Phosphoric acid ester containing unsaturated group, thermosetting resin composition containing same, and resin material

Abstract

The present invention provides a thermosetting resin composition that can be used in a high-frequency printed circuit board capable of coping with next-generation communication standards. Provided is a phosphoric acid ester compound having an ethylenically unsaturated bond. The compound can be added as a modifier to a thermosetting resin such as a poly(phenylene ether) resin having an ethylenically unsaturated bond. The compound has high solubility in a nonpolar organic solvent and is advantageous for the production of a laminated board. Also provided is a thermosetting resin composition that comprises the modifier and a thermosetting resin. The thermosetting resin composition can achieve excellent dielectric properties and high heat resistance required for printed circuit boards that cope with next-generation communication standards.

Description

Unsaturated group-containing phosphate ester, thermosetting resin composition containing the same, and resin material

[0001] The present invention relates to a phosphate ester having a copolymerizable unsaturated bond. In particular, the present invention relates to an unsaturated group-containing phosphate ester useful as a modifier for printed circuit boards, etc. The present invention also relates to a resin composition usable for printed circuit boards compatible with next-generation communication standards, such as 5G or 6G communication standards.

[0002] It is known that reactive phosphate esters can be used as flame retardants in printed circuit boards. For example, WO 2021 / 237695 (Patent Document 1) and WO 2021 / 237696 (Patent Document 2) disclose phosphate esters of diallyl bisphenol A (page 30, paragraph 0133 of Patent Document 1, page 9, paragraph 0037 of Patent Document 2).

[0003] Furthermore, Patent Documents 1 and 2 disclose the production of laminated boards using methyl ethyl ketone as a solvent (page 35, paragraph 0161 of Patent Document 1, and page 30, paragraph 0153 of Patent Document 1).

[0004] However, resin compositions using diallyl bisphenol A phosphate esters have the drawback of lower heat resistance than resin compositions not using diallyl bisphenol A phosphate esters. High heat resistance is required for substrates for next-generation communication standards. Therefore, the low heat resistance of resin compositions using diallyl bisphenol A phosphate esters is a serious problem.

[0005] Furthermore, since diallyl bisphenol A phosphate esters have low solubility in non-polar organic solvents (e.g., toluene), when laminates are produced using non-polar organic solvents, only small amounts can be added to the resin, which presents the disadvantage that high flame retardancy cannot be imparted to the laminates.

[0006] In Patent Documents 1 and 2, methyl ethyl ketone, an aprotic polar organic solvent, is used to prepare laminates. However, when a polar solvent is used to prepare a laminate, the polar solvent adversely affects the dielectric properties and interlayer adhesive strength of the laminate. Therefore, a modifier that can be used to produce laminates using a nonpolar organic solvent instead of a polar solvent is desired. That is, a modifier that is highly soluble in a nonpolar organic solvent (e.g., toluene) is desired.

[0007] International Publication No. 2021 / 237695 International Publication No. 2021 / 237696

[0008] An object of the present invention is to provide a compound that can be used as a modifier for printed circuit boards having excellent dielectric properties and high heat resistance, which are required for substrates for next-generation communication standards, a modifier for printed circuit boards, and a thermosetting resin composition.

[0009] The present inventors have conducted extensive research to solve new problems relating to printed circuit boards that arise from the above-mentioned next-generation communication standards, and as a result have found that a phosphate ester compound having a specific structure can solve the above-mentioned problems, thereby completing the present invention.

[0010] Specifically, the present invention provides, for example, the following:

[0011] (Item 1) A compound of general formula (1),

[0012]

[0013] Here, R １ is a benzene ring, biphenyl, or naphthalene ring, the benzene ring being substituted with 1 to 4 ethylenically unsaturated bond-containing groups, the biphenyl being substituted with 1 to 8 ethylenically unsaturated bond-containing groups, and the naphthalene ring being substituted with 1 to 6 ethylenically unsaturated bond-containing groups, wherein the ethylenically unsaturated bond-containing groups are independently selected from the group consisting of ２ ~C １２ R is a straight or branched chain alkenyl group ２ , R ３ , R ４ , and R５ is a phenyl group that is independently unsubstituted or substituted with two or three alkyl groups, each of which is independently selected from the group consisting of C １ ~C ４ and n is an integer from 1 to 3.

[0014] (Item 2) The compound according to item 1, having a structure represented by general formula (1a):

[0015]

[0016] Here, R １ａ is a benzene ring or a naphthalene ring, the benzene ring is substituted with two ethylenically unsaturated bond-containing groups, and the naphthalene ring is substituted with two ethylenically unsaturated bond-containing groups, wherein the ethylenically unsaturated bond-containing groups are independently selected from the group consisting of C ２ ~C ４ R is a straight or branched chain alkenyl group ２ａ , R ２ｂ , R ３ａ , R ３ｂ , R ４ａ , R ４ｂ , R ５ａ and R ５ｂ are independently １ ~C ２ R is an alkyl group of the formula ２ｃ , R ３ｃ , R ４ｃ and R ５ｃ are independently hydrogen or C １ ~C ２ and n ａ is an integer from 1 to 2.

[0017] (Section 3) R １ａ is a benzene ring or a naphthalene ring, the benzene ring is substituted with two allyl groups, the naphthalene ring is substituted with two allyl groups, R ２ｃ , R ３ｃ , R ４ｃ and R ５ｃ is hydrogen, and n ａItem 3. The compound according to item 2, wherein is 1.

[0018] (Item 4) The compound is represented by the following general formula (1a-1):

[0019]

[0020] or the following general formula (1a-2):

[0021]

[0022] The compound according to item 1 or 2, particularly the compound according to item 1, having any one of the following structures:

[0023] (Item 5) The compound according to item 1, having a structure represented by general formula (1b):

[0024]

[0025] Here, R １ｂ is biphenyl, the biphenyl being substituted with two ethylenically unsaturated bond-containing groups, each of which is independently selected from the group consisting of: ２ ~C ４ R is a straight or branched chain alkenyl group ２ａ , R ２ｂ , R ３ａ , R ３ｂ , R ４ａ , R ４ｂ , R ５ａ and R ５ｂ are independently １ ~C ２ R is an alkyl group of the formula ２ｃ , R ３ｃ , R ４ｃ and R ５ｃ are independently hydrogen or C １ ~C ２ and n ａ is an integer from 1 to 2.

[0026] (Section 6) R １ａ is a biphenyl, the biphenyl being substituted with two allyl groups, and R ２ｃ , R ３ｃ , R ４ｃ and R ５ｃis hydrogen, and n ａ Item 6. The compound according to item 5, wherein is 1.

[0027] (Item 7) The compound is represented by the following general formula (1b-1):

[0028]

[0029] The compound according to any one of items 1, 5 and 6, particularly the compound according to item 1, having the structure:

[0030] (Item 8) A compound of general formula (11),

[0031]

[0032] Here, R １１ is a benzene ring, biphenyl or naphthalene ring, R １２ and R １５ is a phenyl group independently substituted with 1 to 5 ethylenically unsaturated bond-containing groups and 0 to 4 alkyl groups, and the alkyl groups are independently selected from the group consisting of C １ ~C ４ wherein the total number of the ethylenically unsaturated bond-containing groups and the alkyl groups is 1 to 5, and each of the ethylenically unsaturated bond-containing groups is independently selected from the group consisting of C ２ ~C １２ R is a straight-chain or branched alkenyl group, or an acryloyloxy group or a methacryloyloxy group; １３ and R １４ is a phenyl group independently substituted with two or three alkyl groups, each independently selected from the group consisting of C １ ~C ４ and n is a straight or branched chain alkyl group of １ is an integer from 0 to 6.

[0033] (Item 9) The compound according to item 8, having a structure represented by general formula (11a):

[0034]

[0035] Here, R １１ａis a benzene ring, biphenyl or naphthalene ring, R １２ａ , R １２ｂ , R １５ａ and R １５ｂ are independently hydrogen or C １ ~C ２ R is an alkyl group of the formula １３ｃ and R １４ｃ are independently hydrogen or C １ ~C ２ R is an alkyl group of the formula １３ａ , R １３ｂ , R １４ａ and R １４ｂ are independently １ ~C ２ R is an alkyl group of the formula １２ｃ and R １５ｃ are independently an ethylenically unsaturated bond-containing group, wherein the ethylenically unsaturated bond-containing group is independently ２ ~C ４ is a straight-chain or branched alkenyl group or an acryloyloxy group or a methacryloyloxy group, and n １ａ is an integer from 0 to 6.

[0036] (Item 10) R １３ｃ and R １４ｃ is hydrogen, and R １２ｃ and R １５ｃ are independently an allyl group, an acryloyloxy group, or a methacryloyloxy group and are located in the para position relative to the phosphate group, and n １ａ 10. The compound according to item 9, wherein is an integer of 0 to 4.

[0037] (Item 11) The compound is represented by the following general formula (11a-1):

[0038]

[0039] where n Ｓ１ is an integer of 0 to 4. The compound according to any one of items 8 to 10, particularly item 8.

[0040] (Item 12) A modifier for use in a thermosetting resin composition, comprising the compound according to any one of items 1 to 11 above.

[0041] (Item 13) A thermosetting resin composition comprising the compound according to any one of items 1 to 11 above and a thermosetting resin.

[0042] (Item 14) The thermosetting resin composition according to item 13, wherein the thermosetting resin comprises a thermosetting resin having an ethylenically unsaturated bond.

[0043] (Item 15) The thermosetting resin composition according to item 13, wherein the thermosetting resin comprises a polyphenylene ether resin modified with an ethylenically unsaturated group.

[0044] (Item 16) The thermosetting resin composition according to any one of Items 13 to 15, particularly Item 13, further comprising a crosslinking agent having an ethylenically unsaturated bond.

[0045] (Item 17) The thermosetting resin composition according to item 16, wherein the crosslinking agent is triallyl isocyanurate.

[0046] (Item 18) The thermosetting resin composition according to any one of items 13 to 17, particularly item 13, for producing an insulating layer in a high-frequency printed circuit board.

[0047] (Item 19) A resin material obtained by curing the thermosetting resin composition according to any one of items 13 to 18, particularly item 13.

[0048] (Item 20) A high frequency printed circuit board comprising a conductor layer and an insulating layer, the insulating layer comprising the resin material according to item 19 above.

[0049] (Item 21) A method for producing a high-frequency printed circuit board having a conductor layer and an insulating layer, the method comprising a step of curing the thermosetting resin composition according to any one of Items 13 to 18, particularly the thermosetting resin composition according to Item 13, to form the insulating layer.

[0050] According to the present invention, there are provided a compound usable as a modifier for printed circuit boards having excellent heat resistance, a modifier for printed circuit boards, and a thermosetting resin composition. Also, according to the present invention, there are provided a compound usable as a modifier for printed circuit boards having excellent dielectric properties and high heat resistance required for boards for next-generation communication standards, a modifier for printed circuit boards, and a thermosetting resin composition.

[0051] Compounds (101a) and (101b) １ The H-NMR charts of compounds (102a) and (102b) are shown below. １ The H-NMR chart of compound (103) is shown below. １ The H-NMR chart of compound (104) is shown below. １ The H-NMR chart of compound (105) is shown below. １ The H-NMR chart of compound (106) is shown below. １ The H-NMR chart is shown below.

[0052] According to the present invention, there is provided a phosphoric acid ester compound having an ethylenically unsaturated bond, which will be described in detail below.

[0053] <Compound> (Compound of General Formula (1)) According to one embodiment of the present invention, there is provided a compound of general formula (1).

[0054]

[0055] The compound of general formula (1) will be explained below.

[0056] R １ is a benzene ring, a biphenyl ring, or a naphthalene ring. When n is 2 or more, two or more R １ are the same. １ With respect to a group having two phosphate groups and one or more ethylenically unsaturated bond-containing groups bonded thereto, the terms "benzene ring," "biphenyl," and "naphthalene ring" respectively refer to groups having three or more substituents.

[0057] (Benzene ring) The bonding positions of the benzene ring and the two phosphate groups are not particularly limited. The two phosphate groups may be bonded to the ortho, meta, or para positions of the benzene ring. The meta or para positions are preferred.

[0058] R in general formula (1) １ In the formula (I), the benzene ring is substituted with 1 to 4 ethylenically unsaturated bond-containing groups, preferably 1 to 3 ethylenically unsaturated bond-containing groups, and more preferably 2 ethylenically unsaturated bond-containing groups.

[0059] The bonding position between the benzene ring and the ethylenically unsaturated bond-containing group is not particularly limited.

[0060] When two phosphate groups are bonded to the ortho-positions of the benzene ring, the positions to which the two phosphate groups are bonded are defined as the 1st and 2nd positions of the benzene ring, and the ethylenically unsaturated bond-containing group may be bonded to any of the 3rd to 6th positions of the benzene ring, preferably the 3rd and 6th positions.

[0061] When two phosphate groups are bonded at the meta positions, the positions to which the two phosphate groups are bonded are defined as the 1st and 3rd positions of the benzene ring, and the ethylenically unsaturated bond-containing group may be bonded to any of the 2nd, 4th, 5th, and 6th positions of the benzene ring. The 2nd, 4th, and 6th positions are preferred. In one preferred embodiment, two phosphate groups are bonded to the 1st and 3rd positions, and two ethylenically unsaturated bond-containing groups are bonded to the 2nd and 4th positions or the 4th and 6th positions.

[0062] When two phosphate groups are bonded at the para-position, the positions to which the two phosphate groups are bonded are defined as the 1st and 4th positions of the benzene ring, and the ethylenically unsaturated bond-containing group may be bonded to any of the 2nd, 3rd, 5th, and 6th positions of the benzene ring. The 2nd, 3rd, and 5th positions are preferred. In one preferred embodiment, two phosphate groups are bonded to the 1st and 4th positions, and two ethylenically unsaturated bond-containing groups are bonded to the 2nd and 3rd positions or the 2nd and 5th positions.

[0063] (Biphenyl) The bonding positions of the biphenyl and the two phosphate groups are not particularly limited as long as one phosphate group is bonded to each of the two benzene rings of the biphenyl. In this case, one phosphate group is bonded to each of the 2- to 6-positions, and one phosphate group is bonded to each of the 2'- to 6'-positions.

[0064] In the present specification, the 2- to 6-positions and 2'- to 6'-positions of biphenyl refer to the following positions.

[0065]

[0066] For example, one phosphate group may be bound to the 2-position and one phosphate group may be bound to the 2'-4'-position, one phosphate group may be bound to the 3-position and one phosphate group may be bound to the 2'-4'-position, or one phosphate group may be bound to the 4-position and one phosphate group may be bound to the 2'-4'-position. In one preferred embodiment, one phosphate group is bound to each of the 2- and 2'-positions, one phosphate group is bound to each of the 3- and 3'-positions, or one phosphate group is bound to each of the 4- and 4'-positions. In a particularly preferred embodiment, one phosphate group is bound to each of the 4- and 4'-positions.

[0067] R in general formula (1) １ In the formula (I), the biphenyl is substituted with 1 to 8 ethylenically unsaturated bond-containing groups. Preferably, it is substituted with 1 to 6 ethylenically unsaturated bond-containing groups. More preferably, it is substituted with 1 to 4 ethylenically unsaturated bond-containing groups. Even more preferably, it is substituted with 1 to 3 ethylenically unsaturated bond-containing groups. Particularly preferably, it is substituted with 2 ethylenically unsaturated bond-containing groups.

[0068] The bonding position of the biphenyl and the ethylenically unsaturated bond-containing group is not particularly limited. That is, the ethylenically unsaturated bond-containing group may be bonded to any of the eight carbon atoms not bonded to a phosphate group among the carbon atoms at positions 2 to 6 and positions 2' to 6' in the biphenyl. In a preferred embodiment, one phosphate group and one ethylenically unsaturated bond-containing group are bonded to one benzene ring in the biphenyl, and one phosphate group and one ethylenically unsaturated bond-containing group are bonded to the other benzene ring in the biphenyl. In a particularly preferred embodiment, one phosphate group is bonded to each of positions 4 and 4', and one ethylenically unsaturated bond-containing group is bonded to each of positions 3 and 3'.

[0069] (Naphthalene Ring) The bonding positions of the naphthalene ring and the two phosphate groups are not particularly limited. That is, the phosphate groups may be bonded to any of the eight carbon atoms in the naphthalene ring to which a substituent can be bonded. Two phosphate groups may be bonded to one benzene ring in the naphthalene ring, or one phosphate group may be bonded to each of the two benzene rings in the naphthalene ring. When two phosphate groups are bonded to one benzene ring in the naphthalene ring, the phosphate groups may be bonded to any of the 1st to 4th positions of the naphthalene ring. For example, they may be bonded to the 1st and 2nd positions, the 1st and 3rd positions, the 1st and 4th positions, or the 2nd and 3rd positions. When one phosphate group is bonded to each of the two benzene rings in the naphthalene ring, one phosphate group may be bonded to any of the 1st to 4th positions of the naphthalene ring, and the other phosphate group may be bonded to any of the 5th to 8th positions of the naphthalene ring.

[0070] Preferably, one phosphate group is bonded to each of the two benzene rings in the naphthalene ring. In one preferred embodiment, the phosphate groups are bonded to the 1- and 5-positions or the 1- and 6-positions of the naphthalene ring.

[0071] In this specification, the 1st to 8th positions of the naphthalene ring refer to the following positions.

[0072]

[0073] R in general formula (1) １ In the formula (I), the naphthalene ring is substituted with 1 to 6 ethylenically unsaturated bond-containing groups. Preferably, it is substituted with 1 to 4 ethylenically unsaturated bond-containing groups. More preferably, it is substituted with 1 to 3 ethylenically unsaturated bond-containing groups. Even more preferably, it is substituted with 2 ethylenically unsaturated bond-containing groups.

[0074] The bonding position of the naphthalene ring and the ethylenically unsaturated bond-containing group is not particularly limited. That is, the ethylenically unsaturated bond-containing group may be bonded to any of the six carbon atoms among the carbon atoms at positions 1 to 8 in the naphthalene ring that do not have a phosphate group bonded to them. In a preferred embodiment, one phosphate group and one to three ethylenically unsaturated bond-containing groups are bonded to one benzene ring in the naphthalene ring, and one phosphate group and one to three ethylenically unsaturated bond-containing groups are bonded to the other benzene ring in the naphthalene ring. In a more preferred embodiment, one phosphate group is bonded to each of positions 1 and 5 and one ethylenically unsaturated bond-containing group is bonded to each of positions 2 and 6, or one phosphate group is bonded to each of positions 1 and 6 and one ethylenically unsaturated bond-containing group is bonded to each of positions 2 and 5, or one ethylenically unsaturated bond-containing group is bonded to each of positions 2 to 5, 7 and 8. In a particularly preferred embodiment, one phosphate group is bonded to each of the 1- and 6-positions, and one ethylenically unsaturated bond-containing group is bonded to each of the 2- and 5-positions, or one ethylenically unsaturated bond-containing group is bonded to each of the 2- to 5-, 7-, and 8-positions.

[0075] (R ２ ~R ５ and n) in general formula (1), R ２ , R ３ , R ４ , and R ５ is a phenyl group that is independently unsubstituted or substituted with two or three alkyl groups. ２ , R ３, R ４ , and R ５ is preferably a phenyl group substituted with two alkyl groups.

[0076] The alkyl groups are independently selected from the group consisting of C １ ~C ４ is a straight or branched chain alkyl group of the formula C １ ~C ３ A straight-chain or branched-chain alkyl group is more preferred, a methyl group or an ethyl group is particularly preferred, and a methyl group is particularly preferred.

[0077] n is an integer of 1 to 3, preferably an integer of 1 or 2, and more preferably 1.

[0078] (Ethylenically unsaturated bond-containing group) In the compound of general formula (1), the ethylenically unsaturated bond-containing group is ２ ~C １２ Preferably, the alkenyl group is a straight or branched chain alkenyl group of the formula C ２ ~C ４ A straight-chain or branched alkenyl group is preferred. An allyl group is more preferred.

[0079] (Compound of General Formula (1a)) In one embodiment, the compound of general formula (1) has a structure represented by general formula (1a).

[0080]

[0081] Here, R １ａ is a benzene ring or a naphthalene ring. The benzene ring is substituted with two ethylenically unsaturated bond-containing groups. Preferably, the benzene ring is substituted with two allyl groups, and the naphthalene ring is substituted with two ethylenically unsaturated bond-containing groups. Preferably, the naphthalene ring is substituted with two allyl groups.

[0082] wherein the ethylenically unsaturated bond-containing group is independently selected from the group consisting of C ２ ~C ４ is a straight-chain or branched alkenyl group.

[0083] R ２ａ , R ２ｂ , R３ａ , R ３ｂ , R ４ａ , R ４ｂ , R ５ａ and R ５ｂ are independently １ ~C ２ is an alkyl group of the formula (I), preferably methyl.

[0084] R ２ｃ , R ３ｃ , R ４ｃ and R ５ｃ are independently hydrogen or C １ ~C ２ is an alkyl group of the formula (I), and is preferably hydrogen.

[0085] n ａ is an integer of 1 to 2, preferably 1.

[0086] (Compound of General Formula (1b)) In one embodiment, the compound of general formula (1) has a structure represented by general formula (1b).

[0087]

[0088] Here, R １ｂ is biphenyl, and the biphenyl is substituted with two ethylenically unsaturated bond-containing groups. Preferably, each of the two benzene rings of the biphenyl is substituted with one ethylenically unsaturated bond-containing group.

[0089] wherein the ethylenically unsaturated bond-containing group is independently selected from the group consisting of C ２ ~C ４ and preferably an allyl group.

[0090] R ２ａ , R ２ｂ , R ３ａ , R ３ｂ , R ４ａ , R ４ｂ , R ５ａ and R ５ｂ are independently １ ~C ２ The alkyl group is preferably a methyl group.

[0091] R ２ｃ , R３ｃ , R ４ｃ and R ５ｃ are independently hydrogen or C １ ~C ２ is an alkyl group of the formula (I), and is preferably hydrogen.

[0092] n ａ is an integer of 1 to 2, preferably 1.

[0093] (Specific Examples of Compounds of General Formula (1)) Specific examples of compounds of general formula (1) include the following compounds.

[0094]

[0095]

[0096]

[0097] (Compound of General Formula (11)) According to one embodiment of the present invention, there is provided a compound of general formula (11).

[0098]

[0099] The compound of general formula (11) will be explained below.

[0100] R １１ is a benzene ring, biphenyl or naphthalene ring. When n is 2 or more, two or more R １ are the same. １１ With respect to a group having two bonded phosphate groups, such as: the terms "benzene ring," "biphenyl," and "naphthalene ring" each refer to a group having two substituents.

[0101] (Benzene ring) The bonding positions of the benzene ring and the two phosphate groups are not particularly limited. The two phosphate groups may be bonded to the ortho, meta, or para positions of the benzene ring. The meta or para positions are preferred.

[0102] (Biphenyl) The bonding positions of the two phosphate groups are not particularly limited as long as one phosphate group is bonded to each of the two benzene rings in the biphenyl. In this case, one phosphate group is bonded to the 2- to 6-positions, and one phosphate group is bonded to the 2'- to 6'-positions.

[0103] In the present specification, the 2- to 6-positions and 2'- to 6'-positions of biphenyl refer to the following positions.

[0104]

[0105] For example, one phosphate group may be bound to the 2-position and one phosphate group may be bound to the 2'-4'-position, one phosphate group may be bound to the 3-position and one phosphate group may be bound to the 2'-4'-position, or one phosphate group may be bound to the 4-position and one phosphate group may be bound to the 2'-4'-position. In one preferred embodiment, one phosphate group is bound to each of the 2- and 2'-positions, one phosphate group is bound to each of the 3- and 3'-positions, or one phosphate group is bound to each of the 4- and 4'-positions. In a particularly preferred embodiment, one phosphate group is bound to each of the 4- and 4'-positions.

[0106] (Naphthalene Ring) The bonding positions of the naphthalene ring and the two phosphate groups are not particularly limited. That is, the phosphate groups may be bonded to any of the eight carbon atoms in the naphthalene ring to which a substituent can be bonded. Two phosphate groups may be bonded to one benzene ring in the naphthalene ring, or one phosphate group may be bonded to each of the two benzene rings in the naphthalene ring. When two phosphate groups are bonded to one benzene ring in the naphthalene ring, the phosphate groups may be bonded to any of the 1st to 4th positions of the naphthalene ring. For example, they may be bonded to the 1st and 2nd positions, the 1st and 3rd positions, the 1st and 4th positions, or the 2nd and 3rd positions. When one phosphate group is bonded to each of the two benzene rings in the naphthalene ring, one phosphate group may be bonded to any of the 1st to 4th positions of the naphthalene ring, and the other phosphate group may be bonded to any of the 5th to 8th positions of the naphthalene ring.

[0107] Preferably, one phosphate group is attached to each of the two benzene rings in the naphthalene ring. In one preferred embodiment, a phosphate group is attached to each of the 1- and 6-positions of the naphthalene ring.

[0108] (Ethylenically unsaturated bond-containing group) In the compound of general formula (11), the ethylenically unsaturated bond-containing group is C ２ ~C １２ Preferably, the alkyl group is a linear or branched alkenyl group of the formula C, or an acryloyloxy group or a methacryloyloxy group. ２ ~C ４ and n is a straight-chain or branched-chain alkenyl group, or an acryloyloxy group or a methacryloyloxy group, and more preferably an allyl group or a methacryloyloxy group.

[0109] R １２ and R １５ represents a phenyl group independently substituted with 1 to 5 ethylenically unsaturated bond-containing groups, preferably substituted with 1 to 3 ethylenically unsaturated bond-containing groups, and more preferably substituted with 1 ethylenically unsaturated bond-containing group.

[0110] R １２ and R １５ is also independently substituted with 0 to 4 alkyl groups, preferably substituted with 0 to 2 alkyl groups.

[0111] The alkyl groups are independently C １ ~C ４ The total number of the ethylenically unsaturated bond-containing groups and the alkyl groups is 1 to 5, preferably 1 to 4, and more preferably 1 to 3.

[0112] R １３ and R １４ is a phenyl group independently substituted with two or three alkyl groups, each independently selected from the group consisting of C １ ~C ４is a straight or branched chain alkyl group.

[0113] n １ is an integer of 0 to 6, preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and particularly preferably 1.

[0114] In one embodiment, the compound of general formula (11) has a structure represented by general formula (11a).

[0115]

[0116] Here, R １１ａ is a benzene ring, biphenyl or naphthalene ring.

[0117] R １２ａ , R １２ｂ , R １５ａ and R １５ｂ are independently hydrogen or C １ ~C ２ The alkyl group is preferably a methyl group.

[0118] R １３ｃ and R １４ｃ are independently hydrogen or C １ ~C ２ is an alkyl group of the formula (I), and is preferably hydrogen.

[0119] R １３ａ , R １３ｂ , R １４ａ and R １４ｂ are independently １ ~C ２ The alkyl group is preferably a methyl group.

[0120] R １２ｃ and R １５ｃ are independently an ethylenically unsaturated bond-containing group. Here, the ethylenically unsaturated bond-containing group is independently ２ ~C ４ is a straight-chain or branched alkenyl group, an acryloyloxy group, or a methacryloyloxy group, and preferably an allyl group, an acryloyloxy group, or a methacryloyloxy group. １２ｃ and R １５ｃis in the para position relative to the phosphate group.

[0121] n １ａ is an integer of 0 to 6, preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and particularly preferably 1.

[0122] (Specific Examples of Compounds of General Formula (11)) Specific examples of compounds of general formula (11) include the following compounds.

[0123]

[0124] (Method for synthesizing aromatic phosphate ester) The compound of the present invention can be synthesized by combining known methods.

[0125] <Method for synthesizing a compound represented by general formula (1)> General formula (1):

[0126]

[0127] [where R １ is a benzene ring, biphenyl, or naphthalene ring, the benzene ring being substituted with 1 to 4 ethylenically unsaturated bond-containing groups, the biphenyl being substituted with 1 to 8 ethylenically unsaturated bond-containing groups, and the naphthalene ring being substituted with 1 to 6 ethylenically unsaturated bond-containing groups, wherein the ethylenically unsaturated bond-containing groups are independently selected from the group consisting of ２ ~C １２ is a straight-chain or branched alkenyl group of the formula R ２ , R ３ , R ４ , and R ５ is a phenyl group that is independently unsubstituted or substituted with two or three alkyl groups, each of which is independently selected from the group consisting of C １ ~C ４ and n is an integer of 1 to 3.]. There is no particular limitation on the method for synthesizing the compound of the formula (1).

[0128] For example, with reference to the method described in JP 2014-101299 A, a compound of the following formula (A):

[0129]

[0130] [where R １ is defined as in the above formula (1).

[0131] A compound of formula (A) and a compound of formula (B):

[0132]

[0133] [where R Ａ and R Ｂ is R in the above formula (1). ２ and R ３ and X represents a halogen atom such as Br or Cl.], the compound of formula (1) can be synthesized by reacting the compound of formula (1) with a phosphorochloridate represented by the formula (1).

[0134] When synthesizing the compound represented by formula (1), a catalyst (for example, a pyridine compound such as 4-dimethylaminopyridine), an acidic gas scavenger (for example, a trialkylamine such as triethylamine), or a solvent (for example, toluene) may be used, if necessary.

[0135] <Method for synthesizing a compound represented by general formula (11)> General formula (11):

[0136]

[0137] [where R １１ is a benzene ring, biphenyl or naphthalene ring, and R １２ and R １５ is a phenyl group independently substituted with 1 to 5 ethylenically unsaturated bond-containing groups and 0 to 4 alkyl groups, and the alkyl groups are independently selected from the group consisting of C １ ~C ４ wherein the total number of the ethylenically unsaturated bond-containing groups and the alkyl groups is 1 to 5, and each of the ethylenically unsaturated bond-containing groups is independently selected from the group consisting of C ２ ~C １２ is a linear or branched alkenyl group, an acryloyloxy group, or a methacryloyloxy group, １３ and R １４is a phenyl group independently substituted with two or three alkyl groups, each independently selected from the group consisting of C １ ~C ４ and n １ is an integer of 0 to 6]. The method for synthesizing the compound is not particularly limited.

[0138] The compound represented by general formula (11) may be, for example, a compound represented by the following formula (C):

[0139]

[0140] [where R Ｃ is R in the above formula (11). １３ and X represents a halogen atom such as Br or Cl.] and a phosphorodichloridate represented by the following formula (D):

[0141]

[0142] [where R １１ is defined as the same as in formula (11).

[0143]

[0144] [where R １１ , R １３ , R １４ , n １ is the same as the above formula (11), and X represents a halogen atom such as Br or Cl.]. Subsequently, an oligomer represented by the following formula (F):

[0145]

[0146] [where R Ｄ is R in the above formula (11) １２ The definition is the same as that of the compound represented by formula (11).

[0147] When synthesizing the compound of formula (11), a catalyst (for example, a pyridine compound such as 4-dimethylaminopyridine), an acidic gas scavenger (for example, a trialkylamine such as triethylamine), or a solvent (for example, toluene) may be used, if necessary.

[0148] The above compounds can be used as they are as modifiers in the present invention.

[0149] <Thermosetting Resin Composition> The thermosetting resin composition of the present invention contains a thermosetting resin and the above-described modifier.

[0150] The modifier is used to improve the performance of the thermosetting resin composition. The modifier may be a compound of formula (1) or a compound of formula (11).

[0151] <Thermosetting Resin> A conventionally known thermosetting resin can be used in the thermosetting resin composition of the present invention. In one preferred embodiment, a thermosetting resin having an ethylenically unsaturated bond is used.

[0152] In this specification, the term "ethylenically unsaturated bond" refers to an aliphatic double or triple bond that can undergo radical polymerization in the presence of radicals. Examples of groups having such unsaturated bonds include various well-known substituents such as acryloyl, methacryloyl, vinyl, allyl, and maleimide groups. Resins obtained by bonding these groups having unsaturated bonds to resins are thermosetting resins having ethylenically unsaturated bonds, and are therefore suitable for use in the present invention.

[0153] As the thermosetting resin having an ethylenically unsaturated bond, any known resin can be used, such as a polyphenylene ether resin, a maleimide resin, or a styrene-based resin modified with an ethylenically unsaturated group.

[0154] <Polyphenylene ether resin modified with an ethylenically unsaturated group> In one embodiment, the thermosetting resin is a polyphenylene ether resin modified with an ethylenically unsaturated group. The polyphenylene ether resin modified with an ethylenically unsaturated group is a resin in which an ethylenically unsaturated group is bonded to the terminal of a polyphenylene ether resin.

[0155] The polyphenylene ether resin modified with an ethylenically unsaturated group is represented, for example, by the following general formula A:

[0156]

[0157] (General Formula A) In general formula A, an ethylenically unsaturated group is bonded to the hydrogen atom of the hydroxy group at both ends of the main chain of the polyphenylene ether. ２１ ~R ４２ are each independently a hydrogen atom or a substituent. Examples of the substituent include a linear or branched alkyl group having 1 to 8 carbon atoms, a linear or branched alkenyl group having 2 to 8 carbon atoms, a linear or branched alkynyl group having 2 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, a carboxyl group, an aldehyde group, a hydroxy group, an amino group, etc. X, Y, and Z are each independently a single bond, a carbonyl group (>C=O), a thiocarbonyl group (>C=S), a methylene group (-CH ２ -), ethylene group (dimethylene group) (-CH ２ -CH ２ -), isopropenyl group (-C(CH ３ ) ２ -), trimethylene group (-CH ２ -CH ２ -CH ２ -) or a tetramethylene group (-CH ２ -CH ２ -CH ２ -CH ２ -) etc. １ is preferably 1 to 100, more preferably 3 to 20. ２ is preferably 1 to 100, more preferably 3 to 20.

[0158] In one embodiment, R ２６ , R ２７ , R ３０ , R ３１ , R ３２ , R ３３ , R ３６ , and R ３７ is hydrogen. In one embodiment, R ２４ , R ２５ , R ２８ , R ２９ , R ３４ , R ３５ , R ３８ , and R ３９ is alkyl, and in one embodiment, R ２４ , R ２５ , R ２８ , R ２９ , R ３４ , R ３５ , R ３８ , and R ３９ is methyl.

[0159] In one embodiment, X and Z are carbonyl groups (>C=O) and Y is an isopropenyl group (-C(CH ３ ) ２ In one embodiment, X is a benzylene group (-C ６ H ４ CH ２ -), Y is an isopropenyl group (-C(CH ３ ) ２ -), and Z is a benzylene group (-CH ２ C ６ H ４ -).

[0160] In one embodiment, R ２３ and R ４２ is methyl. In one embodiment, R ２３ and R ４２ is hydrogen.

[0161] In one embodiment, R ２１ , R ２２ , R ４０ and R ４１ is hydrogen.

[0162] The molecular weight of the polyphenylene ether resin modified with an ethylenically unsaturated group is not particularly limited. For example, the number average molecular weight is preferably 500 or more, more preferably 1,000 or more. Furthermore, for example, the number average molecular weight is preferably 10,000 or less, more preferably 7,000 or less, and in one embodiment, 5,000 or less. In one embodiment, it is 3,000 or less. If the molecular weight is too small, the Tg of the cured product is likely to be low and the heat resistance is likely to be reduced. If the molecular weight is too large, the flowability is reduced, which may make it difficult to mold the cured product.

[0163] Specific preferred resins include those having the following structures:

[0164]

[0165] A specific example of a resin product having such a structure is commercially available as Noryl (registered trademark) SA9000 resin manufactured by SABIC Japan LLC.

[0166] Furthermore, resins having the following structures can also be used as preferred resins.

[0167]

[0168] A specific example of a resin product having such a structure is commercially available as MEGTRON (registered trademark) manufactured by Panasonic Corporation.

[0169] In one embodiment, polyphenylene ethers described in JP-A Nos. 2003-515642, 2006-516297, JP-A Nos. 2013-23517, 2013-23519, WO 2014 / 034103, and JP-A No. 2019-194312 can also be used in the present invention as thermosetting resins.

[0170] <Maleimide Resin> In one embodiment, a maleimide resin can also be used as the thermosetting resin. Any known maleimide resin can be used as the maleimide resin. Specific examples include 4,4'-bismaleimide diphenylmethane, N,N'-p-phenylene bismaleimide, N,N'-m-phenylene bismaleimide, N,N'-m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, and N,N'-(sulfonyldi-p-phenylene)dimaleimide.

[0171] <Styrene-based resin> In one embodiment, the thermosetting resin may be a corresponding styrene-based resin in which an allyl group is bonded to the side chain of polystyrene. For example, a polymer having a structural unit represented by the following formula in the molecule is known, and can be used in the present invention.

[0172]

[0173] Here, Z ａ represents an arylene group, and R ５１ ~R ５３ each independently represents a hydrogen atom or an alkyl group, and R ５４ ~R ５６ and each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Specific examples of such styrene-based resins include ODV-XET (X03) manufactured by Nippon Steel Chemical & Material Co., Ltd., ODV-XET (X04) manufactured by Nippon Steel Chemical & Material Co., Ltd., and ODV-XET (X05) manufactured by Nippon Steel Chemical & Material Co., Ltd.

[0174] <Other Resins> In the thermosetting resin composition of the present invention, if necessary, a thermosetting resin not having an ethylenically unsaturated bond can also be used in addition to the thermosetting resin having an ethylenically unsaturated bond.

[0175] For example, an epoxy resin can be used. However, in order to fully exert the effects of the present invention, it is preferable to use a small amount of the thermosetting resin having no ethylenically unsaturated bond. The amount of the thermosetting resin having no ethylenically unsaturated bond is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 10 parts by mass or less, per 100 parts by mass of the thermosetting resin having an ethylenically unsaturated bond.

[0176] In the thermosetting resin composition of the present invention, a thermoplastic resin can be used in addition to the thermosetting resin, if necessary. However, in order to fully exert the effects of the present invention, it is preferable to use a small amount of the thermoplastic resin. The amount of the thermoplastic resin is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 10 parts by mass or less, per 100 parts by mass of the thermosetting resin having an ethylenically unsaturated bond. In one embodiment, the thermosetting resin composition of the present invention does not contain a thermoplastic resin.

[0177] <Crosslinking Agent> The thermosetting resin composition of the present invention optionally contains a monomer compound having an ethylenically unsaturated bond as a crosslinking agent. The crosslinking agent having an ethylenically unsaturated bond copolymerizes with the thermosetting resin having an ethylenically unsaturated bond during the thermosetting reaction, and provides the resulting cured product with good physical properties.

[0178] As the crosslinking agent, a monomer known as a crosslinking agent for thermosetting resins having an ethylenically unsaturated bond can be used. For example, triallyl isocyanurate, triallyl cyanurate, diallyl phthalate, styrene, etc. can be used. A monomer having two or more ethylenically unsaturated bonds in one molecule is preferred, and a monomer having three or more ethylenically unsaturated bonds in one molecule is more preferred. Furthermore, a monomer having four or less ethylenically unsaturated bonds in one molecule is preferred. In one embodiment, the crosslinking agent is a monomer having three ethylenically unsaturated bonds in one molecule.

[0179] Examples of the moiety having an ethylenically unsaturated bond in the crosslinking agent include an allyl group, an acryloyl group, and a methacryloyl group. An allyl group is preferred. The molecular weight of the crosslinking agent is preferably 100 or more, more preferably 200 or more. The molecular weight of the crosslinking agent is preferably 700 or less, more preferably 500 or less, and even more preferably 300 or less.

[0180] The amount of the crosslinking agent used is not particularly limited. The amount of the crosslinking agent used is preferably 1 part by mass or more, more preferably 3 parts by mass or more, even more preferably 5 parts by mass or more, and particularly preferably 10 parts by mass or more, relative to 100 parts by mass of the thermosetting resin having an ethylenically unsaturated bond in the thermosetting resin composition. If necessary, the amount may be 20 parts by mass or more, or may be 30 parts by mass or more, relative to 100 parts by mass of the thermosetting resin having an ethylenically unsaturated bond.

[0181] The amount of the crosslinking agent used is preferably 200 parts by mass or less, more preferably 150 parts by mass or less, and even more preferably 100 parts by mass or less, relative to 100 parts by mass of the thermosetting resin having an ethylenically unsaturated bond in the thermosetting resin composition. If necessary, it can also be 120 parts by mass or less, or even 100 parts by mass or less, relative to 100 parts by mass of the thermosetting resin having an ethylenically unsaturated bond.

[0182] If the amount of crosslinking agent used is too small, the cured product obtained by curing the thermosetting resin composition may not have sufficient heat resistance, whereas if the amount of crosslinking agent used is too large, the cured product obtained by curing the thermosetting resin composition may not have sufficient tensile strength and impact strength.

[0183] Although a modifier compound having an ethylenically unsaturated bond can also function as a crosslinking agent, in the present invention, a modifier compound having an ethylenically unsaturated bond exhibits a remarkable effect as a modifier, and therefore, in this specification, a modifier compound having an ethylenically unsaturated bond is not included in the crosslinking agent.

[0184] <Radical Generator> The thermosetting resin composition of the present invention optionally contains a radical generator. The radical generator may be one that generates radicals upon heating or one that generates radicals upon irradiation with light (for example, visible light or ultraviolet light).

[0185] As the radical generator, any compound known as a radical polymerization initiator for a compound having an ethylenically unsaturated bond can be used, such as a peroxide initiator or an azo initiator.

[0186] The amount of radical generator used is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, even more preferably 0.1 parts by mass or more, and particularly preferably 0.5 parts by mass or more, per 100 parts by mass of the total amount of thermosetting resin and crosslinking agent. The amount of radical generator used is preferably 10 parts by mass or less, more preferably 7 parts by mass or less, and even more preferably 5 parts by mass or less, per 100 parts by mass of the total amount of thermosetting resin and crosslinking agent. If the amount of radical generator used is too small, it tends to be difficult to sufficiently cure the thermosetting resin composition. If the amount of radical generator used is too large, the physical properties of the cured product obtained by curing the thermosetting resin composition as a resin material may be insufficient, resulting in deterioration of electrical properties.

[0187] <Modifier> The thermosetting resin composition of the present invention uses the above-described phosphate ester compound having an ethylenically unsaturated bond as a modifier. In this specification, "modification" refers to improving the properties of a resin, and "modifier" refers to a compound added to a resin to improve the properties of the resin. The modifier of the present invention is effective for improving the properties of thermosetting resins, particularly those having an ethylenically unsaturated bond. In one embodiment, the modifier of the present invention can improve the dielectric properties of a thermosetting resin composition. The modifier of the present invention is effective for improving either the dielectric loss tangent or the transmission loss of a thermosetting resin composition, and is also effective for improving both the dielectric loss tangent and the transmission loss. Therefore, the modifier of the present invention is suitable for use in thermosetting resin compositions for printed circuit boards, particularly for high-frequency printed circuit boards. The modifier of the present invention also allows the thermosetting resin composition to maintain high heat resistance.

[0188] The amount of the modifier used is not particularly limited. The amount of the modifier used is preferably 1 part by mass or more, more preferably 3 parts by mass or more, even more preferably 5 parts by mass or more, and particularly preferably 10 parts by mass or more, per 100 parts by mass of the thermosetting resin having an ethylenically unsaturated bond in the thermosetting resin composition. If necessary, the amount of the modifier used may be 20 parts by mass or more, or even 30 parts by mass or more, per 100 parts by mass of the thermosetting resin having an ethylenically unsaturated bond.

[0189] The amount of modifier used is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and even more preferably 30 parts by mass or less, per 100 parts by mass of the thermosetting resin having an ethylenically unsaturated bond in the thermosetting resin composition. If necessary, it can be 20 parts by mass or less, or even 10 parts by mass or less, per 100 parts by mass of the thermosetting resin having an ethylenically unsaturated bond. If the amount of modifier used is too small or too large, the cured product obtained by curing the thermosetting resin composition may not have sufficient physical properties.

[0190] <Reinforcing Material> A reinforcing material can be used in the thermosetting resin composition of the present invention, if necessary.

[0191] As the reinforcing material, any material known as a reinforcing material for thermosetting resins can be used. For example, a fibrous reinforcing material that has conventionally been used as a reinforcing material for epoxy resins can be used. Specifically, for example, glass fiber can be used.

[0192] The reinforcing material may be one that can be uniformly mixed in the thermosetting resin composition, or one that cannot be mixed in. Examples of reinforcing materials that can be uniformly mixed in the thermosetting resin composition include short glass fibers, and examples of reinforcing materials that cannot be uniformly mixed in the thermosetting resin composition include long glass fibers.

[0193] For example, glass fibers formed into a sheet or mat can be impregnated with a thermosetting resin composition and used as a molding material in the form of a so-called prepreg.

[0194] The amount of the reinforcing material used is not particularly limited. Specifically, for example, the amount of the reinforcing material can be 1 part by mass or more, 10 parts by mass or more, 30 parts by mass or more, or 50 parts by mass or more per 100 parts by mass of the total amount of the thermosetting resin, crosslinking agent, radical generator, and modifier in the thermosetting resin composition. Furthermore, the amount of the reinforcing material can be 300 parts by mass or less, 200 parts by mass or less, 150 parts by mass or less, or 100 parts by mass or less per 100 parts by mass of the total amount of the thermosetting resin, crosslinking agent, radical generator, and modifier in the thermosetting resin composition.

[0195] <Other Additives> The thermosetting resin composition of the present invention may further contain various additives other than the above-described modifiers and reinforcing materials, depending on the properties desired for the resin composition, as long as the effects of the present invention are not adversely affected. For example, known flame retardants, flame retardant assistants, ultraviolet absorbers, antioxidants, light stabilizers, colorants (e.g., dyes or pigments), surface modifiers, antibacterial agents, insect repellents, antistatic agents, fillers (e.g., inorganic fillers), etc. may be added.

[0196] The types and amounts of these additives are not particularly limited, and commonly used additives can be used within the range of their usual amounts. Specifically, for example, the amount of each of these additives can be 0.01 parts by mass or more, 0.1 parts by mass or more, or 1 part by mass or more, and 20 parts by mass or less, 10 parts by mass or less, or 5 parts by mass or less, per 100 parts by mass of the thermosetting resin.

[0197] However, the thermosetting resin composition of the present invention does not necessarily require the above-mentioned additives such as colorants, ultraviolet absorbers, hydrolysis inhibitors, and fillers. It is sufficient to use the minimum amount of these additives required based on the performance required for the intended product produced from the thermosetting resin.

[0198] <Method of Preparing Composition> The mixing and stirring operations during the preparation of the thermosetting resin composition can be carried out using a conventional stirring device, such as various mills, a Henschel mixer (FM mixer), etc. The order of addition of the various components is not important as long as they can be mixed uniformly. All components may be added to the stirring device at once and mixed and stirred. For example, a procedure can be adopted in which materials other than the radical generator are mixed first, and then the radical generator is mixed.

[0199] <Thermosetting Reaction> The thermosetting resin composition of the present invention can be cured by a conventionally known method. For example, if a radical generator is heated or irradiated with light to generate radicals, the generated radicals will cause a polymerization reaction of the ethylenically unsaturated bonds in the thermosetting resin, resulting in a cured resin. Furthermore, if a crosslinking agent is included in the thermosetting resin composition, the ethylenically unsaturated bonds in the thermosetting resin and the ethylenically unsaturated bonds in the crosslinking agent will cause a polymerization reaction, resulting in a cured resin. Furthermore, since the compound and modifier of the present invention also have ethylenically unsaturated groups, the radicals will cause a polymerization reaction of the compound and modifier of the present invention.

[0200] The conditions for curing the thermosetting resin composition are appropriately selected depending on the type and amount of the radical generator used. For example, when a radical generator that decomposes relatively quickly even at room temperature to generate radicals is used, room temperature may be used. When a radical generator that cannot be decomposed quickly unless it is at a high temperature is used, a high temperature is used. Specifically, the temperature when curing the thermosetting resin composition can be, for example, 80°C or higher or 100°C or higher, and can be, for example, 250°C or lower or 230°C or lower. Furthermore, the heating time can be, for example, 1 minute or longer or 3 minutes or longer, and can be, for example, 120 minutes or shorter or 90 minutes or shorter.

[0201] It is believed that when a curing reaction is carried out in the thermosetting resin composition of the present invention, a copolymer containing a residue of a thermosetting resin having an ethylenically unsaturated bond and a residue of the compound of the present invention or the modifier of the present invention is formed. Furthermore, when a crosslinking agent is added to the thermosetting resin composition of the present invention and a curing reaction is carried out, a copolymer containing a residue of a thermosetting resin having an ethylenically unsaturated bond, a residue of the compound of the present invention or the modifier of the present invention, and a residue of the crosslinking agent is formed. Because the copolymer thus formed has excellent dielectric properties and heat resistance, it is understood that a substrate manufactured using the thermosetting resin composition of the present invention has excellent dielectric properties and heat resistance. The cured product obtained by the curing reaction of the thermosetting resin composition of the present invention has excellent dielectric properties and heat resistance, and can therefore be preferably used as a material for manufacturing printed circuit boards. In this specification, the term "resin material" refers to a cured product obtained by the curing reaction of a thermosetting resin composition and can be used for various applications.

[0202] It is assumed that the chemical structure of the resin in the cured product is a structure in which multiple molecules are bonded together due to a radical polymerization reaction occurring at the ethylenically unsaturated bond in the molecule of each component in the thermosetting resin composition, but it is difficult to precisely identify the chemical structure. In particular, when multiple types of molecules having ethylenically unsaturated bonds are present, both homopolymerization and copolymerization are possible, making it difficult to precisely identify the chemical structure of the product. Even if it is theoretically possible, this would require a great deal of cost and time and is therefore impractical. Therefore, the cured product is described using the term "product-by-process," which means that the composition of the thermosetting resin composition before the curing reaction is specified and the cured product obtained by curing the composition.

[0203] <Molded Article> The thermosetting resin composition of the present invention can be molded by any known method for molding a thermosetting resin. A desired molded article can be easily obtained by using a molding machine, mold, etc. appropriate for the desired molded article. For example, a desired molded article can be obtained by molding and a curing reaction of the thermosetting resin using a method such as a hot press. The step of performing the curing reaction of the thermosetting resin composition and the step of molding into a desired shape may be performed simultaneously or separately. The curing reaction may be performed first and the resulting cured product may be molded, or the molding step may be performed first and then the curing reaction may be performed.

[0204] The resulting molded article has excellent dielectric properties and has the advantage that the decrease in heat resistance due to the addition of the modifier is small.

[0205] <Printed Circuit Board> A substrate usable for a printed circuit board can be obtained by curing a thermosetting resin composition containing the above-mentioned thermosetting resin and modifier. A printed circuit board usually has a conductor layer and an insulating layer. The modifier and thermosetting resin composition of the present invention can be used to form the insulating layer of a printed circuit board.

[0206] In this specification, the term "high frequency" is not particularly limited, but is preferably 100 MHz or higher, in one embodiment 1 GHz or higher, and in another embodiment 10 GHz or higher. Furthermore, the high frequency may be, for example, 100 GHz or lower, or 50 GHz or lower. In this specification, a "high frequency printed circuit board" refers to a printed circuit board used at such high frequencies.

[0207] High heat resistance is required for high frequency printed circuit boards. When a board is manufactured using the thermosetting resin of the present invention, excellent heat resistance can be achieved. Furthermore, when a board is manufactured using the thermosetting resin of the present invention, excellent dielectric properties and heat resistance can be achieved, making it suitable for use in high frequency printed circuit boards.

[0208] The present invention will be explained in more detail by the following synthesis examples and examples, but the present invention is not limited to these examples.

[0209] (Synthesis Examples) In the synthesis examples, the following compounds were used as raw materials: phosphorus oxychloride (manufactured by Tokyo Chemical Industry Co., Ltd.), resorcinol (manufactured by Tokyo Chemical Industry Co., Ltd.), 2,6-dimethylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.), 4,4'-dihydroxybiphenyl (manufactured by Tokyo Chemical Industry Co., Ltd.), hydroquinone (manufactured by Tokyo Chemical Industry Co., Ltd.), 4-hydroxyphenyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), allyl bromide (manufactured by Tokyo Chemical Industry Co., Ltd.), anhydrous potassium carbonate (manufactured by Kishida Chemical Co., Ltd.), anhydrous magnesium chloride (manufactured by Kishida Chemical Co., Ltd.), 4-dimethylaminopyridine (manufactured by Tokyo Chemical Industry Co., Ltd.), triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.), PX-200 (tetrakis(2,6-dimethylphenyl)-m-phenylene bisphosphate, manufactured by Daihachi Chemical Industry Co., Ltd.), and 2,2'-diallyl bisphenol A (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).

[0210] An example of synthesis of raw materials for the modifier will be described below.

[0211] (Synthesis Example A1) <Synthesis of 2,6-xylyl phosphorodichloridate (MXPC)> 920 g (6.0 mol) of phosphorus oxychloride, 366.5 g (3.0 mol) of 2,6-dimethylphenol, and 0.72 g (0.0075 mol) of magnesium chloride as a catalyst were charged into a 1 L four-neck flask equipped with a stirrer, thermometer, and hydrochloric acid recovery device (a condenser connected to a water scrubber). The resulting mixed solution was gradually heated from 20°C to 120°C over approximately 4 hours while stirring to allow the reaction to occur, and the generated hydrogen chloride gas was recovered using a water scrubber. The mixture was then cooled to 90°C, and the pressure in the flask was gradually reduced to 20 kPa. Unreacted phosphorus oxychloride, 2,6-dimethylphenol, and by-product hydrogen chloride were removed, yielding 670 g of a reaction product composed primarily of 2,6-xylyl phosphorodichloridate. The reaction product was purified by vacuum distillation using a vacuum pump to obtain 532 g (yield 74.1%) of a main fraction having a chlorine content of 29.9 mass% (theoretical 29.7 mass%).

[0212] Synthesis Example A2: Synthesis of di-2,6-xylyl phosphorochloridate (DXPC) A 2-L four-neck flask equipped with a stirrer, thermometer, and hydrochloric acid recovery device (a condenser connected to a water scrubber) was charged with 767 g (5 mol) of phosphorus oxychloride, 1200 g (9.8 mol) of 2,6-dimethylphenol, 140 g of xylene as a solvent, and 6.2 g (0.065 mol) of magnesium chloride as a catalyst. The resulting mixed solution was gradually heated to 160°C over approximately 3 hours with stirring to allow the reaction to occur, and the generated hydrogen chloride gas was collected using a water scrubber. Thereafter, the pressure in the flask was gradually reduced to 20 kPa at the same temperature, and xylene, unreacted phosphorus oxychloride and 2,6-dimethylphenol, and by-product hydrogen chloride were removed to obtain 1700 g of a reaction product composed primarily of di-2,6-xylyl phosphorochloridate. The chlorine content of the reaction mixture was 10.9% by mass.

[0213] (Synthesis Example A3) <Synthesis of Allylphenols> Synthesis of 4-allyl-2,6-dimethylphenol 400 g of acetone, 173.3 g (1.25 mol) of anhydrous potassium carbonate, and 122.2 g (1.0 mol) of 2,6-dimethylphenol were placed in a 2 L four-neck flask equipped with a stirrer, thermometer, and cooling condenser. With stirring, the vessel temperature was raised to 60°C, and 151.2 g (1.25 mol) of allyl bromide was added over 1 hour. Stirring was then continued for 26 hours while maintaining the temperature at 60°C. After completion of the reaction, 400 g of toluene and 400 ml of hot water were added, and the toluene layer was separated using a separatory funnel. The toluene layer was washed with 150 g of 10% aqueous sodium hydroxide solution and then washed with water (400 g × 1 time). After removing the toluene under reduced pressure, 148.8 g of an allyl ether of 2,6-dimethylphenol (yield: 91.7%) was obtained by vacuum distillation.

[0214] Next, 146.3 g of the obtained allyl ether of 2,6-dimethylphenol was placed in a 300 ml four-neck flask equipped with a stirrer, a thermometer, and a cooling condenser. With stirring and careful attention to heat generation, the mixture was heated to 165°C and aged for 6 hours to carry out Claisen rearrangement. The obtained product was confirmed to be 4-allyl-2,6-dimethylphenol by NMR.

[0215] Synthesis Example A4 Synthesis of Diallyl Resorcinol 600 g of acetone, 145.1 g (1.05 mol) of anhydrous potassium carbonate, and 55.1 g (0.5 mol) of resorcinol were placed in a 1 L four-neck flask equipped with a stirrer, thermometer, and cooling condenser. With stirring, 127 g (1.05 mol) of allyl bromide was added over 1 hour at a vessel temperature of 20°C, and then the mixture was stirred for 48 hours while maintaining the temperature at 20°C. After completion of the reaction, the mixture was filtered to remove solids, and the acetone was removed using an evaporator. The resulting product was transferred to a separatory funnel, and 200 g of toluene and 200 g of a 12% aqueous sodium hydroxide solution were added to separate the toluene layer. The toluene layer was washed with 200 ml of water. After removing the toluene under reduced pressure, vacuum distillation was performed to obtain 62 g of a diallyl ether of resorcinol (yield: 65.1%).

[0216] Next, 60 g of the obtained diallyl ether of resorcinol was placed in a 200 ml four-neck flask equipped with a stirrer, a thermometer, and a cooling condenser. With stirring and careful attention to heat generation, the mixture was heated to 190°C and aged for 6 hours to carry out Claisen rearrangement. The obtained product was an isomer mixture of 2,4-diallylresorcinol and 4,6-diallylresorcinol.

[0217] Synthesis Example A5 Synthesis of Diallyl Hydroquinone 200 g of acetone, 172.8 g (1.25 mol) of anhydrous potassium carbonate, and 55.1 g (0.5 mol) of hydroquinone were placed in a 1 L four-neck flask equipped with a stirrer, thermometer, and cooling condenser. With stirring, 151.2 g (1.25 mol) of allyl bromide was added over 1 hour at a vessel temperature of 20°C, and the mixture was then heated to 60°C and stirred for 10 hours. After completion of the reaction, solids were removed by filtration, and the acetone was removed using an evaporator. The resulting product was transferred to a separatory funnel, and 200 g of toluene and 200 g of a 12% aqueous sodium hydroxide solution were added to separate the toluene layer. The toluene layer was washed with 200 ml of water, and the toluene was removed under reduced pressure. 73.9 g of a diallyl ether of hydroquinone (yield: 77.7%) was obtained by vacuum distillation.

[0218] Next, 60 g of the obtained diallyl ether of resorcinol was placed in a 200 ml four-neck flask equipped with a stirrer, a thermometer, and a cooling condenser. The mixture was heated to 180°C while stirring, taking care to avoid heat generation, and then aged for 4 hours to carry out Claisen rearrangement. The obtained product was an isomer mixture of 2,3-diallylhydroquinone and 2,5-diallylhydroquinone.

[0219] Synthesis Example A6: Synthesis of Diallyl Biphenol 200 g of acetone, 145.1 g (1.05 mol) of anhydrous potassium carbonate, and 93.1 g (0.5 mol) of biphenol were placed in a 1 L four-neck flask equipped with a stirrer, thermometer, and cooling condenser. With stirring, 151.2 g (1.25 mol) of allyl bromide was added over 1 hour at a kettle temperature of 40°C, and the mixture was then heated to 60°C and stirred for 6 hours. After cooling to 50°C, the reaction product was transferred to a beaker containing 200 g of toluene and 350 g of water, and the precipitated crystals were filtered. The crystals were further washed with 200 g of water and dried in a vacuum dryer at 80°C under reduced pressure (1.6 kPa) for 5 hours to obtain 120.2 g of diallylated biphenol (yield: 90.2%).

[0220] Next, 30 g of the obtained diallyl ether of biphenol was placed in a 200 ml four-neck flask equipped with a stirrer, thermometer, and cooling condenser. The mixture was heated to 190°C while stirring, taking care to avoid heat buildup, and then aged for 6 hours to carry out Claisen rearrangement. The resulting product was confirmed to be diallyl biphenol by NMR.

[0221] The synthesis examples of the compounds used in the examples are described below.

[0222] (Synthesis Example 1)

[0223]

[0224] A 1 L four-neck flask equipped with a stirrer, thermometer, and cooling condenser was charged with 57.0 g (0.3 mol) of the diallyl resorcinol obtained in Synthesis Example A4, 214.3 g (0.66 mol) of di-2,6-xylyl phosphorochloridate (DXPC), 1.8 g (0.01 mol) of 4-dimethylaminopyridine, and 330 g of toluene. While stirring, 66.8 g (0.66 mol) of triethylamine was added dropwise using an addition funnel while maintaining the vessel temperature at 30°C. The vessel temperature was then raised to 40°C and stirring was continued for 4 hours. After completion of the reaction, the vessel temperature was raised to 70°C for post-treatment. Post-treatment consisted of washing with water, washing with hydrochloric acid, and neutralization using an aqueous sodium carbonate solution, followed by further washing with water, yielding a treated toluene layer. After removing the toluene using an evaporator, the mixture was evacuated using a vacuum pump at 70°C, yielding 151.4 g of a brown viscous liquid reaction product. The obtained product was a mixture mainly composed of the compound of formula (101a) and the compound of formula (101b). The GPC purity of the major component (the proportion of the sum of the amount of the compound of formula (101a) and the amount of the compound of formula (101b) to the total amount of the product) was 92.6%. １ The H-NMR chart is shown in Figure 1.

[0225] (Synthesis Example 2)

[0226]

[0227] A 1 L four-neck flask equipped with a stirrer, thermometer, and cooling condenser was charged with 47.6 g (0.25 mol) of diallylhydroquinone obtained in Synthesis Example A5, 178.6 g (0.55 mol) of di-2,6-xylylphosphorochloridate (DXPC), 1.52 g (0.013 mol) of 4-dimethylaminopyridine, and 200 g of toluene. While stirring, 58.4 g (0.58 mol) of triethylamine was added dropwise using an addition funnel while maintaining the vessel temperature at 30°C. The vessel temperature was then maintained at 30°C and stirred for 4 hours. After completion of the reaction, the vessel temperature was raised to 65°C and post-treatment was carried out. Post-treatment consisted of washing with water, washing with hydrochloric acid, and neutralization using an aqueous sodium carbonate solution, followed by further washing with water, yielding a treated toluene layer. After removing the toluene using an evaporator, the mixture was evacuated at 70°C using a vacuum pump to obtain 183.9 g of a black-brown solid reaction product. The obtained product was a mixture mainly composed of the compound of formula (102a) and the compound of formula (102b). The GPC purity of the major component (the ratio of the sum of the amount of the compound of formula (102a) and the amount of the compound of formula (102b) to the total amount of the product) was 91.8%. A single melting point of 121.6°C was measured for the product. １ The H-NMR chart is shown in FIG.

[0228] (Synthesis Example 3)

[0229]

[0230] A 1 L four-neck flask equipped with a stirrer, thermometer, and cooling condenser was charged with 53.3 g (0.2 mol) of diallylbiphenol, 136.4 g (0.42 mol) of di-2,6-xylylphosphorochloridate (DXPC), 1.2 g (0.01 mol) of 4-dimethylaminopyridine, and 250 g of toluene. While stirring, 44.3 g (0.43 mol) of triethylamine was added dropwise via an addition funnel while maintaining the vessel temperature at 40°C. Stirring was then continued for 3 hours while maintaining the temperature at 40°C. After completion of the reaction, the vessel temperature was raised to 80°C for post-treatment. Post-treatment consisted of washing with water, washing with hydrochloric acid, and neutralization using an aqueous sodium carbonate solution, followed by further washing with water, yielding a treated toluene layer. The toluene was removed using an evaporator. The mixture was then evacuated at 90°C using a vacuum pump, yielding 166.4 g of a brown solid reaction product. The resulting product was washed with methanol and dried to obtain a pale yellow solid. The melting point of the main component compound was 88.7°C, and the GPC purity was 97.5%. １ The H-NMR chart is shown in FIG.

[0231] (Synthesis Example 4)

[0232]

[0233] A 500 ml four-neck flask equipped with a stirrer, thermometer, and hydrochloric acid recovery device (a condenser connected to a water scrubber) was charged with 22.0 g (0.2 mol) of resorcinol, 138.6 g (0.58 mol) of 2,6-xylyl phosphorodichloridate (MXPC), and 0.29 g (0.003 mol) of anhydrous magnesium chloride. With stirring, the vessel temperature was raised to 125°C over 1 hour, and stirring was continued for 3 hours. Hydrogen chloride gas evolved as the reaction progressed was recovered using a scrubber, and the pressure was gradually reduced to 2 kPa to perform deoxidation. After cooling the vessel to 80°C, the excess MXPC was recovered under a reduced pressure of 0.2 kPa until the vessel temperature reached 165°C. Next, the mixture was cooled to room temperature under stirring, and 140 g of toluene, 66.5 g (0.41 mol) of 4-allyl-2,6-dimethylphenol, and 1.2 g (0.01 mol) of 4-dimethylaminopyridine were added. While maintaining the temperature at 30°C, 43.5 g (0.43 mol) of triethylamine was slowly added dropwise using an addition funnel. After stirring for 3 hours, the vessel temperature was raised to 70°C and post-treatment was carried out. Post-treatment consisted of washing with water, washing with hydrochloric acid, and neutralization using an aqueous sodium carbonate solution, in that order, followed by further washing with water to obtain a treated toluene layer. After removing the toluene using an evaporator, the mixture was evacuated at 70°C using a vacuum pump to obtain 151.4 g of a yellowish-brown viscous liquid reaction product. The obtained product had the structure shown above, where n １０４ The mixture was composed mainly of a compound with n = 1 (GPC purity 76.6%). １０４ = 1 to 3) and the monomer obtained by reacting MXPC with 4-allyl 2,6-dimethylphenol (n １０４ = 0). １ The H-NMR chart is shown in FIG.

[0234] (Synthesis Example 5)

[0235]

[0236] A 500 ml four-neck flask equipped with a stirrer, thermometer, and hydrochloric acid recovery device (a condenser connected to a water scrubber) was charged with 22.0 g (0.2 mol) of resorcinol, 138.6 g (0.58 mol) of 2,6-xylyl phosphorodichloridate (MXPC), and 0.29 g (0.003 mol) of anhydrous magnesium chloride. With stirring, the vessel temperature was raised to 125°C over 1 hour, and stirring was continued for 3 hours. Hydrogen chloride gas evolved as the reaction proceeded was recovered using a scrubber, and the pressure was gradually reduced to 2 kPa for deoxidation. After cooling the vessel to 80°C, the excess MXPC was recovered under a reduced pressure of 0.2 kPa until the vessel temperature reached 165°C. Next, the mixture was cooled to room temperature under stirring, and then 200 g of toluene, 71.3 g (0.40 mol) of 4-hydroxyphenyl methacrylate, and 1.2 g (0.01 mol) of 4-dimethylaminopyridine were added. While maintaining the temperature at 30°C, 42.5 g (0.42 mol) of triethylamine was slowly added dropwise using an addition funnel. After stirring for 3 hours, the vessel temperature was raised to 60°C and post-treatment was carried out. The post-treatment consisted of washing with water, washing with hydrochloric acid, and neutralization using an aqueous sodium carbonate solution, in that order, followed by further washing with water to obtain a treated toluene layer. After removing the toluene using an evaporator, the mixture was evacuated at 70°C using a vacuum pump to obtain 153.4 g of a reaction product as a brown viscous liquid. The obtained product had the structure shown above, where n １０５ The mixture was composed mainly of a compound with n = 1 (GPC purity 76.3%). １０５ = 1 to 3) and a monomer obtained by reacting MXPC with 4-hydroxyphenyl methacrylate (n １０５ = 0). １ The H-NMR chart is shown in FIG.

[0237] (Synthesis Example 6)

[0238]

[0239] A 1 L four-neck flask equipped with a stirrer, thermometer, and cooling condenser was charged with 77.0 g (0.25 mol) of 2,2'-diallylbisphenol A, 178.7 g (0.55 mol) of di-2,6-xylylphosphorochloridate (DXPC), 1.54 g (0.013 mol) of 4-dimethylaminopyridine, and 220 g of toluene. While stirring, 58.5 g (0.58 mol) of triethylamine was added dropwise using an addition funnel while maintaining the vessel temperature at 25°C. The vessel temperature was then raised to 30°C and stirring was continued for 3 hours. After completion of the reaction, the vessel temperature was raised to 60°C and post-treatment was carried out. Post-treatment consisted of washing with water, washing with hydrochloric acid, and neutralization using an aqueous sodium carbonate solution, followed by further washing with water, yielding a treated toluene layer. After removing the toluene using an evaporator, the mixture was evacuated at 70°C using a vacuum pump to obtain 216.1 g of a pale yellow solid reaction product. The resulting product was a mixture containing the compound represented by the above structural formula as the main component (GPC purity: 92.5%). The product was measured to have a single melting point of 126.9°C. １ The H-NMR chart is shown in FIG.

[0240] < １ H-NMR measurement> １ H-NMR measurements were carried out using a JEOL JNM-ECS4100 (400 MHz). The deuterated solvent was chloroform-d for compounds (101) and (103) to (106). １ (Tokyo Chemical Industry Co., Ltd.), and dimethyl sulfoxide-d ６ (manufactured by Tokyo Chemical Industry Co., Ltd.) were used.

[0241] <Evaluation of Solubility in Varnish Using Non-Polar Solvent> In order to evaluate the solubility of the modifier compound in a varnish using a non-polar solvent, the following experiment was carried out using toluene as the non-polar solvent.

[0242] The following raw materials were used to prepare the varnish: Methacrylic-modified PPE resin (SA-9000, manufactured by SABIC) Triallyl isocyanurate (TAIC, manufactured by Tokyo Chemical Industry Co., Ltd.) Perbutyl P (manufactured by NOF Corporation) A varnish was prepared by blending the various components in the proportions shown in Table 1. The varnish was then left to stand at 23°C for 24 hours, and the presence or absence of precipitation of the modifier in the varnish was visually confirmed.

[0243] If no precipitate was observed 24 hours after the varnish was prepared, it was rated as "good", and if precipitate was observed, it was rated as "poor".

[0244]

[0245] <Evaluation of Presence or Absence of Precipitation During Glass Cloth Impregnation> The varnish prepared in the proportions shown in Table 1 above was poured into a tray, and one glass cloth (E10T, manufactured by Unitika, 90 mm length x 160 mm width) was impregnated with the varnish. The glass cloth was then removed from the liquid surface. At this time, the appearance of the glass cloth impregnated with the varnish was visually confirmed.

[0246] When the glass cloth was entirely impregnated with the varnish, if no crystalline substance was precipitated and the appearance of the varnish-impregnated glass cloth was transparent, it was judged as "good."When the glass cloth was entirely impregnated with the varnish, if crystalline substance was precipitated and the appearance of the varnish-impregnated glass cloth was cloudy and opaque, it was judged as "poor."

[0247] <Electrical Property Test> <Preparation of Cured Methacrylic-Modified PPE Resin> A varnish (using a toluene solvent) prepared by blending various components according to the ratios shown in Table 2 below was poured into a tray, and one sheet of glass cloth (E10T, manufactured by Unitika, 90 mm length x 160 mm width) was impregnated with the varnish. The glass cloth was then removed from the liquid surface. This was then air-dried for 10 minutes, followed by drying at 130°C for 3 minutes in a hot-air circulating oven to obtain a prepreg. Eight prepregs obtained in the same manner were stacked and pressed at 210°C and a pressure of 3 MPa for 1 hour to obtain a 0.6 mm-thick laminate with a resin content of 40 wt% and a glass content of 60 wt%.

[0248]

[0249] <Specimen for measuring electrical properties> The laminate was cut using a rotary diamond cutter to obtain a rod-shaped test piece measuring 80 mm (L) x 1.5 mm (W), which was used as a specimen for measuring electrical properties.

[0250] <Electrical Property Measuring Instrument> The electrical properties of the specimens for electrical property measurement were measured using a PNA network analyzer N5222B (manufactured by Keysight Technology) and a 10 GHz cavity resonator CP531 (manufactured by Kanto Electronics Application Development Co., Ltd.).

[0251] <Glass Transition Temperature> <Preparation of Cured Methacrylic-Modified PPE Resin> Three types of varnishes were prepared by adding 2, 3, or 4 parts by weight of a radical generator (Perbutyl P) to the various components blended in the proportions shown in Table 3 below. Each varnish was poured into a tray, and a sheet of glass cloth (Unitika E10T, 90 mm long x 160 mm wide) was impregnated with the varnish. The glass cloth was then removed from the liquid surface. The resulting prepreg was then air-dried for 10 minutes and then dried at 130°C for 3 minutes in a hot-air circulating oven to obtain a prepreg. Eight prepregs prepared from varnishes containing the same amount of radical generator were stacked and pressed at 210°C and 3 MPa for 1 hour. This resulted in three types of laminates (resin content: 40 wt%, glass content: 60 wt%, thickness: 0.6 mm) with different radical generator contents.

[0252]

[0253] <Specimens for measuring glass transition temperature> The laminated plates were cut using a rotary diamond cutter to obtain three types of plate-shaped test pieces (size: 50 mm (L) × 10 mm (W)) with different radical generator contents for each of the examples and comparative examples. These were used as specimens for measuring glass transition temperature.

[0254] <Glass transition temperature measuring device> The glass transition temperatures of the specimens for glass transition temperature measurement were measured using a DMA7100 dynamic viscoelasticity measuring device (DMA: double-support bending mode) manufactured by Hitachi High-Tech Science Corp. The glass transition temperatures of three types of test pieces with different radical generator contents were compared, and the maximum value was taken as the maximum DMA (°C).

[0255] <Flame Retardancy Evaluation> <Preparation of Methacrylic-Modified PPE Resin Cured Product> A varnish prepared by blending various components according to the ratios shown in Table 4 below was poured into a tray, and a sheet of glass cloth (E10T, manufactured by Unitika, 90 mm length x 160 mm width) was impregnated with the varnish. The glass cloth was then removed from the liquid surface. This was then air-dried for 10 minutes, followed by drying at 130°C for 3 minutes in a hot air circulating oven to obtain a prepreg. Sixteen prepregs obtained in the same manner were stacked and pressed at 210°C and a pressure of 3 MPa for 1 hour to obtain a laminate for flame retardancy testing with a resin content of 40 wt%, a glass content of 60 wt%, and a thickness of 1.2 mm.

[0256]

[0257] Note 1: In Comparative Example 3, the solubility in toluene was low, so the laminate was prepared using a saturated solution.

[0258] <Flame Retardancy Test> Test specimens were prepared from the laminate for the flame retardancy test, and a vertical combustion test was carried out using five test specimens in accordance with the UL-94 test method.

[0259] The combustion behavior of each example and comparative example was evaluated in accordance with the UL-94 test method, except that a case in which all five test pieces burned completely was rated as "total burn," and a case in which the flame was confirmed to have disappeared but the burning time was too long to meet any of the V-0, V-1, or V-2 criteria was rated as "Not-V."

[0260] (Example 1) Using the compounds of formula (101a) and formula (101b) obtained in Synthesis Example 1 as modifiers, laminates were produced and evaluated by the above-mentioned method. In addition, the weight percentage of phosphorus atoms present in the compound relative to the molecular weight of the compound, calculated from the molecular formula of the compound, is shown in the "Theoretical P%" column in the table.

[0261] Regarding the results of the electrical properties, the values ​​obtained by the above-mentioned measuring methods are entered in the absolute value column, and the ratio of each value to the value of Comparative Example 2 is entered in the relative value column.

[0262] The results are shown in Table 5 below.

[0263] Example 2 A laminate was produced and evaluated in the same manner as in Example 1, except that the compounds of formula (102a) and formula (102b) obtained in Synthesis Example 2 were used as modifiers. The results are shown in Table 5 below.

[0264] Example 3 A laminate was produced and evaluated in the same manner as in Example 1, except that the compound of formula (103) obtained in Synthesis Example 3 was used as a modifier. The results are shown in Table 5 below.

[0265] Example 4 A laminate was produced and evaluated in the same manner as in Example 1, except that the compound of formula (104) obtained in Synthesis Example 4 was used as a modifier. The results are shown in Table 5 below.

[0266] Example 5 A laminate was produced and evaluated in the same manner as in Example 1, except that the compound of formula (105) obtained in Synthesis Example 5 was used as a modifier. The results are shown in Table 5 below.

[0267] Comparative Example 1 An experiment was carried out in the same manner as in Example 1, except that no modifier compound was used. The results are shown in Table 6 below.

[0268] Comparative Example 2 An experiment was carried out in the same manner as in Example 1, except that a commercially available flame retardant having the structure of the following formula (111) (PX-200 manufactured by Daihachi Chemical Industry Co., Ltd.) was used. The results are shown in Table 6 below.

[0269]

[0270] Comparative Example 3 An experiment was carried out in the same manner as in Example 1, except that the compound of formula (106) synthesized in Synthesis Example 6 was used. The results are shown in Table 6 below.

[0271]

[0272]

[0273] (Discussion) It was confirmed that the modifiers of Examples 1 to 5 have significantly improved solubility in toluene, a non-polar organic solvent, compared to Comparative Example 3. In other words, it was confirmed that a sufficient amount of modifier can be used when producing a laminate using a non-polar organic solvent. The modifier of the present invention is very advantageous in producing a laminate.

[0274] The modifiers of Examples 1 to 3 had reduced dielectric constants and dielectric losses compared to Comparative Example 1. The modifiers of Examples 1, 3, and 4 had reduced dielectric loss tangents compared to Comparative Example 1. The modifiers of Examples 1 to 5 had reduced dielectric constants compared to Comparative Example 3.

[0275] It was confirmed that the modifiers of Examples 1 to 5 significantly improved heat resistance while maintaining high flame retardancy compared to Comparative Examples 2 and 3. Since high heat resistance is required for substrates for next-generation communication standards, the modifier of the present invention is useful as a modifier for use in substrates for next-generation communication standards.

[0276] The above results confirm that the modifier of the present invention can achieve high performance in terms of solubility in non-polar solvents, dielectric properties, heat resistance, and flame retardancy.

[0277] According to the present invention, a modifier and a thermosetting resin composition for printed circuit boards having excellent heat resistance are provided. According to the present invention, a modifier and a thermosetting resin composition suitable for high-frequency printed circuit boards that comply with next-generation communication standards are provided. The modifier and the thermosetting resin composition of the present invention provide printed circuit boards having high electrical signal transmission efficiency and excellent heat resistance.

[0278] As described above, the present invention has been illustrated using preferred embodiments of the present invention, but the present invention should not be construed as being limited to these embodiments. It is understood that the scope of the present invention should be interpreted only by the claims. It is understood that a person skilled in the art can implement an equivalent scope based on the description of the present invention and common general knowledge from the description of specific preferred embodiments of the present invention. It is understood that the contents of the patents, patent applications, and literature cited in this specification should be incorporated by reference into this specification as if the contents themselves were specifically set forth in this specification.

Claims

1. A compound of general formula (1): Here, R １ is a benzene ring, a biphenyl or a naphthalene ring, the benzene ring is substituted with 1 to 4 ethylenically unsaturated bond-containing groups, the biphenyl is substituted with 1 to 8 ethylenically unsaturated bond-containing groups, and the naphthalene ring is substituted with 1 to 6 ethylenically unsaturated bond-containing groups, wherein the ethylenically unsaturated bond-containing groups are independently selected from the group consisting of ２ ~C １２ R is a straight or branched alkenyl group of the formula ２ , R ３ , R ４ , and R ５ is a phenyl group that is independently unsubstituted or substituted with two or three alkyl groups, each of which is independently selected from the group consisting of １ ~C ４ and n is an integer from 1 to 3.

2. The compound according to claim 1, having a structure represented by general formula (1a): Here, R １ａ is a benzene ring or a naphthalene ring, the benzene ring is substituted with two ethylenically unsaturated bond-containing groups, and the naphthalene ring is substituted with two ethylenically unsaturated bond-containing groups, each of which is independently selected from the group consisting of ２ ~C ４ R is a straight or branched alkenyl group of the formula ２ａ , R ２ｂ , R ３ａ , R ３ｂ , R ４ａ , R ４ｂ , R ５ａ and R ５ｂ is independently １ ~C ２ R is an alkyl group of the formula ２ｃ , R ３ｃ , R ４ｃ and R ５ｃ are independently hydrogen or C １ ~C ２ and n ａ is an integer from 1 to 2.

3. R １ａ is a benzene ring or a naphthalene ring, the benzene ring is substituted with two allyl groups, the naphthalene ring is substituted with two allyl groups, R ２ｃ , R ３ｃ , R ４ｃ and R ５ｃ is hydrogen, and n ａ The compound according to claim 2, wherein is 1.

4. The compound has the following general formula (1a-1): Or the following general formula (1a-2):

2. The compound of claim 1 having the structure:

5. The compound according to claim 1, having a structure represented by general formula (1b): Here, R １ｂ is a biphenyl substituted with two ethylenically unsaturated bond-containing groups, each of which is independently selected from the group consisting of ２ ~C ４ R is a straight or branched alkenyl group of the formula ２ａ , R ２ｂ , R ３ａ , R ３ｂ , R ４ａ , R ４ｂ , R ５ａ and R ５ｂ is independently １ ~C ２ R is an alkyl group of the formula ２ｃ , R ３ｃ , R ４ｃ and R ５ｃ are independently hydrogen or C １ ~C ２ and n ａ is an integer from 1 to 2.

6. R １ａ is a biphenyl, the biphenyl being substituted with two allyl groups, R ２ｃ , R ３ｃ , R ４ｃ and R ５ｃ is hydrogen, and n ａ The compound according to claim 5 , wherein is 1.

7. The compound has the following general formula (1b-1):

2. The compound of claim 1 having the structure:

8. A compound represented by the general formula (11): Here, R １１ is a benzene ring, a biphenyl ring or a naphthalene ring; R １２ and R １５ is a phenyl group independently substituted with 1 to 5 ethylenically unsaturated bond-containing groups and 0 to 4 alkyl groups, each of which is independently selected from the group consisting of C １ ~C ４ wherein the total number of the ethylenically unsaturated bond-containing groups and the alkyl groups is 1 to 5, and each of the ethylenically unsaturated bond-containing groups is independently selected from the group consisting of C ２ ~C １２ R is a straight-chain or branched-chain alkenyl group, an acryloyloxy group, or a methacryloyloxy group; １３ and R １４ is a phenyl group independently substituted with two or three alkyl groups, each of which is independently selected from the group consisting of １ ~C ４ and n is a straight or branched alkyl group; １ is an integer from 0 to 6.

9. The compound according to claim 8, having a structure represented by general formula (11a): Here, R １１ａ is a benzene ring, a biphenyl ring or a naphthalene ring; R １２ａ , R １２ｂ , R １５ａ and R １５ｂ are independently hydrogen or C １ ~C ２ R is an alkyl group of the formula １３ｃ and R １４ｃ are independently hydrogen or C １ ~C ２ R is an alkyl group of the formula １３ａ , R １３ｂ , R １４ａ and R １４ｂ is independently １ ~C ２ R is an alkyl group of the formula １２ｃ and R １５ｃ are independently an ethylenically unsaturated bond-containing group, ２ ~C ４ n is a straight-chain or branched alkenyl group, or an acryloyloxy group or a methacryloyloxy group; １ａ is an integer from 0 to 6.

10. R １３ｃ and R １４ｃ is hydrogen, R １２ｃ and R １５ｃ is independently an allyl group, an acryloyloxy group, or a methacryloyloxy group and is located in the para position relative to the phosphate group, and n １ａ The compound according to claim 9, wherein is an integer from 0 to 4.

11. The compound represented by the following general formula (11a-1): where n Ｓ１ The compound according to claim 8, wherein is an integer from 0 to 4.

12. A modifier for use in a thermosetting resin composition, comprising a compound according to any one of claims 1 to 11.

13. A thermosetting resin composition comprising the compound according to any one of claims 1 to 11 and a thermosetting resin.

14. The thermosetting resin composition according to claim 13, wherein the thermosetting resin comprises a thermosetting resin having an ethylenically unsaturated bond.

15. The thermosetting resin composition of claim 13, wherein the thermosetting resin comprises a polyphenylene ether resin modified with ethylenically unsaturated groups.

16. The thermosetting resin composition according to claim 13, further comprising a crosslinking agent having an ethylenically unsaturated bond.

17. The thermosetting resin composition according to claim 16, wherein the crosslinking agent is triallyl isocyanurate.

18. The thermosetting resin composition according to claim 13 for producing an insulating layer in a high frequency printed circuit board.

19. A resin material obtained by curing the thermosetting resin composition according to claim 13.

20. A high frequency printed circuit board comprising a conductor layer and an insulating layer, the insulating layer comprising the resin material according to claim 19.

21. A method for producing a high frequency printed circuit board having a conductor layer and an insulating layer, comprising the step of curing the thermosetting resin composition according to claim 13 to form the insulating layer.

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