Resin composition comprising substituted polyphenylene sulfide resin

Abstract

Provided is a resin composition which has a low dielectric loss tangent and can be cured at low temperatures. The resin composition contains a substituted polyphenylene sulfide resin (A) and a radical polymerizable compound (B) and / or a styrene polymer (copolymer) (C), and the substituted polyphenylene sulfide resin (A) contains a structural unit represented by general formula (I). [In formula (I), R1, R2, R3, and R4 are each independently H, an alkyl group, an alkoxy group, an aryl 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. ]

Description

Technical Field

[0001] This disclosure relates to resin compositions comprising substituted polyphenylene sulfide resins. Background Technology

[0002] In recent years, mobile communication systems have been developing towards higher speeds and larger capacities. With this advancement, higher frequency bands are being used in communication. For example, the 5G mobile communication system, which is already in practical use, uses higher frequency bands than 4G and earlier mobile communication systems.

[0003] For terminals in mobile communication systems, there will be attenuation of electrical signals transmitted through the printed circuit board (PCB), also known as transmission loss. Transmission loss also depends on the dielectric properties of the PCB substrate (dielectric). Generally speaking, the higher the frequency used, the greater the influence of the dielectric loss tangent, and the greater the transmission loss.

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

[0005] Traditionally, materials used for wiring substrates such as printed wiring boards have been resin compositions with polyphenylene ether (PPE) resin (e.g., Patent Document 1) and unsubstituted polyphenylene sulfide (PPS) resin as the main components.

[0006] Patent Document 1: Japanese Patent Application Publication No. 2023-1134 Summary of the Invention

[0007] However, wiring board materials using PPE resin or unsubstituted PPS resin tend to have a high dielectric loss tangent, which may lead to increased transmission loss in high-frequency communication applications. Furthermore, since PPE resin itself has low flame retardancy, it must be mixed with flame-retardant materials to impart flame retardancy to the resin composition in order to be used as a wiring board material.

[0008] The inventors have discovered that substituted polyphenylene sulfide (substituted PPS) resins can achieve a lower dielectric loss tangent than PPE resins and unsubstituted PPS resins. However, it is known that substituted PPS resins are difficult to generate the active species necessary for curing unless a high temperature exceeding 240°C is reached, and therefore, curing is difficult without high temperatures.

[0009] The objective of this disclosure is to provide a resin composition having a low dielectric loss tangent and being capable of curing at low temperatures.

[0010] This disclosure includes the following methods.

[0011] [1] Method 1

[0012] [1-1] A resin composition comprising:

[0013] Substituted polyphenylene sulfide resin (A), and

[0014] Free radical polymerizable compounds (B) and / or styrene-based polymers (copolymers) (C),

[0015] The aforementioned substituted polyphenylene sulfide resin (A) comprises structural units represented by general formula (I).

[0016]

[0017] [In formula (I), R1, R2, R3 and R4 are independently H, alkyl, alkoxy, aryl, or alkenyl organic groups, and one or more of R1, R2, R3 and R4 are alkyl or alkoxy].

[0018] [2] Method 2

[0019] [2-1] An article for wiring substrate comprising the resin composition described in [1-1].

[0020] [3] Method 3

[0021] [3-1] A wiring substrate comprising the resin composition described in [1-1].

[0022] [4] Method 4

[0023] [4-1] A printed wiring board comprising the resin composition described in [1-1].

[0024] [5] Method 5

[0025] [5-1] A method for manufacturing a wiring substrate, the method comprising curing a resin composition,

[0026] The above resin composition comprises a substituted polyphenylene sulfide resin (A), a free radical polymerizable compound (B), and / or a styrene polymer (copolymer) (C).

[0027] The aforementioned substituted polyphenylene sulfide resin (A) comprises structural units represented by general formula (I).

[0028]

[0029] [In formula (I), R1, R2, R3, and R4 are independently H, alkyl, alkoxy, aryl, or alkenyl-containing organic groups, and one or more of R1, R2, R3, and R4 are alkyl or alkoxy],

[0030] The curing process includes heating the resin composition at a temperature below 240°C.

[0031] According to this disclosure, a resin composition having a low dielectric loss tangent and capable of curing at low temperatures can be provided. Detailed Implementation

[0032] The following describes one embodiment of this disclosure in detail. However, the various components and combinations thereof in each embodiment are examples, and appropriate additions, omissions, substitutions, and other modifications can be made without departing from the spirit of this disclosure. The various methods disclosed in this specification can be combined with any other features disclosed in this specification. When multiple upper and lower limits are specified for a particular parameter, any upper and lower limit values ​​within these upper and lower limits can be combined to form a suitable numerical range. The lower and / or upper limits of the numerical ranges described in this disclosure are values ​​within that numerical range and can be replaced with the values ​​shown in the embodiments. The expression "X~Y" representing a numerical range means "above X and below Y". Where a specific description described for one embodiment is also suitable for other embodiments, its description may sometimes be omitted in other embodiments.

[0033] [First Embodiment: Resin Composition]

[0034] The resin composition of this embodiment (hereinafter also referred to as the "resin composition") comprises a substituted polyphenylene sulfide resin (A) (hereinafter also referred to as "substituted PPS resin (A)"), and a free radical polymerizable compound (B) and / or a styrene polymer (copolymer) (C), wherein the substituted polyphenylene sulfide resin (A) comprises a structural unit represented by general formula (I).

[0035]

[0036] [In formula (I), R1, R2, R3 and R4 are independently H, alkyl, alkoxy, aryl, or alkenyl organic groups, and one or more of R1, R2, R3 and R4 are alkyl or alkoxy].

[0037] By incorporating a substituted PPS resin (A) and a radical polymerizable compound (B) and / or a styrene-based polymer (copolymer) (C), a resin composition exhibiting a low dielectric loss tangent and capable of curing at low temperatures can be obtained. "Low temperature" refers to a temperature lower than that at which the substituted PPS resin (A) is cured alone, for example, a temperature below 240°C. As a non-limiting mechanism, it can be considered that by making the substituted PPS resin (A) compatible with the radical polymerizable compound (B) and / or the styrene-based polymer (copolymer) (C), it can reach a molten state at a heating temperature below 240°C (e.g., around 200°C), generating active species necessary for curing. As a result, curing occurs at a low curing temperature while maintaining the low dielectric loss tangent of the substituted PPS resin (A). Resin compositions curing below 240°C do not require special curing equipment and can be cured using general heating and drying equipment. To date, it has not been known that free radical polymerizable compounds (B) and styrene polymers (copolymers) (C) can reduce the curing temperature while maintaining the low dielectric loss tangent of substituted PPS resins (A).

[0038] (Substituted polyphenylene sulfide resin (A))

[0039] The substituted PPS resin (A) contains structural units represented by the general formula (I).

[0040]

[0041] [In formula (I), R1, R2, R3, and R4 are independently H, alkyl, alkoxy, aryl, or alkenyl-containing organic groups (preferably H, alkyl, alkoxy, or alkenyl-containing organic groups), and one or more of R1, R2, R3, and R4 are alkyl or alkoxy]. The structural unit represented by general formula (I) can be one type, or it can contain two or more types of substituents with different types and numbers.

[0042] The alkyl group can be straight-chain, branched, or cyclic, preferably a straight-chain, branched, or cyclic alkyl group with 1 to 10 carbon atoms. Examples of straight-chain, branched, or cyclic alkyl groups with 1 to 10 carbon atoms include: methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, s-isobutyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, n-heptyl, n-octyl, isooctyl, n-nonyl, isonyl, n-decyl, isodecyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc. There can be one type of alkyl group or more than one type.

[0043] In one embodiment, the alkyl group is preferably methyl, ethyl, and / or isopropyl.

[0044] The alkoxy group can be straight-chain, branched, or cyclic, preferably a straight-chain, branched, or cyclic alkoxy group with 1 to 10 carbon atoms. Examples of straight-chain or branched alkoxy groups with 1 to 10 carbon atoms include: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, sec-butoxy, isobutoxy, n-pentoxy, isopentoxy, neopentoxy, n-hexyloxy, isohexyloxy, sec-hexyloxy, tert-hexyloxy, neohexyloxy, n-heptoxy, n-octoxy, isooctoxy, n-nonoxy, isononoxy, n-decoxy, isodexyloxy, cyclopropoxy, cyclobutoxy, cyclopentoxy, cyclohexyloxy, cycloheptoxy, cyclooctoxy, cyclononoxy, cyclodecoxy, etc. There can be one type of alkoxy group, or more than two types.

[0045] In one embodiment, the alkoxy group is preferably a methoxy group.

[0046] In one embodiment, considering the ease of synthesis of the substituted PPS resin (A), the alkyl group is preferably linear or branched. The alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 5, and even more preferably 1 to 4. In one embodiment, the alkyl group can be an alkyl group with 4 carbon atoms, an alkyl group with 3 carbon atoms, an alkyl group with 2 carbon atoms, or an alkyl group with 1 carbon atom.

[0047] In one embodiment, considering the ease of synthesis of substituted PPS(A) resin, the alkoxy group is preferably linear or branched. The alkoxy group preferably has 1 to 6 carbon atoms, more preferably 1 to 5, and even more preferably 1 to 4. In one embodiment, the alkoxy group can be an alkoxy group with 4 carbon atoms, an alkoxy group with 3 carbon atoms, an alkoxy group with 2 carbon atoms, or an alkoxy group with 1 carbon atom.

[0048] Considering the ease of synthesis of the substituted PPS resin (A), alkyl or alkoxy is preferred to be alkyl, more preferably linear alkyl, even more preferably linear alkyl with 1 to 4 carbon atoms, and even more preferably ethyl or methyl, and even more preferably methyl.

[0049] The substitution positions of alkyl or alkoxy groups in general formula (I) are not limited, and can be one or more of R1, R2, R3 and R4, or two or more, three or more, or even four.

[0050] When general formula (I) contains one alkyl or alkoxy group, the substitution position can be any one of R1, R2, R3, and R4. The substitution position can be R1, R2, R3, or R4.

[0051] When general formula (I) contains a total of two or more alkyl and / or alkoxy groups, the combination of substitution positions is not limited. For example, when containing two alkyl and / or alkoxy groups, 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 and / or alkoxy groups can be any two of R1, R3, and R4. When the substitution positions are any two of R1, R3, and R4, they can be any combination of R1 and R3, or R1 and R4.

[0052] When the general formula (I) contains a total of 3 alkyl and / or alkoxy groups, 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.

[0053] In one embodiment, for the substituted PPS resin (A), in the structural unit represented by general formula (I), one or more of R1, R2, R3, and R4 can be an aryl group having 1 to 10 carbon atoms. Examples of aryl groups having 1 to 10 carbon atoms include phenyl and naphthyl groups.

[0054] By including one or more alkyl, alkoxy and / or aryl groups in general formula (I), the dielectric loss tangent of resin compositions containing substituted PPS resins (A) can be easily reduced.

[0055] In the structural unit represented by general formula (I), there are also cases where one or more of R1, R2, R3 and R4 are alkyl or alkoxy, but one or more of the non-alkyl or alkoxy members of R1, R2, R3 and R4 are aryl and / or alkenyl-containing organic groups.

[0056] In the substituted PPS resin (A), in formula (I), the non-alkyl or alkoxy groups of R1, R2, R3, and R4 can each be an alkenyl-containing organic group independently. When the structural unit represented by formula (I) has an alkenyl-containing organic group, the structural unit represented by formula (I) can also simultaneously satisfy formula (II).

[0057] Here, regarding the alkenyl-containing organic group, there is no limitation on the range of having one or more alkenyl groups within the substituent, and it can be an alkenyl group interposed with a COO group (ester) or a CO group (ketone). The alkenyl-containing organic group can be a straight-chain, branched, or cyclic alkenyl group, preferably a straight-chain, branched, or cyclic alkenyl group with 2 to 10 carbon atoms. As a straight-chain, branched, or cyclic alkenyl group with 2 to 10 carbon atoms, examples can be given of substituents containing one or more carbon-carbon double bonds in the chain of an alkyl group with 2 or more carbon atoms, specifically including: 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, methacryloyl group, acryloyloxyalkyl, methacryloyloxyalkyl, etc. The alkenyl group can be one type or contain two or more types.

[0058] In one embodiment, the alkenyl-containing organic group is preferably vinyl, allyl, and / or acryloyl.

[0059] In one embodiment, considering the ease of synthesis of the substituted PPS resin (A), the alkenyl-containing organic group is preferably linear or branched. Regarding the number of carbon atoms in the alkenyl-containing organic group, 2 to 6 carbon atoms are preferred, more preferably 2 to 5 carbon atoms, even more preferably 2 to 4 carbon atoms, and even more preferably 2 to 3 carbon atoms. In one embodiment, the alkenyl-containing organic group can be an alkenyl or acryloyl group with 3 carbon atoms, or an alkenyl group with 2 carbon atoms.

[0060] In one embodiment, when one or more of R1, R2, R3 and R4 in the structural unit represented by general formula (I) are alkenyl-containing organic groups, the resin composition containing the substituted PPS resin (A) is prone to exhibit thermosetting properties even if the substituted PPS resin (A) is composed only of the structural unit represented by general formula (I), or even if it contains one or more structural units other than the structural unit represented by general formula (I).

[0061] Furthermore, unsubstituted PPS resins exhibit good flame retardancy. Therefore, substituted PPS resins (A) containing structural units represented by general formula (I) with the same basic skeleton as unsubstituted PPS also exhibit good flame retardancy. This also applies to other structural units with a PPS skeleton that have the same basic skeleton as unsubstituted PPS; substituted PPS resins (A) containing structural units represented by general formula (II) and substituted PPS resins (A) containing end structures represented by general formula (III), as described below, also exhibit good flame retardancy.

[0062] As a result, the resin composition containing the substituted PPS resin (A) exhibits good flame retardancy.

[0063] In one embodiment, the substituted PPS resin (A) preferably comprises a structural unit represented by general formula (II).

[0064]

[0065] In formula (II), R 5a R 6a R 7a and R 8a Each of the following is an organic group that is independently H, alkyl, alkoxy, aryl, or alkenyl (preferably alkyl, alkoxy, or alkenyl), R 5a R 6a R 7a and R 8a [One or more of the components are alkenyl-containing organic groups]. Resin compositions containing substituted PPS resin (A) readily exhibit thermosetting properties by including structural units represented by general formula (II). Furthermore, they readily exhibit good reflow soldering resistance. The structural unit represented by general formula (II) can be one type, or it can contain two or more types of substituents in different kinds and numbers.

[0066] The structural unit represented by general formula (II) means that in the structural units contained in the substituted PPS resin (A), excluding the structural unit located at the end of the resin, one or more of the substituents are alkenyl-containing organic groups.

[0067] Examples of alkyl, alkoxy, aryl, and alkenyl-containing organic groups in general formula (II), as well as the number of carbon atoms, can be exemplified as those for general formula (I).

[0068] Considering the ease of synthesizing substituted PPS resins, the number of carbon atoms in the alkenyl-containing organic group in general formula (II) is preferably 2 to 6, more preferably 2 to 5, further preferably 2 to 4, and even more preferably 2 to 3. In one embodiment, the alkenyl-containing organic group can be an alkenyl-containing organic group with 3 carbon atoms or an alkenyl-containing organic group with 2 carbon atoms, for example, it can be an allyl or acryloyl group with 3 carbon atoms, and / or a vinyl group with 2 carbon atoms.

[0069] Here, the substitution position of the alkenyl-containing organic group in general formula (II) is not limited, and is R 5a R 6a R 7a and R 8a One or more of the following can be used, or two or more, or three or more, or even four.

[0070] In the case where general formula (II) contains one alkenyl-containing organic group, the substitution position only needs to be R. 5a R 6a R 7a and R 8a Either one of them is acceptable. Its replacement position can be R. 5a It can be R 6a It can be R 7a Or it could be R 8a .

[0071] When general formula (II) contains two or more alkenyl-containing organic groups, the combination of substitution positions is not limited. For example, when it contains two alkenyl-containing organic groups, the substitution positions can be R. 5a With R 6a R 5a With R 7a R 5a With R 8a R 6a With R 7a R 6a With R 8a R 7a With R 8a Any combination thereof. In one embodiment, the substitution position of the alkenyl-containing organic group can 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 of.

[0072] For example, in the case where general formula (II) contains three alkenyl-containing organic groups, the substitution position can be R. 5a With R 6a With R 7a R 5a With R 6a With R 8a R 5a With R 7a With R 8a 、or R 6a With R 7a Any combination with R8.

[0073] In general formula (II), R is also included. 5a R 6a R 7a and R 8a One or more of them are alkenyl-containing organic groups, but R 5a R 6a R 7a and R 8a In formula (II), one or more of the non-alkenyl organic groups are alkyl or alkoxy groups. The substitution positions of the alkyl or alkoxy groups in general formula (II) can be R. 5a R 6a R 7a and R 8a Any of these, as examples and preferred embodiments, can be exemplified by the substitution positions shown in the description of general formula (I). When the structural unit represented by formula (II) has an alkyl or alkoxy group, the structural unit represented by formula (II) may also simultaneously satisfy formula (I).

[0074] In one embodiment, the substituted PPS resin (A) may contain an end structure represented by general formula (III-a).

[0075]

[0076] [In formula (III-a), each X is independently H, alkyl, alkoxy, aryl, or an alkenyl-containing organic group (preferably alkyl, alkoxy, or an alkenyl-containing organic group), and one or more are alkenyl-containing organic groups, and n is an integer from 1 to 5]. By including the end structure represented by general formula (III-a), the resin composition readily exhibits thermosetting properties. In the case of including the end structure represented by general formula (III-a), the substituted PPS resin (A) may include the end structure represented by general formula (III-a) at at least one end, or it may include it at both ends.

[0077] Even if the substituted PPS resin (A) does not have the end structure represented by general formula (III-a) at either end, as long as it is a resin containing one or more alkenyl organic groups in general formula (II), the resin composition can easily exhibit the thermosetting properties desired as a wiring substrate material by using it in combination with additives known to those skilled in the art, such as crosslinking agents, to improve its curability.

[0078] In one implementation, the end structure represented by general formula (III-a) can be the end structure represented by general formula (III-b).

[0079]

[0080] In formula (III-b), each X is independently H, alkyl, alkoxy, aryl, or an alkenyl-containing organic group (preferably alkyl, alkoxy, or an alkenyl-containing organic group), and one or more are alkenyl-containing organic groups, n is an integer from 1 to 5, and A is general formula (IV).

[0081]

[0082] {In formula (IV), R1, R2, R3, and R4 are each independently H, alkyl, alkoxy, aryl, or an alkenyl-containing organic group (preferably alkyl, alkoxy, or an alkenyl-containing organic group)}. In one embodiment, one or more of R1, R2, R3, and R4 in formula (IV) may be alkyl or alkoxy.

[0083] In one implementation, the end structure represented by general formula (III-a) can be the end structure represented by general formula (III).

[0084]

[0085] [In formula (III), each X is independently H, alkyl, alkoxy, aryl, or an alkenyl-containing organic group (preferably alkyl, alkoxy, or an alkenyl-containing organic group), and one or more are alkenyl-containing organic groups, and n is an integer from 1 to 5].

[0086] The structural units represented by general formulas (III-a), (III-b) and (III) represent structural units located at one or both ends of the resin in the substituted PPS resin (A), wherein one or more of the substituents are alkenyl-containing organic groups.

[0087] Examples of alkyl, alkoxy, aryl, and alkenyl-containing organic groups in general formulas (III-a), (III-b), and (III), as well as the number of carbon atoms, can be exemplified as those of the same types described for general formula (I).

[0088] Considering the ease of synthesis of substituted PPS resins, the number of carbon atoms in the alkenyl-containing organic groups of general formulas (III-a), (III-b), and (III) is preferably 2 to 6, more preferably 2 to 5, further preferably 2 to 4, and even more preferably 2 to 3. In one embodiment, the alkenyl-containing organic group can be an alkenyl-containing organic group with 3 carbon atoms or an alkenyl-containing organic group with 2 carbon atoms, such as an allyl or acryloyl group with 3 carbon atoms and / or a vinyl group with 2 carbon atoms.

[0089] In general formulas (III-a), (III-b), and (III), there are also cases where one or more of the X groups are alkenyl groups, but one or more of the non-alkenyl organic groups in X are alkyl, alkoxy, or aryl groups. The substitution positions of the alkyl, alkoxy, or aryl groups in general formulas (III-a), (III-b), and (III) are not limited and can be any position among the five X groups.

[0090] The substitution position of the alkenyl-containing organic group in general formulas (III-a), (III-b), or (III) is not limited, as long as it is one or more of the five X groups. When general formulas (III-a), (III-b), or (III) contain one alkenyl-containing organic group, its substitution position relative to S can be ortho, meta, or para.

[0091] When the general formula (III-a), (III-b), or (III) contains a total of two or more alkenyl-containing organic groups, the combination of substitution positions is not limited. For example, when there are two alkenyl-containing organic groups, the substitution positions can be 2,3-position (or 5,6-position), 2,4-position (or 4,6-position), 2,5-position (or 3,6-position), 2,6-position, 3,4-position (or 4,5-position), or 3,5-position.

[0092] For example, in the case where the general formula (III-a), (III-b) or (III) contains 3 alkenyl-containing organic groups, the substitution positions can be 2,3,4-position (or 4,5,6-position), 2,3,5-position (or 3,5,6-position), 2,3,6-position (or 2,5,6-position), 2,4,5-position (or 3,4,6-position), 2,4,6-position, or 3,4,5-position.

[0093] In one embodiment, the substituted PPS resin (A) has a polymer structure comprising two or more structural units (monomer units) capable of constituting a resin. The substituted PPS resin (A) comprises structural units represented by general formula (I) as at least a portion of its structural units, and may also comprise one or more structural units represented by formula other than general formula (I).

[0094] In the substituted PPS resin (A), the bonding order of the structural units is not limited. For example, it can be as follows: structural units represented by general formula (I) with the same combination of substituents are adjacent to each other; structural units represented by general formula (II) with the same combination of substituents are adjacent to each other; structural units represented by general formula (I) with different combinations of substituents are adjacent to each other; structural units represented by general formula (II) with different combinations of substituents are adjacent to each other; structural units represented by general formula (I) are adjacent to structural units represented by general formula (II); and structural units represented by general formula (I) or general formula (II) are adjacent to structural units other than those represented by general formula (I) or (II). In addition, end structures represented by general formula (III-a), (III-b), or (III) can be bonded to one or both ends of the multiple structural units bonded in these arbitrary orders.

[0095] In one embodiment, as a non-limiting example, the substituted PPS resin may comprise the following structural units:

[0096] (1) In general formula (I), R1 and R4 are alkyl groups with 1 to 5 carbon atoms and R2 and R3 are H structural units;

[0097] (2) R2 and R3 are alkyl groups with 1 to 5 carbon atoms and R1 and R4 are H structural units;

[0098] (3) In general formula (I), R1 and R3 are alkyl groups with 1 to 5 carbon atoms and R2 and R4 are H structural units;

[0099] (4) In general formula (I), R2 is an alkyl group with 1 to 5 carbon atoms and R1, R3 and R4 are H structural units;

[0100] (5) In general formula (I), R1 is an alkyl group with 1 to 5 carbon atoms and R2, R3 and R4 are H structural units;

[0101] (6) In general formula (I), R2 and R3 are alkoxy groups with 1 to 5 carbon atoms and R1 and R4 are H structural units;

[0102] (7) In general formula (I), R1 and R4 are methyl groups and R2 and R3 are H structural units;

[0103] (8) In general formula (I), R2 and R3 are methyl groups and R1 and R4 are H structural units;

[0104] (9) In general formula (I), R1 and R3 are methyl groups and R2 and R4 are H structural units;

[0105] (10) In general formula (I), R2 is a methyl group and R1, R3 and R4 are H structural units;

[0106] (11) In general formula (I), R1 is isopropyl and R2, R3 and R4 are H structural units;

[0107] (12) In general formula (I), R2 and R3 are methoxy groups and R1 and R4 are H structural units.

[0108] In one embodiment, as a non-limiting example, the substituted PPS resin may comprise the following structural units:

[0109] (13) R1 or R4 in general formula (I) or general formula (II) (R in general formula (II)) 5a Or R 8a R1 or R4 is an alkyl or non-alkyl group having 1 to 5 carbon atoms (R in general formula (II)). 5a Or R 8a ) is an alkenyl-containing organic group with 2 to 3 carbon atoms, and R2 and R3 (in general formula (II) are R 6a and R 7a ) is a structural unit of H;

[0110] (14) R2 or R3 in general formula (I) or general formula (II) (R in general formula (II)) 6a Or R 7a R2 or R3 is an alkyl or non-alkyl group having 1 to 5 carbon atoms (R in general formula (II)). 6a Or R 7a ) is an alkenyl-containing organic group with 2 to 3 carbon atoms, and R1 and R4 (in general formula (II) are R 5a and R 8a ) is a structural unit of H;

[0111] (15) A structural unit in general formula (III-a), (III-b) or (III) in which the 2-position and 6-position are alkyl groups with 1 to 5 carbon atoms, and the X of the non-alkyl group is H or an alkenyl group with 2 to 3 carbon atoms.

[0112] (16) A structural unit in general formula (III-a), (III-b) or (III) in which the 2-position or 6-position is an alkyl group having 1 to 5 carbon atoms, and the 2-position or 6-position of the non-alkyl group is H or an alkenyl group having 2 to 3 carbon atoms.

[0113] (17) Structural units in general formula (III-a), (III-b) or (III) where the 2-position and 6-position are methyl and the non-methyl X is H or an alkenyl organic group with 2 to 3 carbon atoms;

[0114] (18) A structural unit in general formula (III-a), (III-b) or (III) in which the 3-position or 5-position is an alkyl group having 1 to 5 carbon atoms, and the 3-position or 5-position of the non-alkyl group is H or an alkenyl group having 2 to 3 carbon atoms.

[0115] (19) A structural unit of general formula (III-a), (III-b) or (III) in which the 3-position or 5-position is methyl, and the 3-position or 5-position of the non-methyl is H or an alkenyl group having 2 to 3 carbon atoms;

[0116] (20) In general formula (III-a), (III-b) or (III), at least one of the 2-position, 3-position, 4-position, 5-position, and 6-position is an alkenyl-containing organic group with 2 to 3 carbon atoms, and the X of the non-alkenyl-containing organic group is H or an alkyl unit with 1 to 5 carbon atoms, and in general formula (I), R2 and R3 are alkyl units with 1 to 5 carbon atoms and R1 and R4 are H units;

[0117] (21) In general formula (III-a), (III-b) or (III), at least one of the 2-position, 3-position, 4-position, 5-position, and 6-position is an alkenyl-containing organic group with 2 to 3 carbon atoms, and the X of the non-alkenyl-containing organic group is H or an alkyl unit with 1 to 5 carbon atoms, and in general formula (I), R1 and R4 are alkyl units with 1 to 5 carbon atoms and R2 and R3 are H units;

[0118] (22) R1 or R4 in general formula (I) or general formula (II) (R in general formula (II)) 5a Or R 8a R1 or R4 is methyl, non-methyl (in general formula (II) is R) 5a Or R 8a R1 is a vinyl group, and R2 and R3 (in general formula (II) are R1 and R2) are vinyl groups. 6a and R 7a ) is a structural unit of H;

[0119] (23) R2 or R3 in general formula (I) or general formula (II) (R in general formula (II)) 6a Or R 7a R2 or R3 is methyl, non-methyl (in general formula (II) is R) 6a Or R 7a R1 and R4 are vinyl groups, and R1 and R4 are R in general formula (II). 5aand R 8a ) is a structural unit of H;

[0120] (24) A structural unit in general formula (III-a), (III-b) or (III) in which at least one of the 2-position, 3-position, 4-position, and 5-position is vinyl and the non-vinyl X is H or methyl respectively, and a structural unit in general formula (I) in which R2 or R3 is methyl and R1 and R4 are H.

[0121] In one embodiment, as a non-limiting example, the substituted PPS resin may comprise the following structural units:

[0122] (25) In general formula (III-a), (III-b) or (III), at least one of the 2- and 6-positions is an alkenyl-containing organic group having 2 to 3 carbon atoms, and the X of the non-alkenyl-containing organic group is H or an alkyl unit having 1 to 5 carbon atoms, and in general formula (I), R1 and R4 are alkyl units having 1 to 5 carbon atoms and R2 and R3 are H units;

[0123] (26) A structural unit in general formula (III-a), (III-b) or (III) in which at least one of the 2- and 6-positions is vinyl and the non-vinyl X is H or methyl, and a structural unit in general formula (I) in which R1 or R4 is methyl and R2 and R3 are H.

[0124] In one embodiment, as a non-limiting example, the substituted PPS resin may comprise the following structural units:

[0125] (27) In general formula (III-a), (III-b) or (III), at least one of the 3- and 5-positions is an alkenyl-containing organic group having 2 to 3 carbon atoms, and the X of the non-alkenyl-containing organic group is H or an alkyl unit having 1 to 5 carbon atoms, and in general formula (I), R2 and R3 are alkyl units having 1 to 5 carbon atoms and R1 and R4 are H structural units;

[0126] (28) A structural unit in general formula (III-a), (III-b) or (III) in which at least one of the 3- and 5-positions is vinyl and the non-vinyl X is H or methyl, and a structural unit in general formula (I) in which R2 or R3 is methyl and R1 and R4 are H.

[0127] In one embodiment, the substituted PPS resin may have an alkenyl-containing organic group at any substitution position in general formula (I), general formula (II) and / or general formula (III-a), (III-b) or (III), wherein the alkenyl-containing organic group may have 2 to 3 carbon atoms and may be vinyl.

[0128] In one embodiment, the substituted PPS resin may be selected from one or more of the following: 2,6-dimethyl PPS resin, 3,5-dimethyl PPS resin, 2,5-dimethyl PPS resin, 3-monomethyl PPS resin, and 2-isopropyl PPS resin, which optionally have one or more alkenyl-containing organic groups having 2 to 3 carbon atoms (preferably having one or more alkenyl-containing organic groups having 2 to 3 carbon atoms). In another embodiment, the substituted PPS resin may be selected from one or more of the following: 2,6-dimethyl PPS resin, 3,5-dimethyl PPS resin, 2,5-dimethyl PPS resin, 3-monomethyl PPS resin, and 2-isopropyl PPS resin, which optionally have one or more vinyl groups.

[0129] In one embodiment, the content of alkyl and / or alkoxy structural units in the substituted PPS resin (A) is preferably 30 mol% or more. In the case of 30 mol% or more, it can 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 even 100 mol%.

[0130] The content of alkyl and / or alkoxy structural units in substituted PPS resin (A) can be calculated based on the monomer feed rate. Alternatively, it can be determined by... 1 The determination was performed using H-NMR analysis.

[0131] By making the content of alkyl and / or alkoxy structural units in the substituted PPS resin 30 mol% or more, the dielectric loss tangent of the resin composition containing the substituted PPS resin (A) can be easily reduced.

[0132] In one embodiment, the content of structural units having alkenyl-containing organic groups in the substituted PPS resin (A) is preferably 1 or more structural units (e.g., 2 or more structural units) and less than 20 mol%, more preferably 0.1 to 20 mol% (e.g., 1 to 20 mol%), further preferably 0.2 to 18 mol% (e.g., 1 to 18 mol%), even more preferably 0.5 to 15 mol% (e.g., 2 to 10 mol%), and particularly preferably 0.8 to 10 mol% (e.g., 2 to 7 mol%).

[0133] In one embodiment, only one structural unit may have an alkenyl-containing organic group. Even in substituted PPS resins (A) where only one structural unit has an alkenyl-containing organic group, the resin composition readily exhibits thermosetting properties.

[0134] In one embodiment, the content of structural units having alkenyl-containing organic groups in the substituted PPS resin (A) can be set to a range formed by any combination of the above-mentioned upper and lower limits.

[0135] The content of structural units with alkenyl-containing organic groups in substituted PPS resin (A) can be calculated based on the monomer feed rate. Additionally, it can be determined by... 1 The determination was performed using H-NMR analysis.

[0136] The glass transition temperature (Tg) of the substituted PPS resin (A) is preferably 250°C or less, more preferably 245°C or less. By setting the glass transition temperature (Tg) of the substituted PPS resin (A) to 250°C or less, the glass transition temperature (Tg) of the resin composition formulated with the free radical polymerizable compound (B) and / or styrene polymer (copolymer) (C) described later is easily lowered, and it is easy to cure at low temperatures (below 240°C).

[0137] In one embodiment, the glass transition temperature (Tg) of the substituted PPS resin (A) is preferably 25~250°C (e.g., 90~250°C), and can be 30~245°C (e.g., 100~245°C).

[0138] The glass transition temperature can be determined by differential scanning calorimetry (DSC) from room temperature at a rate of 20°C / min, according to the JIS standard (JIS K 7121: Method for determination of glass transition temperature of plastics).

[0139] The weight-average molecular weight (Mw) of the substituted PPS resin (A) is preferably 1000~33000, and can be 3000~33000 (e.g., 10000~33000, 15000~33000, 20000~30000, or 23000~30000), or 5000~28000 (e.g., 15000~28000), or 6000~27000 (e.g., 10000~27000). By making the weight-average molecular weight (Mw) of the substituted PPS resin (A) 1000 or more, the dielectric loss tangent is easily reduced. By making the weight-average molecular weight (Mw) of the substituted PPS resin (A) 33000 or less, the glass transition temperature can easily reach the desired temperature.

[0140] The weight-average molecular weight (Mw) is the standard polystyrene conversion value obtained by GPC determination using tetrahydrofuran solvent.

[0141] The synthesis method of the substituted PPS resin (A) is not limited. For example, it can be manufactured by conventional methods in the art, such as mixing one or more monomer materials required to manufacture the desired substituted PPS resin (A) and polymerizing them under appropriate conditions to obtain a polymer structure, or polymerizing pre-prepared oligomers to obtain a polymer structure. In the case of a structural unit containing an alkenyl-containing organic group, it is also possible to synthesize a substituted PPS resin (A) containing an alkyl-containing structural unit and deprotonate a portion of the alkyl group to obtain a substituted PPS resin (A) substituted with an alkenyl-containing organic group.

[0142] (Free radical polymerizable compound (B))

[0143] The preferred resin composition preferably contains a free radical polymerizable compound (B). By including the free radical polymerizable compound (B), the curing temperature of the resin composition containing the substituted PPS resin (A) can be easily lowered while maintaining the low dielectric loss tangent characteristic of the substituted PPS resin (A). In other words, the free radical polymerizable compound (B) can function as a curing temperature reducer for the resin composition containing the substituted PPS resin (A).

[0144] The free radical polymerizable compound (B) is a compound capable of polymerization via thermal free radical polymerization and possesses free radical polymerizable unsaturated bonds. It should be noted that although the substituted PPS resin (A) is also a compound capable of polymerization via thermal free radical polymerization, the term "free radical polymerizable compound (B)" is used in this disclosure to distinguish it from the substituted PPS resin (A). That is, the free radical polymerizable compound (B) does not include the substituted PPS resin (A). In one embodiment, the free radical polymerizable compound (B) does not have the structural structure represented by the above-described general formula (I). In another embodiment, the free radical polymerizable compound (B) does not have a PPS backbone.

[0145] As a free radical polymerizable compound (B), for example, a compound having at least one selected from carbon-carbon unsaturated double bonds and maleimide groups can be exemplified.

[0146] Examples of carbon-carbon unsaturated double bonds include those contained in allyl, vinyl, acrylate, and methacrylate groups. Examples of free radical polymerizable compounds (B) possessing carbon-carbon unsaturated double bonds include monofunctional compounds such as 1-octadecene, stearyl methacrylate, dicyclopentyl methacrylate, and isobornyl methacrylate; and polyfunctional compounds such as divinylbenzene, 1,2-bis(4-vinylphenyl)ethane (BVPE), dicyclopentadiene, methylcyclopentadiene dimer, trivinylcyclohexane, triallyl isocyanurate (TAIC), dicyclopentadiene-dimethylethanol dimethacrylate, nonanediol dimethacrylate, 1,3-diisopropenylbenzene, and trimethylolpropane triacrylate. Examples of commercially available free radical polymerizable compounds (B) include DD-1 manufactured by Shikoku Chemical Industry Co., Ltd.

[0147] Examples of free radical polymerizable compounds (B) with maleimide groups include: phenylmaleimide, cyclohexylmaleimide, 4,4'-diphenylmethane bismaleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, and 1,6-bismaleimide-(2,2,4-trimethyl)hexane.

[0148] The free radical polymerizable compound (B) preferably comprises one or more compounds selected from the compounds exemplified above. The free radical polymerizable compound (B) can be used alone or in combination of two or more compounds.

[0149] The molecular weight (weight-average molecular weight) of the free radical polymerizable compound (B) is preferably 100-3000, more preferably 130-2000, and even more preferably 150-1000, but can also be 180-500. By setting the molecular weight of the free radical polymerizable compound (B) to 100-3000, the crosslinking density is increased, and the glass transition temperature is less likely to decrease. The molecular weight can be determined or calculated using commonly used methods. In the case of a weight-average molecular weight, it is assumed to be the standard polystyrene conversion value obtained by GPC determination using tetrahydrofuran solvent.

[0150] (Styrene-based polymers (copolymers) (C))

[0151] The resin composition preferably contains a styrene-based polymer (copolymer) (C). In this disclosure, the term "styrene-based polymer (copolymer) (C)" can include homopolymers of styrene monomers and copolymers of styrene monomers with other vinyl monomers. The styrene-based polymer (copolymer) (C) can also be referred to as a styrene homopolymer or a styrene copolymer. By including the styrene-based polymer (copolymer) (C), the curing temperature of the resin composition containing the substituted PPS resin (A) can be easily lowered while maintaining the low dielectric loss tangent characteristic of the substituted PPS resin (A). In other words, the styrene-based polymer (copolymer) (C) can also function as a curing temperature reducer for the resin composition containing the substituted PPS resin (A). Furthermore, the toughness of the resin composition is easily improved. As a result, cracking is less likely to occur even if the cured film deforms.

[0152] In one embodiment, the resin composition preferably comprises a substituted polyphenylene sulfide resin (A) and a styrene polymer (copolymer) (C). By comprising a substituted polyphenylene sulfide resin (A) and a styrene polymer (copolymer) (C), it is easy to obtain a resin composition that, in addition to readily exhibiting a low dielectric loss tangent and easy curing at low temperatures, also possesses excellent toughness.

[0153] In one embodiment, the preferred resin composition comprises a substituted polyphenylene sulfide resin (A), a free radical polymerizable compound (B), and a styrene-based polymer (copolymer) (C). By comprising the substituted polyphenylene sulfide resin (A), the free radical polymerizable compound (B), and the styrene-based polymer (copolymer) (C), it is easy to obtain a resin composition that readily exhibits a low dielectric loss tangent, is more easily cured at low temperatures, and possesses excellent toughness.

[0154] Examples of styrene-based polymers (copolymers) (C) include general-purpose polystyrene (GPPS), high-impact polystyrene (HIPS), and styrene-based thermoplastic elastomers. A styrene-based polymer (copolymer) (C) may be one type or may contain two or more types.

[0155] Examples of styrene-based thermoplastic elastomers include copolymers comprising styrene units and conjugated diene units. The styrene unit is a structural unit derived from a styrene monomer. The styrene monomer can be selected from at least one selected from styrene and styrene with substituents. Substituents include, for example, alkyl groups such as methyl. The conjugated diene unit is a structural unit derived from a conjugated diene monomer. Examples of conjugated diene units include: ethylene units, propylene units, butene units, α-olefin units, butadiene units, hydrogenated butadiene units, isoprene units, and hydrogenated isoprene units. The olefin units particularly preferably include hydrogenated isoprene units and hydrogenated butadiene units. There can be one type of olefin unit or more than two types.

[0156] Specific examples of styrene-based thermoplastic elastomers include: styrene-butadiene copolymers, styrene-butadiene-styrene copolymers (SBS), styrene-butadiene-butene-styrene copolymers, styrene-isoprene copolymers, styrene-isoprene-styrene copolymers (SIS), styrene-ethylene-isoprene-styrene copolymers, and other unhydrogenated styrene-conjugated diene copolymers; styrene-ethylene / propylene-styrene copolymers (SEPS: hydride of styrene-isoprene-styrene copolymers), styrene-ethylene / butene-styrene copolymers (SEBS: hydride of styrene-butadiene copolymers), hydrogenated methylstyrene (ethylene / ethylene propylene) methylstyrene copolymers, and other hydrogenated styrene-conjugated diene copolymers.

[0157] In one embodiment, the styrene-based polymer (copolymer) (C) preferably comprises a styrene-based thermoplastic elastomer. By comprising a styrene-based thermoplastic elastomer, a lower dielectric constant can be easily achieved, and superior toughness can be readily exhibited. In one embodiment, the styrene-based polymer (copolymer) (C) preferably comprises a hydride of a styrene-based copolymer.

[0158] The content of styrene units (hereinafter also referred to as "styrene ratio") in the styrene polymer (copolymer) (C) is preferably 20-100% by mass, more preferably 20-90% by mass, further preferably 25-80% by mass, and particularly preferably 30-70% by mass, out of all monomer units (100% by mass). In one embodiment, the styrene ratio can be 45-100% by mass or 50-100% by mass. In one embodiment, the styrene ratio can be 30% by mass, 49% by mass, 62% by mass, 67% by mass, 68% by mass, or 100% by mass, or a range combining these values, or a range where these values ​​are the upper or lower limits of the above ranges. By making the styrene ratio 20% by mass or more, the resin composition readily exhibits a low dielectric loss tangent. By making the styrene ratio 90% by mass or less, the resin composition readily achieves a lower dielectric constant.

[0159] The styrene ratio can also be calculated based on the amount of raw material monomers used, or it can be calculated by... 1 The resin composition was analyzed and determined by ¹H-NMR.

[0160] The weight-average molecular weight (Mw) of styrene polymers (copolymers) (C) can be, for example, less than 150,000 or less than 100,000. The method for determining the weight-average molecular weight (Mw) is as described above.

[0161] (Content of ingredients A through C)

[0162] Hereinafter, the substituted PPS resin (A), the free radical polymerizable compound (B), and the styrene polymer (copolymer) (C) will be collectively referred to as components (A) to (C).

[0163] The content of the substituted PPS resin (A) in the resin composition, relative to the total of 100 parts by mass of components (A) to (C), is preferably 30 to 95 parts by mass, more preferably 35 to 93 parts by mass, further preferably 40 to 92 parts by mass, even more preferably 43 to 90 parts by mass, and particularly preferably 45 to 90 parts by mass. By setting the content of the substituted PPS resin (A) in the resin composition to 30 to 95 parts by mass relative to the total of 100 parts by mass of components (A) to (C), the low dielectric loss tangent effect of the substituted PPS resin (A) is easily exhibited. By combining it with a free radical polymerizable compound (B) and a styrene polymer (copolymer) (C), the resin fluidity at low temperatures is easily improved, and the effect of lowering the curing temperature is more easily obtained.

[0164] In one embodiment, the content of the substituted PPS resin (A) in the resin composition may be 48 parts by mass, 70 parts by mass, 80 parts by mass, or 90 parts by mass relative to a total of 100 parts by mass of components (A) to (C), or may be a range formed by combining them, or may be a range obtained by using them as the upper or lower limit of the above range.

[0165] From the viewpoint that the resin composition readily possesses the desired dielectric loss tangent, the content of the substituted PPS resin (A) in the resin composition is preferably 30% by mass or more in the total resin composition (100% by mass). Where it is 30% by mass or more, it can be 40% by mass or more, or even 45% by mass or more.

[0166] In one embodiment, the resin composition may also include other resin components such as unsubstituted PPS resin, unsubstituted or substituted PPE as resin components other than substituted PPS resin (A) and styrene polymer (copolymer) (C). From the viewpoint of easily having a low dielectric loss tangent and easily curing at low temperatures, the total content of substituted PPS resin (A) and styrene polymer (copolymer) (C) is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more in all resin components (100% by mass) contained in the resin composition. In one embodiment, the content of substituted PPS resin (A) in the thermoplastic resin contained in the resin composition may be 95% by mass or more, or 98% by mass or more, or 100% by mass.

[0167] In one embodiment, the ratio of the substituted PPS resin (A) to the free radical polymerizable compound (B), expressed as the ratio of (content of substituted PPS resin (A)) to (content of free radical polymerizable compound (B)) (A / B), is preferably 1.2 to 6.0, more preferably 1.3 to 5.5, and even more preferably 1.5 to 4.7. Regarding one embodiment, the above ratio (A / B) can be 1.5, 4.7, or a range obtained by taking these as the upper or lower limit of the above numerical range.

[0168] In one embodiment, the content ratio of the substituted PPS resin (A) to the styrene polymer (copolymer) (C) is expressed as the ratio of (content of substituted PPS resin (A)) to (content of styrene polymer (copolymer) (C)) (A / C), preferably 1.5 to 10.0, more preferably 2.0 to 9.5, and even more preferably 2.3 to 9.0. Regarding one embodiment, the above ratio (A / C) can be 2.3, 2.4, 4.0, 4.7, or 9.0, or a range obtained by taking these as the upper or lower limit of the above numerical range, or a range formed by combining these values.

[0169] The content of the free radical polymerizable compound (B) in the resin composition, relative to the total 100 parts by mass of components (A) to (C), is preferably 0 to 40 parts by mass, more preferably 5 to 40 parts by mass, further preferably 8 to 38 parts by mass, even more preferably 10 to 35 parts by mass, and particularly preferably 15 to 35 parts by mass. By making the content of the free radical polymerizable compound (B) relative to the total 100 parts by mass of components (A) to (C) 5 parts by mass or more, the resin composition is easily cured at low temperatures. By making it 40 parts by mass or less, the resin composition is more likely to have a low dielectric loss tangent.

[0170] In one embodiment, the content of the free radical polymerizable compound (B) in the resin composition may be 15 parts by mass or 32 parts by mass relative to a total of 100 parts by mass of components (A) to (C), or it may be a range formed by combining them, or it may be a range obtained by taking them as the upper or lower limit of the above range.

[0171] The content of the styrene polymer (copolymer) (C) in the resin composition, relative to the total of 100 parts by mass of components (A) to (C), is preferably 5 to 40 parts by mass, more preferably 5 to 35 parts by mass, further preferably 8 to 33 parts by mass, and particularly preferably 10 to 30 parts by mass. By making the content of the styrene polymer (copolymer) (C) 5 parts by mass or more relative to the total of 100 parts by mass of components (A) to (C), the toughness of the resin composition is easily improved. By making it 40 parts by mass or less, excessive reduction of the glass transition temperature can be prevented.

[0172] In one embodiment, the content of the styrene polymer (copolymer) (C) in the resin composition may be 10 parts by mass, 15 parts by mass, 20 parts by mass, or 30 parts by mass relative to a total of 100 parts by mass of components (A) to (C), or a range formed by combining them, or a range obtained by using them as the upper or lower limit of the above range.

[0173] When the resin composition comprises a free radical polymerizable compound (B) and a styrene-based polymer (copolymer) (C), the ratio of the free radical polymerizable compound (B) to the styrene-based polymer (copolymer) (C), expressed as the ratio of (content of free radical polymerizable compound (B)) to (content of styrene-based polymer (copolymer) (C)) (B / C), is preferably 0.8 to 2.0, more preferably 0.9 to 1.8, and even more preferably 1.0 to 1.6. By setting the ratio of (content of B) to (content of C) to 0.8 to 2.0, the resin composition readily exhibits a low dielectric loss tangent and readily cures at low temperatures. Furthermore, toughness is readily improved.

[0174] In one embodiment, the total content of the substituted PPS resin (A), the free radical polymerizable compound (B), and the styrene polymer (copolymer) (C) in the resin composition (100% by mass) is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more. In another embodiment, the total content of the substituted PPS resin (A), the free radical polymerizable compound (B), and the styrene polymer (copolymer) (C) in the resin composition (100% by mass) may be 95% by mass or more, 98% by mass or more, or 100% by mass.

[0175] (Organic peroxides (D))

[0176] The resin composition preferably contains an organic peroxide (D). By containing an organic peroxide (D), when the resin composition does not contain a free radical polymerizable compound (B) and contains a styrene polymer (copolymer) (C), it is easy to have a low dielectric loss tangent and easy to cure at low temperatures.

[0177] Examples of organic peroxides (D) include: 1,3-bis(tert-butylperoxyisopropyl)benzene, dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne, benzoyl peroxide, 3,3',5,5'-tetramethyl-1,4-dibenzoquinone, chloroquinone, 2,4,6-tri-tert-butylphenoxyl, tert-butyl peroxyisopropyl carbonate, and azobisisobutyronitrile. An organic peroxide (D) may be one type or may contain two or more types.

[0178] The content of organic peroxide (D) relative to the total of 100 parts by mass of the substituted polyphenylene sulfide resin (A), the free radical polymerizable compound (B), and the styrene polymer (copolymer) (C) is preferably 0 to 100 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass. By making the content of organic peroxide (D) 0.1 parts by mass or more relative to the total of 100 parts by mass of the substituted polyphenylene sulfide resin (A), the free radical polymerizable compound (B), and the styrene polymer (copolymer) (C), the resin composition is easily cured at low temperatures. By making it 10 parts by mass or less, the resin composition is more likely to have a low dielectric loss tangent.

[0179] (solvent)

[0180] The resin composition may contain a solvent. When a solvent is included, the resin composition can be used as a varnish. The varnish is generally preferably a polymer solution formed by dissolving the resin component in an organic solvent. In one embodiment, it is sufficient that at least a portion of the polymer dissolves at a liquid temperature of 25°C, preferably all of the polymer dissolves.

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

[0182] The lower limit of the content of solute (components other than solvent) in the polymer solution is not limited as long as it is within the range that is operable and sufficient to produce a polymer solution for commercialization. For example, it can be 5 to 50% by mass, 7 to 45% by mass, 10 to 40% by mass, or 10 to 35% by mass relative to 100% by mass of the polymer solution.

[0183] (Other additives)

[0184] As needed, the resin composition may further include additives such as inorganic fillers, silane coupling agents, defoamers, antioxidants, heat stabilizers, antistatic agents, ultraviolet absorbers, dyes, pigments, and lubricants.

[0185] Examples of inorganic fillers include: silica, alumina, talc, aluminum hydroxide, magnesium hydroxide, titanium dioxide, mica, aluminum borate, barium sulfate, boron nitride, forsterite, zinc oxide, magnesium oxide, and calcium carbonate. The inorganic filler may also be surface-treated. When the inorganic filler is included, its content is preferably 30 to 80 parts by mass, more preferably 40 to 70 parts by mass, relative to a total of 100 parts by mass of the substituted polyphenylene sulfide resin (A), the free radical polymerizable compound (B), and the styrene polymer (copolymer) (C).

[0186] The resin composition may also contain a flame retardant, but as described above, since the substituted PPS resin (A) has good flame retardancy, the content of the flame retardant (e.g., a flame retardant containing bromine or phosphorus) in the resin composition may be less than 10% by mass, less than 8% by mass, less than 5% by mass, less than 3% by mass, or less than 1% by mass. In one embodiment, the resin composition may not contain a flame retardant.

[0187] (Resin Composition)

[0188] There is no limitation on the method of manufacturing the resin composition; it can be carried out using equipment and methods commonly used in the preparation of resin compositions. Generally, resin compositions containing substituted PPS resin (A) are mostly prepared as polymer solutions (resin varnishes) dissolved in organic solvents.

[0189] To prepare such a resin varnish, a substituted PPS resin (A), a free radical polymerizable compound (B) and / or a styrene polymer (copolymer) (C), and other additives soluble in organic solvents, used as needed, can be added to an organic solvent and mixed using a mixer. Heating may also be performed as needed. Then, by appropriately adding components insoluble in organic solvents (e.g., inorganic fillers), and dispersing them to a given dispersion state using a ball mill, bead mill, planetary mixer, roller mill, etc., the resin varnish is prepared.

[0190] In one embodiment, the dielectric loss tangent of the resin composition at 10 GHz is preferably 0.003 or less, more preferably 0.002 or less, even more preferably less than 0.002, and even more preferably 0.0018 or less. The lower the dielectric loss tangent, the easier it is to suppress transmission loss when the resin composition is used as a material for a wiring substrate. By setting the dielectric loss tangent at 10 GHz to 0.003 or less, transmission loss at 10 GHz is easily suppressed when the resin composition is used as a material for a wiring substrate.

[0191] In one embodiment, the dielectric loss tangent of the resin composition at 40 GHz is preferably 0.003 or less, more preferably 0.002 or less, and even more preferably less than 0.002. By making the dielectric loss tangent at 40 GHz less than 0.003, transmission loss at 40 GHz can be easily suppressed when the resin composition is used as a material for a wiring substrate.

[0192] In one embodiment, the dielectric constant of the resin composition at 10 GHz is preferably less than 3.00, more preferably less than 2.80, and even more preferably less than 2.60. The lower the dielectric constant, the easier it is to suppress transmission loss when the resin composition is used as a material for a wiring substrate. By making the dielectric constant at 10 GHz less than 3.00, transmission loss at 10 GHz is easily suppressed when the resin composition is used as a material for a wiring substrate.

[0193] In one embodiment, the dielectric constant of the resin composition at 40 GHz is preferably less than 3.00, more preferably less than 2.90, and even more preferably less than 2.85. By making the dielectric constant at 40 GHz less than 3.00, transmission loss at 40 GHz can be easily suppressed when the resin composition is used as a material for a wiring substrate.

[0194] For the determination of dielectric loss tangent and dielectric constant, a sheet of resin composition is used, and the measurements are performed at a given frequency using a vector network analyzer and a split cylindrical resonator.

[0195] In one embodiment, the glass transition temperature (Tg) of the resin composition is preferably below 240°C, more preferably below 240°C, further preferably below 230°C, even more preferably below 220°C, and particularly preferably below 200°C. By setting the glass transition temperature (Tg) of the resin composition to below 240°C, it is easier to cure at low temperatures (below 240°C).

[0196] In one embodiment, the glass transition temperature (Tg) of the resin composition is preferably 25-240°C (e.g., 90-240°C), but can be 30-230°C (e.g., 100-230°C), 40-220°C (e.g., 120-220°C), 50-210°C (e.g., 150-210°C), or 60-200°C (e.g., 170-200°C). The method for determining the glass transition temperature is as described above.

[0197] In one embodiment, for the resin composition, the toughness of the cured film with a thickness of 100 μm, as determined by a simple mandrel test, is preferably 40 mm or less in diameter, more preferably 30 mm or less in diameter, and even more preferably 20 mm or less in diameter. By ensuring that the toughness determined by the simple mandrel test is 30 mm or less in diameter, when the resin composition is used as a material for a wiring substrate, the wiring substrate is less likely to be damaged even when stress is applied.

[0198] [Second Embodiment: Article for Wiring Board]

[0199] The wiring substrate article of this embodiment includes the above-described resin composition. Because it includes the above-described resin composition, the wiring substrate formed using the wiring substrate article has a low dielectric loss tangent. Examples of wiring substrate articles include: interlayer insulating films, prepregs, metal-clad laminates, and substrates.

[0200] (Interlayer insulating film)

[0201] Examples of interlayer insulating films include those used in printed wiring boards and the like. This interlayer insulating film can also be used as a material for multilayer printed wiring boards.

[0202] Interlayer insulating films can be made, for example, by coating other materials with a varnish containing the aforementioned resin composition and organic solvent, and allowing the solvent to evaporate. These interlayer insulating films can also be used to prepare multilayer printed circuit board stacks.

[0203] (prepreg)

[0204] As a prepreg, an example is a prepreg obtained by impregnating a substrate with a varnish comprising a resin composition and an organic solvent and then drying it. The substrate used for the prepreg is not limited, and those skilled in the art can choose from materials known in the art, such as natural fiber substrates, organic synthetic fiber substrates, and inorganic fiber substrates.

[0205] (Metal-clad laminate)

[0206] Examples of metal-clad laminates include those comprising the aforementioned prepreg. Such a metal-clad laminate can be obtained, for example, by overlapping multiple sheets of prepreg and then pressing them with metal foil on one or both sides under heat and pressure. Examples of metal foils include copper foil, aluminum foil, tin foil, gold foil, silver foil, platinum foil, nickel foil, etc., which can be selected by those skilled in the art based on the required properties and applications of the metal-clad laminate.

[0207] (substrate)

[0208] A substrate is a base used with semiconductor chips, such as CPUs and memory chips, to protect them and mount them onto a printed circuit board (PCB). For example, it can be the substrate portion of an FC-BGA (Flip Chip-Ball Grid Array) or FC-CSP (Flip Chip Scale Package). The substrate can be manufactured, for example, by molding a resin composition into a plate shape using known molding apparatus and methods.

[0209] [Third Embodiment: Wiring Substrate]

[0210] The wiring substrate of this embodiment comprises the resin composition described above. Because it comprises the resin composition described above, the wiring substrate has a low dielectric loss tangent.

[0211] A wiring substrate is a substrate used to mount electronic components such as semiconductors and to implement wiring, and is not limited by its structure and / or application. In this specification, a wiring substrate includes the portion of a printed wiring board excluding electronic components such as semiconductors. A printed circuit board (PCB) is an example of a printed wiring board. The printed circuit board can be, for example, a multilayer printed circuit board as described above in the section on "interlayer insulating film". The printed circuit board also includes any substrate selected from rigid substrates, flexible substrates, rigid-flex substrates, and metal-based substrates, on which electronic components can be mounted to form a printed wiring board.

[0212] [Fourth Embodiment: Printed Wiring Board]

[0213] The printed wiring board of this embodiment includes the above-described resin composition and electronic components. The structure and / or application of the printed wiring board are not limited. For example, the printed wiring board can be any material on which electronic components are mounted on a printed substrate, such as a rigid substrate, a flexible substrate, a rigid-flexible substrate, or a metal substrate.

[0214] The electronic components are not limited and can include semiconductor chips, resistors, capacitors, etc. As a structure, for example, wiring and electronic components can be mounted on one or both sides of a wiring substrate (printed substrate). Alternatively, wiring and electronic components can be mounted between the layers of a multilayer wiring substrate.

[0215] For example, rigid printed circuit boards with electronic components mounted on a rigid substrate can be used in terminals, base stations, servers, routers, millimeter-wave radars, probe cards, etc. in mobile communication systems, while flexible printed circuit boards with electronic components mounted on a flexible substrate can be used for connecting cables, antennas, antenna cables, etc.

[0216] [Fifth Embodiment: Method for Manufacturing a Wiring Substrate]

[0217] The method for manufacturing a wiring substrate according to this embodiment includes curing a resin composition comprising a substituted polyphenylene sulfide resin (A), a free radical polymerizable compound (B), and / or a styrene polymer (copolymer) (C), wherein the substituted polyphenylene sulfide resin (A) comprises a structural unit represented by general formula (I).

[0218]

[0219] [In formula (I), R1, R2, R3, and R4 are each independently H, alkyl, alkoxy, aryl, or an alkenyl-containing organic group (preferably H, alkyl, alkoxy, or an alkenyl-containing organic group), and one or more of R1, R2, R3, and R4 are alkyl or alkoxy]. Details regarding the resin composition are as described above.

[0220] The resin composition can be cured at low temperatures, and therefore can be cured at a lower temperature than when the substituted PPS resin (A) is cured alone.

[0221] Curing includes heating the resin composition at a temperature below 240°C. The heating temperature is below 240°C, preferably below 235°C, more preferably below 230°C, further preferably below 225°C, and particularly preferably below 220°C.

[0222] There are no restrictions on the heating method; any known heating and drying apparatus can be used.

[0223] In one embodiment, the method for manufacturing a wiring substrate may include, prior to the curing step, a step of preparing a varnish comprising a resin composition; and a step of applying (or impregnating) the varnish onto (or impregnating) a substrate with the varnish. In another embodiment, the method for manufacturing a wiring substrate may include a step of preparing a prepreg comprising a resin composition prior to the curing step. The method for manufacturing a wiring substrate may also further include a drying step.

[0224] The following is a non-limiting list of exemplary embodiments and combinations thereof of the present disclosure.

[0225] [1] A resin composition comprising a substituted polyphenylene sulfide resin (A), a free radical polymerizable compound (B), and / or a styrene polymer (copolymer) (C), wherein the substituted polyphenylene sulfide resin (A) comprises a structural unit represented by general formula (I).

[0226]

[0227] [In formula (I), R1, R2, R3 and R4 are independently H, alkyl, alkoxy, aryl, or alkenyl organic groups, and one or more of R1, R2, R3 and R4 are alkyl or alkoxy].

[0228] [2] The resin composition according to [1] comprises the above-described substituted polyphenylene sulfide resin (A) and the above-described styrene polymer (copolymer) (C).

[0229] [3] The resin composition according to [1] or [2] comprises the above-described substituted polyphenylene sulfide resin (A), the above-described free radical polymerizable compound (B), and the above-described styrene polymer (copolymer) (C).

[0230] [4] The resin composition according to any one of [1] to [3], wherein,

[0231] The content of the above-mentioned substituted polyphenylene sulfide resin (A) is 30 to 95 parts by mass relative to the total of 100 parts by mass of the above-mentioned substituted polyphenylene sulfide resin (A), the above-mentioned free radical polymerizable compound (B), and the above-mentioned styrene polymer (copolymer) (C).

[0232] [5] The resin composition according to any one of [1] to [4], wherein,

[0233] The content of the free radical polymerizable compound (B) is 0 to 40 parts by mass relative to the total of 100 parts by mass of the substituted polyphenylene sulfide resin (A), the free radical polymerizable compound (B), and the styrene polymer (copolymer) (C).

[0234] [6] The resin composition according to any one of [1] to [5], wherein,

[0235] The content of the above-mentioned styrene polymer (copolymer) (C) is 5 to 40 parts by mass relative to the total of 100 parts by mass of the above-mentioned substituted polyphenylene sulfide resin (A), the above-mentioned free radical polymerizable compound (B), and the above-mentioned styrene polymer (copolymer) (C).

[0236] [7] The resin composition according to any one of [1] to [6] contains an organic peroxide (D).

[0237] [8] The resin composition according to any one of [1] to [7], wherein,

[0238] The aforementioned substituted polyphenylene sulfide resin (A) comprises structural units represented by general formula (II).

[0239]

[0240] In formula (II), R 5a R 6a R 7a and R 8a Each of the following is an organic group that is independently H, alkyl, alkoxy, aryl, or alkenyl-containing: R 5a R 6a R 7a and R 8a One or more of them are alkenyl-containing organic groups.

[0241] [9] The resin composition according to any one of [1] to [8], wherein,

[0242] The styrene content of the above-mentioned styrene polymers (copolymers) (C) is 20-100% by mass.

[0243]

[10] The resin composition according to any one of [1] to [9] contains a solvent.

[0244]

[11] An article for wiring board comprising any one of [1] to [9].

[0245]

[12] The article according to

[11] is an interlayer insulating film, a prepreg, a metal-clad laminate, or a substrate.

[0246]

[13] A wiring substrate comprising any one of the resin compositions described in [1] to [9].

[0247]

[14] A printed wiring board comprising any one of [1] to [9] a resin composition and an electronic component.

[0248]

[15] A method for manufacturing a wiring substrate, the method comprising curing a resin composition,

[0249] The above resin composition comprises a substituted polyphenylene sulfide resin (A), a free radical polymerizable compound (B), and / or a styrene polymer (copolymer) (C), wherein the substituted polyphenylene sulfide resin (A) comprises a structural unit represented by general formula (I).

[0250]

[0251] [In formula (I), R1, R2, R3, and R4 are independently H, alkyl, alkoxy, aryl, or alkenyl-containing organic groups, and one or more of R1, R2, R3, and R4 are alkyl or alkoxy],

[0252] The curing process includes heating the resin composition at a temperature below 240°C.

[0253] Example

[0254] The following embodiments illustrate the present disclosure in more detail, but the interpretation of the present disclosure is not limited to these embodiments.

[0255] [Synthesis Example 1: Preparation of DMPPS]

[0256] In an argon atmosphere, 4.0 L of dichloromethane was introduced into a 10 L four-necked flask. 3,3',5,5'-tetramethyldiphenyl disulfide (1 kg, 3.64 mol), 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ, 3.64 mol), and trifluoromethanesulfonic acid (2.55 mol) were added, and the mixture was stirred at room temperature for 2 hours to carry out oxidative polymerization. The reaction solution was added dropwise to acidic methanol with hydrochloric acid, and the powder was recovered by filtration. The powder was then washed with a 0.1 M potassium hydroxide aqueous solution and pure water, and vacuum dried to obtain 2,6-dimethyl PPS resin (DMPPS), which is a polymer equivalent to the substituted PPS resin (A). This substituted PPS resin (A) has structural units in general formula (I) where R1 and R4 are methyl groups and R2 and R4 are H groups. 1 H-NMR analysis revealed that the content of the methyl-containing structural unit was 100 moles in the substituted PPS resin.

[0257] For the obtained polymer, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) of polystyrene were determined by gel permeation chromatography (GPC), and the results were: Mw = 26000 and Mn = 5800.

[0258] [Synthetic Example 2: Preparation of MVPPS]

[0259] In a 20 L four-necked flask, poly(2,6-dimethyl-1,4-phenyl sulfide) (285.0 g), N-bromosuccinimide (NBS) (0.05 mol, 8.94 g), and AIBN (0.06 mol, 10.3 g) obtained in Synthesis Example 1 were added and dissolved in chlorobenzene. The mixture was then refluxed for 24 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 acidic methanol. After recovery using a glass filter and vacuum drying, bromoPPS with a partially proton-substituted methyl group (MXPPS) was obtained (yield: 85%, 853.3 g). Next, MXPPS (850 g) and triphenylphosphine (0.74 mol) were added to a four-necked flask, dissolved in THF, and the mixture was refluxed for 24 hours. The solution was then cooled to room temperature, and 37 wt% formaldehyde aqueous solution (5.55 mol, 409 ml) was added. After stirring for 23 minutes, the precipitate disappeared. Potassium tert-butoxide (0.86 mol) was then added, and the reaction was continued for 17 hours. After the reaction was complete, the solution was concentrated to approximately half its original volume and purified by precipitation using hydrochloric acid and acidic methanol. The purified product was then recovered by centrifugation and vacuum dried to obtain 2,6-dimethyl PPS resin (MVPPS), equivalent to substituted PPS resin (A), with 2% of the total methyl groups replaced by vinyl groups (yield: 95%, 810 g).

[0260] The substituted PPS resin (A) has the following structural units A and B.

[0261] Structural unit A: R1 or R4 in general formula (I) (R in general formula (II)) 5a Or R 8a R1 or R4 is methyl, non-methyl (in general formula (II) is R) 5a Or R 8a R1 is a vinyl group, and R2 and R3 (in general formula (II) are R1 and R2) are vinyl groups. 6a Or R 7a ) is H.

[0262] Structural unit B: R1 and R4 in general formula (I) are methyl groups, and R2 and R4 are H groups.

[0263] pass 1 H-NMR was used to calculate the content of each structural unit. The results showed that the content of structural unit A (containing vinyl and methyl structural units) in the substituted PPS resin was 2 mol%, and the content of structural unit B (containing methyl structural units) in the substituted PPS resin was 98 mol%.

[0264] For the obtained polymer, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) of polystyrene were determined by gel permeation chromatography (GPC), and the results were: Mw = 30,000 and Mn = 8,600.

[0265] [Material]

[0266] The materials used in the embodiments and comparative examples are shown below.

[0267] (Main ingredient)

[0268] A1: Polyphenylene oxide (PPE), manufactured by SABIC, "SA9000"

[0269] A2: The polymer obtained in Synthetic Example 2 (VDMPPS: 2,6-dimethyl PPS resin in which 7% of the methyl groups are replaced by vinyl groups).

[0270] A3: The polymer obtained in Synthesis Example 1 (DMPPS: 2,6-dimethylPPS resin)

[0271] (Free radical polymeric compounds)

[0272] B1: Triallyl isocyanurate, manufactured by Nippon Chemical Co., Ltd. under the brand name "TAIC", molecular weight 249.7.

[0273] B2: "DD-1" manufactured by Shikoku Chemical Industry Co., Ltd.

[0274] B3: 1,2-Bis(4-vinylphenyl)ethane (BVPE), molecular weight 234.3

[0275] (Styrene-based polymers (copolymers))

[0276] C1: Hydrogenated methylstyrene (ethylene / ethylene propylene) methylstyrene copolymer, manufactured by Kuraray Co., Ltd., "Septon (registered trademark) V9461", styrene content (catalog value) 30% by mass.

[0277] C2: Styrene-ethylene / butadiene-styrene copolymer, Kuraray Co., Ltd.'s "Septon (registered trademark) 8007L", styrene content (catalog value) 30% by mass.

[0278] C3: General purpose polystyrene (PS), weight average molecular weight (Mw) 150,000, styrene content 100% by mass

[0279] C4: Styrene-ethylene / butadiene-styrene (SEBS), Asahi Kasei Corporation "Tuftec (registered trademark) P5051", styrene content (catalog value) 49% by mass.

[0280] C5: Styrene-ethylene / butadiene-styrene (SEBS), manufactured by Asahi Kasei Corporation, "Tuftec (registered trademark) P2000", styrene content (catalog value) 68% by mass.

[0281] C6: Styrene-ethylene / butadiene-styrene (SEBS), manufactured by Asahi Kasei Corporation, "Tuftec (registered trademark) S1609", styrene content (catalog value) 68% by mass.

[0282] C7: Styrene-ethylene / butadiene-styrene (SEBS), manufactured by Asahi Kasei Corporation, "Tuftec (registered trademark) S1611", styrene content (catalog value) 62% by mass.

[0283] C8: Styrene-ethylene / butadiene-styrene (SEBS), Asahi Kasei Corporation "Tuftec (registered trademark) H1043", styrene content (catalog value) 67% by mass.

[0284] (Organic peroxides)

[0285] D1: 1,3-Bis(butylperoxyisopropyl)benzene (manufactured by Nippon Oil Co., Ltd., "PERBUTYL P")

[0286] (solvent)

[0287] Toluene

[0288] [Example 1]

[0289] The VMPPS (4.8 g) obtained in Synthesis Example 2 was dissolved in toluene (10 g). Further, free radical polymerizable compound B2 (DD-1, 3.2 g, manufactured by Shikoku Chemical Industry Co., Ltd.), styrene-based thermoplastic elastomer D1 (Hybrar 8007L, manufactured by Kuraray Co., Ltd., 2.0 g), and organic peroxide D1 (PERBUTYL P, manufactured by Nippon Yu Co., Ltd., 0.2 g) were added, and the mixture was stirred at 50°C for 2 hours to obtain a varnish as a resin composition.

[0290] [Examples 2-10, Comparative Examples 1-9]

[0291] A varnish as a resin composition was obtained by the same method as in Example 1, according to the proportions described in Table 1 or 2.

[0292] [Comparative Example 10]

[0293] The DMPPS powder obtained in Synthesis Example 1 was used alone.

[0294] [Comparative Example 11]

[0295] The VMPPS powder obtained in Synthesis Example 2 was used alone.

[0296] [Preparation of cured materials]

[0297] (Drying process)

[0298] The varnishes obtained in Examples 1-10 and Comparative Examples 1-9 were injected into polytetrafluoroethylene (PTFE) containers and dried on a heating plate at 130°C for 5 minutes. The resulting film-like solid was pulverized and dried again on a heating plate at 130°C for 5 minutes to obtain a powdered solid.

[0299] (Curing process)

[0300] A polytetrafluoroethylene (PTFE) film was sandwiched between a 120 μm thick polyimide film obtained in the drying process and a PTFE film as a spacer, and vacuum-pressed using a vacuum press. The temperature was increased from 80 °C at a rate of 20 °C / min and held at 200 °C for 2 hours. A pressure of 10 kN was applied when the hot plate temperature reached 110 °C, resulting in a cured film with a thickness of approximately 100 μm and a diameter of approximately 10 cm.

[0301] For Comparative Examples 10 and 11, the DMPPS powder obtained in Synthesis Example 1 (Comparative Example 10) or the VMPPS powder obtained in Synthesis Example 2 (Comparative Example 11) were used directly without a drying process, and a film-like cured product was obtained.

[0302] Specifically, a polytetrafluoroethylene (PTFE) film sandwiching a 120 μm polyimide film (either the DMPPS powder obtained in Synthesis Example 1 or the VMPPS powder obtained in Synthesis Example 2) as a spacer was vacuum-pressed using a vacuum press. For temperature, the temperature was increased from 160 °C at a rate of 20 °C / min and held at 245 °C for 2 hours. For pressure, a pressure of 2 kN was applied when the hot plate temperature reached 235 °C, and a pressure of 5 kN was applied at 245 °C, thereby obtaining a cured film with a thickness of approximately 100 μm and a diameter of approximately 10 cm.

[0303] [evaluate]

[0304] Various physical properties were measured using the following methods. The results are shown in Tables 1-3.

[0305] (Determination of dielectric loss tangent and dielectric constant)

[0306] The dielectric loss tangent and dielectric constant were determined using the cured film obtained by the above method. The dielectric loss tangent and dielectric constant were measured at 10 GHz or 40 GHz using a Keysight Technologies vector network analyzer (N5290A) and a split cylindrical resonator, employing the cavity resonator perturbation method under standard environmental conditions (23±2℃) and relative humidity of 45–55%.

[0307] (toughness)

[0308] Cylindrical tubes with diameters of 50 mm, 40 mm, 27 mm, 18 mm, 10 mm, or 5 mm were prepared, and cured products (approximately 100 μm thick) obtained from the resin compositions of Examples 1-10 and Comparative Examples 10 and 11 were wound around each tube to cover half of the tube. At this time, if no cracks occurred, it was considered "acceptable"; if cracks occurred, it was considered "unacceptable". Evaluation was performed sequentially starting with the largest diameter; if cracks occurred, smaller diameters were not evaluated.

[0309] (Transparency)

[0310] For the cured film (approximately 100 μm thick) obtained by the above method, the film was visually inspected for turbidity. The cured film was then placed on paper with text in size 14, and the legibility of the text was determined by visual inspection. A film that was not turbid, or where the text was legible even with turbidity, was rated as "transparent." A film that was cloudy and where the text was illegible was rated as "turbid." Transparent cured films are resin-compatible and suitable for applications requiring high insulation reliability.

[0311]

[0312]

[0313]

[0314] As shown in Table 1, the resin compositions of Examples 1-10 all exhibit a dielectric loss tangent of 0.002 or less at 10 GHz, achieving a low dielectric loss tangent. Furthermore, they can be cured at a low temperature of 200°C. Additionally, as shown in Table 3, the resin compositions of Examples 1-10 did not crack even when wound into a thin cylinder with a diameter of 27 mm, resulting in the additional effect of excellent toughness. Similar to Examples 1, 3, and 6, by adjusting the styrene ratio and content of the styrene-based polymer (copolymer) (C), no cracks occurred even when wound into a thinner cylinder with a diameter of 10 mm, resulting in the additional effect of even better toughness.

[0315] In contrast, the resin compositions of Comparative Examples 1-9, which used substituted PPE resins, yielded dielectric loss tangents exceeding 0.003. Comparative Examples 10 and 11, which used substituted PPS resins alone (i.e., without the use of free radical polymerizable compound (B) and / or styrene polymers (copolymers) (C)), showed that they could not cure unless the temperature exceeded 240°C. Furthermore, as shown in Table 3, the resin compositions of Comparative Examples 10 and 11 cracked even when simply wound onto coarse cylinders with diameters of 50 mm or 40 mm, resulting in poor toughness.

[0316] Industrial applicability

[0317] The resin composition of this embodiment has a low dielectric loss tangent and can be cured at low temperatures, thus it can be suitably used in the manufacture of wiring substrates and has industrial applicability.

Claims

1. A resin composition comprising: Substituted polyphenylene sulfide resin (A), and Free radical polymerizable compounds (B) and / or styrene-based polymers (copolymers) (C), The substituted polyphenylene sulfide resin (A) comprises structural units represented by general formula (I). ， In formula (I), R1, R2, R3 and R4 are independently H, alkyl, alkoxy, aryl or alkenyl organic groups, and one or more of R1, R2, R3 and R4 are alkyl or alkoxy.

2. The resin composition according to claim 1, comprising the substituted polyphenylene sulfide resin (A) and the styrene polymer (copolymer) (C).

3. The resin composition according to claim 1, comprising the substituted polyphenylene sulfide resin (A), the free radical polymerizable compound (B), and the styrene polymer (copolymer) (C).

4. The resin composition according to claim 1, wherein, The content of the substituted polyphenylene sulfide resin (A) is 30 to 95 parts by mass relative to the total of 100 parts by mass of the substituted polyphenylene sulfide resin (A), the free radical polymerizable compound (B), and the styrene polymer (copolymer) (C).

5. The resin composition according to claim 1, wherein, The content of the free radical polymerizable compound (B) is 0 to 40 parts by mass relative to the total of 100 parts by mass of the substituted polyphenylene sulfide resin (A), the free radical polymerizable compound (B), and the styrene polymer (copolymer) (C).

6. The resin composition according to claim 1, wherein, The content of the styrene polymer (copolymer) (C) is 5 to 40 parts by mass relative to the total of 100 parts by mass of the substituted polyphenylene sulfide resin (A), the free radical polymerizable compound (B), and the styrene polymer (copolymer) (C).

7. The resin composition according to any one of claims 1 to 6, comprising an organic peroxide (D).

8. The resin composition according to any one of claims 1 to 6, wherein, The substituted polyphenylene sulfide resin (A) comprises structural units represented by general formula (II). ， In equation (II), R 5a R 6a R 7a and R 8a Each of the following is an organic group that is independently H, alkyl, alkoxy, aryl, or alkenyl-containing: R 5a R 6a R 7a and R 8a One or more of them are alkenyl-containing organic groups.

9. The resin composition according to any one of claims 1 to 6, wherein, The styrene content of the styrene polymer (polymer) (C) is 20-100% by mass.

10. The resin composition according to any one of claims 1 to 6, wherein it comprises a solvent.

11. An article for a wiring substrate comprising the resin composition according to any one of claims 1 to 6.

12. The article of claim 11, wherein it is an interlayer insulating film, a prepreg, a metal-clad laminate, or a substrate.

13. A wiring substrate comprising the resin composition according to any one of claims 1 to 6.

14. A printed wiring board comprising: The resin composition according to any one of claims 1 to 6, and Electronic components.

15. A method for manufacturing a wiring substrate, the method comprising curing a resin composition, The resin composition comprises a substituted polyphenylene sulfide resin (A), and a free radical polymerizable compound (B) and / or a styrene polymer (copolymer) (C). The substituted polyphenylene sulfide resin (A) comprises structural units represented by general formula (I). ， In formula (I), R1, R2, R3, and R4 are independently H, alkyl, alkoxy, aryl, or alkenyl-containing organic groups, and one or more of R1, R2, R3, and R4 are alkyl or alkoxy groups. The curing process involves heating the resin composition at a temperature below 240°C.

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