Substituted polyphenylene sulfide resin

Abstract

The present invention provides a resin having a low dielectric loss tangent. This substituted polyphenylene sulfide resin contains a structural unit represented by general formula (I), in which R1, R2, R3 and R4 are each independently H, an alkyl group, an alkoxy group, or an alkenyl group-containing organic group, and at least one of R1, R2, R3 and R4 is an alkyl group or an alkoxy group. # imgabs0 #

Description

Technical Field

[0001] The present disclosure relates to a substituted polyphenylene sulfide resin. Background Art

[0002] In recent years, the high-speed / large-capacity of mobile communication systems has been developing. With the progress of such mobile communication systems, higher frequency bands have been used in communication. For example, in the fifth-generation mobile communication system that has started practical use, a higher frequency band than that of the previous fourth-generation mobile communication system is used.

[0003] For terminals of mobile communication systems, attenuation of electrical signals through the circuits of printed wiring boards, so-called transmission loss, occurs. The transmission loss also depends on the dielectric properties of the substrates (dielectrics) of printed wiring boards. Generally, the higher the frequency used, the greater the influence of the tangent of the dielectric loss angle, and the greater the transmission loss.

[0004] In order to achieve faster mobile communication, it is required to suppress the transmission loss of printed wiring boards used for high-frequency band communication. Therefore, resins and resin compositions used as materials for printed wiring boards are also required to have low transmission loss. In order to achieve low transmission loss, resins and resin compositions with a low tangent of the dielectric loss angle are required.

[0005] As materials for wiring substrates such as printed wiring boards, resin compositions mainly composed of polyphenylene ether (PPE) resins (for example, Patent Document 1 etc.) and polyphenylene sulfide (PPS) resins (for example, Patent Documents 2 and 3 etc.) have been widely used in the past. However, since PPE resins themselves have low flame retardancy, there is a problem that in order to use them as materials for wiring substrates, it is necessary to mix with flame retardant materials to impart flame retardancy to the resin composition. In addition, unsubstituted PPS resins have a high tangent of the dielectric loss angle, so there is a problem that the transmission loss also becomes high in high-frequency band communication applications.

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

[0010] In view of the above problems, the inventors of the present application conducted in-depth research and found that a substituted polyphenylene sulfide (also referred to as substituted PPS) resin containing a structural unit represented by a given chemical formula has a low tangent of the dielectric loss angle.

[0011] That is, the present disclosure has the following aspects.

[0012] [1] First aspect

[0013] [1-1] A substituted polyphenylene sulfide resin for a wiring substrate, which contains a structural unit represented by the general formula (I),

[0014]

[0015] [In the formula (I), R1, R2, R3 and R4 are each independently H, an alkyl group, an alkoxy group, or an organic group containing an alkenyl group, and one or more of R1, R2, R3 and R4 are an alkyl group or an alkoxy group].

[0016] [1-2] The substituted polyphenylene sulfide resin for a wiring substrate according to [1-1], wherein the dielectric loss tangent at 10 GHz is less than 0.002.

[0017] [1-3] The substituted polyphenylene sulfide resin for a wiring substrate according to [1-1] or [1-2], which contains a structural unit represented by the general formula (II) and / or a terminal structure represented by the general formula (III-a),

[0018]

[0019] [In the formula (II), R 5a , R 6a , R 7a and R 8a are each independently H, an alkyl group, an alkoxy group, or an organic group containing an alkenyl group, and one or more of R 5a , R 6a , R 7a and R 8a are an organic group containing an alkenyl group],

[0020]

[0021] [In the formula (III-a), X is each independently H, an alkyl group, an alkoxy group, or an organic group containing an alkenyl group, and one or more of them are an organic group containing an alkenyl group, and n is an integer from 1 to 5].

[0022] [1-4] The substituted polyphenylene sulfide resin for a wiring substrate according to [1-3], wherein

[0023] the terminal structure represented by the general formula (III-a) is the terminal structure represented by the general formula (III-b),

[0024]

[0025] [In formula (III-b), X is independently H, an alkyl group, an alkoxy group, or an organic group containing an alkenyl group, and one or more of them are organic groups containing an alkenyl group, n is an integer from 1 to 5, A is of general formula (IV),

[0026]

[0027] {In formula (IV), R1, R2, R3, and R4 are independently H, an alkyl group, an alkoxy group, or an organic group containing an alkenyl group, and one or more of R1, R2, R3, and R4 are an alkyl group or an alkoxy group}].

[0028] [1-5] The substituted polyphenylene sulfide resin for a wiring board according to [1-3], wherein

[0029] The terminal structure represented by general formula (III-a) is the terminal structure represented by general formula (III),

[0030]

[0031] [In formula (III), X is independently H, an alkyl group, an alkoxy group, or an organic group containing an alkenyl group, and one or more of them are organic groups containing an alkenyl group, n is an integer from 1 to 5].

[0032] [1-6] The substituted polyphenylene sulfide resin for a wiring board according to any one of [1-1] to [1-5], having a glass transition temperature of 250 °C or lower.

[0033] [1-7] The substituted polyphenylene sulfide resin for a wiring board according to any one of [1-1] to [1-6], wherein

[0034] The content of the structural unit containing an alkyl group and / or an alkoxy group is 30 mol% or more.

[0035] [1-8] The substituted polyphenylene sulfide resin for a wiring board according to [1-1] to [1-7], wherein

[0036] The content of the structural unit containing an organic group with an alkenyl group is 20 mol% or less.

[0037] [1-9] A resin composition comprising the substituted polyphenylene sulfide resin for a wiring board according to any one of [1-1] to [1-8].

[0038] [1-10] A varnish comprising the resin according to any one of [1-1] to [1-8] or the resin composition according to [1-9], and a solvent.

[0039] [1-11] An interlayer insulating material comprising the resin according to any one of [1-1] to [1-8] or the resin composition according to [1-9].

[0040] [1-12] A prepreg comprising the resin according to any one of [1-1] to [1-8] or the resin composition according to [1-9], and a substrate.

[0041] [1-13] A metal-clad laminate comprising the resin according to any one of [1-1] to [1-8] or the resin composition according to [1-9], and a metal foil.

[0042] [1-14] A substrate comprising the resin according to any one of [1-1] to [1-8] or the resin composition according to [1-9].

[0043] [1-15] A wiring board comprising the resin according to any one of [1-1] to [1-8] or the resin composition according to [1-9].

[0044] [1-16] A printed wiring board comprising the wiring board according to [1-15], and electronic components.

[0045] [1-17] The printed wiring board according to [1-16], having a dielectric loss tangent of less than 0.002 at 10 GHz.

[0046] [2] Second mode

[0047] [2-1] A substituted polyphenylene sulfide resin comprising a structural unit represented by the general formula (I),

[0048]

[0049] [In the formula (I), R1, R2, R3 and R4 are each independently H, an alkyl group, an alkoxy group, or an organic group containing an alkenyl group, and one or more of R1, R2, R3 and R4 are an alkyl group or an alkoxy group],

[0050] The substituted polyphenylene sulfide resin has a dielectric loss tangent of less than 0.002 at 10 GHz.

[0051] [2-2] The substituted polyphenylene sulfide resin according to [2-1], comprising a structural unit represented by the general formula (II) and / or a terminal structure represented by the general formula (III-a),

[0052]

[0053] [In the formula (II), R 5a , R 6a, R 7a and R 8a are each independently H, an alkyl group, an alkoxy group, or an organic group containing an alkenyl group, and one or more of R 5a , R 6a , R 7a and R 8a are alkenyl groups],

[0054]

[0055] [In formula (III-a), X are each independently H, an alkyl group, an alkoxy group, or an organic group containing an alkenyl group, and one or more of them are organic groups containing an alkenyl group, and n is an integer from 1 to 5].

[0056] [2-3] The substituted polyphenylene sulfide resin according to [2-2], wherein

[0057] the terminal structure represented by the general formula (III-a) is the terminal structure represented by the general formula (III-b),

[0058]

[0059] [In formula (III-b), X are each independently H, an alkyl group, an alkoxy group, or an organic group containing an alkenyl group, and one or more of them are organic groups containing an alkenyl group, n is an integer from 1 to 5, and A is the general formula (IV),

[0060]

[0061] {In formula (IV), R1, R2, R3 and R4 are each independently H, an alkyl group, an alkoxy group, or an organic group containing an alkenyl group, and one or more of R1, R2, R3 and R4 are alkyl groups or alkoxy groups}].

[0062] [2-4] The substituted polyphenylene sulfide resin according to [2-2], wherein

[0063] the terminal structure represented by the general formula (III-a) is the terminal structure represented by the general formula (III),

[0064]

[0065] [In formula (III), X are each independently H, an alkyl group, an alkoxy group, or an organic group containing an alkenyl group, and one or more of them are organic groups containing an alkenyl group, and n is an integer from 1 to 5].

[0066] [2-5] The substituted polyphenylene sulfide resin according to any one of [2-1] to [2-4], having a glass transition temperature of 250 °C or lower.

[0067] [2-6] The substituted polyphenylene sulfide resin according to any one of [2-1] to [2-5], wherein

[0068] the content of the structural unit containing an alkyl group and / or an alkoxy group is 30 mol% or more.

[0069] [2-7] The substituted polyphenylene sulfide resin according to any one of [2-1] to [2-6], wherein

[0070] the content of the structural unit containing an alkenyl-containing organic group is 20 mol% or less.

[0071] [2-8] A resin composition comprising the substituted polyphenylene sulfide resin according to any one of [2-1] to [2-7].

[0072] [2-9] A varnish comprising the resin according to any one of [2-1] to [2-7] or the resin composition according to [2-8], and a solvent.

[0073] [2-10] An interlayer insulating material comprising the resin according to any one of [2-1] to [2-7] or the resin composition according to [2-8].

[0074] [2-11] A prepreg comprising the resin according to any one of [2-1] to [2-7] or the resin composition according to [2-8], and a substrate.

[0075] [2-12] A metal-clad laminate comprising the resin according to any one of [2-1] to [2-7] or the resin composition according to [2-8], and a metal foil.

[0076] [2-13] A substrate comprising the resin according to any one of [2-1] to [2-7] or the resin composition according to [2-8].

[0077] [2-14] A wiring board comprising the resin according to any one of [2-1] to [2-7] or the resin composition according to [2-8].

[0078] [2-15] A printed wiring board comprising the wiring board according to [2-14], and electronic components.

[0079] [2-16] The printed wiring board according to [2-15], wherein the dielectric loss tangent at 10 GHz is less than 0.002.

[0080] [3] The third mode

[0081] [3-1] A substituted polyphenylene sulfide resin having a terminal structure represented by the general formula (III-a),

[0082]

[0083] [In formula (III-a), X is independently H, an alkyl group, an alkoxy group, or an organic group containing an alkenyl group, and one or more of them are organic groups containing an alkenyl group, and n is an integer from 1 to 5].

[0084] [3-2] The substituted polyphenylene sulfide resin according to [3-1], wherein

[0085] The terminal structure represented by the general formula (III-a) is the terminal structure represented by the general formula (III-b),

[0086]

[0087] [In formula (III-b), X is independently H, an alkyl group, an alkoxy group, or an organic group containing an alkenyl group, and one or more of them are organic groups containing an alkenyl group, n is an integer from 1 to 5, and A is the general formula (IV),

[0088]

[0089] [In formula (IV), R1, R2, R3, and R4 are independently H, an alkyl group, an alkoxy group, or an organic group containing an alkenyl group, and one or more of R1, R2, R3, and R4 are an alkyl group or an alkoxy group}].

[0090] [3-3] The substituted polyphenylene sulfide resin according to [3-1], wherein

[0091] The terminal structure represented by the general formula (III-a) is the terminal structure represented by the general formula (III),

[0092]

[0093] [In formula (III), X is independently H, an alkyl group, an alkoxy group, or an organic group containing an alkenyl group, and one or more of them are organic groups containing an alkenyl group, and n is an integer from 1 to 5].

[0094] [3-4] The substituted polyphenylene sulfide resin according to any one of [3-1] to [3-3], which contains a structural unit represented by the general formula (I),

[0095]

[0096] [In formula (I), R1, R2, R3, and R4 are independently H, an alkyl group, an alkoxy group, or an organic group containing an alkenyl group, and one or more of R1, R2, R3, and R4 are an alkyl group or an alkoxy group].

[0097] [3-5] The substituted polyphenylene sulfide resin according to [3-1] or [3-2] has a dielectric loss tangent of less than 0.002 at 10 GHz.

[0098] [3-6] The substituted polyphenylene sulfide resin according to any one of [3-1] to [3-5] contains a structural unit represented by the general formula (II),

[0099]

[0100] [In the formula (II), R 5a , R 6a , R 7a and R 8a are each independently H, an alkyl group, an alkoxy group, or an organic group containing an alkenyl group, and one or more of R 5a , R 6a , R 7a and R 8a are organic groups containing an alkenyl group].

[0101] [3-7] The substituted polyphenylene sulfide resin according to any one of [3-1] to [3-6] has a glass transition temperature of 250 °C or lower.

[0102] [3-8] In the substituted polyphenylene sulfide resin according to any one of [3-1] to [3-7],

[0103] the content of the structural unit containing an alkyl group and / or an alkoxy group is 30 mol% or more.

[0104] [3-9] In the substituted polyphenylene sulfide resin according to any one of [3-1] to [3-8],

[0105] the content of the structural unit containing an organic group containing an alkenyl group is 20 mol% or less.

[0106] [3-10] A resin composition comprising the substituted polyphenylene sulfide resin according to any one of [3-1] to [3-9].

[0107] [3-11] A varnish comprising the resin according to any one of [3-1] to [3-9] or the resin composition according to [3-6], and a solvent.

[0108] [3-12] An interlayer insulating material comprising the resin according to any one of [3-1] to [3-9] or the resin composition according to [3-6].

[0109] [3-13] A prepreg comprising the resin according to any one of [3-1] to [3-9] or the resin composition according to [3-6], and a substrate.

[0110] [3-14] A metal-clad laminate comprising the resin according to any one of [3-1] to [3-9] or the resin composition according to [3-6], and a metal foil.

[0111] [3-15] A substrate comprising the resin according to any one of [3-1] to [3-9] or the resin composition according to [3-6].

[0112] [3-16] A wiring substrate comprising the resin according to any one of [3-1] to [3-9] or the resin composition according to [3-6].

[0113] [3-17] A printed wiring board comprising the wiring substrate according to [3-16], and electronic components.

[0114] [3-18] The printed wiring board according to [3-17], having a dielectric loss tangent of less than 0.002 at 10 GHz.

[0115] According to the first and second aspects of the present disclosure, a resin having a low dielectric loss tangent can be provided.

[0116] According to the third aspect of the present disclosure, a novel substituted PPS resin can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0117] Figure 1 The synthesis scheme of vinyl-substituted PPS resin (terminal) is shown.

[0118] FIG. 2 is a diagram (a) showing the high-field shift of the signal of the terminal aromatic protons obtained by NMR analysis for the substituted PPS of Examples 15 to 18, and a diagram (b) showing the presence of terminal vinyl. DETAILED DESCRIPTION

[0119] Hereinafter, one 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 modifications within the scope that does not impair the effects of the present disclosure.

[0120] Each configuration and their combinations in each embodiment are examples, and additions, omissions, substitutions, and other changes to the configuration can be appropriately made without departing from the gist of the present disclosure. The present disclosure is not limited by the embodiments, but only by the claims.

[0121] Each aspect disclosed in this specification can be combined with any other feature disclosed in this specification.

[0122] In cases where the specific description given for one embodiment is also applicable to other embodiments, the description thereof may sometimes be omitted in the other embodiments. In the present disclosure, the expression "X to Y" for a numerical range means "X or more and Y or less".

[0123] ==First Embodiment (Replacement-Type PPS Resin for Wiring Substrate)==

[0124] [Replacement-Type PPS Resin for Wiring Substrate]

[0125] The resin of the first embodiment is a replacement-type PPS resin for a wiring substrate containing a structural unit represented by the general formula (I).

[0126] General formula (I):

[0127]

[0128] [In formula (I), R1, R2, R3, and R4 are each independently H, an alkyl group, an alkoxy group, or an organic group containing an alkenyl group, and one or more of R1, R2, R3, and R4 are an alkyl group or an alkoxy group]

[0129] (For wiring substrate)

[0130] In the present specification, the "wiring substrate" in "for wiring substrate" includes all parts other than electronic components such as semiconductor chips in a printed wiring board (also referred to as a printed circuit board). Generally, a printed wiring board has a structure in which a semiconductor package having electronic components such as semiconductor chips mounted on a base called a substrate is mounted on a printed substrate (PCB, Print Circuit Board), and the "substrate" in "for wiring substrate" also includes the substrate.

[0131] Therefore, "for wiring substrate" means that the replacement-type PPS resin can be used as a material for a wiring substrate for mounting electronic components such as semiconductor chips and implementing wiring.

[0132] The replacement-type PPS resin for a wiring substrate of the present embodiment has the characteristic of a low dielectric loss tangent by including a structural unit represented by the general formula (I), and thus can preferably be used as a material for a wiring substrate.

[0133] In one embodiment, the replacement-type PPS resin for a wiring substrate may be composed only of the replacement-type PPS resin described below, or may also contain resins other than this.

[0134] For example, the replacement-type PPS resin for a wiring substrate of the present embodiment may contain one or more resins such as a replacement-type PPS resin other than the replacement-type PPS resin described in the present embodiment, an unsubstituted PPS resin, and / or a resin other than a PPS resin.

[0135] (Substituted PPS resin containing structural units having an alkyl group or an alkoxy group)

[0136] The substituted PPS resin of the first embodiment contains a structural unit represented by the general formula (I).

[0137] General formula (I):

[0138]

[0139] [In formula (I), R1, R2, R3 and R4 are each independently H, an alkyl group, an alkoxy group, or an organic group containing an alkenyl group, and one or more of R1, R2, R3 and R4 are an alkyl group or an alkoxy group]

[0140] Here, the alkyl group may be a linear, branched or cyclic alkyl group, preferably a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. Examples of the linear, branched or cyclic alkyl group having 1 to 10 carbon atoms include: methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, sec-isobutyl group, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, n-heptyl, n-octyl, isooctyl, n-nonyl, isononyl, n-decyl, isodecyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc.

[0141] In one embodiment, the alkyl group is preferably methyl, ethyl and / or isopropyl.

[0142] The alkoxy group may be a linear, branched or cyclic alkoxy group, preferably a linear, branched or cyclic alkoxy group having 1 to 10 carbon atoms. Examples of the linear or branched alkoxy group having 1 to 10 carbon atoms include: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, sec-butoxy, isobutoxy, n-pentyloxy, isopentyloxy, neopentyloxy, n-hexyloxy, isohexyloxy, sec-hexyloxy, tert-hexyloxy, neohexyloxy, n-heptyloxy, n-octyloxy, isooctyloxy, n-nonyloxy, isononyloxy, n-decyloxy, isodecyloxy, cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, cyclooctyloxy, cyclononyloxy, cyclodecyloxy, etc.

[0143] In one embodiment, the alkoxy group is preferably methoxy.

[0144] In one embodiment, considering the ease of synthesis of the substituted PPS resin, the alkyl group is preferably linear or branched. The number of carbon atoms of the alkyl group is preferably 1 to 6, more preferably 1 to 5, and still more preferably 1 to 4. In one embodiment, the alkyl group can be an alkyl group having 4 carbon atoms, an alkyl group having 3 carbon atoms, an alkyl group having 2 carbon atoms, or an alkyl group having 1 carbon atom.

[0145] In one embodiment, considering the ease of synthesis of the substituted PPS resin, the alkoxy group is preferably linear or branched. The number of carbon atoms of the alkoxy group is preferably 1 to 6, more preferably 1 to 5, and still more preferably 1 to 4. In one embodiment, the alkoxy group can be an alkoxy group having 4 carbon atoms, an alkoxy group having 3 carbon atoms, an alkoxy group having 2 carbon atoms, or an alkoxy group having 1 carbon atom.

[0146] Considering the ease of synthesis of the substituted PPS resin, the alkyl group or alkoxy group is preferably an alkyl group, more preferably a linear alkyl group, still more preferably a linear alkyl group having 1 to 4 carbon atoms, still more preferably an ethyl group or a methyl group, and still more preferably a methyl group.

[0147] The substitution position based on the alkyl group or alkoxy group in the general formula (I) is not limited and can be one or more of R1, R2, R3, and R4.

[0148] When one alkyl group or alkoxy group is included in the general formula (I), its substitution position can be any one of R1, R2, R3, and R4. Its substitution position can be R1, can be R2, can be R3, or can be R4.

[0149] When two or more alkyl groups and / or alkoxy groups are included in the general formula (I), the combination of their substitution positions is not limited. For example, when two alkyl groups and / or alkoxy groups are included, the substitution positions can be any combination of R1 and R2, R1 and R3, R1 and R4, R2 and R3, R2 and R4, and R3 and R4. In one embodiment, the substitution positions of the alkyl group and / or alkoxy group can be any two of R1, R2, and R3. When the substitution positions are any two of R1, R2, and R3, it can be any combination of R1 and R3, or R2 and R3.

[0150] When a total of three alkyl groups and / or alkoxy groups are included in the general formula (I), it can be any combination of R1 and R2 and R3, R1 and R2 and R4, R1 and R3 and R4, or R2 and R3 and R4.

[0151] In one embodiment, for a substituted PPS resin, in the structural unit represented by the general formula (I), one or more of R1, R2, R3, and R4 may be an aryl group having 1 to 10 carbon atoms. Examples of the aryl group having 1 to 10 carbon atoms include a phenyl group and a naphthyl group.

[0152] By including one or more alkyl groups, alkoxy groups, and / or aryl groups in the general formula (I), the dielectric loss tangent of the substituted PPS resin containing the structural unit represented by the general formula (I) is likely to be reduced. As a result, the dielectric loss tangent of the resin composition containing the substituted PPS resin is likely to be reduced.

[0153] In the structural unit represented by the general formula (I), there is also a case where one or more of R1, R2, R3, and R4 are an alkyl group or an alkoxy group, but one or more of those other than the alkyl group or the alkoxy group among R1, R2, R3, and R4 are an organic group containing an alkenyl group.

[0154] In the substituted PPS resin, in formula (I), those other than the alkyl group or the alkoxy group among R1, R2, R3, and R4 may each independently be an organic group containing an alkenyl group.

[0155] Here, regarding the organic group containing an alkenyl group, there is no limitation as long as one or more alkenyl groups are included in the substituent, and it may be a sub-alkenyl group with a COO group (ester) or a CO group (ketone) interposed. The organic group containing an alkenyl group may be a linear, branched, or cyclic alkenyl group, preferably a linear, branched, or cyclic alkenyl group having 2 to 10 carbon atoms. Examples of the linear, branched, or cyclic alkenyl group having 2 to 10 carbon atoms include substituents containing one or more carbon-carbon double bonds in the chain of an alkyl group having 2 or more carbon atoms. Specifically, examples include 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, acryloyl group (acrylyl group), methacryloyl group (methacrylyl group), acryloyloxyalkyl group, methacryloyloxyalkyl group, etc.

[0156] In one embodiment, the organic group containing an alkenyl group is preferably vinyl, allyl, and / or acryloyl group.

[0157] In one embodiment, considering the ease of synthesis of the substituted PPS resin, the alkenyl-containing organic group is preferably linear or branched. Regarding the number of carbon atoms of the alkenyl-containing organic group, the number of carbon atoms is preferably 2 to 6, more preferably 2 to 5, further preferably 2 to 4, and still further preferably 2 to 3. In one embodiment, the alkenyl-containing organic group may be an alkenyl group having 3 carbon atoms or an acrylic group, or may be an alkenyl group having 2 carbon atoms.

[0158] In one embodiment, in the structural unit represented by the general formula (I), when one or more of R1, R2, R3, and R4 are alkenyl-containing organic groups, even if the substituted PPS resin is composed only of the structural unit represented by the general formula (I), or even if it contains one or more structural units other than the structural unit represented by the general formula (I), the substituted PPS resin is likely to exhibit thermosetting properties and / or is likely to exhibit good reflow soldering resistance. As a result, the resin composition containing the substituted PPS resin is likely to exhibit thermosetting properties and / or is likely to exhibit good reflow soldering resistance.

[0159] In addition, the unsubstituted PPS resin has good flame retardancy. Therefore, the substituted PPS resin containing the structural unit represented by the general formula (I) having the same basic skeleton as the unsubstituted PPS has good flame retardancy. This is also the same for other structural units having a PPS skeleton with the same basic skeleton as the unsubstituted PPS. The substituted PPS resin containing the structural unit represented by the general formula (II) or the terminal structure represented by the general formula (III) described below also has good flame retardancy.

[0160] As a result, the resin composition containing the substituted PPS resin has good flame retardancy.

[0161] (Substituted PPS resin containing a structural unit having an alkenyl-containing organic group)

[0162] In one embodiment, the substituted PPS resin of the first embodiment may contain the structural unit represented by the general formula (II) and / or the terminal structure represented by the general formula (III-a).

[0163]

[0164] [In the formula (II), R 5a , R 6a , R 7a and R 8a are each independently H, an alkyl group, an alkoxy group, or an alkenyl-containing organic group, and R 5a , R 6a , R 7a and R 8amore than one of them is an alkenyl-containing organic group

[0165]

[0166] [In formula (III-a), X is independently H, an alkyl group, an alkoxy group, or an alkenyl-containing organic group, and more than one of them is an alkenyl-containing organic group, and n is an integer from 1 to 5].

[0167] The terminal structure represented by general formula (III-a) can be the terminal structure represented by general formula (III-b).

[0168]

[0169] [In formula (III-b), X is independently H, an alkyl group, an alkoxy group, or an alkenyl-containing organic group, and more than one of them is an alkenyl-containing organic group, n is an integer from 1 to 5, and A is general formula (IV).

[0170]

[0171] [In formula (IV), R1, R2, R3, and R4 are independently H, an alkyl group, an alkoxy group, or an alkenyl-containing organic group, and more than one of R1, R2, R3, and R4 is an alkyl group or an alkoxy group.]]

[0172] The terminal structure represented by general formula (III-a) can be the terminal structure represented by general formula (III).

[0173]

[0174] [In formula (III), X is independently H, an alkyl group, an alkoxy group, or an alkenyl-containing organic group, and more than one of them is an alkenyl-containing organic group, and n is an integer from 1 to 5].

[0175] The structural unit represented by general formula (II) means that among the structural units contained in the substituted PPS resin, in the structural units other than the structural units at the ends of the resin, more than one of the substituents is an alkenyl-containing organic group.

[0176] The structural units represented by general formulas (III-a), (III-b), and (III) mean that among the structural units contained in the substituted PPS resin, in the structural units at one or both ends of the resin, more than one of the substituents is an alkenyl-containing organic group.

[0177] Examples of the alkyl, alkoxy, and alkenyl-containing organic groups in General Formula (II), and General Formulae (III-a), (III-b), and (III), and preferred examples thereof include the alkyl, alkoxy, and alkenyl-containing organic groups exemplified in the description of General Formula (I). Regarding the number of carbon atoms in the alkyl and alkoxy groups, the number of carbon atoms exemplified in the description of General Formula (I) may also be used.

[0178] In consideration of the ease of synthesis of the substituted PPS resin, the number of carbon atoms in the alkenyl-containing organic group in General Formula (II), and General Formulae (III-a), (III-b), and (III) is preferably 2 to 6, more preferably 2 to 5, still more preferably 2 to 4, and still more preferably 2 to 3. In one embodiment, the alkenyl-containing organic group may be an alkenyl-containing organic group having 3 carbon atoms or an alkenyl-containing organic group having 2 carbon atoms. For example, it may be allyl or acryloyl having 3 carbon atoms and / or vinyl having 2 carbon atoms.

[0179] Here, the substitution position of the alkenyl-containing organic group in General Formula (II) is not limited and may be one or more of R 5a , R 6a , R 7a and R 8a .

[0180] When General Formula (II) contains one alkenyl-containing organic group, its substitution position only needs to be any one of R 5a , R 6a , R 7a and R 8a . Its substitution position may be R 5a , may be R 6a , may be R 7a , or may be R 8a .

[0181] When General Formula (II) contains two or more alkenyl-containing organic groups, the combination of their substitution positions is not limited. For example, when two alkenyl-containing organic groups are included, the substitution positions may be R 5a and R 6a , R 5a and R 7a , R 5a and R 8a , R 6a and R 7a , R 6a and R 8a , R 7a and R 8a in any combination. In one embodiment, the substitution position of the alkenyl-containing organic group may be R 5a, R 6a and R 7a Any two of them can be R 5a and R 7a , or R 6a and R 7a Any combination.

[0182] For example, when the general formula (II) contains three organic groups containing alkenyl, the substitution position can be R 5a and R 6a and R 7a , R 5a and R 6a and R 8a , R 5a and R 7a and R 8a , or R 6a and R 7a Any combination with R8.

[0183] In the general formula (II), it also includes the case where one or more of R 5a , R 6a , R 7a and R 8a are organic groups containing alkenyl, but one or more of the organic groups that are not alkenyl-containing in R 5a , R 6a , R 7a and R 8a are alkyl or alkoxy. In addition, in the general formulas (III-a), (III-b) and (III), it also includes the case where one or more of X are alkenyl, but one or more of the organic groups that are not alkenyl-containing in X are alkyl or alkoxy. The substitution position based on alkyl or alkoxy in the general formula (II) can be any one of R 5a , R 6a , R 7a and R 8a . As an example and a preferred example thereof, the substitution positions exemplified in the description of the general formula (I) can be cited. The substitution position based on alkyl or alkoxy in the general formulas (III-a), (III-b) and (III) is not limited and can be any X among the five Xs.

[0184] Here, the substitution position based on the organic group containing alkenyl in the general formula (III-a), (III-b) or (III) is not limited as long as it is one or more of the five Xs. When the general formula (III-a), (III-b) or (III) contains one organic group containing alkenyl, its substitution position relative to S can be ortho, meta or para.

[0185] When there are a total of two or more alkenyl-containing organic groups in the general formula (III-a), (III-b) or (III), the combination of the substitution positions is not limited. For example, when there are two alkenyl-containing organic groups, the substitution positions can be the 2,3-positions (or 5,6-positions), can be the 2,4-positions (or 4,6-positions), can be the 2,5-positions (or 3,6-positions), can be the 2,6-positions, can be the 3,4-positions (or 4,5-positions), or can be the 3,5-positions.

[0186] For example, when there are three alkenyl-containing organic groups in the general formula (III-a), (III-b) or (III), the substitution positions can be the 2,3,4-positions (or 4,5,6-positions), can be the 2,3,5-positions (or 3,5,6-positions), can be the 2,3,6-positions (or 2,5,6-positions), can be the 2,4,5-positions (or 3,4,6-positions), can be the 2,4,6-positions, or can be the 3,4,5-positions.

[0187] By including one or more alkenyl-containing organic groups in the general formula (II) and the general formula (III-a), general formula (III-b) or general formula (III), the substituted PPS resin containing the structural unit represented by the general formula (II) and / or the terminal structure represented by the general formula (III-a), (III-b) or (III) is likely to exhibit thermosetting properties and / or is likely to exhibit good reflow soldering resistance. As a result, the resin composition containing the substituted PPS resin is likely to exhibit thermosetting properties and / or is likely to exhibit good reflow soldering resistance. From the viewpoint of easily exhibiting thermosetting properties and good reflow soldering resistance, the substituted PPS resin preferably contains the terminal structure represented by the general formula (III-a), (III-b) or (III) at at least one of its terminals, and more preferably contains the terminal structure represented by the general formula (III-a), (III-b) or (III) at both of its terminals. Even when the substituted PPS resin does not have the terminal structure represented by the general formula (III-a), (III-b) or (III) at any of its terminals, as long as it is a resin containing one or more alkenyl-containing organic groups in the general formula (II), additives known to those skilled in the art for improving its curability, such as crosslinking agents, can be used in combination to impart the desired thermosetting properties and / or the desired reflow soldering resistance to the resin composition containing the substituted PPS resin.

[0188] (Polymer structure)

[0189] The substituted PPS resin has a polymer structure including two or more structural units (monomer units) that can constitute the resin. The substituted PPS resin of the first embodiment includes a structural unit represented by the general formula (I) as at least a part of its structural units, and may also include one or more structural units represented by other than the general formula (I).

[0190] Here, the structural unit represented by the general formula (I) may be one structural unit, or may be two or more structural units within the scope represented by the general formula (I), and the structural unit represented by the general formula (I) includes two or more structural units having different combinations of substituents of R1, R2, R3 and R4 exemplified in the description of the general formula (I).

[0191] Here, one or more structural units represented by other than general formula (I) are not limited, and include, for example, unsubstituted PPS (PPS in which all substituents of general formula (I) are H) units, structural units represented by general formula (II), and terminal structures represented by general formula (III-a), (III-b) or (III).

[0192] The structural unit represented by the general formula (II) may be one structural unit, or may be two or more structural units within the scope of the general formula (II). The structural unit represented by the general formula (II) includes the structural units exemplified in the description of the general formula (II), R 5a , R 6a , R 7a and R 8a Two or more structural units having different combinations of substituents.

[0193] The terminal structure represented by the general formula (III-a), (III-b) or (III) may be one terminal structure, that is, both terminals of the resin may have the same general formula and the same substituent; or, within the range represented by the general formula (III-a), (III-b) or (III), there may be two terminal structures, that is, the terminals of the resin may have different structures, and the terminal structures represented by the general formula (III-a), (III-b) and (III) include two or more terminal structures with different combinations of substituents of the five Xs exemplified in the description of the general formula (III-a), (III-b) and (III). From the viewpoint of easy presentation of thermosetting properties and / or good reflow resistance, the terminal structure may be one terminal structure or two terminal structures, but considering the ease of synthesis of the substituted PPS resin, it is preferred that both terminals of the resin have one terminal structure, that is, have the same general formula and the same substituent.

[0194] In the substituted PPS resin, the bonding order of the structural units is not limited. For example, it can be in the following ways: structural units represented by the general formula (I) with the same substituent combination are adjacent to each other, structural units represented by the general formula (II) with the same substituent combination are adjacent to each other, structural units represented by the general formula (I) with different substituent combinations are adjacent to each other, structural units represented by the general formula (II) with different substituent combinations are adjacent to each other, structural units represented by the general formula (I) are adjacent to structural units represented by the general formula (II), and structural units represented by the general formula (I) or (II) are adjacent to structural units other than those represented by the general formula (I) or (II). In addition, terminal structures represented by the general formula (III-a), (III-b), or (III) can be bonded to one or both ends of a plurality of structural units bonded in any of these orders.

[0195] In one embodiment, the substituted PPS resin can include a structural unit in which R2 and R3 in the general formula (I) are alkyl groups having 1 to 5 carbon atoms and R1 and R4 are H, can include a structural unit in which R1 and R3 in the general formula (I) are alkyl groups having 1 to 5 carbon atoms and R2 and R4 are H, can include a structural unit in which R2 in the general formula (I) is an alkyl group having 1 to 5 carbon atoms and R1, R3, and R4 are H, can include a structural unit in which R1 in the general formula (I) is an alkyl group having 1 to 5 carbon atoms and R2, R3, and R4 are H, can include a structural unit in which R2 and R3 in the general formula (I) are alkoxy groups having 1 to 5 carbon atoms and R1 and R4 are H, can include a structural unit in which R2 and R3 in the general formula (I) are methyl groups and R1 and R4 are H, can include a structural unit in which R1 and R3 in the general formula (I) are methyl groups and R2 and R4 are H, can include a structural unit in which R2 in the general formula (I) is a methyl group and R1, R3, and R4 are H, can include a structural unit in which R1 is an isopropyl group and R2, R3, and R4 are H, can include a structural unit in which R2 and R3 in the general formula (I) are methoxy groups and R1 and R4 are H.

[0196] In one embodiment, the substituted PPS resin can include in the general formula (I) or (II) where R2 or R3 (in the general formula (II) is R 6a or R 7a ) is an alkyl group having 1 to 5 carbon atoms, R2 or R3 that is not an alkyl group (in the general formula (II) is R 6a or R 7a ) is an alkenyl-containing organic group having 2 to 3 carbon atoms, and R1 and R4 (in the general formula (II) are R 5a or R 8a) The structural unit of H, which can be included in the general formula (III-a), (III-b) or (III), where at least one of the 2-position, 3-position, 4-position, and 5-position is an alkenyl-containing organic group with 2 to 3 carbon atoms, and X of the non-alkenyl-containing organic group is H or an alkyl group with 1 to 5 carbon atoms, and the structural unit in the general formula (I) where R2 and R3 are alkyl groups with 1 to 5 carbon atoms and R1 and R4 are H, can be included in R2 or R3 in the general formula (I) or (II) (R in the general formula (II)) 6a or R 7a ) is methyl, and non-methyl R2 or R3 (R in the general formula (II)) 6a or R 7a ) is vinyl, and R1 and R4 (R in the general formula (II)) 5a or R 8a ) is H, and can also be included in the general formula (III-a), (III-b) or (III), where at least one of the 2-position, 3-position, 4-position, and 5-position is vinyl, and X of the non-vinyl group is H or methyl, and the structural unit in the general formula (I) where R2 or R3 is methyl and R1 and R4 are H.

[0197] In one embodiment, the substituted PPS resin can include the structural unit where R2 or R3 in the general formula (I) or (II) (R in the general formula (II)) 6a or R 7a ) is an alkyl group with 1 to 5 carbon atoms, and non-alkyl R2 or R3 (R in the general formula (II)) 6a or R 7a ) is an alkenyl-containing organic group with 2 to 3 carbon atoms, and R1 and R4 (R in the general formula (II)) 5a or R 8a ) is H, which can be included in the general formula (III-a), (III-b) or (III), where at least one of the 3-position and 5-position is an alkenyl-containing organic group with 2 to 3 carbon atoms, and X of the non-alkenyl-containing organic group is H or an alkyl group with 1 to 5 carbon atoms, and the structural unit in the general formula (I) where R2 and R3 are alkyl groups with 1 to 5 carbon atoms and R1 and R4 are H, and can be included in R2 or R3 in the general formula (I) or (II) (R in the general formula (II)) 6a or R 7a ) is methyl, and non-methyl R2 or R3 (R in the general formula (II)) 6a or R 7a ) is vinyl, and R1 and R4 (R in the general formula (II)) 5a or R 8a) is a structural unit of H, and may also include a structural unit in which at least one of the 3-position and 5-position in the general formula (III-a), (III-b) or (III) is vinyl, and X that is not vinyl is H or methyl, and a structural unit in the general formula (I) in which R2 or R3 is methyl and R1 and R4 are H.

[0198] In one embodiment, the substituted PPS resin may have an alkenyl-containing organic group at any substitution position in the general formula (I), general formula (II) and / or general formula (III-a), (III-b) or (III). The number of carbon atoms of the alkenyl-containing organic group may be 2 to 3, and may be vinyl.

[0199] In one embodiment, the substituted PPS resin may be one or more selected from 3,5-dimethyl PPS resin, 2,5-dimethyl PPS resin, 3-monomethyl PPS resin, 2-isopropyl PPS resin, which optionally have one or more alkenyl-containing organic groups having 2 to 3 carbon atoms. In one embodiment, the substituted PPS resin may be one or more selected from 3,5-dimethyl PPS resin, 2,5-dimethyl PPS resin, 3-monomethyl PPS resin, 2-isopropyl PPS resin, which optionally have one or more vinyl groups.

[0200] The content of the structural unit represented by the general formula (I) in the substituted PPS resin, or the content of the structural unit represented by the general formula (I) and the structural unit represented by the general formula (II) is not limited within the range that makes the resin composition containing the substituted PPS resin and / or the substituted PPS resin have a desired dielectric loss tangent. The content of the structural unit containing an alkyl group and / or an alkoxy group in the substituted PPS resin is preferably 30 mol% or more. When it is 30 mol% or more, it may be 40 mol% or more, 50 mol% or more, 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, or 100 mol%.

[0201] By making the content of the structural unit containing an alkyl group and / or an alkoxy group in the substituted PPS resin 30 mol% or more, the dielectric loss tangent of the substituted PPS resin easily reaches the desired range. As a result, the dielectric loss tangent of the resin composition containing the substituted PPS resin easily reaches the desired range.

[0202] In one embodiment, the content of the structural unit having an alkenyl-containing organic group in the substituted PPS resin is not limited as long as it enables a resin composition containing the substituted PPS resin and / or the substituted PPS resin to exhibit a desired thermosetting property. As the upper limit, it is 20 mol% or less, preferably 18 mol% or less, more preferably 1 to 18 mol%, further preferably 2 to 10 mol%, and still further preferably 2 to 7 mol%. When it is 18 mol% or less, it can be 15 mol% or less, 10 mol% or less, 7 mol% or less, 5 mol% or less, 4 mol% or less, 3 mol% or less, or 1 mol% or less. In addition, as the lower limit, the content of the structural unit having an alkenyl-containing organic group in the substituted PPS resin is preferably at least 1 structural unit or more. Here, when the content of the structural unit having an alkenyl-containing organic group in the substituted PPS resin is 1 structural unit, one terminal structure of the substituted PPS resin may have an alkenyl-containing organic group, or 1 structural unit other than the terminal structure may have an alkenyl-containing organic group. Even in the case of a resin in which only 1 structural unit of the substituted PPS resin has an alkenyl-containing organic group, the substituted PPS resin is likely to exhibit thermosetting property and / or good reflow solder resistance.

[0203] When the lower limit of the content of the structural unit having an alkenyl-containing organic group in the substituted PPS resin is 1 structural unit or more, it can be 2 structural units or more, 0.1 mol% or more, 0.2 mol% or more, 0.5 mol% or more, or 0.8 mol% or more.

[0204] In one embodiment, the content of the structural unit having an alkenyl-containing organic group in the substituted PPS resin can be set within a range formed by arbitrarily combining the above upper and lower limits.

[0205] For example, the content of the structural unit having an alkenyl-containing organic group in the substituted PPS resin may be 1 or more structural units and 18 mol% or less, may be 1 or more structural units and 15 mol% or less, may be 1 or more structural units and 10 mol% or less, may be 1 or more structural units and 7 mol% or less, may be 1 or more structural units and 5 mol% or less, may be 1 or more structural units and 4 mol% or less, may be 1 or more structural units and 3 mol% or less, may be 1 or more structural units and 1 mol% or less. Additionally, it may be 2 or more structural units and 18 mol% or less, may be 2 or more structural units and 15 mol% or less, may be 2 or more structural units and 10 mol% or less, may be 2 or more structural units and 7 mol% or less, may be 2 or more structural units and 5 mol% or less, may be 2 or more structural units and 4 mol% or less, may be 2 or more structural units and 3 mol% or less, may be 2 or more structural units and 1 mol% or less. Additionally, it may be 0.1 mol% or more and 18 mol% or less, may be 0.1 mol% or more and 15 mol% or less, may be 0.1 mol% or more and 10 mol% or less, may be 0.1 mol% or more and 7 mol% or less, may be 0.1 mol% or more and 5 mol% or less, may be 0.1 mol% or more and 4 mol% or less, may be 0.1 mol% or more and 3 mol% or less, may be 0.1 mol% or more and 1 mol% or less. Additionally, it may be 0.2 mol% or more and 18 mol% or less, may be 0.2 mol% or more and 15 mol% or less, may be 0.2 mol% or more and 10 mol% or less, may be 0.2 mol% or more and 7 mol% or less, may be 0.2 mol% or more and 5 mol% or less, may be 0.2 mol% or more and 4 mol% or less, may be 0.2 mol% or more and 3 mol% or less, may be 0.2 mol% or more and 1 mol% or less. Additionally, it may be 0.5 mol% or more and 18 mol% or less, may be 0.5 mol% or more and 15 mol% or less, may be 0.5 mol% or more and 10 mol% or less, may be 0.5 mol% or more and 7 mol% or less, may be 0.5 mol% or more and 5 mol% or less, may be 0.5 mol% or more and 4 mol% or less, may be 0.5 mol% or more and 3 mol% or less, may be 0.5 mol% or more and 1 mol% or less. Additionally, it may be 0.8 mol% or more and 18 mol% or less, may be 0.8 mol% or more and 15 mol% or less, may be 0.8 mol% or more and 10 mol% or less, may be 0.8 mol% or more and 7 mol% or less, may be 0.8 mol% or more and 5 mol% or less, may be 0.8 mol% or more and 4 mol% or less, may be 0.8 mol% or more and 3 mol% or less, may be 0.8 mol% or more and 1 mol% or less.

[0206] By making the content of the structural unit having an alkenyl-containing organic group in the substituted PPS resin be 1 or more and 20 mol% or less of the structural units, the substituted PPS resin is liable to exhibit thermosetting properties and / or is liable to exhibit good reflow soldering resistance. As a result, the resin composition containing the substituted PPS resin is liable to exhibit thermosetting properties and / or is liable to exhibit good reflow soldering resistance.

[0207] In addition, by making the content of the structural unit having an alkenyl-containing organic group in the substituted PPS resin be 1 or more and 20 mol% or less of the structural units, the tangent of the dielectric loss angle of the substituted PPS resin at 10 GHz is liable to be less than 0.002, and the tangent of the dielectric loss angle at 40 GHz is liable to be less than 0.003. Further, by making the content of the structural unit having an alkenyl-containing organic group in the substituted PPS resin be 1 or more and 20 mol% or less of the structural units, the dielectric constant at 10 GHz is liable to be less than 3.00.

[0208] (Tangent of the dielectric loss angle)

[0209] In one embodiment, the tangent of the dielectric loss angle of the substituted PPS resin at 10 GHz is preferably less than 0.002. As a result, the tangent of the dielectric loss angle of the resin composition containing the substituted PPS resin at 10 GHz is liable to be less than 0.002.

[0210] In one embodiment, the tangent of the dielectric loss angle of the substituted PPS resin at 10 GHz is more preferably less than 0.0015. As a result, the tangent of the dielectric loss angle of the resin composition containing the substituted PPS resin at 10 GHz is liable to be less than 0.0015.

[0211] In one embodiment, the tangent of the dielectric loss angle of the substituted PPS resin at 10 GHz is more preferably less than 0.001. As a result, the tangent of the dielectric loss angle of the resin composition containing the substituted PPS resin at 10 GHz is liable to be less than 0.001.

[0212] In one embodiment, when the tangent of the dielectric loss angle of the substituted PPS resin at 10 GHz is less than 0.001, it may be less than 0.00095, may be less than 0.0009, may be less than 0.00085, may be less than 0.0008.

[0213] In one embodiment, the tangent of the dielectric loss angle of the substituted PPS resin at 40 GHz is preferably less than 0.003. As a result, the tangent of the dielectric loss angle of the resin composition containing the substituted PPS resin at 40 GHz is liable to be less than 0.003.

[0214] In one embodiment, when the dielectric loss tangent of the substituted PPS resin at 40 GHz is less than 0.003, it can be less than 0.0025, less than 0.002, less than 0.0015, or less than 0.0012.

[0215] In one embodiment, the dielectric loss tangent of the substituted PPS resin at 80 GHz is preferably less than 0.004. As a result, the dielectric loss tangent of the resin composition containing the substituted PPS resin is likely to be less than 0.004 at 80 GHz.

[0216] In one embodiment, when the dielectric loss tangent of the substituted PPS resin at 80 GHz is less than 0.004, it can be less than 0.003, less than 0.0025, or less than 0.002.

[0217] The lower the dielectric loss tangent of the substituted PPS resin, the more easily transmission loss can be further suppressed when using the substituted PPS resin or a resin composition containing the substituted PPS resin as a material for a wiring substrate.

[0218] Examples of the method for adjusting the dielectric loss tangent include the following methods: adjusting the content of the structural units represented by general formula (I), general formula (II), and / or general formula (III-a), (III-b), or (III) in the substituted PPS resin; adjusting the number of carbon atoms of the alkyl or alkoxy group in the structural units represented by general formula (I), general formula (II), and / or general formula (III-a), (III-b), or (III); adjusting the number of substituents in the structural units represented by general formula (I), general formula (II), and / or general formula (III-a), (III-b), or (III); adjusting the substitution position in the structural units represented by general formula (I), general formula (II), and / or general formula (III-a), (III-b), or (III). By using any one of these methods or a combination thereof, the dielectric loss tangent can be adjusted to be lower, the dielectric loss tangent at 10 GHz can be adjusted to be less than 0.002, the dielectric loss tangent at 40 GHz can be adjusted to be less than 0.003, and the dielectric loss tangent at 80 GHz can be adjusted to be less than 0.004.

[0219] For example, the more the content of the structural unit represented by general formula (I) in the substituted PPS resin, the more the dielectric loss tangent can be lowered. For example, by making the substituted PPS resin contain 30 mol% or more of the structural unit represented by general formula (I), the dielectric loss tangent can be adjusted to be lower.

[0220] In addition, for example, by reducing the number of carbon atoms in the alkyl or alkoxy group in the structural unit represented by the general formula (I) in the substituted PPS resin, the tangent of the dielectric loss angle can be adjusted to be lower. For example, in the substituted PPS resin, by reducing the number of carbon atoms in the alkyl or alkoxy group in the structural unit represented by the general formula (I), the tangent of the dielectric loss angle can be adjusted to be lower. More specifically, for example, by making the substituted PPS resin contain the structural unit represented by the general formula (I) substituted with an alkyl group having a low number of carbon atoms (for example, 1 to 5 carbon atoms), compared with the case of containing the structural unit substituted with an alkyl or alkoxy group having a higher number of carbon atoms, the tangent of the dielectric loss angle can be adjusted to be lower.

[0221] In one embodiment, it is preferred that the substituted PPS resin contains the structural unit represented by the general formula (I), and its tangent of the dielectric loss angle at 10 GHz is less than 0.002.

[0222] In one embodiment, it is preferred that the substituted PPS resin contains the structural unit represented by the general formula (II), and its tangent of the dielectric loss angle at 10 GHz is less than 0.002.

[0223] In one embodiment, it is preferred that the substituted PPS resin contains the terminal structure represented by the general formula (III), and its tangent of the dielectric loss angle at 10 GHz is less than 0.002.

[0224] (Dielectric constant)

[0225] In one embodiment, it is preferred that the substituted PPS resin has a dielectric constant less than 3.00 at 10 GHz. As a result, the dielectric constant of the resin composition containing the substituted PPS resin is likely to be less than 3.00 at 10 GHz.

[0226] In one embodiment, it is more preferred that the substituted PPS resin has a dielectric constant less than 2.80 at 10 GHz. As a result, the dielectric constant of the resin composition containing the substituted PPS resin is likely to be less than 2.80 at 10 GHz.

[0227] In one embodiment, when the dielectric constant of the substituted PPS resin is less than 2.80 at 10 GHz, it can be less than 2.75, can be less than 2.65, can be less than 2.60, can be less than 2.50, or can also be less than 2.40.

[0228] The lower the dielectric constant of the substituted PPS resin, the more easily the transmission loss can be suppressed when the substituted PPS resin or the resin composition containing the substituted PPS resin is used as the material for the wiring board.

[0229] The methods for adjusting the dielectric constant can be listed as follows: adjusting the content of the structural units represented by General Formula (I), General Formula (II), and / or General Formula (III-a), (III-b), or (III) in the substituted PPS resin; adjusting the number of carbon atoms of the alkyl or alkoxy group in the structural units represented by General Formula (I), General Formula (II), and / or General Formula (III-a), (III-b), or (III); adjusting the number of substituents in the structural units represented by General Formula (I), General Formula (II), and / or General Formula (III-a), (III-b), or (III); adjusting the substitution position in the structural units represented by General Formula (I), General Formula (II), and / or General Formula (III-a), (III-b), or (III). By any one of these methods or a combination thereof, the dielectric constant can be adjusted to be lower, and the dielectric loss tangent at 10 GHz can be adjusted to be less than 3.00.

[0230] For example, the more the content of the structural unit represented by General Formula (I) in the substituted PPS resin, the lower the dielectric constant can be adjusted. For example, by making the substituted PPS resin contain 30 mol% or more of the structural unit represented by General Formula (I), the dielectric constant can be adjusted to be lower. More specifically, for example, by making the substituted PPS resin contain 40 mol% or more of this structural unit, the dielectric constant at 10 GHz can be adjusted to be less than 3.00.

[0231] In addition, for example, by reducing the number of carbon atoms of the alkyl or alkoxy group in the structural unit represented by General Formula (I) in the substituted PPS resin, the dielectric constant can be adjusted to be lower. For example, in the substituted PPS resin, by reducing the number of carbon atoms of the alkyl or alkoxy group in the structural unit represented by General Formula (I), the dielectric constant can be adjusted to be lower. More specifically, for example, by making the substituted PPS resin contain the structural unit represented by General Formula (I) substituted with an alkyl group having a low number of carbon atoms (for example, 1 to 5 carbon atoms), compared with the case of containing the structural unit substituted with an alkyl or alkoxy group having a higher number of carbon atoms, the dielectric constant can be adjusted to be lower.

[0232] (Measurement of Dielectric Loss Tangent and Dielectric Constant)

[0233] In order to measure the dielectric loss tangent and the dielectric constant, a film of a resin or resin composition with a thickness adjusted to 50 to 250 μm can be heated at 200°C to 250°C for 120 minutes to prepare a specimen piece of the resin or resin composition for measurement and then used.

[0234] For the dielectric loss tangent and the dielectric constant, measurements can be made at 10 GHz, 40 GHz, or 80 GHz using a vector network analyzer (N5290A) manufactured by Keysight Technologies and a split cylinder resonator under standard environmental conditions (23 ± 2°C) and a relative humidity of 45 - 55%.

[0235] In one embodiment, the preferred substituted PPS resin contains a structural unit represented by the general formula (I), and its dielectric loss tangent at 10 GHz is less than 0.002. In addition, the dielectric constant at 10 GHz can be less than 3.00.

[0236] In one embodiment, the preferred substituted PPS resin contains structural units represented by the general formula (I) and the general formula (II), and its dielectric loss tangent at 10 GHz is less than 0.002. In addition, the dielectric constant at 10 GHz can be less than 3.00.

[0237] In one embodiment, the preferred substituted PPS resin contains terminal structures represented by the general formula (I) and the general formula (III-a), (III-b), or (III), and its dielectric loss tangent at 10 GHz is less than 0.002. In addition, the dielectric constant at 10 GHz can be less than 3.00.

[0238] (Glass transition temperature)

[0239] In one embodiment, the upper limit of the glass transition temperature (Tg) of the substituted PPS resin is preferably 250°C or lower, more preferably 200°C or lower, and still more preferably 170°C or lower. Additionally, the lower limit of the glass transition temperature is preferably 25°C or higher. When it is 25°C or higher, it can be 30°C, can be 40°C, can be 50°C, can be 60°C, can be 70°C, can be 80°C, can be 90°C, or can also be 100°C.

[0240] In one embodiment, the glass transition temperature of the substituted PPS resin is preferably 250°C or lower, more preferably 25°C to 250°C. When the glass transition temperature is 25°C to 250°C, it can be set to a range formed by arbitrarily combining the above upper and lower limits. For example, the glass transition temperature of the substituted PPS resin can be 25 to 200°C, can be 25 to 170°C, can be 30 to 250°C, can be 30 to 200°C, can be 30 to 170°C, can be 40 to 250°C, can be 40 to 200°C, can be 40 to 170°C, can be 50 to 250°C, can be 50 to 200°C, can be 50 to 170°C, can be 60 to 250°C, can be 60 to 200°C, can be 60 to 170°C, can be 70 to 250°C, can be 70 to 200°C, can be 70 to 170°C, can be 80 to 250°C, can be 80 to 200°C, can be 80 to 170°C, can be 90 to 250°C, can be 90 to 200°C, can be 90 to 170°C, can be 100 to 250°C, can be 100 to 200°C, or can also be 100 to 170°C.

[0241] By making the glass transition temperature of the substituted PPS resin 250°C or lower, the glass transition temperature of the resin composition containing the substituted PPS resin also easily reaches 250°C or lower.

[0242] The wiring substrate can be formed, for example, by a molding method including a heating process and a curing process. Therefore, depending on the difference between the glass transition temperature of the material and the curing temperature, it sometimes becomes difficult to mold. By making the glass transition temperature of the substituted PPS resin 250°C or lower, it is possible to easily form the wiring substrate by using the substituted PPS resin or the resin composition containing the substituted PPS resin based on the molding method including the heating process and the curing process. When the glass transition temperature of the material is too low, the tackiness increases, and it is sometimes difficult to form the wiring substrate. By making the glass transition temperature of the substituted PPS resin 25°C or higher, it is easy to form the wiring substrate based on the molding method including the heating process and the curing process. In addition, by making the glass transition temperature of the substituted PPS resin 25 to 250°C, it is easy to manufacture the products exemplified in the "products" in this embodiment.

[0243] The methods for adjusting the glass transition temperature can be listed as follows: adjusting the content of the structural units represented by the general formula (I), general formula (II), and / or general formula (III-a), (III-b), or (III) in the substituted PPS resin; adjusting the number of carbon atoms of the alkyl or alkoxy group in the structural units represented by the general formula (I), general formula (II), and / or general formula (III-a), (III-b), or (III); adjusting the number of substituents in the structural units represented by the general formula (I), general formula (II), and / or general formula (III); adjusting the substitution position in the structural units represented by the general formula (I), general formula (II), and / or general formula (III-a), (III-b), or (III); adjusting the weight-average molecular weight of the substituted PPS resin. By any one of these methods or a combination thereof, the glass transition temperature of the substituted PPS resin can be adjusted to 250 °C or lower.

[0244] For example, by setting the weight-average molecular weight of the substituted PPS resin to 33,000 or less, it is easy to adjust the glass transition temperature to a desired range. More specifically, by setting the weight-average molecular weight to 33,000 or less, the glass transition temperature can be adjusted to 250 °C or lower. When the weight-average molecular weight is 33,000 or less, it can be less than 21,000.

[0245] Regarding the glass transition temperature, it can be measured by differential scanning calorimetry (DSC) according to the JIS standard (JIS K 7121: Method for Measuring the Glass Transition Temperature of Plastics) under the temperature-rising condition of 20 °C / min starting from room temperature.

[0246] In one embodiment, it is preferable that the substituted PPS resin contains the structural unit represented by the general formula (I), and its dielectric loss tangent at 10 GHz is less than 0.002 and the glass transition temperature is 250 °C or lower.

[0247] In one embodiment, it is preferable that the substituted PPS resin contains the structural unit represented by the general formula (II), and its dielectric loss tangent at 10 GHz is less than 0.002 and the glass transition temperature is 250 °C or lower.

[0248] In one embodiment, it is preferable that the substituted PPS resin contains the terminal structure represented by the general formula (III-a), (III-b), or (III), and its dielectric loss tangent at 10 GHz is less than 0.002 and the glass transition temperature is 250 °C or lower.

[0249] (Molecular weight)

[0250] In one embodiment, the weight average molecular weight (Mw) of the substituted PPS resin is not limited as long as it is in the range that enables the substituted PPS resin to have a desired dielectric loss tangent and / or a desired glass transition temperature, and is preferably 33,000 or less. When the weight average molecular weight of the substituted PPS resin is 33,000 or less, it may be less than 21,000, may be 20,000 or less, may be 18,000 or less, may be 15,000 or less, may be 13,000 or less, may be 11,000 or less, or may be 10,000 or less.

[0251] By making the weight average molecular weight of the substituted PPS resin 33,000 or less, the glass transition temperature can easily reach the desired temperature.

[0252] The weight average molecular weight of the substituted PPS resin is preferably 1,000 or more. When the weight average molecular weight of the substituted PPS resin is 1,000 or more, it may be greater than 1,200, may be 1,500 or more, may be 2,000 or more, may be 2,200 or more, may be 3,000 or more, may be 3,600 or more, may be 4,000 or more, may be 4,500 or more, may be 4,900 or more, may be 5,500 or more, may be 6,000 or more, may be 7,000 or more, may be 7,300 or more, may be 8,000 or more, may be 8,400 or more, may be 10,000 or more, may be 15,000 or more, may be 20,000 or more, may be 24,000 or more, or may be 30,000 or more.

[0253] By making the weight average molecular weight of the substituted PPS resin 1,000 or more, the dielectric loss tangent and the dielectric constant can easily reach the desired ranges, and / or the storage modulus at 260 °C can easily reach the desired range, that is, it is easy to exhibit good reflow soldering resistance.

[0254] The weight average molecular weight (Mw) is a standard polystyrene conversion value obtained by GPC measurement using a tetrahydrofuran solvent.

[0255] In one embodiment, it is preferred that the substituted PPS resin contains a structural unit represented by the general formula (I), and has a dielectric loss tangent of less than 0.002 at 10 GHz, a glass transition temperature of 250 °C or less, and a weight average molecular weight of 33,000 or less. The weight average molecular weight may be less than 21,000.

[0256] In one embodiment, it is preferred that the substituted PPS resin contains a structural unit represented by the general formula (II), and has a dielectric loss tangent of less than 0.002 at 10 GHz, a glass transition temperature of 250 °C or less, and a weight average molecular weight of 33,000 or less. The weight average molecular weight may be less than 21,000.

[0257] In one embodiment, the preferred substituted PPS resin contains a terminal structure represented by the general formula (III-a), (III-b) or (III), and has a dielectric loss tangent at 10 GHz of less than 0.002, a glass transition temperature of 250 °C or less, and a weight average molecular weight of 33,000 or less. The weight average molecular weight may be less than 21,000.

[0258] In one embodiment, the preferred substituted PPS resin contains a terminal structure represented by the general formula (III-a), (III-b) or (III), and has a dielectric loss tangent at 10 GHz of less than 0.002, a glass transition temperature of 250 °C or less, and a weight average molecular weight of 1,000 or more and 33,000 or less. The weight average molecular weight may be less than 21,000.

[0259] (Storage modulus)

[0260] In one embodiment, the storage modulus of the substituted PPS resin at 260 °C is preferably 1×10 5 Pa or more. When the storage modulus at 260 °C is 1×10 5 or more, it may be 4×10 5 Pa or more, it may be 8×10 5 Pa or more, it may be 8.5×10 5 Pa or more, it may be 1×10 6 Pa or more, it may be 1.7×10 6 Pa or more, it may be 1×10 5 Pa, it may be 4×10 5 Pa, it may be 8×10 5 Pa, it may be 8.5×10 5 Pa, it may be 1×10 6 Pa, or it may be 1.7×10 6 Pa.

[0261] By making the storage modulus of the substituted PPS resin at 260 °C 1×10 5 Pa or more, the substituted PPS resin is likely to exhibit good reflow soldering resistance. In addition, by making the storage modulus of the substituted PPS resin at 260 °C 1×10 5 Pa or more, the storage modulus of the resin composition containing the substituted PPS resin is likely to reach 1×10 5 Pa or more. Therefore, the resin composition containing the substituted PPS resin is likely to exhibit good reflow soldering resistance, and / or the wiring board made of the resin composition is likely to exhibit good reflow soldering resistance.

[0262] For example, in the case of fabricating a printed wiring board by mounting electronic components such as semiconductors on a wiring board such as a printed board and performing wiring, the electronic components are bonded and mounted on the wiring board with solder by heating using a reflow soldering furnace. By making the storage modulus of the substituted PPS resin at 260 °C 1×10 -5 Pa or more, the wiring board can easily maintain its shape even in the heating process of the reflow soldering furnace, that is, the wiring board is likely to exhibit good reflow soldering resistance.

[0263] Examples of the method for adjusting the storage modulus include the following methods: adjusting the content of the structural unit represented by general formula (I), general formula (II) and / or general formula (III-a), (III-b) or (III) containing an alkenyl group in the substituted PPS resin; adjusting the content of the alkenyl group in general formula (I), general formula (II) and / or general formula (III-a), (III-b) or (III); adjusting the weight average molecular weight of the substituted PPS resin. By any one of these methods or a combination thereof, the storage modulus of the substituted PPS resin at 260 °C can be adjusted to 1×10 -5 Pa or more.

[0264] For example, in order to adjust the storage modulus of the substituted PPS resin at 260 °C to 1×10 -5 Pa or more, it preferably contains a terminal structure represented by general formula (III-a), (III-b) or (III) at at least one of its terminals, and more preferably contains a terminal structure represented by general formula (III-a), (III-b) or (III) at both of its terminals.

[0265] For example, by increasing the content of the structural unit having an organic group containing an alkenyl group in the substituted PPS resin, the storage modulus of the substituted PPS resin at 260 °C can easily reach 1×10 -5 Pa or more. In addition, for example, by setting the weight average molecular weight of the substituted PPS resin to 1000 or more, it is easy to adjust the storage modulus of the substituted PPS resin at 260 °C to 1×10 - 5 Pa or more.

[0266] The storage modulus of the substituted PPS resin at 260 °C refers to the value measured at a frequency of 1 Hz and 260 °C using a dynamic viscoelasticity measuring device (RSA-G2, manufactured by TA Instruments). More specifically, the storage modulus at 260 °C can be measured using a dynamic viscoelasticity measuring device (RSA-G2, manufactured by TA Instruments), while heating from room temperature at a rate of 5 °C / min and measuring at 260 °C. A measurement sample (30 mm × 3 mm) is cut out from a film with a uniform thickness in the range of about 0.1 to 0.3 mm that does not interfere with the measurement, and the thickness is accurately determined for the measurement. The main measurement parameters related to the measurement are as follows.

[0267] · Measurement frequency: 10 Hz

[0268] · Heating rate: 5 °C / min

[0269] · Sample measurement length: 15 mm

[0270] · Strain: 0.05%

[0271] In one embodiment, it is preferred that the substituted PPS resin contains a structural unit represented by the general formula (I), and its dielectric loss tangent at 10 GHz is less than 0.002, the glass transition temperature is 250 °C or lower, the weight average molecular weight is 1000 or more and 33000 or less, and the storage modulus at 260 °C is 1×10 -5 Pa or more.

[0272] In one embodiment, it is preferred that the substituted PPS resin contains a structural unit represented by the general formula (II), and its dielectric loss tangent at 10 GHz is less than 0.002, the glass transition temperature is 250 °C or lower, the weight average molecular weight is 1000 or more and 33000 or less, and the storage modulus at 260 °C is 1×10 -5 Pa or more.

[0273] In one embodiment, it is preferred that the substituted PPS resin contains a terminal structure represented by the general formula (III-a), (III-b) or (III), and its dielectric loss tangent at 10 GHz is less than 0.002, the glass transition temperature is 250 °C or lower, the weight average molecular weight is 1000 or more and 33000 or less, and the storage modulus at 260 °C is 1×10 -5 Pa or more.

[0274] In one embodiment, the preferred substituted PPS resin contains an end structure represented by the general formula (III-a), (III-b) or (III), and has a dielectric loss tangent at 10 GHz of less than 0.002, a glass transition temperature of 250 °C or lower, a weight average molecular weight of 1,000 or more and 33,000 or less, and a storage modulus at 260 °C of 1×10 -5 Pa or more.

[0275] [Resin composition containing substituted PPS resin for wiring substrate]

[0276] The resin composition of the first embodiment is a resin composition containing a substituted PPS resin for a wiring substrate.

[0277] The resin composition may be composed only of the substituted PPS resin for a wiring substrate, or may contain components other than it.

[0278] For example, in addition to the substituted PPS resin for a wiring substrate, the resin composition may contain one or more components such as a curing catalyst, a flame retardant, a flame retardancy synergist, a fiber reinforcing agent, a filler, a thermosetting additive, and / or a thermoplastic additive.

[0279] The content of the substituted PPS resin for a wiring substrate in the resin composition of the present embodiment is not limited as long as it is within a range that gives the resin composition a desired dielectric loss tangent, and is preferably 30% by mass or more. 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 100% by mass or more.

[0280] By making the content of the substituted PPS resin in the resin composition 30% by mass or more, the dielectric loss tangent of the resin composition easily reaches a desired range. In addition, the resin composition easily exhibits thermosetting properties and easily exhibits good reflow soldering resistance.

[0281] Since the resin composition has a low dielectric loss tangent, exhibits thermosetting properties, and / or exhibits good reflow soldering resistance by containing the substituted PPS resin for a wiring substrate, it can be suitably used as a material for a wiring substrate.

[0282] [Manufacturing method]

[0283] The manufacturing method of the substituted PPS resin is not limited. For example, it can be manufactured by a general method in the art such as mixing one or more monomer materials required to manufacture the desired substituted PPS resin and polymerizing them under appropriate conditions to obtain a polymer structure.

[0284] More specifically, for example, oxidative polymerization can be carried out by adding 3,3'-dimethyldiphenyldisulfide, 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ), trifluoromethanesulfonic acid and dichloromethane and stirring at room temperature. The reaction solution can be dropped into hydrochloric acid-acidic methanol, the powder can be recovered by filtration, and then the powder can be washed with an aqueous potassium hydroxide solution and pure water and dried under vacuum to obtain the polymer.

[0285] In addition, a substituted PPS resin containing a structural unit having an alkenyl-containing organic group can be produced by the following method. Here, as an example, an example of producing a substituted PPS resin containing a structural unit having a vinyl group will be described.

[0286] Specifically, for example, poly(2,6-dimethyl-1,4-phenylene sulfide), N-bromosuccinimide (NBS), and AIBN are added and reacted under reflux of chlorobenzene. After the reaction, the solution is cooled with ice water, and the precipitated succinimide is filtered off with a glass filter. The filtrate is purified by precipitation with 5 wt% hydrochloric acid-acidic methanol to obtain a bromo-PPS pure product in which a part of the protons of the methyl group are substituted with bromine. Then, the pure product and triphenylphosphine are mixed in THF and heated under reflux for 24 hours. Then, it is cooled to room temperature, an aqueous formaldehyde solution is added to the reaction solution and stirred, and the precipitate disappears. Then, potassium tert-butoxide is added and reacted. After the reaction is completed, it is purified by precipitation with hydrochloric acid-acidic methanol, and after recovery, a vinyl-substituted PPS resin in which the methyl group is converted to a vinyl group can be obtained.

[0287] In addition, for example, DDQ is dispersed in dichloromethane, trifluoroacetic acid is added, and then bis(2,6-dimethylphenyl) disulfide is added and stirred. Then, 4,4'-divinyldiphenyldisulfide is further added and stirred, and the precipitate is purified in hydrochloric acid-acidic methanol, and the crude product is recovered by filtration. Then, an operation of dissolving the crude product in chloroform and reprecipitating with hydrochloric acid-acidic methanol is carried out, so that a vinyl-substituted PPS resin having a vinyl group at the terminal structure of the resin can be obtained in the form of a white powder.

[0288] For example, DDQ is dispersed in dichloromethane, trifluoroacetic acid is added, and then bis(2,6-dimethylphenyl) disulfide is added and stirred. Then, through precipitation in methanol, a polymer (white solid) can be obtained. After adding tetrahydrofuran and 4-chloromethylstyrene to the polymer and dissolving it, an aqueous sodium borohydride solution is added and stirred. Then, through precipitation purification of the reaction solution in methanol, a vinyl-substituted PPS resin having a vinyl group at the terminal structure of the resin can be obtained.

[0289] In addition, for example, by subjecting terminal bromo-PPS to a coupling reaction with 4-vinylphenylboronic acid or vinylmagnesium bromide, a vinyl-substituted PPS resin having a vinyl group in the terminal structure of the resin can be obtained.

[0290] Specifically, for example, terminal bromo-PPS can be synthesized by adding poly(2,6-dimethyl-1,4-phenylene sulfide) to a solution of a sulfonium cation (Br-DPS+) derived from Br-DPS (bis(4-bromophenyl) disulfide) in dichloromethane and performing post-polymerization modification. A vinyl-substituted PPS resin having a vinyl group in the terminal structure of the resin can be obtained by subjecting poly(2,6-dimethyl-1,4-phenylene sulfide) and 4-vinylphenylboronic acid to a Suzuki-Miyaura coupling reaction using a Pd catalyst ( Figure 1 "terminal vinyl-substituted PPS1"). As another method, terminal bromo-PPS and vinylmagnesium bromide can be subjected to a Kumada-Tamao coupling reaction using Ni(dppp)Cl2 ([1,3-bis(diphenylphosphino)propane]nickel(II) dichloride), and after precipitation, recovery, and drying processes, a white powder can be obtained, yielding a vinyl-substituted PPS resin having a vinyl group in the terminal structure of the resin ( Figure 1 "terminal vinyl-substituted PPS2").

[0291] The method for manufacturing a resin composition containing a substituted PPS resin is not limited and can be carried out by equipment and methods commonly used for the preparation of resin compositions. Generally, in many cases, the resin composition is prepared as a polymer solution (resin varnish) in which a substituted PPS resin is dissolved in an organic solvent.

[0292] To prepare such a resin varnish, the substituted PPS resin and other components soluble in the organic solvent can be added to the organic solvent and mixed by stirring with a stirrer, etc. At this time, heating can be carried out as needed. Then, by appropriately adding components insoluble in the organic solvent (e.g., inorganic fillers, etc.) and dispersing them to a given dispersed state using a ball mill, bead mill, planetary mixer, roll mill, etc., a resin varnish can be prepared. Examples of the organic solvent are the same as those described in the "varnish" section below.

[0293] [Product]

[0294] The substituted PPS resin for a wiring substrate and / or the resin composition containing the substituted PPS resin for a wiring substrate can be widely used as a material for a wiring substrate.

[0295] There is no limitation on the products using the substituted PPS resin and / or resin composition. By including a substituted PPS resin containing a structural unit represented by the general formula (I), it 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 addition, when thermosetting property of the material is required for the product or in its manufacturing process, a substituted PPS resin and / or resin composition showing thermosetting property can be preferably used. Further, when reflow soldering resistance of the material is required for the product or in its manufacturing process, a substituted PPS resin and / or resin composition showing good reflow soldering resistance can be preferably used.

[0296] As products using the substituted PPS resin and / or resin composition of the present embodiment, examples include: varnish containing the substituted PPS resin and / or resin composition and a solvent, an interlayer insulating material containing the substituted PPS resin and / or resin composition, a prepreg containing the substituted PPS resin and / or resin composition and a substrate, a metal-clad laminate containing the substituted PPS resin and / or resin composition and a metal foil, a substrate containing the substituted PPS resin and / or resin composition, a wiring board containing the substituted PPS resin and / or resin composition, and a printed wiring board containing the wiring board and electronic components.

[0297] There is no limitation on the uses of these products, and they can be used in various applications requiring high-speed communication. For example, they can be mounted on network devices / terminals, servers, AI processors, in-vehicle / aerospace devices, home game consoles, etc.

[0298] Here, the above-mentioned products using the substituted PPS resin and / or resin composition preferably have a dielectric loss tangent at 10 GHz of less than 0.002, more preferably less than 0.001. When the dielectric loss tangent of the product at 10 GHz is less than 0.001, it can be less than 0.00095, less than 0.0009, or less than 0.00085.

[0299] The lower the dielectric loss tangent of the product, the easier it is to further suppress transmission loss.

[0300] In one embodiment, a printed wiring board containing a wiring board (containing the substituted PPS resin and / or resin composition) and electronic components preferably has a dielectric loss tangent at 10 GHz of less than 0.002, more preferably less than 0.001. When the dielectric loss tangent of the printed wiring board at 10 GHz is less than 0.001, it can be less than 0.00095, less than 0.0009, or less than 0.00085. The lower the dielectric loss tangent of the printed wiring board, the easier it is to further suppress transmission loss.

[0301] (Varnish)

[0302] As a varnish, a polymer solution (resin varnish) obtained by dissolving a substituted PPS resin and / or a resin composition in an organic solvent can be exemplified. In this polymer solution, it is sufficient that at least a part of the polymer is dissolved at a liquid temperature of 25°C, and it is preferable that all of the polymer is dissolved.

[0303] The organic solvent used in the polymer solution is not limited, and those skilled in the art can select from organic solvents well-known in the art, and examples thereof include: acetone, ethyl acetate, cyclohexane, heptane, tetrahydrofuran, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, ethylene glycol, cellosolve, carbitol, anisole, N-methylpyrrolidone, propylene glycol monomethyl ether, methyl ether acetate, toluene, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, etc. The organic solvents can be used in combination of one or more selected from these.

[0304] The lower limit of the content of the substituted PPS resin and / or the resin composition in the polymer solution is not limited as long as it is within a range where it can be handled and a polymer solution sufficient for productization can be obtained. For example, relative to 100% by mass of the polymer solution, it can be, for example, 5% by mass or more, 7% by mass or more, 10% by mass or more, 15% by mass or more. On the other hand, the upper limit of the content of the substituted PPS resin and / or the resin composition in the polymer solution can be, for example, 50% by mass or less, 45% by mass or less, 40% by mass or less, 35% by mass or less relative to 100% by mass of the polymer solution.

[0305] (Interlayer insulating material)

[0306] As an interlayer insulating material, an interlayer insulating material that can be used for printed wiring boards and the like can be exemplified. This interlayer insulating material can also be used as a material for multilayer printed wiring boards.

[0307] For example, a varnish containing a substituted PPS resin and / or a resin composition is an example of an interlayer insulating material, and this varnish can also be coated on other materials to volatilize the solvent to form an insulating film layer, thereby preparing a stacked structure of a multilayer printed circuit board.

[0308] (Prepreg)

[0309] As a prepreg, a prepreg obtained by impregnating a substrate with a varnish containing a substituted PPS resin and / or a resin composition and an organic solvent and drying it can be exemplified. The substrate used for the prepreg is not limited, and those skilled in the art can select from materials well-known in the art, and examples thereof include: natural fiber substrates, organic synthetic fiber substrates, inorganic fiber substrates, etc.

[0310] (Metal-clad laminate)

[0311] As a metal-clad laminate, a metal-clad laminate containing the above prepreg can be exemplified. Such a metal-clad laminate can be obtained, for example, by overlapping a plurality of prepregs and heating and pressing them after overlapping metal foils on one or both sides thereof. Examples of the metal foil include 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 the required characteristics and uses of the metal-clad laminate.

[0312] (Substrate)

[0313] The substrate is a base used together with semiconductor chips such as CPUs and memories to protect them and is mounted on a printed circuit board (PCB). For example, it can be the substrate part in FC-BGA (Flip Chip-Ball Grid Array), FC-CSP (Flip Chip Chip Scale Package), etc.

[0314] (Wiring substrate)

[0315] 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 use. In this specification, the wiring substrate includes the part other than electronic components such as semiconductors in a printed wiring board. As the wiring substrate, a printed circuit board (PCB) in a printed wiring board can be exemplified. The printed circuit board can be, for example, a multilayer printed circuit board described in the above "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 form a printed wiring board.

[0316] (Printed wiring board)

[0317] The printed wiring board is not limited by its structure and / or use within the range including the above wiring substrate and electronic components. For example, the printed wiring board can be a material in which electronic components are mounted on any printed circuit board among a rigid substrate, a flexible substrate, a rigid-flexible substrate, a metal-based substrate, etc.

[0318] The electronic components are not limited, and examples include semiconductor chips, resistors, capacitors, etc. As a structure, for example, wirings and electronic components can be mounted on one or both sides of the wiring substrate (printed circuit board), and in addition, wirings and electronic components can also be mounted between the layers of a multilayer-structured wiring substrate.

[0319] As applications, for example, a rigid printed wiring board with electronic components mounted on a rigid substrate can be used in terminals, base stations, servers, routers, millimeter-wave radars, probe cards, etc. of a mobile communication system, and a flexible printed wiring board with electronic components mounted on a flexible substrate can be used in connection cables, antennas, antenna cables, etc.

[0320] ==Second Embodiment (Substituted PPS Resin with Low Dielectric Loss Tangent)==

[0321] [Substituted PPS resin with a dielectric loss tangent less than 0.002 at 10 GHz]

[0322] The resin of the second embodiment is a substituted PPS resin containing a structural unit represented by the general formula (I) and having a dielectric loss tangent less than 0.002 at 10 GHz.

[0323] General formula (I):

[0324]

[0325] [In formula (I), R1, R2, R3, and R4 are each independently H, an alkyl group, an alkoxy group, or an organic group containing an alkenyl group, and one or more of R1, R2, R3, and R4 are an alkyl group or an alkoxy group]

[0326] (Dielectric loss tangent)

[0327] The substituted PPS resin of this embodiment has a dielectric loss tangent less than 0.002 at 10 GHz. As a result, the resin composition containing the substituted PPS resin easily has a dielectric loss tangent less than 0.002 at 10 GHz.

[0328] The range of the dielectric constant and the preferred range, etc., in the second embodiment, as well as the method for adjusting the dielectric constant, are the same as those described in "Dielectric loss tangent" of the first embodiment.

[0329] The lower the dielectric loss tangent of the substituted PPS resin, the more easily the transmission loss can be further suppressed when used as a material for a wiring substrate or the like.

[0330] (Dielectric constant)

[0331] The range of the dielectric constant and the preferred range, etc., in the second embodiment, as well as the method for adjusting the dielectric constant, are the same as those described in "Dielectric constant" of the first embodiment.

[0332] The lower the dielectric constant of the substituted PPS resin, the more easily the transmission loss can be further suppressed when using the substituted PPS resin or a resin composition containing the substituted PPS resin as a material for a wiring substrate or the like.

[0333] (Measurement of Dielectric Loss Tangent and Dielectric Constant)

[0334] In the second embodiment, the measurement of the dielectric loss tangent and the dielectric constant can be performed as described in “Measurement of Dielectric Loss Tangent and Dielectric Constant” of the first embodiment.

[0335] In one embodiment, the substituted PPS resin preferably contains a structural unit represented by the general formula (I), and has a dielectric loss tangent of less than 0.002 at 10 GHz and a dielectric constant of less than 3.00 at 10 GHz.

[0336] (Substituted PPS Resin Containing a Structural Unit Having an Alkyl Group or an Alkoxy Group)

[0337] The substituted PPS resin contains a structural unit represented by the general formula (I).

[0338] General formula (I):

[0339]

[0340] [In formula (I), R1, R2, R3, and R4 are each independently H, an alkyl group, an alkoxy group, or an organic group containing an alkenyl group, and one or more of R1, R2, R3, and R4 are an alkyl group or an alkoxy group]

[0341] Examples, preferred examples, etc. related to “substituted PPS resin containing a structural unit having an alkyl group or an alkoxy group” in the second embodiment are the same as those described in “substituted PPS resin containing a structural unit having an alkyl group or an alkoxy group” in the first embodiment.

[0342] (Substituted PPS Resin Containing a Structural Unit Having an Organic Group Containing an Alkenyl Group)

[0343] In one embodiment, the substituted PPS resin of the second embodiment may contain a structural unit represented by the general formula (II) and / or a terminal structure represented by the general formula (III).

[0344]

[0345] [In formula (II), R 5a , R 6a , R 7a , and R 8a are each independently H, an alkyl group, an alkoxy group, or an organic group containing an alkenyl group, and one or more of R 5a , R 6a , R 7a , and R 8a are an organic group containing an alkenyl group],

[0346]

[0347] [In formula (III-a), X is independently H, an alkyl group, an alkoxy group, or an organic group containing an alkenyl group, and one or more of them are organic groups containing an alkenyl group, and n is an integer of 1 to 5].

[0348] The terminal structure represented by the general formula (III-a) may be the terminal structure represented by the general formula (III-b).

[0349]

[0350] [In formula (III-b), X is independently H, an alkyl group, an alkoxy group, or an organic group containing an alkenyl group, and one or more of them are organic groups containing an alkenyl group, n is an integer of 1 to 5, and A is the general formula (IV).

[0351]

[0352] [In formula (IV), R1, R2, R3, and R4 are independently H, an alkyl group, an alkoxy group, or an organic group containing an alkenyl group, and one or more of R1, R2, R3, and R4 are an alkyl group or an alkoxy group.

[0353] The terminal structure represented by the general formula (III-a) may be the terminal structure represented by the general formula (III).

[0354]

[0355] [In formula (III), X is independently H, an alkyl group, an alkoxy group, or an organic group containing an alkenyl group, and one or more of them are organic groups containing an alkenyl group, and n is an integer of 1 to 5].

[0356] Examples, preferred examples, etc. related to the "substituted PPS resin containing a structural unit having an organic group containing an alkenyl group" in the second embodiment are the same as the description of the "substituted PPS resin containing a structural unit having an organic group containing an alkenyl group" in the first embodiment.

[0357] In one embodiment, it is preferred that the substituted PPS resin is a substituted PPS resin containing a structural unit represented by the general formula (I) and having a dielectric loss tangent of less than 0.002 at 10 GHz, and containing a structural unit represented by the general formula (II) and / or a terminal structure represented by the general formula (III-a), (III-b), or (III).

[0358] By making the general formula (II) and / or the general formula (III-a), (III-b) or (III) contain one or more alkenyl-containing organic groups, the substituted PPS resin containing the structural unit represented by the general formula (II) and / or the terminal structure represented by the general formula (III-a), (III-b) or (III) is likely to exhibit thermosetting properties. As a result, the resin composition containing the substituted PPS resin is likely to exhibit thermosetting properties.

[0359] (Polymer structure)

[0360] Examples, preferred examples, etc. related to the "polymer structure" in the second embodiment are the same as the descriptions of the "polymer structure" in the first embodiment.

[0361] (Glass transition temperature)

[0362] Examples, preferred examples, etc. related to the "glass transition temperature" in the second embodiment, as well as the method for adjusting the glass transition temperature, are the same as the descriptions of the "glass transition temperature" in the first embodiment.

[0363] (Molecular weight)

[0364] Examples, preferred examples, etc. related to the "molecular weight" in the second embodiment are the same as the descriptions of the "molecular weight" in the first embodiment.

[0365] (Storage modulus)

[0366] Examples, preferred examples, etc. related to the "storage modulus" in the second embodiment, as well as the method for adjusting the storage modulus, are the same as the descriptions of the "storage modulus" in the first embodiment.

[0367] [Resin composition containing substituted PPS resin]

[0368] The resin composition of the second embodiment is a resin composition containing a substituted PPS resin having a dielectric loss tangent of less than 0.002 at 10 GHz.

[0369] The resin composition may consist only of the substituted PPS resin, or may contain other components in addition to it.

[0370] For example, in addition to containing a substituted PPS resin having a dielectric loss tangent of less than 0.002 at 10 GHz, the resin composition may further contain one or more components such as a curing catalyst, a flame retardant, a flame retardant synergist, a fiber reinforcing agent, a filler, a thermosetting additive, and / or a thermoplastic additive.

[0371] The content of the substituted PPS resin in the resin composition of the present embodiment, having a dielectric loss tangent of less than 0.002 at 10 GHz, is not limited as long as it is within the range that gives the resin composition a desired dielectric loss tangent, and is preferably 30% by mass or more. When it is 30% by mass or more, it can 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 100% by mass or more.

[0372] By making the content of the substituted PPS resin in the resin composition 30% by mass or more, the dielectric loss tangent of the resin composition easily reaches the desired range. In addition, the resin composition easily exhibits thermosetting properties and easily exhibits good reflow soldering resistance.

[0373] By containing a substituted PPS resin having a dielectric loss tangent of less than 0.002 at 10 GHz, the resin composition has a low dielectric loss tangent, exhibits thermosetting properties, and / or exhibits good reflow soldering resistance, and thus can be suitably used as a material for wiring substrates and the like.

[0374] [Manufacturing method]

[0375] The manufacturing method of the substituted PPS resin in the second embodiment is the same as that described in the "Manufacturing method" of the first embodiment.

[0376] [Product]

[0377] The substituted PPS resin having a dielectric loss tangent of less than 0.002 at 10 GHz and / or the resin composition containing the substituted PPS resin having a dielectric loss tangent of less than 0.002 in the second embodiment can be widely used as a material for wiring substrates and the like.

[0378] The wiring substrate includes all parts of a printed wiring board (also called a printed circuit board) other than electronic components such as semiconductors. Generally, a printed wiring board has a structure in which a semiconductor package having electronic components such as semiconductors mounted on a base called a substrate is mounted on a printed substrate (PCB, Print Circuit Board), and the "substrate" for "wiring substrate use" also includes the substrate.

[0379] There is no limitation on the products using the substituted PPS resin and / or resin composition. By including a substituted PPS resin containing a structural unit represented by the general formula (I), it 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 addition, when thermosetting properties of the material are required for the product or in its manufacturing process, the resin composition of the present embodiment showing thermosetting properties can be preferably used. Furthermore, when reflow soldering resistance of the material is required for the product or in its manufacturing process, a substituted PPS resin and / or resin composition showing good reflow soldering resistance can be preferably used.

[0380] Examples of the products using the substituted PPS resin and / or resin composition of the present embodiment include: varnish containing a substituted PPS resin and / or resin composition and a solvent, an interlayer insulating material containing a substituted PPS resin and / or resin composition, a prepreg containing a substituted PPS resin and / or resin composition and a substrate, a metal-clad laminate containing a substituted PPS resin and / or resin composition and a metal foil, a substrate containing a substituted PPS resin and / or resin composition, a wiring board containing a substituted PPS resin and / or resin composition, and a printed wiring board containing the wiring board and electronic components.

[0381] There is no limitation on the uses of these products, and they can be used in various applications requiring high-speed communication. For example, they can be mounted on network devices / terminals, servers, AI processors, in-vehicle / aerospace devices, home game consoles, etc.

[0382] Here, the above products using the substituted PPS resin and / or resin composition preferably have a dielectric loss tangent less than 0.002 at 10 GHz, and more preferably less than 0.001. When the dielectric loss tangent of the product at 10 GHz is less than 0.001, it can be less than 0.00095, less than 0.0009, or less than 0.00085.

[0383] The lower the dielectric loss tangent of the product, the easier it is to further suppress transmission loss.

[0384] In one embodiment, the dielectric loss tangent of a printed wiring board containing a wiring board (containing a substituted PPS resin and / or resin composition) and electronic components is preferably less than 0.002 at 10 GHz, and more preferably less than 0.001. When the dielectric loss tangent of the printed wiring board at 10 GHz is less than 0.001, it can be less than 0.00095, less than 0.0009, or less than 0.00085. The lower the dielectric loss tangent of the printed wiring board, the easier it is to further suppress transmission loss.

[0385] (Varnish)

[0386] Examples, preferred examples, etc. related to "varnish" in the second embodiment are the same as those described in "varnish" of the first embodiment.

[0387] (Interlayer insulating material)

[0388] Examples, preferred examples, etc. related to "interlayer insulating material" in the second embodiment are the same as those described in "interlayer insulating material" of the first embodiment.

[0389] (Prepreg)

[0390] Examples, preferred examples, etc. related to "prepreg" in the second embodiment are the same as those described in "prepreg" of the first embodiment.

[0391] (Metal-clad laminate)

[0392] Examples, preferred examples, etc. related to "metal-clad laminate" in the second embodiment are the same as those described in "metal-clad laminate" of the first embodiment.

[0393] (Substrate)

[0394] Examples, preferred examples, etc. related to "substrate" in the second embodiment are the same as those described in "substrate" of the first embodiment.

[0395] (Wiring board)

[0396] Examples, preferred examples, etc. related to "wiring board" in the second embodiment are the same as those described in "wiring board" of the first embodiment.

[0397] (Printed wiring board)

[0398] Examples, preferred examples, etc. related to "printed wiring board" in the second embodiment are the same as those described in "printed wiring board" of the first embodiment.

[0399] ==Third Embodiment (Substituted PPS Resin with Terminal Structure Containing Alkenyl-Containing Organic Group)==

[0400] [Substituted PPS resin]

[0401] (Substituted PPS resin with terminal structure containing alkenyl-containing organic group)

[0402] The resin of the third embodiment is a substituted PPS resin containing a terminal structure represented by the general formula (III-a).

[0403] General formula (III-a):

[0404]

[0405] [In formula (III-a), X is independently H, an alkyl group, an alkoxy group, or an organic group containing an alkenyl group, and one or more of them are organic groups containing an alkenyl group, and n is an integer from 1 to 5.]

[0406] The terminal structure represented by general formula (III-a) may be the terminal structure represented by general formula (III-b).

[0407]

[0408] [In formula (III-b), X is independently H, an alkyl group, an alkoxy group, or an organic group containing an alkenyl group, and one or more of them are organic groups containing an alkenyl group, n is an integer from 1 to 5, and A is the general formula (IV).

[0409]

[0410] [In formula (IV), R1, R2, R3, and R4 are independently H, an alkyl group, an alkoxy group, or an organic group containing an alkenyl group, and one or more of R1, R2, R3, and R4 are an alkyl group or an alkoxy group.]

[0411] The terminal structure represented by general formula (III-a) may be the terminal structure represented by general formula (III).

[0412]

[0413] [In formula (III), X is independently H, an alkyl group, an alkoxy group, or an organic group containing an alkenyl group, and one or more of them are organic groups containing an alkenyl group, and n is an integer from 1 to 5.]

[0414] In the third embodiment, the terminal structures represented by general formulas (III-a), (III-b), and (III) mean that one or more substituents in the terminal structures located at one or both ends of the structural units contained in the substituted PPS resin are organic groups containing an alkenyl group.

[0415] The substituted PPS resin of the third embodiment contains a phenylene group optionally having a substituent as one terminal and / or at least a part of the structural units other than the terminal. As the substituent of the phenylene group, H, an alkyl group, an alkoxy group, or an organic group containing an alkenyl group can be cited. The phenylene group optionally having a substituent is preferably the structural unit represented by general formula (I) and / or general formula (II) described in the "substituted PPS resin containing a structural unit having an alkyl group or an alkoxy group" in the present embodiment.

[0416] Examples and preferred examples of the alkyl, alkoxy, and alkenyl-containing organic groups in the general formulas (III-a), (III-b), and (III) are the alkyl, alkoxy, and alkenyl-containing organic groups exemplified in the description of the general formula (I) in the first embodiment. Regarding the number of carbon atoms of the alkyl and alkoxy groups, the number of carbon atoms exemplified in the description of the general formula (I) in the first embodiment may be used.

[0417] The number of carbon atoms of the alkenyl group in the general formula (III) may be the number of carbon atoms exemplified in the descriptions of the general formulas (III-a), (III-b), and (III) in the first embodiment.

[0418] Here, the substitution position of the alkenyl-containing organic group in the general formulas (III-a), (III-b), and (III) may be the substitution position described in the general formulas (III-a), (III-b), and (III) in the first embodiment.

[0419] By including one or more alkenyl-containing organic groups in the general formulas (III-a), (III-b), and (III), the substituted PPS resin containing the terminal structure represented by the general formula (III) is likely to exhibit thermosetting properties and good reflow soldering resistance. As a result, the resin composition containing the substituted PPS resin is likely to exhibit thermosetting properties and good reflow soldering resistance.

[0420] (Substituted PPS resin containing a structural unit having an alkyl or alkoxy group)

[0421] In one embodiment, the substituted PPS resin of the third embodiment may contain a structural unit represented by the general formula (I),

[0422]

[0423] [In the formula (I), R1, R2, R3, and R4 are each independently H, an alkyl group, an alkoxy group, or an alkenyl-containing organic group, and one or more of R1, R2, R3, and R4 are an alkyl group or an alkoxy group].

[0424] Examples, preferred examples, etc. related to the "substituted PPS resin containing a structural unit having an alkyl or alkoxy group" in the third embodiment are the same as those described in the "substituted PPS resin containing a structural unit having an alkyl or alkoxy group" in the first embodiment.

[0425] In one embodiment, it is preferred that the substituted PPS resin contains a terminal structure represented by the general formula (III) and a structural unit represented by the general formula (I).

[0426] By including one or more alkyl groups or alkoxy groups in the general formula (I), the dielectric loss tangent of the substituted PPS resin containing the structural unit represented by the general formula (I) can be easily reduced. As a result, the dielectric loss tangent of the resin composition containing the substituted PPS resin can be easily reduced.

[0427] (Substituted PPS resin containing a structural unit having an organic group containing an alkenyl group)

[0428] In one embodiment, the substituted PPS resin may contain a structural unit represented by the general formula (II),

[0429]

[0430] [In the formula (II), R 5a , R 6a , R 7a and R 8a are each independently H, an alkyl group, an alkoxy group, or an organic group containing an alkenyl group, and one or more of R 5a , R 6a , R 7a and R 8a are organic groups containing an alkenyl group].

[0431] The structural unit represented by the general formula (II) means that one or more substituents in the structural units other than the terminal structural units of the resin contained in the substituted PPS resin are organic groups containing an alkenyl group.

[0432] As examples and preferred examples of the alkyl group, alkoxy group, and organic group containing an alkenyl group in the general formula (II) in the third embodiment, the alkyl group, alkoxy group, and organic group containing an alkenyl group exemplified in the description of the general formula (I) in the first embodiment can be cited. Regarding the number of carbon atoms of the alkyl group and alkoxy group, it can be set to the number of carbon atoms exemplified in the description of the general formula (I) in the first embodiment.

[0433] The number of carbon atoms of the organic group containing an alkenyl group in the general formula (II) can be set to the number of carbon atoms exemplified in the description of the general formula (II) in the first embodiment.

[0434] Here, the substitution position based on the organic group containing an alkenyl group in the general formula (II) can be set to the substitution position described in the general formula (II) in the first embodiment.

[0435] By including one or more organic groups containing an alkenyl group in the general formula (II), the substituted PPS resin containing the structural unit represented by the general formula (II) easily exhibits thermosetting properties. As a result, the resin composition containing the substituted PPS resin easily exhibits thermosetting properties.

[0436] (Polymer structure)

[0437] The substituted PPS resin has a polymer structure including two or more structural units (monomer units) capable of forming the resin. The substituted PPS resin of the third embodiment includes the terminal structures represented by the general formula (III-a), (III-b), or (III) as either or both of its terminals. The substituted PPS resin may include one or more structural units represented by formulas other than the general formula (III-a), (III-b), and (III).

[0438] Here, the terminal structure represented by the general formula (III-a), (III-b), or (III) may be one type of terminal structure, that is, the two terminals of the resin may have the same general formula and the same substituents; or, within the range represented by the general formula (III-a), (III-b), or (III), it may be two types of terminal structures, that is, the terminals of the resin may be different structures respectively, and there are two or more terminal structures with different combinations of the five X substituents exemplified in the description of the general formula (III-a), (III-b), or (III). From the viewpoint of easily exhibiting thermosetting properties and / or the viewpoint of easily improving reflow soldering resistance, the terminal structure may be one type of terminal structure or two types of terminal structures, but considering the ease of synthesis of the substituted PPS resin, it is preferred that the two terminals of the resin be one type of terminal structure, that is, having the same general formula and the same substituents.

[0439] Here, the one or more structural units represented by formulas other than the general formula (III-a), (III-b), and (III) are not limited, and include, for example, the structural unit represented by the general formula (I), the structural unit represented by the general formula (II), and unsubstituted PPS (PPS in which all substituents of the general formula (I) are H) units.

[0440] The structural unit represented by the general formula (I) may be one type of structural unit, or may be two or more structural units within the range represented by the general formula (I). The structural unit represented by the general formula (I) includes two or more structural units with different combinations of the substituents R1, R2, R3, and R4 exemplified in the description of the general formula (I) of the first embodiment.

[0441] The structural unit represented by the general formula (II) may be one type of structural unit, or may be two or more structural units within the range represented by the general formula (II). The structural unit represented by the general formula (II) includes two or more structural units with different combinations of the substituents R 5a 、R 6a 、R 7a and R 8a exemplified in the description of the general formula (II) of the first embodiment.

[0442] In the substituted PPS resin, the bonding order of the structural units is not limited. For example, it can be in the following ways: the structural units represented by the general formula (I) with the same substituent combination are adjacent to each other, the structural units represented by the general formula (II) with the same substituent combination are adjacent to each other, the structural units represented by the general formula (I) with different substituent combinations are adjacent to each other, the structural units represented by the general formula (II) with different substituent combinations are adjacent to each other, the structural units represented by the general formula (I) are adjacent to the structural units represented by the general formula (II), and the structural units represented by the general formula (I) or (II) are adjacent to the structural units other than those represented by the general formula (I) or (II). In addition, terminal structures represented by the general formula (III-a), (III-b), or (III) can be bonded to one or both ends of a plurality of structural units bonded in any of these orders.

[0443] In one embodiment, the substituted PPS resin may include a structural unit in which at least one of the 2-position, 3-position, 4-position, and 5-position in the general formula (III-a), (III-b), or (III) is an alkenyl-containing organic group having 2 to 3 carbon atoms, and X of the non-alkenyl-containing organic group is H or an alkyl group having 1 to 5 carbon atoms, and a structural unit in the general formula (I) in which R2 and R3 are alkyl groups having 1 to 5 carbon atoms and R1 and R4 are H, and may include a structural unit in which at least one of the 2-position, 3-position, 4-position, and 5-position in the general formula (III-a), (III-b), or (III) is vinyl, and X of the non-vinyl group is H or methyl, and a structural unit in the general formula (I) in which R2 or R3 is methyl and R1 and R4 are H.

[0444] In one embodiment, the substituted PPS resin may include a structural unit in which at least one of the 3-position and 5-position in the general formula (III-a), (III-b), or (III) is an alkenyl-containing organic group having 2 to 3 carbon atoms, and X of the non-alkenyl-containing organic group is H or an alkyl group having 1 to 5 carbon atoms, and a structural unit in the general formula (I) in which R2 and R3 are alkyl groups having 1 to 5 carbon atoms and R1 and R4 are H, and may include a structural unit in which at least one of the 3-position and 5-position in the general formula (III) is vinyl, and X of the non-vinyl group is H or methyl, and a structural unit in the general formula (I) in which R2 or R3 is methyl and R1 and R4 are H.

[0445] In one embodiment, the substituted PPS resin may have an alkenyl-containing organic group at any substitution position in the general formula (I), general formula (II), and / or general formula (III-a), (III-b), or (III). The carbon atoms of the alkenyl-containing organic group may be 2 to 3 and may be vinyl.

[0446] In one embodiment, the substituted PPS resin may be a 3,5-dimethyl PPS resin optionally having one or more alkenyl-containing organic groups with 2 to 3 carbon atoms at two or one terminal structures. In one embodiment, the substituted PPS resin may be a 3,5-dimethyl PPS resin optionally having one or more vinyl groups at two or one terminal structures.

[0447] In one embodiment, the content of the structural unit represented by the general formula (I) in the substituted PPS resin, or the content of the structural unit represented by the general formula (I) and the structural unit represented by the general formula (II) is not limited as long as the substituted PPS resin and / or the resin composition containing the substituted PPS resin have a desired dielectric loss tangent. The content of the structural unit containing an alkyl group and / or an alkoxy group in the substituted PPS resin is preferably 30 mol% or more. When it is 30 mol% or more, it may be 40 mol% or more, 50 mol% or more, 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, or 100 mol%.

[0448] By making the content of the structural unit containing an alkyl group and / or an alkoxy group in the substituted PPS resin 30 mol% or more, the dielectric loss tangent of the substituted PPS resin easily reaches a desired range. As a result, the dielectric loss tangent of the resin composition containing the substituted PPS resin easily reaches a desired range.

[0449] In one embodiment, the content of the structural unit having an alkenyl-containing organic group in the substituted PPS resin is not limited as long as the substituted PPS resin and / or the resin composition containing the substituted PPS resin exhibit a desired thermosetting property. As the upper limit, it is 20 mol% or less, preferably 18 mol% or less, more preferably 1 to 18 mol%, further preferably 2 to 10 mol%, and further preferably 2 to 7 mol%. When it is 18 mol% or less, it may be 15 mol% or less, 10 mol% or less, 7 mol% or less, 5 mol% or less, 4 mol% or less, 3 mol% or less, or 1 mol% or less.

[0450] In addition, the lower limit of the content of the structural unit having an organic group containing an alkenyl group in the substituted PPS resin is 1 structural unit. Here, when the content of the structural unit having an organic group containing an alkenyl group in the substituted PPS resin of the third embodiment is 1 structural unit, any one of the terminal structures of the substituted PPS resin is a terminal structure having an organic group containing an alkenyl group. Even in the case of a resin in which only 1 structural unit of the substituted PPS resin has an organic group containing an alkenyl group, since this structural unit is a terminal structure, the substituted PPS resin easily exhibits thermosetting properties.

[0451] When the lower limit of the content of the structural unit having an organic group containing an alkenyl group in the substituted PPS resin is 1 or more structural units, it may be 2 or more structural units, it may be 0.1 mol% or more, it may be 0.2 mol% or more, it may be 0.5 mol% or more, or it may be 0.8 mol% or more.

[0452] In one embodiment, the content of the structural unit having an organic group containing an alkenyl group in the substituted PPS resin may be set to a range formed by arbitrarily combining the above upper and lower limits.

[0453] For example, the content of the structural unit having an alkenyl-containing organic group in the substituted PPS resin may be 1 or more structural units and 18 mol% or less, may be 1 or more structural units and 15 mol% or less, may be 1 or more structural units and 10 mol% or less, may be 1 or more structural units and 7 mol% or less, may be 1 or more structural units and 5 mol% or less, may be 1 or more structural units and 4 mol% or less, may be 1 or more structural units and 3 mol% or less, may be 1 or more structural units and 1 mol% or less. Additionally, it may be 2 or more structural units and 18 mol% or less, may be 2 or more structural units and 15 mol% or less, may be 2 or more structural units and 10 mol% or less, may be 2 or more structural units and 7 mol% or less, may be 2 or more structural units and 5 mol% or less, may be 2 or more structural units and 4 mol% or less, may be 2 or more structural units and 3 mol% or less, may be 2 or more structural units and 1 mol% or less. Additionally, it may be 0.1 mol% or more and 18 mol% or less, may be 0.1 mol% or more and 15 mol% or less, may be 0.1 mol% or more and 10 mol% or less, may be 0.1 mol% or more and 7 mol% or less, may be 0.1 mol% or more and 5 mol% or less, may be 0.1 mol% or more and 4 mol% or less, may be 0.1 mol% or more and 3 mol% or less, may be 0.1 mol% or more and 1 mol% or less. Additionally, it may be 0.2 mol% or more and 18 mol% or less, may be 0.2 mol% or more and 15 mol% or less, may be 0.2 mol% or more and 10 mol% or less, may be 0.2 mol% or more and 7 mol% or less, may be 0.2 mol% or more and 5 mol% or less, may be 0.2 mol% or more and 4 mol% or less, may be 0.2 mol% or more and 3 mol% or less, may be 0.2 mol% or more and 1 mol% or less. Additionally, it may be 0.5 mol% or more and 18 mol% or less, may be 0.5 mol% or more and 15 mol% or less, may be 0.5 mol% or more and 10 mol% or less, may be 0.5 mol% or more and 7 mol% or less, may be 0.5 mol% or more and 5 mol% or less, may be 0.5 mol% or more and 4 mol% or less, may be 0.5 mol% or more and 3 mol% or less, may be 0.5 mol% or more and 1 mol% or less. Additionally, it may be 0.8 mol% or more and 18 mol% or less, may be 0.8 mol% or more and 15 mol% or less, may be 0.8 mol% or more and 10 mol% or less, may be 0.8 mol% or more and 7 mol% or less, may be 0.8 mol% or more and 5 mol% or less, may be 0.8 mol% or more and 4 mol% or less, may be 0.8 mol% or more and 3 mol% or less, may be 0.8 mol% or more and 1 mol% or less.

[0454] By making the content of the structural unit having an alkenyl-containing organic group in the substituted PPS resin be 1 or more and 20 mol% or less of structural units, the substituted PPS resin is likely to exhibit thermosetting properties and / or is likely to exhibit good reflow soldering resistance. As a result, the resin composition containing the substituted PPS resin is likely to exhibit thermosetting properties and / or is likely to exhibit good reflow soldering resistance.

[0455] (Dielectric loss tangent)

[0456] The range and preferred range of the dielectric constant in the third embodiment, etc., and the method for adjusting the dielectric constant are the same as those described in "Dielectric loss tangent" of the first embodiment.

[0457] The lower the dielectric loss tangent of the substituted PPS resin, the more easily the transmission loss can be further suppressed when used as a material for a wiring board or the like.

[0458] (Dielectric constant)

[0459] The range and preferred range of the dielectric constant in the third embodiment, etc., and the method for adjusting the dielectric constant are the same as those described in "Dielectric constant" of the first embodiment.

[0460] The lower the dielectric constant of the substituted PPS resin, the more easily the transmission loss can be further suppressed when the substituted PPS resin or the resin composition containing the substituted PPS resin is used as a material for a wiring board or the like.

[0461] (Measurement of dielectric loss tangent and dielectric constant)

[0462] In the third embodiment, the measurement of the dielectric loss tangent and the dielectric constant can be carried out as described in "Measurement of dielectric loss tangent and dielectric constant" of the first embodiment.

[0463] In one embodiment, it is preferred that the substituted PPS resin contains a terminal structure represented by the general formula (III-a), (III-b) or (III), and its dielectric loss tangent at 10 GHz is less than 0.002. Further, in one embodiment, the dielectric constant at 10 GHz can be less than 3.00.

[0464] In one embodiment, it is preferred that the substituted PPS resin contains a terminal structure represented by the general formula (III-a), (III-b) or (III) and a structural unit represented by the general formula (I), and its dielectric loss tangent at 10 GHz is less than 0.002. Further, in one embodiment, the dielectric constant at 10 GHz can be less than 3.00.

[0465] In one embodiment, the preferred substituted PPS resin contains a terminal structure represented by the general formula (III-a), (III-b), or (III) and a structural unit represented by the general formula (II), and its dielectric loss tangent at 10 GHz is less than 0.002. Further, in one embodiment, the dielectric constant at 10 GHz can be less than 3.00.

[0466] (Glass transition temperature)

[0467] Examples, preferred examples, etc. related to the "glass transition temperature" in the third embodiment, and the method for adjusting the glass transition temperature are the same as those described in the "glass transition temperature" of the first embodiment.

[0468] In one embodiment, the preferred substituted PPS resin contains a terminal structure represented by the general formula (III-a), (III-b), or (III), and its dielectric loss tangent at 10 GHz is less than 0.002 and the glass transition temperature is 250 °C or lower.

[0469] In one embodiment, the preferred substituted PPS resin contains a terminal structure represented by the general formula (III-a), (III-b), or (III) and a structural unit represented by the general formula (I), and its dielectric loss tangent at 10 GHz is less than 0.002 and the glass transition temperature is 250 °C or lower.

[0470] In one embodiment, the preferred substituted PPS resin contains a terminal structure represented by the general formula (III-a), (III-b), or (III) and a structural unit represented by the general formula (II), and its dielectric loss tangent at 10 GHz is less than 0.002 and the glass transition temperature is 250 °C or lower.

[0471] (Molecular weight)

[0472] Examples, preferred examples, etc. related to the "molecular weight" in the third embodiment are the same as those described in the "molecular weight" of the first embodiment.

[0473] In one embodiment, the preferred substituted PPS resin contains a structural unit represented by the general formula (III-a), (III-b), or (III), and its dielectric loss tangent at 10 GHz is less than 0.002, the glass transition temperature is 250 °C or lower, and the weight average molecular weight is 33,000 or lower. The weight average molecular weight can be less than 21,000.

[0474] In one embodiment, preferably, the substituted PPS resin contains structural units represented by general formula (III-a), (III-b) or (III) and general formula (I), and has a dielectric loss tangent at 10 GHz of less than 0.002, a glass transition temperature of 250 °C or lower, and a weight-average molecular weight of 33,000 or lower. The weight-average molecular weight may be less than 21,000.

[0475] In one embodiment, preferably, the substituted PPS resin contains terminal structures represented by general formula (III-a), (III-b) or (III) and general formula (II), and has a dielectric loss tangent at 10 GHz of less than 0.002, a glass transition temperature of 250 °C or lower, and a weight-average molecular weight of 33,000 or lower. The weight-average molecular weight may be less than 21,000.

[0476] In one embodiment, preferably, the substituted PPS resin contains terminal structures represented by general formula (III-a), (III-b) or (III) and general formula (II), and has a dielectric loss tangent at 10 GHz of less than 0.002, a glass transition temperature of 250 °C or lower, and a weight-average molecular weight of 1,000 or more and 33,000 or lower. The weight-average molecular weight may be less than 21,000.

[0477] (Storage modulus)

[0478] Examples, preferred examples, etc. related to the "storage modulus" in the third embodiment, and the method for adjusting the storage modulus are the same as those described in the "storage modulus" of the first embodiment.

[0479] In one embodiment, preferably, the substituted PPS resin contains structural units represented by general formula (III-a), (III-b) or (III), and has a dielectric loss tangent at 10 GHz of less than 0.002, a glass transition temperature of 250 °C or lower, a weight-average molecular weight of 1,000 or more and 33,000 or lower, and a storage modulus at 260 °C of 1×10 -5 Pa or more.

[0480] In one embodiment, preferably, the substituted PPS resin contains structural units represented by general formula (III-a), (III-b) or (III) and general formula (I), and has a dielectric loss tangent at 10 GHz of less than 0.002, a glass transition temperature of 250 °C or lower, a weight-average molecular weight of 1,000 or more and 33,000 or lower, and a storage modulus at 260 °C of 1×10 -5 Pa or more.

[0481] In one embodiment, the preferred substituted PPS resin contains an end structure represented by the general formula (III-a), (III-b) or (III), and has a dielectric loss tangent at 10 GHz of less than 0.002, a glass transition temperature of 250 °C or lower, a weight average molecular weight of 1,000 or more and 33,000 or less, and a storage modulus at 260 °C of 1 × 10 -5 Pa or more.

[0482] [Resin composition containing substituted PPS resin]

[0483] The resin composition of the third embodiment is a resin composition containing the substituted PPS resin of the third embodiment.

[0484] The resin composition may consist only of the substituted PPS resin, or may contain components other than it.

[0485] For example, the resin composition may contain one or more components such as a curing catalyst, a flame retardant, a flame retardancy synergist, a fiber reinforcing agent, a filler, a thermosetting additive, and / or a thermoplastic additive.

[0486] The content of the substituted PPS resin in the resin composition of the present embodiment is not particularly limited, and those skilled in the art can appropriately determine it according to the use of the resin composition and considering the characteristics of the substituted PPS resin and components other than it. For example, it may be 30% by mass or more, may be 40% by mass or more, may be 50% by mass or more, may be 60% by mass or more, may be 70% by mass or more, may be 80% by mass or more, may be 90% by mass or more, or may be 100% by mass.

[0487] By making the content of the substituted PPS resin in the resin composition 30% by mass or more, the dielectric loss tangent of the resin composition is likely to be less than 0.002, and / or the resin composition is likely to exhibit thermosetting properties.

[0488] When the resin composition is used as a material for a wiring board, the characteristics of a low dielectric loss tangent and / or thermosetting properties are suitable.

[0489] [Manufacturing method]

[0490] The manufacturing method of the substituted PPS resin in the third embodiment is the same as that described in the "Manufacturing method" of the first embodiment.

[0491] [Product]

[0492] When the substituted PPS resin of the third embodiment and / or the resin composition containing the substituted PPS resin has a low dielectric loss tangent, exhibits thermosetting properties, and / or exhibits good reflow soldering resistance, it can be widely used as a material for wiring boards and the like.

[0493] The wiring board includes all parts of a printed wiring board (also referred to as a printed circuit board) other than electronic components such as semiconductors. Generally, a printed wiring board has a structure in which a semiconductor package having electronic components such as semiconductors mounted on a base called a substrate is mounted on a printed substrate (PCB, Print Circuit Board), and the "substrate" for "wiring board" also includes the substrate.

[0494] There is no limitation on the products using the substituted PPS resin and / or the resin composition. When it has a low dielectric loss tangent, it can preferably be used as an insulator component in a terminal of a mobile communication system. In addition, when thermosetting properties of the material are required for the product or in its manufacturing process, the resin composition of this embodiment that exhibits thermosetting properties can preferably be used. Furthermore, when reflow soldering resistance of the material is required for the product or in its manufacturing process, the substituted PPS resin and / or the resin composition that exhibits good reflow soldering resistance can preferably be used.

[0495] Examples of the products using the substituted PPS resin and / or the resin composition of this embodiment include: varnishes containing the substituted PPS resin and / or the resin composition and a solvent, interlayer insulating materials containing the substituted PPS resin and / or the resin composition, prepregs containing the substituted PPS resin and / or the resin composition and a base material, metal-clad laminates containing the substituted PPS resin and / or the resin composition and a metal foil, substrates containing the substituted PPS resin and / or the resin composition, wiring boards containing the substituted PPS resin and / or the resin composition, and printed wiring boards containing the wiring board and electronic components.

[0496] The uses of these products are not limited, and they can be used in various applications requiring high-speed communication. For example, they can be mounted on network devices / terminals, servers, AI processors, in-vehicle / aerospace devices, home game consoles, etc.

[0497] Here, the above products using the substituted PPS resin and / or the resin composition preferably have a dielectric loss tangent at 10 GHz of less than 0.002, more preferably less than 0.001. When the dielectric loss tangent of the product at 10 GHz is less than 0.001, it can be less than 0.00095, less than 0.0009, or less than 0.00085.

[0498] The lower the dielectric loss tangent of the product, the easier it is to further suppress transmission loss.

[0499] In one embodiment, the dielectric loss tangent of a printed wiring board including a wiring substrate (including a substituted PPS resin and / or a resin composition) and electronic components at 10 GHz is preferably less than 0.002, more preferably less than 0.001. When the dielectric loss tangent of the printed wiring board at 10 GHz is less than 0.001, it can be less than 0.00095, less than 0.0009, or less than 0.00085. The lower the dielectric loss tangent of the printed wiring board, the easier it is to further suppress transmission loss.

[0500] (Varnish)

[0501] Examples and preferred examples related to "varnish" in the third embodiment are the same as those described in "varnish" in the first embodiment.

[0502] (Interlayer insulating material)

[0503] Examples and preferred examples related to "interlayer insulating material" in the third embodiment are the same as those described in "interlayer insulating material" in the first embodiment.

[0504] (Prepreg)

[0505] Examples and preferred examples related to "prepreg" in the third embodiment are the same as those described in "prepreg" in the first embodiment.

[0506] (Metal-clad laminate)

[0507] Examples and preferred examples related to "metal-clad laminate" in the third embodiment are the same as those described in "metal-clad laminate" in the first embodiment.

[0508] (Substrate)

[0509] Examples and preferred examples related to "substrate" in the third embodiment are the same as those described in "substrate" in the first embodiment.

[0510] (Wiring substrate)

[0511] Examples and preferred examples related to "wiring substrate" in the third embodiment are the same as those described in "wiring substrate" in the first embodiment.

[0512] (Printed wiring board)

[0513] Examples and preferred examples related to "printed wiring board" in the third embodiment are the same as those described in "printed wiring board" in the first embodiment.

[0514] Examples

[0515] Examples are shown below to illustrate the present disclosure in more detail, but the interpretation of the present disclosure is not limited by these examples.

[0516] [Resin]

[0517] The resin used for evaluation is the following resin. Refer to Table 1.

[0518] (Example)

[0519] (1) 3,5-Dimethyl PPS resin (Mw: 3000)

[0520] (2) 3,5-Dimethyl PPS resin (Mw: 4400)

[0521] (3) 3,5-Dimethyl PPS resin (Mw: 6500)

[0522] (4) 3,5-Dimethyl PPS resin (Mw: 9000)

[0523] (5) 3,5-Dimethyl PPS resin (Mw: 19500)

[0524] (6) 3,5-Dimethyl PPS resin (Mw: 22500)

[0525] (7) 2,5-Dimethyl PPS resin (Mw: 1000)

[0526] (8) 3-Methyl PPS resin (Mw: 9200)

[0527] (9) 2-Isopropyl PPS resin (Mw: 5200)

[0528] (10) 3,5-Dimethyl PPS resin (Mw: 7600)

[0529] (11) 3,5-Dimethyl PPS resin (Mw: 4900; vinyl-containing structural unit: 1 mol% (random))

[0530] (12) 3,5-Dimethyl, 3-methyl PPS resin (Mw: 5200; vinyl-containing structural unit: 4 mol% (random))

[0531] (13) 3,5-Dimethyl PPS resin (Mw: 15000; vinyl-containing structural unit: 7 mol% (random))

[0532] (14) 3,5-Dimethyl PPS resin (Mw: 7300; vinyl-containing structural unit: 18 mol% (random))

[0533] (15) 3,5-Dimethyl PPS resin (Mn: 2200; vinyl group-containing structural unit: 13 mol% (terminal))

[0534] (16) 3,5-Dimethyl PPS resin (Mw: 15000; vinyl group-containing structural unit: 4 mol% (terminal))

[0535] (17) 3,5-Dimethyl PPS resin (Mw: 14000; vinyl group-containing structural unit: 4 mol% (terminal))

[0536] (18) 3,5-Dimethyl PPS resin (Mw: 16400; vinyl group-containing structural unit: 3 mol% (terminal))

[0537] (19) 3,5-Dimethyl PPS resin (Mw: 24000; vinyl group-containing structural unit: 1 mol% (random))

[0538] (20) 3,5-Dimethyl PPS resin (Mw: 26000; vinyl group-containing structural unit: 2 mol% (random))

[0539] (21) 3,5-Dimethyl PPS resin (Mw: 24000; vinyl group-containing structural unit: 4 mol% (random))

[0540] (22) 3,5-Dimethyl PPS resin (Mw: 33000; vinyl group-containing structural unit: 5 mol% (random))

[0541] (23) 3,5-Dimethyl PPS resin (Mw: 30000; vinyl group-containing structural unit: 9 mol% (random))

[0542] (24) 3,5-Dimethyl PPS resin (Mw: 8400; vinyl group-containing structural unit: 4 mol% (random))

[0543] (25) 2-Methyl-6-ethyl PPS resin (Mn: 3600)

[0544] In the resins of Examples 1 to 25, the content of unsubstituted PPS structural units was 0%.

[0545] (Comparative Example)

[0546] (1) Unsubstituted PPS resin (Mw: 1200; Mn: 800; content of unsubstituted PPS structural units 100%)

[0547] (2) Styrene-modified polyphenylene ether (PPE) resin (Mn: 1200) (Mitsubishi Gas Chemical Company, Inc., OPE-2St-1200) (vinyl-containing structural unit: 15 mol% (terminal))

[0548] [Preparation]

[0549] (Preparation of Resin 1: Example 4)

[0550] 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 the mixture was stirred at room temperature for 6 hours to carry out oxidative polymerization. The reaction solution was dropped into hydrochloric acid-acidic methanol, and the powder was recovered by filtration. Then, the powder was washed with an aqueous potassium hydroxide solution (0.1 M) and pure water and dried under vacuum to obtain a polymer. The Mw of the polymer was 9000 and the Mn was 4100.

[0551] (Preparation of Resin 2: Examples 1 to 3, 5 to 10, 25)

[0552] In the same manner as in the preparation of Resin 1, substituted PPS resins of Examples 1 to 3 and 5 to 10 were prepared using methods well known to those skilled in the art.

[0553] (Preparation of Resin 3: Examples 11 to 14, 19 to 24)

[0554] ·Synthesis of vinyl-substituted PPS resin (random)

[0555] Poly(2,6-dimethyl-1,4-phenylene sulfide) (10.0 g), N-bromosuccinimide (NBS) (9.75 mmol, 1.81 g), and AIBN (2.25 mmol, 0.37 g) were added to a 1000 ml pear-shaped flask. After dissolving in chlorobenzene, the reaction was carried out under reflux for 4 hours. After the reaction, the solution was cooled with ice water, and the precipitated succinimide was filtered off using a glass filter. The filtrate was purified by precipitation with 5 wt% hydrochloric acid in methanol, recovered using a glass filter, and dried under vacuum to obtain brominated PPS (MXPPS) in which a part of the protons of the methyl group was substituted with bromine (yield: 85%, 9.05 g). Next, MXPPS (8.79 g) and triphenylphosphine (27.5 mmol) were added to a 2000 ml three-necked flask. After dissolving in THF, the mixture was heated under reflux for 24 hours. Then, it was cooled to room temperature. When an aqueous solution of 37 wt% formaldehyde (248 mmol) was added to the reaction solution and stirred for 10 minutes, the precipitate disappeared. Next, potassium tert-butoxide (33 mmol) was added, and the reaction was carried out for 1 hour. After the reaction was completed, the solution was concentrated to about 2 / 3, purified by precipitation with hydrochloric acid in methanol, recovered by centrifugation, and dried under vacuum to obtain vinyl-substituted PPS resin (MVPPS) in which 7% of the methyl groups were substituted with vinyl groups (yield: 93%, 7.89 g).

[0556] (Preparation of Resin 4: Examples 15 - 17)

[0557] ·Synthesis of Vinyl-Substituted PPS Resin (Terminal)

[0558] (First Method (Example 15))

[0559] 2,3-Dichloro-5,6-dicyano-p-benzoquinone (DDQ, 5.25 mmol) was dispersed in dichloromethane (3.5 ml). After adding trifluoroacetic acid (1.75 mmol), bis(2,6-dimethylphenyl) disulfide (2.63 mmol) was added, and the mixture was stirred at room temperature for 1 hour. Then, 4,4'-divinyldiphenyl disulfide (2.63 mmol) was further added, and the mixture was stirred at room temperature for 15 hours. The crude product was purified by precipitation in hydrochloric acid in methanol and recovered by filtration. Then, the operation of dissolving the crude product in chloroform and reprecipitating with hydrochloric acid in methanol was carried out to obtain a vinyl-substituted PPS resin having a vinyl group in the terminal structure of the resin in the form of a white powder.

[0560] (Second Method (Examples 16 - 17))

[0561] To a solution of sulfonium cation (Br-DPS+) derived from Br-DPS (bis(4-bromophenyl) disulfide) in dichloromethane, poly(2,6-dimethyl-1,4-phenylene sulfide) was added, and terminal bromo PPS was synthesized by post-polymerization modification. Specifically, Br-DPS (1.88 g, 5 mmol) was dissolved in dichloromethane (25 ml) in a 50 ml flask, and TFA (trifluoroacetic acid) (0.83 ml, 12.5 mmol) and DDQ (1.14 g, 5 mmol) were added, followed by stirring at room temperature. Further, PMPS (0.68 g, 5 mmol in terms of repeating structural units) was added, and the mixture was stirred at room temperature for 40 hours. The solution was precipitated in methanol (1000 ml) containing 5 vol% hydrochloric acid, and the solid was recovered by filtration, washed with methanol, aqueous potassium hydroxide solution, and water, and dried in vacuo. The solid was reprecipitated in THF (tetrahydrofuran) / hexane (20 ml / 800 ml), the precipitate was recovered, washed with hexane, and dried in vacuo to obtain Br-PMPS (0.63 g, yield: 91%) ( Figure 1 "Terminal vinyl-substituted PPS1").

[0562] The Kumada-Tamao coupling reaction of terminal bromo PPS and vinylmagnesium bromide was carried out using Ni(dppp)Cl2 ([1,3-bis(diphenylphosphino)propane]nickel(II) dichloride). Specifically, terminal bromo PPS (96 mg, Br 10 μmol) and Ni(dppp)Cl2 (11 mg, 20 μmol) were added to a 30 ml flask and dissolved in THF (7.6 ml) under an argon atmosphere. Further, a 1 M solution of vinylmagnesium bromide in THF (0.4 ml, 0.4 mmol) was added, and the mixture was stirred at room temperature for 24 hours. The solution was precipitated in methanol (300 ml) containing 5 vol% hydrochloric acid. The precipitate was recovered by filtration, washed with methanol and water, and dried in vacuo to obtain a white powder (28 mg, yield: 29%, Mn = 5.1×10 3 , Mw / Mn = 2.3) ( Figure 1 "Terminal vinyl-substituted PPS2").

[0563] (The 3rd method: Example 18)

[0564] 2,3 - Dichloro - 5,6 - dicyano - p - benzoquinone (DDQ, 26.3 mmol) was dispersed in dichloromethane (35 ml). After adding trifluoroacetic acid, bis(2,6 - dimethylphenyl) disulfide (26.3 mmol) was added, and the mixture was stirred at room temperature for 5 hours. After purification by precipitation in methanol, the corresponding polymer (white solid) was obtained. To this polymer (5 g), tetrahydrofuran (76.5 ml) and 4 - chloromethylstyrene (2.4 ml) were added and dissolved, and an aqueous solution of sodium borohydride (0.645 g) in water (8.5 ml) was further added, and the mixture was stirred at room temperature for 20 hours. After purification by precipitation of the reaction solution in methanol, a vinyl - substituted PPS resin having a vinyl group at the terminal structure of the resin was obtained.

[0565] · Evaluation of the synthesis of vinyl - substituted PPS resin (terminal) by NMR

[0566] The 1H NMR spectrum (500 MHz) was recorded by JEOL JNM - ECX500. The chemical shift was corrected using tetramethylsilane as an internal standard. The IR spectrum was performed by JASCO FT / IR - 6100. Size - exclusion chromatography (SEC) was carried out using a TOSOH TSKgel SuperHM - N column and a SHIMADZU SPD - M20A UV detector (wavelength: 254 nm) (eluent: chloroform, flow rate: 0.3 ml min -1 , and the molecular weight was corrected with polystyrene standard substances), and was performed by SHIMADZU LC - 20AD / CBM - 20A. The diffusion - ordered NMR spectroscopy (DOSY) spectrum (600 MHz) was recorded by Bruker AVANCE 600 NEO (pulse sequence: ledbpgp2s). Cyclic voltammetry (CV) was carried out using BAS ALS 660D, with a Pt wire, a Pt electrode (Φ: 1.6 mm), and an Ag / AgCl electrode as the counter electrode, working electrode, and reference electrode, respectively. The potential of the electrode was corrected by the ferrocene / ferrocenium redox couple (E1 / 2 = 0.45 V vs Ag / AgCl). Differential scanning calorimetry (DSC) was performed using TA Instruments Q200 (scan rate: 20℃ min -1 ).

[0567] (Preparation of resin 5: Comparative Example 1)

[0568] In a nitrogen atmosphere, 56 ml of dichloromethane was introduced into a 100 ml three-necked flask. Diphenyldisulfide (42 mmol), 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ, 42 mmol), and trifluoromethanesulfonic acid (42 mmol) were added thereto, and the mixture was stirred at room temperature for 6 hours to conduct oxidative polymerization. The reaction solution was dropped into hydrochloric acid-acidic methanol, and the powder was recovered by filtration. Then, the powder was washed with an aqueous potassium hydroxide solution (0.1 M) and pure water and dried under vacuum to obtain a polymer. The Mw of the polymer was 1200, and the Mn was 800.

[0569] [Measurement]

[0570] (Measurement of dielectric loss tangent and dielectric constant)

[0571] To measure the dielectric loss tangent and dielectric constant, for each resin, a resin sample piece for measurement was prepared by heating a resin film with a thickness adjusted to 50 - 250 μm at 200°C to 250°C for 120 minutes.

[0572] The dielectric loss tangent and dielectric constant were measured at 10 GHz, 40 GHz, or 80 GHz under standard conditions (23 ± 2°C) and a relative humidity of 45 - 55% using a vector network analyzer (N5290A) manufactured by Keysight Technologies, Inc. and a split cylinder resonator, by the cavity resonator perturbation method.

[0573] Regarding the dielectric loss tangent measured at 10 GHz, the determination was made as follows.

[0574] · 0.002 or more: Non-conforming

[0575] · Less than 0.002: Conforming

[0576] · Less than 0.0015: Good

[0577] · Less than 0.001: Excellent

[0578] · Less than 0.0008: Outstanding

[0579] Regarding the dielectric loss tangent measured at 40 GHz, the determination was made as follows.

[0580] · 0.003 or more: Non-conforming

[0581] · Less than 0.003: Conforming

[0582] · Less than 0.002: Good

[0583] · Less than 0.0015: Excellent

[0584] · Less than 0.0012: Outstanding

[0585] Regarding the dielectric loss tangent measured at 80 GHz, the determination was made as described below.

[0586] · 0.004 or more: Unqualified

[0587] · Less than 0.004: Qualified

[0588] · Less than 0.003: Good

[0589] · Less than 0.0025: Excellent

[0590] · Less than 0.002: Outstanding

[0591] Regarding the relative permittivity measured at 10 GHz, the determination was made as described below.

[0592] · 3.00 or more: Unqualified

[0593] · Less than 3.00: Qualified

[0594] · Less than 2.80: Good

[0595] · Less than 2.60: Excellent

[0596] · Less than 2.40: Outstanding

[0597] (Measurement of glass transition temperature)

[0598] For each resin shown in Table 1, the glass transition temperature (Tg) was measured by differential scanning calorimetry (DSC) starting from room temperature under a temperature-increasing condition of 20 °C / min according to the JIS standard (JIS K 7121: Method for measuring the glass transition temperature of plastics).

[0599] (Weight-average molecular weight (Mw) and number-average molecular weight (Mn))

[0600] For each resin (or resin composition) shown in Table 1, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) in terms of polystyrene were measured by gel permeation chromatography (GPC).

[0601] (Storage modulus)

[0602] The storage modulus at 260 °C of the substituted PPS resin was measured at a frequency of 1 Hz and 260 °C using a dynamic viscoelasticity measuring device (RSA-G2, manufactured by TA Instruments). More specifically, the storage modulus at 260 °C was measured using a dynamic viscoelasticity measuring device (RSA-G2, manufactured by TA Instruments) while heating from room temperature at a rate of 5 °C / min, and the measurement was carried out at 260 °C. A measurement sample (30 mm × 3 mm) was cut out from a film with a uniform thickness in the range of about 0.1 to 0.3 mm that did not interfere with the measurement, and the thickness was accurately determined for the measurement. The main measurement parameters related to the measurement are as follows.

[0603] · Measurement frequency: 10 Hz

[0604] · Heating rate: 5 °C / min

[0605] · Sample measurement length: 15 mm

[0606] · Strain: 0.05%

[0607]

[0608] As shown in Table 1, the dielectric loss tangent at 10 GHz of the substituted PPS resins of Examples 1 to 25 was "qualified" (less than 0.002) to "excellent" (less than 0.0008).

[0609] On the other hand, the dielectric loss tangent at 10 GHz of the unsubstituted PPS resin of Comparative Example 1 and the PPE resin of Comparative Example 2 was "unqualified" (0.002 or more).

[0610] In addition, for the dielectric loss tangent at 40 GHz, it was "qualified" (less than 0.003) to "excellent" (less than 0.0012) in the substituted PPS resins of Examples 1 to 25. On the other hand, in the unsubstituted PPS resin of Comparative Example 1 and the PPE resin of Comparative Example 2, they were "unqualified" (0.003 or more) and "qualified" (less than 0.003), respectively.

[0611] For the dielectric loss tangent at 80 GHz, it was "good" (less than 0.0025) in the substituted PPS resin of Example 5. On the other hand, in the unsubstituted PPS resin of Comparative Example 1 and the PPE resin of Comparative Example 2, they were "unqualified" (0.004 or more) and "qualified" (less than 0.004), respectively.

[0612] In addition, as shown in Table 1, the dielectric constants of the substituted PPS resins of Examples 1 to 25 at 10 GHz were "qualified" (less than 3.00) to "excellent" (less than 2.40). On the other hand, the dielectric constants of the unsubstituted PPS resin of Comparative Example 1 and the PPE resin of Comparative Example 2 at 10 GHz were "qualified" (less than 3.00) and "good" (less than 2.80), respectively.

[0613] For the substituted PPS resins of Examples 15 to 18, the synthesis of the vinyl-substituted PPS resin (terminal) was evaluated by the NMR method according to the above method. The results are shown in Figure 2. According to the high-field shift of the signal of the terminal aromatic proton and the presence of the signal of the terminal vinyl group, the terminal vinylation was confirmed.

[0614] Based on the above results, it was confirmed that the substituted PPS resins described in the first to third embodiments have a low dielectric loss tangent.

[0615] In addition, as shown in Table 1, the storage modulus of the substituted PPS resins of Examples 11 to 24 was "2" (1×10 5 or more), on the other hand, it was "1" (less than 1×10 5 ) in the substituted PPS resins of Examples 1 to 10 and 25. The unsubstituted PPS resin of Comparative Example 1 was "1", and the PPE resin of Comparative Example 2 was "2".

[0616] The storage modulus of the substituted PPS resin of Example 20 was 8.5×10 5 Pa, and the storage modulus of the substituted PPS resin of Example 21 was 1.7×10 6 Pa.

[0617] This result confirmed that for the substituted PPS resins described in the first to third embodiments into which a structural unit containing an unsaturated bond was introduced, the storage modulus was 1×10 5 or more and the reflow soldering resistance was good.

[0618] Industrial Applicability

[0619] The substituted polyphenylene sulfide resin of the present disclosure has a low dielectric loss tangent, and thus can be suitably used as a material for printed wiring boards and the like, and has industrial applicability.

Claims

1. A substituted polyphenylene sulfide resin for a wiring substrate, which contains a structural unit represented by the general formula (I), ， In the formula (I), R1, R2, R3 and R4 are each independently H, an alkyl group, an alkoxy group, or an organic group containing an alkenyl group, and one or more of R1, R2, R3 and R4 are an alkyl group or an alkoxy group.

2. The substituted polyphenylene sulfide resin for a wiring substrate according to claim 1, wherein the tangent of the dielectric loss angle at 10 GHz is less than 0.

002.

3. The substituted polyphenylene sulfide resin for a wiring substrate according to claim 1 or 2, which contains a structural unit represented by the general formula (II) and / or a terminal structure represented by the general formula (III-a), ， In formula (II), R 5a , R 6a , R 7a and R 8a are each independently H, an alkyl group, an alkoxy group, or an organic group containing an alkenyl group, and one or more of R 5a , R 6a , R 7a and R 8a are organic groups containing an alkenyl group. ， In the formula (III-a), X are each independently H, an alkyl group, an alkoxy group, or an organic group containing an alkenyl group, and one or more of them are an organic group containing an alkenyl group, and n is an integer from 1 to 5.

4. The substituted polyphenylene sulfide resin for a wiring substrate according to claim 1 or 2, wherein the glass transition temperature is 250 °C or lower.

5. The substituted polyphenylene sulfide resin for a wiring substrate according to claim 1 or 2, wherein the content of the structural unit containing an alkyl group and / or an alkoxy group is 30 mol% or more.

6. The substituted polyphenylene sulfide resin for a wiring substrate according to claim 5, wherein the content of the structural unit containing an organic group containing an alkenyl group is 20 mol% or less.

7. A resin composition, which contains the substituted polyphenylene sulfide resin for a wiring substrate according to claim 1.

8. A substituted polyphenylene sulfide resin, which contains a structural unit represented by the general formula (I), ， In the formula (I), R1, R2, R3 and R4 are each independently H, an alkyl group, an alkoxy group, or an organic group containing an alkenyl group, and one or more of R1, R2, R3 and R4 are an alkyl group or an alkoxy group, and the tangent of the dielectric loss angle of the substituted polyphenylene sulfide resin at 10 GHz is less than 0.

002.

9. The substituted polyphenylene sulfide resin according to claim 8, which contains a structural unit represented by the general formula (II) and / or a terminal structure represented by the general formula (III-a), ， In formula (II), R 5a , R 6a , R 7a and R 8a are each independently H, alkyl, alkoxy, or an organic group containing an alkenyl group, and one or more of R 5a , R 6a , R 7a and R 8a are organic groups containing an alkenyl group. ， In the formula (III-a), X are each independently H, an alkyl group, an alkoxy group, or an organic group containing an alkenyl group, and one or more of them are an organic group containing an alkenyl group, and n is an integer from 1 to 5.

10. The substituted polyphenylene sulfide resin according to claim 8 or 9, wherein the glass transition temperature is 250 °C or lower.

11. The substituted polyphenylene sulfide resin according to claim 8 or 9, wherein the content of the structural unit containing an alkyl group and / or an alkoxy group is 30 mol% or more.

12. The substituted polyphenylene sulfide resin according to claim 11, wherein the content of the structural unit containing an organic group containing an alkenyl group is 20 mol% or less.

13. A resin composition, which contains the substituted polyphenylene sulfide resin according to claim 8.

14. A substituted polyphenylene sulfide resin, which has a terminal structure represented by the general formula (III-a), ， In formula (III-a), X is independently H, an alkyl group, an alkoxy group, or an organic group containing an alkenyl group, and one or more of them are organic groups containing an alkenyl group, and n is an integer from 1 to 5.

15. The substituted polyphenylene sulfide resin according to claim 14, which contains a structural unit represented by general formula (I), ， In formula (I), R1, R2, R3, and R4 are independently H, an alkyl group, an alkoxy group, or an organic group containing an alkenyl group, and one or more of R1, R2, R3, and R4 are an alkyl group or an alkoxy group.

16. The substituted polyphenylene sulfide resin according to claim 15, whose dielectric loss tangent at 10 GHz is less than 0.

002.

17. The substituted polyphenylene sulfide resin according to claim 14 or 15, which contains a structural unit represented by general formula (II), ， In formula (II), R 5a , R 6a , R 7a and R 8a are each independently H, an alkyl group, an alkoxy group, or an organic group containing an alkenyl group, and one or more of R 5a , R 6a , R 7a and R 8a are organic groups containing an alkenyl group.

18. The substituted polyphenylene sulfide resin according to claim 14 or 15, whose glass transition temperature is 250 °C or lower.

19. The substituted polyphenylene sulfide resin according to claim 14 or 15, wherein the content of the structural unit containing an alkyl group and / or an alkoxy group is 30 mol% or more.

20. The substituted polyphenylene sulfide resin according to claim 19, wherein the content of the structural unit containing an organic group with an alkenyl group is 20 mol% or less.

21. A resin composition, which contains the substituted polyphenylene sulfide resin according to claim 14.

22. A varnish, which contains: the resin according to claims 1, 2, 8, 9, 14, or 15, or the resin composition according to claims 7, 13, or 21; and a solvent.

23. An interlayer insulating material, which contains the resin according to claims 1, 2, 8, 9, 14, or 15, or the resin composition according to claims 7, 13, or 21.

24. A prepreg, which contains: the resin according to claims 1, 2, 8, 9, 14, or 15, or the resin composition according to claims 7, 13, or 21; and a substrate.

25. A metal-clad laminate, which contains: the resin according to claims 1, 2, 8, 9, 14, or 15, or the resin composition according to claims 7, 13, or 21; and a metal foil.

26. A substrate, which contains the resin according to claims 1, 2, 8, 9, 14, or 15, or the resin composition according to claims 7, 13, or 21.

27. A wiring board, which contains the resin according to claims 1, 2, 8, 9, 14, or 15, or the resin composition according to claims 7, 13, or 21.

28. A printed wiring board, which contains: the wiring board according to claim 27, and electronic components.

29. The printed wiring board according to claim 28, whose dielectric loss tangent at 10 GHz is less than 0.002.

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