Resin composition and product thereof

Abstract

The invention relates to the technical field of electronic materials, and discloses a resin composition and a product thereof. The resin composition provided by the invention comprises the following components in parts by weight: 100 parts of maleimide resin containing an indane structure; 5 to 30 parts by weight of an amino-modified hydrogenated styrene polymer; 10 to 30 parts by weight of a (meth) acrylate-terminated phosphate ester resin; and 10-30 parts by weight of a vinyl-containing polyphenyl ether resin. The product prepared from the resin composition comprises a prepreg, a resin film, a laminated board, a printed circuit board or a cured insulator, and at least one of the characteristics of dielectric loss, X-axis thermal expansion coefficient, carrier copper tension, heat resistance after moisture absorption, water absorption after pressure cooking, interlayer tension, long bubble stripes and the like is improved.

Description

Technical Field

[0001] This invention relates to the field of electronic materials technology, specifically to a resin composition and articles thereof, particularly to a resin composition applicable to prepregs, resin films, laminates, printed circuit boards or cured insulators, and articles thereof. Background Technology

[0002] With the rapid development of technologies such as 5G communication, the Internet of Things, and artificial intelligence, electronic products are evolving towards higher integration, lower power consumption, and higher performance. As the basic material for printed circuit boards (PCBs), copper clad laminates directly determine the performance and reliability of the final electronic products through the performance of the resin composition used in them.

[0003] To meet the requirements of PCB flatness and dense circuit layout, the PCB substrate must have a low coefficient of thermal expansion. With increasingly smaller line widths and spacings, and thinner copper foils being used, carrier copper has become a new option to reduce skin effect losses and ensure the integrity of high-frequency signal transmission. Therefore, improving the adhesion between the carrier copper and the substrate (carrier copper pull strength) has become a focus. Secondly, to meet the electrical, heat resistance, and reliability requirements of PCBs, other characteristics such as dielectric loss, heat resistance after moisture absorption, water absorption rate after pressure cooking, interlayer pull strength, and elongated bubble streaks also need attention. Therefore, developing a copper-clad laminate that combines a low coefficient of thermal expansion, high carrier copper pull strength, and excellent other properties has become a problem to be solved in the industry. Summary of the Invention

[0004] The present invention provides a resin composition and articles thereof, the articles including prepreg, resin film, laminate, printed circuit board and cured insulator, to solve the technical problem in the prior art that it is impossible to simultaneously meet the requirements of low coefficient of thermal expansion and high carrier copper pull force, and thus other excellent properties.

[0005] In a first aspect, the present invention provides a resin composition comprising: 100 parts by weight of maleimide resin containing indane structure; 5-30 parts by weight of amino-modified hydrogenated styrene polymer; 10-30 parts by weight of a (meth)acrylate-terminated phosphate resin, wherein the structure of the (meth)acrylate-terminated phosphate resin is as shown in formula (I):

[0006] Formula (I) Among them, R L1 and R L7 Each can be independently H or CH3, RL2 R L3 R L4 R L5 and R L6 Each of the following is an alkyl group with 1 to 4 carbon atoms; y2, y3, y4, y5, and y6 are each an integer from 0 to 4, where y2+y3+y4+y5+y6≥5, and multiple R are present. L2 R L3 R L4 R L5 or R L6 In the case of multiple R L2 R L3 R L4 R L5 or R L6 They can be the same or different, and z is an integer from 0 to 10; 10 to 30 parts by weight of vinyl polyphenylene ether resin.

[0007] The maleimide resin containing the indane structure includes one or a combination of two of the structures shown in formula (A-2) and formula (A-3):

[0008] Equation (A-2) In equation (A-2), Ra, Rb, Rc, Rd, and R 11 R 12 R 13 Each is an alkyl group with 1 to 4 carbon atoms, and each of them is an integer from 0 to 4. Each of them is an integer from 0 to 3. Each of them is the number of repeating units, and is a value from 1 to 20. Each of them is a divalent alkyl group with 1 to 4 carbon atoms. Equation (A-3) In equation (A-3), Re, Rf, Rg, Rh, Ri, Rj, Rk, and R are... 21 R 22 R 23 R 24 R 25 R 26 Each of them is an alkyl group with 1 to 4 carbon atoms, and each of them is an integer from 0 to 4. Each of them is an integer from 0 to 3. Each of them is an integer from 0 to 3. Each of them is a number-average repeating unit, and each of them is an integer from 0 to 20. Each of them is an integer from 0 to 20. Each of them is an integer from 0 to 20. Each of them is an integer from 0.5 to 20. Each of them is a divalent alkyl group with 1 to 4 carbon atoms. In one exemplary embodiment, the maleimide resin containing an indane structure of formula (A-2) may include the structure shown in formula (A-2-1): Equation (A-2-1) Among them, Ra1, Ra2, Rd1, Rd2, R 13 Each is an alkyl group consisting of 1 to 4 hydrogen atoms or carbon atoms; n1 is the number of repeating units, and is a value from 1 to 20. In one exemplary embodiment, the maleimide resin containing an indane structure of formula (A-3) may include the structure shown in formula (A-3-1): Equation (A-3-1) Among them, Re1~Re2, Rh1~Rh2, Rk1~Rk2, R 23 R 26 Each is an alkyl group with 1 to 4 hydrogen or carbon atoms; n2 and n3 are the number of repeating units, each with a value of 0 to 20, and n2 + n3 has a value of 0.5 to 20.

[0010] In one exemplary embodiment, the maleimide resin containing an indene structure of formula (A-2-1) includes at least one of the structures shown in formulas (A-2-2) to (A-2-6).

[0011] Equation (A-2-2)

[0012] Equation (A-2-3)

[0013] Equation (A-2-4)

[0014] Equation (A-2-5)

[0015] Equation (A-2-6) Where n1 is the average number of repeating units, and is a value from 1 to 20; In one exemplary embodiment, the maleimide resin containing an indane structure of formula (A-3-1) includes at least one of the structures shown in formulas (A-3-2) to (A-3-8).

[0016] Equation (A-3-2)

[0017] Equation (A-3-3)

[0018] Equation (A-3-4)

[0019] Equation (A-3-5)

[0020] Equation (A-3-6)

[0021] Equation (A-3-7)

[0022] Equation (A-3-8) In the structures of equations (A-3-2) to (A-3-8), n2 and n3 are the average number of repeating units, and each is an independent value of 0 to 20, and n2 + n3 is a value of 0.5 to 20.

[0023] In one exemplary embodiment, the molecular structure of the amino-modified hydrogenated styrene polymer has an amino group (amino group) and a styrene monomer unit; In one exemplary embodiment, the amino group is a primary amino group or a secondary amino group; In one exemplary embodiment, the amino-modified hydrogenated styrene-based polymer includes amino-modified hydrogenated styrene-butadiene copolymer, amino-modified hydrogenated styrene-isoprene copolymer, amino-modified hydrogenated styrene-butadiene-styrene copolymer, amino-modified hydrogenated styrene-isoprene-styrene copolymer, amino-modified hydrogenated styrene-isobutylene-styrene copolymer, or combinations thereof. In one exemplary embodiment, the structure of the (meth)acrylate-terminated phosphate resin of formula (I) is as shown in formula (I-1):

[0024] Formula (I-1) Among them, R L1 and R L7 Each can be H or CH3, R independently j1 R j2 R j3 H or CH3, K1, K2 and K3 are 0, 1 or 2, and W is 0, 1, 2 or 3; In one exemplary embodiment, the phosphorus content in the (meth)acrylate-terminated phosphate resin of formula (I) is 2.0% to 10.0% by weight. In one exemplary embodiment, the vinyl-containing polyphenylene ether resin includes terminal methacrylate polyphenylene ether resin, terminal vinyl benzyl polyphenylene ether resin, terminal allyl polyphenylene ether resin, or a combination thereof; In one exemplary embodiment, the resin composition further includes a vinyl crosslinking agent, a maleimide triazine resin, a styrene maleic anhydride resin, an epoxy resin, a phenolic resin, a benzoxazine resin, a cyanate ester resin, a polyester resin, a polyamide resin, a polyimide resin, or a combination thereof.

[0025] In one exemplary embodiment, the resin composition further includes an amine curing agent, an inorganic filler, a curing accelerator, a polymerization inhibitor, a colorant, a solvent, a toughening agent, a silane coupling agent, or a combination thereof.

[0026] In a second aspect, the present invention also provides an article made of the resin composition, including a prepreg, a resin film, a laminate, a printed circuit board, or a cured insulator.

[0027] In one exemplary embodiment, the article of manufacture has one, more, or all of the following characteristics: The dielectric loss measured at a frequency of 10 GHz using the method described in JISC2565 is less than or equal to 0.00180. The X-axis thermal expansion coefficient measured according to the method described in IPC-TM-650 2.4.24.5 is less than or equal to 9.3 ppm / ℃; The carrier copper tensile strength measured according to the method described in IPC-TM-650 2.4.8 is greater than or equal to 4.60 lb / in; After absorbing moisture for 5 hours according to the methods described in IPC-TM-650 2.6.16.1 and IPC-TM-650 2.4.23, no heat resistance test was performed and no plate bursting occurred. The water absorption rate measured after moisture absorption by pressure cooking test (PCT) according to the method described in IPC-TM-650 2.6.16.1 is less than or equal to 0.35%; The interlaminar tensile strength measured according to the method described in IPC-TM-650 2.4.8 is greater than or equal to 3.38 lb / in; The product was observed to be free of elongated bubble streaks under an optical microscope. Attached Figure Description

[0028] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0029] Figure 1 It is a sample that exhibits elongated bubble streaks when observed under an optical microscope.

[0030] Figure 2 Samples that do not exhibit elongated bubble streaks when observed under an optical microscope. Detailed Implementation

[0031] The following embodiments are provided to better understand the present invention, but the following embodiments do not constitute a limitation on the content and scope of protection of the present invention. Any product that is the same as or similar to the present invention, derived by any person under the guidance of the present invention or by combining the features of the present invention with other prior art, falls within the scope of protection of the present invention.

[0032] Unless otherwise specified, the experimental steps or conditions in the examples were performed in accordance with conventional experimental procedures and conditions in the art. Reagents or instruments whose manufacturers are not specified are all commercially available products.

[0033] The terms used herein (including technical and scientific terms) have the same meaning as commonly understood by those skilled in the art. Unless otherwise specified, the terms used herein shall prevail.

[0034] The terms “contains,” “including,” “has,” “contains,” or any other similar words used in this article are all open-ended conjunctions, meaning they can also include other elements not listed. The terms “composed of,” “consisting of,” and “remaining as” used in this article are all closed-ended conjunctions.

[0035] The term "a composition comprising A, B and C, wherein A comprises a1, a2 or a3" used in this article has the same meaning as "a composition comprising A, B and C, wherein A comprises a1, a2, a3 or a combination thereof," which is equivalent to "a composition comprising A, B and C, wherein A comprises a1, a2, a3, a combination of a1 and a2, a combination of a1 and a3, a combination of a2 and a3, or a combination of a1, a2 and a3."

[0036] The numerical range used in this article includes all individual numerical values ​​(including integers and fractions) within the range.

[0037] The values ​​used in this article include all values ​​that are the same as this value after rounding to the number of significant digits.

[0038] In the structure of this paper, "*" represents the bonding site.

[0039] As used herein, "aryl" refers to an unsaturated aromatic carbon ring having 6 to 30 carbon atoms and being a monocyclic (such as phenyl) or polycyclic fused (such as naphthyl or anthracene) ring, preferably having 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms. Preferred aryl groups include phenyl, biphenyl, naphthyl, etc.

[0040] The polymers used in this article refer to the products formed by the polymerization reaction of monomers. Polymers include homopolymers (also known as self-polymers), copolymers, prepolymers, etc., but this invention is not limited to these. Polymers also include oligomers, but this invention is not limited to these. Oligomers, also known as low-molecular-weight polymers, are polymers composed of 2 to 20 repeating units, typically 2 to 5 repeating units. For example, diene polymers include diene homopolymers, diene copolymers, diene prepolymers, and also diene oligomers, etc.

[0041] A copolymer is a product formed by the polymerization of two or more different monomers, including random copolymers, alternating copolymers, graft copolymers, or block copolymers, but this invention is not limited thereto. For example, a styrene-butadiene copolymer is a product formed by the polymerization of only styrene and butadiene monomers. For example, styrene-butadiene copolymers include styrene-butadiene random copolymers, styrene-butadiene alternating copolymers, styrene-butadiene graft copolymers, or styrene-butadiene block copolymers, but this invention is not limited thereto. Styrene-butadiene block copolymers include, for example, the molecular structure of styrene-styrene-styrene-butadiene-butadiene-butadiene-butadiene polymerized from styrene, but this invention is not limited thereto. Styrene-butadiene block copolymers include, for example, styrene-butadiene-styrene block copolymers, but this invention is not limited thereto. Styrene-butadiene-styrene block copolymers comprise, for example, the polymerized molecular structure of styrene-styrene-butadiene-butadiene-butadiene-butadiene-styrene-styrene-styrene, but the invention is not limited thereto. Similarly, hydrogenated styrene-butadiene copolymers comprise 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 comprise, for example, hydrogenated styrene-butadiene-styrene block copolymers, but the invention is not limited thereto.

[0042] The term "resin" can include monomers, polymers thereof, combinations of monomers, combinations of polymers thereof, or combinations of monomers and polymers, but the present invention is not limited thereto. For example, "maleimide resin" includes maleimide monomers (maleimide small molecule compounds), maleimide polymers, combinations of maleimide monomers, combinations of maleimide polymers, or combinations of maleimide monomers and maleimide polymers.

[0043] "Contains vinyl" includes vinyl, vinyl benzyl, vinylyl, allyl, or (meth)acrylate.

[0044] The alkyl groups described in this invention include their various isomers; for example, propyl should be interpreted as including n-propyl and isopropyl.

[0045] The part by weight represents the number of parts by weight, which can be any unit of weight, such as kilograms, grams, pounds, etc., but the present invention is not limited thereto. For example, 100 parts by weight of maleimide resin containing an indane structure can represent 100 kilograms of maleimide resin containing an indane structure or 100 pounds of maleimide resin containing an indane structure.

[0046] Resin composition: This invention provides a resin composition comprising: 100 parts by weight of maleimide resin containing indane structure, 5–30 parts by weight of amine-modified hydrogenated styrene polymer, 10–30 parts by weight of (meth)acrylate-terminated phosphate resin, 10–30 parts by weight of vinyl polyphenylene ether resin, The structure of the (meth)acrylate-terminated phosphate resin is shown in formula (I):

[0047] Formula (I) Among them, R L1 and R L7 Each can be independently H or CH3, R L2 R L3 R L4 R L5 and R L6 Each of the following is an alkyl group with 1 to 4 carbon atoms; y2, y3, y4, y5, and y6 are each an integer from 0 to 4, where y2+y3+y4+y5+y6≥5, and multiple R are present. L2 R L3 R L4 R L5 or R L6 In the case of multiple RL2 R L3 R L4 R L5 or R L6 They can be the same or different, and z is an integer from 0 to 10.

[0048] (A) Maleimide resin containing indane structure In maleimide resins containing an indane structure, the indane structure is a substituted or unsubstituted divalent indane. The substituent can be located on the benzene ring or on the cyclopentane ring, as exemplified by the structure shown in formula (A-1):

[0049] Equation (A-1) In this context, R and R1 to R3 are each independently hydrogen atoms or alkyl groups with 1 to 4 carbon atoms, m is an integer from 0 to 3, and "*" indicates a bonding site.

[0050] In one exemplary embodiment, the maleimide resin containing an indane structure may include the structures shown in formula (A-2), formula (A-3), or combinations thereof:

[0051] Equation (A-2) In equation (A-2), Ra, Rb, Rc, Rd, and R 11 R 12 R 13 Each is an alkyl group with 1 to 4 hydrogen atoms or carbon atoms; m1, m3, and m4 are each an integer from 0 to 4; m2 is an integer from 0 to 3; n1 is the number of repeating units, and is a value from 1 to 20; X1 and X2 are each divalent alkyl groups with 1 to 4 carbon atoms.

[0052]

[0053] Equation (A-3) In equation (A-3), Re, Rf, Rg, Rh, Ri, Rj, Rk, and R are... 21 R 22 R 23 R 24 R 25 R 26 Each is an alkyl group with 1 to 4 carbon atoms, and each of m4, m6, m8, and m10 is an integer from 0 to 4; each of m5, m7, and m9 is an integer from 0 to 3; n2 and n3 are the number of repeating units, and each is an integer from 0 to 20, and n2 + n3 is an integer from 0.5 to 20; each of X3, X4, X5, and X6 is a divalent alkyl group with 1 to 4 carbon atoms.

[0054] In one exemplary embodiment, the maleimide resin containing an indane structure of formula (A-2) may include the structure shown in formula (A-2-1):

[0055] Equation (A-2-1) Among them, Ra1, Ra2, Rd1, Rd2, and R13 are each independently hydrogen atoms or alkyl groups with 1 to 4 carbon atoms; n1 is the number of repeating units, and is a value from 1 to 20.

[0056] In one exemplary embodiment, the maleimide resin containing the indane structure of formula (A-2-1) can be exemplified by the structures shown in formulas (A-2-2) to (A-2-6), but is not limited thereto:

[0057] Equation (A-2-2)

[0058] Equation (A-2-3)

[0059] Equation (A-2-4)

[0060] Equation (A-2-5)

[0061] Equation (A-2-6) Where n1 is the average number of repeating units, and is a value from 1 to 20.

[0062] In an exemplary embodiment, the maleimide resin containing the indane structure of formula (3) may include the structure shown in formula (3-1): Equation (A-3-1) Among them, Re1~Re2, Rh1~Rh2, Rk1~Rk2, R 23 R 26 Each is an alkyl group with 1 to 4 hydrogen or carbon atoms; n2 and n3 are the number of repeating units, each with a value of 0 to 20, and n2 + n3 has a value of 0.5 to 20.

[0063] In one exemplary embodiment, the maleimide resin containing the indane structure of formula (A-3-1) can be exemplified by the structures shown in formulas (A-3-2) to (A-3-8), but is not limited thereto:

[0064] Equation (A-3-2)

[0065] Equation (A-3-3)

[0066] Equation (A-3-4)

[0067] Equation (A-3-5)

[0068] Equation (A-3-6)

[0069] Equation (A-3-7)

[0070] Equation (A-3-8) In the structures of equations (A-3-2) to (A-3-8), n2 and n3 are the average number of repeating units, and each is an independent value of 0 to 20, and n2 + n3 is a value of 0.5 to 20.

[0071] In one exemplary embodiment, the maleimide resin containing the indum structure may be a maleimide resin manufactured by DIC (Dai Nippon Ink Chemical Co., Ltd.) under the trade names X9-470, NE-X-9470S, NE-X-9480, or other commercially available or self-synthesized bismaleimide resin containing the indum structure.

[0072] (B) Amine-modified hydrogenated styrene polymers The molecular structure of amine-modified hydrogenated styrene polymers contains an amino group and styrene monomer units. The amino group can be a primary or secondary amino group, and its position in the molecular chain is not limited; for example, it can be located at the end of the molecular chain, in the side chain, on the main chain, or on the benzene ring. Hydrogenation refers to the process of converting the conjugated diene bond in the styrene polymer into a saturated bond through a hydrogenation reaction; this can be partial or complete hydrogenation.

[0073] There are no particular limitations on the method for amine modification of styrene-based polymers. Any known method may be used, such as, but not limited to, a method of amine modification by polymerizing block copolymers using an amino-containing polymerization initiator; a method of amine modification of polymers by using an amino-containing unsaturated monomer as a polymerization raw material; or a method of amine modification by reacting an amino-modifying agent having two or more amino groups with a styrene-based polymer containing carboxyl groups to form an amide structure or an imide structure.

[0074] In one exemplary embodiment, the amino-modified hydrogenated styrene polymer includes amino-modified hydrogenated styrene-butadiene copolymer, amino-modified hydrogenated styrene-isoprene copolymer, amino-modified hydrogenated styrene-butadiene-styrene copolymer, amino-modified hydrogenated styrene-isoprene-styrene copolymer, amino-modified hydrogenated styrene-isobutylene-styrene copolymer, or combinations thereof.

[0075] In one exemplary embodiment, the weight-average molecular weight (Mw) of the amino-modified hydrogenated styrene polymer is between 40,000 and 80,000, for example, but not limited to 40,000, 44,000, 45,000, 47,000, 50,000, 55,000, 57,000, 58,000, 59,000, 60,000, 65,000, 70,000, 80,000, or any range between the two. The weight-average molecular weight is determined by gel permeation chromatography (GPC). The determination method is as follows: using a WATERS 1515 instrument, tetrahydrofuran as the mobile phase, a Styragel HR4 7.8*300mm column, a flow rate of 1 ml / min, a tetrahydrofuran solution with a sample concentration of 1–3 mg / ml, an injection volume of 200 μL, and after injection, the instrument acquires data to obtain a molecular weight distribution chromatogram. The test results are obtained by processing the data using the instrument software.

[0076] In one exemplary embodiment, the styrene monomer unit content of the amino-modified hydrogenated styrene polymer is between 10 wt% and 50 wt%, for example, but not limited to, between 15 wt% and 45 wt%, between 20 wt% and 40 wt%, or between 25 wt% and 35 wt%.

[0077] In one exemplary embodiment, from the perspective of dielectric properties, the amino-modified hydrogenated styrene polymer is more preferably an amino-modified hydrogenated styrene-butadiene-styrene copolymer or an amino-modified hydrogenated styrene-isoprene-styrene copolymer.

[0078] In one exemplary embodiment, the amino-modified hydrogenated styrene polymer may be traded under the names Tuftec N528, Tuftec MP10, or Tuftec MPLH. 01. Tuftec MPHF 02. Tuftec N501 and other amino-modified hydrogenated styrene polymers produced by Asahi Kasei Chemicals Co., Ltd.

[0079] In one exemplary embodiment, the amount of the amino-modified hydrogenated styrene polymer is preferably 5 to 30 parts by weight relative to 100 parts by weight of the maleimide resin containing an indane structure, for example, but not limited to 5, 8, 10, 12, 15, 18, 20, 25, 28, or 30 parts by weight. In one embodiment, the addition of the above-mentioned amount of the amino-modified hydrogenated styrene polymer tends to improve at least one of the following: X-axis coefficient of thermal expansion, carrier copper tensile strength, heat resistance after moisture absorption, water absorption rate after pressure cooking, interlayer tensile strength, and elongated bubble streaks.

[0080] (C) Phosphate resins capped with (meth)acrylate: The structure of the (meth)acrylate-terminated phosphate resin is shown in Formula (I):

[0081] Formula (I) Among them, R L1 and R L7 Each can be H or CH3, R independently L2 R L3 R L4 R L5 and R L6 Each y2, y3, y4, y5, and y6 are each an integer from 0 to 4, where y2 + y3 + y4 + y5 + y6 ≥ 5. The presence of multiple R... L2 R L3 R L4 R L5 Or R L6 In the case of multiple R L2 R L3 R L4 R L5 RL6 can be the same or different, and z is an integer from 0 to 10.

[0082] In formula (I), y2, y3, y4, y5 and y6 represent the number of substitutions of the alkyl group attached to the benzene ring, wherein y2, y3 and y4 are preferably integers from 1 to 3, y5 and y6 are preferably integers from 0 to 3, and more preferably, y2, y3, y4, y5 and y6 are 0, 2 or 3.

[0083] For example, in one exemplary embodiment, R L2 R L3 R L4 R L5 and R L6 Specific examples include, but are not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, etc., with methyl being preferred. When multiple R... L2 R L3 R L4 R L5 Or R L6 In the case of multiple R L2 R L3 R L4 R L5 Or R L6 They can be the same or different. For example, in an exemplary embodiment, when y2 is 2, an R L2 It can be methyl, and the other R L2 It can be ethyl; in another exemplary embodiment, when y2 is 2, the two R... L2 Both can be methyl.

[0084] The substitution position of (meth)acrylate on the benzene ring is not particularly limited, but is preferably at the para position of the phosphate ester bond. L2 R L3 R L4 R L5 and R L6 The substitution position on the benzene ring is not particularly limited. R is preferred. L2 R L3 R L4 R L5 and R L6 The substituents are independently located at the ortho or meta position relative to the phosphate ester bond, and R L2 R L3 and R L4 At least one of the substituents is present at the meta position, R L5 and R L6 At least one of the substituents exists in the adjacent position.

[0085] In formula (I), z is an integer from 0 to 10, representing the number of repetitions of the phosphate ester bond. z is preferably an integer from 0 to 5, and more preferably an integer from 0 to 3.

[0086] The phosphorus content in the (meth)acrylate-terminated phosphate resin shown in Formula (I) is preferably 2.0% to 10.0% by weight. For example, the phosphorus content is 2.5%, 3.0%, 3.5%, 4.0%, 4.5%, 5.0%, 5.5%, 6.0%, 7.0%, 7.5%, 8.0%, 8.5%, 9.0%, and 10.0%. Unless otherwise specified, the phosphorus content is calculated as: relative atomic weight of phosphorus atoms * number of atoms / molecular weight of the compound * 100%.

[0087] For example, in one exemplary embodiment, the (meth)acrylate-terminated phosphate resin comprises any one or a combination thereof of the structures shown in formula (I-1).

[0088]

[0089] Formula (I-1) Among them, R L1 and R L7 Each of them is H or CH3 independently, Rj1, Rj2, and Rj3 are H or CH3, K1, K2, and K3 are 0, 1, or 2, and W is 0, 1, 2, or 3.

[0090] In one exemplary embodiment, the phosphorus content of the (meth)acrylate-terminated phosphate resin shown in formula (I-1) is greater than or equal to 5.0%, greater than or equal to 7.0%, or greater than or equal to 8.0%, and is not limited thereto. When R L1 R L7 When Rj1, Rj2, and Rj3 are CH3, and Rj1, Rj2, and Rj3 are H, and W=0, the phosphorus content of the (meth)acrylate-terminated phosphate resin with the structure shown in formula (I-1) is 5.36%; in an exemplary embodiment, when R L1 R L7 When Rj1, Rj2, and Rj3 are CH3, and Rj1, Rj2, and Rj3 are H, and W=1, the phosphorus content of the (meth)acrylate-terminated phosphate resin with the structure shown in formula (I-1) is 7.03%; in an exemplary embodiment, when R... L1 R L7 When Rj1, Rj2, and Rj3 are CH3, and Rj1, Rj2, and Rj3 are H, and W=2, the phosphorus content of the (meth)acrylate-terminated phosphate resin with the structure shown in formula (I-1) is 7.84%; in an exemplary embodiment, when R... L1 R L7 When the phosphate resin with (meth)acrylate end-capped by CH3, Rj1, Rj2 and Rj are H, and W=3, the phosphorus content of the phosphate resin with the structure shown in formula (I-1) is 8.32%.

[0091] In one exemplary embodiment, the (meth)acrylate-terminated phosphate resin with the structure shown in Formula (I) can be purchased from Nippon Steel Chemicals' trade name VX2309 (meth)acrylate-terminated phosphate resin, or can be synthesized by known methods, but is not limited thereto.

[0092] In one exemplary embodiment, the amount of (meth)acrylate-terminated phosphate resin is preferably 10 to 30 parts by weight, for example, but not limited to, 10, 15, 20, 25, 28, or 30 parts by weight, relative to 100 parts by weight of maleimide resin containing an indene structure. In one exemplary embodiment, the addition of the above-mentioned amount of (meth)acrylate-terminated phosphate resin tends to improve at least one of dielectric loss, X-axis coefficient of thermal expansion, carrier copper tensile strength, heat resistance after moisture absorption, water absorption rate after pressure cooking, interlayer tensile strength, and elongated bubble streaks.

[0093] (D) Vinyl polyphenylene ether resin The vinyl-containing polyphenylene ether resin used in this invention refers to a polyphenylene ether compound or mixture having an vinyl carbon-carbon double bond (C=C) or its derivative functional groups. Examples of the aforementioned vinyl carbon-carbon double bond (C=C) or its derivative functional groups may include, but are not limited to, functional groups containing vinyl, vinylidene, allyl, vinylbenzyl, methacrylate, etc., in the structure. Unless otherwise specified, the position of the aforementioned functional groups is not particularly limited; for example, they may be located at the end of a long chain structure. In other words, in this invention, for example, a vinyl-containing polyphenylene ether resin represents a polyphenylene ether resin containing reactive vinyl or its derivative functional groups, examples of which may include, but are not limited to, polyphenylene ether resins containing vinyl, vinylidene, allyl, vinylbenzyl, or methacrylate.

[0094] In one exemplary embodiment, the vinyl-containing polyphenylene ether resin used in this invention includes terminal vinyl benzyl polyphenylene ether resin, terminal methacrylate polyphenylene ether resin (i.e., terminal methacryloyl polyphenylene ether resin), terminal allyl polyphenylene ether resin, or a combination thereof.

[0095] In one exemplary embodiment, the vinyl polyphenylene ether resin may be a methacrylate polyphenylene ether resin (e.g., SA9000, available from Sabic Corporation), a vinyl benzyl polyphenylene ether resin with a number average molecular weight of approximately 1200 (e.g., OPE-2st 1200, available from Mitsubishi Gas Chemical Corporation), a vinyl benzyl polyphenylene ether resin with a number average molecular weight of approximately 2200 (e.g., OPE-2st 2200, available from Mitsubishi Gas Chemical Corporation), a vinyl benzyl modified bisphenol A polyphenylene ether resin with a number average molecular weight of approximately 2400 to 2800, a vinyl chain-extended polyphenylene ether resin with a number average molecular weight of approximately 2200 to 3000, or a combination thereof. The vinyl chain-extended polyphenylene ether resin may include various polyphenylene ether resins disclosed in U.S. Patent Application Publication No. 2016 / 0185904 A1, the entire contents of which are incorporated herein by reference.

[0096] In one exemplary embodiment, the amount of vinyl polyphenylene ether resin is preferably 10 to 30 parts by weight, for example, but not limited to, 10, 12, 15, 18, 20, 25, 28, or 30 parts by weight, relative to 100 parts by weight of maleimide resin containing an indane structure. In one exemplary embodiment, adding the above-mentioned amount of vinyl polyphenylene ether resin tends to improve at least one of dielectric loss, X-axis coefficient of thermal expansion, carrier copper tensile strength, heat resistance after moisture absorption, water absorption rate after pressure cooking, interlayer tensile strength, and elongated bubble streaks.

[0097] In one exemplary embodiment, the resin composition may further include at least one of the following: a vinyl crosslinking agent, a maleimide triazine resin, a styrene maleic anhydride resin, an epoxy resin, a phenolic resin, a benzoxazine resin, a cyanate ester resin, a polyester resin, a polyamide resin, and a polyimide resin.

[0098] In one exemplary embodiment, the resin composition includes a vinyl-containing crosslinking agent. The vinyl-containing crosslinking agent refers to a compound, polymer, or mixture having an vinyl carbon-carbon double bond (C=C) or a derivative functional group therein, and capable of crosslinking with maleimide resins. Furthermore, the vinyl-containing crosslinking agent differs from the aforementioned maleimide resins containing an indane structure.

[0099] For example, the vinyl crosslinking agent refers to a vinyl compound or polymer with a molecular weight of less than or equal to 5,000, preferably with a molecular weight between 100 and 4,000, and more preferably with a molecular weight between 100 and 3,000.

[0100] For example, vinyl crosslinking agents may include styrene, divinylbenzene, divinylnaphthalene, divinylbiphenyl, tert-butylstyrene, bis(vinylbenzyl) ether, 1,2,4-trivinylcyclohexane (TVCH), bis(vinylphenyl) ethane (BVPE), di(vinylphenyl) hexane, divinylphenyldimethyl ether, divinylphenyldimethylbenzene, triallyl isocyanurate (TAIC), triallyl cyanurate (TAC), diallyl bisphenol A, butadiene, decanadiene, octadiene, vinylcarbazole, acrylates, or combinations thereof, but the invention is not limited thereto and also includes isomers or polymers of these components.

[0101] In one exemplary embodiment, the resin composition comprises a maleimide triazine resin. The maleimide triazine resin may be any one or more maleimide triazine resins suitable for manufacturing prepregs, resin films, laminates, printed circuit boards, or cured insulators. The maleimide triazine resin may be obtained by polymerizing a cyanate ester resin with a maleimide resin, particularly by polymerizing a bisphenol A cyanate ester resin with a maleimide resin, a bisphenol F cyanate ester resin with a maleimide resin, a phenolic phenolic cyanate ester resin with a maleimide resin, or a dicyclopentadiene-containing cyanate ester resin with a maleimide resin. Maleimide triazine resin can be obtained by polymerization of cyanate resin and maleimide resin in any molar ratio, particularly by polymerization of cyanate resin and maleimide resin in a molar ratio of (1-10):1, especially (1-6):1, and even more particularly 1:1, 2:1, 4:1 or 6:1.

[0102] In one exemplary embodiment, the resin composition comprises a styrene-maleic anhydride resin. The molar ratio of styrene to maleic anhydride in the styrene-maleic anhydride resin may be (1–8):1, for example, 1:1, 2:1, 3:1, 4:1, 6:1, or 8:1. The styrene-maleic anhydride resin may be a styrene-maleic anhydride copolymer. The styrene-maleic anhydride copolymer may be a styrene-maleic anhydride copolymer purchased from Cray Valley under trade names such as SMA-1000, SMA-2000, SMA-3000, EF-30, EF-40, EF-60, EF-80, etc., or a styrene-maleic anhydride copolymer sold by Polyscope under trade names such as C400, C500, C700, C900, etc., but is not limited thereto. The styrene-maleic anhydride resin may be an esterified styrene-maleic anhydride copolymer. The esterified styrene-maleic anhydride copolymer may be, but is not limited to, esterified styrene-maleic anhydride copolymers purchased from Cray Valley under trade names such as SMA1440, SMA17352, SMA2625, SMA3840, and SMA31890. The resin composition may include one of the styrene-maleic anhydride resins, or a combination of multiple styrene-maleic anhydride resins.

[0103] In one exemplary embodiment, the resin composition may further comprise an epoxy resin. For example, the epoxy resin may be any type of epoxy resin known in the art, including but not limited to bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AD ​​epoxy resin, phenolic (novolac) epoxy resin (e.g., multifunctional phenolic epoxy resin), trifunctional epoxy resin, tetrafunctional epoxy resin, dicyclopentadiene (DCPD) epoxy resin, phosphorus-containing epoxy resin, p-xylene epoxy resin, naphthalene-type epoxy resin (e.g., naphthol-type epoxy resin), benzofuran-type epoxy resin, isocyanate-modified epoxy resin, or combinations thereof.

[0104] Phenolic epoxy resins may be phenol novolac epoxy resins, bisphenol A novolac epoxy resins, bisphenol F novolac epoxy resins, biphenylnovolac epoxy resins, phenol benzaldehyde epoxy resins, phenolaralkyl novolac epoxy resins, or o-cresol novolac epoxy resins, or combinations thereof.

[0105] The phosphorus-containing epoxy resin may be DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) epoxy resin, DOPO-HQ epoxy resin, or a combination thereof. The aforementioned DOPO epoxy resin may be selected from one or more of the following: DOPO-containing phenolic novolac epoxy resin, DOPO-containing cresol novolac epoxy resin, and DOPO-containing bisphenol-A novolac epoxy resin; the aforementioned DOPO-HQ epoxy resin may be selected from at least one of the following: DOPO-containing phenolic novolacepoxy resin, DOPO-HQ-containing cresol novolacepoxy resin, and DOPO-HQ-containing bisphenol-A novolac epoxy resin.

[0106] In one exemplary embodiment, the epoxy resin may include biphenyl-type phenolic epoxy resin, dicyclopentadiene epoxy resin, o-methylphenolic epoxy resin, naphthol-type epoxy resin, or a combination thereof. In one exemplary embodiment, the resin composition comprises a phenolic resin. The phenolic resin may be a monofunctional phenolic resin, a polyfunctional phenolic resin, or a combination thereof, but is not limited thereto. The phenolic resin may include phenoxy resin, phenolic resin, or a combination thereof, but is not limited thereto.

[0107] In one exemplary embodiment, the resin composition comprises a benzoxazine resin. The benzoxazine resin may include, but is not limited to, bisphenol A type benzoxazine resin, bisphenol F type benzoxazine resin, phenolphthalein type benzoxazine resin, dicyclopentadiene benzoxazine resin, phosphorus-containing benzoxazine resin, diamine type benzoxazine resin, and vinyl or allyl modified benzoxazine resins or combinations thereof. Examples of benzoxazine resins include, for instance, Huntsman's trade name LZ-8270 (phenolphthalein type benzoxazine resin), LZ-8280 (bisphenol F type benzoxazine resin), LZ-8290 (bisphenol A type benzoxazine resin), or Showa Polymer's trade name HFB-2006M. The diamine-type benzoxazine resin may be a diaminodiphenylmethane benzoxazine resin, a diaminodiphenyl ether benzoxazine resin, a diaminodiphenyl sulfone benzoxazine resin, a diaminodiphenyl sulfide benzoxazine resin, or a combination thereof.

[0108] In one exemplary embodiment, the resin composition comprises a cyanate ester resin. The cyanate ester resin may be any type of cyanate ester resin known in the art. The cyanate ester resin may include, but is not limited to, a cyanate ester resin having an Ar–O–C≡N structure (where Ar is an aromatic group, such as benzene, naphthalene, or anthracene). The cyanate ester resin may include, but is not limited to, phenolic cyanate ester resins, bisphenol A cyanate ester resins, bisphenol A phenolic cyanate ester resins, bisphenol F cyanate ester resins, bisphenol F phenolic cyanate ester resins, cyanate ester resins containing a dicyclopentadiene structure, cyanate ester resins containing a naphthalene ring structure, phenolphthalein cyanate ester resins, or combinations thereof. Cyanate ester resins may include, but are not limited to, cyanate ester resins manufactured by Lonza under trade names such as Primaset PT-15, PT-30S, PT-60S, BA-200, BA-230S, BA-3000S, BTP-2500, BTP-6020S, DT-4000, DT-7000, ULL950S, HTL-300, CE-320, LVT-50, LeCy, etc.

[0109] In one exemplary embodiment, the resin composition comprises a polyester resin. The polyester resin is formed by esterification of an aromatic compound having a dicarboxylic acid group with an aromatic compound having a dihydroxyl group. The polyester resin may be, but is not limited to, HPC-8000, HPC-8150, HPC-8200, or combinations thereof, available from Dai Nippon Ink Chemical Co., Ltd.

[0110] In one exemplary embodiment, the resin composition comprises a polyamide resin. The polyamide resin may be any type of polyamide resin known in the art, including but not limited to various commercially available polyamide resin products.

[0111] In one exemplary embodiment, the resin composition comprises a polyimide resin. The polyimide resin may be any type of polyimide resin known in the art, including but not limited to various commercially available polyimide resin products.

[0112] In one exemplary embodiment, the resin composition disclosed in this invention may further include, as needed, amine curing agents, inorganic fillers, curing accelerators, polymerization inhibitors, colorants, solvents, toughening agents, silane coupling agents, or combinations thereof.

[0113] In one exemplary embodiment, the resin composition includes an amine curing agent. The amine curing agent may include, but is not limited to, dicyandiamide, diaminodiphenyl sulfone, diaminodiphenylmethane, diaminodiphenyl ether, diaminodiphenyl sulfide, or combinations thereof.

[0114] In one exemplary embodiment, the resin composition includes an inorganic filler. The inorganic filler may be any one or more fillers suitable for manufacturing resin films, prepregs, laminates, printed circuit boards, or cured insulators. The inorganic filler may be silica (molten, non-molten, porous, or hollow), alumina, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, silicon aluminum carbide, silicon carbide, titanium dioxide, zinc oxide, zirconium oxide, mica, boehmite (AlOOH), calcined talc, talc, silicon nitride, calcined kaolin, or combinations thereof, but is not limited thereto. The inorganic filler may be spherical, fibrous, plate-like, granular, flake-like, or needle-like. The inorganic filler may be pretreated with a silane coupling agent. The inorganic filler may be spherical silica with a surface treated with an acrylate-based silane coupling agent.

[0115] The amount of the inorganic filler is not particularly limited. In one exemplary embodiment, the resin composition may contain 20 to 350 parts by weight of inorganic filler, preferably 30 to 300 parts by weight, but not limited thereto, based on 100 parts by weight of all resins in the resin composition (excluding silane coupling agents, curing accelerators, solvents and inorganic fillers).

[0116] In one exemplary embodiment, the resin composition includes a curing accelerator. The curing accelerator may include catalysts such as Lewis bases and Lewis acids. Lewis bases may include, but are not limited to, imidazole, boron trifluoride amine complex, ethyltriphenyl phosphonium chloride, 2-methylimidazole (2MI), 2-phenyl-1H-imidazole (2PZ), 2-ethyl-4-methylimidazole (2E4MI), triphenylphosphine (TPP), 4-dimethylaminopyridine (DMAP), or combinations thereof. Lewis acids may include metal salt compounds, such as manganese, iron, cobalt, nickel, copper, and zinc salts, particularly metal catalysts such as zinc octoate and cobalt octoate. The curing accelerator may include a curing initiator (i.e., an initiator). The curing initiator may include peroxides that can generate free radicals. Curing initiators include, but are not limited to, 2,3-dimethyl-2,3-diphenylbutane, dicumyl peroxide, tert-butyl peroxide, tert-butyl isopropyl percarbonate, dibenzoyl peroxide (BPO), 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne (25B), bis(tert-butylperoxyisopropyl)benzene, azobisisobutyronitrile, or combinations thereof. For example, in one exemplary embodiment, the resin composition of the present invention may further include 0.01 to 2.0 parts by weight of a curing accelerator, preferably 0.1 to 1.0 parts by weight, but not limited to, relative to 100 parts by weight of maleimide resin.

[0117] In one exemplary embodiment, the resin composition includes a polymerization inhibitor. The polymerization inhibitor may be any type of polymerization inhibitor known in the art, including but not limited to various commercially available polymerization inhibitor products. The polymerization inhibitor may include, but is not limited to, 1,1-diphenyl-2-trinitrophenylhydrazine, methacrylonitrile, disulfide, nitroxide-stabilized free radicals, triphenylmethyl free radicals, metal ion free radicals, sulfur free radicals, hydroquinone, p-methoxyphenol, p-benzoquinone, phenthiazide, β-phenylnaphthylamine, p-tert-butylcatechol, methylene blue, 4,4′-butylenebis(6-tert-butyl-3-methylphenol), 2,2′-methylenebis(4-ethyl-6-tert-butylphenol), or combinations thereof, but is not limited thereto. The polymerization inhibitor may include or consist of nitroxide-stabilized free radicals. Nitrogen oxide-stabilized free radicals may include, but are not limited to, 2,2,6,6-tetrasubstituted piperidine-1-oxo radicals, 2,2,5,5-tetrasubstituted pyrrolidine-1-oxo radicals, or combinations thereof derived from cyclic hydroxylamines. The term "substituent" here refers to alkyl groups having 4 or fewer carbon atoms, such as methyl, ethyl, propyl, butyl, particularly methyl or ethyl. Nitrogen oxide-stabilized free radicals may be, but are not limited to, 2,2,6,6-tetramethylpiperidine-1-oxo radicals, 2,2,6,6-tetraethylpiperidine-1-oxo radicals, 2,2,6,6-tetramethyl-4-oxopiridine-1-oxo radicals, 2,2,5,5-tetramethylpyrrolidine-1-oxo radicals, 1,1,3,3-tetramethylisoindoline-2-oxo radicals, N,N-di-tert-butylamine-oxo radicals, or combinations thereof. Stable free radicals such as galvinoxyl radicals can also be used to replace nitrogen and oxygen free radicals. Inhibitors can also be products derived from the substitution of hydrogen atoms or groups in the aforementioned inhibitors by other atoms or groups, such as products derived from the substitution of hydrogen atoms in the inhibitor by amino, hydroxyl, or ketone carbonyl groups.

[0118] In one exemplary embodiment, the resin composition includes a dyeing agent. The dyeing agent may include, but is not limited to, dyes or pigments.

[0119] In one exemplary embodiment, the resin composition includes a solvent. Adding a solvent can alter the solid content of the resin composition and adjust its viscosity. Solvents may include, but are not limited to, methanol, ethanol, ethylene glycol monomethyl ether, acetone, butanone (also known as methyl ethyl ketone), methyl isobutyl ketone, cyclohexanone, toluene, xylene, methoxyethyl acetate, ethoxyethyl acetate, propoxyethyl acetate, ethyl acetate, dimethylformamide, dimethylacetamide, propylene glycol methyl ether, or combinations thereof. The solvent added to the resin composition may evaporate and be removed during the processing of the resin composition into a prepreg or resin film, so that the insulating layer of the prepreg or resin film contains no solvent or only trace amounts of solvent less than or equal to 3 wt% (i.e., 3% by weight). Therefore, the presence or absence of solvent in the resin composition does not affect the properties of the product.

[0120] In one exemplary embodiment, the resin composition includes a toughening agent. The toughening agent can improve the toughness of the resin composition. The toughening agent may include, but is not limited to, carboxyl-terminated butadieneacrylonitrile rubber (CTBN), core-shell rubber, or combinations thereof.

[0121] In one exemplary embodiment, the resin composition includes a silane coupling agent. The silane coupling agent may include silane compounds, including but not limited to siloxane compounds. Silane coupling agents may include, but are not limited to, amino silane compounds, epoxide silane compounds, vinyl silane compounds, acrylate-based silane compounds, methacrylate-based silane compounds, hydroxysilane compounds, isocyanate-based silane compounds, methacryloxysilane compounds, acryloyloxysilane compounds, or combinations thereof, but are not limited thereto.

[0122] The resin compositions of the foregoing embodiments can be made into various articles, such as components used in various electronic products, including but not limited to prepregs, resin films, laminates, printed circuit boards, or cured insulators.

[0123] The article may include the resin composition in a semi-cured (B-stage) or cured (C-stage) state. The article may include a resin layer, which is the resin composition in a semi-cured or cured state. The article may include an insulating layer, which is the resin composition in a cured state.

[0124] In one exemplary embodiment, the present invention provides a prepreg. The prepreg may include a reinforcing material and a semi-cured layer disposed on the reinforcing material, wherein the semi-cured layer is a semi-cured resin composition. The semi-cured layer can be obtained by heating the resin composition to form a semi-cured state. In one exemplary embodiment, the present invention provides a method for preparing a prepreg, comprising: disposing a resin composition on a reinforcing material, semi-curing the resin composition, particularly heating the resin composition, to form a prepreg comprising the reinforcing material and the semi-cured layer. Disposing the resin composition on the reinforcing material may include coating the resin composition onto the reinforcing material. The heating may be baking heating. The heating may be heating to a semi-curing temperature. The semi-curing temperature may be between 100°C and 200°C. The reinforcing material may be a fibrous material, woven fabric, nonwoven fabric, or a combination thereof, and is not limited thereto. The woven fabric may include fiberglass cloth. There is no particular limitation on the type of fiberglass cloth; it may be commercially available fiberglass cloth suitable for various printed circuit boards. The fiberglass cloth can be type E, type D, type S, type T, type L, or type Q, wherein the fiber type includes yarn or roving, and the form can include open or closed fibers. The fabric can include liquid crystal resin fabric. Liquid crystal resin fabric can include polyester fabric, polyurethane fabric, or combinations thereof, and is not limited thereto. The nonwoven fabric can include liquid crystal resin nonwoven fabric. Liquid crystal resin nonwoven fabric can include polyester nonwoven fabric, polyurethane nonwoven fabric, or combinations thereof, and is not limited thereto. The reinforcing material can, for example, increase the mechanical strength of the prepreg. In an exemplary embodiment, the reinforcing material can also be pretreated with a silane coupling agent.

[0125] In one exemplary embodiment, the present invention provides a resin film. The resin film may include a semi-cured resin composition. In one aspect, the present invention provides a method for preparing a resin film, including semi-curing the resin composition, particularly heating the resin composition. The method for preparing the resin film may further include coating the resin composition onto a substrate. In one exemplary embodiment, the present invention provides a resin film assembly, including a substrate and the resin film disposed on the substrate. In one aspect, the present invention provides a method for preparing a resin film assembly, including providing a substrate and disposing the resin film on the substrate. In one exemplary embodiment, disposing the resin film on the substrate includes: coating the resin composition onto the substrate, and semi-curing the resin composition, particularly heating the resin composition. The substrate may be a polyethylene terephthalate film (PET film), a polyimide film (PI film), copper foil, adhesive-backed copper foil, or a combination thereof, but is not limited thereto. The heating may be, for example, baking heating. The heating may be heating to a semi-curing temperature. The semi-curing temperature may be between 100°C and 200°C.

[0126] In one exemplary embodiment, the present invention provides a laminate. The laminate may include at least two metal foils and an insulating layer disposed between the metal foils. In one exemplary embodiment, the insulating layer separates the metal foils. The metal foils may include copper, aluminum, nickel, platinum, silver, gold, or alloys thereof, particularly copper foil. The insulating layer may be obtained by heating and curing the aforementioned resin composition or the aforementioned semi-cured resin composition. The heating may be, for example, baking. The heating and curing may be heating to a curing temperature. The curing temperature may be between 180°C and 250°C, particularly between 210°C and 240°C. The curing time may be between 80 minutes and 180 minutes, particularly between 100 minutes and 150 minutes. The curing may further include applying pressure to the semi-cured resin composition. The insulating layer may be formed by curing the aforementioned semi-cured sheet or resin film (C-stage). The laminate may be, for example, a copper clad laminate (CCL).

[0127] The multilayer board can be further processed into a circuit board, such as a printed circuit board, through circuit fabrication processes. One method of manufacturing the printed circuit board of this invention involves using a double-sided copper-clad laminate (e.g., product EM-890, available from Taikoo Electronics Materials) of a certain thickness, for example 28 mil, with a 0.5 ounce (oz) HVLP (hyper very low profile), copper foil. After drilling, electroplating is performed to create electrical conductivity between the upper and lower copper foil layers. The upper and lower copper foil layers are then etched to form the inner layer circuitry. Next, the inner layer circuitry undergoes a browning roughening treatment to create a surface texture and increase roughness. Then, the copper foil, the aforementioned prepreg, the aforementioned inner layer circuit board, the aforementioned prepreg, and the copper foil are stacked sequentially, and then heated in a vacuum lamination apparatus at a temperature of 180°C to 250°C for 80 to 180 minutes to cure the insulating layer material of the prepreg. Next, various circuit board processes known in the art, such as blackening, drilling, and copper plating, are performed on the outermost copper foil to obtain a printed circuit board.

[0128] In one exemplary embodiment, the present invention provides a cured insulator. In another exemplary embodiment, the present invention provides a method for preparing a cured insulator, comprising: curing the resin composition once or curing the resin composition through a multiple curing process. Multiple curing refers to two or more curing processes. For example, the resin composition may be semi-cured first, particularly by heating the resin composition to obtain a semi-cured resin composition; then the semi-cured resin composition may be further cured, particularly by heating the semi-cured resin composition. The cured insulator may include the cured resin composition, the cured resin composition containing reinforcing materials, or a combination thereof. Heating may be, for example, baking. In one embodiment, the semi-curing of the resin composition is achieved by heating to a semi-curing temperature. The semi-curing temperature may be 100°C to 200°C.

[0129] In one exemplary embodiment, the primary curing of the resin composition or the curing of the semi-cured resin composition is performed by heating to a curing temperature. The curing temperature may be between 180°C and 250°C, preferably between 210°C and 240°C. In one exemplary embodiment, the curing time is between 80 minutes and 180 minutes, particularly between 100 minutes and 150 minutes. The curing may further include applying pressure to the resin composition or the semi-cured resin composition.

[0130] The cured insulator may include the cured resin composition. In one exemplary embodiment, the present invention provides a method for preparing a cured insulator, comprising: curing the resin film, particularly heating the resin film. The method for preparing a cured insulator may further comprise coating the resin composition onto a substrate, and / or semi-curing the resin composition to form a resin film.

[0131] The cured insulator may include the cured resin composition in a cured state containing reinforcing material. In an exemplary embodiment, the present invention provides a method for preparing a cured insulator, comprising: curing the prepreg, particularly heating the prepreg. The method for preparing a cured insulator may further comprise disposing a resin composition on a reinforcing material, prepreg, particularly heating the resin composition, to form a prepreg comprising the reinforcing material and a prepreg layer.

[0132] The method for preparing the cured insulator may further include molding. For example, the resin composition or semi-cured resin composition may be placed in a mold, and the resin composition or semi-cured resin composition may be formed and cured in the mold under curing temperature and certain pressure to obtain a cured insulator of a specific shape.

[0133] The cured insulator may be an insulating layer with a metal-free surface obtained by removing the surface metal foil from the aforementioned laminate or printed circuit board.

[0134] Preferably, the resin composition or product thereof provided by the present invention can be improved in one or more aspects such as dielectric loss, X-axis coefficient of thermal expansion, carrier copper tensile strength, heat resistance after moisture absorption (PCT), water absorption rate after pressure cooking, interlayer tensile strength or elongated bubble streaks.

[0135] For example, the resin composition or articles thereof provided by the present invention may satisfy one, more or all of the following characteristics: The dielectric loss measured at a frequency of 10 GHz using the method described in JISC2565 is less than or equal to 0.00180. The X-axis thermal expansion coefficient measured according to the method described in IPC-TM-650 2.4.24.5 is less than or equal to 9.3 ppm / ℃; The carrier copper tensile strength measured according to the method described in IPC-TM-650 2.4.8 is greater than or equal to 4.60 lb / in; After absorbing moisture for 5 hours according to the methods described in IPC-TM-650 2.6.16.1 and IPC-TM-650 2.4.23, no heat resistance test was performed and no plate bursting occurred. The water absorption rate measured after moisture absorption by pressure cooking test (PCT) according to the method described in IPC-TM-650 2.6.16.1 is less than or equal to 0.35%; The interlaminar tensile strength measured according to the method described in IPC-TM-650 2.4.8 is greater than or equal to 3.38 lb / in; The product was observed to be free of elongated bubble streaks under an optical microscope.

[0136] This invention uses various raw materials from the following sources, and prepares the resin compositions of the embodiments and comparative examples of this invention according to the amounts in Tables 1 to 3, and further manufactures them into various test samples or articles. The composition and test results of the resin compositions of the embodiments and comparative examples are shown in Tables 4 and 5 (all units are parts by weight).

[0137] X9-470: Maleimide resin with the structure shown in formula (A-2-3), purchased from DIC.

[0138] BMI-1: Maleimide resin with the structure shown in formula (A-3-4): commercially available, wherein n2 is a value of 0 to 20, n3 is a value of 0 to 20, and n2+n3 is a value of 0.5 to 20.

[0139] BMI-2300: Benzene maleimide oligomer, purchased from Yamato Chemical.

[0140] MIR-3000: Biphenyl aryl maleimide resin (structural formula as follows), where is an integer from 1 to 10, purchased from Nippon Kayaku.

[0141] BMI-3000: A maleimide resin containing an aliphatic long-chain structure, with the structural formula as described above, purchased from the designer molecule.

[0142] N528: Amine-modified hydrogenated styrene-butadiene-styrene copolymer, purchased from Asahi Kasei.

[0143] MP10: Amino-modified hydrogenated styrene-butadiene-styrene copolymer, purchased from Asahi Kasei.

[0144] SKHM-2: Amino-modified hydrogenated styrene-butadiene-styrene copolymer, purchased from Asahi Kasei.

[0145] SKHM-1: Amino-modified hydrogenated styrene-butadiene-styrene copolymer, purchased from Asahi Kasei.

[0146] MPLH-01: Amine-modified hydrogenated styrene-butadiene-styrene copolymer, purchased from Asahi Kasei.

[0147] G1726: Hydrogenated styrene-butadiene-styrene copolymer, purchased from KRATON.

[0148] VX-2309: A phosphate resin with (meth)acrylate end caps as shown in formula (I-1), purchased from Nippon Steel.

[0149] SA9000: Terminal methacrylate polyphenylene ether resin, purchased from Sabic.

[0150] OPE-2st 1200: Terminally vinyl benzyl polyphenylene ether resin, purchased from Mitsubishi Gas Chemical Co., Ltd.

[0151] PX-200: Resorcinol bis-(xylyl phosphate) (condensation polymer), or tetra(2,6-dimethylphenyl) 1,3-phenylene phosphate (condensation polymer), purchased from Daihachi Chemical, Japan.

[0152] SC-2050-SMJ: Spherical silica treated with acrylate-based silane coupling agent, purchased from Admatechs.

[0153] Toluene: Purchased from Qiangdi.

[0154] Butyl ketone (MEK): Commercially available, source is not limited.

[0155] 25B: 2,5-Dimethyl-2,5-Di(tert-butylperoxy)-3-hexyne, purchased from Nippon Oil Co., Ltd.

[0156] In the table, "Z" represents the total amount of all components in the resin composition of each example or comparative example, excluding (i.e., not containing) curing accelerators, inorganic fillers, and solvents. For example, "Z*1.0" means that the amount of inorganic filler added is 1.0 times the aforementioned Z. For example, "Z*1.3" in Example E1 means that the amount of inorganic filler added is 201.5 parts by weight (155 parts by weight multiplied by 1.3).

[0157] In the table, "appropriate amount" for solvent addition means the amount of solvent used to achieve the ideal solid content of the overall resin composition. For resin compositions using both methyl ethyl ketone (MEK) and toluene as solvents, "appropriate amount" means the total amount of these two solvents is sufficient to achieve the ideal solid content of the overall resin composition, for example, but not limited to, a solid content of 70% by weight.

[0158] The composition and test results of the resin compositions in the examples and comparative examples are shown in Tables 1-5 (all units are parts by weight): Table 1: Resin composition of Examples E1-E9 (solvent amount ensures the overall solid content of the resin composition is 70% by weight)

[0159] Table 2: Resin composition of Examples E10-E18 (solvent amount ensures the overall solid content of the resin composition is 75% by weight)

[0160] Table 3: Resin composition of Comparative Examples C1-C13 (solvent amount ensures the overall solid content of the resin composition is 65% by weight)

[0161] The various resin compositions shown in Tables 1-3 were prepared as follows: varnish and various test samples were prepared according to the following methods, and the characteristics were measured according to specific test conditions to obtain test results.

[0162] Varnish (or adhesive) Each of the embodiments (represented by E, such as E1 to E18) or comparative examples (represented by C, such as C1 to C13) is added to a mixing tank according to the amounts in Tables 1 to 3 and stirred. The resin composition formed after uniform mixing is called resin varnish.

[0163] Taking Example E1 as an example, 100 parts by weight of maleimide resin (X9-470) containing indane structure, 20 parts by weight of amino-modified hydrogenated styrene polymer (N528), 20 parts by weight of (meth)acrylate-terminated phosphate resin (VX-2309) and 15 parts by weight of polyphenylene ether resin (SA9000) were added to a stirrer containing an appropriate amount of toluene and an appropriate amount of butanone (the solvent "appropriate amount" in Tables 1-3 represents the amount of solvent used to obtain the ideal solid content of the resin composition, for example, the solid content of the varnish is 70% by weight), and stirred until the solid components were dissolved into a homogeneous liquid phase. Next, add “Z*1.3” parts by weight of spherical silica SC-2050-SMJ (i.e., 201.5 parts by weight) and stir until completely dispersed. Then add 0.5 parts by weight of curing accelerator (25B, which is first dissolved in an appropriate amount of solvent to make the overall solid content of the resin composition 70% by weight) and stir for 1 hour to obtain the varnish of resin composition E1.

[0164] In addition, according to the ingredient amounts listed in Tables 1-3 and the method for preparing the varnish of Example E1, varnishes of other Examples E2-E18 and Comparative Examples C1-C13 were prepared.

[0165] Prepreg 1 (using 2116 L-glass fiber cloth) The resin compositions listed in Tables 1-3 for different examples and comparative examples were added in batches to a mixing tank, mixed evenly, and stirred until completely dissolved into varnish. The resin compositions were then placed in an impregnation tank. Fiberglass cloth (e.g., L-fiberglass cloth of specification 2116) was passed through the impregnation tank to adhere the resin composition to the fiberglass cloth. The mixture was then heated at 150°C to a semi-cured state (B-Stage) to obtain semi-cured sheet 1 (resin content approximately 52%).

[0166] Prepreg 2 (using 1078 L-glass fiber cloth) The resin compositions listed in Tables 1-3 for different examples and comparative examples were added in batches to a mixing tank, mixed evenly, and stirred until completely dissolved into varnish. The resin compositions were then placed in an impregnation tank. Fiberglass cloth (e.g., L-fiberglass cloth of specification 1078) was passed through the impregnation tank to adhere the resin composition to the fiberglass cloth. The mixture was then heated at 120°C to a semi-cured state (B-Stage) to obtain semi-cured sheet 2 (resin content approximately 70%).

[0167] Prepreg 3 (using 1017 L-glass fiber cloth) The resin compositions from the different examples and comparative examples listed in Tables 1 to 3 were added in batches to a mixing tank, mixed evenly, and stirred until completely dissolved into varnish. The resin compositions were then placed in an impregnation tank. Fiberglass cloth (e.g., L-fiberglass cloth of specification 1017) was passed through the impregnation tank to adhere the resin composition to the fiberglass cloth. The mixture was then heated at 110°C to a semi-cured state (B-Stage) to obtain semi-cured sheet 3 (resin content approximately 79%).

[0168] Copper foil substrate 1 (made by laminating eight prepreg sheets 1) Two very low profile copper foils (VLP copper foils) with a thickness of 12 micrometers are prepared in batches, along with eight prepreg sheets (using 2116 L-glass fiber cloth) made from various resin compositions. Each prepreg sheet has a resin content of approximately 52%. The copper foils, eight prepreg sheets, and copper foils are stacked in that order and pressed together under vacuum at 200°C for 2 hours to form the copper foil substrates. The eight stacked prepreg sheets are then cured (C-stage) to form an insulating layer between the two copper foils, with the insulating layer having a resin content of approximately 52%.

[0169] Copper foil substrate 2 (formed by laminating two prepreg sheets 1) Two very low profile copper foils (VLP copper foils) with a thickness of 12 micrometers and two prepreg sheets 1 (using 2116 L-glass fiber cloth) made from various resin compositions are prepared in batches. Each prepreg sheet has a resin content of approximately 52%. The copper foils, the two prepreg sheets 1, and the copper foils are stacked in that order and pressed together under vacuum at 200°C for 2 hours to form the copper foil substrates. The two stacked prepreg sheets are cured (C-stage) to form an insulating layer between the two copper foils, and the insulating layer has a resin content of approximately 52%.

[0170] Copper foil substrate 3 (made by laminating two prepreg sheets 2) Two very low profile copper foils (VLP copper foils) with a thickness of 12 micrometers and two prepregs (using 1078 L-glass fiber cloth) are prepared in batches. Each prepreg has a resin content of approximately 70%. The copper foils, two prepregs, and copper foils are stacked in that order and pressed under vacuum at 200°C for 2 hours to form the copper foil substrates. The two stacked prepregs are cured (C-stage) to form an insulating layer between the two copper foils, with a resin content of approximately 70%.

[0171] Copper foil substrate 4 (formed by laminating a prepreg 2) Two very low profile copper foils (VLP copper foils) with a thickness of 12 micrometers are prepared in batches, along with a prepreg (using 1078 L-glass fiber cloth) made from various resin compositions. Each prepreg has a resin content of approximately 70%. The copper foils, the prepreg, and the copper foils are stacked in that order and pressed together under vacuum at 200°C for 2 hours to form the copper foil substrates. The prepreg cures (C-stage) to form an insulating layer between the two copper foils, with the insulating layer having a resin content of approximately 70%.

[0172] Copper-free substrate 1 (made of eight prepreg sheets 1 laminated together) The copper foil substrate 1 is etched to remove the copper foil on both sides to obtain a copper-free substrate 1, which is formed by pressing eight prepreg sheets 1 together and has a resin content of about 52%.

[0173] Copper-free substrate 2 (made by laminating two prepreg sheets 1) The copper foil substrate 2 is etched to remove the copper foil on both sides to obtain a copper-free substrate 2, which is formed by pressing two prepreg sheets 1 together and has a resin content of about 52%.

[0174] Copper-free substrate 3 (made by laminating two prepreg sheets 2) The copper foil substrate 3 is etched to remove the copper foil on both sides to obtain a copper-free substrate 3, which is formed by pressing two prepreg sheets 2 together and has a resin content of about 70%.

[0175] Copper-free substrate 4 (made by laminating one semi-cured sheet 2) The copper foil substrate 4 is etched to remove the copper foil on both sides to obtain a copper-free substrate 4, which is formed by pressing a prepreg 2 and has a resin content of about 70%.

[0176] The test methods and their characteristic analysis items are described below.

[0177] 1. Dielectric loss (dissipation factor, Df) The copper-free substrate 3 mentioned above was selected as the test sample. The dielectric loss of each test sample was measured at a frequency of 10 GHz using a microwave dielectric constant analyzer (purchased from AET Corporation, Japan) according to the method described in JISC2565.

[0178] A lower dielectric loss indicates better dielectric properties of the sample under test. At a measurement frequency of 10 GHz, when the Df value is less than or equal to 0.00200, a difference in Df value less than 0.00005 indicates that there is no significant difference in dielectric loss between the substrates, while a difference in Df value greater than or equal to 0.00005 indicates that there is a significant difference in dielectric loss between different substrates (which presents significant technical difficulties).

[0179] For example, an article made from the resin composition disclosed in this invention has a dielectric loss of less than or equal to 0.00180 when measured at a frequency of 10 GHz, for example, between 0.00165 and 0.00180, as described by the method in JISC2565.

[0180] 2. X-axis coefficient of thermal expansion (CTE) In the measurement of the X-axis thermal expansion coefficient, the aforementioned copper-free substrate 3 was selected as the test sample for thermomechanical analysis (TMA). The copper-free substrate was cut into samples with a length of 15 mm and a width of 2 mm, and a thickness of 8 mils. The samples were heated at a rate of 10°C per minute, from 30°C to 260°C. The X-axis thermal expansion coefficient (in ppm / °C) of each test sample was measured within the temperature range (α1) from 40°C to 125°C, according to the method described in IPC-TM-650 2.4.24.5. A lower X-axis thermal expansion coefficient indicates better dimensional expansion and contraction characteristics. A difference in X-axis thermal expansion coefficient greater than or equal to 0.1 ppm / °C is considered significant (presenting significant technical difficulty).

[0181] For example, articles made from the resin compositions disclosed in this invention have a low X-axis coefficient of thermal expansion when measured with reference to the method described in IPC-TM-6502.4.24.5, for example, an X-axis coefficient of thermal expansion less than or equal to 9.3 ppm / ℃, for example, between 8.0 ppm / ℃ and 9.3 ppm / ℃.

[0182] 3. Copper tensile test of carrier The core board is fabricated as follows: Prepare four prepreg sheets (using 7628 glass cloth, resin content (RC) of 42%). A copper foil is then laminated onto both sides of each of the four laminated prepreg sheets. The core is then pressed and cured under vacuum, high temperature (195°C), and high pressure (360 psi) conditions for 2 hours to obtain a copper-containing core board. This core board can then be processed using a browning line process to obtain a browned core board. Prepreg 2, prepared from the resin compositions of the aforementioned embodiments and comparative examples, is stacked on both sides of the outer layer of the browned core board. Each prepreg has a resin content of approximately 70%. A 1.5 μm ultrathin copper foil (MT18FL) is then stacked on the outer layer of each of the two prepregs. The stacking is performed in the following order: ultrathin copper foil (ultrathin copper surface adhered to the prepreg, carrier layer away from the prepreg surface), one prepreg, browned copper foil substrate, one prepreg, and ultrathin copper foil. The substrate is then pressed under vacuum at 200°C for 2 hours to form a multilayer board containing ultrathin copper foil. The carrier copper on the ultrathin copper surface of the outer layer of the multilayer board containing ultrathin copper foil is peeled off, and the cleaning process is omitted. The entire board is then electroplated to a copper layer thickness of 30 μm to form a four-layer circuit board containing ultrathin copper foil.

[0183] The four-layer circuit board prepared above was cut into rectangular samples with a width of 24 mm and a length greater than 60 mm. The surface copper foil was then etched, leaving only a strip of copper foil with a width of 3.18 mm and a length greater than 60 mm. Using a universal tensile testing machine at room temperature (approximately 25°C), the force required to pull the electroplated copper foil away from the substrate surface was measured (in lb / in).

[0184] In this field, the higher the copper pull strength of the carrier, the better, and a difference of 0.1 lb / in or more in the copper pull strength of the carrier is considered a significant difference (indicating significant technical difficulty).

[0185] For example, an article made from the resin composition disclosed in this invention has a carrier copper tensile strength greater than or equal to 4.60 lb / in, measured with reference to the method described in IPC-TM-650 2.4.8, for example, between 4.60 lb / in and 5.70 lb / in, or for example, between 4.80 lb / in and 5.70 lb / in.

[0186] 4. Heat resistance after moisture absorption (PCT heat resistance) The aforementioned copper-free substrate 3 was selected as the test sample. Following the method described in IPC-TM-650 2.6.16.1, it underwent a pressure cooking test (PCT) for 5 hours (test temperature 121℃, relative humidity 100%) to absorb moisture. Then, following the method described in IPC-TM-650 2.4.23, it was immersed in a solder bath at a constant temperature of 288℃. After immersion for 20 seconds, it was removed and observed for board bursting. For example, interlayer delamination between insulating layers constitutes board bursting. Interlayer delamination will cause bubbling and separation between any layers of the substrate (visible to the naked eye). If board bursting occurs, it is marked "NG"; if no board bursting occurs, it is marked "pass".

[0187] For example, articles made from the resin composition disclosed in this invention, after being subjected to a heat resistance test for 5 hours of moisture absorption according to the methods described in IPC-TM-650 2.6.16.1 and IPC-TM-650 2.4.23, do not exhibit board cracking (the industry standard for multilayer boards or printed circuit boards is that they should not exhibit board cracking after 1 hour of moisture absorption).

[0188] 5. Water absorption rate after pressure cooking (PCT) A copper-free substrate 1 (composed of eight prepreg sheets laminated together, with a resin content of approximately 52%) with a length and width of 2 inches was selected as the test sample. Each test sample was placed in an oven at 105±10℃ and baked for 1 hour. After being removed and cooled at room temperature (approximately 25℃) for 10 minutes, the weight of the copper-free substrate 1 was measured as W1. Then, following the method described in IPC-TM-650 2.6.16.1, a pressure cooking test (PCT) was performed for 5 hours (test temperature: 121℃, relative humidity: 100%) to absorb moisture. After wiping off the residual water on the substrate surface, the weight of the copper-free substrate 1 after absorbing moisture was measured as W2. The water absorption rate (%) was calculated using the formula: Water absorption rate (%) = [(W2-W1) / W1]×100%, with the unit of water absorption rate being W2.

[0189] In this field, a lower water absorption rate measured after moisture absorption via a pressure cooker test is preferred. A difference in PCT (5-hour) water absorption rate greater than or equal to 0.05% indicates a significant difference in PCT (5-hour) water absorption rate between different substrates (presenting significant technical difficulty). For example, an article made from the resin composition disclosed in this invention, after moisture absorption via a pressure cooker test (PCT) as described in IPC-TM-650 2.6.16.1, has a water absorption rate less than or equal to 0.35%, for example, between 0.25% and 0.35%.

[0190] 6. Bonding strength (B / S) For interlayer tensile testing, the aforementioned copper-containing substrate 1 (composed of eight prepreg sheets laminated together, with a resin content of approximately 52%) was selected and cut into rectangular samples with a width of 12.7 mm and a length greater than 60 mm. Tensile strength was measured using a universal tensile testing machine, following the method described in IPC-TM-650 2.4.8. No surface copper foil etching was required during the process, and the test location was the interface between the second and third prepreg layers. The force required to separate the two layers of the cured insulating substrate was measured at room temperature (approximately 25°C), with units expressed as lb / in.

[0191] In this field, higher interlayer tensile strength is preferred. An interlayer tensile strength greater than or equal to 0.3 lb / in indicates a significant difference in interlayer tensile strength between different substrates (representing significant technical difficulty). For example, an article made from the resin composition disclosed in this invention has an interlayer tensile strength greater than or equal to 3.38 lb / in, for example, between 3.38 lb / in and 3.75 lb / in, measured according to the method described in IPC-TM-650 2.4.8.

[0192] 7. Long bubble stripes In the measurement to observe the presence of elongated bubble streaks on a copper-free substrate, the aforementioned copper-free substrate 4 (formed by laminating a prepreg 2) was selected as the test sample for optical microscopy observation. The tester observed the presence of elongated bubble streaks within the insulating layer of the copper-free substrate 4 using an optical microscope. If elongated bubble streaks with a length greater than or equal to 12 mils were present, the sample was judged as "present," and the number of elongated bubble streaks was recorded. If no elongated bubble streaks with a length greater than or equal to 12 mils were present, the sample was judged as "absent," and the number of elongated bubble streaks was recorded as 0. For example, refer to... Figure 1 , Figure 1 There are elongated bubble streaks with a length greater than or equal to 12 mils (12 mils equals 304.8 micrometers), which are transmitted through... Figure 1 The long vertical line marked inside the black ellipse indicates the presence of an elongated bubble stripe with a length greater than or equal to 12 mils. Figure 2 There are no elongated bubble streaks with a length greater than or equal to 12 mils. If elongated bubble streaks exist in the insulating layer of the copper foil substrate, the copper-free substrate, or the printed circuit board, it will cause short circuits due to the migration of conductive ions (CAF) in subsequent printed circuit boards, resulting in the failure and scrapping of the printed circuit board.

[0193] Table 4: Performance test data for each embodiment (unit)

[0194] Table 5: Performance test data for each comparative example (unit)

[0195] Based on the test results in Tables 4 and 5, the following phenomena can be observed.

[0196] By comparing Examples E1-E2 and Comparative Examples C1-C5, it can be confirmed that the use of maleimide resin containing indimpedance structure in the resin composition of the present invention, compared with maleimide resin containing maleimide resin without indimpedance structure, can reduce dielectric loss, reduce X-axis thermal expansion coefficient, increase carrier copper tensile strength, reduce water absorption rate after pressure cooking, increase interlayer tensile strength, and improve one or more technical effects of elongated bubble streaks.

[0197] By comparing and contrasting Examples E1, E3 to E6 and Comparative Examples C6 and C7, it can be confirmed that the use of amino-modified hydrogenated styrene polymers within the numerical range in the resin composition of the present invention, compared with the use of amino-modified hydrogenated styrene polymers outside the numerical range, can reduce dielectric loss, reduce the coefficient of thermal expansion along the X-axis, increase the copper tensile strength of the carrier, improve heat resistance after moisture absorption, reduce water absorption after pressure cooking, and increase interlayer tensile strength, among other technical effects.

[0198] By comparing and contrasting Examples E1, E15-E18 and Comparative Example C8, it can be confirmed that the use of amine-modified hydrogenated styrene polymers in the resin compositions of the present invention, compared with the use of other styrene polymers, such as hydrogenated styrene polymers, can reduce the coefficient of thermal expansion along the X-axis, increase the tensile strength of the carrier copper, improve the heat resistance after moisture absorption, reduce the water absorption rate after pressure cooking, increase the interlayer tensile strength, and improve one or more technical effects of elongated bubble streaks.

[0199] By comparing and contrasting Examples E1, E7-E9 and Comparative Examples C9-C10, it can be confirmed that the phosphate resin with (meth)acrylate end-capped within the numerical range used in the resin composition of the present invention, compared with the phosphate resin with (meth)acrylate end-capped outside the numerical range, can reduce dielectric loss, reduce the coefficient of thermal expansion along the X-axis, increase the copper tensile strength of the carrier, improve the heat resistance after moisture absorption, reduce the water absorption rate after pressure cooking, increase the interlayer tensile strength, and improve one or more of the technical effects of elongated bubble streaks.

[0200] By comparing Example E1 and Comparative Example C13, it can be confirmed that the phosphate resin with (meth)acrylate end-capped resin used in the resin composition of the present invention, compared with other phosphate esters, such as PX-200, can reduce the coefficient of thermal expansion along the X-axis, increase the tensile strength of the carrier copper, improve the heat resistance after moisture absorption, reduce the water absorption rate after pressure cooking, and increase the interlayer tensile strength, or one or more of the following technical effects.

[0201] By comparing and contrasting Examples E1, E10-E12 and Comparative Examples C11-C12, it can be confirmed that the use of vinyl polyphenylene ether resins within the numerical range in the resin composition of the present invention, compared with vinyl polyphenylene ether resins outside the numerical range, can reduce dielectric loss, reduce the coefficient of thermal expansion along the X-axis, increase the copper tensile strength of the carrier, improve heat resistance after moisture absorption, reduce water absorption rate after pressure cooking, and increase interlayer tensile strength, or achieve one or more of the following technical effects.

[0202] By comparing Examples E1-E18 with Comparative Examples C1-C13, it can be confirmed that the articles made from the resin composition of the present invention simultaneously achieve one, more, or all of the technical effects of an X-axis thermal expansion coefficient less than or equal to 9.3 ppm / ℃ and a carrier copper tensile strength greater than or equal to 2.5 lb / in. Conversely, Comparative Examples C1-C13, which did not use the technical solution of the present invention, could not simultaneously achieve the aforementioned technical effects.

[0203] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A resin composition, characterized in that, include: 100 parts by weight of maleimide resin containing indane structure; 5-30 parts by weight of amino-modified hydrogenated styrene polymer; 10-30 parts by weight of a (meth)acrylate-terminated phosphate resin, wherein the structure of the (meth)acrylate-terminated phosphate resin is as shown in formula (I): Formula (I) Among them, R L1 and R L7 Each can be independently H or CH3, R L2 R L3 R L4 R L5 and R L6 Each of the following is an alkyl group with 1 to 4 carbon atoms; y2, y3, y4, y5, and y6 are each an integer from 0 to 4, where y2+y3+y4+y5+y6≥5, and multiple R are present. L2 R L3 R L4 R L5 or R L6 In the case of multiple R L2 R L3 R L4 R L5 or R L6 They can be the same or different, and z is an integer from 0 to 10; 10 to 30 parts by weight of vinyl polyphenylene ether resin.

2. The resin composition according to claim 1, characterized in that, The maleimide resin containing the indane structure includes one or a combination of two of the maleimide resins shown in formula (A-2) and formula (A-3): Equation (A-2) In equation (A-2), Ra, Rb, Rc, Rd, and R 11 R 12 R 13 Each is an alkyl group with 1 to 4 carbon atoms, and each of them is an integer from 0 to 4. Each of them is an integer from 0 to 3. Each of them is the number of repeating units, and is a value from 1 to 20. Each of them is a divalent alkyl group with 1 to 4 carbon atoms. Equation (A-3) In equation (A-3), Re, Rf, Rg, Rh, Ri, Rj, Rk, and R are... 21 R 22 R 23 R 24 R 25 R 26 Each is an alkyl group with 1 to 4 carbon atoms, and each of m4, m6, m8, and m10 is an integer from 0 to 4; each of m5, m7, and m9 is an integer from 0 to 3; n2 and n3 are the number of repeating units, and each is an integer from 0 to 20, and n2 + n3 is an integer from 0.5 to 20; each of X3, X4, X5, and X6 is a divalent alkyl group with 1 to 4 carbon atoms.

3. The resin composition according to claim 2, characterized in that, The maleimide resin containing the indane structure of formula (A-2) includes the structure shown in formula (A-2-1): Equation (A-2-1) Among them, Ra1, Ra2, Rd1, Rd2, R 13 Each is an alkyl group consisting of 1 to 4 hydrogen or carbon atoms; n1 is the number of repeating units, ranging from 1 to 20.

4. The resin composition according to claim 3, characterized in that, The maleimide resin containing the indane structure of formula (A-3) includes the structure shown in formula (A-3-1): Equation (A-3-1) Among them, Re1~Re2, Rh1~Rh2, Rk1~Rk2, R 23 R 26 Each is an alkyl group with 1 to 4 hydrogen or carbon atoms; n2 and n3 are the number of repeating units, each with a value of 0 to 20, and n2 + n3 has a value of 0.5 to 20.

5. The resin composition according to claim 4, characterized in that, The maleimide resin containing the indane structure of formula (A-2-1) includes at least one of the structures shown in formulas (A-2-2) to (A-2-6): Equation (A-2-2) Equation (A-2-3) Equation (A-2-4) Equation (A-2-5) Equation (A-2-6) Where n1 is the average number of repeating units, and is a value from 1 to 20.

6. The resin composition according to claim 5, characterized in that, The maleimide resin containing the indane structure of formula (A-3-1) includes at least one of the structures shown in formulas (A-3-2) to (A-3-8): Equation (A-3-2) Equation (A-3-3) Equation (A-3-4) Equation (A-3-5) Equation (A-3-6) Equation (A-3-7) Equation (A-3-8) Wherein, n2 and n3 are the average number of repeating units, and each is an independent value from 0 to 20, and n2 + n3 is a value from 0.5 to 20.

7. The resin composition according to claim 6, characterized in that, The amino-modified hydrogenated styrene polymers include amino-modified hydrogenated styrene-butadiene copolymers, amino-modified hydrogenated styrene-isoprene copolymers, amino-modified hydrogenated styrene-butadiene-styrene copolymers, amino-modified hydrogenated styrene-isoprene-styrene copolymers, amino-modified hydrogenated styrene-isobutylene-styrene copolymers, or combinations thereof.

8. The resin composition according to claim 7, characterized in that, The meth)acrylate-terminated phosphate resin of formula (I) has a structure as shown in formula (I-1): Formula (I-1) Among them, R L1 and R L7 Each can be H or CH3, R independently j1 R j2 R j3 H or CH3, K1, K2 and K3 are 0, 1 or 2, and W is 0, 1, 2 or 3.

9. The resin composition according to claim 8, characterized in that, The phosphorus content in the meth)acrylate-terminated phosphate resin of formula (I) is 2.0% to 10.0 wt%.

10. The resin composition according to claim 9, characterized in that, The vinyl-containing polyphenylene ether resin includes terminal methacrylate polyphenylene ether resin, terminal vinyl benzyl polyphenylene ether resin, terminal allyl polyphenylene ether resin, or a combination thereof.

11. The resin composition according to claim 10, characterized in that, It also includes vinyl crosslinking agents, maleimide triazine resins, styrene maleic anhydride resins, epoxy resins, phenolic resins, benzoxazine resins, cyanate ester resins, polyester resins, polyamide resins, polyimide resins, or combinations thereof.

12. The resin composition according to claim 11, characterized in that, The resin composition further includes amine curing agents, inorganic fillers, curing accelerators, polymerization inhibitors, colorants, solvents, toughening agents, silane coupling agents, or combinations thereof.

13. An article characterized in that, The article is made from the resin composition according to any one of claims 1 to 9, and the article includes a prepreg, a resin film, a laminate, a printed circuit board, or a cured insulator.

14. The article of claim 13, characterized in that, The article has one, more, or all of the following characteristics: The dielectric loss measured at a frequency of 10 GHz using the method described in JISC2565 is less than or equal to 0.00180. The X-axis coefficient of thermal expansion measured according to the method described in IPC-TM-650 2.4.24.5 is less than or equal to 9.3 ppm / ℃; The carrier copper pull force measured according to the method described in IPC-TM-650 2.4.8 is greater than or equal to 4.60 lb / in; After absorbing moisture for 5 hours according to the methods described in IPC-TM-650 2.6.16.1 and IPC-TM-650 2.4.23, no heat resistance test was conducted and no plate bursting occurred. The water absorption rate measured after moisture absorption by pressure cooking test (PCT) according to the method described in IPC-TM-650 2.6.16.1 is less than or equal to 0.35%; The interlaminar tensile strength measured according to the method described in IPC-TM-650 2.4.8 is greater than or equal to 3.38 lb / in; The product was observed to be free of elongated bubble streaks under an optical microscope.

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