or a (meth)acrylate group.

If not otherwise specified, the unsaturated bonds described in the present invention 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.

If not otherwise specified, in this article, when a specific example of a compound is written in the form of "(substituent)", it should be understood that it includes both the case where the substituent is contained and the case where the substituent is not contained. For example, cyclohexanedimethanol di(meth)acrylate should be interpreted as including cyclohexanedimethanol diacrylate and cyclohexanedimethanol dimethacrylate, and (meth)acrylate should be interpreted as including acrylate and methacrylate.

It should be understood that the features disclosed in the various embodiments herein can be arbitrarily combined to form the technical solution of this application, as long as there is no contradiction in the combination of these features.

Unless otherwise specified, in this document, parts by weight represent the number of parts by weight, which can be any weight unit, such as but not limited to kilograms, grams, pounds, etc. For example, 100 parts by weight of a thermosetting resin represents 100 kilograms of thermosetting resin or 100 pounds of thermosetting resin. If the resin solution contains a solvent and a resin, the parts by weight of the (solid or liquid) resin generally refers to the weight unit of the (solid or liquid) resin, and does not include the weight unit of the solvent in the solution, while the parts by weight of the solvent refers to the weight unit of the solvent.

The following specific embodiments are merely illustrative in nature and are not intended to limit the present invention and its uses. In addition, this article is not limited by the aforementioned prior art or invention content or any theory described in the following specific embodiments or examples. The methods, reagents and conditions used in the examples are conventional methods, reagents and conditions in the art unless otherwise specified.

In the present invention, if a specific model of a product sold by a certain manufacturer has been disclosed, it should be deemed that the present invention has also disclosed the specific chemical structure and chemical name or its IUPAC name of the product, and the catalog, sales manual and product description documents of the product including the specific model disclosed by the manufacturer are incorporated herein by reference as part of the disclosure of the present invention.

One embodiment of the present invention provides a resin composition, which includes: 100 parts by weight of a thermosetting resin, wherein the thermosetting resin includes a vinyl polyphenylene ether resin, a maleimide resin or a combination thereof; 10 to 20 parts by weight of a phosphine oxide having a structure shown in formula (1); and 10 to 20 parts by weight of an isocyanurate having a structure shown in formula (2), wherein m is an integer from 2 to 18.

The phosphine oxide having the structure shown in formula (1) has the following structural formula: Formula (1).

The isocyanurate having the structure shown in formula (2) has the following structural formula: Formula (2).

In the above formula (2), m is an integer from 2 to 18, preferably an integer from 4 to 10.

The content of the thermosetting resin in the aforementioned resin composition is 100 parts by weight, and the content of other components is the relative content relative to 100 parts by weight of the thermosetting resin. For example, if not otherwise specified, when 100 parts by weight of the thermosetting resin is 100 parts by weight of a vinyl-containing polyphenylene ether resin, the content of the phosphine oxide having a structure represented by formula (1) is 10 to 20 parts by weight relative to 100 parts by weight of the vinyl-containing polyphenylene ether resin. For example, the resin composition of an embodiment of the present invention may contain 100 kg of a vinyl-containing polyphenylene ether resin and 10 to 20 kg of a phosphine oxide having a structure represented by formula (1). For example, the resin composition of one embodiment of the present invention may contain 100 pounds of a vinyl polyphenylene ether resin and 10 to 20 pounds of a phosphine oxide having a structure represented by formula (1). Similarly, when 100 parts by weight of the thermosetting resin is 100 parts by weight of a maleimide resin, the content of the isocyanurate having a structure represented by formula (2) is 10 to 20 parts by weight relative to 100 parts by weight of the maleimide resin. For example, the resin composition of one embodiment of the present invention may contain 100 kilograms of a maleimide resin and 10 to 20 kilograms of an isocyanurate having a structure represented by formula (2). For example, the resin composition of one embodiment of the present invention may contain 100 pounds of maleimide resin and 10 to 20 pounds of isocyanurate having the structure represented by formula (2).

In one embodiment, the aforementioned 100 parts by weight of thermosetting resin may be 100 parts by weight of vinyl-containing polyphenylene ether resin, 100 parts by weight of maleimide resin, or a total of 100 parts by weight of vinyl-containing polyphenylene ether resin and maleimide resin.

In one embodiment, the vinyl-containing polyphenylene ether resin may include, but is not limited to, vinylbenzyl-containing polyphenylene ether resin or (meth)acrylate-containing polyphenylene ether resin. The aforementioned vinyl-containing polyphenylene ether resin may be polymerized via the vinyl group (i.e., carbon-carbon unsaturated bond) at the end of its structure.

In one embodiment, the vinyl-containing polyphenylene ether resin may include various types of vinyl-containing polyphenylene ether resins known in the art. The vinyl-containing polyphenylene ether resin applicable to the present invention is not particularly limited and may be any one or more commercially available products. In certain embodiments, any one or more of the following vinyl-containing polyphenylene ether resins may be used: vinyl benzyl biphenyl polyphenylene ether resins (e.g., OPE-2st 1200 or OPE-2st 2200, available from Mitsubishi Gas Chemical Co., Ltd.) or methacrylate-containing polyphenylene ether resins (e.g., SA9000, available from Sabic Corporation). However, the vinyl-containing polyphenylene ether resin of the present invention is not limited thereto.

In one embodiment, the maleimide resin may include a monomer, a polymer or a combination thereof having one or more maleimide functional groups in the molecule. Unless otherwise specified, the maleimide resin applicable to the present invention is not particularly limited. In certain embodiments, any one or more of the following maleimide resins may be used: 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, bismaleimide) (also known as bis(3-ethyl-5-methyl-4-maleimidephenyl) methane), 3,3'-dimethyl-5,5'-dipropyl-4,4'-diphenylmethane bismaleimide, m-phenylene bismaleimide, 4-methyl-1,3-phenylene bismaleimide, maleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, N-2,3-dimethylphenylmaleimide, N-2,6-dimethylphenylmaleimide, N-phenylmaleimide, vinyl benzyl maleimide, maleimide containing biphenyl structure, maleimide containing indane structure, maleimide containing aliphatic long chain structure (aliphatic long chain structure is aliphatic long chain with carbon number of 10 to 50).

For example, specific examples of maleimide resins may include, but are not limited to, maleimide resins produced by Daiwakasei Industry under the trade names of BMI-1000, BMI-1000H, BMI-1100, BMI-1100H, BMI-2000, BMI-2300, BMI-3000, BMI-3000H, BMI-4000, BMI-5000, BMI-5100, BMI-TMH, BMI-7000, and BMI-7000H; maleimide resins produced by K.I. Chemical Co., Ltd. under the trade names of BMI-70, BMI-80, etc.; or maleimide resins produced by Nippon Kayaku Co., Ltd. under the trade names of MIR-3000 or MIR-5000, etc.

For example, specific examples of maleimide containing a _C10 to _C50 aliphatic long chain structure may include, but are not limited to, maleimide resins produced by designer molecular companies under the trade names of BMI-689, BMI-1400, BMI-1500, BMI-1700, BMI-2500, BMI-3000, BMI-5000 and BMI-6000.

In one embodiment, the resin composition may further include a polyolefin resin. In one embodiment, the content of the polyolefin resin may be 10 to 30 parts by weight, such as 10, 15, 20, 25, or 30 parts by weight relative to 100 parts by weight of the thermosetting resin, but the present invention is not limited thereto. In one embodiment, the content of the polyolefin resin may be 0 to 30 parts by weight relative to 100 parts by weight of the thermosetting resin, but the present invention is not limited thereto. In another embodiment, the resin composition may not include a polyolefin resin, and the content of the polyolefin resin is 0 parts by weight, which means that the resin composition does not specifically add a polyolefin resin.

In one embodiment, the polyolefin resin may include a vinyl-containing polyolefin, a hydrogenated polyolefin, or a combination thereof.

In one embodiment, the type of vinyl-containing polyolefin is not limited, and may include various vinyl-containing olefin polymers known in the art. For example, specific examples of vinyl-containing polyolefins may include, but are not limited to, polybutadiene, polyisoprene, styrene-butadiene copolymer, styrene-butadiene-styrene block copolymer, styrene-isoprene copolymer, styrene-butadiene-divinylbenzene terpolymer, maleic anhydride-added styrene-butadiene copolymer, vinyl-polybutadiene-urea oligomer, maleic anhydride-added polybutadiene, or a combination thereof. For example, specific examples of vinyl polyolefins may include, but are not limited to, vinyl polyolefins produced by Cray Valley Corporation under the trade names Ricon 100, Ricon 150, Ricon 184MA6, Ricon 130MA10, Ricon 257, etc.; or vinyl polyolefins produced by Nippon Soda Corporation under the trade names B-1000, B-2000, B-3000, etc.

In one embodiment, when the resin composition includes a vinyl-containing polyolefin, the content of the vinyl-containing polyolefin may be greater than 0 parts by weight to 30 parts by weight, preferably 5 parts by weight to 20 parts by weight, relative to 100 parts by weight of the thermosetting resin. In another embodiment, the resin composition may not include the vinyl-containing polyolefin, and the content of the vinyl-containing polyolefin is 0 parts by weight, which means that the resin composition does not specifically add the vinyl-containing polyolefin. However, the present invention is not limited thereto, and the content of the vinyl-containing polyolefin can be adjusted as needed.

In one embodiment, the type of hydrogenated polyolefin is not limited, and may include various types of hydrogenated polyolefins known in the art. The hydrogenated polyolefin applicable to the present invention is not particularly limited, and may be any one or more commercially available products, self-made products, or combinations thereof. For example, the hydrogenated polyolefin may include hydrogenated styrene-butadiene-styrene block copolymers (also known as styrene-ethylene/butylene-styrene copolymers), hydrogenated styrene-butadiene-styrene block copolymers substituted with maleic anhydride, or combinations thereof. That is, the hydrogenated polyolefin may include unsubstituted hydrogenated styrene-butadiene-styrene triblock copolymers, hydrogenated styrene-butadiene-styrene triblock copolymers substituted with maleic anhydride, or combinations thereof. For example, specific examples of hydrogenated polyolefins may include hydrogenated polyolefins produced by Asahi KASEI with trade names such as H1221, H1062, H1521, H1052, H1041, H1053, H1051, H1517, H1043, N504, H1272, M1943, M1911, M1913, P1500, etc.; hydrogenated polyolefins produced by KRATON with trade names such as G1650, G1651, G1652, G1654, G1657, G1726, FG1901, FG1924, etc.; or hydrogenated polyolefins produced by Kuraray with trade names such as 8004, 8006, 8007L, etc.

In one embodiment, when the resin composition includes a hydrogenated polyolefin (e.g., a hydrogenated styrene-butadiene-styrene block copolymer), the content of the hydrogenated polyolefin may be greater than 0 parts by weight to 30 parts by weight, or may be 5 parts by weight to 15 parts by weight relative to 100 parts by weight of the thermosetting resin. In another embodiment, the resin composition may not include the hydrogenated polyolefin, and the content of the hydrogenated polyolefin is 0 parts by weight, which means that the resin composition does not specifically add the hydrogenated polyolefin. However, the present invention is not limited thereto, and the content of the hydrogenated polyolefin may be adjusted as required.

In one embodiment, the resin composition of the present invention may further include an inorganic filler, a silane coupling agent, a hardening accelerator, an inhibitor, a flame retardant, a dye, a toughening agent (such as core-shell rubber), a solvent or a combination thereof. The content of the aforementioned components is not limited, and they can be used alone or in combination. In one embodiment, the content of the aforementioned components can be 0 parts by weight, or can be 0.001 parts by weight to 400 parts by weight.

In one embodiment, the resin composition of the present invention may further include an inorganic filler, and the content of the inorganic filler is not limited. In one embodiment, the content of the inorganic filler may be 1.5 to 2.1 times the total content of all other components in the resin composition except the inorganic filler, the hardening accelerator and the solvent. In other words, the resin composition of the present invention may further include an inorganic filler in an amount of 1.5 to 2.1 times the total weight of all other components, and the aforementioned all other components refer to all other components in the resin composition except the inorganic filler, the hardening accelerator and the solvent. However, the present invention is not limited thereto, and the content of the inorganic filler can be adjusted as needed.

In one embodiment, the inorganic filler may be silicon dioxide. In one embodiment, the inorganic filler may be spherical silicon dioxide. In one embodiment, the spherical silicon dioxide may include various types of spherical silicon dioxide known in the art. The spherical silicon dioxide applicable to the present invention is not particularly limited and may be any one or more commercially available products, such as but not limited to spherical silicon dioxide purchased from Admatechs.

In one embodiment, the inorganic filler may be an inorganic filler different from spherical silica, and its content may be adjusted as required. In one embodiment, relative to 100 parts by weight of the thermosetting resin, the content of the inorganic filler different from spherical silica may be 1 part by weight to 100 parts by weight.

In one embodiment, the inorganic filler other than spherical silica may include non-spherical silica (i.e., known irregular silica, which is not spherical), aluminum oxide, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, aluminum silicon carbide, silicon carbide, titanium dioxide, barium titanate, , lead titanium oxide, strontium titanium oxide, calcium titanium oxide, magnesium titanium oxide, barium zirconate, lead zirconate, magnesium zirconate, lead zirconate titanium oxide, zinc molybdate, calcium molybdate, magnesium molybdate, ammonium molybdate, zinc molybdate-modified talc, zinc oxide, zirconium oxide, mica, boehmite (AlOOH), calcined talc, talc, silicon nitride or calcined kaolin. In addition, except for the aforementioned non-spherical silicon dioxide, the remaining aforementioned inorganic fillers may be spherical, fibrous, plate-like, granular, flake or needle-whisker-like.

In one embodiment, the inorganic filler can be selectively pre-treated with a siloxane compound as required. The content of the siloxane compound used to pre-treat the inorganic filler is common knowledge in the art and will not be elaborated herein.

If not specifically specified, the silane coupling agent applicable to the present invention may include silane compounds (such as but not limited to siloxane compounds), which can be further divided into amino silane compounds, epoxide silane compounds, vinyl silane compounds, ester silane compounds, hydroxy silane compounds, isocyanate silane compounds, methacryloxy silane compounds and acryloxy silane compounds according to the type of functional groups. The content of the silane coupling agent is not particularly limited, and the content of the silane coupling agent can be adjusted depending on the dispersibility of the inorganic filler in the resin composition.

In one embodiment, the resin composition of the present invention may further include a hardening accelerator (including a hardening initiator), and the content of the hardening accelerator may be adjusted as needed. In one embodiment, relative to 100 parts by weight of the thermosetting resin, the content of the hardening accelerator may be 0.01 parts by weight to 0.5 parts by weight, for example, 0.02 parts by weight, 0.05 parts by weight, 0.1 parts by weight, 0.3 parts by weight, 0.45 parts by weight, 0.5 parts by weight, but the present invention is not limited thereto. In another embodiment, the resin composition may not include a hardening accelerator, and the content of the hardening accelerator is 0 parts by weight, which means that the resin composition does not specifically add a hardening accelerator.

If not specifically specified, the hardening accelerator applicable to the present invention may be any one or more hardening accelerators applicable to the production of backing copper foil, laminated board or printed circuit board. The hardening accelerator may include a catalyst such as Lewis base or Lewis acid. Among them, 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). Lewis acids may include metal salt compounds, such as metal salt compounds of manganese, iron, cobalt, nickel, copper, zinc, etc., such as metal catalysts such as zinc octoate and cobalt octoate. Hardening accelerators also include hardening initiators, such as peroxides that can generate free radicals. Hardening initiators include but are not limited to: diisopropylbenzene peroxide, tert-butyl peroxybenzoate, dibenzoyl peroxide (BPO), 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne (25B) and di(tert-butylperoxyisopropyl)benzene or a combination thereof.

In one embodiment, the resin composition of the present invention may further include an inhibitor, and the content of the inhibitor is not limited. In one embodiment, relative to 100 parts by weight of the thermosetting resin, the content of the inhibitor may be 0.01 parts by weight to 0.5 parts by weight, but the present invention is not limited thereto. When the resin composition includes an inhibitor, the content of the inhibitor may be 0.01 parts by weight to 0.5 parts by weight, for example, 0.05 parts by weight, 0.1 parts by weight, or 0.3 parts by weight. However, the present invention is not limited thereto, and the content of the inhibitor may be adjusted as needed. In another embodiment, the resin composition may not include an inhibitor, and the content of the inhibitor is 0 parts by weight, which means that the resin composition does not intentionally add an inhibitor.

If not specifically specified, the inhibitor applicable to the present invention may be any one or more inhibitors applicable to the production of backing copper foil, laminated board or printed circuit board. The inhibitor may include various molecular inhibitors or stable free radical inhibitors known in the art. The molecular inhibitor may include but is not limited to phenolic compounds, quinone compounds, aromatic amine compounds, aromatic nitro compounds, sulfur-containing compounds or variable valence metal chlorides. For example, the molecular inhibitor may include but is not limited to phenol, hydroquinone, 4-tert-butyl catechol, benzoquinone, chloranil, l,4-naphthoquinone, trimethylquinone, aniline, nitrobenzene, _Na2S , _FeCl3 or _CuCl2 . For example, the stable free radical inhibitor may include, but is not limited to, 1,1-diphenyl-2-trinitrophenylhydrazine (DPPH), triphenylmethyl radical, 2,2,6,6-tetramethylpiperidine-1-oxide, or a derivative of 2,2,6,6-tetramethylpiperidine-1-oxide.

In one embodiment, the resin composition of the present invention may further include a flame retardant. When the resin composition includes a flame retardant, the content of the flame retardant may be 1 to 60 parts by weight relative to 100 parts by weight of the thermosetting resin, for example, 1 part by weight, 5 parts by weight, 10 parts by weight, 20 parts by weight, 30 parts by weight, 40 parts by weight, 50 parts by weight or 60 parts by weight. However, the present invention is not limited thereto, and the content of the flame retardant may be adjusted as required. In another embodiment, the resin composition may not include a flame retardant, and the content of the flame retardant is 0 parts by weight, which means that the resin composition does not specifically add a flame retardant.

If not otherwise specified, the flame retardant applicable to the present invention may be any one or more flame retardants applicable to the production of adhesive-backed copper foil, laminated boards or printed circuit boards, such as but not limited to phosphorus-containing flame retardants. For example, the phosphorus-containing flame retardant may include ammonium polyphosphate, hydroquinone bis(diphenyl phosphate), bisphenol A bis(diphenylphosphate), tri(2-carboxyethyl) phosphine (TCEP), tri(chloroisopropyl phosphate), trimethyl phosphate (TMP), dimethyl methyl phosphonate (DMMP), resorcinol bis(dixylenyl phosphate), resorcinol bis(di-2,6-dimethylphenyl phosphate), and bis(di-2,6-dimethylphenyl phosphate). phosphate, such as the commercial product PX-200), hydroquinone bis(di-2,6-dimethylphenyl phosphate), such as the commercial product PX-201, 4,4'-biphenol bis(di-2,6-dimethylphenyl phosphate), such as the commercial product PX-202, phosphazene (such as SPB-100, SPH-100, SPV-100 and other commercial products), melamine polyphosphate (such as melamine phosphate), 4,4'-biphenol bis(di-2,6-dimethylphenyl phosphate), such as the commercial product PX-203, 4,4'-biphenol bis(di-2,6-dimethylphenyl phosphate), such as the commercial product PX-204, 4,4'-biphenol bis(di-2,6-dimethylphenyl phosphate), such as the commercial product PX-205, 4,4'-biphenol bis(di-2,6-dimethylphenyl phosphate), such as the commercial product PX-206, 4,4'-biphenol bis(di-2,6-dimethylphenyl phosphate), such as the commercial product PX-207, 4,4'-biphenol bis(di-2,6-dimethylphenyl phosphate), such as the commercial product PX-208, 4,4'-biphenol bis(di-2,6-dimethylphenyl phosphate), such as the commercial product PX-201, 4,4'-biphenol bis(di-2,6-dimethylphenyl phosphate), such as the commercial product PX-202, 4,4'-biphenol bis(di-2,6-dimethylphenyl phosphate), such as the commercial product PX-203 ... polyphosphate), 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide (DOPO) and its derivatives (e.g., bis-DOPO compounds) or resins (e.g., DOPO-HQ, DOPO-NQ, DOPO-PN, DOPO-BPN), DOPO-bonded epoxy resins, diphenylphosphine oxide (DPPO) and its derivatives (e.g., bis-DPPO compounds) or resins, melamine cyanurate, tri-hydroxyethyl isocyanurate, or aluminum phosphinate (e.g., OP-930, OP-935, etc.). Among them, DOPO-PN is DOPO phenol novolac resin, and DOPO-BPN can be bisphenol novolac resins such as DOPO-BPAN (DOPO-bisphenol A novolac), DOPO-BPFN (DOPO-bisphenol F novolac) or DOPO-BPSN (DOPO-bisphenol S novolac).

In one embodiment, the content of the coloring agent or toughening agent (such as core-shell rubber) can be 0.01 to 10 parts by weight, such as but not limited to 0.01 to 3 parts by weight, 0.05 to 1 part by weight. However, the present invention is not limited thereto, and the content of the aforementioned components can be adjusted as needed.

If not otherwise specified, the dyes applicable to the present invention may include but are not limited to dyes or pigments.

The main function of the toughening agent is to improve the toughness of the resin composition. If not specifically indicated, the toughening agent applicable to the present invention may include but is not limited to carboxyl-terminated butadiene acrylonitrile rubber (CTBN) or core-shell rubber. If not specifically indicated, the core-shell rubber applicable to the present invention may include various commercially available core-shell rubbers.

The main function of the solvent is 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, butanone (also known as methyl ethyl ketone), methyl isobutyl ketone, cyclohexanone, toluene, xylene, methoxyethyl acetate, ethoxyethyl acetate, propoxyethyl acetate, ethyl acetate, propylene glycol methyl ether, dimethylformamide, dimethylacetamide, nitrogen methyl pyrrolidone or a mixed solvent thereof. The amount of the aforementioned solvent added is not particularly limited, and the amount of the solvent added can be adjusted according to the required viscosity of the resin composition. If a solvent is added to the resin composition, the solvent will be volatilized and removed when the resin composition is heated at a high temperature to form a semi-cured state, so there is no solvent in the adhesive copper foil, or only a trace amount of solvent exists in the adhesive copper foil.

The resin composition of an embodiment of the present invention can be made into various articles by various processing methods, including but not limited to adhesive-backed copper foil, laminated boards or printed circuit boards.

For example, the resin composition of an embodiment of the present invention can be made into a resin coated copper foil. For example, the resin composition of an embodiment of the present invention is coated on a copper foil, and then the resin composition is formed into a semi-cured state after baking and heating, thereby obtaining the resin coated copper foil. The aforementioned baking temperature can be between 95°C and 150°C, preferably between 100°C and 130°C, and the aforementioned baking time can be 1 minute to 6 minutes, preferably 3 minutes to 5 minutes. The aforementioned resin coated copper foil can include a copper foil and a semi-cured resin layer attached to one side of the copper foil, and the semi-cured resin layer is obtained by forming the aforementioned resin composition into a semi-cured state.

For example, the aforementioned backing copper foil may further include a protective film layer. That is, the backing copper foil may include a copper foil, a semi-cured resin layer attached to one side of the copper foil, and a protective film layer attached to the other side of the copper foil relative to the semi-cured resin layer.

For example, the type of copper foil of the aforementioned backing copper foil is not limited, and can be various copper foils commonly used in the art, such as but not limited to, high temperature elongation (HTE) copper foil, reverse treated foil (RTF) copper foil, reverse 2 (RTF2) copper foil, very low profile (VLP) copper foil, hyper very low profile (HVLP) copper foil, hyper very low profile 2 (HVLP2) copper foil, carrier copper foil, etc. The thickness of the aforementioned copper foil is not limited, and can be the thickness of copper foil commonly used in the art, such as but not limited to Toz (ounce), Hoz, 1oz, 2oz, etc. The aforementioned carrier copper foil may be any of various carrier copper foils commonly used in the art, for example, a carrier copper foil comprising an 18 micron carrier copper foil and a 3 micron thin copper foil, wherein the 3 micron thin copper foil is attached to the 18 micron carrier copper foil. A specific example of the aforementioned carrier copper foil may be a carrier copper foil with the trade name MT18FL purchased from Mitsui Metals.

For example, the resin composition of an embodiment of the present invention can be made into a laminate. For example, the laminate can include at least two metal foils and at least one insulating layer, and the insulating layer is disposed between the two metal foils. The insulating layer can be obtained by curing the semi-cured resin composition in a known high-temperature, high-pressure pressing process (C-stage). For example, the semi-cured resin layer on one side of the two aforementioned copper foils with backings are butt-jointed and overlapped, so that the copper foil layers of the two copper foils with backings face outward, and then cured and pressed by high temperature and high pressure to obtain a laminate. For example, a semi-cured resin layer on one side of a copper foil with adhesive backing is stacked on another copper foil, so that the two copper foil layers are on the outside of the semi-cured resin layer, and then cured and pressed by high temperature and high pressure to obtain a laminate. The applicable curing temperature may be between 190°C and 230°C, preferably between 200°C and 230°C. The applicable curing time may be between 60 and 300 minutes, preferably between 100 and 200 minutes. The applicable pressure may be between 150 psi and 500 psi, preferably between 250 psi and 400 psi. For example, the insulating layer of the laminate can be obtained by curing and laminating at least one semi-cured resin layer of a backing copper foil. The laminate can be a copper clad laminate (also known as a copper clad laminate).

For example, the aforementioned laminate can be further processed into a printed circuit board. The manufacturing method of the printed circuit board can be any known manufacturing method.

For example, an article made of the resin composition of an embodiment of the present invention may satisfy one, more or all of the following characteristics: In the circuit substrate filling test, there are no cavitations in the filling area of the circuit substrate; In the board edge tree stripe test after the circuit substrate is pressed, the length of the board edge tree stripe is less than or equal to 5 millimeters (mm), for example, between 3 mm and 5 mm; In the evaluation of the board edge tree stripe after the circuit substrate is pressed, the evaluation of the board edge tree stripe is "○"; The X/Y axis thermal expansion coefficient measured by the method described in IPC-TM-650 2.4.24.5 is less than or equal to 40 ppm/°C, for example, between 25 ppm/°C and 40 ppm/°C;  The copper foil peel strength measured by the method described in IPC-TM-650 2.4.8 is greater than or equal to 3.0 pounds per inch (lb/in), such as between 3.0 lb/in and 3.5 lb/in;  The fold resistance rating measured in the fold resistance test is less than or equal to 3; and  The flame retardancy measured by the method described in UL94 specification reaches V-0 level.

The resin compositions of the embodiments and comparative examples of the present invention were prepared using various raw materials from the following sources according to the amounts shown in Tables 1 to 4, and were further prepared into various test samples.

The chemical raw materials used in the embodiments of the resin composition and the comparative examples of the resin composition are as follows: OPE-2st 1200: polyphenylene ether resin containing vinylbenzylbiphenyl, purchased from Mitsubishi Gas Chemical. SA9000: polyphenylene ether resin containing methacrylate, purchased from Sabic. BMI-2300: polyphenylmethane maleimide, purchased from Yamato Chemical Co., Ltd. BMI-70: 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane dimaleimide, purchased from K.I Chemical. Phosphine oxide having the structure shown in formula (1): purchased from Zhuhai Feiyang New Materials Co., Ltd. PQ-60: p-xylylene bis(diphenylphosphine) oxide, purchased from Jinyi Chemical. BPO-13: paraphenylenebisdiphenylphosphine oxide, purchased from Katayama Chemical. TPPO: triphenylphosphine oxide, purchased from Hokuko Chemical Industry. SPB-100: cyclic phosphazene compound, purchased from Otsuka Chemical. SPV-100: allylphosphazene compound, purchased from Otsuka Chemical. Isocyanurate (m=6) having a structure represented by formula (2): see Preparation Example 1. Isocyanurate (m=4) having a structure represented by formula (2): see Preparation Example 2. Isocyanurate (m=10) having a structure represented by formula (2): see Preparation Example 3. TAIC: triallyl isocyanurate, commercially available. B-3000: polybutadiene, purchased from Nippon Soda. Ricon 100: Styrene-butadiene copolymer, purchased from Cray Valley. H1043: Hydrogenated styrene-butadiene-styrene block copolymer, purchased from Asahi KASEI. Styrene: Commercially available. 157BQT: Unsaturated polyester, purchased from Showa Highpolymer. 25B: 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne, purchased from NOF Corporation. SC2050: Spherical silica, purchased from Admatechs. Methyl ethyl ketone and toluene: Commercially available.

Manufacturing Example 1

400 mL of N,N-dimethylformamide (DMF) and 60 g (0.286 mol) of unmodified diallyl isocyanurate were added to the reactor, and the unmodified diallyl isocyanurate was dissolved in DMF under continuous stirring. Then, 39.5 g (0.286 mol) of potassium carbonate and 34.9 g (0.143 mol) of 1,6-dibromohexane were added to the reactor, and the temperature was raised to 120 ^° C and stirred at a constant temperature for 6 hours, and then cooled to room temperature.

After filtering the above solution, DMF is removed from the obtained filtrate, and the residue is redissolved in 400 mL of ethyl acetate and extracted with 200 mL of deionized water, 200 mL of 5 vol% hydrochloric acid, and 200 mL of saturated sodium chloride solution in sequence. The obtained organic solution is dried over magnesium sulfate, filtered, and all solvents are removed to obtain an isocyanurate having a structure shown in formula (2), wherein m is 6.

Manufacturing Example 2

400 mL of N,N-dimethylformamide (DMF) and 60 g (0.286 mol) of unmodified diallyl isocyanurate were added to the reactor, and the unmodified diallyl isocyanurate was dissolved in DMF under continuous stirring. Then, 39.5 g (0.286 mol) of potassium carbonate and 30.9 g (0.143 mol) of 1,4-dibromobutane were added to the reactor, the temperature was raised to 120 ^° C, and the mixture was stirred at a constant temperature for 6 hours, and then cooled to room temperature.

After filtering the above solution, DMF is removed from the obtained filtrate, and the residue is redissolved in 400 mL of ethyl acetate and extracted with 200 mL of deionized water, 200 mL of 5 vol% hydrochloric acid, and 200 mL of saturated sodium chloride solution in sequence. The obtained organic solution is dried with magnesium sulfate, filtered, and all solvents are removed to obtain an isocyanurate having a structure shown in formula (2), wherein m is 4.

Manufacturing Example 3

400 mL of N,N-dimethylformamide (DMF) and 60 g (0.286 mol) of unmodified diallyl isocyanurate were added to the reactor, and the unmodified diallyl isocyanurate was dissolved in DMF under continuous stirring. Then, 39.5 g (0.286 mol) of potassium carbonate and 42.9 g (0.143 mol) of 1,10-dibromodecane were added to the reactor, and the temperature was raised to 120 ^° C and stirred at a constant temperature for 6 hours, and then cooled to room temperature.

After filtering the above solution, DMF was removed from the filtrate, and the residue was dissolved in 400 mL of ethyl acetate and extracted with 200 mL of deionized water, 200 mL of 5 vol% hydrochloric acid, and 200 mL of saturated sodium chloride solution in sequence. The obtained organic solution was dried with magnesium sulfate, filtered, and all solvents were removed to obtain an isocyanurate having a structure shown in formula (2), wherein m is 10. [Table 1] Composition (unit: weight parts) and characteristic tests of the resin composition of the embodiment Element Name E1 E2 E3 E4 E5 E6 E7 Vinyl polyphenylene ether resin OPE-2st 1200 100 100 100 100 100 60 SA9000 15 Maleimide resin BMI-2300 100 20 BMI-70 5 Phosphine oxide Formula (1) structure 15 10 20 15 15 15 15 PQ-60 BPO-13 TPPO Phosphazene compounds SPB-100 SPV-100 Isocyanurate Formula (2) structure (m=6) 15 15 15 15 10 20 15 Formula (2) structure (m=4) Formula (2) structure (m=10) TAIC Polyolefin resin B-3000 Ricon 100 H1043 Styrene Styrene Unsaturated polyester 157BQT Hardening accelerator 25B 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Inorganic fillers SC2050 R*200% R*200% R*200% R*200% R*200% R*200% R*200% Solvent Butanone 50 50 50 50 50 50 50 Toluene 50 50 50 50 50 50 50 characteristic Unit E1 E2 E3 E4 E5 E6 E7 Circuit board filling properties without pass through pass through pass through pass through pass through pass through pass through The tree-like stripes on the edge of the circuit substrate after lamination mm 5 5 5 4 5 5 4 Evaluation of the tree-like stripes on the edge of the board without O O O O O O O X/Y axis thermal expansion coefficient ppm/°C 34 35 34 25 34 33 30 Copper foil peeling strength lb/in 3.0 3.2 3.3 3.5 3.1 3.2 3.3 Folding resistance without 3 3 3 3 3 3 3 Flame retardant without V-0 V-0 V-0 V-0 V-0 V-0 V-0 [Table 2] Composition of the resin composition of the embodiment (unit: weight part) and property test Element Name E8 E9 E10 E11 E12 E13 Vinyl polyphenylene ether resin OPE-2st 1200 100 100 100 100 15 60 SA9000 60 15 Maleimide resin BMI-2300 20 5 BMI-70 5 20 Phosphine oxide Formula (1) structure 15 15 20 15 10 10 PQ-60 BPO-13 TPPO Phosphazene compounds SPB-100 SPV-100 Isocyanurate Formula (2) structure (m=6) 20 15 10 10 Formula (2) structure (m=4) 15 Formula (2) structure (m=10) 15 TAIC Polyolefin resin B-3000 5 10 Ricon 100 5 20 5 10 H1043 5 10 15 5 Styrene Styrene Unsaturated polyester 157BQT Hardening accelerator 25B 0.1 0.1 0.1 0.1 0.1 0.3 Inorganic fillers SC2050 R*150% R*200% R*200% R*200% R*190% R*210% Solvent Butanone 50 50 50 50 40 60 Toluene 50 50 50 50 40 60 characteristic Unit E8 E9 E10 E11 E12 E13 Circuit board filling properties without pass through pass through pass through pass through pass through pass through The tree-like stripes on the edge of the circuit substrate after lamination mm 5 4 4 4 3 3 Evaluation of the tree-like stripes on the edge of the board without O O O O O O X/Y axis thermal expansion coefficient ppm/°C 34 35 36 40 34 33 Copper foil peeling strength lb/in 3.0 3.5 3.3 3.5 3.5 3.2 Folding resistance without 3 3 2 1 2 1 Flame retardant without V-0 V-0 V-0 V-0 V-0 V-0 [Table 3] Composition of comparative resin composition (unit: weight parts) and property tests Element Name C1 C2 C3 C4 C5 Vinyl polyphenylene ether resin OPE-2st 1200 100 100 100 100 100 SA9000 Maleimide resin BMI-2300 BMI-70 Phosphine oxide Formula (1) structure PQ-60 15 BPO-13 15 TPPO 15 Phosphazene compounds SPB-100 15 SPV-100 Isocyanurate Formula (2) structure (m=6) 15 15 15 15 15 Formula (2) structure (m=4) Formula (2) structure (m=10) TAIC Polyolefin resin B-3000 Ricon 100 H1043 Styrene Styrene Unsaturated polyester 157BQT Hardening accelerator 25B 0.1 0.1 0.1 0.1 0.1 Inorganic fillers SC2050 R*200% R*200% R*200% R*200% R*200% Solvent Butanone 50 50 50 50 50 Toluene 50 50 50 50 50 characteristic Unit C1 C2 C3 C4 C5 Circuit board filling properties without pass through pass through pass through pass through pass through The tree-like stripes on the edge of the circuit substrate after lamination mm 12 15 18 twenty four 20 Evaluation of the tree-like stripes on the edge of the board without X X X X X X/Y axis thermal expansion coefficient ppm/°C 36 35 37 41 39 Copper foil peeling strength lb/in 2.8 2.5 2.6 2.4 2.6 Folding resistance without 4 4 4 4 4 Flame retardant without V-1 V-0 V-0 V-0 V-0 [Table 4] Composition of comparative resin composition (unit: weight parts) and property tests Element Name C6 C7 C8 C9 C10 Vinyl polyphenylene ether resin OPE-2st 1200 100 100 100 100 SA9000 Maleimide resin BMI-2300 BMI-70 Phosphine oxide Formula (1) structure 50 15 15 15 PQ-60 BPO-13 TPPO Phosphazene compounds SPB-100 SPV-100 15 Isocyanurate Formula (2) structure (m=6) 15 15 15 Formula (2) structure (m=4) Formula (2) structure (m=10) TAIC 15 Polyolefin resin B-3000 Ricon 100 H1043 Styrene Styrene 70 Unsaturated polyester 157BQT 30 Hardening accelerator 25B 0.1 0.1 0.1 0.1 0.1 Inorganic fillers SC2050 R*200% R*200% R*200% R*200% R*200% Solvent Butanone 50 50 50 50 50 Toluene 50 50 50 50 50 characteristic Unit C6 C7 C8 C9 C10 Circuit board filling properties without pass through pass through pass through pass through Invalidation The tree-like stripes on the edge of the circuit substrate after lamination mm 13 7 10 9 36 Evaluation of the tree-like stripes on the edge of the board without X △ X △ X X/Y axis thermal expansion coefficient ppm/°C 35 45 40 38 47 Copper foil peeling strength lb/in 2.4 2.7 2.9 3.0 2.0 Folding resistance without 4 3 4 4 4 Flame retardant without V-0 V-0 V-0 V-0 V-0

"R" in the table represents the multiple of the content of the inorganic filler in the resin composition of each embodiment or comparative example as the total amount of all other components in the resin composition except the inorganic filler, hardening accelerator and solvent. "R*200%" in the table represents that the content of the inorganic filler is twice the total amount of all other components mentioned above. For example, R*200% in Example E1 represents that the amount of the inorganic filler added is 260 parts by weight (the total amount of all other components in E1 except the inorganic filler, hardening accelerator and solvent is 130 parts by weight, so the content of the inorganic filler is 130 parts by weight multiplied by 200%, so it is 260 parts by weight).

The above characteristics are prepared by referring to the following method to prepare the object to be tested (sample), and then the characteristics are analyzed according to specific conditions.

Varnish

The components of each embodiment (denoted by E, such as E1 to E13) and comparative example (denoted by C, such as C1 to C10) were added into a stirring tank according to the dosage in Tables 1 to 4, and stirred. The resin composition formed after uniform mixing was referred to as a resin gel.

Adhesive copper foil

Using any of the resin compositions of Examples E1 to E13 and Comparative Examples C1 to C10, each resin composition was added to a stirring tank and mixed evenly to form a varnish, which was then coated on a copper foil (trade name MT18FL, containing 18 micron carrier copper foil and 3 micron thin copper, purchased from Mitsui Metal) to make the resin composition evenly adhered, and then heated and baked at a temperature of 120° C. for 5 minutes to form a semi-cured resin layer to obtain a backing copper foil. The backing copper foil contains a carrier copper foil layer, a thin copper layer and a semi-cured resin layer, wherein the thickness of the semi-cured resin layer is 70 microns (μm).

The first copper-containing substrate (made by laminating two adhesive-backed copper foils)

Two copper foils with backings of each embodiment and each comparative example prepared on the same day by the aforementioned method were prepared, and the two copper foils with backings were stacked, wherein the semi-cured resin layers of the two copper foils with backings were adjacent to each other on the inner side and the two outer sides were copper foil layers, and pressed and cured for 2 hours at a pressing surface pressure of 300 psi and a pressing temperature of 220° C. in a high-temperature press in a vacuum environment to form a first copper-containing substrate (formed by pressing two copper foils with backings).

The first copper-free substrate (made by laminating two adhesive-backed copper foils)

The copper foils on both outer sides of the first copper-containing substrate are etched away to obtain a first copper-free substrate (formed by laminating two copper foils with adhesive backings).

The second copper-containing substrate (made by laminating two copper foils with adhesive backing and a brown core board)

Two copper foils with backing glue of each embodiment and each comparative example prepared on the same day by the aforementioned method are prepared, and are stacked with a first brown-based core board (e.g., a brown-based core board with product name EM-S526, which can be purchased from Taiwan Optoelectronics Materials Co., Ltd.), wherein the semi-cured resin layer of one copper foil with backing glue is adjacent to one side of the first brown-based core board, and the semi-cured resin layer of another copper foil with backing glue is adjacent to the other side of the first brown-based core board. The two foils are pressed and cured for 2 hours at a pressing surface pressure of 300 psi and a pressing temperature of 220°C in a high-temperature press in a vacuum environment to form a second copper-containing substrate (two copper foils with backing glue and a brown-based core board pressed together). The manufacturing method of the first browning core board is as follows: prepare a prepreg (e.g., product EM-S526, available from Taiwan Optoelectronics Materials Co., Ltd., using 1078 E-glass fiber cloth, resin content RC=65%), stack a copper foil on both sides of the prepreg, and then press and cure for 2 hours under vacuum, high temperature (195°C) and high pressure (360 psi) conditions to obtain a copper-containing core board. Then, the copper-containing core board is subjected to a known copper foil browning process to obtain a first browning core board.

The third copper-containing substrate

Prepare two backing copper foils of each embodiment and each comparative example made on the same day by the aforementioned method and one aforementioned first copper-containing substrate, wherein each backing copper foil is 30 cm long and 21 cm wide. Please refer to Figures 1 and 2, Figure 1 is a schematic diagram of a partial area of the first copper-containing substrate 1, and Figure 2 is an enlarged view of area P in Figure 1. Circuit areas are made on the surface copper foils on both sides of the aforementioned first copper-containing substrate 1, so that it is divided into a copper-containing area 11 and a copper-free area 12 (the copper-free area is also called a void area). The aforementioned circuit area is made using the known photolithography technology. Then, the surface copper foil of the copper-containing area 11 of the first copper-containing substrate 1 is subjected to the known browning treatment to obtain a second browning core board. As shown in FIG. 2 , the second browning core board at least comprises the following areas: a browning-treated large copper surface area X’ (length D is 6 cm, width C is 4.5 cm), a copper-free empty area a1’ (length A is 1 cm, width B is 1 cm), a copper-free empty area a2’ (length F is 1 cm, width G is 0.5 cm), a copper-free empty area There are hollow areas a3’ (length I is 0.5 cm, width H is 0.5 cm) and hollow areas a4’ (length K is 1.5 cm, width J is 1 cm) that do not contain copper; wherein the spacing distance E between the hollow areas a2’ and the hollow areas a1’ is 0.1 cm, and the hollow areas a2’ and a3’ are located within the range of the large copper surface area X’. Next, a copper foil with adhesive backing, a second brown-coated core board, and a copper foil with adhesive backing are stacked in sequence, with the semi-cured resin layers of the two copper foils with adhesive backing facing the second brown-coated core board, and pressed and cured for 2 hours at 220° C. under a vacuum environment and a pressure of 300 psi to form a third copper-containing substrate. After the third copper-containing substrate is pressed, the resin composition is filled into the copper-free area 12 and covers the copper-containing area 11 during the pressing process, and the resin composition is cured after pressing. In FIG3 , the copper-containing area covered with the cured resin composition is represented by the copper-containing area 23, and the copper-free area covered with the cured resin composition is represented by the filling area 24. The empty area of the copper-free area (empty area a1′ to empty area a4′ in FIG2 ) is filled with the resin composition of the backing copper foil and cured to form the filling area 24. The empty areas a1′ to a4′ and the large copper surface area X′ in FIG. 2 correspond to the filling areas a1 to a4 and the large copper surface area X in FIG. 3 , respectively, that is, the empty areas a1′ form the filling areas a1 after the resin composition is filled and cured, and the empty areas a2′ to a4′ form the filling areas a2 to a4, respectively.

First circuit substrate

The copper foil on both outermost layers of the third copper-containing substrate is etched away to obtain a first circuit substrate. The outer layers of both sides of the first circuit substrate do not contain copper foil, but the first circuit substrate contains the copper-containing circuit area of the second brown-treated core board. Please refer to FIG. 3, which is a schematic diagram of a partial area of the first circuit substrate 2. The first circuit substrate 2 can be divided into a circuit area 21 and a board edge area 22, and includes a copper-containing area 23 treated with browning and a filler area 24.

The fourth copper-containing substrate (made by laminating two copper foils with adhesive backing and a brown core board)

The carrier copper foils on both sides of the second copper-containing substrate are peeled off, and the outer copper foil is directly electroplated to a thickness of 35 microns without cleaning, so as to obtain a fourth copper-containing substrate (two backing copper foils and a brown core board pressed together).

For the aforementioned samples to be tested, each test method and its characteristic analysis items are described as follows.

Circuit board filling properties

In the test of the filling property of the circuit substrate, the aforementioned first circuit substrate is selected, and the tester uses an optical microscope to observe whether cavitation occurs in the insulating layer on the filling area (including the filling area a1 to the filling area a4) of the first circuit substrate. Please refer to Figures 4A and 4B, which are schematic diagrams of a local circuit area of the circuit substrate, wherein Figure 4A is a schematic diagram of the filling area of the circuit substrate with cavitation, and Figure 4B is a schematic diagram of the filling area of the circuit substrate without cavitation, and the position of the cavitation is marked with a dotted line in Figure 4A. Specifically, the tester uses an optical microscope to observe the surface of the first circuit substrate. If there is a spherical or quasi-spherical unfilled area with a diameter of more than 0.5 mm, it is considered that there is a bubble; if there is an irregular unfilled area that is non-spherical and has a length of more than 0.5 mm, it is also considered that there is a bubble. If there is no bubble in the glue filling area of the first circuit substrate (including the glue filling area a1 to the glue filling area a4), it is judged that the corresponding empty area can be filled and marked as "passed"; if there is at least one bubble in the glue filling area of the first circuit substrate (including the glue filling area a1 to the glue filling area a4), it is judged that the corresponding empty area cannot be filled and marked as "failed".

The tree-like stripes on the edge of the circuit substrate after lamination

In the test of the tree-like stripes on the board edge after the circuit substrate is pressed, the first circuit substrate mentioned above is selected. Please refer to Figure 3. The board edge area 22 is designed with an air guide strip area 25 (also called a flow guide area), that is, an air guide strip known in the field of printed circuit boards. Please also refer to Figure 5, which is an enlarged view of the board edge area 22 in Figure 3. Here, it can be observed that the board edge area 22 has tree-like stripes 26 and flow mark color difference area 27. When the board edge area 22 generates tree-like stripes 26 and flow mark color-different areas 27, visually observe and measure the farthest distance from the innermost tree-like stripes 26 and/or flow mark color-different areas 27 to the outer board edge, and define it as the length L (in millimeters, mm) of the tree-like stripes on the board edge after the circuit substrate is pressed.

In the field, the smaller the dendrites on the board edge after the circuit substrate is pressed, the more uniform the flow of the resin composition during filling. When the difference in the length of the dendrites on the board edge after the circuit substrate is pressed is greater than or equal to 2 mm, it means that there are significant differences in the dendrites on the board edge after the circuit substrate is pressed between different samples (there is a significant technical difficulty). For example, the dendrites on the board edge of the circuit substrate of an article made from the resin composition disclosed in the present invention after the circuit substrate is pressed are less than or equal to 5 mm, for example, between 3 mm and 5 mm.

Evaluation of tree-like stripes on the board edge after circuit substrate pressing

The length of the tree-like stripes on the edge of the board after the circuit substrate is pressed (rounded to an integer) is evaluated according to the following criteria: 'O': The length of the tree-like stripes on the edge of the board is less than or equal to 5 mm; '△': The length of the tree-like stripes on the edge of the board is between 6 mm and 9 mm; 'X': The length of the tree-like stripes on the edge of the board is greater than or equal to 10 mm.

X/Y-axis coefficient of thermal expansion (X/Y-CTE)

In the measurement of the X/Y axis thermal expansion coefficient, the first copper-free substrate (made of two copper foils with adhesive backing pressed together) is selected as the sample to be tested for thermal mechanical analysis (TMA). The first copper-free substrate is cut into samples with a length of 15 mm and a width of 2 mm. The sample is heated at a heating rate of 5°C per minute from 50°C to 260°C, and the X/Y axis thermal expansion coefficient (unit: ppm/°C) of each sample to be tested is measured in the temperature range of 35°C to 120°C (α1) according to the method described in IPC-TM-650 2.4.24.5.

In the art, the lower the X/Y axis thermal expansion coefficient, the better the dimensional expansion characteristics. When the difference in the X/Y axis thermal expansion coefficient is greater than or equal to 2 ppm/°C, it means that there is a significant difference in the X/Y axis thermal expansion coefficient between different substrates (there is a significant technical difficulty). For example, the X/Y axis thermal expansion coefficient of an article made from the resin composition disclosed in the present invention is less than or equal to 40 ppm/°C, for example, between 25 ppm/°C and 40 ppm/°C, as measured by the method described in IPC-TM-650 2.4.24.5.

Copper foil peel strength (peel strength, P/S)

In the measurement of the copper foil peeling strength, the fourth copper-containing substrate (two backing copper foils and one brown core board pressed together) was cut into rectangular test 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 universal tensile strength tester was used to measure the force required to pull the copper foil away from the substrate surface at room temperature (about 25°C) according to the method described in IPC-TM-650 2.4.8 to measure the force (in pounds/inch, lb/in) required to pull the copper foil away from the substrate surface.

In the art, the higher the copper foil peel strength, the better. When the difference in copper foil peel strength is greater than or equal to 0.2 lb/in, it means that there is a significant difference in copper foil peel strength between different substrates (there is a significant technical difficulty). For example, the copper foil peel strength of an article made from the resin composition disclosed in the present invention is greater than or equal to 3.0 lb/in, for example, between 3.0 lb/in and 3.5 lb/in, as measured by the method described in IPC-TM-650 2.4.8.

Folding bend resistance

In the fold resistance test, the above-mentioned copper foil with adhesive backing is cut into a rectangular sample with a width of 210 mm and a length of 297 mm. At room temperature (about 25°C), the semi-cured resin layer (adhesive surface) of the sample is facing outward and the copper foil layer is facing inward. The sample is bent to facilitate fixing the lower edge of the sample to the upper edge with adhesive tape and then placed on the table. The sample is fixed with a hard object. After the sample is folded 180 degrees and pressed flat, the sample is spread flat on the table and the rubber surface of the sample is visually observed. If there is no white edge on the rubber surface after folding 180 degrees, it is marked as Grade 1; if there is a white edge on the rubber surface, it is marked as Grade 2; if there is an obvious white edge on the rubber surface and the copper foil layer is slightly exposed, it is marked as Grade 3; if the copper foil layer is obviously exposed on the rubber surface, it is marked as Grade 4.

In the art, the smaller the fold resistance level, the better the bending performance. When the fold resistance difference is greater than or equal to 1 level, it means that there is a significant difference in fold resistance between different substrates (there is a significant technical difficulty). For example, the fold resistance level of the article made from the resin composition disclosed in the present invention is less than or equal to level 3, for example, between level 1 and level 3.

Flame retardancy

In the flame retardancy test, the first copper-free substrate (made of two copper foils with adhesive backing pressed together) is cut into a rectangular sample with a width of 13 mm and a length of 125 mm. The flame retardancy analysis results are expressed as V-0, V-1, and V-2 according to the method described in the UL94 specification, where the flame retardancy of V-0 is better than that of V-1, and the flame retardancy of V-1 is better than that of V-2. The worst is when the sample burns out. For example, the flame retardancy test of the article made of the resin composition disclosed in the present invention is V-0 grade when measured according to the method described in the UL94 specification.

By referring to the test results in Tables 1 to 4, the following phenomena can be clearly observed.

Embodiments E1 to E13 using a resin composition comprising 100 parts by weight of a thermosetting resin (including a vinyl polyphenylene ether resin, a maleimide resin or a combination thereof), 10 to 20 parts by weight of a phosphine oxide having a structure represented by formula (1), and 10 to 20 parts by weight of an isocyanurate having a structure represented by formula (2) can all achieve the following: passing the circuit substrate filling test, the length of the board edge dendrites after the circuit substrate is pressed is less than or equal to 5 mm, the evaluation of the board edge dendrites after the circuit substrate is pressed is "O", the X/Y axis thermal expansion coefficient is less than or equal to 40 ppm/°C, and the copper foil peeling strength is greater than or equal to 3.0 lb/in, flexural resistance level less than or equal to level 3, and flame retardancy test is V-0 level. In contrast, Comparative Examples C1 to C10 fail to meet the requirements in at least one of the above-mentioned properties.

Compared with Example E1, Comparative Example C1, which does not use the phosphine oxide having the structure shown in Formula (1) of the present invention, fails to meet the requirements in terms of the dendrites on the board edge after circuit substrate pressing, the evaluation of the dendrites on the board edge after circuit substrate pressing, the copper foil peeling strength, the dead bending resistance and the flame retardancy.

Compared with Example E1, Comparative Examples C2, C3 and C4, which do not use the phosphine oxide having the structure shown in formula (1) of the present invention but use phosphine oxides of other structures, fail to meet the requirements in terms of the dendrites on the board edge after circuit substrate pressing, the evaluation of the dendrites on the board edge after circuit substrate pressing, the copper foil peeling strength and the fold resistance.

Compared with Example E1, Comparative Examples C5 and C6, which do not use the phosphine oxide having the structure shown in formula (1) of the present invention but use phosphazene compounds instead, fail to meet the requirements in terms of the dendrites on the board edge after circuit substrate pressing, the evaluation of the dendrites on the board edge after circuit substrate pressing, the copper foil peeling strength and the fold resistance.

Compared with Example E1, Comparative Example C7, which uses 50 parts by weight of phosphine oxide having the structure shown in formula (1) instead of 10 to 20 parts by weight of phosphine oxide having the structure shown in formula (1), fails to meet the requirements in terms of the tree-like stripes on the board edge after circuit substrate pressing, the evaluation of the tree-like stripes on the board edge after circuit substrate pressing, the X/Y axis thermal expansion coefficient, and the copper foil peeling strength.

Compared to Example E1, Comparative Example C8, which does not use the isocyanurate having the structure shown in Formula (2) of the present invention, fails to meet the requirements in terms of the tree-like stripes on the board edge after circuit substrate pressing, the evaluation of the tree-like stripes on the board edge after circuit substrate pressing, the copper foil peeling strength and the dead bending resistance.

Compared with Example E1, Comparative Example C9, which does not use the isocyanurate having the structure shown in formula (2) of the present invention but uses isocyanurate of other structures, fails to meet the requirements in terms of the tree-like stripes on the board edge after circuit substrate pressing, the evaluation of the tree-like stripes on the board edge after circuit substrate pressing, and the dead bending resistance.

Compared to Example E1, Comparative Example C10, which does not use the thermosetting resin of the present invention but uses styrene and unsaturated polyester instead, fails to meet the requirements in terms of the filling property of the circuit substrate, the dendritic stripes on the board edge after the circuit substrate is pressed, the evaluation of the dendritic stripes on the board edge after the circuit substrate is pressed, the X/Y axis thermal expansion coefficient, the copper foil peeling strength and the fold resistance.

In general, the resin composition of the present invention and articles made therefrom can simultaneously achieve the following characteristics: passing the circuit substrate filling test, the board edge dendrites after circuit substrate pressing are less than or equal to 5 mm, the board edge dendrites after circuit substrate pressing are rated as "O", the X/Y axis thermal expansion coefficient is less than or equal to 40 ppm/°C, the copper foil peeling strength is greater than or equal to 3.0 lb/in, the dead bending resistance level is less than or equal to level 3, and the flame retardancy test is V-0 level.

The above embodiments are essentially only for auxiliary explanation and are not intended to limit the embodiments of the subject matter of the application or the application or use of such embodiments. In this article, the term "exemplary" means "serving as an example, example or illustration". Any exemplary embodiment in this article is not necessarily interpreted as being better or more advantageous than other embodiments.

In addition, although at least one exemplary embodiment or comparative example has been presented in the foregoing embodiments, it should be understood that a large number of variations are possible in the present invention. It should also be understood that the embodiments described herein are not intended to limit the scope, use or configuration of the claimed subject matter in any way. On the contrary, the foregoing embodiments will provide a simple guide for those with ordinary knowledge in the art to implement one or more of the embodiments described. Furthermore, various changes may be made to the functions and arrangements of the components without departing from the scope defined by the scope of the patent application, and the scope of the patent application includes known equivalents and all foreseeable equivalents at the time of filing the present patent application.

1: First copper-containing substrate P: Area 11: Copper-containing area 12: Non-copper-containing area 2: First circuit substrate 21: Circuit area 22: Board edge area 23: Copper-containing area 24: Glue filling area 25: Air guide area 26: Tree-like stripes 27: Flow mark color difference area A, D, F, I, K: Length B, C, G, H, J: Width E: Spacing distance a1, a2, a3, a4: Glue filling area a1’, a2’, a3’, a4’: Empty area X,: Large copper surface area X’: Large copper surface area L: Length

FIG1 is a schematic diagram of a partial area of a copper-containing substrate. FIG2 is an enlarged view of a partial area of FIG1. FIG3 is a schematic diagram of a partial area of a circuit substrate. FIG4A and FIG4B are schematic diagrams of a local circuit area of a circuit substrate. FIG5 is an enlarged view of the board edge area in FIG3.

without.

Claims (10)

A resin composition comprising: 100 parts by weight of a thermosetting resin, the thermosetting resin comprising a vinyl polyphenylene ether resin, a maleimide resin or a combination thereof; 10 to 20 parts by weight of a phosphine oxide having a structure represented by formula (1); and 10 to 20 parts by weight of an isocyanurate having a structure represented by formula (2), wherein m is an integer from 2 to 18; Formula (1) Formula (2). The resin composition as described in claim 1, wherein the vinyl-containing polyphenylene ether resin comprises a vinylbenzyl biphenyl polyphenylene ether resin, a methacrylate-containing polyphenylene ether resin or a combination thereof. The resin composition as claimed in claim 1, wherein the maleimide resin comprises 4,4'-diphenylmethane dimaleimide, polyphenylmethane maleimide, bisphenol A diphenyl ether dimaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane dimaleimide, 3,3'-dimethyl-5,5'-dipropyl-4,4'-diphenylmethane dimaleimide , m-phenylenebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, N-2,3-dimethylphenylmaleimide, N-2,6-dimethylphenylmaleimide, N-phenylmaleimide, vinylbenzylmaleimide, maleimide containing a biphenyl structure, maleimide containing an indane structure, maleimide containing a _C10 to _C50 aliphatic long chain structure, or a combination thereof. The resin composition as described in claim 1 further comprises 10 to 30 parts by weight of a polyolefin resin. The resin composition as described in claim 4, wherein the polyolefin resin comprises a vinyl-containing polyolefin, a hydrogenated polyolefin or a combination thereof. The resin composition as described in claim 1 further comprises an inorganic filler, a silane coupling agent, a hardening accelerator, an inhibitor, a flame retardant, a dye, a toughening agent, a solvent or a combination thereof. An article made of the resin composition of any one of claims 1 to 6, the article comprising a backing copper foil, a laminate or a printed circuit board. For the article as described in claim 7, in a circuit substrate press test, the length of the tree-like stripes on the board edge produced after pressing is less than or equal to 5 mm. An article as described in claim 7, wherein the flexural resistance rating measured in the flexural resistance test is less than or equal to 3. The article as described in claim 7 has a copper foil peel strength greater than or equal to 3.0 lb/in as measured in accordance with the method described in IPC-TM-650 2.4.8.