Resin composition, prepreg, metal-clad laminate, and method for producing same

Abstract

Provided are a resin composition having excellent electrical characteristics and flame retardancy, a prepreg, a metal-clad laminate, and a method for manufacturing the same. A resin composition containing a resin having at least an alpha-olefin structure represented by formula (1), an organic phosphorus compound, and a compound having at least one of an oxygen atom and a nitrogen atom. In formula (1), each R1 independently represents a hydrocarbon group having 1 to 10 carbon atoms or a haloalkyl group, p1 represents a real number of 0 to 4, and each represents a bonding position, a prepreg using the resin composition, a metal-clad laminate, and a method for producing a metal-clad laminate.

Description

Technical Field

[0001] This invention relates to resin compositions, prepregs, metal-coated laminates, and methods for manufacturing the same. Background Technology

[0002] Laminates used in printed circuit boards for high-speed communications are demanding higher performance. The resin compositions used in these laminates are required to possess a variety of practical properties, including electrical characteristics.

[0003] Patent Document 1 discloses a polymer based on a specific diisoenylpropadiene and containing an indane structure, which has sufficient electronic properties.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 2022-100270 Summary of the Invention

[0007] The problem that the invention aims to solve

[0008] When using polymers containing a large number of indane structures as described in Patent Document 1 for metal-coated laminates, it is sometimes difficult to balance electrical properties and flame retardancy.

[0009] This disclosure was made in view of the above-mentioned problems, and its object is to provide a resin composition, prepreg, metal-coated laminate and a method for manufacturing the same, which have excellent electrical properties and flame retardancy.

[0010] means for solving problems

[0011] The resin composition, prepreg, metal-coated laminate and manufacturing method of the present invention are shown below [1] to

[23] .

[0012] [1] A resin composition comprising: a resin having at least an α-olefin structure represented by the following formula (1), an organophosphorus compound, and a compound having at least one atom selected from oxygen and nitrogen atoms.

[0013]

[0014] (In equation (1), R) 1 Each group independently represents a hydrocarbon group or a haloalkyl group with 1 to 10 carbon atoms, and p1 represents a real number from 0 to 4. Each represents a bonding position.

[0015] [2] The resin composition according to [1], wherein the iodine value of the resin is 70 or more and 200 or less.

[0016] [3] The resin composition according to [1] or [2], wherein the weight-average molecular weight Mw of the resin is 2,500 or more and 500,000 or less.

[0017] [4] The resin composition according to any one of [1] to [3], wherein the content of the α-olefin structure represented by the formula (1) in the resin is 1.0 mmol / g or more and 6.3 mmol / g or less.

[0018] [5] The resin composition according to any one of [1] to [4], wherein the parameter FA, expressed as the content of the α-olefin structure represented by the formula (1), the content of the indene structure represented by the formula (2) and the content of the inner olefin structure represented by the formula (3) in the resin, is 0.39 or more.

[0019] FA = [content of α-olefin structure] / ([content of internal olefin structure] + [content of indene structure] + [content of α-olefin structure])

[0020] (In equation (2), R) 2 Each group independently represents a hydrocarbon group or a haloalkyl group with 1 to 10 carbon atoms, p2 represents a real number from 0 to 4, and q1 represents a real number from 0 to 3. Each represents a bonding position.

[0021]

[0022] (In equation (3), R) 3 Each group independently represents a hydrocarbon group or a haloalkyl group with 1 to 10 carbon atoms, and p3 represents a real number from 0 to 4. Each represents a bonding position.

[0023] [6] The resin composition according to any one of [1] to [5], wherein the following parameter FI, expressed as the content of the α-olefin structure represented by the above formula (1), the content of the indane structure represented by the above formula (2) and the content of the inner olefin structure represented by the above formula (3) in the resin, is less than 0.58.

[0024] FI = [content of indene structure] / ([content of internal olefin structure] + [content of indene structure] + [content of α-olefin structure] / 2).

[0025] [7] The resin composition according to any one of [1] to [6], wherein the content of heteroatoms other than carbon atoms and hydrogen atoms in the resin is 3% by mass or less.

[0026] [8] The resin composition according to [7], wherein the resin does not contain the heteroatoms.

[0027] [9] The resin composition according to any one of [1] to [8], wherein the resin has an olefin structure at the end.

[0028]

[10] The resin composition according to any one of [1] to [9], wherein the resin further has a side chain olefin structure having an olefin structure in the side chain portion.

[0029]

[11] The resin composition according to any one of [1] to

[10] , wherein the total content of the α-olefin structure, the terminal olefin structure and the side chain olefin structure having an olefin structure in the side chain portion is 1.8 mmol / g or more.

[0030]

[12] The resin composition according to any one of [1] to

[11] , wherein the content of the indane structure represented by the above formula (2) in the resin is 3.0 mmol / g or less.

[0031]

[13] The resin composition according to any one of [1] to

[12] , wherein the organophosphorus compound has a solubility of less than 5 g in 100 g of toluene at 25 °C.

[0032]

[14] The resin composition according to any one of [1] to

[13] , wherein the organophosphorus compound is incompatible with the resin.

[0033]

[15] The resin composition according to any one of [1] to

[14] , wherein the organophosphorus compound has a melting point of 240°C or higher.

[0034]

[16] The resin composition according to any one of [1] to

[15] , wherein the organophosphorus compound has a phosphonic acid structure or a phosphonic acid structure.

[0035]

[17] The resin composition according to any one of [1] to

[16] , wherein the number average molecular weight Mn of the compound having at least one atom selected from oxygen and nitrogen atoms is 300 to 50,000.

[0036]

[18] The resin composition according to any one of [1] to

[17] , wherein the compound having at least one atom selected from oxygen and nitrogen atoms contains a free radical polymerizable group.

[0037]

[19] The resin composition according to any one of [1] to

[18] , wherein the total content of oxygen atoms and nitrogen atoms is 0.01% to 10% by mass.

[0038]

[20] The resin composition according to any one of [1] to

[19] , wherein the content of the solid component of the resin composition is: the resin: 1% to 80% by mass, the organophosphorus compound: 0.1% to 30% by mass, and the compound having at least one atom selected from oxygen and nitrogen atoms: 1% to 80% by mass.

[0039]

[21] A prepreg comprising any one of the resin compositions described in [1] to

[20] .

[0040]

[22] A metal-clad laminate, wherein the metal-clad laminate comprises a cured resin composition of any one of [1] to

[20] and a metal foil.

[0041]

[23] A method for manufacturing a metal-clad laminate, wherein a prepreg comprising any one of the resin compositions described in [1] to

[20] is laminated with a metal foil.

[0042] Invention Effects

[0043] According to this disclosure, a resin composition, prepreg, metal-coated laminate, and a method for manufacturing the same are provided, all possessing excellent electrical properties and flame retardancy. Detailed Implementation

[0044] In this specification, the numerical range represented by “~” contains the values ​​listed before and after the “~” as the minimum and maximum values, respectively.

[0045] In the numerical ranges described step by step in this specification, the upper or lower limit value described in one numerical range can be replaced with the upper or lower limit value of other numerical ranges described step by step. Additionally, within the numerical ranges described in this specification, the upper or lower limit value of that range can be replaced with the values ​​shown in the embodiments.

[0046] It should be noted that when the same symbol exists in a chemical formula, the same symbol can be the same structure as each other, or it can be a structure that is different from each other within a specified range.

[0047] As mentioned above, the compositions (resin compositions) used in laminates mounted on electrical and electronic components are required to possess a variety of practical properties, represented by electrical characteristics.

[0048] Especially in laminates used for high-speed communications, it is desirable to use resins with extremely low loss, where the dielectric loss tangent is 0.004 or less (more preferably 0.0015 or less) at a frequency of 10 GHz.

[0049] Hydrocarbon resins composed of carbon and hydrogen atoms and fluorinated resins have been used to date. More specifically, examples of such hydrocarbon resins include: polyfunctional vinyl aromatic polymers, cyclic polyolefin resins, and vinyl aromatic compound-conjugated diene copolymers. Examples of such fluorinated resins include polytetrafluoroethylene (PTFE).

[0050] Patent Document 1 discloses a polymer as a resin having sufficient electronic properties, which is understood to be based on a specific diisoalkenylpropadiene and contains a large amount of indmium structure described later.

[0051] However, when using the polymer described in Patent Document 1 in laminates, it is sometimes difficult to achieve both electrical properties and flame retardancy. The inventors have discovered that by using a resin composition comprising a resin having an α-olefin structure represented by the following formula (1), an organophosphorus compound, and a compound having at least one atom of oxygen and nitrogen atoms in a metal-clad laminate, it is possible to impart excellent electrical properties and flame retardancy.

[0052] Furthermore, in recent years, in order to address the environmental problems associated with the manufacture and disposal of printed wiring boards using metal-clad laminates, there has been a demand for metal-clad laminates using halogen-free resin compositions that do not contain halogen materials. The resin composition disclosed herein can also be a halogen-free resin composition that can easily achieve both electrical properties and flame retardancy even without the use of halogen materials.

[0053] Hereinafter, embodiments of the resin composition of this disclosure (hereinafter also referred to as "this composition") will be described in detail, but this disclosure is not limited to these embodiments. In addition, modifications can be made as desired without departing from the spirit of this disclosure.

[0054] <Resin Composition>

[0055] This composition comprises at least a resin having an α-olefin structure represented by formula (1) above (hereinafter also referred to as resin A), an organophosphorus compound (hereinafter also referred to as compound B), and a compound having at least one atom selected from oxygen and nitrogen atoms (hereinafter also referred to as compound C). By combining these resins and compounds, this composition can suppress the dielectric loss tangent Df to a low level, thereby imparting excellent flame retardancy. It should be noted that the molecular structures of the resins and compounds contained in the composition can be... 1 H-NMR and 13 The composition is determined by C-NMR and other methods. Details are provided below. The components contained in this composition are described in detail below.

[0056] (Resins having an α-olefin structure represented by formula (1))

[0057] Resin A has at least an α-olefin structure represented by the following formula (1) as a unit structure. This composition, by having resin A, can impart excellent electrical properties, thereby improving heat resistance and adhesion to metal foils. Resin A can be used alone or in combination with two or more types. Furthermore, resin A can be a curable resin.

[0058]

[0059] In equation (1), R 1 Each group independently represents a hydrocarbon group or a haloalkyl group with 1 to 10 carbon atoms, and p1 represents a real number from 0 to 4. Each represents a bonding position.

[0060] In equation (1), R 1 The alkyl group is a hydrocarbon group with 1 to 10 carbon atoms, or a haloalkyl group. From the viewpoint of imparting excellent electrical properties and producing a halogen-free product, a hydrocarbon group with 1 to 5 carbon atoms is preferred, and a hydrocarbon group with 1 to 3 carbon atoms is more preferred. Examples of such hydrocarbon groups include methyl, ethyl, n-propyl, isopropyl, isopropenyl, tert-butyl, and n-butyl. The haloalkyl group is a group obtained by substituting a hydrogen atom of an alkyl group with a halogen atom. Examples of halogen atoms include F, Cl, Br, and I. It should be noted that the number of carbon atoms in the alkyl group is, for example, 1 to 10.

[0061] In equation (1), p1 is a real number from 0 to 4, preferably from 0 to 3, and more preferably 0.

[0062] The resin A described above can be a resin obtained by polymerizing a compound having multiple isopropenyl groups (e.g., a diisopropenyl compound) under an acid catalyst and at a specific reaction temperature, as detailed below. Examples of compounds having multiple isopropenyl groups include 1,3-diisopropenylbenzene and 1,4-diisopropenylbenzene. These isopropenyl compounds can be compounds manufactured by known methods. For example, diisopropenyl compounds can be synthesized by intramolecular dehydration from a diol compound, which can be obtained by oxidizing isopropylphenyl and then reducing it with hydrogen. Furthermore, diisopropenyl compounds can also be manufactured by adding propylene to an aromatic compound and then performing a dehydrogenation reaction.

[0063] It should be noted that the raw material monomer used to prepare resin A can be a precursor of a compound having multiple isopropenyl groups (e.g., a diisopropenyl compound precursor).

[0064] From the viewpoints of flexibility, adhesion to metal foil, and curability, the iodine value of the aforementioned resin A is preferably, for example, one of the following values: iodine value of the aforementioned resin A is preferably 70 or higher, 71 or higher, 72 or higher, 73 or higher, 74 or higher, 75 or higher, 76 or higher, 77 or higher, 78 or higher, 79 or higher, 80 or higher, 81 or higher, 82 or higher, 83 or higher, 84 or higher, 85 or higher, 86 or higher, 87 or higher, 88 or higher, 89 or higher, 90 or higher, 91 or higher, 92 or higher, 93 or higher, greater than 93, 94 or higher, or 95 or higher.

[0065] Furthermore, from the viewpoint of adjustability of degree of polymerization, heat resistance, and curability, the iodine value of the above-mentioned resin A is preferably, for example, the following values. That is, the iodine value of the above-mentioned resin A is preferably, for example, 200 or less, 195 or less, 190 or less, 185 or less, 180 or less, 175 or less, 170 or less, 165 or less, 160 or less, 155 or less, or 150 or less.

[0066] Here, the iodine value refers to the number of grams of iodine (I₂) that can undergo an addition (reaction) with 100 grams of the sample (in this case, resin A). Therefore, a higher value indicates a higher degree of unsaturation in the sample, meaning a greater number of unsaturated bonds (double bonds) in the structure. Since the aforementioned α-olefin structure contains double bonds, this iodine value can serve as a rough standard for determining the proportion of α-olefin structures in resin A. The iodine value can be determined using the Wijs method.

[0067] From the viewpoint of curability and heat resistance, the weight-average molecular weight Mw of the above-mentioned resin A is preferably, for example, the following values. That is, the weight-average molecular weight Mw of the resin A is preferably, for example, 2500 or more, 2550 or more, 2600 or more, 2650 or more, 2700 or more, 2750 or more, 2800 or more, 2850 or more, 2900 or more, 2950 or more, 3000 or more, 3100 or more, 3200 or more, 3300 or more, 3400 or more, 3500 or more, 3600 or more, 3700 or more, 3800 or more, 3900 or more, 4000 or more, 4100 or more, 4200 or more, 4300 or more, 4400 or more, 4500 or more, 4600 or more, 4700 or more. The molecular weights of the resins are as follows: 4800 and above, 4900 and above, 5000 and above, 5100 and above, 5200 and above, 5300 and above, 5400 and above, 5500 and above, 5600 and above, 5700 and above, 5800 and above, 5900 and above, 6000 and above, greater than 6000, 6100 and above, 6200 and above, 6300 and above, 6400 and above, 6500 and above, 6600 and above, 6700 and above, 6800 and above, 6900 and above, 7000 and above, 7500 and above, 8000 and above, 8500 and above, 9000 and above, 9500 and above, 10000 and above. Furthermore, from the viewpoint of solvent solubility, the weight-average molecular weight Mw of the resin A is preferably, for example, the following values. That is, the weight-average molecular weight Mw of the resin A is preferably, for example, 500,000 or less, 450,000 or less, 400,000 or less, 350,000 or less, 300,000 or less, 250,000 or less, 200,000 or less, 190,000 or less, 180,000 or less, 170,000 or less, 160,000 or less, 150,000 or less, 140,000 or less, 130,000 or less, 120,000 or less, 110,000 or less, or 100,000 or less. The method for determining the weight-average molecular weight is described below.

[0068] The number-average molecular weight Mn of the above-mentioned resin A is preferably 700 or more, more preferably 1000 or more. Furthermore, the number-average molecular weight Mn of this resin A is preferably 5000 or less. The method for determining the number-average molecular weight is described below.

[0069] From the viewpoint of electrical properties, heat resistance, and adhesion to metal foil, the content of the α-olefin structure represented by the above formula (1) in the above resin A (hereinafter also referred to as α-olefin content) is preferably, for example, the following values. That is, the α-olefin content (content ratio) is preferably, for example, 1.0 mmol / g or more, 1.1 mmol / g or more, 1.2 mmol / g or more, 1.3 mmol / g or more, 1.4 mmol / g or more, 1.5 mmol / g or more, 1.6 mmol / g or more, 1.7 mmol / g or more, 1.8 mmol / g or more, 1.9 mmol / g or more, 2.0 mmol / g or more, 2.1 mmol / g or more, 2.2 mmol / g or more, 2.3 mmol / g or more, or 2.35 mmol / g or more.

[0070] Furthermore, from the viewpoint of heat resistance and curability, the content of the α-olefin structure in the above-mentioned resin A is preferably, for example, the following values. That is, the α-olefin content is preferably, for example, 6.3 mmol / g or less, 6.2 mmol / g or less, 6.1 mmol / g or less, 6.0 mmol / g or less, 5.9 mmol / g or less, 5.8 mmol / g or less, 5.7 mmol / g or less, 5.6 mmol / g or less, 5.5 mmol / g or less, 5.4 mmol / g or less, 5.3 mmol / g or less, 5.2 mmol / g or less, 5.1 mmol / g or less, or 5.0 mmol / g or less.

[0071] From an electrical property point of view, resin A preferably contains 3% by mass or less of heteroatoms other than carbon and hydrogen atoms, and more preferably does not contain such heteroatoms. It should be noted that the heteroatom content in resin A can be determined by elemental analysis using a combustion method, etc.

[0072] As described above, resin A can be a polymer of diisopropylene compounds, the details of which are described below. In addition to the α-olefin structure represented by formula (1) above, resin A can also contain olefin structures located at the end of the molecular structure (terminal olefin structure), side-chain olefin structures having olefin structures in the side chain portion, indene structures represented by formula (2) below, internal olefin structures represented by formula (3) below, and other structures as unit structures.

[0073] It should be noted that, in addition to the aforementioned α-olefin structure, preferred resin A also possesses any one or both of the aforementioned terminal olefin structure and side-chain olefin structure. By having these terminal olefin structure and side-chain olefin structure, resin A exhibits improved adhesion to the metal foil, thereby imparting high metal peel strength.

[0074] More specifically, the total content of the aforementioned α-olefin structure, the terminal olefin structure of the molecular structure (terminal olefin structure), and the side-chain olefin structure having an olefin structure in the side chain portion of resin A is preferably the following values. That is, from the viewpoint of peel strength, the total content of these three structures (hereinafter also referred to as the tri-structure content) is preferably, for example, the following values. That is, the tri-structure content is preferably, for example, 1.8 mmol / g or more, 1.9 mmol / g or more, 2.0 mmol / g or more, 2.1 mmol / g or more, 2.2 mmol / g or more, or 2.3 mmol / g or more.

[0075] Furthermore, from the viewpoint of heat resistance and curability, the total content of these three structures in resin A is preferably, for example, the following values: that is, the content of these three structures is preferably, for example, 6.5 mmol / g or less, 6.4 mmol / g or less, 6.3 mmol / g or less, 6.2 mmol / g or less, 6.1 mmol / g or less, 6.0 mmol / g or less, 5.9 mmol / g or less, 5.8 mmol / g or less, 5.7 mmol / g or less, 5.6 mmol / g or less, 5.5 mmol / g or less, 5.4 mmol / g or less, 5.3 mmol / g or less, 5.2 mmol / g or less, 5.1 mmol / g or less, and 5.0 mmol / g or less.

[0076] Furthermore, from the viewpoint of peel strength, the total content of terminal olefin structures and side-chain olefin structures in resin A (hereinafter also referred to as the distructure content) is preferably, for example, the following values. That is, the distructure content is preferably, for example, 0.1 mmol / g or more, 0.11 mmol / g or more, 0.12 mmol / g or more, 0.13 mmol / g or more, 0.14 mmol / g or more, 0.15 mmol / g or more, 0.16 mmol / g or more, 0.17 mmol / g or more, 0.18 mmol / g or more, 0.19 mmol / g or more, 0.2 mmol / g or more, 0.25 mmol / g or more, or 0.3 mmol / g or more.

[0077] Furthermore, from the viewpoint of heat resistance and curability, the total content of terminal olefin structures and side-chain olefin structures in resin A is preferably, for example, the following values. That is, the content of these two structures is preferably, for example, 6.0 mmol / g or less, 5.9 mmol / g or less, 5.8 mmol / g or less, 5.7 mmol / g or less, 5.6 mmol / g or less, 5.5 mmol / g or less, 5.4 mmol / g or less, 5.3 mmol / g or less, 5.2 mmol / g or less, 5.1 mmol / g or less, 5.0 mmol / g or less, 4.9 mmol / g or less, 4.8 mmol / g or less, 4.7 mmol / g or less, 4.6 mmol / g or less, 4.5 mmol / g or less, 4.4 mmol / g or less, 4.3 mmol / g or less, 4.2 mmol / g or less, 4.1 mmol / g or less, or 4.0 mmol / g or less.

[0078] Furthermore, the total content of these three structures in resin A can consist of two of the three structures, or it can consist of one (e.g., the α-olefin structure). That is, resin A can have only one of the three structures mentioned above (e.g., the α-olefin structure), only two of the three structures, or all three of the three structures.

[0079] As described above, the resin A can be a polymer having an α-olefin structure, a terminal olefin structure, a side-chain olefin structure, and, as needed, an indene structure, an inner olefin structure, and other structures as repeating units.

[0080] The terminal olefin structure mentioned above is an olefin structure located at the end of the molecular structure. This structure is not particularly limited and can be represented by, for example, by the following formula (4).

[0081]

[0082] Here, in formula (4), A represents a polymer chain, which may include at least one of the following structures: an α-olefin structure represented by formula (1) above, a side-chain olefin structure represented by formula (5) below, an indene structure represented by formula (2) below, and an inner olefin structure represented by formula (3) below. It should be noted that in this embodiment, A includes at least the α-olefin structure represented by formula (1) above.

[0083] Alternatively, the aforementioned terminal olefin structure can also be represented by the following formula (4-1).

[0084]

[0085] Here, in equation (4-1), A 1The polymer chain may contain at least one of the following structures: an α-olefin structure represented by formula (1) above, a side-chain olefin structure represented by formula (5) below, an indene structure represented by formula (2) below, and an internal olefin structure represented by formula (3) below. It should be noted that in this embodiment, A contains at least the α-olefin structure represented by formula (1) above. Furthermore, in formula (4-1), R... 4 Each group independently represents a hydrocarbon group or a haloalkyl group with 1 to 10 carbon atoms, and p4 represents a real number from 0 to 4.

[0086] In equation (4-1), R 4 The alkyl group is a hydrocarbon group with 1 to 10 carbon atoms, or a haloalkyl group. From the viewpoint of electrical properties and halogen-free nature, a hydrocarbon group with 1 to 5 carbon atoms is preferred, and a hydrocarbon group with 1 to 3 carbon atoms is more preferred. Examples of such hydrocarbon groups include methyl, ethyl, n-propyl, isopropyl, isopropenyl, tert-butyl, and n-butyl. The haloalkyl group is a group obtained by substituting a hydrogen atom of an alkyl group with a halogen atom. Examples of halogen atoms include F, Cl, Br, and I. In addition, the number of carbon atoms in the alkyl group is, for example, 1 to 10.

[0087] In addition, in equation (4-1), p4 is a real number from 0 to 4, preferably from 0 to 3, and more preferably 0.

[0088] The above-mentioned side-chain olefin structure can be any structure that has an olefin structure in the side chain portion, and there are no particular restrictions on its structure. For example, it can be a structure represented by the following formula (5).

[0089]

[0090] In equation (5), R 5 Each group independently represents a hydrocarbon group or a haloalkyl group with 1 to 10 carbon atoms, and p5 represents a real number from 0 to 4. Each represents a bonding position.

[0091] In equation (5), R 5 The alkyl group is a hydrocarbon group with 1 to 10 carbon atoms, or a haloalkyl group. From the viewpoint of electrical properties and halogen-free nature, a hydrocarbon group with 1 to 5 carbon atoms is preferred, and a hydrocarbon group with 1 to 3 carbon atoms is more preferred. Examples of such hydrocarbon groups include methyl, ethyl, n-propyl, isopropyl, isopropenyl, tert-butyl, and n-butyl. The haloalkyl group is a group obtained by substituting a hydrogen atom of an alkyl group with a halogen atom. Examples of halogen atoms include F, Cl, Br, and I. In addition, the number of carbon atoms in the alkyl group is, for example, 1 to 10.

[0092] In addition, in equation (5), p5 is a real number from 0 to 4, preferably from 0 to 3, and more preferably 0.

[0093] The above-mentioned indimite structure is represented by the following equation (2).

[0094]

[0095] In equation (2), R 2 Each group independently represents a hydrocarbon group or a haloalkyl group with 1 to 10 carbon atoms, p2 represents a real number from 0 to 4, and q1 represents a real number from 0 to 3. Each represents a bonding position.

[0096] In equation (2), R 2 The alkyl group is a hydrocarbon group with 1 to 10 carbon atoms, or a haloalkyl group. From the viewpoint of electrical properties and halogen-free nature, a hydrocarbon group with 1 to 5 carbon atoms is preferred, and a hydrocarbon group with 1 to 3 carbon atoms is more preferred. Examples of such hydrocarbon groups include methyl, ethyl, n-propyl, isopropyl, isopropenyl, tert-butyl, and n-butyl. The haloalkyl group is a group obtained by substituting a hydrogen atom of an alkyl group with a halogen atom. Examples of halogen atoms include F, Cl, Br, and I. It should be noted that the number of carbon atoms in the alkyl group is, for example, 1 to 10.

[0097] In addition, in equation (2), p2 is a real number from 0 to 4, preferably from 0 to 3, and more preferably 0.

[0098] Furthermore, q1 is a real number from 0 to 3, preferably from 0 to 2, and more preferably 0.

[0099] The above-mentioned internal olefin structure is represented by the following formula (3).

[0100]

[0101] In equation (3), R 3 Each group independently represents a hydrocarbon group or a haloalkyl group with 1 to 10 carbon atoms, and p3 represents a real number from 0 to 4. Each represents a bonding position.

[0102] In equation (3), R 3 The alkyl group is a hydrocarbon group with 1 to 10 carbon atoms, or a haloalkyl group. From the viewpoint of electrical properties and halogen-free nature, a hydrocarbon group with 1 to 5 carbon atoms is preferred, and a hydrocarbon group with 1 to 3 carbon atoms is more preferred. Examples of such hydrocarbon groups include methyl, ethyl, n-propyl, isopropyl, isopropenyl, tert-butyl, and n-butyl. The haloalkyl group is a group obtained by substituting a hydrogen atom of an alkyl group with a halogen atom. Examples of halogen atoms include F, Cl, Br, and I. It should be noted that the number of carbon atoms in the alkyl group is, for example, 1 to 10.

[0103] In addition, in equation (3), p3 is a real number from 0 to 4, preferably from 0 to 3, and more preferably 0.

[0104] Here, the indane structure, due to its good balance of aromatic and aliphatic properties, improves solvent solubility, compatibility with other polymers, and imparts excellent heat resistance. However, if the proportion of indane structure in resin A is high, there is a tendency for reduced adhesiveness to the metal foil. Therefore, the content of indane structure in resin A (hereinafter also referred to as indane content) is preferably lower than that of α-olefin structure. The content of indane structure in resin A is preferably, for example, the following values. That is, the content of indane structure in resin A is preferably 4.2 mmol / g or less, 4.1 mmol / g or less, 4.0 mmol / g or less, 3.9 mmol / g or less, 3.8 mmol / g or less, 3.7 mmol / g or less, 3.6 mmol / g or less, 3.5 mmol / g or less, 3.4 mmol / g or less, 3.3 mmol / g or less, 3.2 mmol / g or less, 3.1 mmol / g or less, 3.0 mmol / g or less, 2.9 mmol / g or less, 2.8 mmol / g or less, 2.7 mmol / g or less, 2.6 mmol / g or less, 2.5 mmol / g or less, 2.4 mmol / g or less, 2.3 mmol / g or less, 2.2 mmol / g or less, 2.1 mmol / g or less, 2.0 mmol / g or less, 1.9 mmol / g or less, 1.8 mmol / g or less, 1.7 mmol / g or less, 1.6 mmol / g or less, or 1.5 mmol / g or less. Furthermore, from the viewpoint of ease of manufacture, the indane content in resin A is preferably, for example, the following values: that is, the indane content in resin A is preferably 0.01 mmol / g or more, 0.02 mmol / g or more, 0.03 mmol / g or more, 0.04 mmol / g or more, or 0.05 mmol / g or more.

[0105] For example, when using diisopropylene compounds as raw material monomers to produce resin A (diisopropylene compound homopolymer), it is believed that when the above-mentioned iodine value shows a small value, the content of the above-mentioned indane structure is high.

[0106] Internal olefin structures improve electrical properties and heat resistance, and impart good curability, but α-olefin structures contribute more significantly to curability. Therefore, the content of α-olefin structures (α-olefin content) in resin A is preferably higher than the content of internal olefin structures (hereinafter also referred to as internal olefin content).

[0107] Furthermore, in resin A, the parameter FA, which is expressed by the content of the α-olefin structure, the content of the internal olefin structure, and the content of the indene structure, is preferably 0.39 or more.

[0108] ·FA = [content of α-olefin structure] / ([content of internal olefin structure] + [content of indene structure] + [content of α-olefin structure])

[0109] Here, if the FA is 0.39 or higher, the adhesion to the metal foil is excellent, and it is easy to produce resins with good electrical properties and heat resistance. Furthermore, from the same perspective, the aforementioned FA is preferably 0.40 or higher, 0.41 or higher, 0.42 or higher, 0.43 or higher, 0.44 or higher, 0.45 or higher, 0.46 or higher, 0.47 or higher, 0.48 or higher, 0.49 or higher, 0.50 or higher, 0.51 or higher, 0.52 or higher, 0.53 or higher, 0.54 or higher, 0.55 or higher, 0.56 or higher, 0.57 or higher, 0.58 or higher, 0.59 or higher, 0.60 or higher, 0.61 or higher, 0.62 or higher, 0.63 or higher, 0.64 or higher, 0.65 or higher, 0.66 or higher, 0.67 or higher, 0.68 or higher, 0.69 or higher, 0.70 or higher, 0.71 or higher, 0.72 or higher, 0.73 or higher, 0.74 or higher, or 0.75 or higher. Also from the same perspective, the aforementioned FA is preferably 0.95 or lower.

[0110] Furthermore, in resin A, the parameter FI, which is expressed by the content of the α-olefin structure, the content of the internal olefin structure, and the content of the indene structure, is preferably less than 0.58.

[0111] ·FI = [Indene structure content] / ([Inner olefin structure content] + [Indene structure content] + [α-olefin structure content] / 2)

[0112] Here, if the FI value is less than 0.58, it is easy to produce a resin with excellent adhesion to metal foil. Furthermore, from the same perspective, the aforementioned FI is, for example, 0.579 or less, 0.575 or less, 0.57 or less, 0.56 or less, 0.55 or less, 0.54 or less, 0.53 or less, 0.52 or less, 0.51 or less, 0.50 or less, 0.49 or less, 0.48 or less, 0.47 or less, 0.46 or less, 0.45 or less, 0.44 or less, 0.43 or less, 0.42 or less, 0.41 or less, 0.40 or less, 0.39 or less, 0.38 or less, 0.37 or less, 0.36 or less, 0.35 or less, 0.34 or less, 0.33 or less, 0.32 or less, 0.31 or less, 0.30 or less, 0.29 or less, 0.28 or less, 0.27 or less, 0.26 or less, and 0.25 or less. Furthermore, from the same perspective, the aforementioned FI is preferably, for example, 0.15 or more.

[0113] From the viewpoint of maintaining the preferred form in the form of a resin varnish, when resin A is dissolved in a solvent at a concentration of 60% by mass, the proportion of the insoluble component is preferably 5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less. Examples of solvents include methyl ethyl ketone and toluene.

[0114] From a practical point of view, the dielectric loss tangent of resin A at a frequency of 10 GHz is preferably 0.004 or less, more preferably 0.0015 or less, even more preferably 0.001 or less, and particularly preferably 0.0008 or less. The method for measuring the dielectric loss tangent is described below.

[0115] In this specification, the glass transition temperature (Tg) refers to the glass transition temperature of the cured product obtained by curing resin A or the resin composition disclosed herein. The cured product exhibits a good glass transition temperature and thus exhibits superior heat resistance. The glass transition temperature of the cured product is preferably 125°C or higher, more preferably 150°C or higher, even more preferably 175°C or higher, and particularly preferably 200°C or higher. The method for determining the glass transition temperature is described below.

[0116] Even when resin A is thermocured at the temperature used in manufacturing substrate materials such as prepregs, it still exhibits the aforementioned glass transition temperature. This thermocure temperature is at least 250°C or lower, for example, 150°C to 230°C.

[0117] Furthermore, as described above, the cured product exhibiting the aforementioned heat resistance can be a cured product obtained by curing the resin composition of this disclosure.

[0118] It should be noted that resin A can be composed of one polymer or multiple polymers. When resin A is composed of multiple polymers, the aforementioned proportions of insoluble components relative to the solvent, glass transition temperature, dielectric loss tangent, and other physical properties are values ​​for a mixture of these multiple polymers (resin).

[0119] From the viewpoint of electrical properties, heat resistance, and adhesiveness to metal foil, the content of resin A in the solid component of this composition is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more. Furthermore, from the viewpoint of flame retardancy, the content of resin A in the solid component of this composition is preferably 80% by mass or less, more preferably 70% by mass or less, even more preferably 50% by mass or less, even more preferably 40% by mass or less, and particularly preferably 30% by mass or less.

[0120] (organophosphorus compounds)

[0121] Organophosphorus compounds (compound B) can be any conventionally known compounds, as long as they are organic compounds containing carbon and phosphorus atoms (e.g., in the form of carbon-phosphorus bonds), without particular restriction. It should be noted that organophosphorus compounds can function as flame retardants. One organophosphorus compound can be used alone, or two or more can be used in combination.

[0122] From the viewpoint of improving flame retardancy, the solubility of the aforementioned organophosphorus compound in 100g of toluene at 25°C is preferably 5g or less, more preferably 4g or less, and even more preferably 3g or less. In other words, from the viewpoint of heat resistance and chemical resistance, the organophosphorus compound is preferably incompatible with toluene.

[0123] Furthermore, from the viewpoint of heat resistance and chemical resistance, organophosphorus compounds are preferably incompatible with the aforementioned resin A.

[0124] Furthermore, from the viewpoint of heat resistance, the melting point of the organophosphorus compound is preferably 240°C or higher, more preferably 250°C or higher, and even more preferably 260°C or higher. If the melting point of the organophosphorus compound is 240°C or higher, volume changes at high temperatures can be easily suppressed, which can have a positive impact on improving the reliability of printed wiring boards and reducing substrate warpage.

[0125] From the viewpoint of improving flame retardancy, organophosphorus compounds are preferably pentavalent organophosphorus compounds having P=O bonds in their molecular structure. Examples of such pentavalent organophosphorus compounds include organophosphorus compounds having a phosphine oxide structure represented by formula (6), organophosphorus compounds having a phosphonic acid structure represented by formula (7), organophosphorus compounds having a phosphonic acid structure represented by formula (8), and organophosphorus compounds having a phosphoric acid structure represented by formula (9). From the viewpoint of electrical properties, the organophosphorus compounds used in this composition preferably have a phosphine oxide structure, a phosphonic acid structure, or a phosphoric acid structure, and more preferably have a phosphine oxide structure or a phosphonic acid structure. It should be noted that compounds obtained by multiple coordination of these organophosphorus compounds with metals (e.g., Al, Mg, Ca) can also be used as compound B. Furthermore, these organophosphorus compounds can form dimers as represented by formulas (10) and (11) below, or they can form trimers.

[0126]

[0127] In formulas (6) to (11), R independently represents a substituted or unsubstituted hydrocarbon group, and R can bond with each other to form a ring structure. In formulas (10) and (11), Ra independently represents a substituted or unsubstituted divalent hydrocarbon group.

[0128] It should be noted that multiple R values ​​can be the same or different from each other.

[0129] The hydrocarbon group represented by R can be, for example, a saturated hydrocarbon group, an unsaturated hydrocarbon group, an aromatic hydrocarbon group, or a group composed of these groups.

[0130] The saturated hydrocarbon group can be straight-chain, branched, or cyclic, and examples include alkyl groups. The number of carbon atoms in the saturated hydrocarbon group is preferably 1 to 20.

[0131] The unsaturated hydrocarbon group can be straight-chain, branched, or cyclic; for example, alkenyl groups can be used. The number of carbon atoms in the saturated hydrocarbon group is preferably 1 to 20.

[0132] As an aromatic hydrocarbon group, it is preferred to have a group with 5 to 20 carbon atoms, such as aryl groups such as phenyl and monovalent biphenyl.

[0133] These hydrocarbon groups can contain heteroatoms (such as oxygen atoms and nitrogen atoms) in their structure.

[0134] Furthermore, these hydrocarbon groups may or may not have substituents, and there is no particular limitation on the number of substituents. Examples of such substituents include alkyl, halogen, and alkoxy groups. However, from an environmental perspective, alkyl or alkoxy substituents are preferred.

[0135] Ra can represent divalent hydrocarbon groups, including divalent saturated hydrocarbon groups, divalent unsaturated hydrocarbon groups, divalent aromatic hydrocarbon groups, etc., or groups formed by combining these groups.

[0136] The divalent saturated hydrocarbon group can be straight-chain, branched, or cyclic, and examples include alkylene groups. The number of carbon atoms in the divalent saturated hydrocarbon group is preferably 1 to 20.

[0137] As a divalent aromatic hydrocarbon group, it is preferred to have a group with 5 to 20 carbon atoms, such as phenylene and divalent biphenyl (-C6H5-C6H5-).

[0138] As a divalent unsaturated hydrocarbon group, it is preferred to have a group with 2 to 20 carbon atoms, such as alkenyl or alkyne.

[0139] These divalent hydrocarbon groups can contain heteroatoms (such as oxygen atoms and nitrogen atoms) in their structure.

[0140] Furthermore, examples of substituents found in these divalent hydrocarbon groups include alkyl groups, halogen groups, alkoxy groups, and heterocyclic groups. However, from an environmental perspective, alkyl, alkoxy, or heterocyclic groups are preferred. Examples of heterocyclic groups include furan rings, thiophene rings, pyrrole rings, imidazole rings, pyridine rings, pyrimidine rings, pyrazine rings, and triazine rings.

[0141] As an organophosphorus compound included in this composition, the following compounds may be used, for example. These compounds can be manufactured by methods known in the art. It should be noted that commercially available organophosphorus compounds may also be used. It should be noted that compounds P-1 to P-15 are described below.

[0142] Compound P-1: Aluminum tris(diethylphosphonic acid)

[0143] Compound P-2: Diphenylvinylphosphine oxide

[0144] Compound P-3: The compound disclosed in Japanese Patent No. 6635415

[0145] Compound P-4: A compound described in International Publication No. 2020-031495 and International Publication No. 2022-259851.

[0146] Compound P-5: The compound described in U.S. Patent No. 10,626,250.

[0147] Compound P-6: The compound described in Japanese Patent No. 3897138

[0148] Compound P-7: The compound described in Chinese Patent Application Publication No. 115710424

[0149] Compound P-8: MC-4 (trade name, manufactured by Katayama Chemical Industry)

[0150] Compound P-9: The compound disclosed in Japanese Patent No. 6635415

[0151] Compound P-10: S-4 (trade name, manufactured by Katayama Chemical Industry)

[0152] Compound P-11: The compound described in Japanese Patent No. 6757215

[0153] Compound P-12: PX-200 (trade name, manufactured by Daihachi Science & Technology Co., Ltd.)

[0154] Compound P-13: SPV-100 (trade name, manufactured by Otsuka Chemical Co., Ltd.)

[0155] Compound P-14: SPB-100 (trade name, manufactured by Otsuka Chemical Co., Ltd.)

[0156] Compound P-15: FP-700TP (trade name, manufactured by Fushimi Pharmaceutical Co., Ltd.)

[0157] From the viewpoint of flame retardancy, the content of organophosphorus compounds in the solid components of this composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, and even more preferably 10% by mass or more. Furthermore, from the viewpoint of electrical properties, the content of organophosphorus compounds in the solid components of this composition is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less.

[0158] (A compound having at least one of oxygen and nitrogen atoms)

[0159] Compound C can be used as long as it contains at least one of oxygen and nitrogen atoms, and its structure is not particularly limited. Compound C can be, for example, a polymer or an elastomer. It should be noted that substances belonging to resin A and organophosphorus compound (compound B) are not included in compound C. In addition, compound C can be used alone or in combination with two or more.

[0160] From the viewpoint of heat resistance, the number average molecular weight Mn of compound C is preferably 300 or more, more preferably 500 or more, and even more preferably 1000 or more. Furthermore, from the viewpoint of resin flowability, the number average molecular weight Mn of compound C is preferably 50,000 or less, more preferably 35,000 or less, and even more preferably 20,000 or less.

[0161] From the viewpoints of electrical properties, heat resistance, and polymerizability, the weight-average molecular weight Mw of compound C is preferably 1000 or more. Furthermore, from the viewpoints of solubility in solvents, the weight-average molecular weight Mw of compound C is preferably 500,000 or less, more preferably 100,000 or less, even more preferably 50,000 or less, and particularly preferably 10,000 or less.

[0162] Compound C preferably has a free radical polymerizable group in its molecular structure. The free radical polymerizable group can be any group capable of free radical polymerization and may contain unsaturated double or triple bonds. Examples of free radical polymerizable groups include: vinyl, vinylidene, vinylene, ethynyl, allyl, isopropenyl, 1-butenyl, 2-butenyl, acryloyl, methacryloyl, fumaroyl, maleyl, acryloyloxy, methacryloyloxy, vinylphenyl, fluorovinyl, vinyl ether, allyl ether, styrene, vinylnaphthyl, norbornyl, cinnamoyl, and maleimide (2,5-dihydro-2,5-dioxo-1H-pyrrole-1-yl). Among these, vinyl, vinylidene, isopropenyl, acryloyl, methacryloyl, and styrene are preferred as free radical polymerizable groups.

[0163] As compound C, for example, a radical polymerizable compound having at least one of oxygen and nitrogen atoms can be used.

[0164] More specifically, as compound C, examples include: (meth)acrylic acid radical polymerizable compounds having one or more acryloyl groups and / or methacryloyl groups; styrene radical polymerizable compounds having one or more vinyl or vinylidene groups directly bonded to an aromatic carbon atom and at least one atom selected from oxygen and nitrogen atoms; allyl radical polymerizable compounds having one or more allyl groups and at least one atom selected from oxygen and nitrogen atoms; maleimide radical polymerizable compounds having one or more maleimide groups; etc.

[0165] Compound C can be exemplified by, for example, maleimide compounds, bismaleimide compounds, and compounds having two or more structures (ether structures) represented by the following formula (A) in the molecule and having heterocyclic structures.

[0166] Maleimide and bismaleimide compounds can be polymers or contain other structures (e.g., indene skeletons).

[0167]

[0168] In equation (A), R a Each group is independently a hydroxyl group, a halogen group, an aromatic hydrocarbon group with 6 to 20 substituted or unsubstituted carbon atoms, an alkyl group with 1 to 20 substituted or unsubstituted carbon atoms, a cycloalkyl group with 5 to 20 substituted or unsubstituted carbon atoms, or an aralkyl group with 7 to 20 substituted or unsubstituted carbon atoms, where n1 represents a real number from 0 to 4. and Each represents a bonding position. It should be noted that in compounds having structures represented by formula (A) above and heterocyclic structures, R bonded to the benzene ring of formula (A) above... a There are no particular restrictions on the bonding positions of the bonding groups, as long as they have the above-mentioned ether structure.

[0169] As a result of R a Halogen groups that can be represented include, for example: -F, -Cl, -Br and -I.

[0170] Aromatic hydrocarbon groups that can have 6 to 20 carbon atoms (including the carbon atoms of the substituents) can include, for example, monovalent aromatic hydrocarbon groups such as phenyl, naphthyl, and biphenyl. Substituents that can be present in this aromatic hydrocarbon group can include alkyl groups such as methyl, ethyl, propyl, and butyl, hydroxyl groups, halogen groups, etc., but are not limited to these groups.

[0171] Alkyl groups that can have 1 to 20 carbon atoms (including the carbon atoms of the substituents) can include, for example, straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and hexyl, and branched alkyl groups. Substituents that can be present in such alkyl groups can include, but are not limited to, hydroxyl groups, halogen groups, etc.

[0172] Cycloalkyl groups that can have 5 to 20 carbon atoms (including the carbon atoms of the substituents) can include, for example, cyclopentyl and cyclohexyl. Substituents that can be present in such cycloalkyl groups can include, but are not limited to, alkyl groups such as methyl, ethyl, propyl, and butyl, hydroxyl groups, and halogen groups.

[0173] Aryl alkyl groups that can have 7 to 20 carbon atoms (including the carbon atoms of the substituents) can include, for example, phenylmethyl, phenylethyl, phenylpropyl, diphenylmethyl, etc. Substituents that can be present in this aryl alkyl group can include, but are not limited to, hydroxyl groups, halogen groups, etc.

[0174] In formula (A), n1 is a real number from 0 to 4. From the viewpoint of balancing polymerizability and heat resistance, it is preferably 0 to 3, and more preferably 0 or 1.

[0175] Compound C preferably has the structure represented by formula (B) as the structure represented by formula (A) above. It should be noted that, from an environmental point of view, it is preferable that the structure represented by formula (A) above and the structure represented by formula (B) below do not contain halogen atoms.

[0176]

[0177] In equation (B), R b and R c Each of the following groups is independently a hydroxyl group, a halogen group, a substituted or unsubstituted aromatic hydrocarbon group with 6 to 20 carbon atoms, a substituted or unsubstituted alkyl group with 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group with 5 to 20 carbon atoms, or a substituted or unsubstituted aralkyl group with 7 to 20 carbon atoms. n3 and n4 each independently represent real numbers from 0 to 4. X is a single bond, an aromatic hydrocarbon group with 6 to 20 carbon atoms (substituted or unsubstituted), an alkylene group with 1 to 20 carbon atoms (substituted or unsubstituted), a cycloalkylene group with 5 to 20 carbon atoms (substituted or unsubstituted), an alkylidene group with 1 to 20 carbon atoms (substituted or unsubstituted), a cycloalkylidene group with 5 to 20 carbon atoms (substituted or unsubstituted), an arylalkylene group with 8 to 20 carbon atoms (substituted or unsubstituted), or an arylalkylidene group with 7 to 20 carbon atoms (substituted or unsubstituted), or a group composed of these groups. and Each represents a bonding position.

[0178] R b and R c The halogen groups, substituted or unsubstituted aromatic hydrocarbon groups having 6 to 20 carbon atoms, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 5 to 20 carbon atoms, and substituted or unsubstituted aralkyl groups having 7 to 20 carbon atoms, including their preferred forms, are the same as those in Formula (A) above, and therefore descriptions are omitted.

[0179] In equation (3), n3 and n4 are real numbers from 0 to 4. From the viewpoint of heat resistance, they are preferably from 0 to 3, and more preferably 0 or 1.

[0180] It should be noted that in the above formula (B), R, which is bonded to the benzene ring, b and R c There are no particular restrictions on the bonding positions of the bonding groups, etc.

[0181] The aromatic hydrocarbon group represented by X can have 6 to 20 carbon atoms (total carbon atoms including substituents) of substituents. Examples include: phenylene, naphthylene, biphenylene, divalent fluorene (e.g., 9,9-fluorene), divalent anthracene, and other divalent aromatic hydrocarbon groups. It should be noted that the aromatic hydrocarbon group can be a monocyclic or polycyclic aromatic hydrocarbon group. Examples of substituents that can be present in this aromatic hydrocarbon group include: alkyl groups such as methyl, ethyl, propyl, and butyl; hydroxyl groups; halogen groups, etc., but are not limited to these groups.

[0182] Examples of alkylene groups that can have 1 to 20 carbon atoms (including the carbon atoms of the substituents) include: methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, etc. Examples of substituents in this alkylene group include: hydroxyl groups, halogen groups, etc., but are not limited to these groups.

[0183] Examples of cyclohexene alkyl groups that can have 5 to 20 carbon atoms (including the carbon atoms of the substituents) can be cyclopentylene and cyclohexylene. Examples of substituents that can be found in these cyclohexene alkyl groups include alkyl groups such as methyl, ethyl, propyl, and butyl, hydroxyl groups, and halogen groups, but are not limited to these groups. For example, 3,3,5-trimethylcyclohexylene can be listed as an example of a substituted alkyl group.

[0184] Alkyl groups that can have 1 to 20 carbon atoms (including the carbon atoms of the substituents) can include, for example, ethoxyyl and hexoxyyl. Substituents that can be present in this alkyl group can include hydroxyl groups, halogen groups, etc., but are not limited to these groups.

[0185] Examples of cycloalkylidene groups that can have 5 to 20 carbon atoms (including the carbon atoms of the substituents) include cyclopentylidene and cyclohexylidene. Examples of substituents that can be present in this cycloalkylidene group include alkyl groups such as methyl, ethyl, propyl, and butyl, hydroxyl groups, and halogen groups, but are not limited to these groups.

[0186] Examples of arylalkylene groups that can have 8 to 20 carbon atoms (including the carbon atoms of the substituents) include phenyldimethyl, naphthyldimethyl, and biphenyldimethyl. Examples of substituents in this arylalkylene group include alkyl groups such as methyl, ethyl, propyl, and butyl, hydroxyl groups, and halogen groups, but are not limited to these groups.

[0187] Aryl alkylidene groups that can have 7 to 20 carbon atoms (including the carbon atoms of the substituents) can include, for example, phenylmethylene, phenylethoxy, and phenylpropene. Substituents that can be present in this aryl alkylidene group can include alkyl groups such as methyl, ethyl, propyl, and butyl, hydroxyl groups, and halogen groups, but are not limited to these groups.

[0188] The group represented by X, which combines these groups, can be exemplified by, for example, a divalent group formed by combining at least two of the above-mentioned aromatic hydrocarbon groups, alkylene groups, cycloalkylene groups, alkylidene groups, cycloalkylidene groups, arylalkylene groups, and arylalkylidene groups. There are no particular restrictions on the bonding positions, arrangements, etc., of each group; they can be appropriately determined.

[0189] The heterocyclic structure of compound C is not particularly limited, but is preferably a heterocyclic structure that may have substituents and contains at least one of nitrogen and oxygen atoms, i.e., a substituted or unsubstituted nitrogen-containing heterocyclic structure, an oxygen-containing heterocyclic structure, or an oxygen-nitrogen heterocyclic structure, and more preferably a substituted or unsubstituted nitrogen-containing heteroaromatic ring structure.

[0190] Examples of heterocycles found in compound C include: pyrrole rings, pyrrolidine rings, pyridine rings, pyrimidine rings, pyrazine rings, pyridazine rings, triazine rings, quinoline rings, isoquinoline rings, quinoxaline rings, phthalazine rings, quinazoline rings, naphthidine rings, carbazole rings, acridine rings, phenazine rings, piperidine rings, tetrahydropyran rings, morpholine rings, tetrahydrofuran rings, furan rings, thiazoline rings, thiazoline rings, thiazoline rings, and oxobutane rings. From the viewpoint of reactivity and solubility in various organic solvents, pyrimidine rings and triazine rings are preferred.

[0191] There are no particular restrictions on the bonding positions of the other structures of the above heterocycle (e.g., the structure represented by the above formula (A)). When it is bonded to two other structures, that is, when there are two bonding positions, from the point of view of reactivity, the meta position is preferred.

[0192] Examples of substituents that can be used in the above-mentioned heterocyclic structures include: halogen groups, hydrocarbon groups with 1 to 20 carbon atoms, halohydrocarbon groups with 1 to 20 carbon atoms, groups obtained by substituting one or more of these hydrocarbon groups or halohydrocarbon groups with at least one atom selected from oxygen and sulfur atoms, nitro groups, cyano groups, amino groups, and salts of amino groups.

[0193] Halogen groups that can be used as substituents include, for example, -F, -Cl, -Br and -I.

[0194] Examples of hydrocarbon groups with 1 to 20 carbon atoms among the above-mentioned substituents include: chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups.

[0195] Examples of the aforementioned chain hydrocarbon groups include: alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and n-pentyl; alkenyl groups such as vinyl, propenyl, butenyl, and pentenyl; and alkynyl groups such as ethynyl, propynyl, butynyl, and pentynyl.

[0196] Examples of the aforementioned alicyclic hydrocarbon groups include: monocyclic cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl; polycyclic cycloalkyl groups such as norbornyl and adamantyl; monocyclic cycloalkenyl groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, and cyclohexenyl; and polycyclic cycloalkenyl groups such as norbornyl.

[0197] Examples of aromatic hydrocarbon groups mentioned above include: aryl groups such as phenyl, tolyl, xylyl, naphthyl, and anthracene; and aralkyl groups such as benzyl, phenethyl, phenylpropyl, and naphthylmethyl.

[0198] As a substituent, a haloalkyl group with 1 to 20 carbon atoms can be exemplified by a group obtained by replacing part or all of the hydrogen atoms of the hydrocarbon group with 1 to 20 carbon atoms with halogen atoms such as fluorine, chlorine, bromine, or iodine atoms.

[0199] A group obtained by substituting a hydrocarbon group or a halohydrocarbon group having 1 to 20 carbon atoms among the above-mentioned substituents with at least one selected from oxygen and sulfur atoms, for example, groups obtained by substituting the hydrocarbon group or a halohydrocarbon group with -O-, -S-, ester group or sulfonyl group.

[0200] There are no particular restrictions on the amino group used as a substituent; it can be a primary amino group (-NH2), a secondary amino group (-NHR), or a tertiary amino group (-NR2).

[0201] There are no particular restrictions on the substituents (R) in the secondary and tertiary amino groups; for example, hydrocarbon groups with 1 to 20 carbon atoms can be listed above.

[0202] There are no particular restrictions on the anion sites in the salts that constitute the above-mentioned amino groups; Cl can be listed as an example. - Anions such as those commonly known.

[0203] From the viewpoint of reactivity and solubility, the substituents in the above-mentioned heterocyclic structures are preferably halogen groups, hydrocarbon groups with 1 to 6 carbon atoms, halohydrocarbon groups with 1 to 6 carbon atoms, nitro groups, cyano groups, amino groups or salts of amino groups, and more preferably fluorine atoms, chlorine atoms, methyl groups, nitro groups, cyano groups, tert-butyl groups, phenyl groups, and primary amino groups.

[0204] From the viewpoint of heat resistance and electrical properties, the above-mentioned heterocyclic structure is preferably selected from the structures represented by the following formulas (C) to (E), and more preferably the structure represented by formula (C).

[0205]

[0206] In equations (C) to (E), R d ~R h Each is independently an alkyl group with 1 to 20 carbon atoms, either substituted or unsubstituted, or an aromatic hydrocarbon group with 6 to 20 carbon atoms, either substituted or unsubstituted. n5 represents a real number from 0 to 4. n6, n8, and n9 each independently represent real numbers from 0 to 3. n7 represents a real number between 0 and 2. Q 1 ~Q 25 Each can be independently a nitrogen atom or a carbon atom, where Q 1 ~Q 6 At least one of them is a nitrogen atom, Q 7 ~Q 15 At least one of them is a nitrogen atom, Q 16 ~Q 25 At least one of them is a nitrogen atom, in Q11 and Q 12 If at least one of the atoms in Q is a nitrogen atom, then 11 With Q 12 The key and Q 7 With Q 12 The key and Q 12 With Q 13 The key is a single key, or Q. 11 With Q 12 The key and Q 10 With Q 11 The key and Q 11 With Q 15 The key is a single key, in Q. 20 and Q 21 If at least one of the atoms in Q is a nitrogen atom, then 20 With Q 21 The key and Q 16 With Q 21 The key and Q 21 With Q 22 The key is a single key, or Q. 20 With Q 21 The key and Q 19 With Q 20 The key and Q 20 With Q 25 The key is a single key. and Each is a bonding position.

[0207] As R d ~R h The alkyl groups represented by carbon atoms numbering 1 to 20 include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, etc.

[0208] As R d ~R h The aromatic hydrocarbon groups represented by carbon atoms from 6 to 20 include, for example, aryl groups such as phenyl, tolyl, xylyl, naphthyl, and anthracene; and aralkyl groups such as benzyl, phenethyl, phenylpropyl, and naphthylmethyl.

[0209] As R d ~R h The alkyl and aromatic hydrocarbon groups represented may have substituents, for example, the substituents of the heterocyclic structures described above can be listed similarly.

[0210] n5 is a real number from 0 to 4. From the point of view of aggregation, it is preferably 0 to 3, and more preferably 0 to 2.

[0211] n6, n8 and n9 are each independent real numbers from 0 to 3. From the point of view of aggregation, they are preferably 0 to 2, and more preferably 0 or 1.

[0212] n7 is a real number from 0 to 2. From the perspective of aggregation, it is preferable to be 0 or 1.

[0213] It should be noted that in equations (C) to (E) above, R is bonded to the ring structure. d ~R h There are no particular restrictions on the bonding positions of the equipotential bonding groups.

[0214] As mentioned above, in the heterocyclic structures represented by formulas (C) to (E), there are no particular restrictions on the arrangement of nitrogen atoms, and the positions of the double bonds in the ring structure can be appropriately selected accordingly without any particular restrictions.

[0215] Compound C can be represented, for example, by the structures represented by the following formulas (F) and (Z).

[0216] R 1 -O-(A 1 -BO-) n2 -(A 2 ) q1 -R 2 (F)

[0217] R 1 -O-(BOA 1 -) n2 -(BO) q2 -R 2 (Z)

[0218] In equations (F) and (Z), R 1 and R 2 Each of these groups can be independently a group containing an olefinic unsaturated double bond with 2 to 50 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group with 6 to 50 carbon atoms, a substituted or unsubstituted aliphatic hydrocarbon group with 6 to 50 carbon atoms, or a substituted or unsubstituted nitrogen-containing heteroaromatic ring. A 1 and A 2 Each is independently a group having a structure represented by formula (A) above or a group having a structure represented by formula (B) above, wherein, in formula (F) above, the groups in formula (A) and formula (B) above... Indicates with B or R 2 The bonding positions, in the above formula (Z), in the above formulas (A) and (B) Indicates with B or R 2 The bonding position, B is an independent divalent group with a nitrogen-containing heterocyclic structure. n2 are each an independent real number greater than 1. q1 is either 0 or 1. When q1 is 0, (A) 2 ) q1 Indicates a single key. q2 is either 0 or 1. When q2 is 0, (BO) q2 Indicates a single key.

[0219] As R 1 and R 2 The groups containing olefinic unsaturated double bonds and having 2 to 50 carbon atoms are represented, for example: 3-isopropenylphenyl, 4-isopropenylphenyl, 2-allylphenyl, 2-methoxy-4-allylphenyl, 4-(1-propenyl)-2-methoxyphenyl, 3-isopropenylbenzyl, 4-isopropenylbenzyl, 4-vinylbenzyl, 3-vinylbenzyl, 2-vinylbenzyl, etc., containing aromatic rings, allyl, acryloyl, methacryloyl.

[0220] Examples of aromatic hydrocarbon groups with 6 to 50 carbon atoms include: aryl groups such as phenyl, biphenyl, tolyl, xylyl, naphthyl, and anthracene; and aralkyl groups such as benzyl, phenethyl, phenylpropyl, and naphthylmethyl.

[0221] Examples of aliphatic hydrocarbon groups with 6 to 50 carbon atoms include: monocyclic cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl; polycyclic cycloalkyl groups such as norbornyl and adamantyl; monocyclic cycloalkenyl groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, and cyclohexenyl; and polycyclic cycloalkenyl groups such as norbornyl.

[0222] As the aforementioned nitrogen-containing heteroaromatic ring, the same rings as those exemplified with respect to the aforementioned heterocyclic structures can be listed.

[0223] As R 1 and R 2 The substituents that can be present include: groups other than hydroxyl groups, specifically including: allyl, halogen groups, hydrocarbon groups with 1 to 20 carbon atoms, haloalkyl groups with 1 to 20 carbon atoms, alkoxy groups with 1 to 20 carbon atoms, alkylthio groups with 1 to 20 carbon atoms, nitro, cyano, carboxyl, sulfonic acid, phosphonic acid, phosphoric acid, hydroxyl, primary amino, secondary amino, tertiary amino, salts of carboxyl, salts of sulfonic acid, salts of phosphonic acid, salts of phosphoric acid, salts of hydroxyl, or salts of primary amino, secondary amino, or tertiary amino groups. Allyl is preferred.

[0224] The halogen groups, hydrocarbon groups with 1 to 20 carbon atoms, and halohydrocarbon groups with 1 to 20 carbon atoms in the above-mentioned substituents can be groups that are the same as the substituents in the above-mentioned heterocyclic structures.

[0225] Examples of alkoxy groups with 1 to 20 carbon atoms include: methoxy, ethoxy, n-propoxy, isopropoxy, butoxy, pentoxy, hexoxy, and octoxy.

[0226] Examples of alkylthio groups with 1 to 20 carbon atoms include: methylthio, ethylthio, n-propylthio, isopropylthio, butylthio, pentylthio, hexylthio, and octylthio.

[0227] The substituents (R) in secondary amines (-NHR) and tertiary amines (-NR2) are not particularly limited; for example, hydrocarbon groups with 1 to 20 carbon atoms can be listed. As specific examples, groups exemplified as substituents in the above heterocyclic structures can also be listed.

[0228] There are no particular restrictions on the cation at the cation site in salts constituting carboxyl groups, sulfonic acid groups, phosphonic acid groups, phosphate groups, and hydroxyl groups; examples include Na. + Well-known cations.

[0229] There are no particular restrictions on the anion sites in the salts that constitute amino groups; examples include Cl. - Anions such as those commonly known.

[0230] It should be noted that A 1 and A 2 The group representing the structure indicated by formula (A) above is preferably the group represented by formula (B) above. In this case, in the case of formula (F), the group in formula (B) Indicates the bonding position with O. Indicates with B or R 2 The bonding positions. Similarly, in the case of equation (Z), in equation (B) Indicates the bonding position with O. Indicates with B or R 2 The bonding positions.

[0231] Furthermore, the divalent group with a nitrogen-containing heterocyclic structure represented by B is preferably a group selected from the structures represented by formulas (C) to (E) above. In this case, the groups in formulas (C) to (E) and Each represents A in equation (F). 1 Or the bonding position of O, and indicates the relationship with O and A in equation (Z). 1 Or R 2 The bonding positions.

[0232] n2 is a real number greater than or equal to 1, for example, a real number between 1 and 100.

[0233] Furthermore, compound C is preferably a compound represented by the following formula (G).

[0234]

[0235] In equation (G), R 10 and R 16 Each of these groups can be independently a group containing an olefinic unsaturated double bond with 2 to 50 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group with 6 to 50 carbon atoms, a substituted or unsubstituted aliphatic hydrocarbon group with 6 to 50 carbon atoms, or a substituted or unsubstituted nitrogen-containing heteroaromatic ring. R 11 R 12 R 14 and R 15 Each of the following groups is independently a hydroxyl group, a halogen group, a substituted or unsubstituted aromatic hydrocarbon group with 6 to 20 carbon atoms, a substituted or unsubstituted alkyl group with 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group with 5 to 20 carbon atoms, or a substituted or unsubstituted aralkyl group with 7 to 20 carbon atoms. R 13 Each is independently an alkyl group with 1 to 20 carbon atoms, either substituted or unsubstituted, or an aromatic hydrocarbon group with 6 to 20 carbon atoms, either substituted or unsubstituted. X 1 and X 2 Each of these groups is independently a single bond, an aromatic hydrocarbon group with 6 to 20 substituted or unsubstituted carbon atoms, an alkylene group with 1 to 20 substituted or unsubstituted carbon atoms, a cycloalkylene group with 5 to 20 substituted or unsubstituted carbon atoms, an alkylidene group with 1 to 20 substituted or unsubstituted carbon atoms, a cycloalkylidene group with 5 to 20 substituted or unsubstituted carbon atoms, an arylalkylene group with 8 to 20 substituted or unsubstituted carbon atoms, or an arylalkylidene group with 7 to 20 substituted or unsubstituted carbon atoms, or a group composed of these groups. Q is each independently either a nitrogen atom or a carbon atom, wherein at least two of Q are nitrogen atoms. m1, m2, m4 and m5 are real numbers from 0 to 4. From the viewpoint of polymerizability and heat resistance, 0 to 2 are preferred, and 0 or 1 are more preferred.

[0236] m3 is a real number from 0 to 2. From the viewpoint of polymerizability and heat resistance, it is preferred to be 0 or 1.

[0237] p1 is a real number greater than or equal to 1, for example, a real number between 1 and 100.

[0238] It should be noted that R 10 and R 16 Each of the structures represented is related to R in the above equation (F). 1 and R 2 Similarly, the preferred method is also the same. Additionally, R... 11 R 12R 14 and R 15 Each of the structures represented is related to R in equation (B) above. b and R c Similarly, the preferred method is also the same. Furthermore, R 13 The structures represented are all related to R in equations (C) to (E) above. d ~R h Similarly, the preferred method is also the same. Additionally, X 1 and X 2 The structures represented are the same as X in the above formula (B), and the preferred methods are also the same.

[0239] Furthermore, compound C is particularly preferred to be a compound represented by the following formula (G-1).

[0240]

[0241] In equation (G-1), R 10 ~R 16 X 1 and X 2 m1 to m5 and p1 are the same as those represented by the above formula (G), and the preferred method is also the same.

[0242] It should be noted that, for example, the following compounds can also be used as compound C mentioned above.

[0243] Modified polyphenylene ether (PPE) resin, vinyl benzyl ether resin, curable resin having heterocyclic ether bonds such as triazine ether in the main chain, polyfunctional methacrylate compounds having two or more methacryloyl groups in the molecule, polyfunctional acrylate compounds having two or more acryloyl groups in the molecule, isocyanurate trimeryl ester compounds such as TAIC, polyfunctional acrylate compounds, and polyfunctional methacrylate compounds can also be used as compound C. The aforementioned vinyl benzyl ether resin (compound having vinyl benzyl ether groups) can be synthesized, for example, by reacting phenolic resins such as biphenyl aralkyl phenol, aralkyl phenol, and naphthol aralkyl resin with chloromethylstyrene under an alkaline catalyst. As the aforementioned modified PPE resin, for example, it can be manufactured under the trade name Noryl (registered trademark) SA-9000 by Saudi Basic Innovation Plastics Company.

[0244] From the viewpoint of heat resistance, the content of compound C in the solid component of this composition is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more. Furthermore, from the viewpoint of electrical properties, the content of compound C in the solid component of this composition is preferably 80% by mass or less, more preferably 70% by mass or less, even more preferably 50% by mass or less, even more preferably 40% by mass or less, and particularly preferably 30% by mass or less.

[0245] (Other ingredients)

[0246] This composition may also contain other curable resins besides resin A, flame retardants besides the organophosphorus compounds, crosslinking agents, fillers, elastomers, and other additives. Additionally, this composition may contain polymerization initiators such as dicumyl peroxide, 2,3-dimethyl-2,3-diphenylbutane (CCDFB), and azo initiators. It should be noted that the other components do not contain any of the components belonging to resin A, compound B, and compound C. Furthermore, from an environmental perspective, it is preferable that these other components do not contain halogenated materials.

[0247] This composition can be used in conjunction with other curing resins as needed. As other curing resins, known resins can be used appropriately, such as ODV, soluble divinylbenzene polymers.

[0248] By adding a crosslinking agent to this composition and then curing it, a cured composition with good properties can be obtained.

[0249] Examples of crosslinking agents include compounds having reactive functional groups such as styrene (St) or allyl groups in their molecules. From the viewpoint of reactivity with the composition, styrene is preferred as the reactive functional group. More specifically, from the viewpoint of electrical properties, 1,2-bis(vinylphenyl)ethane (BVPE), fluorene compounds having a vinyl benzyl group as described in Japanese Patent No. 3681170, indene compounds having a vinyl benzyl group, divinylbenzene, and other vinyl compounds are preferred, with BVPE being more preferred. The crosslinking agent can be a mixture of two or more compounds (polymers) having repeating units; for example, vinyl compounds represented by formula (H) or vinyl compounds represented by formula (I) can be used.

[0250]

[0251] In equation (H), X a It indicates a hydrocarbon group containing at least one selected from aromatic cyclic groups and aliphatic cyclic groups, with 6 or more carbon atoms, n a Represents integers from 1 to 10.

[0252]

[0253] In equation (I), X b This represents any one or more of (a) to (h) described in the following formula (J). Here, there are multiple X... b In the case of multiple X b They can be the same or different. A 2 The symbol represents a methylene group or an oxygen atom. Q represents a hydrocarbon group or a haloalkyl group with 1 to 10 carbon atoms. Multiple Qs can be the same or different. R represents a hydrocarbon group or a haloalkyl group with 1 to 10 carbon atoms. When multiple Rs are present, they can be the same or different. l and m each represent an integer from 0 to 3, and n... b For repeating units, l≤n b ≤20, p is a repeating unit, 1.1≤p≤20.

[0254]

[0255] In equation (11), Each represents a bonding position.

[0256] Examples of crosslinking agents include compounds obtained by reacting a compound with a partially fluorene or indene skeleton with a halogenated compound having a St group, such as chloromethylstyrene, in the presence of a base catalyst. In the above reaction, a phase transfer catalyst can be used, and the solvent is preferably an aprotic organic solvent or a solvent containing an aprotic organic catalyst. More specifically, examples of crosslinking agents include compounds represented by the following formula (K), obtained by reacting a compound with a partially fluorene skeleton with chloromethylstyrene.

[0257]

[0258] In equation (K), R 30 X represents a hydrogen atom, a hydrocarbon group with 1 to 10 carbon atoms, or a haloalkyl group. 10 Represents integers from 0 to 4.

[0259] Furthermore, as the aforementioned crosslinking agent, vinyl compounds (polyfunctional vinyl compounds) having two or more vinyl groups in their molecules, such as polybutadiene and styrene-butadiene copolymers, polyfunctional aromatic copolymers obtained by copolymerizing divinylbenzene with styrene derivatives, and vinyl benzyl compounds such as styrene and divinylbenzene having vinyl benzyl groups in their molecules can be used. Among these, substances having two or more carbon-carbon double bonds in their molecules are preferred. Specifically, examples include polyfunctional aromatic copolymers and divinylbenzene compounds. It is believed that if these substances are used, crosslinking can be formed more appropriately through the curing reaction, which can further improve the heat resistance of the cured product of this composition. In addition, the crosslinking agent shown can be used alone, or two or more can be used in combination. Furthermore, as a crosslinking agent, compounds having two or more carbon-carbon unsaturated double bonds in their molecules and compounds having one carbon-carbon unsaturated double bond in their molecules can be used together. As a compound having one carbon-carbon unsaturated double bond in its molecules, specifically, compounds having one vinyl group in their molecules (monovinyl compounds) can be included.

[0260] It should be noted that, regarding the aforementioned crosslinking agent, the average number of carbon-carbon unsaturated double bonds (terminal double bond number) per molecule of crosslinking agent varies depending on the weight-average molecular weight of the crosslinking agent. From the viewpoint of the heat resistance of the cured product, it is preferable to have 1 or more, more preferably 2 or more. Furthermore, from the viewpoints of reactivity, shelf life of the composition, and flowability, the number of terminal double bonds per molecule of crosslinking agent is preferably 20 or less, more preferably 18 or less.

[0261] When considering the weight-average molecular weight of the crosslinking agent, if the weight-average molecular weight of the crosslinking agent is less than 500 (e.g., greater than or equal to 100 and less than 500), the number of terminal double bonds in the crosslinking agent is preferably 1 to 4. Furthermore, if the weight-average molecular weight of the crosslinking agent is 500 or more (e.g., 500 or more and less than 5000), the number of terminal double bonds in the crosslinking agent is preferably 3 to 20. In each case, if the number of terminal double bonds is above the lower limit of the above range, the crosslinking agent tends to have good reactivity, easily imparts a suitable crosslinking density to the cured resin composition, and easily improves heat resistance and Tg. On the other hand, if the number of terminal double bonds is below the upper limit of the above range, gelation of the composition can be easily prevented.

[0262] The number of terminal double bonds in the crosslinking agent can be determined from the specifications of the product. Here, the number of terminal double bonds refers to the average number of double bonds per molecule of all crosslinking agents present in 1 mole of the crosslinking agent.

[0263] Other flame retardants mentioned above include, for example, halogenated flame retardants such as brominated flame retardants. Each flame retardant can be used alone or in combination with two or more. However, from an environmental perspective, this composition preferably does not contain halogenated materials. When using a halogenated flame retardant, for example, SAYTEX 8010 (trade name, manufactured by Albemarle Corporation) can be used. These compounds can be manufactured using conventionally known methods. It should be noted that commercially available halogenated flame retardants can also be used. The structure of SAYTEX 8010 is described below.

[0264]

[0265] As the filler mentioned above, silica, hollow silica, etc., can be used. From the viewpoint of dielectric properties, it is preferable that the filler has fewer silanol groups. In addition, by making silica hollow, a composition with a low dielectric constant can be obtained. Fillers with silica surface modified treatment can also be used. Specifically, fillers treated with functional groups containing carbon-carbon unsaturated double bonds and / or treated with trimethylsilylation can be used.

[0266] Examples of such elastomers include styrene-based elastomers, such as styrene-butadiene-styrene copolymers, hydrogenated styrene-butadiene-styrene copolymers, styrene-isoprene-styrene copolymers, hydrogenated styrene-isoprene-styrene copolymers, and hydrogenated styrene (butadiene / isoprene)-styrene copolymers.

[0267] In addition, acenaphthene and indene, and their derivatives, may be incorporated into this composition as needed. The proportion of these compounds relative to this composition may be 75% by mass or less.

[0268] Furthermore, this composition may contain a fluorinated resin. From the viewpoint of improving adhesiveness, the fluorinated resin may have functional groups.

[0269] Furthermore, in this composition, the total content of oxygen and nitrogen atoms in the organic matter other than the inorganic filler can be, for example, 0.01% to 10% by mass. This content can be calculated by determination using elemental analysis based on combustion method, or by calculation when using raw materials with known structures.

[0270] <Method for manufacturing resin composition>

[0271] This composition can be prepared by mixing the above-mentioned resin A, organophosphorus compound (compound B) and compound C, and various additives as needed.

[0272] (Manufacturing method of resin A)

[0273] The resin A described above can be obtained, for example, by polymerizing a compound having multiple isopropenyl groups (e.g., a diisopropenyl compound) under an acid catalyst at a reaction temperature of 10°C to 75°C.

[0274] It should be noted that, as described above, in addition to the α-olefin structure represented by formula (1), resin A may also have the aforementioned terminal olefin structure, side-chain olefin structure, indene structure represented by formula (2), and internal olefin structure represented by formula (3). Here, these structures are generated through the reaction between molecules containing isopropenyl groups in the raw materials. The indene structure has an advantage in terms of equilibrium (thermodynamics), while the α-olefin structure has an advantage in terms of kinetics. Therefore, the proportions of each structure contained in resin A can be controlled according to the reaction conditions, such as the type of catalyst and temperature.

[0275] Here, the aforementioned compound having multiple isoalkenyl groups refers to a compound having two or more isoalkenyl groups in one molecule. As this compound, compounds manufactured by conventionally known methods can be used as described above, such as diisopropenylbenzene derivatives like 1,3-diisopropenylbenzene and 1,4-diisopropenylbenzene. Alternatively, its precursor (e.g., α,α,α',α'-tetramethyl-1,3-benzenedimethanol) can also be used as this compound.

[0276] It should be noted that in the manufacturing method of resin A, other compounds can be copolymerized with the aforementioned compound having multiple isopropyl groups. That is, resin A can be a homopolymer (homogene) of a compound having multiple isopropyl groups, or it can be a copolymer (copolymer) using multiple compounds containing that compound.

[0277] Other compounds mentioned above may include, for example, monovinyl compounds and divinyl compounds. More specifically, other compounds may include α-methylstyrene, α-methylstyrene dimers, α-olefin compounds such as diphenylethylene, monoisopropyl compounds, and cyclic dienes. For example, the aforementioned monoisopropyl compounds can be used as terminators to stop growth reactions.

[0278] Furthermore, from the perspective of adjusting physical properties and molecular weight by introducing functional groups, structures such as phenolic structures, aromatic amine structures, aromatic ether structures, and maleimide structures can be introduced into resin A. When introducing such structures, it is preferable to introduce them into the structure during the polymerization reaction using an electrophilic substitution reaction based on the cation generated from the isoalkenyl group of the raw material.

[0279] However, as mentioned above, resin A may also not contain heteroatoms other than carbon and hydrogen atoms.

[0280] From a reactivity point of view, the moisture content in the raw materials used to obtain resin A, such as monomers, is preferably below 500 ppm. If necessary, the raw materials can be dehydrated using molecular sieves, alumina, or similar materials.

[0281] Examples of acid catalysts used in polymerization reactions include inorganic acids, solid acids, organic sulfonic acids, Lewis acids, and Brønsted acids, as listed below. It should be noted that an acid can belong to multiple categories, including inorganic acids, solid acids, organic sulfonic acids, Lewis acids, and Brønsted acids.

[0282] Inorganic acids: such as sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, Solid acids: such as activated clay, acidic clay, silica-alumina, zeolite, sulfonated carbon, strong acid ion exchange resins, heteropoly acids, tungstic acid, etc. Organic sulfonic acids: such as benzenesulfonic acid, toluenesulfonic acid, xylenesulfonic acid, methanesulfonic acid, fluoromethanesulfonic acid, CF3SO3H, C2F5SO3H and C6F5SO3H and other perfluoroalkane sulfonic acids, Lewis acids: such as AlCl3, TiCl4, SnCl4, B(C6F5)3, BF3, and Lewis bases and their complexes, methylaluminoxanes, metallocene halides and methylaluminoxanes, combinations of metallocene halides and methylaluminoxanes, and combinations of the above substances. Brønsted acids: such as boric acid, acetic acid, and benzoic acid.

[0283] The Lewis base described above, which acts as a co-catalyst component, may, for example, be one or more selected from the group consisting of esters, thioesters, ketones, amines, ethers, thioethers, and phosphines.

[0284] Ester compounds: such as ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, phenyl acetate, methyl propionate, dimethyl carbonate, diethyl carbonate, ethylene carbonate, etc. Thioester compounds: such as methyl mercaptopropionate, ethyl mercaptopropionate, Ketone compounds: such as methyl ethyl ketone, methyl isobutyl ketone, benzophenone, Amine compounds: such as methylamine, ethylamine, propylamine, butylamine, cyclohexylamine, methylethylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, etc. Ether compounds: such as diethyl ether, methyl tert-butyl ether, diethylene glycol dimethyl ether, propylene glycol dimethyl ether, tetrahydrofuran, cyclopentylmethyl ether, Thioether compounds: such as diethyl sulfide, diphenyl sulfide, Phosphine compounds: such as tripropylphosphine, tributylphosphine, trihexylphosphine, tricyclohexylphosphine, trioctylphosphine, vinylphosphine, propenylphosphine, cyclohexenylphosphine, dienylphosphine, and trienylphosphine.

[0285] In the method for manufacturing resin A, from the viewpoint of easily generating α-olefin structures (and terminal olefin structures, side-chain olefin structures) and easily controlling molecular weight, it is preferable to use a combination (mixture) of one or more of the above-mentioned ester compounds, ketone compounds, and ether compounds with one or more of the above-mentioned acid catalysts. Here, examples of acid catalysts include the above-mentioned Brønsted acids, Lewis acids, organic sulfonic acids, and inorganic acids. Furthermore, from the same viewpoint, it is preferable to use an acid catalyst selected from the group consisting of methanesulfonic acid, BF3 complex, tin chloride, and toluenesulfonic acid.

[0286] The amount of the co-catalyst relative to the acid catalyst can be changed according to the reaction conditions, so there is no particular limitation. The co-catalyst is preferably more than 1 mole relative to 1 mole of acid catalyst.

[0287] For example, as an acid catalyst, a mixture of Lewis acid (e.g., BF3·O(C2H5)2) and Lewis base (e.g., isopropyl acetate) can be used.

[0288] The above polymerization reaction can be carried out in a solvent. Examples of such solvents include: nonpolar organic solvents such as hexane, decane, dodecane, cyclohexane, benzene, toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, and trimethylbenzene; chlorinated organic solvents such as dichloromethane, trichloromethane, carbon tetrachloride, 1,2-dichloroethane, trichloroethane, and perchloroethane; and aromatic compounds such as halobenzenes, nitrobenzenes, and trifluoromethylbenzene. In addition to the solvents mentioned above, the above-mentioned ester compounds, ketone compounds, and ether compounds can also be used as solvents.

[0289] In the manufacturing method of resin A, the reaction temperature during polymerization is preferably 10°C to 75°C. When the reaction temperature is above 10°C, the reaction can be easily terminated within an appropriate time. In addition, when the reaction temperature is below 75°C, the formation of indene structures and internal olefin structures is easily suppressed, while α-olefin structures, terminal olefin structures, and side-chain olefin structures are easily formed.

[0290] In the method for manufacturing resin A, it is preferable to add the raw material (e.g., a diisopropylene compound) to a reaction solution containing an acid catalyst and then carry out a aging reaction. Here, the reaction temperature and reaction time in the polymerization reaction each refer to the temperature and time from the start of the polymerization reaction of the added raw material to the end of the polymerization reaction. That is, the reaction time begins at the stage when the polymerization reaction of a portion of all the raw materials begins. On the other hand, the aging temperature and aging time in the polymerization reaction each refer to the temperature and time from the end of the addition of all the raw materials to the reaction system (or after all the raw materials are added dropwise in the case of adding the raw materials dropwise) to the end of the reaction (during the aging reaction). That is, the reaction time mentioned above is the same as the end time of the aging time mentioned above. It should be noted that the polymerization reaction in the method for manufacturing resin A can be stopped by adding an alkaline raw material to the reaction system and quenching it, or by lowering the temperature in the reaction system, or by removing the catalyst through washing with water, etc. In this case, even if there are residual raw materials, the reaction can be stopped when the desired proportions of each structure are obtained. In this way, when the polymerization reaction stops, the stopping time is taken as the end time of the above-mentioned reaction time and ripening time.

[0291] From the viewpoint of controlling the proportion and molecular weight of α-olefin structures (and terminal olefin structures, side-chain olefin structures) and controlling the formation of insoluble components, the above-mentioned aging time is preferably 72 hours or less, more preferably 32 hours or less, even more preferably 24 hours or less, and particularly preferably 12 hours or less.

[0292] Furthermore, from the viewpoint of controlling molecular weight, the above-mentioned ripening time is preferably 5 minutes or more, more preferably 10 minutes or more, and even more preferably 15 minutes or more.

[0293] Furthermore, from the viewpoint of controlling molecular weight and structure, the above-mentioned aging temperature is preferably 10℃~75℃.

[0294] In the method for manufacturing resin A, the solution containing the polymer (polymer) after the polymerization reaction has stopped can be purified by known methods to obtain the target product (resin A). Examples of purification methods include: washing water-soluble compounds with water and removing them by separation; removing low-boiling-point compounds such as solvents by distillation under reduced pressure; and reprecipitating by mixing with a poor solvent.

[0295] The obtained polymer can be further purified using known methods to achieve high purity. Purification methods include, for example, methods for repeated dissolution and reprecipitation, washing with unsuitable solvents, vacuum drying, and adsorption treatment using cation exchange adsorbents or anion exchange adsorbents.

[0296] After the above operations, resin A can be obtained. It should be noted that different curable functional groups such as hydroxyl and amino groups can be introduced into resin A to produce cured products with phenolic resin, epoxy resin, polyimide resin, etc., or resin A can be modified and used as maleimide resin or benzo[a]azine resin.

[0297] (Method for manufacturing organophosphorus compound (compound B))

[0298] Organophosphorus compounds can be commercially available or manufactured using methods known in the past. For example, the organophosphorus compounds shown below can be manufactured using the following methods.

[0299]

[0300] First, phosphorus oxychloride, 2,6-xylenol, xylene as a solvent, and magnesium chloride as a catalyst are reacted under heating conditions (e.g., at 160°C) to synthesize the following bis(2,6-xylenyl) chlorophosphate. It should be noted that the hydrogen chloride (hydrogen chloride gas) generated in the reaction is recovered, and xylene, unreacted phosphorus oxychloride, 2,6-xylenol, and byproduct hydrogen chloride are removed by vacuum depressurization.

[0301]

[0302] Next, the obtained bis(2,6-dimethyl) chlorophosphate and bisphenol were added to the solvents toluene and tetrahydrofuran, and triethylamine was added dropwise under heating conditions (e.g., 65°C) while stirring. Then, the organophosphorus compound was obtained by distillation and purification as needed.

[0303] (Method for manufacturing compound C)

[0304] There are no particular restrictions on the method of manufacturing compound C, and well-known methods can be used appropriately. For example, if compound C is represented by the structure shown in formula (F) above, it can be manufactured by making A, which is a component of formula (F). 1 The monomers of some raw materials become those containing A 2 The monomer of the raw material, becoming the monomer of the raw material containing B, becoming the monomer of the raw material containing R 1 The monomers of some raw materials become those containing R 2 The monomers, along with other monomers as needed, are synthesized by heating in an organic solvent with alkali metals, alkali metal compounds, etc. It should be noted that this process involves heating to obtain a product containing A. 1 The monomers of some raw materials and become containing A 2 The monomers in some of the raw materials can be the same monomer or different monomers. Additionally, it becomes a component containing R... 1The monomers of some raw materials and becoming containing R 2 The monomers in some of the raw materials can be the same monomer or different monomers. For example, it can be a mixture containing A 1 After the monomers of the raw material containing B are polymerized, they will become the monomers of the raw material containing R. 1 Or R 2 The monomers or other monomers of the raw materials are heated, mixed, and reacted.

[0305] As mentioned above, it includes A. 1 Or A 2 Some of the raw materials are monomers, for example: dihydroxyphenyl compounds such as hydroquinone, resorcinol, catechol, and phenylhydroquinone; 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3-phenylphenyl)fluorene, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, bis(4-hydroxyphenyl)diphenylmethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-allylphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3-phenylphenyl)propane, 4,4'-(1,3-dimethylphenyl)propane, etc. Bisphenol compounds including butylene(2-(4-hydroxyphenyl)-bisphenol, 1,1-bis(4-hydroxyphenyl)-nonane, bis(4-hydroxyphenyl)sulfone, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(3-methyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(3-cyclohexyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,4-bis[2-(4-hydroxyphenyl)-2-propyl]benzene, 1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene, 4,4'-cyclododecylidene bisphenol, 4,4'-decylidene bisphenol, etc.; Priplast Diol compounds such as 1901, 1838, 3186, 3192, 3197, and 3199 (all trade names, manufactured by Croda Japan Co., Ltd.). It should be noted that these monomers can be used alone or in combination.

[0306] Monomers that serve as raw materials comprising part B, as described above, include, for example: 4,6-dichloropyrimidine, 4,6-dibromopyrimidine, 2,4-dichloropyrimidine, 2,5-dichloropyrimidine, 2,5-dibromopyrimidine, 5-bromo-2-chloropyrimidine, 5-bromo-2-fluoropyrimidine, 5-bromo-2-iodopyrimidine, 2-chloro-5-fluoropyrimidine, 2-chloro-5-iodopyrimidine, 2-phenyl-4,6-dichloropyrimidine, 2-methylthio-4,6-dichloropyrimidine, 2-methylsulfonyl-4,6-dichloropyrimidine, 5-methyl-4,6-dichloropyrimidine, 2-amino-4,6-dichloropyrimidine, 5-amino-4,6-dichloropyrimidine, 2,5-diamino-4,6-dichloropyrimidine, 4-amino-2,6-dichloropyrimidine, 5-methoxy- Pyrimidine compounds such as 4,6-dichloropyrimidine, 5-methoxy-2,4-dichloropyrimidine, 2-methyl-4,6-dichloropyrimidine, 6-methyl-2,4-dichloropyrimidine, 5-methyl-2,4-dichloropyrimidine, 5-nitro-2,4-dichloropyrimidine, 4-amino-2-chloro-5-fluoropyrimidine, 2-methyl-5-amino-4,6-dichloropyrimidine, and 5-bromo-4-chloro-2-methylthiopyrimidine; pyridazine compounds such as 3,6-dichloropyridazine, 3,5-dichloropyridazine, and 4-methyl-3,6-dichloropyridazine; and pyrazine compounds such as 2,3-dichloropyrazine, 2,6-dichloropyrazine, 2,5-dibromopyrazine, 2,6-dibromopyrazine, 2-amino-3,5-dibromopyrazine, and 5,6-dicyano-2,3-dichloropyrazine. It should be noted that these monomers can be used individually or in combination.

[0307] As mentioned above, it includes R. 1 R 2 Some of the raw materials can be monomers, for example: monohydric phenols such as tert-butylphenol, nonylphenol, 4-isopropenylphenol, 4-vinylphenol, 2-allylphenol, isoeugenol, tocotrienol, α-tocopherol, 4-hydroxyphenylmaleimide, and 2-phenylphenol; monohydric amines such as 4-hexylaniline and diallylamine; monohydric thiols such as 1-octanethiol; monohydric aliphatic halides such as allyl chloride, 4-(chloromethyl)styrene, and 3-(chloromethyl)styrene; monohydric acyl halides such as acryloyl chloride, methacryloyl chloride, crotonyl chloride, and cinnamoyl chloride; and monohydric anhydrides such as acrylic anhydride, crotonic anhydride, and methacrylic anhydride. It should be noted that one or more of these monomers can be used.

[0308] Other monomers include, for example, compounds derived from diphenyl carbonate, thiodiphenyl carbonate, selenodiphenyl carbonate, phosgene, thiophosgene, and selenophosgene that contain structural units containing carbonate bonds, thiocarbonate bonds, or selenocarbonate bonds; dihydroxy compounds such as benzenediethanol and cyclohexanediethanol; phosphine oxide compounds such as bis(fluorophenyl)phenylphosphine oxide, bis(fluorophenyl)naphthylphosphine oxide, and bis(fluorophenyl)anthraylphosphine oxide; and dihalides of dicarboxylic acids such as phthaloyl chloride, isophthaloyl chloride, and terephthaloyl chloride. It should be noted that these monomers can be used individually or in combination.

[0309] In the synthesis of compound C, when phenolic compounds or other compounds with hydroxyl groups are used as raw materials, the aforementioned alkali metals and alkali metal compounds react with the hydroxyl-containing compounds to form alkali metal salts.

[0310] Examples of such alkali metals and alkali metal compounds include: Alkali metals such as lithium, sodium, and potassium; Lithium hydride, sodium hydride, potassium hydride, and other alkali metal hydrides; Alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; Alkali metal carbonates such as lithium carbonate, sodium carbonate, and potassium carbonate; Alkali metal bicarbonates such as lithium bicarbonate, sodium bicarbonate, and potassium bicarbonate.

[0311] Alkali metal carbonates are preferred, and potassium carbonate is even more preferred.

[0312] When using a compound having hydroxyl groups in the synthesis of compound C, the amount of alkali metal and alkali metal compound used is such that the lower limit of the ratio of the number of moles of alkali metal atoms to the number of moles of hydroxyl groups in all compounds used to synthesize compound C is preferably 1, more preferably 1.1, and even more preferably 1.2, and the upper limit of the ratio is preferably 3, more preferably 2, and even more preferably 1.8.

[0313] Examples of organic solvents mentioned above include: Ether solvents such as tetrahydrofuran (THF), dialkyl, cyclopentylmethyl ether, anisole, phenethyl ether, diphenyl ether, dialkoxybenzene, and trialkoxybenzene; Nitrogen-containing solvents such as N,N-dimethylacetamide (DMAc), N,N-dimethylformamide, N-methyl-2-pyrrolidone, and 1,3-dimethyl-2-imidazolinone; Ester solvents such as γ-butyrolactone; Sulfur-containing solvents such as sulfolane, dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, diethyl sulfone, diisopropyl sulfone, and diphenyl sulfone; Ketone solvents such as benzophenone, 2-heptanone, cyclohexanone, and methyl ethyl ketone; Halogen solvents such as dichloromethane, trichloromethane, and chlorobenzene; Aromatic hydrocarbon solvents such as benzene, toluene, and xylene.

[0314] Among these organic solvents, 2-heptanone, cyclohexanone, N-methyl-2-pyrrolidone, toluene, and xylene are preferred, and N-methyl-2-pyrrolidone, 2-heptanone, and cyclohexanone are more preferred.

[0315] The reaction temperature during the above synthesis is preferably 50°C or higher, more preferably 80°C or higher, more preferably 300°C or lower, and even more preferably 200°C or lower.

[0316] The reaction time for the above synthesis is preferably 1 hour or more, more preferably 2 hours or more, even more preferably 3 hours or more, preferably 100 hours or less, more preferably 50 hours or less, and even more preferably 24 hours or less.

[0317] From the perspective of inhibiting gelation of the polymerization reaction solution, adding a product containing R after polymerization is recommended. 1 R 2 The reaction temperature for the monomer of a portion of the raw materials is preferably 0°C or higher, more preferably 10°C or higher, preferably 130°C or lower, and more preferably 110°C or lower.

[0318] Add after aggregation to include the above R. 1 R 2 The reaction time for reacting monomers of a portion of the raw materials is preferably 1 hour or more, more preferably 2 hours or more, even more preferably 3 hours or more, preferably 48 hours or less, more preferably 24 hours or less, and even more preferably 10 hours or less.

[0319] <Prepreg>

[0320] The prepreg disclosed herein (hereinafter also referred to as the prepreg) comprises the composition described above. The prepreg can be manufactured, for example, by the following method. Specifically, firstly, the composition, to which other additives (elastomers, crosslinking agents, curing agents, etc.) as described above are added as needed, is mixed and stirred to prepare a resin varnish. Next, the resin varnish is impregnated into a fibrous material and dried to obtain the prepreg.

[0321] Here, from the viewpoints of processability and electrical properties, glass cloth of any composition is preferred as the fibrous material in which the resin varnish is impregnated, and from the viewpoint of electrical properties, quartz cloth is more preferred.

[0322] <Metal-coated laminates and their manufacturing methods>

[0323] The metal-clad laminate disclosed herein (hereinafter referred to as the laminate) comprises a cured product of the above-described composition and a metal foil. The laminate can be obtained by laminating the prepreg containing the composition to the metal foil. More specifically, the laminate can be manufactured by laminating the metal foil (e.g., copper foil) to both sides of the prepreg impregnated with the composition using a laminator or similar means under conditions such as heating and pressure.

[0324] From a practical point of view, the metal foil peel strength (peel strength) of the metal-coated laminate obtained by pressing, heating and bonding a prepreg obtained using this composition with a metal foil is preferably 2.0 N / cm or more, and more preferably 2.5 N / cm or more.

[0325] Example

[0326] The present disclosure is illustrated in more detail below using several examples, but the disclosure is not limited to these examples. It should be noted that Examples 1 to 23 are embodiments of the present disclosure, and Examples 24 to 27 are comparative examples.

[0327] <Structural Analysis Methods>

[0328] use 1 H-NMR and 13 C-NMR determined the proportions of the various structures in resin A, compound B, and compound C used in each example.

[0329] ( 1 H-NMR)

[0330] The analyte (e.g., resin A) is dissolved in chloroform-d1, and then... 1 The determination was performed using ¹H NMR (manufactured by Bruker, trade name: Avance NEO400). Tetramethylsilane was used as an internal standard. Peaks from hydrogen atoms of the α-olefin structure, inner olefin structure, terminal olefin, and side-chain olefin of this invention were confirmed in the range of 4.70–5.40 ppm.

[0331] ( 13 C-NMR)

[0332] The analyte (e.g., resin A) was dissolved in chloroform-d1 at a concentration of 20% by mass, and then... 13 The determination was performed using C-NMR (manufactured by JEOL Corporation, trade name: ECZ600). Hexamethyldisiloxane was used as an internal standard. Spectroscopic analysis was performed using Delta v6.0 (analysis software manufactured by NEC Corporation).

[0333] (Calculation of the content of each structure in resin A)

[0334] Peaks were assigned using two-dimensional NMR and DEPT methods. Specifically, in 13 The baselines of each peak in the C-NMR were drawn. Based on the area a (16.8 ppm to 18.2 ppm) of carbon belonging to the inner olefin structure, the area b (59.1 ppm to 60.2 ppm) of carbon belonging to the indene structure, the area c (114.3 ppm to 118.1 ppm) of carbon belonging to the α-olefin structure, terminal olefin structure, and side-chain olefin structure, the area d (21.6 ppm to 22.3 ppm) of carbon belonging to the terminal olefin structure and side-chain olefin structure, the area e (1.4 ppm to 2.5 ppm) of the internal standard, and the amount of hexamethyldisiloxane added f (g), the content (mmol / g) of each structure in 1 g of the target substance (resin A) was calculated using the formula shown below, based on the amount of the target substance (resin A) g (g).

[0335] Internal olefin content: a / (e / 6)×f / 162.38 / g×1000

[0336] Indene content: b / (e / 6)×f / 162.38 / g×1000

[0337] α-olefin content: (cd) / (e / 6)×f / 162.38 / g×1000

[0338] Content of terminal olefins and side chain olefins: d / (e / 6)×f / 162.38 / g×1000.

[0339] FA = [content of α-olefin structure] / ([content of internal olefin structure] + [content of indene structure] + [content of α-olefin structure])

[0340] FI = [Indene structure content] / ([Inner olefin structure content] + [Indene structure content] + [α-olefin structure content] / 2)

[0341] <Methods for determining iodine value>

[0342] The iodine value of the analyte (resin A) was determined according to the method of JIS K0070. Specifically, the analyte was reacted with Wijs reagent (iodine monochloride-acetic acid solution) and placed in the dark. Then, excess iodine monochloride was titrated with sodium thiosulfate, and the iodine value was calculated.

[0343] <Methods for determining molecular weight>

[0344] Weight-average molecular weight (Mw), number-average molecular weight (Mn), and molecular weight distribution (Mw / Mn) were determined using gel permeation chromatography (GPC) (manufactured by Tosoh Corporation, trade name: HLC-8420GPC). Columns were prepared by connecting guard columns manufactured by Tosoh Corporation: “HXL-L” (trade name), “SuperH-RC” (trade name), “TSKgel SuperHZ2000” (trade name), “TSKgel SuperHZ2500” (trade name), “TSKgel SuperHZ3000” (trade name), and “TSKgel SuperHZ4000” (trade name). The determination was performed using tetrahydrofuran as the developing solvent, a flow rate of 1.0 ml / min, a column temperature of 40 °C, and a RI (differential refractometer) detector, and using a calibration curve obtained using monodisperse polystyrene. Data processing uses the "GPC EcoSEC-Work Station" (trade name) manufactured by Tosoh Corporation.

[0345] <Determination of Dielectric Loss Tangent (Df)>

[0346] The film-cured material described later and the substrate obtained by etching to remove the copper foil from the evaluation copper-clad laminate described later were used as test pieces. The dielectric loss tangent (Df) at a frequency of 10 GHz was measured using a vector network analyzer (Agilent Technologies "E8361C" (trade name)) at room temperature (25°C) via the SPDR method. It should be noted that the measurement without glass cloth used the film-cured material described later, and the measurement with glass cloth used the substrate obtained by etching to remove the copper foil from the evaluation copper-clad laminate described later.

[0347] It should be noted that the dielectric loss tangent (Df) of the copper-clad laminate is evaluated according to the following criteria.

[0348] (Evaluation Criteria)

[0349] A+: Below 0.0015

[0350] A: Greater than 0.0015 and less than or equal to 0.0025

[0351] B: Greater than 0.0025 and less than or equal to 0.004

[0352] C: Greater than 0.004

[0353] <Preparation of Film-like Solidified Materials>

[0354] The above-mentioned film-like cured material is prepared by the following operation.

[0355] Specifically, 10 parts by mass and 2 parts by mass of each of the resins obtained from Manufacturing Examples A1 to A8 (described later) were dissolved in 12 parts by mass of toluene. Next, the resulting toluene solution was allowed to flow between the PTFE spacers and sandwiched between the polyimide films. It was held in place by an SUS plate and cured using a vacuum press at a pressure of 2 MPa and a temperature of 200°C for 2 hours, thereby obtaining a cured film.

[0356] (Manufacturing of Resin A)

[0357] [Manufacturing Example A1]

[0358] Under N2 flow, 480 g of p-xylene, 4.80 g (33.8 mmol) of boron trifluoride / diethyl ether complex (Tokyo Chemicals) as an acid catalyst, and 6.91 g (67.6 mmol) of propyl acetate as a co-catalyst were added to a 1 L glass reaction vessel equipped with stirring blades and a thermocouple coated with fluorinated resin. The reaction was maintained at 25°C for 2 hours. Then, 120.0 g of 1,3-diisopropenylbenzene (Tokyo Chemicals) was added dropwise to the reaction vessel over 2 hours using a syringe pump while maintaining the reaction temperature at 50°C. Following the dropwise addition, as a curing step, the reaction was carried out for 15 minutes (curing time) while maintaining the temperature at 50°C. The reaction was then terminated by adding 100 g of a 5% (w / w) sodium bicarbonate aqueous solution to the reaction vessel. The aqueous phase in the reaction vessel was then discarded, and the vessel was washed three times with 300 ml of deionized water to obtain a resin solution.

[0359] Next, 2200g of methanol was added to another 6L flask, and the above resin solution was slowly added to allow the resin to precipitate again. Then, the resin filter cake was obtained by filtration. The resin filter cake was redispersed in 2200g of methanol and washed and filtered. This operation was repeated twice. The obtained resin was then vacuum dried at 60°C to obtain 107.9g of resin A-1.

[0360] The obtained resin A-1 was subjected to structural analysis, iodine value determination, and molecular weight determination according to the above method. The results showed that the molecular weight of resin A-1 was Mn: 1770, Mw: 7090. Furthermore, the iodine value of resin A-1 was 131. It should be noted that when resin A-1 was dissolved in toluene at a concentration of 60% by mass, no insoluble matter was formed. 13 C-NMR confirmed that the obtained resin A-1 contained an α-olefin structure.

[0361] [Manufacturing Example A2]

[0362] Except for the boron trifluoride / ethyl ether complex being 0.96 g (6.76 mmol), propyl acetate being 1.38 g (13.5 mmol), the reaction temperature and aging temperature being set to 37.5 °C, and the aging time being set to 25 minutes, the process was carried out in the same manner as in manufacturing example A1, yielding 112.7 g of resin A-2. The structure, iodine value, and molecular weight of the obtained resin A-2 were determined according to the above method. The results showed that the molecular weight of the obtained resin A-2 was Mn: 2260, Mw: 19130. Furthermore, the iodine value of this resin A-2 was 124. The content of each structure in the obtained resin A-2 is as follows.

[0363] It should be noted that when resin A-2 was dissolved in toluene at a concentration of 60% by mass, no insoluble matter was produced.

[0364] Content of each structure: α-olefin structure: 1.97 mmol / g, indenium structure: 0.53 mmol / g, inner olefin structure: 0.16 mmol / g, terminal and side chain olefin structure: 0.96 mmol / g.

[0365] [Manufacturing Example A3]

[0366] Except for the boron trifluoride / diethyl ether complex (0.96 g, 6.76 mmol), propyl acetate (1.38 g, 13.5 mmol), reaction and aging temperatures (37.5 °C), and aging time (45 min), the process was carried out in the same manner as in manufacturing example A1, yielding 110.3 g of resin A-3. The structure, iodine value, and molecular weight of the obtained resin A-3 were determined according to the above method. The results are as follows. It should be noted that when resin A-3 was dissolved in toluene at 60% by mass, no insoluble matter was formed.

[0367] Molecular weight: Mn: 2680, Mw: 40683 Iodine value: 119 Content of each structure: α-olefin structure: 2.18 mmol / g, indenium structure: 0.53 mmol / g, inner olefin structure: 0.14 mmol / g, terminal and side chain olefin structure: 0.62 mmol / g.

[0368] [Manufacturing Example A4]

[0369] Except for the boron trifluoride / ethyl ether complex being 2.0 g (14.1 mmol), propyl acetate being 2.87 g (28.1 mmol), and the curing time being set to 60 minutes, the process was the same as in manufacturing example A1, yielding 98.1 g of resin A-4. The structure, iodine value, and molecular weight of the obtained resin A-4 were determined according to the above method. The results are as follows. It should be noted that when resin A-4 was dissolved in toluene at 60% by mass, no insoluble matter was formed.

[0370] Molecular weight: Mn: 2460, Mw: 23800 Iodine value: 114 Content of each structure: α-olefin structure: 3.55 mmol / g, indenium structure: 1.37 mmol / g, inner olefin structure: 0.14 mmol / g, terminal and side chain olefin structure: 0.27 mmol / g.

[0371] [Manufacturing Example A5]

[0372] Except that the curing time was set to 120 minutes, the process was carried out in the same manner as in Manufacturing Example A1, yielding 99.1 g of resin A-5. The structure, iodine value, and molecular weight of the obtained resin A-5 were analyzed according to the above method. The results are as follows. It should be noted that when resin A-5 was dissolved in toluene at a concentration of 60% by mass, no insoluble matter was formed.

[0373] Molecular weight: Mn: 3040, Mw: 35720 Iodine value: 96 Content of each structure: α-olefin structure: 2.25 mmol / g, indenium structure: 1.03 mmol / g, inner olefin structure: 0.47 mmol / g, terminal and side chain olefin structure: 0.07 mmol / g.

[0374] [Manufacturing Example A6]

[0375] Except that the reaction temperature and aging temperature were set to 55°C and the aging time was set to 90 minutes, the process was carried out in the same manner as in Manufacturing Example A1, yielding 111.0 g of resin A-6. The structure, iodine value, and molecular weight of the obtained resin A-6 were determined according to the above method. The results are as follows. It should be noted that when resin A-6 was dissolved in toluene at a concentration of 60% by mass, no insoluble matter was formed.

[0376] Molecular weight: Mn: 2640, Mw: 20900 Iodine value: 110 Content of each structure: α-olefin structure: 2.50 mmol / g, indenium structure: 0.89 mmol / g, inner olefin structure: 0.73 mmol / g, terminal and side chain olefin structure: 0.15 mmol / g.

[0377] [Manufacturing Example A7]

[0378] Except that the reaction temperature and aging temperature were set to 75°C and the aging time was set to 60 minutes, the process was carried out in the same manner as in manufacturing example A1, yielding 109.1 g of resin A-7. The structure, iodine value, and molecular weight of the obtained resin A-7 were determined according to the above method. The results are as follows.

[0379] Molecular weight: Mn: 2700, Mw: 15530 Iodine value: 65 Content of each structure: α-olefin structure: 1.61 mmol / g, indenium structure: 2.00 mmol / g, inner olefin structure: 0.65 mmol / g, terminal and side chain olefin structures: 0.07 mmol / g [Manufacturing Example A8] Under nitrogen flow, 500 g of p-xylene and 17.5 g of p-toluenesulfonic acid monohydrate were added to a 1 L glass flask equipped with a thermometer and stirrer, and the temperature was set to 60 °C. 250 g of 1,3-diisopropenylbenzene (manufactured by TCI) was added dropwise over 2 hours while maintaining the reaction temperature at 60 °C. After the addition was complete, the reaction was aged at 60 °C for 1 hour. After natural cooling, 160 g of water was added to dissolve and remove the catalyst. The mixture was repeatedly washed with 160 g of water until neutral. Then, the solvent and monomer were removed by distillation under reduced pressure, yielding 136 g of viscous resin A-8. The structure, iodine value, and molecular weight of the obtained resin A-8 were determined according to the above method. The molecular weight of the obtained resin A-8 was Mn: 390, Mw: 570, and the iodine value was 210. The obtained resin A-8 was analyzed by NMR, and the peak of isopropenyl group was confirmed in the 4.70-5.40 ppm region in the 1H-NMR spectrum.

[0380] The reaction conditions, molecular weight, and content of each structure of the resins obtained in Manufacturing Examples A1 to A8 are shown in Table 1 below. Furthermore, the Df of the cured film produced using each resin was measured according to the above method and is shown in Table 1.

[0381] Table 1

[0382] (The manufacture of compound C)

[0383] [Manufacturing Example C1]

[0384] Weigh 33.85 g of 1,1-bis(4-hydroxy-3-methylphenyl)-3,3,5-trimethylcyclohexane, 16.65 g of 4,6-dichloro-2-phenylpyrimidine, and 18.65 g of potassium carbonate. Place them in a four-necked separable flask equipped with a stirrer, and add 50.50 g of N-methyl-2-pyrrolidone. React at 100 °C for 6 hours under a nitrogen atmosphere. After the reaction, while the container is cooled to 10 °C, add 11.53 g of m, p-(chloromethyl)styrene dropwise, and then react at 100 °C for 4 hours. Remove salts from the resulting solution by filtration after diluting with 55.0 g of N-methyl-2-pyrrolidone, and then dissolve the resulting solution in 6900 g of methanol. The precipitated solid was filtered and separated, washed with a small amount of methanol, filtered again and recovered, and then dried under reduced pressure at 60°C for 12 hours using a vacuum dryer to obtain polymer C-1 (compound C-1) represented by the following formula (C-1). The number average molecular weight (Mn) of this polymer is 1800, and the weight average molecular weight (Mw) is 4000.

[0385]

[0386] [Manufacturing Example C2]

[0387] Weigh 2,2-bis(4-hydroxy-3-methylphenyl)propane (26.43 g), 4,6-dichloro-2-phenylpyrimidine (17.08 g), and potassium carbonate (19.23 g), and add them to a four-necked separable flask equipped with a stirrer. Add N-methyl-2-pyrrolidone (42.50 g) and react at 100 °C for 6 hours under a nitrogen atmosphere. After the reaction, while the container is cooled to 10 °C, add m,p-(chloromethyl)styrene (11.53 g) dropwise, and then react at 100 °C for 4 hours. Remove salts from the resulting solution by filtration after diluting with N-methyl-2-pyrrolidone (55.0 g), and then add the resulting solution to methanol (6900 g). The precipitated solid was filtered and separated, washed with a small amount of methanol, filtered again and recovered, and then dried under reduced pressure at 60°C for 12 hours using a vacuum dryer to obtain polymer C-2 (compound C-2) represented by the following formula (C-2). The number average molecular weight (Mn) of this polymer is 1600, and the weight average molecular weight (Mw) is 3200.

[0388]

[0389] [Manufacturing Example C3]

[0390] Weigh 57.95 g of 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 31.72 g of 4,6-dichloropyrimidine, 7.11 g of isopropenylphenol, and 33.77 g of potassium carbonate. Add these to a four-necked separable flask equipped with a stirrer, and add 42.67 g of N-methyl-2-pyrrolidone. React at 130 °C for 6 hours under a nitrogen atmosphere. After the reaction is complete, dilute with 240.0 g of N-methyl-2-pyrrolidone, and add the solution (after filtration to remove salt) to 12.9 kg of methanol. Filter the precipitated solid, wash it with a small amount of methanol, filter again, and recover the solid. Dry the solid under reduced pressure at 120 °C for 12 hours using a vacuum dryer to obtain polymer C-3 (compound C-3) represented by the following formula (C-3). The polymer has a number-average molecular weight (Mn) of 1500 and a weight-average molecular weight (Mw) of 3100.

[0391]

[0392] [Manufacturing Example C4]

[0393] Except for changing the raw materials and alkali metal compound used to 2,2-bis(4-hydroxyphenyl)propane (30.4 g), isopropenylphenol (5.2 g), 4,6-dichloro-2-phenylpyrimidine (34.3 g), and potassium carbonate (24.0 g), the polymer C-4 (compound C-4), represented by the following formula (C-4), was synthesized using the same operating steps as in manufacturing example C3, and polymer C-4 was obtained. The number average molecular weight (Mn) of this polymer is 1500, and the weight average molecular weight (Mw) is 3100.

[0394]

[0395] [Manufacturing Example C5]

[0396] Except for changing the raw materials and alkali metal compounds used to 1,1-bis(4-hydroxy-3-methylphenyl)-3,3,5-trimethylcyclohexane (36.1 g), 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (10.1 g), 2,4-dichloro-6-phenyl-1,3,5-triazine (34.5 g), isopropenylphenol (5.2 g), potassium carbonate (24.0 g), and N-methyl-2-pyrrolidone (69.1 g), the polymer C-5 (compound C5) represented by the following formula (C5) was synthesized using the same operating steps as in manufacturing example C3, and polymer C-5 (compound C5) was obtained. The number average molecular weight (Mn) of this polymer is 1900, and the weight average molecular weight (Mw) is 4100.

[0397]

[0398] [Manufacturing Example C6]

[0399] Weigh 1,1-bis(4-hydroxy-3-methylphenyl)-3,3,5-trimethylcyclohexane (41.52 g), 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (11.61 g), 2,4-dichloro-6-phenyl-1,3,5-triazine (30.14 g), and potassium carbonate (26.18 g), and add them to a four-necked separable flask equipped with a stirrer. Add N-methyl-2-pyrrolidone (42.67 g), and react at 130 °C for 6 hours under a nitrogen atmosphere. After the reaction, while the container is cooled to 10 °C, add methacryloyl chloride (4.06 g) dropwise, and then react at 50 °C for 6 hours. Remove salts from the resulting solution by filtration after diluting with N-methyl-2-pyrrolidone (240.0 g), and then add the resulting solution to methanol (12.90 kg). The precipitated solid was filtered and separated, washed with a small amount of methanol, filtered again and recovered, and then dried under reduced pressure at 120°C for 12 hours using a vacuum dryer to obtain polymer C6 (compound C6) represented by the following formula (C6). The number average molecular weight (Mn) of this polymer is 1900, and the weight average molecular weight (Mw) is 4100.

[0400]

[0401] [Manufacturing Example C7]

[0402] Except for changing the raw materials and alkali metal compounds used to 1,1-bis(4-hydroxy-3-methylphenyl)-3,3,5-trimethylcyclohexane (30.78 g), 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (8.58 g), 2,4-dichloro-6-phenyl-1,3,5-triazine (20.18 g), m,p-chloromethylstyrene (10.0 g), potassium carbonate (22.1 g), and N-methyl-2-pyrrolidone (69.1 g), the polymer C-7 (compound C-7) represented by the following formula (C-7) was synthesized using the same operating steps as in manufacturing example C1, and polymer C-7 (compound C-7) was obtained. The number average molecular weight (Mn) of this polymer is 1800, and the weight average molecular weight (Mw) is 4000.

[0403]

[0404] Next, using these resins A, compound B (described later), and compound C (described above), a composition (resin varnish) and a metal-coated laminate were prepared according to the following steps, and the laminate was evaluated.

[0405] <Preparation of Resin Varnish>

[0406] Resin A, Compound C, elastomer, crosslinking agent, and initiator (described later) were dissolved in toluene at a solid content of 50% by mass. Furthermore, an organophosphorus compound (Compound B) and an inorganic filler (filler) were added to the resulting toluene solution, and the mixture was mixed and dispersed using a rotor / stator mixer to obtain a resin varnish.

[0407] Resin A: Each resin obtained in Manufacturing Examples A1 to A8, Compound C: The compounds obtained in Manufacturing Examples C1 to C7, modified polyphenylene ether (trade name: SA-9000, manufactured by Saudi Basic Innovative Plastics Company), and maleimide resin (trade name: NE-X9470S, manufactured by DIC Corporation). Elastomer: Tuftec H1043 (trade name, manufactured by Asahi Kasei) Crosslinking agent: 1,2-bis(vinylphenyl)ethane (BVPE), Initiator: CUROX (registered trademark) CC-DC (trade name, manufactured by Unite Group) Inorganic filler: Spherical silica EQ2410-SCM (trade name, manufactured by Zhejiang Sanshiji New Material Technology Co., Ltd.) Organophosphorus compounds (Compound B): ((1,4-Phenylidene)bis(diphenylphosphine oxide) (trade name: BES5-1150P, manufactured by Regina Electronics), [2-(diphenylphosphoyl)ethyl](diphenyl)phosphine oxide (trade name: VHP-4 dimer, manufactured by Osaka Gas Industries), SPV-100 (trade name, manufactured by Otsuka Chemicals). <Evaluation of substrate fabrication> Glass cloth (E glass, #2116) was impregnated with the obtained resin varnish, sandwiched between metal rods, and the glass cloth was pulled out to remove excess varnish. It was then dried at room temperature (25°C) for 10 minutes. Next, it was dried in an air oven at 130°C for 4 minutes to prepare a prepreg. At this point, the resin composition relative to the amount of prepreg, i.e., the resin content (RC), was adjusted to 55% by mass. Two sheets of this prepreg were overlapped, and copper foil (HS1-M2-VSP, trade name, manufactured by Mitsui Metals Mining) was placed on both sides. The mixture was then molded and cured using a vacuum pressing machine to obtain the evaluation substrates (evaluation copper-clad laminates) used in Examples 1 to 22. The curing conditions were a pressure of 3 MPa and a temperature of 200°C for 90 minutes.

[0408] <Evaluation of Flame Retardancy>

[0409] In the fabrication of the evaluation substrates shown in Examples 1 to 27, 12 sheets of prepreg were stacked to obtain an evaluation copper-clad laminate. Copper foil was removed from the obtained evaluation copper-clad laminate by etching. Five samples, each cut to 125 mm × 13 mm, were prepared. Each of the five samples was exposed to a flame for 10 seconds, and their combustion behavior was confirmed.

[0410] Flame retardancy is evaluated according to the following standards.

[0411] (Evaluation Criteria)

[0412] A+: The total burning time of the 5 samples is less than 30 seconds, and the burning time of all 5 samples is less than 10 seconds.

[0413] A: The total burning time of the 5 samples is greater than 30 seconds and less than or equal to 50 seconds, and the burning time of all 5 samples is less than 10 seconds.

[0414] B: The total burning time of the 5 samples is less than 50 seconds, and the burning time of more than one sample is more than 10 seconds.

[0415] C: The combined burning time of the 5 samples is greater than 50 seconds.

[0416] <Determination of Glass Transition Temperature Tg>

[0417] The substrate obtained by etching the copper foil off the evaluation copper-clad laminates shown in Examples 1 to 27 was used as a test piece. Dynamic viscoelasticity (DMA) was measured using a dynamic viscoelasticity measuring device (“DVA-200” (trade name) manufactured by IT Measurement Control Co., Ltd.), and the glass transition temperature (Tg) (°C) was determined. The measurement was performed at a frequency of 10 Hz, a heating rate of 2°C / min, and a temperature range of 25°C to 300°C.

[0418] Tg is evaluated based on the following criteria.

[0419] (Evaluation Criteria)

[0420] A+: above 200℃

[0421] A: 175℃ or higher and less than 200℃

[0422] B: ≥150℃ and <175℃

[0423] C: Less than 150℃

[0424] The measurement results are shown in Tables 2 to 4 below.

[0425] <Copper Foil Peel Strength: Determination of Peel Strength>

[0426] Test pieces with a width of 20 mm and a length of 100 mm were cut from the evaluation copper-clad laminates shown in Examples 1 to 27. Parallel cuts with a width of 10 mm were made on the copper foil side. Subsequently, the copper foil was continuously peeled off at a speed of 50 mm / min in a direction at 90° relative to the copper foil side. The stress at this time was measured using a tensile testing machine, and the lowest value of this stress was recorded as the copper foil peel strength (according to JIS C6481).

[0427] The copper peel strength is evaluated based on the following criteria.

[0428] (Evaluation Criteria)

[0429] A+: Above 4N / cm

[0430] A: Greater than or equal to 3N / cm and less than 4N / cm

[0431] B: Greater than or equal to 2N / cm and less than 3N / cm

[0432] C: Less than 2N / cm

[0433] The measurement results are shown in Tables 2 to 4 below.

[0434] Table 2

[0435] Table 3

[0436] Table 4

[0437] As can be seen from the above, this composition not only has a low dielectric loss tangent but also excellent flame retardancy, and it satisfies practical characteristics in a balanced way, making it an excellent substrate material.

[0438] As can be seen from the above, the composition comprising resin A, compound B, and compound C exhibits excellent electrical properties and flame retardancy. Furthermore, the present invention can provide electronic materials with excellent electrical properties and flame retardancy, including the composition, cured products using the composition, prepregs, and metal-coated laminates.

[0439] It should be noted that this disclosure is not limited to the above-described embodiments, and appropriate modifications can be made without departing from the spirit of the subject. Furthermore, this disclosure can also be implemented by appropriately combining the above-described embodiments and one example thereof.

[0440] This application claims priority based on Japanese Patent Application No. 2023-178264 filed on October 16, 2023 and Japanese Patent Application No. 2024-070640 filed on April 24, 2024, the entire disclosure of which is incorporated herein by reference.

Claims

1. A resin composition, wherein, The resin composition comprises: Resins, organophosphorus compounds, and compounds having at least one atom selected from oxygen and nitrogen atoms, having at least an α-olefin structure represented by formula (1) below. In equation (1), R 1 Each group independently represents a hydrocarbon group or a haloalkyl group with 1 to 10 carbon atoms, and p1 represents a real number from 0 to 4. Each represents a bonding position.

2. The resin composition according to claim 1, wherein, The resin has an iodine value of 70 or higher and 200 or lower.

3. The resin composition according to claim 1, wherein, The weight-average molecular weight (Mw) of the resin is above 2500 and below 500000.

4. The resin composition according to claim 1, wherein, The resin contains an α-olefin structure represented by formula (1) of 1.0 mmol / g or more and 6.3 mmol / g or less.

5. The resin composition according to claim 1, wherein, The parameter FA, expressed as the content of the α-olefin structure represented by formula (1), the content of the indene structure represented by formula (2), and the content of the inner olefin structure represented by formula (3) in the resin, is 0.39 or higher. FA = [content of α-olefin structure] / ([content of internal olefin structure] + [content of indene structure] + [content of α-olefin structure]) In equation (2), R 2 Each group independently represents a hydrocarbon group or a haloalkyl group with 1 to 10 carbon atoms, p2 represents a real number from 0 to 4, and q1 represents a real number from 0 to 3. Each represents a bonding position. In equation (3), R 3 Each group independently represents a hydrocarbon group or a haloalkyl group with 1 to 10 carbon atoms, and p3 represents a real number from 0 to 4. Each represents a bonding position.

6. The resin composition according to claim 1, wherein, The parameter FI, expressed as the content of the α-olefin structure represented by formula (1), the content of the indene structure represented by formula (2), and the content of the internal olefin structure represented by formula (3) in the resin, is less than 0.

58. FI = [Indene structure content] / ([Inner olefin structure content] + [Indene structure content] + [α-olefin structure content] / 2) In equation (2), R 2 Each group independently represents a hydrocarbon group or a haloalkyl group with 1 to 10 carbon atoms, p2 represents a real number from 0 to 4, and q1 represents a real number from 0 to 3. Each represents a bonding position. In equation (3), R 3 Each group independently represents a hydrocarbon group or a haloalkyl group with 1 to 10 carbon atoms, and p3 represents a real number from 0 to 4. Each represents a bonding position.

7. The resin composition according to claim 1, wherein, The content of heteroatoms other than carbon and hydrogen atoms in the resin is less than 3% by mass.

8. The resin composition according to claim 7, wherein, The resin does not contain the heteroatoms.

9. The resin composition according to claim 1, wherein, The resin has an olefin structure at the end.

10. The resin composition according to claim 1, wherein, The resin also has a side-chain olefin structure in which the side chain portion has an olefin structure.

11. The resin composition according to claim 1, wherein, In the resin, the total content of the α-olefin structure, the terminal olefin structure, and the side-chain olefin structure having an olefin structure in the side chain portion is 1.8 mmol / g or more.

12. The resin composition according to claim 1, wherein, The content of the indene structure represented by the following formula (2) in the resin is less than 3.0 mmol / g. In equation (2), R 2 Each group independently represents a hydrocarbon group or a haloalkyl group with 1 to 10 carbon atoms, p2 represents a real number from 0 to 4, and q1 represents a real number from 0 to 3. Each represents a bonding position.

13. The resin composition according to claim 1, wherein, The solubility of the organophosphorus compound in 100g of toluene at 25°C is less than 5g.

14. The resin composition according to claim 1, wherein, The organophosphorus compound is incompatible with the resin.

15. The resin composition according to claim 1, wherein, The organophosphorus compound has a melting point above 240°C.

16. The resin composition according to claim 1, wherein, The organophosphorus compound has a phosphine oxide structure or a phosphonic acid structure.

17. The resin composition according to claim 1, wherein, The number-average molecular weight Mn of the compound having at least one atom selected from oxygen and nitrogen atoms is 300 to 50,000.

18. The resin composition according to claim 1, wherein, The compound having at least one atom selected from oxygen and nitrogen atoms contains a free radical polymerizable group.

19. The resin composition according to claim 1, wherein, The combined content of oxygen and nitrogen atoms is 0.01% to 10% by mass.

20. The resin composition according to claim 1, wherein, The content of the solid components in the resin composition is: The resin: 1% to 80% by mass The organophosphorus compound: 0.1% to 30% by mass The compound having at least one atom selected from oxygen and nitrogen: 1% to 80% by mass.

21. A prepreg, wherein, The prepreg comprises the resin composition according to any one of claims 1 to 20.

22. A metal-clad laminate, wherein, The metal-clad laminate comprises a cured product of the resin composition according to any one of claims 1 to 20 and a metal foil.

23. A method for manufacturing a metal-clad laminate, wherein, A prepreg comprising any one of the resin compositions of claims 1 to 20 is laminated with a metal foil.

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