Phenylene sulfide-phenyl ether copolymer

Abstract

The present invention provides a resin having a low dielectric loss tangent. This phenyl sulfide-phenyl ether copolymer for a wiring board contains a structural unit represented by formula (I):-Ph1-O-Ph2-S-(I) [in formula (I), Ph1 and Ph2 each independently represent a phenylene group that may have a substituent]. It is preferable that at least one of Ph1 and Ph2 has one or more substituents.

Description

Technical Field

[0001] The present disclosure relates to phenylene sulfide-phenylene ether copolymers. Background Art

[0002] In recent years, mobile communication systems have been advancing towards higher speeds and larger capacity. With these advancements, higher frequency bands are being used for communications. For example, the fifth-generation mobile communication system, which has already begun practical use, utilizes higher frequency bands than mobile communication systems prior to the fourth generation.

[0003] Mobile communication system terminals experience attenuation of electrical signals passing through the circuits of printed wiring boards (PCBs), known as transmission loss. Transmission loss also depends on the dielectric properties of the PCB substrate (dielectric). Generally speaking, the higher the frequency used, the greater the influence of the dielectric loss tangent, and the greater the transmission loss.

[0004] To achieve higher-speed mobile communications, it is necessary to suppress transmission loss in printed wiring boards (PCBs) used for high-frequency communications. Therefore, the resins and resin compositions used as materials for PCBs are also required to have low transmission loss. To achieve this, resins and resin compositions with low dielectric loss tangent are required.

[0005] As materials for wiring substrates such as printed wiring boards, resin compositions containing polyphenylene ether (PPO) resin (e.g., Patent Document 1) or polyphenylene sulfide (PPS) resin (e.g., Patent Documents 2 and 3) as main components have been widely used.

[0006] Patent Document 1: Japanese Patent Application Laid-Open No. 2005-60635

[0007] Patent Document 2: Japanese Patent Application Laid-Open No. 2002-225029

[0008] Patent Document 3: Japanese Patent Application Laid-Open No. 5-98157 Summary of the Invention

[0009] However, PPO resin itself has low flame retardancy. Therefore, for use as a wiring board material, it must be mixed with a flame-retardant material to impart flame retardancy to the resin composition. Furthermore, unsubstituted PPS resin has a high dielectric loss tangent, which can increase transmission loss in high-frequency communication applications.

[0010] An object of the present disclosure is to provide a resin having a low dielectric loss tangent.

[0011] The present disclosure has the following aspects.

[0012] <Method 1>

[0013] [1] A phenylene sulfide-phenylene ether copolymer for a wiring board, comprising a structural unit represented by formula (I).

[0014] -Ph 1 -O-Ph 2 -S- (I)

[0015] [In formula (I), Ph 1 and Ph 2 Each independently represents a phenylene group which may have a substituent.]

[0016] [2] The phenylene sulfide-phenylene ether copolymer according to [1], wherein

[0017] In formula (I), Ph 1 and Ph 2 At least one of them has one or more substituents.

[0018] [3] The phenylene sulfide-phenylene ether copolymer according to [1] or [2], wherein

[0019] The structural unit represented by formula (I) includes the structural unit represented by formula (II).

[0020]

[0021] [In formula (II), R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 and R 8 are independently H, alkyl, alkoxy, alkenyl or aryl, R 1 、R 2 、R 3 and R 4 One or more of them are alkyl, alkoxy, alkenyl or aryl, and / or R 5 、R 6 、R 7 and R 8 One or more of them are alkyl, alkoxy, alkenyl or aryl].

[0022] [4] The phenylene sulfide-phenylene ether copolymer according to [3], wherein

[0023] In formula (II), R 1 、R 2 、R 3 and R 4 One or more of them are alkyl, alkoxy, alkenyl or aryl, and R 5 、R6 、R 7 and R 8 One or more of them are alkyl, alkoxy, alkenyl or aryl.

[0024] [5] The phenylene sulfide-phenylene ether copolymer according to any one of [1] to [3], wherein

[0025] The content of the structural unit represented by formula (I) is 60 mol % or more based on all the structural units.

[0026] [6] The phenylene sulfide-phenylene ether copolymer according to any one of [1] to [5], which has a dielectric loss tangent of less than 0.002 at 10 GHz.

[0027] [7] The phenylene sulfide-phenylene ether copolymer according to any one of [1] to [6], which has a dielectric loss tangent of less than 0.002 at 80 GHz.

[0028] [8] The phenylene sulfide-phenylene ether copolymer according to any one of [1] to [7], wherein the dielectric loss tangent tanδ at 80 GHz is 80 and dielectric loss tangent tanδ at 10 GHz 10 ratio tanδ 80 / tanδ 10 Below 1.5.

[0029] [9] A resin composition comprising the phenylene sulfide-phenylene ether copolymer according to any one of [1] to [8].

[0030]

[10] A wiring substrate comprising the phenylene sulfide-phenylene ether copolymer described in any one of [1] to [8], or the resin composition described in [9].

[0031]

[11] A printed wiring board comprising the wiring substrate described in

[10] and an electronic component.

[0032]

[12] A wiring board material comprising the phenylene sulfide-phenylene ether copolymer described in any one of [1] to [8], or the resin composition described in [9].

[0033]

[13] The wiring board material according to

[12] , which is a varnish, an interlayer insulating material, a prepreg, a metal-clad laminate, or a substrate.

[0034]

[14] A compatibilizer comprising the phenylene sulfide-phenylene ether copolymer described in any one of [1] to [8], or the resin composition described in [9].

[0035]

[15] The compatibilizer according to

[14] , which is a compatibilizer for a resin composition containing a polyarylene sulfide resin and a polyarylene ether resin.

[0036] <Method 2>

[0037] (10) A phenylene sulfide-phenylene ether copolymer comprising a structural unit represented by formula (Ia).

[0038] -Ph 1a -O-Ph 2a -S- (Ia)

[0039] [In formula (I), Ph 1a and Ph 2a Each independently represents a phenylene group which may have a substituent, Ph 1a and Ph 2a each having one or more substituents].

[0040] (11) The phenylene sulfide-phenylene ether copolymer according to (10), wherein

[0041] The structural unit represented by formula (Ia) includes the structural unit represented by formula (IIa).

[0042]

[0043] [In formula (IIa), R 1a 、R 2a 、R 3a 、R 4a 、R 5a 、R 6a 、R 7a and R 8a are independently H, alkyl, alkoxy, alkenyl or aryl, R 1a 、R 2a 、R 3a and R 4a One or more of them are alkyl, alkoxy, alkenyl or aryl, and R 5a 、R 6a 、R 7a and R 8a One or more of them are alkyl, alkoxy, alkenyl or aryl].

[0044] (12) The phenylene sulfide-phenylene ether copolymer according to (11), wherein

[0045] In formula (IIa), R 2a 、R 3a 、R 6a and R 7a are independently alkyl, alkoxy, alkenyl or aryl, or R 1a 、R4a 、R 5a and R 8a are each independently an alkyl group, an alkoxy group, an alkenyl group or an aryl group.

[0046] (13) The phenylene sulfide-phenylene ether copolymer according to (10) or (11), wherein

[0047] The content of the structural unit represented by formula (Ia) is 60 mol % or more based on all the structural units.

[0048] (14) The phenylene sulfide-phenylene ether copolymer according to any one of (10) to (13), wherein the dielectric loss tangent tanδ at 80 GHz is 80 and dielectric loss tangent tanδ at 10 GHz 10 ratio tanδ 80 / tanδ 10 Below 1.5.

[0049] (15) A resin composition comprising the phenylene sulfide-phenylene ether copolymer according to any one of (10) to (14).

[0050] (16) A wiring substrate comprising the phenylene sulfide-phenylene ether copolymer according to any one of (10) to (14), or the resin composition according to (15).

[0051] (17) A printed wiring board comprising the wiring substrate described in (16) and an electronic component.

[0052] (18) A wiring board material comprising the phenylene sulfide-phenylene ether copolymer described in any one of (10) to (14), or the resin composition described in (15).

[0053] (19) The wiring board material according to (18), which is a varnish, an interlayer insulating material, a prepreg, a metal-clad laminate, or a substrate.

[0054] (20) A compatibilizer comprising the phenylene sulfide-phenylene ether copolymer described in any one of (10) to (14), or the resin composition described in (15).

[0055] (21) The compatibilizer according to (20), which is a compatibilizer for a resin composition containing a polyarylene sulfide resin and a polyarylene ether resin.

[0056] According to the present disclosure, a resin having a low dielectric loss tangent can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0057] [ Figure 1] (a) is the monomer (3',5'-3,5-DPS) obtained in Synthesis Example 1 1 H-NMR (CD2Cl2) spectrum, (b) is the PMPS-PPO-1 obtained in Example 1 1 H-NMR (CD2Cl2) spectrum.

[0058] [ Figure 2 ] (a) is the monomer (3',5'-3,5-DPS) obtained in Synthesis Example 1 13 C-NMR (CDCl3) spectrum, (b) is the PMPS-PPO-1 obtained in Example 1 13 C-NMR (CDCl3) spectrum.

[0059] [ Figure 3 ] is a coordinate diagram of the dielectric loss tangent at each frequency. DETAILED DESCRIPTION

[0060] Hereinafter, an embodiment of the present disclosure will be described in detail. The present disclosure is not limited to the following embodiments, and can be implemented with appropriate changes within the scope that does not hinder the effects of the present disclosure. Each structure and their combination in each embodiment is an example, and the addition, omission, replacement and other changes of the structure can be appropriately made within the scope that does not deviate from the main purpose of the present disclosure. The present disclosure is not limited by the embodiment, but only by the claims. The various methods disclosed in this specification can be combined with any other features disclosed in this specification. When a specific description recorded for one embodiment is also suitable for other embodiments, its description is sometimes omitted in other embodiments. The expression "X~Y" for the numerical range in this disclosure means "above X and below Y".

[0061] <First embodiment>

[0062] [Phenylene sulfide-phenylene ether copolymer (P1) for wiring boards]

[0063] The phenylene sulfide-phenylene ether copolymer (P1) of the first embodiment is a phenylene sulfide-phenylene ether copolymer for a wiring board, and includes a structural unit represented by formula (I).

[0064] -Ph 1 -O-Ph 2 -S- (I)

[0065] [In formula (I), Ph 1 and Ph 2 Each independently represents a phenylene group which may have a substituent.]

[0066] In one embodiment, preferably Ph 1 and Ph 2At least one of them has one or more substituents.

[0067] In this specification, a "phenylene sulfide-phenylene ether copolymer" refers to a polymer having a phenylene sulfide structure (-Ph-S-) and a phenylene ether structure (-Ph-O-) in one structural unit (Ph represents a phenylene group). Polymers having phenylene sulfide and phenylene ether structures alternating in the molecule are sometimes referred to as "phenylene sulfide-phenylene ether alternating copolymers." "Phenylene sulfide-phenylene ether copolymers" can be obtained, for example, by oxidative polymerization of a disulfide monomer having a phenylene ether backbone. The production method will be described later.

[0068] By including the structural unit represented by formula (I), phenylene sulfide-phenylene ether copolymer (P1) can achieve low dielectric loss tangent. In addition, in formula (I), by making at least one phenylene group have more than one substituent, it is easier to achieve low dielectric loss tangent. These mechanisms are not yet clear at this stage, but as a non-limiting mechanism, it can be considered that by having a phenylene sulfide structure and a phenylene ether structure, the face angle of the phenylene group becomes inconstant, close stacking is suppressed, and the dielectric loss tangent becomes low. Further, it can be considered that when at least one phenylene group has more than one substituent, the torsion angle of the phenylene group becomes difficult to change, thereby, the molecular chain becomes difficult to change, and the dielectric loss tangent is more likely to become low.

[0069] Phenylene sulfide-phenylene ether copolymer (P1) has a low dielectric loss tangent and is therefore suitable for use as a wiring board material. As an additional characteristic, the dielectric loss tangent of the phenylene sulfide-phenylene ether copolymer (P1) is less likely to increase even with increasing frequency bands. This eliminates the need to change the wiring board material design for each frequency, resulting in high versatility and enabling more efficient and economical manufacturing of wiring boards.

[0070] (for wiring substrates)

[0071] In this specification, the term "wiring substrate" in the context of a "wiring substrate" includes all parts of a printed wiring board (also called a printed circuit board) other than electronic components such as semiconductor chips. Generally, a printed wiring board (PCB) consists of a semiconductor package mounted on a base called a substrate, with electronic components such as semiconductor chips mounted on it. Therefore, the term "substrate" in the context of a "wiring substrate" also includes the substrate.

[0072] Therefore, "for wiring boards" means that the phenylene sulfide-phenylene ether copolymer can be used as a material for wiring boards for mounting electronic components such as semiconductor chips and performing wiring.

[0073] The phenylene sulfide-phenylene ether copolymer (P1) for a wiring board of this embodiment has low dielectric loss tangent due to the inclusion of the structural unit represented by formula (I), and can therefore be preferably used as a material for a wiring board.

[0074] (Phenylene sulfide-phenylene ether copolymer (P1))

[0075] The phenylene sulfide-phenylene ether copolymer (P1) comprises a structural unit represented by formula (I),

[0076] -Ph 1 -O-Ph 2 -S- (I)

[0077] [In formula (I), Ph 1 and Ph 2 Each independently represents a phenylene group which may have a substituent.]

[0078] In the present specification, "a phenylene group which may have a substituent" means a substituted or unsubstituted phenylene group.

[0079] In one embodiment, preferably Ph 1 and Ph 2 At least one of the phenylene groups has one or more substituents. “Having one or more substituents” means that one or more hydrogen atoms constituting the phenylene group are substituted with atoms or atomic groups other than hydrogen.

[0080] In formula (I), Ph 1 and Ph 2 When both have substituents, Ph 1 and Ph 2 The types of substituents possessed by each may be the same or different. 1 and Ph 2 The number and position of the substituents in can be the same or different. In one embodiment, preferably Ph 1 and Ph 2 At least one (preferably both) of the substituents has one or more substituents, more preferably two or more substituents, and may have three or four substituents.

[0081] In one embodiment, Ph 1 It may have one or more substituents, two or more substituents, or three or four substituents. 1 Can have 2 substituents. 1 When there are two or more substituents, the substituents may be of the same or different types.

[0082] In one embodiment, Ph 2 It may have one or more substituents, two or more substituents, or three or four substituents. 2 Can have 2 substituents. 2 When there are two or more substituents, the substituents may be of the same or different types.

[0083] In one embodiment, as an additional effect, it is preferable that Ph is 1 and Ph 2 Both of them have one or more substituents, more preferably two or more substituents, and may also have three or four substituents. 1 and Ph 2 Both may have 1 or 2 substituents.

[0084] As a substituent, for example, there can be mentioned: hydroxyl (-OH), carboxyl, amino, cyano (-CN), nitro (-NO2), thiol, sulfo (-SO3H), alkyl, alkenyl, acyl, alkynyl, alkoxy, aryl, and heteroaryl. Among them, from the viewpoint of easily achieving low dielectric loss tangent, the substituent is preferably one or more selected from alkyl, alkoxy, alkenyl and aryl. As a carboxyl group, for example, there can be mentioned C1~10 carboxyl groups. As an amino group, for example, there can be mentioned -NH2, -NHR 11 or -NR 12 R 13 The group represented by (R 11 、R 12 and R 13 Each independently represents a C1 to 10 alkyl group). Examples of the thiol group include -R 14 -SH represented by the group (R 14 represents a C1~10 alkyl group). Examples of the acyl group include R 20 The group represented by C(=O)-(R 20 represents a C1-10 alkyl group). Examples of the alkynyl group include C2-10 alkynyl groups (e.g., ethynyl, propargyl, etc.). Examples of the heteroaryl group include a furan ring, a benzofuran ring, a dibenzofuran ring, a thiophene ring, and a benzothiophene ring.

[0085] Examples of the alkyl group include C1-10 (preferably C1-5, more preferably C1-3, such as C1 or C2) linear, branched, or cyclic alkyl groups. Examples of the C1-10 linear, branched, or cyclic alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, s-isobutyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, n-heptyl, n-octyl, isooctyl, n-nonyl, isononyl, n-decyl, isodecyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups.

[0086] In one embodiment, the alkyl group is preferably methyl, ethyl, and / or isopropyl.

[0087] Examples of the alkoxy group include C1-10 (preferably C1-5, more preferably C1-3, for example, C1 or C2) linear, branched, or cyclic alkoxy groups. Examples of the C1-10 linear, branched, or cyclic alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, sec-butoxy, isobutoxy, n-pentoxy, isopentoxy, neopentoxy, n-hexoxy, isohexoxy, sec-hexoxy, tert-hexoxy, neohexoxy, n-heptoxy, n-octoxy, isooctoxy, n-nonoxy, isononoxy, n-decyloxy, isodecyloxy, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, cyclooctyloxy, cyclononyloxy, and cyclodecyloxy groups.

[0088] In one embodiment, the alkoxy group is preferably a methoxy group and / or an ethoxy group.

[0089] Examples of the alkenyl group include: C2-10 (preferably C2-5, more preferably C2-3) linear, branched or cyclic alkenyl groups. Examples of the C2-10 linear, branched or cyclic alkenyl groups include substituents containing one or more carbon-carbon double bonds in the chain of an alkyl group having 2 or more carbon atoms, specifically vinyl, allyl, 1-propenyl, isopropenyl, 3-butenyl, 2-butenyl, 1-butenyl, 1,3-butadienyl, 4-pentenyl, 3-pentenyl, 2-pentenyl, 1-pentenyl, 1,3-pentadienyl, 2,4-pentadienyl, 1,1-dimethyl-2-propenyl 1-ethyl-2-propenyl, 1,2-dimethyl-1-propenyl, 1-methyl-1-butenyl, 5-hexenyl, 4-hexenyl, 2-hexenyl, 1-hexenyl, 1-methyl-1-hexenyl, 2-methyl-2-hexenyl, 3-methyl-1,3-hexadienyl, 1-heptenyl, 2-octenyl, 3-nonenyl, 4-decenyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, cyclononenyl, cyclodecenyl and the like.

[0090] In one embodiment, the alkenyl group is preferably vinyl and / or allyl.

[0091] Examples of the aryl group include C6-12 aryl groups, specifically phenyl and naphthyl. In one embodiment, the aryl group is preferably phenyl.

[0092] Considering the ease of synthesis of the phenylene sulfide-phenylene ether copolymer (P1), in formula (I), Ph 1 and Ph 2 The one or more substituents optionally possessed by at least one of the alkyl groups are preferably selected from alkyl groups and alkenyl groups, preferably selected from C1-10 alkyl groups and C2-10 alkenyl groups, more preferably selected from C1-4 straight-chain alkyl groups and C2-5 straight-chain alkenyl groups, further preferably contain ethyl, methyl, vinyl and / or allyl groups, and further preferably contain methyl groups.

[0093] Ph 1 The position of the substituent in can be any of the 2-position, 3-position, 5-position or 6-position. In the case of having two substituents, Ph 1 The positions of the substituents in can be 2, 3 (or 5, 6), 2, 5 (or 3, 6), 2, 6, or 3, 5. In the case of having three substituents, Ph 1 The position of the substituent in may be any of the 2, 3, and 5 positions (or the 3, 5, and 6 positions) or the 2, 3, and 6 positions (or the 2, 5, and 6 positions).

[0094] Ph 2 The position of the substituent in can be any of the 2-position, 3-position, 5-position or 6-position. In the case of having two substituents, Ph 2 The positions of the substituents in can be 2, 3 (or 5, 6), 2, 5 (or 3, 6), 2, 6, or 3, 5. In the case of having three substituents, Ph 2 The position of the substituent in may be any of the 2, 3, and 5 positions (or the 3, 5, and 6 positions) or the 2, 3, and 6 positions (or the 2, 5, and 6 positions).

[0095] In one embodiment, at Ph 1 and Ph 2 When any of the two substituents has two substituents, the 1 The 3,5 positions of the alkyl group and the aryl group may have two groups selected from the group consisting of an alkyl group, an alkoxy group, an alkenyl group, and an aryl group. Alternatively, the alkyl group may be present at the position of Ph 2 The 3 and 5 positions of the alkyl group have two groups selected from the group consisting of an alkyl group, an alkoxy group, an alkenyl group, and an aryl group.

[0096] As mentioned above, in Ph 1 and Ph 2When both have substituents, the substituent positions may be the same or different. 1 and Ph 2 When a total of two or more substituents are included, the combination of the substitution positions is not limited.

[0097] In one embodiment, at Ph 1 and Ph 2 In the case of both having two substituents, they can be at positions 3 and 5. In one embodiment, in Ph 1 and Ph 2 When both of these have two substituents, they may have two substituents selected from alkyl groups, alkoxy groups, alkenyl groups, and aryl groups at the 3- and 5-positions.

[0098] In one embodiment, at Ph 1 and Ph 2 When both have two substituents, either one (e.g., Ph 1 ) is substituted at position 3, 5, another (e.g. Ph 2 ) is substituted at 2,6. In one embodiment, in Ph 1 and Ph 2 When both have two substituents, one of them can be (e.g. Ph 1 ) has two selected from alkyl, alkoxy, alkenyl and aryl groups at positions 3 and 5, and the other (e.g. Ph 2 ) has two groups selected from alkyl, alkoxy, alkenyl and aryl groups at the 2 and 6 positions.

[0099] In one embodiment, the structural unit represented by formula (I) preferably includes a structural unit represented by formula (II),

[0100]

[0101] [In formula (II), R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 and R 8 are independently H, alkyl, alkoxy, alkenyl or aryl, R 1 、R 2 、R 3 and R 4 One or more of them are alkyl, alkoxy, alkenyl or aryl, and / or R 5 、R 6 、R 7 and R 8One or more of them are alkyl, alkoxy, alkenyl or aryl].

[0102] Examples and preferred examples of the alkyl group, alkoxy group, alkenyl group, and aryl group in formula (II) include the same groups as those exemplified in the description of formula (I).

[0103] Considering the ease of synthesis of the phenylene sulfide-phenylene ether copolymer (P1), the alkyl, alkoxy, alkenyl or aryl group in formula (II) preferably includes an alkyl group and / or an alkenyl group, more preferably selected from a C1-10 alkyl group and a C2-10 alkenyl group, further preferably includes a C1-4 straight-chain alkyl group and / or a C2-5 straight-chain alkenyl group, further preferably includes an ethyl group, a methyl group, a vinyl group or an allyl group, and further preferably includes a methyl group.

[0104] The position of substitution by alkyl, alkoxy, alkenyl or aryl in formula (II) is not limited, as long as R 1 、R 2 、R 3 and R 4 1 or more (preferably 2 or more, for example 2, 3 or 4) and / or R 5 、R 6 、R 7 and R 8 One or more (preferably two or more, for example, two, three or four) of the above may be sufficient.

[0105] In one embodiment, it is preferable that R 1a 、R 2a 、R 3a and R 4a One or more (preferably two or more, for example, two, three or four) of the R is an alkyl group, an alkoxy group, an alkenyl group or an aryl group, and R 5a 、R 6a 、R 7a and R 8a One or more (preferably two or more, for example, two, three or four) of the groups are alkyl groups, alkoxy groups, alkenyl groups or aryl groups.

[0106] In one embodiment, it may be R 1 、R 2 、R 3 and R 4 2 of them are alkyl, alkoxy, alkenyl or aryl, and R 5 、R 6 、R 7 and R 8 Two of them are alkyl, alkoxy, alkenyl or aryl.

[0107] In one embodiment, the substitution position of the alkyl, alkoxy, alkenyl or aryl group is 1 、R 2 、R 3 and R 4 R 1 , can also be R 2 , can also be R 3 , and / or may also be R 4 , in R 5 、R 6 、R 7 and R 8 R 5 , can also be R 6 , can also be R 7 , and / or may also be R 8 .

[0108] In R 1 、R 2 、R 3 and R 4 When two or more of the alkyl, alkoxy, alkenyl or aryl groups are present, the combination of substitution positions is not limited. 1 、R 2 、R 3 and R 4 When two of them are alkyl, alkoxy, alkenyl or aryl, the substitution position can be R 1 With R 2 、R 1 With R 3 、R 1 With R 4 、R 2 With R 3 、R 2 With R 4 、R 3 With R 4 In R 1 、R 2 、R 3 and R 4 When three of them are alkyl, alkoxy, alkenyl or aryl, the substitution position can be R 1 、R 2 and R 3 、R 1 、R 2 and R 4 、R 1 、R 3 and R 4 , and R 2 、R 3 and R 4 Any combination of .

[0109] In R 5 、R 6 、R 7 and R 8 When two or more of the alkyl, alkoxy, alkenyl or aryl groups are present, the combination of substitution positions is not limited. 5 、R 6 、R 7 and R 8 When two of them are alkyl, alkoxy, alkenyl or aryl, the substitution position can be R 5 With R 6 、R 5 With R 7 、R 5 With R 8 、R 6 With R 7 、R 6 With R 8 、R 7 With R 8 In R 5 、R 6 、R 7 and R 8 When three of them are alkyl, alkoxy, alkenyl or aryl, the substitution position can be R 5 、R 6 and R 7 、R 5 、R 6 and R 8 、R 5 、R 7 and R 8 , and R 6 、R 7 and R 8 Any combination of .

[0110] In one embodiment, R 1 、R 2 、R 3 and R 4 H, R 6 and R 7 Each independently may be an alkyl group, an alkoxy group, an alkenyl group or an aryl group, may be a C1-10 alkyl group or a C2-10 alkenyl group, may be a C1-4 straight-chain alkyl group or a C2-5 straight-chain alkenyl group, may be an ethyl group, a methyl group, a vinyl group or an allyl group, or may be a methyl group.

[0111] In one embodiment, it is preferable that R 2 With R 3 and R6 With R 7 , or R 1 With R 4 and R 6 With R 7 Each is independently an alkyl group, an alkoxy group, an alkenyl group or an aryl group, more preferably a C1-10 alkyl group or a C2-10 alkenyl group, further preferably a C1-4 straight-chain alkyl group or a C2-5 straight-chain alkenyl group, further preferably an ethyl group, a methyl group, a vinyl group or an allyl group, and particularly preferably a methyl group.

[0112] In one embodiment, the structural unit represented by formula (I) preferably includes a structural unit represented by formula (III),

[0113]

[0114] [In formula (III), R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 and R 8 As described in formula (II), n is a number of 4 or more.

[0115] n is preferably 4 to 100, more preferably 4.5 to 50. The phenylene sulfide-phenylene ether copolymer (P1) containing the structural unit represented by formula (III) is a phenylene sulfide-phenylene ether alternating copolymer having a phenylene sulfide structure and a phenylene ether structure alternately in the molecule.

[0116] About R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 and R 8 The description of is the same as that for formula (II).

[0117] In one embodiment, as an example of the structural unit represented by formula (I), the following structural units can be listed, but are not limited to these:

[0118]

[0119]

[0120] In one embodiment, the structural unit represented by formula (I) may include one or more structural units selected from formulas (a) to (q), may include one or more structural units selected from formulas (a) to (d), may include one or more structural units selected from formulas (e) to (k), and may include one or more structural units selected from formulas (m) to (q). In one embodiment, the structural unit represented by formula (I) may include structural units represented by formula (a) and / or formula (b), and may include structural units represented by formula (e) and / or formula (f).

[0121] In one embodiment, the phenylene sulfide-phenylene ether copolymer (P1) for a wiring board may be composed only of the structural unit represented by formula (I), or may contain structural units other than the structural unit represented by formula (I).

[0122] The structural unit represented by formula (I) may be one structural unit or two or more structural units within the range represented by formula (I). The structural unit represented by formula (I) may include two or more structural units having different combinations of substituents exemplified in the description of formula (I).

[0123] As structural units other than the structural units represented by formula (I), one or more of the following may be included: structural units other than the phenylene sulfide-phenylene ether copolymer (P1) having a phenylene sulfide structure and a phenylene ether structure and having one or more substituents; structural units having a phenylene sulfide structure and a phenylene ether structure and not having a substituent; structural units having only a substituted or unsubstituted phenylene sulfide structure; structural units having only a substituted or unsubstituted phenylene ether structure; and / or structural units having neither a phenylene sulfide structure nor a phenylene ether structure.

[0124] In one embodiment, the content of the structural unit represented by formula (I) is preferably 60 mol% or more relative to the total structural units, more preferably 80 mol% or more, and further preferably 90 mol% or more. By making the content of the structural unit represented by formula (I) 60 mol% or more relative to the total structural units, the dielectric loss tangent is more likely to be lowered.

[0125] (Dielectric loss tangent)

[0126] The phenylene sulfide-phenylene ether copolymer (P1) of this embodiment can be preferably used for the production of wiring boards because of its low dielectric loss tangent. The lower the dielectric loss tangent, the easier it is to suppress transmission loss.

[0127] In one embodiment, the dielectric loss tangent of the molded article of the phenylene sulfide-phenylene ether copolymer (P1) at 10 GHz is preferably less than 0.002, more preferably less than 0.0018, and even more preferably less than 0.0017.

[0128] In one embodiment, the dielectric loss tangent of the molded article of the phenylene sulfide-phenylene ether copolymer (P1) at 40 GHz is preferably less than 0.002, more preferably less than 0.0018, and even more preferably less than 0.0017.

[0129] In one embodiment, the dielectric loss tangent of the molded article of the phenylene sulfide-phenylene ether copolymer (P1) at 60 GHz is preferably less than 0.002, more preferably less than 0.0018.

[0130] In one embodiment, the dielectric loss tangent of the molded article of the phenylene sulfide-phenylene ether copolymer (P1) at 80 GHz is preferably less than 0.002, more preferably less than 0.0019.

[0131] The lower the dielectric loss tangent of the phenylene sulfide-phenylene ether copolymer (P1), the easier it is to suppress transmission loss when using the phenylene sulfide-phenylene ether copolymer (P1) or a resin composition containing the phenylene sulfide-phenylene ether copolymer (P1) as a material for a wiring board.

[0132] Resins for general wiring boards tend to have higher dielectric loss tangent as the frequency increases, but the phenylene sulfide-phenylene ether copolymer (P1) of this embodiment has an additional characteristic that the dielectric loss tangent is less likely to increase even if the frequency increases.

[0133] In one embodiment, the dielectric loss tangent tanδ of the molded article of the phenylene sulfide-phenylene ether copolymer (P1) at 80 GHz is 80 and dielectric loss tangent tanδ at 10 GHz 10 ratio tanδ 80 / tanδ 10 It is preferably 1.5 or less, more preferably 1.3 or less, further preferably 1.2 or less, and particularly preferably 1.1 or less.

[0134] Dielectric loss tangent tanδ of molded product at 80GHz 80 and dielectric loss tangent tanδ at 10 GHz 10 ratio tanδ 80 / tanδ 10 Molded products with a dielectric loss tangent of 1.5 or less rarely increase even at higher frequencies, resulting in low frequency dependence. Therefore, there's no need to change the design of wiring board materials for each frequency, resulting in high versatility. As a result, wiring boards can be manufactured more efficiently and economically.

[0135] Methods for adjusting the dielectric loss tangent include adjusting the content of the structural unit represented by formula (I) in the phenylene sulfide-phenylene ether copolymer (P1), or adjusting the presence or absence of substituents in the structural unit represented by formula (I), the number of substituents, etc. By any one or a combination of these methods, the dielectric loss tangent can be adjusted to be lower, and the dielectric loss tangent at 10 GHz, 40 GHz, 60 GHz and 80 GHz can be adjusted to less than 0.002. In addition, the dielectric loss tangent tanδ at 80 GHz can be adjusted to be less than 0.002. 80 and dielectric loss tangent tanδ at 10 GHz 10 ratio tanδ 80 / tanδ 10 For example, the higher the content of the structural unit represented by formula (I) in the phenylene sulfide-phenylene ether copolymer (P1), the lower the dielectric loss tangent. By making Ph in formula (I) 1 and Ph 2 At least one of (preferably both) has one or more substituents, the dielectric loss tangent is more likely to be lowered, and further, by making Ph 1 and Ph 2 Both of them have more than one substituent, which makes it easy to convert tanδ 80 / tanδ 10 Easily adjusted to below 1.5.

[0136] (Dielectric constant)

[0137] In one embodiment, the dielectric constant of the phenylene sulfide-phenylene ether copolymer (P1) at 10 GHz is preferably less than 3.00, more preferably less than 2.90, and further preferably less than 2.80.

[0138] In one embodiment, the dielectric constant of the phenylene sulfide-phenylene ether copolymer (P1) at 40 GHz is preferably less than 3.00, more preferably less than 2.90, further preferably less than 2.80, and particularly preferably less than 2.60.

[0139] In one embodiment, the dielectric constant of the phenylene sulfide-phenylene ether copolymer (P1) at 60 GHz is preferably less than 3.00, more preferably less than 2.90, further preferably less than 2.80, and particularly preferably less than 2.65.

[0140] In one embodiment, the dielectric constant of the phenylene sulfide-phenylene ether copolymer (P1) at 80 GHz is preferably less than 3.00, more preferably less than 2.90, further preferably less than 2.80, and particularly preferably less than 2.65.

[0141] The lower the dielectric constant of the phenylene sulfide-phenylene ether copolymer (P1), the easier it is to suppress transmission loss when the phenylene sulfide-phenylene ether copolymer (P1) or a resin composition containing the phenylene sulfide-phenylene ether copolymer (P1) is used as a material for a wiring board.

[0142] Methods for adjusting the dielectric constant include adjusting the content of the structural unit represented by formula (I) in the phenylene sulfide-phenylene ether copolymer (P1), or adjusting the presence or absence of substituents in the structural unit represented by formula (I), the number of substituents, etc. By any one or a combination of these methods, the dielectric constant can be adjusted to be lower, and the dielectric constant at 10 GHz, 40 GHz, 60 GHz and 80 GHz can be adjusted to be less than 3.00. For example, the more the content of the structural unit represented by formula (I) in the phenylene sulfide-phenylene ether copolymer (P1) is, the easier it is to lower the dielectric constant. By making Ph in formula (I) 1 and Ph 2 When at least one (preferably both) of the two has one or more substituents, the dielectric constant is more likely to be lowered.

[0143] (Determination of dielectric loss tangent and dielectric constant)

[0144] To measure the dielectric loss tangent and dielectric constant, a film of the resin or resin composition adjusted to a thickness of 50 to 250 μm may be heated at 200° C. to 250° C. for 120 minutes to prepare a sample piece of the resin or resin composition for measurement.

[0145] The dielectric loss tangent and dielectric constant can be measured, for example, using a vector network analyzer (N5290A) manufactured by Keysight Technologies and a split cylinder resonator at 10 GHz, 40 GHz, 60 GHz, or 80 GHz under standard environmental conditions (23±2°C) and a relative humidity of 45-55%.

[0146] (Glass transition temperature Tg)

[0147] In one embodiment, the glass transition temperature (Tg) of the phenylene sulfide-phenylene ether copolymer (P1) is preferably higher than 120°C, more preferably higher than 140°C. By setting the glass transition temperature (Tg) to higher than 120°C, the phenylene sulfide-phenylene ether copolymer (P1) can be made to have high heat resistance. The upper limit of the glass transition temperature (Tg) can be, for example, 250°C or lower, or 200°C or lower. The glass transition temperature can be measured by differential scanning calorimetry (DSC) at a temperature increase of 20°C / min from room temperature in accordance with JIS standards (JIS K 7121: Determination of glass transition temperature of plastics).

[0148] (Weight average molecular weight Mw)

[0149] In one embodiment, the weight average molecular weight (Mw) of the phenylene sulfide-phenylene ether copolymer (P1) is not limited within the range that can achieve the effects of the present disclosure, but is preferably less than 30,000. When the weight average molecular weight of the phenylene sulfide-phenylene ether copolymer (P1) is less than 30,000, it may be 28,000 or less, 25,000 or less, or even 24,000 or less.

[0150] The weight average molecular weight (Mw) is a standard polystyrene conversion value determined by GPC measurement using a chloroform solvent.

[0151] [Method for producing phenylene sulfide-phenylene ether copolymer (P1)]

[0152] The production method of the phenylene sulfide-phenylene ether copolymer (P1) is not limited, and it can be produced, for example, by oxidative polymerization of a disulfide monomer having a phenylene ether skeleton.

[0153] As a specific example, Ph in formula (I) is shown 1 and Ph 2 A method for producing a phenylene sulfide-phenylene ether copolymer (P1) having methyl groups at the 3- and 5-positions, respectively.

[0154] First, a disulfide monomer with a phenylene ether skeleton is prepared. Under an inert gas atmosphere (e.g., nitrogen), 4-bromo-2,6-dimethylphenol and 5-iodo-m-xylene are reacted in the presence of copper ferrite, cesium carbonate, and 2,2,6,6-tetramethyl-3,5-heptanedione (THD) in an N-methylpyrrolidone (NMP) solvent at 120-150°C for 18-30 hours to produce a mixture of 5-bromo-2-(3,5-dimethylphenoxy)-1,3-dimethylbenzene and 5-iodo-2-(3,5-dimethylphenoxy)-1,3-dimethylbenzene. The mixture is reacted in an inert gas atmosphere (e.g., nitrogen) in the presence of copper sulfate pentahydrate, potassium hydroxide, and 1,2-ethanedithiol in a DMSO / H2O mixed solvent at 80-140°C for 15-25 hours to obtain 4-(3,5-dimethylphenoxy)-3,5-dimethylbenzenethiol. Chloroform and a methanol solution of iodine are added dropwise with stirring. After reacting at room temperature (24-26°C) for 30 minutes to 2 hours, a 10% by weight aqueous sodium thiosulfate solution is added dropwise to obtain 1,2-bis(4-(3,5-dimethylphenoxy)-3,5-dimethylphenyl) disulfide (hereinafter also referred to as "3',5'-3,5-DPS") as a disulfide monomer having a phenylene ether skeleton.

[0155] Next, 3',5'-3,5-DPS is added to a mixture of DDQ, dichloromethane, and TFA, and the mixture is reacted at room temperature (24-26°C) for 15-25 hours to carry out oxidative polymerization, thereby obtaining poly(3,5-dimethyl-4-(3',5'-dimethyl-1',4'-phenoxy)-1-phenylene sulfide) (hereinafter also referred to as "PMPS-PPO") as a phenylene sulfide-phenylene ether copolymer (P1).

[0156] [Resin composition (C1)]

[0157] The resin composition (C1) of the first embodiment contains the aforementioned phenylene sulfide-phenylene ether copolymer (P1) for wiring substrates. The inclusion of the aforementioned phenylene sulfide-phenylene ether copolymer (P1) allows for a low dielectric loss tangent, making it suitable for use as a resin composition for wiring substrates. The phenylene sulfide-phenylene ether copolymer (P1) is as described above.

[0158] The resin composition (C1) may be composed solely of the aforementioned phenylene sulfide-phenylene ether copolymer (P1) for wiring boards, or may contain other components. Examples of such other components include other resins other than the phenylene sulfide-phenylene ether copolymer for wiring boards, a curing catalyst, a flame retardant, a flame retardant synergist, a fiber reinforcement, an inorganic or organic filler, a thermosetting additive, and / or a thermoplastic additive.

[0159] In one embodiment, the content of the phenylene sulfide-phenylene ether copolymer (P1) in the resin composition (C1) is preferably 30% by mass or more relative to the total amount of the resin composition (C1). When it is 30% by mass or more, it may be 40% by mass or more, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, or even 100% by mass.

[0160] When the content of the phenylene sulfide-phenylene ether copolymer (P1) in the resin composition (C1) is 30% by mass or more, the dielectric loss tangent of the resin composition (C1) tends to be low, and the dielectric constant tends to be low.

[0161] In one embodiment, the content of the above-mentioned phenylene sulfide-phenylene ether copolymer (P1) in the resin component contained in resin combination (C1) is preferably more than 50 mass % relative to the total amount of resin component. In the case of being more than 50 mass %, it can be more than 60 mass %, it can also be more than 70 mass %, it can also be more than 80 mass %, it can also be more than 90 mass %, it can also be more than 95 mass %, it can also be more than 98 mass %, it can also be 100 mass %. By making the content of the phenylene sulfide-phenylene ether copolymer (P1) in resin component be more than 50 mass %, the dielectric loss tangent of resin combination (C1) easily downgrades. In addition, dielectric constant easily downgrades.

[0162] The manufacture method of resin combination (C1) is not limited, and can be carried out by the equipment and method that are usually used for the preparation of resin combination.In general, resin combination (C1) is prepared into the polymer solution (resin varnish) that phenylene sulfide-phenylene ether copolymer is dissolved in organic solvent in many cases.In order to prepare such resin varnish, phenylene sulfide-phenylene ether copolymer (P1) and other components soluble in organic solvent can be added to organic solvent and utilized stirrer to stir etc. and mix.At this point, heating can be carried out as needed.Then, can be dispersed to given dispersion state by appropriately adding component (for example, inorganic filler etc.) that is insoluble in organic solvent and using ball mill, bead mill, planetary mixer, roller mill etc., thereby prepare resin varnish.As the example of organic solvent, the example identical with following " varnish " one item described.

[0163] [Item (A1)]

[0164] The article (A1) of the first embodiment comprises a phenylene sulfide-phenylene ether copolymer (P1) and / or a resin composition (C1). The article (A1) can be used for various purposes and can be preferably used as an insulator component in a terminal of a mobile communication system based on the characteristic of easily having a low dielectric loss tangent. The article (A1) can be used in various applications requiring high-speed communication, for example, it can be carried on network equipment / terminals, servers, AI processors, vehicle-mounted / aviation equipment, home game consoles, etc.

[0165] The dielectric loss tangent of article (A1) at 10 GHz is preferably less than 0.002, more preferably less than 0.0018, and even more preferably less than 0.0017. In one embodiment, the dielectric loss tangent of article (A1) at 40 GHz is preferably less than 0.002, more preferably less than 0.0018, and even more preferably less than 0.0017.

[0166] In one embodiment, the dielectric loss tangent of the article (A1) at 60 GHz is preferably less than 0.002, and more preferably less than 0.0018.

[0167] In one embodiment, the dielectric loss tangent of the article (A1) at 80 GHz is preferably less than 0.002, more preferably less than 0.0019. The lower the dielectric loss tangent of the article (A1), the easier it is to further suppress transmission loss.

[0168] The article (A1) has an additional effect that the dielectric loss tangent is less likely to increase even if the frequency increases.

[0169] In one embodiment, the dielectric loss tangent tanδ of the molded article of article (A1) at 80 GHz is 80 and dielectric loss tangent tanδ at 10 GHz 10 ratio tanδ 80 / tanδ 10 It is preferably 1.5 or less, more preferably 1.3 or less, further preferably 1.2 or less, and particularly preferably 1.1 or less. The dielectric loss tangent at 10 GHz is preferably less than 0.002, more preferably less than 0.001.

[0170] Examples of the article (A1) include wiring boards and wiring board materials.

[0171] (Wiring substrate)

[0172] The wiring board includes a phenylene sulfide-phenylene ether copolymer (P1) and / or a resin composition (C1). Since the wiring board includes the phenylene sulfide-phenylene ether copolymer (P1) and / or the resin composition (C1), a wiring board with a low dielectric loss tangent can be formed.

[0173] The wiring substrate is a substrate for mounting electronic components such as semiconductors and implementing wiring, and is not limited by its structure and / or purpose. In this specification, the wiring substrate includes the parts other than the electronic components other than the semiconductors in the printed wiring board. As the wiring substrate, a printed circuit board (PCB) of the printed wiring board can be exemplified. The printed circuit board can be, for example, a multilayer printed circuit board described in the following "interlayer insulating material". The printed circuit board also includes any substrate among a rigid substrate, a flexible substrate, a rigid-flexible substrate, a metal-based substrate, etc., and electronic components can be mounted on these printed circuit boards to make a printed wiring board. That is, the printed wiring board includes the above-mentioned wiring substrate and electronic components.

[0174] The printed wiring board is not limited to its structure and / or use within the scope of including the above-mentioned wiring substrate and electronic components. For example, the printed wiring board can be a material in which electronic components are mounted on any printed substrate such as a rigid substrate, a flexible substrate, a rigid-flex substrate, or a metal base substrate.

[0175] The electronic components are not limited, and examples thereof include semiconductor chips, resistors, capacitors, etc. As a structure, for example, wiring and electronic components can be mounted on one or both sides of a wiring substrate (printed circuit board), or wiring and electronic components can be mounted between layers of a multi-layer wiring substrate.

[0176] As for applications, for example, a rigid printed wiring board having electronic components mounted on a rigid substrate can be used in terminals, base stations, servers, routers, millimeter-wave radars, probe cards, etc. in mobile communication systems, and a flexible printed wiring board having electronic components mounted on a flexible substrate can be used to connect cables, antennas, antenna cables, etc.

[0177] (Wiring board material)

[0178] A wiring board material is a material for manufacturing a wiring board, and contains a phenylene sulfide-phenylene ether copolymer (P1) and / or a resin composition (C1). The inclusion of the phenylene sulfide-phenylene ether copolymer (P1) or the resin composition (C1) enables formation of a wiring board having a low dielectric loss tangent.

[0179] In one embodiment, the wiring substrate material may be a varnish, an interlayer insulating material, a prepreg, a metal-clad laminate, or a substrate. In one embodiment, the wiring substrate material may be a compatibilizer.

[0180] The varnish comprises a phenylene sulfide-phenylene ether copolymer (P1) and / or a resin composition (C1), and an organic solvent. Examples of the varnish include a polymer solution (resin varnish) in which the phenylene sulfide-phenylene ether copolymer (P1) and / or the resin composition (C1) is dissolved in an organic solvent. In this polymer solution, at least a portion of the polymer is dissolved at a liquid temperature of 25°C, and preferably all of the polymer is dissolved.

[0181] The organic solvent used in the polymer solution is not limited, and those skilled in the art can select from organic solvents known in the art. Examples thereof include acetone, ethyl acetate, cyclohexane, heptane, tetrahydrofuran, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, ethylene glycol, cellosolves, carbitols, anisole, N-methylpyrrolidone, propylene glycol monomethyl ether, methyl ether acetate, toluene, cyclohexanone, methyl ethyl ketone, and methyl isobutyl ketone. One or more organic solvents selected from these can be used in combination.

[0182] The lower limit of the content of the phenylene sulfide-phenylene ether copolymer (P1) in the polymer solution is not particularly limited as long as it is within a range that allows handling and a polymer solution sufficient for commercialization. For example, it may be 5% by mass or more, 7% by mass or more, 10% by mass or more, or 15% by mass or more, relative to 100% by mass of the polymer solution. On the other hand, the upper limit of the content of the phenylene sulfide-phenylene ether copolymer (P1) in the polymer solution may be, for example, 50% by mass or less, 45% by mass or less, 40% by mass or less, or 35% by mass or less, relative to 100% by mass of the polymer solution.

[0183] The interlayer insulating material comprises a phenylene sulfide-phenylene ether copolymer (P1) and / or a resin composition (C1). Examples of the interlayer insulating material include those that can be used for printed wiring boards, etc. This interlayer insulating material can also be used as a material for a multilayer printed wiring board.

[0184] For example, a varnish containing a phenylene sulfide-phenylene ether copolymer (P1) and / or a resin composition (C1) is an example of an interlayer insulating material. This varnish can also be applied to other materials, and the solvent can be volatilized to form an insulating film layer, thereby preparing a laminated structure of a multilayer printed circuit board.

[0185] The prepreg comprises a phenylene sulfide-phenylene ether copolymer (P1) and / or a resin composition (C1), and a substrate. Examples of the prepreg include those obtained by impregnating a substrate with a varnish comprising a phenylene sulfide-phenylene ether copolymer (P1) and / or a resin composition (C1) and an organic solvent and drying the varnish. The substrate used for the prepreg is not limited, and those skilled in the art can select from materials known in the art, including natural fiber substrates, organic synthetic fiber substrates, and inorganic fiber substrates.

[0186] The metal-clad laminate comprises phenylene sulfide-phenylene ether copolymer (P1) and / or resin combination (C1) and metal foil. As the metal-clad laminate, the metal-clad laminate comprising the above-mentioned prepreg can be exemplified. Such a metal-clad laminate can be obtained by, for example, overlapping a plurality of prepregs and heating and pressurizing after overlapping metal foil on one or both sides. Metal foil can exemplify copper foil, aluminum foil, tin foil, gold foil, silver foil, platinum foil, nickel foil etc., and those skilled in the art can select according to characteristic, purposes required by the metal-clad laminate.

[0187] The substrate comprises a phenylene sulfide-phenylene ether copolymer (P1) and / or a resin composition (C1). The substrate is a base used together with semiconductor chips to protect them, such as CPUs and memory chips, and to mount them on printed circuit boards (PCBs). For example, it can be the substrate portion of FC-BGA (Flip Chip-Ball Grid Array) or FC-CSP (Flip Chip Chip Scale Package).

[0188] The compatibilizer comprises a phenylene sulfide-phenylene ether copolymer (P1) and / or a resin composition (C1). Since the phenylene sulfide-phenylene ether copolymer (P1) has a phenylene sulfide structure and a phenylene ether structure (phenylene ether structure), it can be preferably used as a compatibilizer when, for example, a polyarylene sulfide resin is mixed with a polyarylene ether resin.

[0189] In one embodiment, the compatibilizer can be a compatibilizer for a resin composition comprising a polyarylene sulfide resin and a polyarylene ether resin. From the perspective of being easily soluble in a solvent, the polyarylene sulfide resin is preferably a substituted polyarylene sulfide resin having one or more substituents (e.g., a C1-10 alkyl group, a C1-10 alkoxy group, a C1-10 alkenyl group, or an aryl group).

[0190] <Second embodiment>

[0191] [Phenylene sulfide-phenylene ether copolymer (P2)]

[0192] The phenylene sulfide-phenylene ether copolymer (P2) of the second embodiment includes a structural unit represented by formula (Ia),

[0193] -Ph 1a -O-Ph 2a -S- (Ia)

[0194] [In formula (Ia), Ph 1a and Ph 2a Each independently represents a phenylene group which may have a substituent, Ph 1a and Ph 2a each having one or more substituents].

[0195] By including the structural unit represented by formula (Ia), phenylene sulfide-phenylene ether copolymer (P2) can more easily achieve low dielectric loss tangent. In addition, as an additional effect, even if the frequency band becomes higher, the dielectric loss tangent is not easy to become higher. In this case, it is not necessary to change the design of the wiring substrate material for each frequency, and the versatility is higher. Its mechanism is not yet clear at this stage, but as a non-limiting mechanism, it can be considered that: by having a phenylene sulfide structure and a phenylene ether structure, the face angle of the phenylene group becomes non-constant, close stacking is suppressed, and the dielectric loss tangent becomes lower. Further, it can be considered that by making two phenylene groups each have one or more substituents, the torsion angle of the phenylene group becomes less likely to change, thereby, the molecular chain becomes less likely to change, and the dielectric loss tangent is more likely to become lower. Since the dielectric loss tangent is low, the phenylene sulfide-phenylene ether copolymer (P2) can be used in various applications requiring high-speed communication.

[0196] Ph 1a and Ph 2a The types of substituents respectively possessed may be the same or different. 1a and Ph 2a The number and substitution positions of the substituents in the formula (a) may be the same or different.

[0197] Ph 1a and Ph 2a Each has one or more substituents, may have two or more substituents, and may have two, three or four substituents. 1a When there are two or more substituents, the substituents may be of the same type or different types. 2a When there are two or more substituents, the substituents may be of the same or different types.

[0198] Ph 1a The substitution position of the substituent may be any of the 2-position, 3-position, 5-position and 6-position. In the case of having two substituents, Ph 1a The positions of the substituents in can be 2, 3 (or 5, 6), 2, 5 (or 3, 6), 2, 6, or 3, 5. In the case of having three substituents, Ph 1a The position of the substituent in may be any of the 2, 3, and 5 positions (or the 3, 5, and 6 positions) or the 2, 3, and 6 positions (or the 2, 5, and 6 positions).

[0199] Ph 2a The substitution position of the substituent may be any of the 2-position, 3-position, 5-position and 6-position. In the case of having two substituents, Ph 2aThe positions of the substituents in can be 2, 3 (or 5, 6), 2, 5 (or 3, 6), 2, 6, or 3, 5. In the case of having three substituents, Ph 2a The position of the substituent in may be any of the 2, 3, and 5 positions (or the 3, 5, and 6 positions) or the 2, 3, and 6 positions (or the 2, 5, and 6 positions).

[0200] About Ph 1a and Ph 2a The types and preferred types of the substituents can be exemplified by the following: Ph in the formula (I) constituting the phenylene sulfide-phenylene ether copolymer (P1) of the first embodiment. 1 and Ph 2 The substituents optionally possessed are the same as those.

[0201] In one embodiment, it is preferable that Ph is preferably 1a and Ph 2a Both of them have one or more groups selected from an alkyl group, an alkoxy group, an alkenyl group, and an aryl group.

[0202] In one embodiment, considering the ease of synthesis of the phenylene sulfide-phenylene ether copolymer (P2), Ph in formula (Ia) 1a and Ph 2a The one or more substituents are preferably selected from alkyl groups and alkenyl groups, preferably selected from C1-10 alkyl groups and C2-10 alkenyl groups, more preferably selected from C1-4 straight-chain alkyl groups and C2-5 straight-chain alkenyl groups, further preferably include ethyl, methyl, vinyl and / or allyl groups, and further preferably include methyl groups.

[0203] As mentioned above, in Ph 1a and Ph 2a When both have substituents, the substituent positions may be the same or different. 1a and Ph 2a When a total of two or more substituents are contained in each of the groups, the combination of the substitution positions is not limited.

[0204] In one embodiment, at Ph 1a and Ph 2a In the case of both having two substituents, they can be at positions 3 and 5. In one embodiment, in Ph 1a and Ph 2a When both of these have two substituents, they may have two substituents selected from alkyl groups, alkoxy groups, alkenyl groups, and aryl groups at the 3- and 5-positions.

[0205] In one embodiment, at Ph 1aand Ph 2a When both have two substituents, either one (e.g., Ph 1a ) is substituted at position 3, 5, another (e.g. Ph 2a ) is substituted at 2,6. In one embodiment, in Ph 1a and Ph 2a When both have two substituents, one (e.g. Ph 1a ) may have two selected from alkyl, alkoxy, alkenyl and aryl groups at positions 3 and 5, and the other (e.g. Ph 2a ) may have two groups selected from an alkyl group, an alkoxy group, an alkenyl group, and an aryl group at the 2- and 6-positions.

[0206] In one embodiment, the structural unit represented by formula (Ia) preferably includes a structural unit represented by formula (IIa),

[0207]

[0208] [In formula (IIa), R 1a 、R 2a 、R 3a 、R 4a 、R 5a 、R 6a 、R 7a and R 8a are independently H, alkyl, alkoxy, alkenyl or aryl, R 1a 、R 2a 、R 3a and R 4a At least one of them is an alkyl group, an alkoxy group, an alkenyl group or an aryl group, and R 5a 、R 6a 、R 7a and R 8a One or more of them are alkyl, alkoxy, alkenyl or aryl].

[0209] By having the structural unit of formula (IIa), it is easy to have the additional characteristic that the dielectric loss tangent is unlikely to increase even if the frequency increases.

[0210] Examples and preferred examples of the alkyl group, alkoxy group, alkenyl group, and aryl group in formula (IIa) include the same groups as those exemplified in the description of formula (I) constituting the phenylene sulfide-phenylene ether copolymer (P1) in the first embodiment.

[0211] Considering the ease of synthesis of the phenylene sulfide-phenylene ether copolymer (P2), the alkyl, alkoxy, alkenyl or aryl group in formula (IIa) preferably includes an alkyl group and / or an alkenyl group, more preferably selected from a C1~10 alkyl group and a C2~10 alkenyl group, further preferably includes a C1~4 straight-chain alkyl group and / or a C2~5 straight-chain alkenyl group, further preferably includes an ethyl group, a methyl group, a vinyl group and / or an allyl group, and further preferably includes a methyl group.

[0212] The position of substitution by alkyl, alkoxy, alkenyl or aryl in formula (IIa) is not limited, and R 1a 、R 2a 、R 3a and R 4a 1 or more (preferably 2 or more, for example 2, 3 or 4), and R 5a 、R 6a 、R 7a and R 8a One or more (preferably two or more, for example, two, three or four) of the above may be sufficient.

[0213] In one embodiment, R 1a 、R 2a 、R 3a and R 4a 2 of them are alkyl, alkoxy, alkenyl or aryl, and R 5a 、R 6a 、R 7a and R 8a Two of them are alkyl, alkoxy, alkenyl or aryl.

[0214] In one embodiment, the substitution position of the alkyl, alkoxy, alkenyl or aryl group is 1a 、R 2a 、R 3a and R 4a R 1a , can also be R 2a , can also be R 3a , and / or may also be R 4a , in R 5a 、R 6a 、R 7a and R 8a R 5a , can also be R 6a , can also be R 7a , and / or may also be R 8a .

[0215] In R 1a 、R 2a 、R 3a and R 4aWhen two or more of the alkyl, alkoxy, alkenyl or aryl groups are present, the combination of substitution positions is not limited. 1a 、R 2a 、R 3a and R 4a When two of them are alkyl, alkoxy, alkenyl or aryl, the substitution position can be R 1a With R 2a 、R 1a With R 3a 、R 1a With R 4a 、R 2a With R 3a 、R 2a With R 4a 、R 3a With R 4a In R 1a 、R 2a 、R 3a and R 4a When three of them are alkyl, alkoxy, alkenyl or aryl, the substitution position can be R 1a 、R 2a and R 3a 、R 1a 、R 2a and R 4a 、R 1a 、R 3a and R 4a , and R 2a 、R 3a and R 4a Any combination of .

[0216] In R 5a 、R 6a 、R 7a and R 8a When two or more of the alkyl, alkoxy, alkenyl or aryl groups are present, the combination of substitution positions is not limited. 5a 、R 6a 、R 7a and R 8a When two of them are alkyl, alkoxy, alkenyl or aryl, the substitution position can be R 5a With R 6a 、R 5a With R 7a 、R 5a With R 8a 、R 6a With R 7a 、R 6a With R 8a 、R 7a With R 8a In R5a 、R 6a 、R 7a and R 8a When three of them are alkyl, alkoxy, alkenyl or aryl, the substitution position can be R 5a 、R 6a and R 7a 、R 5a 、R 6a and R 8a 、R 5a 、R 7a and R 8a , and R 6a 、R 7a and R 8a Any combination of .

[0217] In one embodiment, R 2a With R 3a and R 6a With R 7a , or R 1a With R 4a and R 6a With R 7a Each independently is preferably an alkyl group, an alkoxy group, an alkenyl group or an aryl group, more preferably a C1-10 alkyl group or a C2-10 alkenyl group, further preferably a C1-4 straight-chain alkyl group or a C2-5 straight-chain alkenyl group, further preferably an ethyl group, a methyl group, a vinyl group or an allyl group, and particularly preferably a methyl group.

[0218] In one embodiment, the structural unit represented by formula (Ia) preferably includes a structural unit represented by formula (IIIa),

[0219]

[0220] [In formula (IIIa), R 1a 、R 2a 、R 3a 、R 4a 、R 5a 、R 6a 、R 7a and R 8a As described in formula (IIa), n is a number of 4 or more.

[0221] n is preferably 4 to 100, more preferably 4.5 to 50. The phenylene sulfide-phenylene ether copolymer (P2) containing the structural unit represented by formula (IIIa) is a phenylene sulfide-phenylene ether alternating copolymer having a phenylene sulfide structure and a phenylene ether structure alternately in the molecule.

[0222] About R 1a 、R 2a 、R 3a 、R4a 、R 5a 、R 6a 、R 7a and R 8a The description is the same as that for formula (IIa).

[0223] In one embodiment, as an example of the structural unit represented by formula (Ia), the following structural units can be listed, but are not limited to these:

[0224]

[0225]

[0226] In one embodiment, the structural unit represented by formula (Ia) may include one or more structural units selected from formulas (e) to (k), and formulas (m) to (q). In one embodiment, the structural unit represented by formula (Ia) may also include structural units represented by formula (e) and / or formula (f).

[0227] In one embodiment, the phenylene sulfide-phenylene ether copolymer (P2) may be composed only of the structural unit represented by formula (Ia), or may contain structural units other than the structural unit represented by formula (Ia).

[0228] The structural unit represented by formula (Ia) may be one structural unit or two or more structural units within the range represented by formula (Ia). The structural unit represented by formula (Ia) may include two or more structural units having different combinations of substituents exemplified in the description of formula (Ia).

[0229] Structural units other than the structural units represented by formula (Ia) may include one or more of the following: structural units having a phenylene sulfide structure and a phenylene ether structure other than the phenylene sulfide-phenylene ether copolymer (P2) and having one or more substituents; structural units having a phenylene sulfide structure and a phenylene ether structure and not having a substituent; structural units having only a substituted or unsubstituted phenylene sulfide structure; structural units having only a substituted or unsubstituted phenylene ether structure; and / or structural units having neither a phenylene sulfide structure nor a phenylene ether structure.

[0230] In one embodiment, the content of the structural unit represented by formula (Ia) is preferably 60 mol% or more relative to the total structural units, more preferably 80 mol% or more, and further preferably 90 mol% or more. By making the content of the structural unit represented by formula (Ia) 60 mol% or more relative to the total structural units, the dielectric loss tangent is more likely to be lowered.

[0231] (Dielectric loss tangent)

[0232] The phenylene sulfide-phenylene ether copolymer (P2) of this embodiment can be preferably used for the production of a wiring board due to its low dielectric loss tangent. The lower the dielectric loss tangent, the easier it is to suppress transmission loss.

[0233] In one embodiment, the dielectric loss tangent of the molded article of the phenylene sulfide-phenylene ether copolymer (P2) at 10 GHz is preferably less than 0.002, more preferably less than 0.0018, and even more preferably less than 0.0017.

[0234] In one embodiment, the dielectric loss tangent of the molded article of the phenylene sulfide-phenylene ether copolymer (P2) at 40 GHz is preferably less than 0.002, more preferably less than 0.0018, and even more preferably less than 0.0017.

[0235] In one embodiment, the dielectric loss tangent of the molded article of the phenylene sulfide-phenylene ether copolymer (P2) at 60 GHz is preferably less than 0.002, more preferably less than 0.0018.

[0236] In one embodiment, the dielectric loss tangent of the molded article of the phenylene sulfide-phenylene ether copolymer (P2) at 80 GHz is preferably less than 0.002, more preferably less than 0.0019.

[0237] The lower the dielectric loss tangent of the phenylene sulfide-phenylene ether copolymer (P2), the easier it is to suppress transmission loss when the phenylene sulfide-phenylene ether copolymer (P2) or a resin composition containing the phenylene sulfide-phenylene ether copolymer (P2) is used as a material for a wiring board.

[0238] Resins used in general wiring boards tend to have higher dielectric loss tangent as the frequency increases. However, the phenylene sulfide-phenylene ether copolymer (P2) of this embodiment has an additional characteristic that the dielectric loss tangent is less likely to increase even if the frequency increases.

[0239] In one embodiment, the dielectric loss tangent tanδ of the molded article of the phenylene sulfide-phenylene ether copolymer (P2) at 80 GHz is 80 and dielectric loss tangent tanδ at 10 GHz 10 ratio tanδ 80 / tanδ 10 It is preferably 1.5 or less, more preferably 1.3 or less, further preferably 1.2 or less, and particularly preferably 1.1 or less.

[0240] Dielectric loss tangent tanδ of molded product at 80GHz 80 and dielectric loss tangent tanδ at 10 GHz 10 ratio tanδ 80 / tanδ10 Molded products with a dielectric loss tangent of 1.5 or less rarely increase even at higher frequencies, resulting in low frequency dependence. Therefore, there's no need to change the design of wiring board materials for each frequency, resulting in high versatility. As a result, wiring boards can be manufactured more efficiently and economically.

[0241] The method for adjusting the dielectric loss tangent can be exemplified by the same method as described in the section on the phenylene sulfide-phenylene ether copolymer (P1).

[0242] The ranges, adjustment methods, and measurement methods of the dielectric constant, glass transition temperature, and weight average molecular weight (Mw) of the phenylene sulfide-phenylene ether copolymer (P2) are the same as those described for the phenylene sulfide-phenylene ether copolymer (P1) in the first embodiment.

[0243] As a method for producing the phenylene sulfide-phenylene ether copolymer (P2), the method described for the phenylene sulfide-phenylene ether copolymer (P1) in the first embodiment can be exemplified.

[0244] [Resin composition (C2)]

[0245] The resin composition (C2) of the second embodiment includes the aforementioned phenylene sulfide-phenylene ether copolymer (P2). Due to the inclusion of the aforementioned phenylene sulfide-phenylene ether copolymer (P2), a low dielectric loss tangent can be achieved. Furthermore, as an additional characteristic, the dielectric loss tangent is less likely to increase even when the frequency band increases. The phenylene sulfide-phenylene ether copolymer (P2) is as described above.

[0246] The resin composition (C2) may consist of only the phenylene sulfide-phenylene ether copolymer (P2), or may contain other components. Examples of the other components include the same other components that may be contained in the resin composition (C1) in the first embodiment.

[0247] The content of the phenylene sulfide-phenylene ether copolymer (P2) in the resin composition (C2) and the content of the phenylene sulfide-phenylene ether copolymer (P2) in the resin component contained in the resin composition (C2) can be exemplified by the same ranges as the content of the phenylene sulfide-phenylene ether copolymer (P1) in the resin composition (C1) and the content of the phenylene sulfide-phenylene ether copolymer (P1) in the resin component contained in the resin composition (C1).

[0248] As the method for producing the resin composition (C2), the same method as the method for producing the resin composition (C1) in the first embodiment can be exemplified.

[0249] [Item (A2)]

[0250] The article (A2) of the second embodiment includes a phenylene sulfide-phenylene ether copolymer (P2) and / or a resin composition (C2). Article (A2) can be used for various purposes and can be preferably used as an insulator component in a terminal of a mobile communication system based on the characteristic of easily having a low dielectric loss tangent. In particular, it can be used in various applications requiring high-speed communication, for example, it can be carried on network equipment / terminals, servers, AI processors, vehicle-mounted / aviation equipment, home game consoles, etc.

[0251] The ranges, adjustment methods, and measurement methods of the dielectric loss tangent and dielectric constant of the article (A2) are the same as those described for the article (A1) in the first embodiment.

[0252] Examples of the article (A2) include a wiring board, a wiring board material, and a compatibilizer.

[0253] The wiring substrate contains a phenylene sulfide-phenylene ether copolymer (P2) and / or a resin composition (C2).

[0254] The wiring substrate material comprises a phenylene sulfide-phenylene ether copolymer (P2) and / or a resin composition (C2). In one embodiment, the wiring substrate material can be a varnish, an interlayer insulating material, a prepreg, a metal-clad laminate, or a substrate.

[0255] The varnish comprises a phenylene sulfide-phenylene ether copolymer (P2) and / or a resin composition (C2), and an organic solvent. The interlayer insulating material comprises a phenylene sulfide-phenylene ether copolymer (P2) and / or a resin composition (C2). The prepreg comprises a phenylene sulfide-phenylene ether copolymer (P2) and / or a resin composition (C2), and a substrate. The metal-clad laminate comprises a phenylene sulfide-phenylene ether copolymer (P2) and / or a resin composition (C2), and a metal foil. The substrate comprises a phenylene sulfide-phenylene ether copolymer (P2) and / or a resin composition (C2).

[0256] The other descriptions regarding the wiring board and various wiring board materials in the first embodiment also apply here.

[0257] The compatibilizer comprises a phenylene sulfide-phenylene ether copolymer (P2) and / or a resin composition (C2). In one embodiment, the compatibilizer can be a compatibilizer for a resin composition comprising a polyarylene sulfide resin and a polyarylene ether resin. From the perspective of being easily soluble in a solvent, the polyarylene sulfide resin is preferably a substituted polyarylene sulfide resin having one or more substituents (e.g., C1-10 alkyl, C1-10 alkoxy, C1-10 alkenyl, or aryl). The other descriptions regarding the compatibilizer in the first embodiment also apply here.

[0258] <Other embodiments>

[0259] (use)

[0260] In one embodiment, a phenylene sulfide-phenylene ether copolymer may be provided for use in manufacturing a wiring substrate. The phenylene sulfide-phenylene ether copolymer comprises a structural unit represented by formula (I).

[0261] -Ph 1 -O-Ph 2 -S- (I)

[0262] [In formula (I), Ph 1 and Ph 2 Each independently represents a phenylene group which may have a substituent.]

[0263] The description of formula (I) is the same as that described in the first embodiment.

[0264] (Method for Manufacturing Wiring Board)

[0265] In one embodiment, a method for manufacturing a wiring substrate may be provided, the method comprising forming a phenylene sulfide-phenylene ether copolymer comprising a structural unit represented by formula (I),

[0266] -Ph 1 -O-Ph 2 -S- (I)

[0267] [In formula (I), Ph 1 and Ph 2 Each independently represents a phenylene group which may have a substituent.]

[0268] The molding method is not limited, and examples thereof include heat pressing or heat compression bonding using known equipment and methods. The explanation of formula (I) is the same as that described in the first embodiment.

[0269] Example

[0270] The present disclosure will be described in more detail below with reference to examples, but the present disclosure is not to be construed as being limited to these examples.

[0271] The corresponding poly(phenylene sulfide) derivatives are obtained through the oxidative polymerization of various aromatic disulfides. The present inventors have successfully synthesized a new copolymer P1 of dimethyl-substituted PPS and poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) by oxidative polymerization of a disulfide monomer M1 having a phenylene ether backbone (see Scheme).

[0272] plan:

[0273]

[0274] P1 is a high molecular weight product (for example, Mw is 2.3×10 4) is obtained in the form of amorphous and general organic solvents, exhibits high heat resistance (for example, glass transition temperature Tg>120°C). Furthermore, it has been confirmed that it exhibits a low dielectric constant comparable to that of PPO. Examples are shown below.

[0275] [Synthesis Example 1] (Synthesis of Monomer)

[0276] The monomers for producing a phenylene sulfide-phenylene ether copolymer were prepared. The reaction scheme is shown below.

[0277] [Scheme 1]:

[0278]

[0279] According to Scheme 1(a), 4-bromo-2,6-dimethylphenol (81 mmol, 1 equivalent, 16.2 g), 5-iodo-m-xylene (323 mmol, 4 equivalents, 75 g), copper ferrite (8.1 mmol, 0.1 equivalent, 1.94 g), cesium carbonate (162 mmol, 2 equivalents, 52.8 g), 2,2,6,6-tetramethyl-3,5-heptanedione (THD) (16.2 mmol, 0.2 equivalents, 3.3 mL), and NMP (162 mL) were added to a 1000 mL pear-shaped flask and stirred at 135° C. for 24 hours under a nitrogen atmosphere.

[0280] After silica gel filtration, separation (ether / saturated brine / 5 wt% potassium hydroxide aqueous solution), dehydration (sodium sulfate), solvent removal, and column chromatography (hexane), a mixture of compound (1) and compound (2) was obtained as a white solid (compound (1): compound (2) = 1.6:1 (mol / mol)). It should be noted that compound (2) is a by-product of the Ullman coupling, presumably due to halogen exchange between bromo and iodo groups between the raw materials or products, and is difficult to separate using the above-mentioned column chromatography.

[0281] Next, according to Scheme 1(b), a mixture of Compound (1) and Compound (2) (Compound (1): Compound (2) = 26.6:16.6 (mmol / mmol), 1 equivalent, 14.0 g), copper sulfate pentahydrate (2.16 mmol, 0.05 equivalent, 39 mg), potassium hydroxide (216 mmol, 5 equivalents, 12 g), 1,2-ethanedithiol (43.2 mmol, 2 equivalents, 3.6 mL), and a DMSO / H2O (100 mL / 10 mL) mixed solvent were added to a 1000 mL pear-shaped flask and stirred at 110°C for 20 hours under a nitrogen atmosphere. After separation (ethyl acetate / 5 vol% hydrochloric acid, pure water, 3.5 wt% saline), dehydration (sodium sulfate), solvent removal, and column chromatography (hexane / chloroform = 5 / 1 (v / v)), Compound (3) was obtained as a white solid.

[0282] Next, according to Scheme 1(c), compound (3) (16 mmol, 1 equivalent, 4.1 g) and chloroform (50 mL) were added to a 100 mL pear-shaped flask. A methanol solution (25 mL) of iodine (8.0 mmol, 0.5 equivalent, 2.0 g) was added dropwise, and the mixture was stirred at room temperature for 1 hour. After the reaction, a 10 wt% aqueous sodium thiosulfate solution was added dropwise until the color of the solution stopped changing. After separation (chloroform / 5 vol% hydrochloric acid, 5 wt% aqueous sodium hydroxide solution, 3.5 wt% saline), dehydration (sodium sulfate), solvent removal, and column chromatography (hexane / chloroform = 3 / 1 (v / v)), 1,2-bis(4-(3,5-dimethylphenoxy)-3,5-dimethylphenyl) disulfide (3',5'-3,5-DPS) (7.8 mmol, 4.0 g) was obtained as a white solid.

[0283] The resulting 3',5'-3,5-DPS 1 H-NMR (CD2Cl2) spectrum is shown in Figure 1 (a) 13 C-NMR (CDCl3) spectrum is shown in Figure 2 (a). The identification results are shown below. It should be noted that, below, a~j and Figure 1 、 2 a~j in the structural formula shown correspond to each other.

[0284] 1 H-NMR (δ:ppm, CD2Cl2): 7.26(s,2H,i), 6.62(s,1H,a), 6.36(s,2H,d), 2.22(s,6H,b), 2.08(s,6H,g)

[0285] 13CNMR (δ: ppm, DCl3): 157.6(e), 151.0(f), 139.5(c), 132.8(j), 132.6(h), 129.2(i), 123.4(a), 112.2(d), 21.4(b), 16.5(g)

[0286] FAB-MS(m / z): 514.2(calc.), 514.5(found)

[0287] [Example 1] PMPS-PPO-1

[0288] Using 3',5'-3,5-DPS as a monomer, a phenylene sulfide-phenylene ether copolymer was produced according to Example 1. The reaction scheme is shown below.

[0289] [Scheme 2]:

[0290]

[0291] According to Scheme 2, 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ, 2.63 mmol, 1 equivalent, 597 mg), dichloromethane, and trifluoroacetic acid (TFA) were added to a 50 mL pear-shaped flask and mixed thoroughly. Then, 3',5'-3,5-DPS (2.63 mmol, 1 equivalent, 1.35 g) was added and stirred at room temperature for 20 hours. After the reaction, dichloromethane (25 mL) was added. The mixture was filtered through a glass filter to remove DDH, purified by precipitation into 2.5 vol% hydrochloric acid-containing methanol (250 mL) and recovered on a glass filter, and purified by precipitation into 2.5 vol% hydrochloric acid-containing 2-propanol and recovered on a glass filter to obtain poly(3,5-dimethyl-4-(3',5'-dimethyl-1',4'-phenoxy)-1-phenylene sulfide) (PMPS-PPO-1) as a white powder.

[0292] In Scheme 2, CH2Cl2 is the solvent, DDQ is the oxidant (1 equivalent relative to 3',5'-3,5-DPS), the reaction time is 20 hours, the reaction temperature is room temperature, and the n of PMPS-PPO-1 is 28.

[0293] The obtained PMPS-PPO-1 1 H-NMR (CD2Cl2) spectrum is shown in Figure 1 (b) 13 C-NMR (CDCl3) spectrum is shown in Figure 2 (b).

[0294] exist 1 In H-NMR, the peak integration value of the aromatic ring and the methyl group was observed at 1:3. 13Ten peaks were observed in CNMR, supporting a structure in which oxygen atoms were selectively substituted at the p-position.

[0295] [Example 2] PMPS-PPO-2

[0296] DDQ (2.63 mmol, 1 equivalent, 597 mg), dichloromethane, and TFA were added to a 50 mL pear-shaped flask and mixed thoroughly. Then, 3',5'-2,6-DPS (2.63 mmol, 1 equivalent, 1.35 g) was added and stirred at room temperature for 20 hours. After the reaction, dichloromethane (25 mL) was added. The mixture was filtered through a glass filter to remove DDH, purified by precipitation into 2.5 vol% hydrochloric acid-containing methanol (250 mL) and recovered using a glass filter, and purified by precipitation into hexane and recovered using a glass filter to obtain poly(2,6-dimethyl-4-(3',5'-dimethyl-1',4'-phenoxy)-1-phenylene sulfide) (PMPS-PPO-2) as a yellow powder.

[0297] PMPS-PPO-2 has the following structural formula:

[0298] .

[0299] n is 4.7.

[0300] [Comparative Examples 1 and 2]

[0301] The following resins were used as the resins in Comparative Examples 1 and 2.

[0302] PPS: Unsubstituted polyphenylene sulfide resin

[0303] PPO: 3,5-dimethyl polyphenylene ether resin

[0304] [Comparative Example 3]

[0305] 3,5-Dimethyl polyphenylene ether resin (PPO) and 3,5-dimethyl PPS (DMPPS) were melt-mixed at a mass ratio of 1:1 to obtain a resin composition of Comparative Example 3 (PPO / DMPPS 1 / 1).

[0306] [Reference example]

[0307] As a reference example, 3,5-dimethyl PPS (DMPPS) was prepared.

[0308] In a nitrogen atmosphere, 56 mL of dichloromethane was introduced into a 100 mL three-necked flask. 3,3'-dimethyldiphenyl disulfide (11.5 g, 42 mmol), 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ, 42 mmol) and trifluoromethanesulfonic acid (8.4 mmol) were added thereto and stirred at room temperature for 6 hours to perform oxidative polymerization. The reaction solution was added dropwise to hydrochloric acid-acidified methanol and the powder was recovered by filtration. The powder was then washed with potassium hydroxide aqueous solution (0.1 M) and pure water and vacuum dried to obtain a polymer.

[0309] [Measurement]

[0310] (Weight average molecular weight Mw)

[0311] The weight average molecular weight (Mw) of each resin in Examples 1 and 2, Comparative Examples 1 and 2, and Reference Example was measured by gel permeation chromatography (GPC) in terms of polystyrene.

[0312] (Glass transition temperature Tg)

[0313] The glass transition temperature (Tg) of each resin in Examples 1 and 2, Comparative Examples 1 and 2, and Reference Example was measured by differential scanning calorimetry (DSC) in accordance with JIS standards (JIS K 7121: Determination of glass transition temperature of plastics) at a temperature increase of 20°C / min from room temperature. The results are shown in Table 1.

[0314] (Determination of dielectric loss tangent and dielectric constant)

[0315] In order to measure the dielectric loss tangent and dielectric constant, for each resin of Examples 1 and 2, Comparative Examples 1 and 2, and the reference example, a resin film prepared to a thickness of 100 μm was heated from room temperature at a rate of 5°C / min under vacuum, a pressure of 5 kN was applied, and the film was maintained at 240°C for 120 minutes to prepare resin sample pieces for measurement.

[0316] The dielectric loss tangent and dielectric constant were measured using a Keysight Technologies vector network analyzer (N5290A) and a split-cylinder resonator using the cavity resonator perturbation method at 10 GHz in a standard environment (23 ± 2°C) and a relative humidity of 45-55%. The results are shown in Table 1.

[0317]

[0318] (Frequency dependence of dielectric loss tangent)

[0319] For the resins of Example 1, Comparative Examples 1 to 3, and Reference Example, the dielectric loss tangent at 40 GHz, 60 GHz, and 80 GHz was measured under the same conditions as above for the same resin specimens as above. The dielectric loss tangent tanδ at 80 GHz was calculated. 80 Compared with the dielectric loss tangent tanδ at 10 GHz shown in Table 1 10 ratio tanδ 80 / tanδ 10 The results are shown in Table 2. Figure 3 , a graph is shown with frequency (GHz) as the horizontal axis and dielectric loss tangent as the vertical axis.

[0320]

[0321] As shown in Table 1, the phenylene sulfide-phenylene ether copolymers of Examples 1 and 2 both had a dielectric loss tangent of less than 0.002 at 10 GHz, demonstrating low dielectric loss tangent. Furthermore, the glass transition temperature (Tg) exceeded 140°C, demonstrating heat resistance.

[0322] As shown in Table 2 and Figure 3 As shown in FIG. 1 , the dielectric loss tangent tanδ of the molded product of the phenylene sulfide-phenylene ether copolymer of Example 1 at 80 GHz is 80 and dielectric loss tangent tanδ at 10 GHz 10 ratio tanδ 80 / tanδ 10 By being 1.5 or less, an additional effect is obtained in that the dielectric loss tangent is less likely to increase even if the frequency increases.

[0323] Industrial Applicability

[0324] The phenylene sulfide-phenylene ether copolymer of the present embodiment can achieve a low dielectric loss tangent and can therefore be used in various applications requiring high-speed communication, thus having industrial applicability.

Claims

1. A phenylene sulfide-phenylene ether copolymer for a wiring substrate, comprising a structural unit represented by formula (I), -Ph 1 -O-Ph 2 -S- (I) In formula (I), Ph 1 and Ph 2 Each independently represents a phenylene group which may have a substituent.

2. The phenylene sulfide-phenylene ether copolymer according to claim 1, wherein In formula (I), Ph 1 and Ph 2 At least one of them has one or more substituents.

3. The phenylene sulfide-phenylene ether copolymer according to claim 1 or 2, wherein The structural unit represented by formula (I) contains the structural unit represented by formula (II), ， In formula (II), R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 and R 8 are independently H, alkyl, alkoxy, alkenyl or aryl, R 1 、R 2 、R 3 and R 4 One or more of them are alkyl, alkoxy, alkenyl or aryl, and / or R 5 、R 6 、R 7 and R 8 One or more of them are alkyl, alkoxy, alkenyl or aryl.

4. The phenylene sulfide-phenylene ether copolymer according to claim 3, wherein In formula (II), R 1 、R 2 、R 3 and R 4 One or more of them are alkyl, alkoxy, alkenyl or aryl, and R 5 、R 6 、R 7 and R 8 One or more of them are alkyl, alkoxy, alkenyl or aryl.

5. The phenylene sulfide-phenylene ether copolymer according to claim 1 or 2, wherein The content of the structural unit represented by formula (I) is 60 mol % or more based on all the structural units. The phenylene sulfide-phenylene ether copolymer according to claim 1 or 2, wherein the dielectric loss tangent at 10 GHz is less than 0.

002.

7. The phenylene sulfide-phenylene ether copolymer according to claim 1 or 2, wherein the dielectric loss tangent at 80 GHz is less than 0.

002.

8. The phenylene sulfide-phenylene ether copolymer according to claim 1 or 2, having a dielectric loss tangent tan δ at 80 GHz. 80 and dielectric loss tangent tanδ at 10 GHz 10 ratio tanδ 80 / tanδ 10 Below 1.

5. 9 . A resin composition comprising the phenylene sulfide-phenylene ether copolymer according to claim 1 .

10. A phenylene sulfide-phenylene ether copolymer comprising a structural unit represented by formula (Ia), -Ph 1a -O-Ph 2a -S- (Ia) In formula (Ia), Ph 1a and Ph 2a Each independently represents a phenylene group which may have a substituent, Ph 1a and Ph 2a Each has one or more substituents.

11. The phenylene sulfide-phenylene ether copolymer according to claim 10, wherein The structural unit represented by formula (Ia) includes the structural unit represented by formula (IIa), ， In formula (IIa), R 1a 、R 2a 、R 3a 、R 4a 、R 5a 、R 6a 、R 7a and R 8a are independently H, alkyl, alkoxy, alkenyl or aryl, R 1a 、R 2a 、R 3a , and R 4a One or more of them are alkyl, alkoxy, alkenyl or aryl, and R 5a 、R 6a 、R 7a and R 8a One or more of them are alkyl, alkoxy, alkenyl or aryl.

12. The phenylene sulfide-phenylene ether copolymer according to claim 11, wherein In formula (IIa), R 2a 、R 3a 、R 6a and R 7a are independently alkyl, alkoxy, alkenyl or aryl, or R 1a 、R 4a 、R 5a and R 8a are each independently an alkyl group, an alkoxy group, an alkenyl group or an aryl group.

13. The phenylene sulfide-phenylene ether copolymer according to claim 10 or 11, wherein The content of the structural unit represented by formula (Ia) is 60 mol % or more based on all the structural units.

14. The phenylene sulfide-phenylene ether copolymer according to claim 10 or 11, wherein the dielectric loss tangent tanδ at 80 GHz is 80 and dielectric loss tangent tanδ at 10 GHz 10 ratio tanδ 80 / tanδ 10 Below 1.

5. A resin composition comprising the phenylene sulfide-phenylene ether copolymer according to claim 10 . 16 . A wiring board comprising the phenylene sulfide-phenylene ether copolymer according to claim 1 , 2, 10 or 11 , or the resin composition according to claim 9 or 15 .

17. A printed wiring board comprising: The wiring substrate according to claim 16, and Electronic components. 18 . A wiring board material comprising the phenylene sulfide-phenylene ether copolymer according to claim 1 , 2, 10 or 11 , or the resin composition according to claim 9 or 15 .

19. The wiring board material according to claim 18, which is a varnish, an interlayer insulating material, a prepreg, a metal-clad laminate, or a substrate. 20 . A compatibilizer comprising the phenylene sulfide-phenylene ether copolymer according to claim 1 , 2, 10 or 11 , or the resin composition according to claim 15 . The compatibilizer according to claim 20, which is a compatibilizer for a resin composition comprising a polyarylene sulfide resin and a polyarylene ether resin.

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