Resin composition containing bifunctional phenylene ether resin

Abstract

Development of a phenylene ether resin having more excellent dielectric properties is desirable. The present invention provides a phenylene ether resin composition having a number average molecular weight (Mn) of 800-3,000, the phenylene ether resin composition containing a resin [alpha] represented by general formula (1) and a resin [beta] represented by general formula (2), the resin [beta] being 20-200 ppm relative to the content of the resin [alpha] (the content of the resin [beta] / the content of the resin [alpha]). In general formula (2), at least one of L1 to L8 is represented by general formula (3). General formula (1) # imgabs 0 # general formula (2) # imgabs 1 # general formula (3) # imgabs 2 #

Description

Technical Field

[0001] The present invention relates to a resin composition containing a bifunctional phenylene ether resin. Background Art

[0002] Phenylene ether resins have excellent dielectric properties, heat resistance, flame retardancy, toughness, processability, low water absorption, etc., and are therefore used in various applications such as molding, bonding, and coating in various industrial fields such as the electrical and electronic fields and the automotive field.

[0003] In particular, in the electrical and electronic fields, as the frequency band used increases, substrate materials for printed wiring boards used in various electronic devices are increasingly required to have excellent dielectric properties.

[0004] For example, Patent Document 1 discloses a bifunctional phenylene ether oligomer having phenolic hydroxyl groups at both ends, obtained by oxidative polymerization of a specific divalent phenol and a specific monovalent phenol. The oligomer of Patent Document 1 is fully soluble in ketone-based solvents, has good compatibility with thermosetting resins, and has the same properties as PPE polymers, such as low dielectric properties and high toughness. Furthermore, the modification reaction of the terminal phenolic hydroxyl group can be easily carried out in a ketone-based solvent.

[0005] In addition, Patent Document 2 discloses a compound obtained by converting the terminal of a bifunctional polyphenylene ether oligomer into a vinyl group. The compound of Patent Document 2 has balanced characteristics such as high glass transition temperature when cured, low dielectric constant and low dielectric loss tangent, and inheriting the excellent properties of polyphenylene ether.

[0006] Prior art literature

[0007] Patent Literature

[0008] Patent Document 1: Japanese Patent Application Publication No. 2003-12796

[0009] Patent Document 2: Japanese Patent Application Publication No. 2004-59644 Summary of the invention

[0010] Problem that the invention aims to solve

[0011] However, the development of phenylene ether resins having more excellent dielectric properties has been desired.

[0012] Solutions for solving problems

[0013] The present inventors have conducted intensive studies and have found that, in a bifunctional phenylene ether resin composition, by setting the content of a bifunctional phenylene ether resin having a specific structure such as an aldehyde group, an alkoxy group, etc. to a specific range, a resin composition having excellent dielectric properties (especially a low dielectric loss tangent) can be obtained, thereby completing the present invention.

[0014] The present invention can provide the following aspects. [1]

[0016] A phenylene ether resin composition, characterized in that it is a phenylene ether resin composition having a number average molecular weight (Mn) of 800 to 3,000,

[0017] The phenylene ether resin composition contains a resin α represented by the following general formula (1) and a resin β represented by the following general formula (2).

[0018] The content of the resin β relative to the resin α (content of the resin β / content of the resin α) is 20 to 200 ppm.

[0019] General formula (1)

[0020]

[0021] [In the general formula (1), A represents a single bond or a linear, branched or cyclic hydrocarbon having 10 or less carbon atoms. Z1 and Z2 may be the same or different and represent a hydrogen atom or a unit containing a polymerizable double bond group. R1 to R 16 may be the same or different, and represent a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group having 6 or less carbon atoms, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group or a substituted aryl group. m and n represent integers of 0 to 20, and at least one of them is an integer of 1 to 20. Preferably, R1 to R 16 At least one of them represents a methyl group.]

[0022] General formula (2)

[0023]

[0024] [In the general formula (2), A, Z1, Z2, R1 to R 16 , m and n are the same as those in the general formula (1). L1 to L8 may be the same or different and are represented by a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group having 6 or less carbon atoms, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group, a substituted aryl group or the following general formula (3). At least one of L1 to L8 is represented by the following general formula (3).

[0025] General formula (3)

[0026]

[0027] [In the general formula (3), X is selected from the group consisting of a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 6 or less carbon atoms, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group, and a substituted aryl group. X is preferably a hydrogen atom. * represents a connecting bond.] [2]

[0029] The phenylene ether resin composition according to the above [1], further comprising a resin γ represented by the following general formula (4):

[0030] The content of the resin γ relative to the resin α (content of the resin γ / content of the resin α) is 150 to 400 ppm,

[0031] General formula (4)

[0032]

[0033] [In the general formula (4), A, Z1, Z2, R1 to R 16 , m and n are the same as those in the above general formula (1). 16 They may be the same or different and are represented by a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group having 6 or less carbon atoms, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group, a substituted aryl group or the following general formula (5). 16 At least one of them is represented by the following general formula (5).

[0034] General formula (5)

[0035]

[0036] [In the general formula (5), Y1 and Y2 are selected from the group consisting of a hydrogen atom, a linear or branched alkyl group having 6 or less carbon atoms, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group, and a substituted aryl group. Y3 is selected from the group consisting of a hydrogen atom, a linear or branched alkyl group having 6 or less carbon atoms, a substituted alkyl group, an alkenyl group, and a substituted alkenyl group.

[0037] * indicates a connection key. ] [3]

[0039] The phenylene ether resin composition according to the above [1], wherein A in the general formula (1) and (2) is a single bond. [4]

[0041] The phenylene ether resin composition according to the above [1], wherein in the general formulas (1) and (2), R1, R2, R3, R6, R7 and R8 represent methyl groups, and R4 and R5 represent hydrogen atoms. [5]

[0043] The phenylene ether resin composition according to the above [1], wherein in the general formulas (1) and (2), R9, R 10 , R 15 and R 16 Represents methyl, R 11 , R 12 , R 13 and R 14 represents a hydrogen atom,

[0044] In the general formula (2), L1, L2, L7 and L8 represent a methyl group or the general formula (3), L3, L4, L5 and L6 represent a hydrogen atom, and at least one of L1, L2, L7 and L8 represents the general formula (3). [6]

[0046] The phenylene ether resin composition according to the above [1], wherein in the general formulas (1) and (2), Z1 and Z2 are represented by any one of the following general formulas (6) or (7),

[0047] General formula (6)

[0048]

[0049] [In general formula (6), R 17 represents a hydrogen atom or a methyl group. 17 Preferably it is a methyl group. * represents a connecting bond.]

[0050] General formula (7)

[0051]

[0052] [In general formula (7), R 18 ~R 21 may be the same or different, and represent a hydrogen atom, a halogen atom, a linear or branched alkyl group having 6 or less carbon atoms, or a phenyl group. 18 ~R 21 All are hydrogen atoms. * indicates a connecting bond.] [7]

[0054] The phenylene ether resin composition according to the above [6], wherein in the general formulas (1) and (2), Z1 and Z2 are represented by the general formula (7). [8]

[0056] The phenylene ether resin composition according to the above [1], wherein in the general formula (3), X is a hydrogen atom. [9]

[0058] The phenylene ether resin composition according to the above [2], wherein in the general formula (5), Y3 is a methyl group.

[10]

[0060] A curable film obtained by using the phenylene ether resin composition described in any one of [1] to [9] above.

[11]

[0062] A laminated plate obtained by using the phenylene ether resin composition described in any one of [1] to [9] above.

[0063] Effects of the Invention

[0064] According to one embodiment of the present invention, a bifunctional phenylene ether resin composition having a low dielectric loss tangent can be provided. DETAILED DESCRIPTION

[0065] Hereinafter, the present invention will be described in detail with reference to synthesis examples and examples, but the present invention is not limited to the synthesis examples and examples, and can be implemented by changing to any method as long as it does not greatly exceed the scope of the content of the present invention.

[0066] The present invention relates to a bifunctional phenylene ether resin composition. The bifunctional phenylene ether resin contained in the present invention is a resin α represented by the following general formula (1).

[0067] General formula (1)

[0068]

[0069] In the general formula (1), A represents a single bond or a linear, branched or cyclic hydrocarbon having 10 or less carbon atoms (preferably 1 to 4). Z1 and Z2 may be the same or different and represent a hydrogen atom or a unit containing a polymerizable double bond group. 16 may be the same or different, and represent a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group having 6 or less carbon atoms, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group or a substituted aryl group. m and n represent integers of 0 to 20, and at least one of them is an integer of 1 to 20. Preferably R1 to R 16 At least one of them represents a methyl group.

[0070] In addition to the resin α, the bifunctional phenylene ether resin contained in the present invention includes a resin β represented by the following general formula (2).

[0071] General formula (2)

[0072]

[0073] In the general formula (2), A, Z1, Z2, R1 to R 16, m and n are the same as those in the above general formula (1). L1 to L8 may be the same or different and are represented by a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group having 6 or less carbon atoms, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group, a substituted aryl group or the following general formula (3). At least one of L1 to L8 is represented by the following general formula (3).

[0074] General formula (3)

[0075]

[0076] In the general formula (3), X is selected from the group consisting of a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 6 or less carbon atoms, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group, and a substituted aryl group. Preferably, X is a hydrogen atom or a hydroxyl group, or a linear or branched alkyl group having 6 or less carbon atoms, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group, or a substituted aryl group, and 1 to 3 hydrogen atoms are bonded to the carbon atom adjacent to the -C=O group. * represents a connecting bond.

[0077] At the end of the resin β, there are phenylene groups having groups L1 to L4 and phenylene groups having groups L5 to L8. As described above, at least one of the groups L1 to L8 is a group represented by the general formula (3). That is, at least one of the groups L1 to L8 has a carbonyl structure such as an aldehyde group or a ketone group, or a carboxyl group.

[0078] In the present invention, the content of resin β is less than that of resin α. The content of resin β relative to resin α "content of resin β / content of resin α" is 20 to 200 ppm, preferably 20 to 180 ppm, more preferably 20 to 150 ppm, further preferably 20 to 100 ppm, and particularly preferably 20 to 50 ppm. If the content of resin β is too much, there is a concern that the value of the dielectric loss tangent becomes larger and the dielectric properties deteriorate. In the case of too little, there is a concern that the oxidative polymerization reaction itself cannot be completed, a large amount of monomers remain, and the polymer cannot be elongated to the desired molecular weight.

[0079] In the present invention, the content of resin β is determined by proton nuclear magnetic resonance ( 1 First, the phenylene ether resin composition of the present invention, to which no other components other than the phenylene ether resin and the components used in its production are added, is concentrated and dried to form a powder, which is then dissolved in a deuterated chloroform solvent or the like to prepare a solution sample for measurement. 1 In the H-NMR measurement, the integrated intensity of the peak at 1.9 to 2.3 ppm was defined as “1,000.” This peak is attributed to the number of protons of the methyl group substituted on the benzene ring in the resin composition.

[0080] For example, when the general formula (3) in the resin β represents an aldehyde group (the resin β in this case may be referred to as an aldehyde body), the content of the aldehyde body can be calculated by the following formula.

[0081] Aldehyde content [ppm]

[0082] =[{(I 9.5-12.5 / P a )×M a} / {(1,000 / P p )×M p}]×10 6

[0083] In the formula,

[0084] I 9.5-12.5 The integrated intensity of 9.5 to 12.5 ppm is shown, which is a measured value of the number of protons of the aldehyde group in the resin composition.

[0085] P a is the number of protons in the aldehyde group, which is "1".

[0086] M a is the molecular weight of the aldehyde group, which is 29.

[0087] P p is the number of protons of the methyl group substituted on the benzene ring of the phenylene ether resin α. It is theoretically calculated based on the amount of monomer added.

[0088] M p is the theoretical molecular weight of phenylene ether resin α, which is calculated theoretically based on the amount of monomer added.

[0089] As an example, when 2,2',3,3',5,5'-hexamethyl-(1,1'-biphenyl)-4,4'-diol (HMBP) is used as the divalent phenol and 2,6-dimethylphenol is used as the monovalent phenol as the monomers for synthesizing the phenylene ether resin composition, various numerical values ​​are as follows.

[0090] [Table 1]

[0091]

[0092] When the integrated intensity of 9.5 to 12.5 ppm is defined as "0.1", the content of the aldehyde body is as follows.

[0093] Aldehyde content [ppm]

[0094] =[{(0.1 / 1)×29} / {(1,000 / 54)×991}]×10 6

[0095] =158

[0096] The content (ppm) of the resin β in the case where the general formula (3) represents a group other than an aldehyde group can be calculated by a method based on the calculation method of the aldehyde body described above.

[0097] For example, when X is a hydroxyl group (that is, when the general formula (3) represents a carboxyl group), the content [ppm] of the resin β can be calculated by the following formula.

[0098] Resin β content [ppm]

[0099] =[{(I 9.5-12.5 / P b )×M b} / {(1,000 / P p )×M p}]×10 6

[0100] In the formula,

[0101] I 9.5-12.5 The integrated intensity of 9.5 to 12.5 ppm is shown, which is a measured value of the number of protons of the carboxyl group in the resin composition.

[0102] P b is the number of protons in the carboxyl group, which is "1".

[0103] M b is the molecular weight of the carboxyl group, which is 45.

[0104] P p is the number of protons of the methyl group substituted on the benzene ring of the phenylene ether resin α. It is theoretically calculated based on the amount of monomer added.

[0105] M p is the theoretical molecular weight of phenylene ether resin α, which is calculated theoretically based on the amount of monomer added.

[0106] Furthermore, for example, when X is a linear or branched alkyl group, substituted alkyl group, alkenyl group, substituted alkenyl group, aryl group or substituted aryl group having 6 or less carbon atoms, and a group having 1 to 3 hydrogen atoms bonded to a carbon atom adjacent to a -C=O group, the content [ppm] of the resin β can be calculated by the following formula.

[0107] Resin β content [ppm]

[0108] =[{(I 2.5-3.1 / P c )×M c} / {(1,000 / P p )×M p}]×10 6

[0109] In the formula,

[0110] I2.5-3.1 It is a measured value of the number of protons bonded to the carbon atom adjacent to the carbonyl group in X of the general formula (3) in the resin composition.

[0111] P c is the number of protons in the above group, i.e. 1, 2 or 3.

[0112] M c The molecular weight of the carbonyl group (—C(═O)), the carbon atom bonded to the carbonyl group, and the hydrogen atom bonded to the carbon atom is 41, 42, or 43.

[0113] P p is the number of protons of the methyl group bonded to the benzene ring of the phenylene ether resin α, and is theoretically calculated from the amount of the monomer charged.

[0114] M p is the theoretical molecular weight of phenylene ether resin α, which is theoretically calculated based on the amount of monomer added.

[0115] In the present invention, as the bifunctional phenylene ether resin, it is preferred that the resin γ represented by the following general formula (4) is contained in addition to the resin α and the resin β.

[0116] General formula (4)

[0117]

[0118] In the general formula (4), A, Z1, Z2, R1 to R 16 , m and n are the same as those in the above general formula (1). 16 They may be the same or different and may be represented by a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group having 6 or less carbon atoms, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group, a substituted aryl group or the following general formula (5). 16 At least one of them is represented by the following general formula (5).

[0119] General formula (5)

[0120]

[0121] In the general formula (5), Y1 and Y2 are selected from the group consisting of a hydrogen atom, a straight-chain or branched alkyl group having 6 or less carbon atoms, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group, and a substituted aryl group. Y3 is selected from the group consisting of a hydrogen atom, a straight-chain or branched alkyl group having 6 or less carbon atoms, a substituted alkyl group, an alkenyl group, and a substituted alkenyl group. Preferably, Y3 is selected from the group consisting of a straight-chain or branched alkyl group having 6 or less carbon atoms, a substituted alkyl group, an alkenyl group, and a substituted alkenyl group, and 1 to 3 hydrogen atoms are bonded to the carbon atom adjacent to the oxygen atom in Y3. * represents a connecting bond.

[0122] In the present invention, the content of resin γ is less than that of resin α. Resin γ contains groups L9 to L 12 Phenylene and having a group L 13 ~L 16 As mentioned above, the groups L9 to L 16 At least one of the groups L9 to L1 is a group represented by the general formula (5). 16 At least one of them contains an alkoxy group such as a hydroxyl group or a methoxy group.

[0123] The content of resin γ relative to resin α "resin γ content / resin α content" is preferably 150 to 400 ppm, more preferably 150 to 350 ppm, further preferably 150 to 250 ppm, and particularly preferably 150 to 200 ppm. If the content of resin γ is too much, there is a concern that the value of the dielectric loss tangent becomes larger and the dielectric properties become worse. If it is too little, there is a concern that the oxidative polymerization reaction itself cannot be completed, a large amount of monomers remain, and the polymer cannot be elongated to the desired molecular weight.

[0124] The content of resin γ can be obtained in the same manner as that of resin β. Specifically, the content of resin γ can be obtained by using the proton nuclear magnetic resonance method ( 1 The measured value of H-NMR was calculated.

[0125] First, the phenylene ether resin of the present invention, to which no other components other than the phenylene ether resin and the components used in its production are added, is concentrated and dried to obtain a powder, and the powder is dissolved in a deuterated chloroform solvent or the like to obtain a solution sample for measurement. 1 In the H-NMR measurement, the integrated intensity of the peak at 1.9 to 2.3 ppm was defined as “1,000.” This peak is attributed to the number of protons of the methyl group substituted on the benzene ring in the resin composition.

[0126] Then, the content of the resin γ was calculated by the following formula.

[0127] Resin γ content [ppm]

[0128] =[{(I 3.2-3.6 / P γ )×M γ} / {(1,000 / P p )×M p}]×10 6

[0129] In the formula,

[0130] I 3.2-3.6 The integrated intensity of 3.2 to 3.6 ppm is shown, which is the measured value of the number of protons on the carbon atom adjacent to the oxygen atom in the group Y3.

[0131] P γ It is the number of protons carried by the carbon atom in the group Y3 and located adjacent to the oxygen atom.

[0132] M γ It is the sum of the atomic weight of the oxygen atom 16 and the molecular weight of the group Y3.

[0133] P p is the number of protons of the methyl group substituted on the benzene ring of the phenylene ether resin α. It is theoretically calculated based on the amount of monomer added.

[0134] M p is the theoretical molecular weight of phenylene ether resin α, which is calculated theoretically based on the amount of monomer added.

[0135] For example, when the general formula (5) in the resin γ contains a methoxy group, that is, when Y3 in the general formula (5) is a methyl group (hereinafter, the resin γ may be referred to as a methoxy form), the methoxy form content is calculated by the following formula.

[0136] Methoxy content [ppm]

[0137] =[{(I 3.2-3.6 / P m )×M m} / {(1,000 / P p )×M p}]×10 6

[0138] In the formula,

[0139] I 3.2-3.6 It shows the integrated intensity of 3.2 to 3.6 ppm and is the measured value of the number of protons of the methoxy group in the resin composition.

[0140] P m is the number of protons in the methoxy group. The methoxy group is -OCH3, so it is "3".

[0141] M m The molecular weight of methoxy is 31.

[0142] P p is the number of protons of the methyl group substituted on the benzene ring of the phenylene ether resin α. It is theoretically calculated based on the amount of monomer added.

[0143] M p is the theoretical molecular weight of phenylene ether resin α, which is calculated theoretically based on the amount of monomer added.

[0144] In addition, for example, when the general formula (5) in the resin γ represents a hydroxyl group, that is, when Y3 in the general formula (5) is a hydrogen atom, the content (ppm) of the resin γ can be calculated by a method based on the calculation method of the methoxyl group described above. Specifically, it is calculated by the following formula.

[0145] Resin γ content [ppm]

[0146] =[{(I 6.0-8.0 / P h )×M h} / {(1,000 / P p )×M p}]×10 6

[0147] In the formula,

[0148] I 6.0-8.0 It shows the integrated intensity of 6.0 to 8.0 ppm and is the measured value of the number of protons of the hydroxyl group in the resin composition.

[0149] P h is the number of protons in the hydroxyl group. The hydroxyl group is -OH, so it is "1".

[0150] M h The molecular weight of the hydroxyl group is 17.

[0151] P p is the number of protons of the methyl group substituted on the benzene ring of the phenylene ether resin α. It is theoretically calculated based on the amount of monomer added.

[0152] M p is the theoretical molecular weight of phenylene ether resin α, which is calculated theoretically based on the amount of monomer added.

[0153] For example, when 2,2',3,3',5,5'-hexamethyl-(1,1'-biphenyl)-4,4'-diol (HMBP) is used as the divalent phenol and 2,6-dimethylphenol is used as the monovalent phenol as the monomers in synthesizing the phenylene ether resin composition, the various numerical values ​​are as described in the above Table 1. When the integrated intensity of 3.2 to 3.6 ppm is set to "0.4", the content of the methoxy form is as follows.

[0154] Methoxy content [ppm]

[0155] =[{(0.4 / 3)×31} / {(1,000 / 54)×991}]×10 6

[0156] =225

[0157] In a preferred embodiment of the present invention, X in the general formula (3) is a hydrogen atom.

[0158] In a preferred embodiment of the present invention, in the general formula (5), Y3 is a methyl group, and in particular, Y1 and Y2 are hydrogen atoms, and Y3 is a methyl group.

[0159] In a preferred embodiment of the present invention, in the general formulae (1) and (2), A is a single bond. More preferably, in the general formulae (1), (2) and (4), A is a single bond.

[0160] In a preferred embodiment of the present invention, in the above general formulae (1) and (2), R1, R2, R3, R6, R7 and R8 represent methyl groups, and R4 and R5 represent hydrogen atoms. More preferably, in the above general formulae (1), (2) and (4), R1, R2, R3, R6, R7 and R8 represent methyl groups, and R4 and R5 represent hydrogen atoms.

[0161] In a preferred embodiment of the present invention, in the above general formulas (1) and (2), R9, R 10 , R 15 and R 16 Represents methyl, R 11 , R 12 , R 13 and R 14 represents a hydrogen atom, in the general formula (2), L1, L2, L7 and L8 represent a methyl group or the general formula (3), L3, L4, L5 and L6 represent a hydrogen atom, and at least one of L1, L2, L7 and L8 represents the general formula (3). More preferably, in the general formulas (1), (2) and (4), R9, R 10 , R 15 and R 16 Represents methyl, R 11 , R 12 , R 13 and R 14 represents a hydrogen atom, in the general formula (2), L1, L2, L7 and L8 represent a methyl group or the general formula (3), L3, L4, L5 and L6 represent a hydrogen atom, at least one of L1, L2, L7 and L8 represents the general formula (3), and in the general formula (4), L9, L 10 , L 15 and L 16 represents a methyl group or the above general formula (5), L 11 , L 12 , L 13 and L 14 Represents hydrogen atom, L9, L 10 , L 15 and L 16 At least one of them represents the general formula (5).

[0162] In a preferred embodiment of the present invention, in the above-mentioned general formulas (1) and (2), Z1 and Z2 represent one of the following general formulas (6) or (7). More preferably, in the above-mentioned general formulas (1), (2) and (4), Z1 and Z2 represent one of the following general formulas (6) or (7). In this embodiment, the phenylene ether resins α, β, and γ have a (meth)acryloyl group (when at least one of Z1 and Z2 is represented by the following general formula (6)) or a substituted or unsubstituted styryl group (when at least one of Z1 and Z2 is represented by the following general formula (7). It is also called vinylphenyl) as a crosslinking group.

[0163] General formula (6)

[0164]

[0165] In the general formula (6), R 17 represents a hydrogen atom or a methyl group. * represents a connecting bond.

[0166] General formula (7)

[0167]

[0168] In the general formula (7), R 18 ~R 21 They may be the same or different and represent a hydrogen atom, a halogen atom, a linear or branched alkyl group having 6 or less carbon atoms, or a phenyl group. * represents a connecting bond.

[0169] In a preferred embodiment of the present invention, from the viewpoint of being able to carry out polymerization without using a polymerization initiator and achieving better dielectric properties, in the above-mentioned general formulas (1) and (2), at least one of Z1 and Z2 represents the above-mentioned general formula (7), and in particular, Z1 and Z2 represent the above-mentioned general formula (7). More preferably, in the above-mentioned general formulas (1), (2) and (4), at least one of Z1 and Z2 represents the above-mentioned general formula (7), and in particular, Z1 and Z2 represent the above-mentioned general formula (7). In this embodiment, the phenylene ether resin α, β, γ has a substituted or unsubstituted styryl group as a crosslinking group.

[0170] In a preferred embodiment of the present invention, in the general formulae (1), (2) and (4), A is a single bond, R1, R2, R7 and R8 are methyl groups, and R4 and R5 are hydrogen atoms. More preferably, A is a single bond, R1, R2, R3, R6, R7 and R8 are methyl groups, and R4 and R5 are hydrogen atoms.

[0171] In a preferred embodiment of the present invention, in the above-mentioned general formulae (1), (2) and (4), A is a single bond, R1, R2, R3, R6, R7 and R8 are methyl groups, R4 and R5 are hydrogen atoms, R9, R 10 , R 15and R 16 Represents methyl, R 11 , R 12 , R 13 and R 14 represents a hydrogen atom, in the general formula (2), L1, L2, L7 and L8 represent a methyl group or the general formula (3), L3, L4, L5 and L6 represent a hydrogen atom, at least one of L1, L2, L7 and L8 represents the general formula (3), and in the general formula (4), L9, L 10 , L 15 and L 16 represents a methyl group or the above general formula (5), L 11 , L 12 , L 13 , L 14 Represents hydrogen atom, L9, L 10 , L 15 and L 16 At least one of them represents the general formula (5).

[0172] In a preferred embodiment of the present invention, in the above-mentioned general formulae (1), (2) and (4), A is a single bond, R1, R2, R3, R6, R7 and R8 are methyl groups, R4 and R5 are hydrogen atoms, R9, R 10 , R 15 and R 16 Represents methyl, R 11 , R 12 , R 13 and R 14 represents a hydrogen atom, Z1 and Z2 represent one of the above general formula (6) or (7), in the general formula (2), L1, L2, L7 and L8 represent a methyl group or the above general formula (3), L3, L4, L5 and L6 represent a hydrogen atom, at least one of L1, L2, L7 and L8 represents the general formula (3), in the general formula (4), L9, L 10 , L 15 and L 16 represents a methyl group or the above general formula (5), L 11 , L 12 , L 13 , L 14 Represents hydrogen atom, L9, L 10 , L 15 and L 16 At least one of them represents the general formula (5).

[0173] In a preferred embodiment of the present invention, in the above-mentioned general formulae (1), (2) and (4), A is a single bond, R1, R2, R3, R6, R7 and R8 are methyl groups, R4 and R5 are hydrogen atoms, R9, R 10 , R 15 and R 16 Represents methyl, R11 , R 12 , R 13 and R 14 represents a hydrogen atom, Z1 and Z2 represent the above general formula (7), in the general formula (2), L1, L2, L7 and L8 represent a methyl group or the above general formula (3), L3, L4, L5 and L6 represent a hydrogen atom, at least one of L1, L2, L7 and L8 represents the general formula (3), in the general formula (4), L9, L 10 , L 15 and L 16 represents a methyl group or the above general formula (5), L 11 , L 12 , L 13 , L 14 Represents hydrogen atom, L9, L 10 , L 15 and L 16 At least one of them represents the general formula (5).

[0174] As specific examples of the phenylene ether resin represented by the above general formula (1), a resin represented by the following structural formula is particularly preferred.

[0175]

[0176] The phenylene ether resin of the present invention has a number average molecular weight (Mn) of 800 to 3,000, preferably 900 to 2,500, more preferably 950 to 2,300, particularly preferably 1,000 to 2,200.

[0177] The weight average molecular weight (Mw) is not particularly limited, but is preferably 900 to 7,000, more preferably 1,000 to 6,000, from the viewpoint of achieving both dielectric properties and solubility in a solvent.

[0178] In the present invention, the number average molecular weight and weight average molecular weight are polystyrene-equivalent values ​​measured by gel permeation chromatography according to a standard method as shown in the Examples described below. The measurement is performed before adding other components except the phenylene ether resin and the components used for its production.

[0179] The dielectric loss tangent (Df) value at 10 GHz when the phenylene ether resin composition of the present invention is cured is preferably as small as possible, and is preferably 0.0005 or more lower than a comparison object such as a value of the prior art when no other components other than the phenylene ether resin and the components used in its production are added. In addition, the dielectric loss tangent can be measured by the method described in the examples described later.

[0180] <Manufacturing method>

[0181] The phenylene ether resin composition of the present invention is preferably produced by the following method.

[0182] The resin composition of the present invention contains a bifunctional phenylene ether resin α as a main resin, and further contains a bifunctional phenylene ether resin β and preferably contains a bifunctional phenylene ether resin γ. The bifunctional phenylene ether resin can be obtained by copolymerization of two monomers of a monohydric phenol and a dihydric phenol. The copolymerization reaction is usually an oxidative polymerization reaction in which oxygen is blown into the reaction system to cause polymerization.

[0183] During the oxidative polymerization reaction, polymerization by-products are generated. The polymerization time is a factor that has a great influence on the generation of polymerization by-products. If the polymerization time is too short, the reaction will stop during the polymerization, so a large amount of monomers will remain in the system, and a phenylene ether resin that has not been elongated to the desired molecular weight will be obtained. If the polymerization time is long, oxygen is continuously blown in even if the monomers in the system have been consumed, and the molecular weight will increase. According to our research, it is known that when the polymerization time is further extended, a part of the molecular structure of the phenylene ether resin generated by the polymerization will be substituted with a specific structure, and in addition to the resin α as the main resin, resin β and resin γ will also be generated. Hereinafter, the phenylene ether resins β and γ substituted with specific structures are sometimes referred to as over-oxidized bodies.

[0184] In addition, we studied polymerization conditions other than polymerization time as factors affecting the by-production of over-oxidized products. As a result, it was found that the ratio of over-oxidized products such as resin β and resin γ varies depending on the equivalent of the metal catalyst to the monomer, the ratio of the metal catalyst to the amine catalyst, the ratio of the two monomers, etc. According to the research of the present inventors, it was found that by adjusting the polymerization time after adjusting the polymerization conditions, a phenylene ether resin composition containing over-oxidized products such as resin β and resin γ in a specific amount in addition to the resin α as the main resin can be obtained.

[0185] As a specific structure in the overoxidized product, the structure of the above general formula (3) or (5) can be cited. More specifically, in the case where the side chain of the phenylene ether resin is a methylphenylene, a structure in which the methyl group in the methylphenylene is substituted with a methoxy-containing group, an aldehyde group, etc. can be cited. Although the detailed reaction mechanism for generating the overoxidized product is not yet clear, it is speculated that by-products are gradually generated due to the relationship between the polymerization time, the amount of oxygen blown into the system, and the type of reaction solvent (alcohols such as methanol).

[0186] The over-oxidized resins β and γ have a structure in which a part of the resin α (main resin) is substituted, that is, have a structure very similar to the resin α. Therefore, it is not easy to remove them by post-treatment or water washing steps after the polymerization reaction.

[0187] In addition, usually, the phenylene ether resin is cured and used for various purposes. Specifically, after the polymerization process, a reaction to introduce a curable group (styrenation, methacrylation reaction, etc.) is carried out to introduce a polymerizable double bond group (styryl, methacryloyl, etc.) at the end of the molecule, thereby becoming a cured state. It is still difficult to remove the over-oxidized body in the reaction process of introducing the curable group and the water washing process after the reaction. This is because the over-oxidized body has a structure very similar to that of the resin α which is the main resin, which has not changed. Therefore, there is a concern that the over-oxidized body will remain in the cured resin composition (product).

[0188] The present inventors thermally cured a phenylene ether resin composition containing an overoxidized body and measured dielectric properties. As a result, a new discovery was obtained that there is a correlation between the content of the overoxidized body and the level of the dielectric loss tangent. Thus, it was found that by making the content of the overoxidized body into a specific range, a resin composition having a low dielectric loss tangent and excellent dielectric properties can be provided.

[0189] The oxidative polymerization reaction can be carried out by dissolving raw materials such as monomers, catalysts, and alkali in a solvent and then heating and stirring the obtained solution for a certain period of time. The terminals of the phenylene ether resin obtained by the oxidative polymerization reaction tend to be mostly hydroxyl groups.

[0190] The phenylene ether resin α having hydroxyl groups at both ends in the phenylene ether resin α represented by the above general formula (1) can be efficiently produced by oxidative polymerization of a divalent phenol represented by the following general formula (8) and a monovalent phenol represented by the following general formula (9), alone or as a mixture, in toluene, toluene-alcohol, toluene-ketone or a ketone-based solvent.

[0191] General formula (8)

[0192]

[0193] General formula (9)

[0194]

[0195] Specific examples of the divalent phenol represented by the general formula (8) include 4,4'-methylenebis(2,6-dimethylphenol), 4,4'-(isopropylidene)bis(2,6-dimethylphenol), 4,4'-methylenebis(2,3,6-trimethylphenol), 4,4'-(isopropylidene)bis(2,3,6-trimethylphenol), 4,4'-cyclohexylenebis[2,6-dimethylphenol], 4,4'-(phenylmethylene)bis-2,3,6-trimethylphenol, 4,4'-[1,4-phenylenebis(1-methylethylidene)]bis[2,6- dimethylphenol], 4,4'-methylenebis[2,6-bis(1,1-dimethylethyl)phenol], 4,4'-cyclopentylidenebis[2,6-dimethylphenol], 4,4'-[2-furylmethylene]bis(2,6-dimethylphenol), 4,4'-[1,4-phenylenebismethylene]bis[2,6-dimethylphenol], 4,4'-(3,3,5-trimethylcyclohexylene)bis[2,6-dimethylphenol], 4,4'-[4-(1-methylethyl)cyclohexylene]bis[2,6-dimethylphenol], 4,4'-(4-methylphenylene)bis 4-[1-[4-(4-hydroxy-3,5-dimethylphenyl)-4-methylcyclohexyl]-1-methylethyl]-2,6-dimethylphenol, 4,4'-(4-methoxyphenylmethylene)bis[2,3,6-trimethylphenol], 4,4'-[4-(1-methylethyl)phenylmethylene]bis[2,3,6-trimethylphenol], 4,4'-(9H-fluoren-9-ylidene)bis[2,6-dimethylphenol] phenol], 4,4'-[1,3-phenylenebis(1-methylethylidene)]bis[2,3,6-trimethylphenol], 4,4'-(1,2-ethanediyl)bis[2,6-di-(1,1-dimethylethyl)phenol], 5,5'-(1-methylethylidene)bis[3-(1,1-dimethylethyl)-1,1-biphenyl-2-ol], 3,3',5,5'-tetramethylbiphenyl-4,4'-diol, 2,2',3,3',5,5'-hexamethyl-(1,1'-biphenyl)-4,4'-diol, etc., but are not limited to these.

[0196] The divalent phenol represented by the general formula (8) is preferably 4,4'-methylenebis(2,6-dimethylphenol), 4,4'-(isopropylidene)bis(2,6-dimethylphenol), 4,4'-methylenebis(2,3,6-trimethylphenol), 4,4'-(isopropylidene)bis(2,3,6-trimethylphenol), 3,3',5,5'-tetramethylbiphenyl-4,4'-diol, 2,2',3,3',5,5'-hexamethylol The present invention further comprises 4,4'-methylenebis(2,6-dimethylphenol), 3,3',5,5'-tetramethylbiphenyl-4,4'-diol, 2,2',3,3',5,5'-hexamethyl-(1,1'-biphenyl)-4,4'-diol, and more preferably 2,2',3,3',5,5'-hexamethyl-(1,1'-biphenyl)-4,4'-diol.

[0197] The monovalent phenol represented by the general formula (9) is preferably a single phenol having substituents at the 2 and 6 positions; a single phenol having substituents at the 3 and 5 positions; a combination of a phenol having substituents at the 2 and 6 positions and a phenol having substituents at the 3 and 3 and 5 positions; and more preferably a single phenol having substituents at the 2 and 6 positions (e.g., 2,6-dimethylphenol).

[0198] The ratio of the amount of monophenol to diphenol added as the polymerization raw material (monomer ratio of monophenol when diphenol is set to 1) is not limited, and may be set to a range that can obtain a bifunctional phenylene ether resin having a number average molecular weight (Mn) of 800 to 3,000. The monomer ratio is preferably 5 to 17.

[0199] As the oxidation method, there are methods using oxygen directly or using air. In addition, there is also a method of electrode oxidation. Any method can be used without particular limitation. Considering safety and low equipment investment, air oxidation is preferred.

[0200] As a catalyst in the case of oxidative polymerization using oxygen or air, one or more copper salts such as CuCl, CuBr, Cu2SO4, CuCl2, CuBr2, CuSO4, CuI, etc. can be used. In addition to the above catalysts, one or more amine catalysts may be used, such as monomethylamine and dimethylamine, monoethylamine and diethylamine, monopropylamine and dipropylamine, mono-n-butylamine and di-n-butylamine, mono-sec-propylamine and di-sec-propylamine, monobenzylamine and dibenzylamine, monocyclohexylamine and dicyclohexylamine, monoethanolamine and diethanolamine, ethylmethylamine, methylpropylamine, butyldimethylamine, allylethylamine, methylcyclohexylamine, morpholine, methyl-n-butylamine, ethylisopropylamine, benzylmethylamine, octylbenzylamine, octyl-chlorobenzylamine, methyl(phenylethyl)amine, benzylethylamine, N-n-butyldimethylamine, di(chlorophenylethyl)amine, monoamine compounds such as 1-methylamino-4-pentene, diamine compounds such as N,N'-di-tert-butylethylenediamine, pyridine, methylpyridine, pyridine derivatives such as 4-dimethylaminopyridine, and piperidine. In the case of a copper salt and an amine catalyst, there are no particular limitations thereto, but a combination of CuBr2, a monoamine compound, and a diamine compound is particularly preferred.

[0201] The amount of the copper salt used as an oxidative polymerization catalyst (copper catalyst equivalent) is preferably in the range of 0.2 to 3.0% relative to the number of hydroxyl groups of the divalent phenol, particularly preferably 0.5 to 2.0%, and most preferably 0.8 to 2.0%, from the viewpoint of obtaining a phenylene ether resin having excellent dielectric properties by making the content of the over-oxidized product fall within the desired range. Furthermore, the amount of the copper salt and the diamine compound as an amine catalyst, "diamine compound / copper salt (catalyst ratio)", is preferably in the range of 0.5 to 4.0, particularly preferably 1.0 to 3.0.

[0202] As the reaction solvent, in addition to aromatic hydrocarbon solvents such as toluene, benzene, and xylene, halogenated hydrocarbon solvents such as methylene chloride, chloroform, and carbon tetrachloride, alcoholic solvents or ketone solvents can also be used in combination. As the alcoholic solvent, methanol, ethanol, butanol, propanol, methyl propylene glycol, diethylene glycol ethyl ether, butyl propylene glycol, propyl propylene glycol, etc. can be listed, as the ketone solvent, acetone, methyl ethyl ketone, diethyl ketone, methyl butyl ketone, methyl isobutyl ketone, etc. can be listed, and tetrahydrofuran, dioxane, etc. can also be listed, but they are not limited to these.

[0203] The polymerization time is not particularly limited and can be appropriately set in a manner that a phenylene ether resin having a desired number average molecular weight (Mn) and a weight average molecular weight (Mw) as required can be obtained. In order to obtain the desired number average molecular weight, the polymerization time needs to be set to a time that is suitable for the relationship between the amount of catalyst, the amount of monomer, etc. On the other hand, as mentioned above, excessive oxidation products can be produced by a side effect when the polymerization time is long. Therefore, the polymerization time is preferably set to a time that is longer than the time that the desired number average molecular weight, etc. can be obtained, and a time that is shorter than the time that a certain amount of excessive oxidation products are not produced by a side effect.

[0204] The reaction temperature is not particularly limited, but is preferably 25 to 50°C.

[0205] The form of polymerization is not particularly limited, but the following two forms are preferred.

[0206] The first method is a method in which all necessary raw materials such as monomers, catalysts, alkali, and solvents are charged into a polymerization apparatus (reactor), and oxygen is blown into the solution (air bubbling) (hereinafter also referred to as a batch method).

[0207] The second method is to add a catalyst, a base and a solvent or a part thereof to a polymerization device (polymerization tank), add the remaining raw materials to another tank (dripping tank), and drip the liquid in the dripping tank into the liquid in the polymerization tank that is bubbling air (hereinafter also referred to as the dripping method).

[0208] According to the selected polymerization form, the amount of raw materials added, the polymerization time, etc. can be set appropriately.

[0209] When the resin composition of the present invention is cured, that is, when polymerizable double bond groups are introduced at both ends of resin α and resin β, and preferably resin γ, the obtained bifunctional resin having phenolic hydroxyl groups at the ends and the compound containing a polymerizable double bond group represented by the following general formula (10) or the following general formula (11) are subjected to a dehydrohalogenation reaction under alkaline conditions in the presence of a phase transfer catalyst.

[0210]

[0211] In the general formulae (10) and (11), B represents a halogen (a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom). 17 The same meaning as in the above general formula (6), R in the general formula (11) 18 ~R 21 The same meaning as in the above general formula (7).

[0212] Alternatively, a carboxylic acid anhydride represented by the following general formula (12) may be used instead of the compound represented by the above general formula (10).

[0213] General formula (12)

[0214]

[0215] In the general formula (12), R 22 and R 23 With R in the above general formula (6) 17 Synonymous.

[0216] The phase transfer catalyst is represented by tertiary amines such as triethylamine and tetramethylethylenediamine, and quaternary ammonium salts or quaternary phosphonium salts such as tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, benzyltri-n-butylammonium chloride, benzyltri-n-butylammonium bromide, and benzyl-n-butylammonium iodide, but is not limited to these.

[0217] The base may be typified by sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate and the like, but is not limited thereto.

[0218] The dehydrohalogenation reaction is preferably carried out at a temperature between -10°C and 80°C.

[0219] <Other ingredients>

[0220] The phenylene ether resin composition of the present invention may contain other components in addition to the bifunctional phenylene ether resin. Specific examples of other components are described below.

[0221] (Thermal Curing Catalyst)

[0222] In order to accelerate the curing speed and improve workability, economy, etc., a heat-curing catalyst may also be added to the phenylene ether resin composition of the present invention. As a heat-curing catalyst, a catalyst that generates a cationic or free radical active species that initiates the polymerization of vinyl by heat or light may be used. For example, as a cationic polymerization initiator, diallyl iodonium salts, triallyl sulfonium salts and aliphatic sulfonium salts using BF4, PF6, AsF6, SbF6 as counter anions may be cited, and commercially available products such as SP70, SP172, CP66 manufactured by Asahi Electric Industries, CI2855, CI2823 manufactured by Nippon Soda, and SI100L, SI150L manufactured by Sanshin Chemical Industries may be used. In addition, examples of the radical polymerization initiator include benzoin compounds such as benzoin and benzoin methyl ester, acetophenone compounds such as acetophenone and 2,2-dimethoxy-2-phenylacetophenone, thioxanthone compounds such as thioxanthone and 2,4-diethylthioxanthone, bisazide compounds such as 4,4'-diazide chalcone, 2,6-bis(4'-azidobenzylidene)cyclohexanone and 4,4'-diazide benzophenone, azo compounds such as azobisisobutyronitrile, 2,2-azobispropane and hydrazone, organic peroxides such as 2,5-dimethyl-2,5-di(tert-butylperoxide)hexane, 2,5-dimethyl-2,5-di(tert-butylperoxide)hexyne-3, and diisopropylbenzene peroxide. In addition, α,α'-di(tert-butylperoxide)diisopropylbenzene ("PERBUTYL P" manufactured by NOF Corporation) can also be preferably used. These thermal curing catalysts may be used alone or in combination of two or more.

[0223] (Inhibitor)

[0224] In the phenylene ether resin composition of the present invention, a polymerization inhibitor may be added to increase storage stability. The polymerization inhibitor may be a known one, for example, quinones and aromatic diols such as hydroquinone, methylhydroquinone, p-benzoquinone, tetrachlorobenzoquinone, and trimethylquinone may be used. In addition, as the polymerization inhibitor, butylated hydroxytoluene (BHT), 4-tert-butylcatechol (TBC), 2-nitrophenol, etc. may also be preferably used. These may be used alone or in combination of two or more.

[0225] (flame retardant, filler, coupling agent)

[0226] The phenylene ether resin composition of the present invention may be added with one or more additives selected from flame retardants, fillers of inorganic or organic materials, and coupling agents as required. In addition, conventional additive components of resin compositions used in the manufacture of electronic devices such as printed circuit boards may also be added.

[0227] [Flame retardant]

[0228] As the flame retardant, a brominated organic compound, such as an aromatic bromine compound, can be used. Specifically, decabromodiphenylethane, 4,4-dibromobiphenyl, ethylenebistetrabromophthalimide, etc. can be used. Preferably, the brominated organic compound may be contained in an amount of 8% by mass or more and 20% by mass or less of bromine relative to the total amount of the resin composition.

[0229] In addition, from the viewpoint of environmental issues, phosphorus compound flame retardants may also be used. Generally speaking, the phosphorus compound used as a flame retardant is not particularly limited as long as it contains a phosphorus atom, and may be an inorganic phosphorus compound or an organic phosphorus compound.

[0230] Examples of the inorganic phosphorus compound include red phosphorus, ammonium phosphate, phosphoric acid amide, phosphoric acid, and phosphine oxide.

[0231] Examples of the organic phosphorus compound include aromatic phosphates, substituted phosphinates, nitrogen-containing phosphorus compounds, and cyclic organic phosphorus compounds.

[0232] The flame retardants may be used alone or in combination of two or more.

[0233] [Bulking Agent]

[0234] Examples of fillers include fibrous fillers such as glass fiber, carbon fiber, aramid fiber, silicon carbide fiber, alumina fiber, boron fiber, inorganic whiskers such as silicon carbide, silicon nitride, magnesium oxide, potassium titanate, aluminum borate, acicular inorganic fillers such as wollastonite, xonotlite, phosphate fiber, sepiolite, spherical inorganic fillers such as ground silica, fused silica, talc, alumina, barium titanate, mica, glass beads, and organic fillers such as microparticle polymers obtained by crosslinking (meth)acrylates, styrene, etc. These may be used alone or in combination of two or more.

[0235] As inorganic fillers, metal oxides, nitrides, silicides, borides, etc. such as silica, boron nitride, wollastonite, talc, kaolin, clay, mica, alumina, zirconia, and titanium oxide can be used. In particular, by adding low dielectric constant fillers such as silica and boron nitride, the dielectric constant of the resin composition can be reduced.

[0236] By adding an organic filler to the phenylene ether resin composition of the present invention, the dielectric constant of the prepreg using the phenylene ether resin composition of the present invention can be reduced. As the organic filler, fluorine-based, polystyrene-based, divinylbenzene-based, polyimide-based, etc. can be used. As the fluorine-based filler (filler of fluorine-containing compound), polytetrafluoroethylene (PTFE), polyperfluoroalkoxy resin, polyfluorinated ethylene propylene resin, polytetrafluoroethylene-polyethylene copolymer, polyvinylidene fluoride, polychlorotrifluoroethylene resin, etc. can be used. These can be used alone or in combination.

[0237] In addition, hollow polymer particles can be used as organic fillers. In particular, by using a hollow body whose outer shell is made of a material having a low dielectric constant such as divinylbenzene or divinylbiphenyl, the dielectric constant of the prepreg can be reduced.

[0238] As inorganic fillers or organic fillers, microparticles with an average particle size of 10 μm or less can be used. The average particle size here can be a value recorded in the catalog of the added filler or the like, or can be an average value or a median value of a plurality of randomly selected fillers. By making the average particle size of the filler meet the above conditions, a prepreg with high smoothness and reliability can be obtained.

[0239] [Coupling agent]

[0240] As the coupling agent, for example, silane coupling agents such as vinyl trichlorosilane, vinyl triethoxysilane, vinyl trimethoxysilane, γ-methacryloxypropyl trimethoxysilane, β (3, 4-epoxycyclohexyl) ethyl trimethoxysilane, γ-glycidoxypropyl methyl diethoxysilane, N-β (aminoethyl) γ-aminopropyl methyl methoxysilane, γ-aminopropyl triethoxysilane, N-phenyl-γ-aminopropyl trimethoxysilane, γ-mercaptopropyl trimethoxysilane, γ-chloropropyl trimethoxysilane, titanate coupling agents, aluminum coupling agents, zirconium aluminate coupling agents, silicone coupling agents, fluorine coupling agents, etc. can be listed. These can be used alone or in combination of two or more.

[0241] (Crosslinking agent)

[0242] From the viewpoint of crosslinking reaction, the crosslinking agent preferably has an average of 2 or more carbon-carbon unsaturated double bonds or isocyanate groups in one molecule. The crosslinking agent may be composed of one compound or may be composed of two or more compounds. The "carbon-carbon unsaturated double bond" in this specification refers to a double bond at the end of a branch from a main chain when the crosslinking agent is a polymer or an oligomer.

[0243] Examples of the crosslinking agent include alkenyl isocyanurate compounds, alkenyl cyanurate compounds, polyfunctional methacrylate compounds having two or more methacryloyl groups in the molecule, polyfunctional acrylate compounds having two or more acryloyl groups in the molecule, polyfunctional vinyl compounds having two or more vinyl groups in the molecule, polyfunctional vinylphenyl compounds having two or more vinylphenyl groups in the molecule, styrene derivatives, polyfunctional maleimide compounds having two or more maleimide groups in the molecule, and polyfunctional isocyanate compounds having an isocyanate group in the molecule.

[0244] The alkenyl isocyanurate compound may be any compound having an isocyanurate structure and an alkenyl group in the molecule, and examples thereof include triallyl isocyanurate compounds such as triallyl isocyanurate (eg, TAIC manufactured by Evonik).

[0245] The alkenyl cyanurate compound may be any compound having a cyanurate structure and an alkenyl group in the molecule, and examples thereof include triallyl cyanurate compounds such as triallyl cyanurate (eg, TAC manufactured by Evonik).

[0246] As said polyfunctional methacrylate compound, tricyclodecane dimethanol dimethacrylate (for example, DCP manufactured by Shin-Nakamura Chemical Co., Ltd.) etc. are mentioned, for example.

[0247] Examples of the polyfunctional vinyl compound include polybutadiene resins. Polybutadiene resins are polymers synthesized from butadiene monomers, such as butadiene homopolymers or copolymers of butadiene and other monomers. For example, Ricon 100, Ricon 184, or Ricon 267 manufactured by Cray Valley Corporation is preferred.

[0248] Examples of the polyfunctional vinylphenyl compound include divinylbenzene, ethynylbenzene, and ODV-XET manufactured by NIPPONSTEEL Chemical & Material Co., Ltd.

[0249] Examples of the styrene derivatives include bromostyrene and dibromostyrene.

[0250] As the maleimide compound, there can be cited compounds having two or more maleimide groups in the molecule, compounds having one maleimide group in the molecule, and modified maleimide compounds, etc. Among them, it is preferred to use a compound having two or more maleimide groups in the molecule. As the modified maleimide compound, for example, there can be cited a modified maleimide compound in which a part of the molecule is modified with amine, and a modified maleimide compound in which a part of the molecule is modified with amine and silicone, etc.

[0251] For example, (4,4'-methylenediphenyl)bismaleimide (for example, BMI-70 manufactured by K.I. Chemical Industry Co., Ltd., BMI-1000, BMI-1000H, BMI-1000S, BMI-1100, or BMI-1100H manufactured by Yamato Chemical Industry Co., Ltd.), phenylmaleimide oligomer (for example, BMI-80 manufactured by K.I. Chemical Industry Co., Ltd., BMI-4000 manufactured by Yamato Chemical Industry Co., Ltd.), ), 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylethane bismaleimide (e.g., BMI-5100 manufactured by Yamato Chemical Industries, Ltd.), (4-methyl-1,3'-phenylene) bismaleimide (e.g., BMI-7000H manufactured by Yamato Chemical Industries, Ltd.), or 1,6-bismaleimide (2,2,4-trimethyl) hexane (e.g., BMI-TMH manufactured by Yamato Chemical Industries, Ltd.).

[0252] The cross-linking agent may be used alone or in combination of two or more thereof. In addition, the cross-linking agent may be not only the cross-linking agent shown above, such as the compound having two or more unsaturated double bonds in the molecule, but also a compound having one unsaturated double bond in the molecule. As the compound having one unsaturated double bond in the molecule, for example, monovinyl compounds having one vinyl group in the molecule may be cited.

[0253] The crosslinking agent preferably has a number average molecular weight of 4,000 or less. When the number average molecular weight of the crosslinking agent is less than 600, the average number of carbon-carbon unsaturated double bonds or isocyanate groups per molecule of the crosslinking agent is preferably 2 to 4. When the number average molecular weight of the crosslinking agent is 600 to 1,500, the average number of carbon-carbon unsaturated double bonds or isocyanate groups per molecule of the crosslinking agent is preferably 4 to 26. When the number average molecular weight of the crosslinking agent is 1,500 to 4,000, the average number of carbon-carbon unsaturated double bonds or isocyanate groups per molecule of the crosslinking agent is preferably 26 to 40.

[0254] (Thermoplastic Elastomer)

[0255] As the thermoplastic elastomer, commercially available ones can be appropriately used, and examples thereof include butadiene-based thermoplastic elastomers such as styrene butadiene copolymer (SBR) and acrylonitrile butadiene copolymer; styrene-based thermoplastic elastomers such as styrene butadiene styrene copolymer (SBS), hydrogenated styrene butadiene styrene copolymer, styrene isoprene styrene copolymer (SIS), hydrogenated styrene isoprene styrene copolymer, and hydrogenated styrene (butadiene / isoprene) styrene copolymer; and thermoplastic resins such as polystyrene, polyester, and polycarbonate. Specific examples include TR2003 manufactured by JSR Corporation, SEPTON 1020, SEPTON 4033, SEPTON 2104, SEPTON 8007L, HYBRAR 5127, and HYBRAR 7311F manufactured by KURARAY CORPORATION, OP501, HA105, HA125, NB125, and PR803 manufactured by ENEOS CORPORATION, and Quintone 1340 and Quintone 2940 manufactured by JAPAN ZEON CORPORATION.

[0256] Among these thermoplastic elastomers, styrene-based thermoplastic elastomers such as styrene-butadiene-styrene copolymers, hydrogenated styrene-butadiene-styrene copolymers, styrene-isoprene-styrene copolymers, hydrogenated styrene-isoprene-styrene copolymers, and hydrogenated styrene-(butadiene / isoprene)-styrene copolymers are preferred. In particular, styrene-isoprene-styrene copolymers, hydrogenated styrene-butadiene-styrene copolymers, hydrogenated styrene-isoprene-styrene copolymers, and hydrogenated styrene-(butadiene / isoprene)-styrene copolymers are more preferred because they can achieve higher heat resistance.

[0257] These thermoplastic elastomers may be used alone or in combination of two or more.

[0258] (Petroleum resin)

[0259] The petroleum resin used in the present invention is a resin obtained by polymerizing the residual components obtained by thermally decomposing naphtha and collecting necessary fractions without separating unsaturated hydrocarbons but without a catalyst or in the presence of a catalyst. The residual fraction mainly includes a C5 fraction (isoprene, pentadiene, cyclopentadiene, pentenes, pentanes, etc.) or a C9 fraction (vinyl toluene, indene, dicyclopentadiene, etc.).

[0260] In the present invention, from the viewpoint of reducing the melt viscosity by combining with a phenylene ether resin, a petroleum resin using a C9 fraction monomer or a dicyclopentadiene-based monomer as a raw material is preferred.

[0261] The catalyst used in the manufacture of petroleum resin is preferably an acidic catalyst. Specifically, solid acids such as Lewis acids such as boron trifluoride phenol complex, boron trifluoride ether complex, aluminum chloride, aluminum bromide, iron chloride (III), iron bromide (III), zeolite, silica, montmorillonite, aluminum oxide, ion exchange resins such as sulfonic acid group-containing fluororesins, sulfonic acid group-containing polystyrene resins, sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, oxalic acid, nitric acid, p-toluenesulfonic acid, protonic acids such as trifluoroacetic acid, etc. can be used. Among these, it is preferred to use Lewis acids and solid acids that are not easy to produce side reactions and have a fast reaction speed, and various complexes of boron trifluoride and aluminum chloride are most preferred in terms of the ease of obtaining and high reactivity.

[0262] The weight average molecular weight of the petroleum resin is not particularly limited, but is preferably 500 to 10,000, more preferably 500 to 5,000. If the weight average molecular weight is higher than this value, the viscosity may be high, and the resin may not be compatible with the phenylene ether resin, and the solubility in the solvent may also be low. If the weight average molecular weight is lower than this value, the heat resistance and mechanical strength of the resin may be reduced.

[0263] The softening point of the petroleum resin is not particularly limited, but is preferably high, preferably 80° C. or higher, and more preferably 100° C. or higher. If the softening point is lower than this, the heat resistance of the resin may decrease.

[0264] Examples of the dicyclopentadiene petroleum resin include resins obtained by polymerizing dicyclopentadiene fractions such as dicyclopentadiene, isopropenylnorbornene, dimethyldicyclopentadiene, and tricyclopentadiene; and resins obtained by polymerizing dicyclopentadiene fractions and other monomers having an unsaturated bond, preferably unsaturated cyclic olefins.

[0265] Examples of the unsaturated cyclic olefins include cyclopentadiene; norbornene monomers such as 2-norbornene, 5-methyl-2-norbornene, 5-ethylidene-2-norbornene, 5-phenylnorbornene, 5-propenyl-2-norbornene, and 5-ethylidene-2-norbornene; and further examples of norbornene monomers having tricyclic or higher rings include tricyclics other than dicyclopentadiene fractions such as diethyldicyclopentadiene and dihydrodicyclopentadiene, tetracyclics such as tetracyclododecene, pentacyclics such as tricyclopentadiene, heptacyclics such as tetracyclopentadiene, and alkyl-substituted, alkylene-substituted, and aryl-substituted forms of these polycyclics. Examples of the alkyl substitution of the polycyclic ring include methyl, ethyl, propyl, and butyl substitutions. Examples of the alkylene substitution of the polycyclic ring include ethylene substitutions. Examples of the aryl substitution of the polycyclic ring include phenyl, tolyl, and naphthyl substitutions.

[0266] Furthermore, as other monomers having an unsaturated bond, olefins having 3 to 12 carbon atoms can be copolymerized, for example, α-olefins such as propylene, butene-1, pentene-1, 1,3-pentadiene, hexene-1, heptene-1, octene-1, diisobutylene, nonene-1, decene-1, 4-phenylbutene-1, 6-phenylhexene-1, 3-methylbutene-1, 4-methylpentene-1, 3-methylpentene-1, 3-methylhexene-1, 4-methylhexene-1, 5-methylhexene-1, 3,3-dimethylpentene-1, 3,4-dimethylpentene-1, 4,4-dimethylpentene-1, vinylcyclohexane, and vinylcyclohexene; and halogen-substituted α-olefins such as hexafluoropropylene, 2-fluoropropylene, 3-fluoropropylene, and 3,4-dichlorobutene-1.

[0267] Furthermore, examples of other monomers having an unsaturated bond include ethylene, tetrafluoroethylene, vinyl fluoride, vinylidene fluoride, and trifluoroethylene; alkyl styrenes such as styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, and p-tert-butylstyrene; halogenated styrenes such as p-chlorostyrene, m-chlorostyrene, o-chlorostyrene, p-bromostyrene, m-bromostyrene, o-bromostyrene, p-fluorostyrene, m-fluorostyrene, o-fluorostyrene, and o-methyl-p-fluorostyrene; maleic anhydride, maleic acid, fumaric acid, allyl alcohol, 3-butene-2-ol, methylbutene-1-ol, vinyl acetate, and vinyl chloride.

[0268] The above-mentioned other monomers having an unsaturated bond may be used alone or in combination of two or more.

[0269] As the petroleum resin, commercially available ones can be used as appropriate. Examples of the aliphatic petroleum resin include Quintone A100, Quintone B170, Quintone K100, Quintone M100, Quintone R100, and Quintone C200S manufactured by Nippon Zeon Co., Ltd., and MARUKAREZ T-100AS and MARUKAREZ R-100AS manufactured by Maruzen Petrochemical Co., Ltd.; and examples of the aromatic petroleum resin include Neopolymer L-90, Neopolymer 120, Neopolymer 130, Neopolymer 140, Neopolymer 150, Neopolymer 170S, Neopolymer 160, Neopolymer E-100, Neopolymer E-130, Neopolymer 130S, and Neopolymer S manufactured by Tosoh Corporation, and Petcoal LX and Petcoal Examples of the copolymer petroleum resin include Quintone D100, Quintone N180, Quintone P195N, Quintone S100, Quintone S195, Quintone U185, Quintone G100B, Quintone G115, Quintone D200, Quintone E200SN, Quintone N295 manufactured by ZEON Corporation, and Petrotack 60, Petrotack 70, Petrotack 90, Petrotack 90V, Petrotack 100S, and Petrotack 100S manufactured by Tosoh Corporation. Examples of the DCPD (dicyclopentadiene)-based petroleum resins include MARUKAREZ M-890A and MARUKAREZ M-845A manufactured by Maruzen Petrochemical Co., Ltd., Quintone 1325, Quintone 1345, Quintone 1500, Quintone 1525L, and Quintone 1700 manufactured by ZEON Corporation of Japan, and HA085, HA103, HA105, HA125, HB103, and HB125 manufactured by ENEOS Corporation.

[0270] <Curing film>

[0271] Next, the curable film of the present invention will be described. The curable film of the present invention is a film made of the phenylene ether resin composition of the present invention, preferably obtained by processing the phenylene ether resin composition of the present invention in a cured state into a film. As a method for processing into a film, for example, a method of dissolving the resin composition in a solvent, applying it to a release film, a conductor foil such as copper foil, and drying it can be cited.

[0272] Examples of the solvent include, but are not limited to, acetone, methyl ethyl ketone, ethylene glycol monomethyl ether acetate, propylene glycol dimethyl ether, toluene, xylene, tetrahydrofuran, and N,N-dimethylformamide. These solvents may be used alone or in combination of two or more.

[0273] The drying conditions when the solvent is dried are not particularly limited. Considering that the solvent is likely to remain in the curable film at a low temperature, and the phenylene ether resin is cured at a high temperature, it is preferably dried at a temperature of 80°C to 200°C for 1 to 90 minutes. The thickness of the curable film can be adjusted by the concentration of the resin composition solution and the coating thickness. Considering that the solvent is likely to remain during drying if the coating thickness is increased, the thickness of the curable film is preferably 0.1 to 500 μm.

[0274] <Prepreg>

[0275] The phenylene ether resin composition of the present invention can be used for the production of prepregs.

[0276] First, the phenylene ether resin composition of the present invention, petroleum resin, and other additives as needed are mixed with an organic solvent to form a varnish. The organic solvent is not particularly limited as long as it dissolves the resin component and does not have an adverse effect on the reaction. For example, appropriate organic solvents such as aromatic hydrocarbons such as toluene, ketones such as methyl ethyl ketone, ethers such as dibutyl ether, esters such as ethyl acetate, and amides such as dimethylformamide are used alone or in combination of two or more.

[0277] The concentration of the resin solid content of the varnish may be appropriately adjusted according to the operation of impregnating the varnish into the base material, and may be, for example, 40% by mass or more and 90% by mass or less.

[0278] The varnish is impregnated into the base material, and then heated and dried to remove the organic solvent and semi-cure the resin in the base material, thereby obtaining a prepreg. As the base material, for example, glass cloth can be used.

[0279] As the impregnation amount of the varnish into the substrate, it is preferred that the mass ratio of the resin solid content in the prepreg be 35% by mass or more. Since the dielectric constant of the substrate is larger than that of the resin, in order to reduce the dielectric constant of the printed circuit board obtained by using the prepreg, the content of the resin solid content in the prepreg can be made higher than the above mass ratio.

[0280] The substrate impregnated with the varnish can be heated at a temperature of 80°C to 200°C for a time of 1 minute to 10 minutes. At this time, the heating is performed in such a manner that the minimum melt viscosity of the resin composition in the prepreg becomes 10,000 Pa·s or less. For example, when heated at a temperature of 150°C, the heating time is preferably 3 minutes to less than 10 minutes, and more preferably 5 minutes to 9 minutes. Although the heating conditions of the substrate impregnated with the varnish are not limited to the above conditions, they are determined in such a manner that the minimum melt viscosity of the resin composition in the prepreg becomes 10,000 Pa·s or less. Here, the minimum melt viscosity of the resin composition in the prepreg is the lowest value of the melt viscosity of the resin composition in the prepreg in the temperature range from room temperature to 200°C.

[0281] In the case of low temperature short-time heating, solvent can remain and melt viscosity reduces, but the dielectric loss tangent variation of plywood is sometimes.In addition, in the case of high temperature long-time heating, solidification is sometimes carried out and melt viscosity becomes too high.Therefore, from the viewpoint of reducing the residual solvent amount caused by heating and suppressing the rise of melt viscosity, it is expected that the minimum melt viscosity of the resin combination before heating is low.

[0282] In the obtained prepreg, the dielectric loss tangent (Df) value of the phenylene ether resin composition of the present invention at 10 GHz in a cured state is preferably as small as possible, and is preferably 0.0005 or more lower than the value of a comparative object such as the prior art in a state where no components other than the phenylene ether resin and the components used in its production are added.

[0283] There are no particular limitations on the substrate, and a substrate known to be used in various printed circuit board materials can be appropriately selected and used according to the target application and performance. Specific examples of the fiber constituting the substrate are not particularly limited, and examples include glass fibers such as E glass, D glass, S glass, Q glass, NE glass, NER glass, L glass, and T glass; inorganic fibers other than glass such as quartz; wholly aromatic polyamides such as poly(p-phenylene terephthalamide) (Kevlar (registered trademark), manufactured by DuPont Co., Ltd.), copoly(p-phenylene terephthalamide) (Technora (registered trademark), manufactured by TEIJIN Co., Ltd.); polyesters such as 2,6-hydroxynaphthoic acid and p-hydroxybenzoic acid (vectran (registered trademark), manufactured by KURARAY Co., Ltd.), zxion (registered trademark, manufactured by KB SEIREN); organic fibers such as poly(p-phenylene benzoxazole) (Zylon (registered trademark), manufactured by Toyobo Co., Ltd.) and polyimide. Among these, at least one selected from the group consisting of E glass, T glass, S glass, Q glass, and organic fiber is preferred from the viewpoint of low thermal expansion coefficient. These substrates may be used alone or in combination of two or more.

[0284] There are no particular limitations on the form of the substrate, and examples thereof include woven fabrics, nonwoven fabrics, rovings, short glass fiber mats, and surface mats. There are no particular limitations on the weaving method of the woven fabric, and examples thereof include plain weave, basket weave, and twill weave. These known weaving methods can be appropriately selected and used according to the target use and performance. In addition, it is preferred to use glass woven fabrics that have been subjected to fiber opening treatment and surface treatment with a silane coupling agent or the like. There are no particular limitations on the thickness and mass of the substrate, and it is generally preferred to use a substrate of about 0.01 to 0.3 mm. In particular, from the viewpoint of strength and water absorption, the substrate is preferably 200 μm or less in thickness and 250 g / m in mass. 2 The following glass woven fabric is more preferably a glass woven fabric containing glass fibers of E glass, S glass, and T glass.

[0285] <Laminated board>

[0286] The phenylene ether resin composition of the present invention can be used to obtain a laminate. For example, the laminate can be produced using the above-mentioned prepreg. Hereinafter, a method for producing a laminate using the prepreg will be described.

[0287] First, a piece of prepreg or a plurality of prepregs are overlapped, and a metal foil such as copper foil is overlapped on both sides or one side above and below, and the laminate is subjected to heating and pressure molding. Through this molding, a laminate (such as a copper-clad laminate) with metal foil on both sides or one side can be made. A circuit is formed by patterning and etching the metal foil of the laminate, thereby obtaining a printed circuit substrate. In addition, the metal foil forming the circuit is sandwiched in the middle and a plurality of prepregs are overlapped and heated and pressed to form a multilayered printed circuit substrate.

[0288] The heating and pressing molding conditions vary depending on the content ratio of the raw materials in the resin composition of the present invention, but are generally performed at 170°C or higher and 230°C or lower, and a pressure of 1.0 MPa or higher and 6.0 MPa or lower (10 kg / cm 2 Above and 60kg / cm 2 It is preferred to heat and pressurize for an appropriate time under the conditions described below).

[0289] As the metal foil, the following can be used: the surface roughness (ten-point average roughness: Rz) is less than 10 μm, the surface of one side of the resin layer formed by the prepreg (the surface in contact with the prepreg) is treated with zinc or zinc alloy for rust prevention or to improve the adhesion with the resin layer, and further subjected to coupling treatment by a vinyl-containing silane coupling agent or the like. Such copper foil has good adhesion with the resin layer (insulating layer), and a printed circuit board with excellent high-frequency characteristics can be obtained. It should be noted that when the copper foil is treated with zinc or zinc alloy, zinc or zinc alloy can be formed on the surface of the copper foil by a plating method.

[0290] The obtained laminated board and printed circuit board can realize low dielectric loss tangent. In addition, the laminated board and printed circuit board with heat resistance, flame retardancy, toughness, processability, low water absorption and high glass transition temperature can be obtained.

[0291] [Example]

[0292] Hereinafter, although the content of the invention is demonstrated in detail together with the Example of this invention and a comparative example, this invention is not limited to these Examples.

[0293] <Determination of number average molecular weight and weight average molecular weight>

[0294] As a measuring device, a high performance liquid chromatograph, HLC-8320GPC manufactured by Tosoh Techno-System Co., Ltd. was used. A standard curve was prepared using standard polystyrene. The number average molecular weight (Mn) and weight average molecular weight (Mw) of the phenylene ether resin were measured using the standard curve. As standard polystyrene, standard polystyrenes with molecular weights of 706,000, 96,400, 5,970, 474, 370, and 266 were used. A column was formed by connecting four TSKgel Super Multipore HZ-N manufactured by Tosoh Corporation. Tetrahydrofuran was used as the solvent, and the measurement was performed at a flow rate of 0.35 mL / min and a column temperature of 40°C. As a sample for measurement, 0.2 g of the phenylene ether solution was dissolved in 3 g of a tetrahydrofuran solution. A built-in RI detector was used for detection.

[0295] <Based on 1 Terminal structure analysis by H-NMR>

[0296] A phenylene ether resin composition without any other components other than the phenylene ether resin and the components used in its production was concentrated and dried to obtain a powder, which was then dissolved in a deuterated chloroform solvent to prepare a solution sample for measurement. 1 H-NMR was measured with AVANCE III HD500 at a measurement temperature of 25° C. and a cumulative number of 64 times.

[0297] <Content of aldehyde and methoxyl groups>

[0298] from 1 The content of aldehyde (group having the general formula (3), X is a hydrogen atom) and methoxy (group having the general formula (5), Y3 is a methyl group) was calculated from the measurement results of H-NMR. The integrated intensity of the peak at 1.9 to 2.3 ppm was set to "1,000". This peak is attributed to the number of protons of the methyl group substituted on the benzene ring in the resin.

[0299] The aldehyde content was calculated by the following formula.

[0300] Aldehyde content [ppm]

[0301] =[{(I 9.5-12.5 / P a )×M a} / {(1,000 / P p )×M p}]×10 6

[0302] In the formula,

[0303] I 9.5-12.5The integrated intensity of 9.5 to 12.5 ppm is shown. This is the measured value of the number of protons of the aldehyde group in the resin composition.

[0304] P a is the number of protons in the aldehyde group, which is "1".

[0305] M a is the molecular weight of the aldehyde group, which is 29.

[0306] P p is the number of protons of the methyl group substituted on the benzene ring of the phenylene ether resin α, and is theoretically calculated based on the amount of the monomer charged.

[0307] M p is the theoretical molecular weight of phenylene ether resin α, which is theoretically calculated based on the amount of monomer added.

[0308] In addition, the content of the methoxy group was calculated by the following formula.

[0309] Methoxy content [ppm]

[0310] =[{(I 3.2-3.6 / P m )×M m} / {(1,000 / P p )×M p}]×10 6

[0311] In the formula,

[0312] I 3.2-3.6 It shows the integrated intensity of 3.2 to 3.6 ppm and is the measured value of the number of protons of the methoxy group in the resin composition.

[0313] P m is the number of protons in the methoxy group. The methoxy group is -OCH3, so it is "3".

[0314] M m The molecular weight of methoxy is 31.

[0315] P p is the number of protons of the methyl group substituted on the benzene ring of the phenylene ether resin α, and is theoretically calculated based on the amount of the monomer charged.

[0316] M p is the theoretical molecular weight of phenylene ether resin α, which is theoretically calculated based on the amount of monomer added.

[0317] <Comparative Example 1>

[0318] (Synthesis Example 1-1)

[0319] The polymerization reaction was carried out according to the following scheme.

[0320] Add the following into a longitudinal reactor equipped with a stirring device, a thermometer, an air inlet pipe and baffles:

[0321] 2,2',3,3',5,5'-hexamethyl-(1,1'-biphenyl)-4,4'-diol 46.21 g (171 mmol),

[0322] 2,6-Dimethylphenol 104.4 g (855 mmol),

[0323] CuBr2 1.37 g (6.1 mmol),

[0324] N,N'-di-tert-butylethylenediamine 1.59 g (9.2 mmol),

[0325] n-Butyldimethylamine 9.26 g (92 mmol),

[0326] 1,000 g of toluene, and

[0327] Methanol 500g,

[0328] The mixture was dissolved by stirring at a reaction temperature of 40° C. Then, the mixed solution was stirred for 230 minutes while bubbling a mixed gas having an oxygen concentration of 8% by mixing nitrogen and air.

[0329] Then, 580 g of water in which 4.72 g (10 mmol) of tetrasodium ethylenediaminetetraacetate was dissolved was added to stop the reaction. The aqueous layer and the organic layer were separated, and the organic layer was washed with 670 g of pure water. 1,310 g of a toluene solution of a phenylene ether resin composition was obtained. The number average molecular weight in terms of polystyrene conversion according to the GPC method was 950, and the weight average molecular weight in terms of polystyrene conversion according to the GPC method was 1,050.

[0330] (Synthesis Example 1-2)

[0331] The terminal modification reaction was carried out according to the following scheme.

[0332] Add to a reactor equipped with a stirrer, thermometer and reflux tube:

[0333] 1,300 g of a toluene solution of the phenylene ether resin composition obtained in Synthesis Example 1-1,

[0334] Vinylbenzyl chloride (manufactured by AGC Seimi Chemical Co., Ltd., "CMS-P") 58.0 g (381 mmol),

[0335] Tetrabutylammonium bromide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 26 g,

[0336] Benzyl dimethylamine 6.20 g (0.046 mol),

[0337] 48% sodium hydroxide aqueous solution 117g,

[0338] 180g pure water, and

[0339] Toluene 70g,

[0340] The mixture was stirred at a reaction temperature of 70°C. After stirring for 3 hours, the aqueous layer and the organic layer were separated, and the organic layer was washed with 1% sulfuric acid and then with pure water. The obtained solution was concentrated to 65% by mass by an evaporator to obtain 900 g of a phenylene ether resin composition (i) whose terminal was modified to a styrene group. The number average molecular weight calculated by the polystyrene conversion according to the GPC method was 1,220, and the weight average molecular weight calculated by the polystyrene conversion according to the GPC method was 1,560.

[0341] Various values ​​of the phenylene ether resin composition (i) obtained in Synthesis Example 1-2 are shown in Table 2. The structure of the main resin (resin α) in the phenylene ether resin composition (i) is as follows.

[0342]

[0343] <Example 1>

[0344] (Synthesis example 2-1)

[0345] The polymerization reaction was carried out by the following scheme.

[0346] 1,300 g of a toluene solution of a phenylene ether resin composition was obtained in the same manner as in Synthesis Example 1-1 except that the polymerization time was changed to 210 minutes. The polystyrene-equivalent number average molecular weight by GPC was 930, and the polystyrene-equivalent weight average molecular weight by GPC was 1,000.

[0347] (Synthesis example 2-2)

[0348] The terminal modification reaction was carried out by the following scheme.

[0349] 900 g of a phenylene ether resin composition (ii) whose terminal was modified with a styryl group was obtained in the same manner as in Synthesis Example 1-2. The polystyrene-equivalent number average molecular weight by GPC was 1,220, and the polystyrene-equivalent weight average molecular weight by GPC was 1,560.

[0350] Table 2 shows various values ​​of the phenylene ether resin composition (ii) obtained in Synthesis Example 2-2.

[0351] <Comparative Example 2>

[0352] (Synthesis example 3-1)

[0353] The polymerization reaction was carried out by the following scheme.

[0354] Add to a vertical reactor equipped with a stirrer, thermometer, air inlet pipe and baffles:

[0355] CuBr2 0.685 g (3.1 mmol),

[0356] N,N'-di-tert-butylethylenediamine 0.21 g (1.2 mmol),

[0357] n-Butyldimethylamine 4.63 g (46 mmol),

[0358] 670 g of toluene, and

[0359] Methanol 320g,

[0360] The mixture was stirred at a reaction temperature of 40° C. to dissolve the mixture (preparation of a polymerization tank).

[0361] On the other hand, add in other containers beforehand:

[0362] 2,2',3,3',5,5'-hexamethyl-(1,1'-biphenyl)-4,4'-diol 46.21 g (171 mmol),

[0363] 2,6-Dimethylphenol 104.4 g (855 mmol),

[0364] CuBr2 0.685 g (3.1 mmol),

[0365] N,N'-di-tert-butylethylenediamine 0.21 g (1.2 mmol),

[0366] n-Butyldimethylamine 4.63 g (46 mmol),

[0367] 440 g of toluene, and

[0368] Methanol 170g,

[0369] The mixture was stirred at a reaction temperature of 40° C. to dissolve the mixture (preparation of a dropping tank).

[0370] Thereafter, the mixed solution in the dropping tank was dropped over 230 minutes while bubbling a mixed gas prepared by mixing nitrogen and air to adjust the oxygen concentration to 8% into the mixed solution in the polymerization tank, and the mixture was stirred.

[0371] After the dropwise addition was completed, 580 g of water in which 4.72 g (10 mmol) of tetrasodium ethylenediaminetetraacetate was dissolved was added to stop the reaction. The aqueous layer and the organic layer were separated, and the organic layer was washed with 670 g of pure water. 1,400 g of a toluene solution of a phenylene ether resin composition was obtained. The number average molecular weight in terms of polystyrene conversion according to the GPC method was 1,040, and the weight average molecular weight in terms of polystyrene conversion according to the GPC method was 1,120.

[0372] (Synthesis example 3-2)

[0373] The terminal modification reaction was carried out by the following scheme.

[0374] In the same manner as in Synthesis Example 1-2, 950 g of a phenylene ether resin composition (iii) whose terminal was modified to a styryl group was obtained. The polystyrene-equivalent number average molecular weight by GPC was 1,240, and the polystyrene-equivalent weight average molecular weight by GPC was 1,670.

[0375] Table 2 shows various values ​​of the phenylene ether resin composition (iii) obtained in Synthesis Example 3-2.

[0376] <Example 2>

[0377] (Synthesis Example 4-1)

[0378] The polymerization reaction was carried out by the following scheme.

[0379] Add to a vertical reactor equipped with a stirrer, thermometer, air inlet pipe and baffles:

[0380] CuBr2 0.31 g (1.4 mmol),

[0381] N,N'-di-tert-butylethylenediamine 0.60 g (3.5 mmol),

[0382] n-Butyldimethylamine 4.63 g (46 mmol),

[0383] Toluene 670g,

[0384] Methanol 320g,

[0385] The mixture was stirred at a reaction temperature of 40° C. to dissolve the mixture (preparation of a polymerization tank).

[0386] On the other hand, add in other containers in advance:

[0387] 2,2',3,3',5,5'-hexamethyl-(1,1'-biphenyl)-4,4'-diol 46.21 g (171 mmol),

[0388] 2,6-Dimethylphenol 129.5 g (1,060 mmol),

[0389] CuBr2 0.31 g (1.4 mmol),

[0390] N,N'-di-tert-butylethylenediamine 0.60 g (3.5 mmol),

[0391] n-Butyldimethylamine 4.63 g (46 mmol),

[0392] 440 g of toluene, and

[0393] Methanol 170g,

[0394] The mixture was stirred at a reaction temperature of 40° C. to dissolve the mixture (preparation of a dropping tank).

[0395] Thereafter, the mixed solution in the dropping tank was dropped over 310 minutes while bubbling a mixed gas prepared by mixing nitrogen and air to adjust the oxygen concentration to 8% into the mixed solution in the polymerization tank, and the mixture was stirred.

[0396] After the dropwise addition was completed, 580 g of water in which 4.72 g (10 mmol) of tetrasodium ethylenediaminetetraacetate was dissolved was added to stop the reaction. The aqueous layer and the organic layer were separated, and the organic layer was washed with 670 g of pure water. 1,400 g of a toluene solution of a phenylene ether resin composition was obtained. The number average molecular weight in terms of polystyrene conversion according to the GPC method was 1,050, and the weight average molecular weight in terms of polystyrene conversion according to the GPC method was 1,170.

[0397] (Synthesis Example 4-2)

[0398] The terminal modification reaction was carried out by the following scheme.

[0399] In the same manner as in Synthesis Example 1-2, 940 g of a phenylene ether resin composition (iv) whose terminal was modified to a styryl group was obtained. The polystyrene-equivalent number average molecular weight by GPC was 1,210, and the polystyrene-equivalent weight average molecular weight by GPC was 1,490.

[0400] Table 2 shows various values ​​of the phenylene ether resin composition (iv) obtained in Synthesis Example 4-2.

[0401] <Comparative Example 3>

[0402] (Synthesis example 5-1)

[0403] The polymerization reaction was carried out by the following scheme.

[0404] Except changing the polymerization time to 350 minutes, the same method as in Synthesis Example 4-1 was carried out to obtain 1,490 g of a toluene solution of a phenylene ether resin composition. The polystyrene-equivalent number average molecular weight by GPC method was 1,150, and the polystyrene-equivalent weight average molecular weight by GPC method was 1,280.

[0405] (Synthesis example 5-2)

[0406] The terminal modification reaction was carried out by the following scheme.

[0407] 930 g of a phenylene ether resin composition (v) terminally modified with a styryl group was obtained in the same manner as in Synthesis Example 1-2. The polystyrene-equivalent number average molecular weight by GPC was 1,240, and the polystyrene-equivalent weight average molecular weight by GPC was 1,500.

[0408] Table 2 shows various values ​​of the phenylene ether resin composition (v) obtained in Synthesis Example 5-2.

[0409] <Comparative Example 4>

[0410] (Synthesis Example 6-1)

[0411] The polymerization reaction was carried out by the following scheme.

[0412] 1,370 g of a toluene solution of a phenylene ether resin composition was obtained in the same manner as in Synthesis Example 4-1 except that methanol was not used. The polystyrene-equivalent number average molecular weight by GPC was 1,070, and the polystyrene-equivalent weight average molecular weight by GPC was 1,180.

[0413] (Synthesis Example 6-2)

[0414] The terminal modification reaction was carried out by the following scheme.

[0415] In the same manner as in Synthesis Example 1-2, 980 g of a phenylene ether resin composition (vi) whose terminal was modified to a styryl group was obtained. The polystyrene-equivalent number average molecular weight by GPC was 1,260, and the polystyrene-equivalent weight average molecular weight by GPC was 1,540.

[0416] Table 2 shows various values ​​of the phenylene ether resin composition (vi) obtained in Synthesis Example 6-2.

[0417] <Example 3>

[0418] (Synthesis Example 7-1)

[0419] The polymerization reaction was carried out by the following scheme.

[0420] 1,090 g of a toluene solution of a phenylene ether resin composition was obtained in the same manner as in Synthesis Example 4-1 except that 2,2',3,3',5,5'-hexamethyl-(1,1'-biphenyl)-4,4'-diol was changed to 34.22 g (171 mmol) of 4,4'-methylenebis(2,6-dimethylphenol) and the polymerization time was changed to 280 minutes. The number average molecular weight in terms of polystyrene by GPC method was 1,040, and the weight average molecular weight in terms of polystyrene by GPC method was 1,130.

[0421] (Synthesis Example 7-2)

[0422] The terminal modification reaction was carried out by the following scheme.

[0423] Except that vinylbenzyl chloride was replaced with 39.9 g (381 mmol) of methacryloyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.), in the same manner as in Synthesis Example 1-2, 910 g of a phenylene ether resin composition (vii) whose terminal was modified with a methacryloyl group was obtained. The number average molecular weight in terms of polystyrene by GPC method was 1,120, and the weight average molecular weight in terms of polystyrene by GPC method was 1,430.

[0424] Various values ​​of the phenylene ether resin composition (vii) obtained in Synthesis Example 7-2 are shown in Table 3. In the phenylene ether resin composition (vii), the structure of the main resin (resin α) is as follows.

[0425]

[0426] <Comparative Example 5>

[0427] (Synthesis example 8-1)

[0428] The polymerization reaction was carried out by the following scheme.

[0429] 1,090 g of a toluene solution of a phenylene ether resin composition was obtained in the same manner as in Synthesis Example 7-1 except that the polymerization time was changed to 320 minutes. The polystyrene-equivalent number average molecular weight by GPC was 1,050, and the polystyrene-equivalent weight average molecular weight by GPC was 1,150.

[0430] (Synthesis example 8-2)

[0431] The terminal modification reaction was carried out by the following scheme.

[0432] In the same manner as in Synthesis Example 7-2, 910 g of a phenylene ether resin composition (viii) whose terminal was modified with a methacryloyl group was obtained. The polystyrene-equivalent number average molecular weight by GPC was 1,130, and the polystyrene-equivalent weight average molecular weight by GPC was 1,460.

[0433] Table 3 shows various values ​​of the phenylene ether resin composition (viii) obtained in Synthesis Example 8-2.

[0434] <Example 4>

[0435] (Synthesis Example 9-1)

[0436] The polymerization reaction was carried out by the following scheme.

[0437] In the same manner as in Synthesis Example 4-1, 1,350 g of a toluene solution of a phenylene ether resin composition was obtained. The polystyrene-equivalent number average molecular weight by GPC was 1,060, and the polystyrene-equivalent weight average molecular weight by GPC was 1,160.

[0438] (Synthesis Example 9-2)

[0439] The terminal modification reaction was carried out by the following scheme.

[0440] In the same manner as in Synthesis Example 8-2, 960 g of a phenylene ether resin composition (ix) whose terminal was modified with a methacryloyl group was obtained. The polystyrene-equivalent number average molecular weight by GPC was 1,120, and the polystyrene-equivalent weight average molecular weight by GPC was 1,470.

[0441] Various values ​​of the phenylene ether resin composition (ix) obtained in Synthesis Example 9-2 are shown in Table 3. The structure of the main resin (resin α) in the phenylene ether resin composition (ix) is as follows.

[0442]

[0443] <Comparative Example 6>

[0444] (Synthesis Example 10-1)

[0445] The polymerization reaction was carried out by the following scheme.

[0446] Except changing the polymerization time to 350 minutes, the same method as in Synthesis Example 9-1 was carried out to obtain 1,340 g of a toluene solution of a phenylene ether resin composition. The polystyrene-equivalent number average molecular weight by GPC was 1,060, and the polystyrene-equivalent weight average molecular weight by GPC was 1,160.

[0447] (Synthesis Example 10-2)

[0448] The terminal modification reaction was carried out by the following scheme.

[0449] In the same manner as in Synthesis Example 9-2, 980 g of a phenylene ether resin composition (x) whose terminal was modified with a methacryloyl group was obtained. The polystyrene-equivalent number average molecular weight by GPC was 1,130, and the polystyrene-equivalent weight average molecular weight by GPC was 1,490.

[0450] Table 3 shows various values ​​of the phenylene ether resin composition (x) obtained in Synthesis Example 10-2.

[0451] <Production of cured resin>

[0452] Using the powders of the phenylene ether resin compositions (i) to (vi) obtained in Comparative Examples 1 to 4 and Examples 1 and 2, cured products were prepared.

[0453] 4.5 g of the powder of the resin composition was spread and filled in a 100 mm×30 mm frame of a stainless steel mold, and placed in a vacuum press (manufactured by Oji Machinery Co., Ltd.), and pressed at 200° C. for 1.5 hours at a surface pressure of 1.9 MPa.

[0454] Furthermore, the powders of the phenylene ether resin compositions (vii) to (x) obtained in Examples 3 and 4 and Comparative Examples 5 and 6 were pressed in the same manner except that 0.1 wt % of α,α'-di(tert-butylperoxy)diisopropylbenzene ("PERBUTYLP" manufactured by NOF Corporation) was added and fully mixed to prepare a resin composition.

[0455] <Measurement of dielectric loss tangent>

[0456] The dielectric loss tangent (Df) of the obtained cured resin at 10 GHz was measured using a perturbation method cavity resonator (Agilent 8722ES, manufactured by Agilent Technologies, Inc.) The measurement temperature was set to 23° C. The measurement results are shown in Tables 2 and 3 below.

[0457] It should be noted that the value of dielectric loss tangent varies due to the molecular structure of the resin, the type and amount of the thermosetting catalyst (polymerization initiator) used when making the cured product, and in order to evaluate the dielectric loss tangent, resins with the same molecular structure can be compared with each other, or resins with the same type and amount of the thermosetting catalyst (polymerization initiator) can be compared with each other. In this embodiment, for example, it is not very meaningful to compare the resins in Table 2 below with the resins in Table 3.

[0458] [Table 2]

[0459] Table 2

[0460]

[0461] [Table 3]

[0462] Table 3

[0463]

[0464] The abbreviations in Table 2 and Table 3 above;

[0465] HMBP;

[0466] 2,2',3,3',5,5'-Hexamethyl-(1,1'-biphenyl)-4,4'-diol

[0467] TMBPF;

[0468] 4,4'-Methylenebis(2,6-dimethylphenol).

Claims

1. A phenylene ether resin composition, characterized in that The present invention is a phenylene ether resin composition having a number average molecular weight (Mn) of 800 to 3,000, The phenylene ether resin composition contains a resin α represented by the following general formula (1) and a resin β represented by the following general formula (2). The content of the resin β relative to the resin α, that is, the content of the resin β / the content of the resin α, is 20 to 200 ppm, General formula (1) In the general formula (1), A represents a single bond or a linear, branched or cyclic hydrocarbon having 10 or less carbon atoms; Z1 and Z2 may be the same or different and represent a hydrogen atom or a unit containing a polymerizable double bond group; R1 to R 16 may be the same or different, and represent a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group having 6 or less carbon atoms, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group or a substituted aryl group; m and n represent integers of 0 to 20, and at least one of them is an integer of 1 to 20; R1 to R 16 At least one of represents a methyl group, General formula (2) In the general formula (2), A, Z1, Z2, R1 to R 16 , m and n are the same as those in the general formula (1); L1 to L8 may be the same or different and are represented by a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group having 6 or less carbon atoms, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group, a substituted aryl group or the following general formula (3); at least one of L1 to L8 is represented by the following general formula (3), General formula (3) In the general formula (3), X is selected from the group consisting of a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 6 or less carbon atoms, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group, and a substituted aryl group; * represents a connecting bond.

2. The phenylene ether resin composition according to claim 1, further comprising a resin γ represented by the following general formula (4): The content of the resin γ relative to the resin α, that is, the content of the resin γ / the content of the resin α is 150 to 400 ppm, General formula (4) In the general formula (4), A, Z1, Z2, R1 to R 16 , m and n are the same as those in the general formula (1); L9~L 16 may be the same or different and are represented by a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group having 6 or less carbon atoms, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group, a substituted aryl group or the following general formula (5); L9 to L 16 At least one of them is represented by the following general formula (5), General formula (5) In the general formula (5), Y1 and Y2 are selected from the group consisting of a hydrogen atom, a straight-chain or branched alkyl group having less than 6 carbon atoms, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group, and a substituted aryl group; Y3 is selected from the group consisting of a hydrogen atom, a straight-chain or branched alkyl group having less than 6 carbon atoms, a substituted alkyl group, an alkenyl group, and a substituted alkenyl group; * represents a connecting bond.

3. The phenylene ether resin composition according to claim 1, wherein In the general formulae (1) and (2), A is a single bond.

4. The phenylene ether resin composition according to claim 1, wherein In the general formulae (1) and (2), R1, R2, R3, R6, R7 and R8 represent methyl groups, and R4 and R5 represent hydrogen atoms.

5. The phenylene ether resin composition according to claim 1, wherein In the general formulas (1) and (2), R9, R 10 , R 15 and R 16 Represents methyl, R 11 , R 12 , R 13 and R 14 represents a hydrogen atom, In the general formula (2), L1, L2, L7 and L8 represent a methyl group or the general formula (3), L3, L4, L5 and L6 represent a hydrogen atom, and at least one of L1, L2, L7 and L8 represents the general formula (3).

6. The phenylene ether resin composition according to claim 1, wherein In the general formulae (1) and (2), Z1 and Z2 are represented by any one of the following general formulae (6) or (7), General formula (6) In the general formula (6), R 17 represents a hydrogen atom or a methyl group; * represents a connecting bond, General formula (7) In the general formula (7), R 18 ~R 21 may be the same or different, and represent a hydrogen atom, a halogen atom, a linear or branched alkyl group having 6 or less carbon atoms, or a phenyl group; * represents a connecting bond.

7. The phenylene ether resin composition according to claim 6, wherein In the general formulae (1) and (2), Z1 and Z2 are represented by the general formula (7).

8. The phenylene ether resin composition according to claim 1, wherein In the general formula (3), X is a hydrogen atom.

9. The phenylene ether resin composition according to claim 2, wherein In the general formula (5), Y3 is a methyl group. 10 . A curable film obtained by using the phenylene ether resin composition according to claim 1 . 11 . A laminated board obtained by using the phenylene ether resin composition according to claim 1 .

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