Compound and method for producing same, polyarylene sulfide resin and method for producing same, and molded article

Abstract

The first problem addressed by the present disclosure is to provide: a compound with which it is easy to control a reaction induction period during resin production and with which it is possible to stably produce a polyarylene sulfide resin having a low dielectric loss tangent; and a method for producing the same. The second problem addressed by the present disclosure is to provide: a polyarylene sulfide resin which has good moldability and which can be applied for use as a wiring board such as a printed wiring board; and a method for producing the same.　The first embodiment of the present disclosure relates to a compound (I) which is represented by formula (1) (in formula (1), R1-R10 each independently represent H, an alkyl group, an alkoxy group, an alkenyl group, or a phenyl group and n represents an integer of 1-8) and which has an iodine content of at least 1 ppb and less than 5,500 ppb. The second embodiment of the present disclosure relates to a polyarylene sulfide resin (II) which includes a monomer unit of the compound (I) and which has an iodine content of at least 1 ppb and less than 5,500 ppb.

Description

Compounds and methods for producing the same, polyarylene sulfide resins and methods for producing the same, and molded articles

[0001] This disclosure relates to compounds and methods for producing the same, polyarylene sulfide resins and methods for producing the same, and molded articles.

[0002] In recent years, mobile communication systems have become faster and have increased capacity. Along with these advancements, higher frequency bands are now used for communication. For example, fifth-generation mobile communication systems, which have already begun practical use, utilize higher frequency bands than fourth-generation and earlier mobile communication systems.

[0003] In mobile communication system terminals, electrical signals transmitted through printed circuit boards (PCBs) undergo attenuation, also known as transmission loss. Transmission loss depends on the dielectric properties of the PCB substrate (dielectric). Generally, the higher the frequency used, the greater the effect of the dielectric loss tangent, and consequently, the greater the transmission loss. To enable higher-speed mobile communication, suppressing transmission loss in PCBs used for high-frequency communication is required. 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 tangent are needed.

[0004] Resin compositions mainly composed of polyphenylene ether (PPE) resin (e.g., Patent Document 1, etc.) or polyphenylene sulfide (PPS) resin (e.g., Patent Documents 2, 3, etc.) are used as materials for printed circuit boards and other wiring substrates.

[0005] Japanese Patent Publication No. 2005-60635, Japanese Patent Publication No. 2002-225029, Japanese Patent Publication No. Hei 5-98157, Japanese Patent Publication No. 2015-160833

[0006] The inventors of the present invention investigated polyarylene sulfide resins that can achieve a low dielectric loss tangent applicable to wiring boards such as printed circuit boards. They found that the reactivity of such polyarylene sulfide resins is prone to variation during manufacturing, making it difficult to control the reaction induction period. Furthermore, they found that the moldability of the resulting polyarylene sulfide resin deteriorated, and that it could not be used as a polyarylene sulfide resin that can achieve a low dielectric loss tangent applicable to wiring boards such as printed circuit boards that carry terahertz signals.

[0007] The first objective of this disclosure is to provide a compound and a method for producing the same that allows for easy control of the reaction induction period during resin production and enables the stable production of polyarylene sulfide resins having a low dielectric loss tangent. The second objective of this disclosure is to provide a polyarylene sulfide resin and a method for producing the same that have good moldability and can be applied to wiring substrates such as printed circuit boards.

[0008] As a result of diligent research, the inventors of the present invention have found that the first problem described above can be solved if the compound contains a predetermined amount of a specific element. Furthermore, they have found that a polyarylene sulfide resin containing monomer units of the said compound and containing a predetermined amount of the specific element can solve the second problem described above. That is, the present disclosure includes the following embodiments. [First Embodiment] [1] Formula (1) below: (In formula (1), R １ ~R １０ Compound (I), in which each independently represents H, an alkyl group, an alkoxy group, an alkenyl group, or a phenyl group, and n is an integer from 1 to 8, and having an iodine content of 1 ppb or more and less than 5500 ppb. [Second Embodiment] Polyarylene sulfide resin (II), comprising monomer units of compound (I) described in [2] [1], and having an iodine content of 1 ppb or more and less than 5500 ppb.

[0009] The present disclosure can solve the first problem described above. Specifically, it can provide a compound and a method for producing the same that allows for easy control of the reaction induction period during resin production and enables the stable production of polyarylene sulfide resin having a low dielectric loss tangent. The present disclosure can solve the second problem described above. Specifically, it can provide a polyarylene sulfide resin and a method for producing the same that has good moldability and can be applied to wiring substrates such as printed circuit boards.

[0010] One embodiment of this disclosure will be described in detail below, but the scope of this disclosure is not limited to the embodiment described herein, and various modifications can be made without departing from the spirit of this disclosure. Each embodiment disclosed herein can be combined with any other features disclosed herein. If multiple upper and lower limits are given for a particular parameter, any combination of these upper and lower limits can be used to create a suitable numerical range. The lower and / or upper limits of the numerical ranges described herein may be replaced with numerical values ​​within that range, as shown in the examples. If multiple numerical ranges are given for multiple parameters, any numerical range can be adopted for each parameter and combined as desired. The expression "X to Y" indicating a numerical range means "X or greater and Y or less". If a particular description given for one embodiment also applies to other embodiments, that description may be omitted in the other embodiments.

[0011] [First Embodiment] [Compound (I)] The first embodiment of the present disclosure is the following compound (1): (In formula (1), R １ ~R １０The present invention relates to compound (I), which is represented by (where each independently represents H, an alkyl group, an alkoxy group, an alkenyl group, or a phenyl group, and n is an integer from 1 to 8), and has an iodine content of 1 ppb or more and less than 5500 ppb. Compound (I) according to the first embodiment contains a very small amount of iodine. According to compound (I) according to the first embodiment (hereinafter referred to as "compound (I)"), the reaction induction period during resin production can be easily controlled, and a polyarylene sulfide resin having a low dielectric loss tangent can be stably produced.

[0012] <Iodine Content> The "iodine content" in compound (I) refers to the total content of iodine, including not only free iodine contained in compound (I) but also inorganic and / or organic compounds to which iodine is bonded. The value of the iodine content in compound (I) refers to the value obtained by inductively coupled plasma mass spectrometry. Specifically, a sample of compound (I) diluted approximately 100 times with 1-methoxy-2-propanol (PGME) is used for analysis using an inductively coupled plasma mass spectrometer (for example, an inductively coupled plasma mass spectrometer manufactured by Agilent Technologies (product name: 8900 Triple Quadrupole ICP-MS)). The induction period is determined from the exothermic curve of the reaction heat obtained using a reaction calorimeter (for example, OMNICAL, model: SuperCRC).

[0013] The content of halogens other than iodine in compound (I) is not particularly limited. In one particularly preferred embodiment, from the viewpoint of easily obtaining the effects described in this disclosure, the halogen in compound (I) is iodine only.

[0014] Compound (I) contains iodine in an amount of 1 ppb or more and less than 5500 ppb. In other words, compound (I) does not contain any compound with an iodine content of 0 or more and less than 1 ppb. Here, "iodine content of 0" means that when compound (I) is analyzed using the method described above, no peaks originating from free iodine, iodine-bound inorganic compounds, and / or organic compounds are observed.

[0015] The inventors of this invention investigated the causes of variations in reactivity and dielectric loss tangent values ​​of polyarylene sulfide resins during production and found that using a compound containing a predetermined amount of a specific element as a monomer raw material makes it easier to control the reaction induction period within an appropriate range and improves the moldability of the resulting resin. Specifically, they found that including a very small amount of iodine in compound (I) allows for control of the reaction induction period during resin production within a desired range, thereby shortening the production time. In particular, they found that in compound (I), which can produce substitutional polyarylene sulfide resins, setting the iodine content to 1 ppb or more and less than 5500 ppb significantly shortens the reaction induction period. On the other hand, they also found that using a compound with an iodine content of less than 1 ppb (including a form with zero iodine content) as a monomer raw material results in a reaction induction period that is too short, making it difficult to control the reaction. In other words, from the viewpoint of easily controlling the reaction induction period during resin production and stably producing polyarylene sulfide resin with a low dielectric loss tangent, it is necessary to use compound (I) with an iodine content of 1 ppb or more and less than 5500 ppb.

[0016] Even more surprisingly, we found that the presence of a very small amount of iodine in compound (I) makes it easier to suppress the cleavage of S-S bonds in compound (I) where n is 2 or greater. Furthermore, the presence of a very small amount of iodine tends to lower the melting point and crystallinity of compound (I), which can be expected to improve handling properties as a result. Compound (I) that can achieve such an iodine content can be obtained, for example, by the manufacturing method described later.

[0017] In one embodiment, from the viewpoint of making it easier to control the reaction induction period during resin production to a more appropriate range, the iodine content in compound (I) is preferably 1 ppb or more and 4500 ppb or less, more preferably 10 ppb or more and 3500 ppb or less, and even more preferably 10 ppb or more and 2500 ppb or less. In a more preferred embodiment, the iodine content may be 10 ppb or more and 1500 ppb or less, 10 ppb or more and 1000 ppb or less, 100 ppb or more and 2000 ppb or less, or more than 150 ppb and less than 2000 ppb.

[0018] In compound (I) represented by formula (1), R １ ~R １０ Each of these independently represents H, an alkyl group, an alkoxy group, an alkenyl group, or a phenyl group. The alkyl group may be linear, branched, or cyclic alkyl group, and linear, branched, or cyclic alkyl groups having 1 to 12 carbon atoms are preferred. Examples of linear, branched, or cyclic alkyl groups having 1 to 12 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, s-isobutyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group, isooctyl group, n-nonyl group, isononyl group, n-decyl group, isodecyl group, n-undecyl group, n-dodecyl group, isododecyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, and cyclooctyl group. In one embodiment, the alkyl group is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, more preferably a methyl group, an ethyl group, and / or an isopropyl group, and even more preferably contains a methyl group.

[0019] The alkoxy group may be a linear, branched, or cyclic alkoxy group, and is 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 a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a tert-butoxy group, an s-butoxy group, an isobutoxy group, an n-pentyloxy group, an isopentyloxy group, a neopentyloxy group, an n-hexyloxy group, an isohexyloxy group, an s-hexyloxy group, a tert-hexyloxy group, a neohexyloxy group, an n-heptyloxy group, an n-octyloxy group, an isooctyloxy group, an n-nonyloxy group, an isononyloxy group, an n-decyloxy group, an isodecyloxy group, a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, a cyclooctyloxy group, a cyclononyloxy group, a cyclodecyloxy group, and the like. In one embodiment, the alkoxy group is preferably a linear alkoxy group having 1 to 5 carbon atoms, and more preferably a methoxy group, an ethoxy group, a propoxy group, or a butoxy group.

[0020] From the viewpoint of ease of resin production, the number of carbon atoms of the alkenyl group 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 group may be an alkenyl group having 3 carbon atoms or an alkenyl group having 2 carbon atoms, and for example, may be an allyl group having 3 carbon atoms and / or a vinyl group having 2 carbon atoms.

[0021] The alkyl group, alkoxy group, alkenyl group, and phenyl group may have a substituent, but from the viewpoint of making the iodine content in the compound 1 ppb or more and less than 5500 ppb, it is particularly preferable not to have a substituent containing iodine.

[0022] In one embodiment, in formula (1), R ６ ~R １０ is R １ ~R ５It may be the same as R. １ and R ６ , R ２ and R ７ , R ３ and R ８ , R ４ and R ９ and R ５ and R １０ These correspond to each other.

[0023] In one embodiment, compound (I) represented by formula (1) is R ２ , R ４ , R ７ and R ９ is an alkyl group having 1 to 5 carbon atoms, R １ , R ３ , R ６ and R １０ It may be a compound of H. In one embodiment, compound (I) represented by formula (1) is R ２ and R ７ is an alkyl group having 1 to 5 carbon atoms, R １ , R ３ ~R ５ , R ６ and R ８ ~R １０ It may be a compound of H. In one embodiment, compound (I) represented by formula (1) is R ２ , R ４ , R ７ and R ９ is an alkoxy group having 1 to 5 carbon atoms, R １ , R ３ , R ５ , R ６ , R ８ and R １０ It may also be a compound in which H is present.

[0024] As for compound (I) represented by formula (1), any compound that can produce a polyarylene sulfide resin having the desired dielectric loss tangent, R １ ~R １０However, it may have any of the substituents described above: alkyl group, alkoxy group, alkenyl group, phenyl group, or H. In one embodiment, compound (I) may be a compound in formula (1) where n is 2 to 8, or a compound where n is 2 to 5. In one particularly preferred embodiment, compound (I) is a diaryl disulfide where n is 2. A preferred example of the case where compound (I) is a diaryl disulfide (hereinafter, diaryl disulfide will be referred to as "compound (I-1)") will be described below.

[0025] <Diaryl Disulfide> Compound (I-1) is a diaryl disulfide in compound (I) represented by formula (1), where n is 2. That is, compound (I-1) is compound (I) represented by the above formula (1), where R １ ~R １０ However, each independently represents H, an alkyl group, an alkoxy group, an alkenyl group, or a phenyl group, and the compound has n = 2. As a diaryl disulfide, R in formula (1) ６ ~R １０ R １ ~R ５ It is preferable that it be the same as [the other one].

[0026] Preferred diaryl disulfides include, for example, diphenyl disulfide; 2,2'-dimethyldiphenyl disulfide; 3,3'-dimethyldiphenyl disulfide; 2,2',6,6'-tetramethyldiphenyl disulfide; 2,2',3,3'-tetramethyldiphenyl disulfide; 2,2',5,5'-tetramethyldiphenyl disulfide; 3,3',5,5'-tetramethyldiphenyl disulfide; 2,2',3,3',5,5'-hexamethyldiphenyl disulfide; 2,2',3,3',6,6'-hexamethyldiphenyl Nyl disulfide; 2,2',3,3',5,5',6,6'-Octamethyldiphenyl disulfide; 2,2'-Diethyldiphenyl disulfide; 3,3'-Diethyldiphenyl disulfide; 2,2',6,6'-Tetraethyldiphenyl disulfide; 2,2',3,3'-Tetraethyldiphenyl disulfide; 2,2',5,5'-Tetraethyldiphenyl disulfide; 3,3',5,5'-Tetraethyldiphenyl disulfide; 2,2',3,3',5,5'-Hexaethyldiphenyl disulfide; 2,2',3,3',6,6' -Hexaethyldiphenyl disulfide; 2,2',3,3',5,5',6,6'-Octaethyldiphenyl disulfide; 2,2'-Dipropyldiphenyl disulfide; 3,3'-Dipropyldiphenyl disulfide; 2,2',6,6'-Tetrapropyldiphenyl disulfide; 2,2',3,3'-Tetrapropyldiphenyl disulfide; 2,2',5,5'-Tetrapropyldiphenyl disulfide; 3,3',5,5'-Tetrapropyldiphenyl disulfide; 2,2',3,3',5,5'-Hexapropyldiphenyl disulfide Diisopropyl diphenyl disulfide; 2,2',3,3',6,6'-Hexapropyl diphenyl disulfide; 2,2',3,3',5,5',6,6'-Octapropyl diphenyl disulfide; 2,2'-Diisopropyl diphenyl disulfide; 3,3'-Diisopropyl diphenyl disulfide; 2,2',6,6'-Tetraisopropyl diphenyl disulfide; 2,2',3,3'-Tetraisopropyl diphenyl disulfide; 2,2',5,5'-Tetraisopropyl diphenyl disulfide; 3,3',5,5'-Tetraisopropyl diphenyl disulfide;Examples include 2,2',3,3',5,5'-hexisopropyl diphenyl disulfide; 2,2',3,3',6,6'-hexisopropyl diphenyl disulfide; and 2,2',3,3',5,5',6,6'-octaisopropyl diphenyl disulfide. Among these, diphenyl disulfide, 2,2'-dimethyldiphenyl disulfide, 3,3'-dimethyldiphenyl disulfide, 2,2',6,6'-tetramethyldiphenyl disulfide, 2,2',3,3'-tetramethyldiphenyl disulfide, 2,2',5,5'-tetramethyldiphenyl disulfide, 3,3',5,5'-tetramethyldiphenyl disulfide, 2,2',3,3',5,5'-hexamethyldiphenyl disulfide, 2,2',3,3',6,6'-hexamethyldiphenyl disulfide, and 2,2',3,3',5,5',6,6'-octamethyldiphenyl disulfide are preferred from the viewpoint of raw material availability. Note that in the above chemical names, 2 represents R in the position of the substituent. １ Corresponding to R, 3 is R ２ Corresponding to 4, 4 is R ３ Corresponding to 5, 5 is R ４ Corresponding to 6 is R ５ This corresponds to R. Also, 2' is R ６ Corresponding to 3', 3' is R ７ Corresponding to 4', 4' is R ８に Correspondingly, 5' is R ９ Corresponding to 6', 6' is R １０ It corresponds to.

[0027] Compound (I-1) contains iodine in an amount of 1 ppb or more and less than 5500 ppb. As with the above, from the viewpoint of making it easier to control the reaction induction period during resin production to a more appropriate range, the iodine content in compound (I-1) is preferably 1 ppb or more and 4500 ppb or less, more preferably 10 ppb or more and 3500 ppb or less, and even more preferably 10 ppb or more and 2500 ppb or less. In a more preferred embodiment, the iodine content may be 10 ppb or more and 1500 ppb or less, 10 ppb or more and 1000 ppb or less, 100 ppb or more and 2000 ppb or less, or more than 150 ppb and less than 2000 ppb.

[0028] Compound (I) represented by formula (1) may be a compound having a halogen content of 1 ppb or more and 10,000 ppb or less. That is, compound (I) may have an iodine content of 1 ppb or more and less than 5,500 ppb, and a total halogen content including iodine of 1 ppb or more and 10,000 ppb or less. If the halogen content of compound (I) is within the above range, it is easier to control the reaction induction period during resin production and easier to stably produce polyarylene sulfide resin having a low dielectric loss tangent.

[0029] <Halogen Content> The halogens contained in compound (I) include free halogens such as free fluorine, free chlorine, free bromine, free iodine, and free astatine, as well as inorganic compounds and / or organic compounds to which one or more halogens are bonded. That is, it is preferable that the total content of the free halogens, inorganic compounds and / or organic compounds in compound (I) is 1 ppb or more and 10,000 ppb or less. Compound (I) may contain iodine and halogens other than iodine, or it may contain only iodine. When iodine and halogens other than iodine are included, the total amount is preferably 10,000 ppb or less, as described above. The halogen content in compound (I) can be measured under the same conditions as the iodine content described above.

[0030] In one embodiment, from the viewpoint of easily controlling the reaction induction period during resin production to a more appropriate range, the halogen content in compound (I) (total amount of halogens including iodine) is preferably 1 ppb or more and less than 5500 ppb, more preferably 1 ppb or more and 4500 ppb or less, even more preferably 10 ppb or more and 3500 ppb or less, and particularly preferably 10 ppb or more and 2500 ppb or less. In a more preferred embodiment, the halogen content may be 10 ppb or more and 1500 ppb or less, 10 ppb or more and 1000 ppb or less, 100 ppb or more and 2000 ppb or less, or more than 150 ppb and less than 2000 ppb.

[0031] In one embodiment, compound (I) may have an iodine content of 1 ppb or more and less than 5500 ppb, and a halogen content other than iodine of 0 ppb or more and 4500 ppb or less. Furthermore, the halogen content other than iodine may be 10 ppb or more and 3500 ppb or less, 10 ppb or more and 2500 ppb or less, 10 ppb or more and 1500 ppb or less, 10 ppb or more and 1000 ppb or less, 100 ppb or more and 2000 ppb or less, or more than 150 ppb and less than 2000 ppb.

[0032] In one embodiment, compound (I-1) may also be a compound having a halogen content of 1 ppb or more and 10,000 ppb or less. Alternatively, compound (I-1) may have an iodine content of 1 ppb or more and less than 5,500 ppb, and a halogen content of 0 ppb or more and 4,500 ppb or less. The preferred values ​​for the iodine content and the halogen content of other than iodine in compound (I-1) can be the same range as the values ​​for compound (I) described above.

[0033] <Method for producing compound (I)> The method for producing compound (I) includes (A1) preparing a precursor of compound (I), and (A2) adjusting the iodine content in the precursor to 1 ppb or more and less than 5500 ppb. Hereinafter, the method for producing compound (I) will be described as "Method (I)".

[0034] ((A1) Prepare a precursor of compound (I)) The manufacturing method (I) includes (A1) preparing a precursor of compound (I) above (hereinafter sometimes referred to as "step (A1)"). Here, "precursor" refers to a compound represented by formula (1) having an iodine content of 5500 ppb or more, and / or a compound represented by formula (1) having an iodine content of less than 1 ppb. For the sake of explanation, a compound with an iodine content of 5500 ppb or more will be referred to as "precursor P1", and a compound with an iodine content of less than 1 ppb will be referred to as "precursor P2".

[0035] Step (A1) includes preparing precursor P1 and / or precursor P2. Preparing precursor P1 and / or precursor P2 may involve preparing commercially available products thereof. In one embodiment, step (A1) may involve preparing precursor P1 and / or precursor P2.

[0036] The method for preparing precursor P1 is not particularly limited, but examples include the method described later in (a1).

[0037] The method for preparing precursor P2 is not particularly limited, but for example, the manufacturing method described in Patent Document 4 may be used.

[0038] In one embodiment, step (A1) may include measuring the iodine content in the precursor. The method for measuring the iodine content in the precursor is preferably the same method as the method for measuring the iodine content in compound (I) described above.

[0039] (The iodine content in the precursor (A2) is adjusted to be between 1 ppb and less than 5500 ppb.) The manufacturing method (I) includes adjusting the iodine content in the precursor (A2) to be between 1 ppb and less than 5500 ppb (hereinafter sometimes referred to as "step (A2)"). In the case of precursor P1, it is preferable to purify the precursor P1 (hereinafter referred to as "step (A2-1)") or to mix precursor P1 and precursor P2 to adjust the iodine content (hereinafter referred to as "step (A2-2)"). In the case of precursor P2, it is preferable to add an iodine source to precursor P2 (hereinafter referred to as "step (A2-3)").

[0040] (Step (A2-1)) Step (A2-1) is to purify the precursor P1 and adjust the iodine content to 1 ppb or more and less than 5500 ppb. As a method for purifying the precursor P1, a method of recrystallizing the precursor P1 to reduce the total amount of iodine-containing impurities in the precursor is preferred. The method of recrystallization is not particularly limited, but from the viewpoint of purity and crystal morphology, the cooling method is preferred. By recrystallization, a liquid containing a high concentration of iodine can be separated, and this liquid may be used as an iodine source in step (A2-3) described later.

[0041] (Step A2-2) Step (A2-2) is to mix precursor P1 and precursor P2. The mixing ratio of precursor P1 and precursor P2 can be arbitrarily adjusted within the range in which the iodine content in compound (I) is 1 ppb or more and less than 5500 ppb.

[0042] (Step (A2-3) Step (A2-3) is to add an iodine source to precursor P2. The iodine source may be the liquid obtained in step (A2-1) or an iodine compound. That is, step (A2-3) may be to add a liquid containing a high concentration of iodine to precursor P2 to adjust the iodine content to 1 ppb or more and less than 5500 ppb. Note that the iodine content may also be adjusted by adding precursor P1 to precursor P2, but this method is included in step (A2-2).

[0043] The process may include adding iodine to the obtained compound (I) after step (A2). For example, after obtaining compound (I) with a relatively low iodine content by step (A2-1), the process may include adding a solution containing a high concentration of iodine to compound (I) to increase the iodine content in compound (I).

[0044] Below, a preferred example of manufacturing method (I) for producing a diaryl disulfide in formula (1) where n is 2, i.e., compound (I-1), will be described. For convenience, this will be referred to as "manufacturing method (I-1)".

[0045] <Method for producing diaryl disulfide> Method (I-1) is a method for producing diaryl disulfide in formula (1) where n is 2, wherein (A1) is (a1) iodine or iodide is used to produce the following formula (2): (In formula (2), R １ ~R ５ The method comprises oxidizing a substrate represented by (where each independently represents H, an alkyl group, an alkoxy group, an alkenyl group, or a phenyl group, and L represents H, an alkali metal element, or an alkaline earth metal element) to obtain the precursor, wherein (A2) comprises purifying the precursor obtained by (a1).

[0046] (Step (A1)) In manufacturing method (I-1), it is preferable that step (A1) includes the above (a1) (hereinafter sometimes referred to as "step (a1)"). That is, it is preferable that step (a1) includes the preparation of a precursor. The precursor prepared by step (a1) is always precursor P1 (iodine content of 5500 ppb or more).

[0047] (a1) Oxidizing the substrate represented by formula (2) using iodine or iodide to obtain a precursor) Step (A1) preferably includes step (a1). In the substrate represented by formula (2) used in step (a1), R １ ~R ５ Each of these independently represents H, an alkyl group, an alkoxy group, an alkenyl group, or a phenyl group, and L represents H, an alkali metal element, or an alkaline earth metal element. Examples of alkyl groups, alkoxy groups, alkenyl groups, or phenyl groups are the same as those described in formula (1) above, and preferred examples are also the same.

[0048] Examples of alkali metal elements include lithium, sodium, potassium, rubidium, or cesium, of which lithium, sodium, potassium, or cesium are preferred, and potassium and sodium are more preferred. Examples of alkaline earth metal elements include beryllium, magnesium, calcium, strontium, or barium, of which magnesium, calcium, barium, beryllium, or magnesium, calcium, and barium are preferred, and magnesium and calcium are more preferred.

[0049] In a preferred embodiment, the substrate represented by formula (2) is a substrate that can give the above preferred diaryl disulfide. That is, R in formula (2) １ ~R ５ However, each of the above preferred diaryl disulfides R １ ~R ５It is preferable that the compound corresponds to the above. In a more preferred embodiment, the substrate represented by formula (2) is a thiol compound in which L is H, and R of the preferred diaryl disulfide is １ ~R ５ These are thiol compounds having the corresponding group. Examples include 3-methylbenzenethiol, 2-methylbenzenethiol, 4-methylbenzenethiol, thiophenol (benzenethiol), 2,3-dimethylbenzenethiol, 2,5-dimethylbenzenethiol, 2,6-dimethylbenzenethiol, 3,5-dimethylbenzenethiol, and the like.

[0050] Iodine is preferred as the iodide used in step (a1). Furthermore, step (a1) is preferably carried out by the method described in Bull. Chem. Soc. Jpn. 1992.65.2029, for example.

[0051] (Step (A2)) In manufacturing method (I-1), step (A2) includes purifying the precursor obtained in step (a1). As described above, the precursor obtained in step (a1) is "precursor P1". As a method for purifying precursor P1, the aforementioned step (A2-1) can be used.

[0052] Furthermore, the manufacturing method (I-1) may also include adding iodine to the obtained compound (I-1) after step (A2). For example, the method may include purifying the precursor P1 obtained in step (a1) to obtain a compound (I-1) with a relatively low iodine content, and then adding a solution containing a high concentration of iodine to the compound (I-1) to increase the iodine content in the compound (I-1).

[0053] <Applications> As described above, compound (I) allows for easy control of the reaction induction period during resin production and enables the stable production of polyarylene sulfide resin with a low dielectric loss tangent. Therefore, it can be suitably used as a raw material (monomer) for producing polyarylene sulfide resin. More preferably, it can be used as a raw material for producing polyarylene sulfide resin for wiring boards. The same applies to compound (I-1).

[0054] [Second Embodiment] [Polyarylene Sulfide Resin (II)] The second embodiment of the present disclosure relates to a polyarylene sulfide resin (II) that contains monomer units of compound (I) and has an iodine content of 1 ppb or more and less than 5500 ppb. The polyarylene sulfide resin (II) according to the second embodiment has good moldability and can be applied to wiring substrates such as printed wiring boards.

[0055] The polyarylene sulfide resin (II) (hereinafter referred to as "PAS resin (II)") according to the second embodiment is a resin containing monomer units of compound (I). Specifically, it contains monomer units represented by the following formula (3): In formula (3), R １ , R ２ , R ４ and R ５ each independently represent H, an alkyl group, an alkoxy group, an alkenyl group, or a phenyl group, and n represents an integer from 1 to 8. Note that R １ , R ２ , R ４ and R ５ in formula (3) correspond to R １ , R ２ , R ４ and R ５ or R ６ , R ７ , R ９ and R １０ in formula (1), and the preferred examples are also the same.

[0056] In one embodiment, in the monomer unit represented by formula (3), R ２ and R ４ are alkyl groups having 1 to 5 carbon atoms, and R １ and R ５ are H. The PAS resin (II) containing this monomer unit becomes a substituted PAS resin (II). In a preferred embodiment of the substituted PAS resin (II), in the monomer unit represented by formula (3), R ２ and R ４ are methyl groups, and R １ and R ５H is the value. From the viewpoint of easily achieving a lower dielectric loss tangent, it is preferable that the PAS resin (II) is a substitutional PAS resin (II).

[0057] In another preferred embodiment, the monomer unit represented by formula (3) is R １ , R ２ , R ４ and R ５ They are all H.

[0058] In one embodiment, the ratio of monomer units represented by formula (3) to the total monomer units constituting the PAS resin (II) is preferably 30 mol% or more, and more preferably 50 mol% or more. Alternatively, the PAS resin (II) may be a resin composed solely of monomer units represented by formula (3). In this case, the moldability is improved, and the iodine content can be reduced to a significantly lower level, thereby minimizing the possibility of corrosion in molding equipment and the like.

[0059] <Iodine Content> PAS resin (II) contains iodine in an amount of 1 ppb or more and less than 5500 ppb. Since PAS resin (II) is a polymer of monomer raw materials containing compound (I) (preferably monomer raw materials containing only compound (I)), trace amounts of iodine derived from compound (I) are contained in the resin. This results in PAS resin (II) with good moldability, making it applicable to wiring boards such as printed circuit boards. The "iodine content" in PAS resin (II) refers to the total content of free iodine, inorganic compounds to which iodine is bound, and / or organic compounds contained in PAS resin (II), just as in compound (I). The value of the iodine content in PAS resin (II) refers to the value obtained by the same method as compound (I) described above.

[0060] In one embodiment, the iodine content in the PAS resin (II) is preferably 1 ppb or more and 4500 ppb or less, more preferably 10 ppb or more and 3500 ppb or less, and even more preferably 10 ppb or more and 2500 ppb or less. In a more preferred embodiment, the iodine content may be 10 ppb or more and 1500 ppb or less, 10 ppb or more and 1000 ppb or less, 100 ppb or more and 2000 ppb or less, or more than 150 ppb and less than 2000 ppb.

[0061] In PAS resin (II), the content of halogens other than iodine is not particularly limited. When components derived from materials containing halogens other than iodine are used during the manufacture of PAS resin (II), these halogen components may remain in the final PAS resin (II). Therefore, PAS resin (II) may contain halogens other than iodine. That is, PAS resin (II) may have a halogen content of 1 ppb or more and 10,000 ppb or less. Also, PAS resin (II) may have an iodine content of 1 ppb or more and less than 5,500 ppb, and a halogen content of 0 ppb or more and 4,500 ppb or less. When PAS resin (II) contains iodine and halogens other than iodine, the preferred content ranges for iodine and halogens other than iodine can be the same as the values ​​described for compound (I) above.

[0062] <Weight-Average Molecular Weight> In one embodiment, the weight-average molecular weight (Mw) of PAS resin (II) is preferably 1,000 to 33,000 from the viewpoint of dielectric loss tangent and glass transition temperature. If the Mw of PAS resin (II) is 1,000 or more, it has good moldability and is likely to be a resin that can be applied to wiring substrates such as printed circuit boards. If the Mw is 33,000 or less, it is easier to control the glass transition temperature of PAS resin (II) within a desired range. The Mw of PAS resin (II) can be set to any value within the above range, for example, it may be 3,000 to 33,000, 5,000 to 28,000, or 6,000 to 27,000. The Mw of PAS resin (II) is the standard polystyrene equivalent value obtained by GPC measurement using tetrahydrofuran solvent. Note that the Mw of PAS resin (II) may be the value measured at the time of resin manufacturing. For example, during the production of resin, if Mw is measured after 6 hours of reaction time and the Mw is 1,000 or more, it can be determined that the Mw of the final PAS resin (II) will also be 1,000 or more.

[0063] <Dielectric Loss Tangent> PAS resin (II) exhibits less variation in dielectric loss tangent and can achieve a low dielectric loss tangent. In particular, substitutional PAS resin (II) is more likely to achieve a lower dielectric loss tangent. In one embodiment, when PAS resin (II) is substitutional PAS resin (II), the dielectric loss tangent at 10 GHz is preferably less than 0.002, more preferably less than 0.0015, and even more preferably less than 0.001. In one embodiment, when PAS resin (II) is substitutional PAS resin (II), the dielectric loss tangent at 40 GHz is preferably less than 0.003, more preferably less than 0.0025, and even more preferably less than 0.002. In one embodiment, when PAS resin (II) is substitutional PAS resin (II), the dielectric loss tangent at 80 GHz is preferably less than 0.004, more preferably less than 0.003, and even more preferably less than 0.0025. The dielectric loss tangent of PAS resin (II) refers to the value measured under the following conditions: (Measurement conditions for dielectric loss tangent) A PAS resin (II) film with a thickness of 50 to 250 μm is heated at 200°C to 250°C for 120 minutes to prepare a resin sample for measurement. Then, using a vector network analyzer (e.g., Keysight Technologies, product name "N5290A") and a split cylinder resonator, the dielectric loss tangent is measured at 10 GHz, 40 GHz, or 80 GHz under standard environmental conditions (23 ± 2°C) and relative humidity of 45 to 55% by the cavity resonator perturbation method.

[0064] <Method for Manufacturing PAS Resin (II)> The method for manufacturing PAS resin (II) includes polymerizing raw materials containing compound (I). Here, "raw materials" refers to monomer raw materials used in the polymerization of PAS resin (II). The method for manufacturing PAS resin (II) will be described below as "Manufacturing Method (II)".

[0065] Because manufacturing method (II) includes compound (I) as a raw material, it is easy to control the reaction induction period during the production of PAS resin (II). The inventors of the present invention have found that this reaction induction period can be controlled by including a trace amount of a specific element, namely iodine, in the monomer raw material used in the production of PAS resin (II). In this disclosure, "reaction induction period" refers to the induction time until the polymerization reaction of diaryl disulfide begins. The reaction induction period can be confirmed by detecting the heat of reaction. Manufacturing method (II) makes it easy to control the reaction induction period during resin production and enables the stable production of PAS resin (II) having a low dielectric loss tangent by using compound (I) containing a trace amount of iodine as a monomer.

[0066] In manufacturing method (II), the proportion of compound (I) in the raw material is preferably 30 to 100 mol%, and more preferably 50 to 100 mol%. From the viewpoint of easily adjusting the iodine content in PAS resin (II) to 1 ppb or more and less than 5500 ppb, it is particularly preferable that the raw material contains only compound (I).

[0067] In manufacturing method (II), from the viewpoint of by-products, it is preferable to include compound (I-1) as a raw material. Furthermore, it is more preferable to include polymerization of a raw material containing only compound (I-1). Compound (I-1) is R ３ and R ８ It is preferable to use a compound containing H.

[0068] The manufacturing method (II) preferably includes oxidative polymerization of the raw materials. In one embodiment, the manufacturing method (II) preferably involves polymerizing the raw materials containing compound (I) in the presence of an oxidizing agent.

[0069] (Oxidizing agent) The oxidizing agent preferably includes one or more selected from quinone-based oxidizing agents and vanadium-based oxidizing agents.

[0070] Examples of quinone-based oxidizing agents include 2,3-dichloro-5,6-dicyano-parabenzoquinone (DDQ), 2,3,5,6-tetrachloroparabenzoquinone (chloranil), 2,3,5,6-tetrabromobenzoquinone (bromanil), 2,3,5,6-tetrafluoroparabenzoquinone, anthraquinone, 1,4-naphthoquinone, 2,3-dichloro-1,4-naphthoquinone, 2,3-dibromo-1,4-naphthoquinone, 2,3-dicyano-1,4-naphthoquinone, 3,4,5,6-tetrachloroorthobenzoquinone (orthochloranil), 3,4,5,6-tetrabromoorthobenzoquinone (orthobromanil), and 3,4,5,6-tetrafluorobenzoquinone. Among these, DDQ is preferred from the viewpoint of redox reactions. The above-mentioned quinone-based oxidizing agents may be used individually or in combination of two or more.

[0071] As vanadium-based oxidizing agents, oxovanadium compounds having a V=O bond in the molecule are preferred. Preferred examples of oxovanadium compounds include N,N'-bissalicylideneethylenediamine oxovanadium, phthalocyanine oxovanadium, and tetraphenylporphyrin oxovanadium. The above vanadium-based oxidizing agents may be used individually or in combination of two or more.

[0072] From the viewpoint of redox reactions, the oxidizing agent preferably contains a quinone-based oxidizing agent, and more preferably contains DDQ.

[0073] (Acid) In one embodiment, the polymerization step may be carried out in the presence of the above-mentioned oxidizing agent and acid. The acid is not particularly limited, and any acid capable of releasing protons can be used. Specifically, examples of organic acids include sulfuric acid; acetic acid; methanesulfonic acid; benzenesulfonic acid; toluenesulfonic acid; trifluoromethanesulfonic acid, trifluoroacetic acid (TFA), 1,1,2,2-tetrafluoroethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoropropanesulfonic acid, heptafluoroisopropanesulfonic acid, and nonafluorobutanesulfonic acid. Of these, trifluoromethanesulfonic acid, 1,1,2,2-tetrafluoroethanesulfonic acid, and trifluoroacetic acid are preferred.

[0074] (Solvent) In one embodiment, the polymerization step may be carried out in a solvent. Preferred solvents include dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, tetrachloroethylene, 1,1,2,2-tetrachloroethane, nitromethane, nitrobenzene, chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, N-methylpyrrolidone, and toluene. When the boiling point of these solvents is below the polymerization temperature, it is preferable to carry out polymerization using a sealed container. Of these, from the viewpoint of the degree of polymerization of PAS resin (II), it is preferable to use dichloromethane and toluene as the solvent.

[0075] (Polymerization Temperature) The polymerization temperature is not particularly limited, but from the viewpoint of the degree of polymerization of PAS resin (II), -10 to 45°C is preferred, and 0 to 40°C is more preferred.

[0076] (Reaction Induction Period) Since manufacturing method (II) includes compound (I) as a raw material, the reaction induction period can be shortened. In one embodiment, the reaction induction period of compound (I) at a reaction temperature of 0 to 25°C is preferably 1 to 360 minutes, and more preferably 1 to 180 minutes. In one embodiment, the reaction induction period may be more than 1 minute and 360 minutes or less, and more than 1 minute and 180 minutes or less.

[0077] It is preferable to further include washing the obtained PAS resin (II) after the polymerization step described above. The washing method is not particularly limited; for example, if the obtained PAS resin (II) is a solid, the solid may be pulverized and then unreacted raw materials may be extracted with an organic solvent (for example, a mixture of methanol and hydrochloric acid). After that, the PAS resin 1 can be washed with water, acid, base, etc. Alternatively, if the obtained PAS resin (II) is dissolved in a solvent, it may be washed directly with water, acid, base, etc. The same solvent as described above may be used as the washing solvent.

[0078] The PAS resin (II) obtained by the above manufacturing method (II) is adjusted to have an iodine content of 1 ppb or more and less than 5500 ppb. This makes it possible to obtain a PAS resin (II) with less variation in dielectric loss tangent.

[0079] Manufacturing method (II) may include manufacturing method (I) described above. That is, after preparing compound (I) by manufacturing method (I), the raw materials containing compound (I) may be polymerized. Below, an example of manufacturing method (II) including the above manufacturing method (I-1) (i.e., the method for producing diaryl disulfide) will be described. For convenience, this manufacturing method will be described as "manufacturing method (II-1)".

[0080] <Manufacturing Method (II-1)> Manufacturing method (II-1) includes (A1) preparing a precursor of compound (I), (A2) adjusting the iodine content in the precursor to 1 ppb or more and less than 5500 ppb, and (A3) polymerizing the compound (I) obtained in (A2), wherein (A1) (a1) using iodine or iodide, the following formula (2): (In formula (2), R １ ~R ５The process includes oxidizing a substrate represented by (where each independently represents H, an alkyl group, an alkoxy group, an alkenyl group, or a phenyl group, and L represents H, an alkali metal element, or an alkaline earth metal element) to obtain the precursor, wherein (A2) includes purifying the precursor obtained by (a1) or (b1). The manufacturing method (II-1) is a method for producing PAS resin (II) using diaryl disulfide obtained in steps (A1) to (A2) as a raw material. Preferred examples of steps (A1) to (A2) are the same as those of the manufacturing method (I-1) above, and preferred examples of step (A3) are the same as those of the manufacturing method (II) above. In the case of manufacturing method (II-1), the reaction induction period is easier to control.

[0081] [Molded Articles] A third embodiment of this disclosure relates to molded articles containing PAS resin (II). The molded articles according to the third embodiment may contain only PAS resin (II) as the resin component. PAS resin (II) has good moldability and can be applied to wiring boards such as printed circuit boards. Furthermore, if the PAS resin (II) is a substitution type PAS resin (II), the moldability is even better and it is easier to apply to wiring boards such as printed circuit boards. Molded articles containing PAS resin (II) can be applied to wiring boards, insulating components, interlayer insulating materials, prepregs, metal-clad laminates, substrates, printed circuit boards, etc.

[0082] The applications of these wiring boards and the like are not limited and can be used in a variety of applications requiring high-speed communication, but they may be installed in network equipment and terminals, servers, AI processors, automotive and aerospace equipment, home game consoles, etc.

[0083] A non-limiting list of exemplary embodiments and combinations of exemplary embodiments of the present disclosure is disclosed below: [1] Formula (1): (In formula (1), R １ ~R １０Compound (I), wherein each of the following formulas (1) is expressed as (a1) and the iodine content is 1 ppb or more and less than 5500 ppb. [2] A method for producing compound (I) as described in [1], comprising: (A1) preparing a precursor of compound (I); and (A2) adjusting the iodine content in the precursor to 1 ppb or more and less than 5500 ppb. [3] Compound (I) is a diaryl disulfide in formula (1) where n is 2, and (A1) is (a1) a diaryl disulfide in formula (2) below using iodine or iodide: (In formula (2), R １ ~R ５ A method for producing compound (I) according to [2], comprising oxidizing a substrate represented by (where each independently represents H, an alkyl group, an alkoxy group, an alkenyl group, or a phenyl group, and L represents H, an alkali metal element, or an alkaline earth metal element) to obtain the precursor, wherein (A2) comprises purifying the precursor obtained by (a1). [4] A polyarylene sulfide resin (II) comprising monomer units of compound (I) according to [1], and having an iodine content of 1 ppb or more and less than 5500 ppb. [5] A method for producing polyarylene sulfide resin (II) according to [4], comprising polymerizing a raw material containing compound (I) according to [1]. [6] A method for producing polyarylene sulfide resin (II) according to [5], comprising polymerizing the raw material in the presence of an oxidizing agent. [7] A method for producing polyarylene sulfide resin (II) according to [6], wherein the oxidizing agent comprises one or more selected from quinone-based oxidizing agents and vanadium-based oxidizing agents. [8] A molded article comprising the polyarylene sulfide resin (II) according to [4].

[0084] The present disclosure will be further illustrated by the following examples, but these examples will not limit the interpretation of the present disclosure.

[0085] The iodine content in the compound and PAS resin, the Mw of the PAS resin, and the dielectric loss tangent were measured under the following conditions. The moldability (film moldability) of the PAS resin was also evaluated under the following conditions.

[0086] <Measurement of Iodine Content> The iodine content in the precursor, compound, and PAS resin was measured under the following conditions. Samples were diluted approximately 100 times with 1-methoxy-2-propanol (PGME) and analyzed using an inductively coupled plasma mass spectrometer (Agilent Technologies, Inc. inductively coupled plasma mass spectrometer (product name: 8900 Triple Quadrupole ICP-MS)). The induction period was determined from the exothermic curve of the reaction heat obtained using a reaction calorimeter (OMNICAL, Inc., model: SuperCRC).

[0087] <Measurement of Weight-Average Molecular Weight (Mw)> For each PAS resin, the weight-average molecular weight (Mw) in polystyrene equivalent was measured by gel permeation chromatography (GPC). After a reaction time of 6 hours, the Mw of the PAS resin was measured by GPC. Those with an Mw of 1000 or more were classified as "pass," and those with an Mw of less than 1000 were classified as "fail."

[0088] <Evaluation of Moldability (Film Moldability)> For each PAS resin, a PAS resin film was prepared with a thickness of 100 μm. Specifically, the film was prepared by placing a spacer of a predetermined thickness between hot plates and applying a pressure of 0.3 MPa at 220°C in a vacuum. The film moldability was also evaluated under the following conditions: Good: When a 100 μm thick film was wrapped around a φ1 m cylinder, no cracks occurred in the film. Acceptable: When a 100 μm thick film was wrapped around a φ1 m cylinder, a crack occurred in one place in the film, but it was at a level that did not cause any problems in use. Unacceptable: When a 100 μm thick film was wrapped around a φ1 m cylinder, cracks occurred in two or more places in the film, causing the film to break.

[0089] <Measurement of Dielectric Loss Tangent> The resin film prepared above was heated at 200°C to 250°C for 120 minutes to prepare a resin sample for measurement. The dielectric loss tangent was measured at 10 GHz under standard environmental conditions (23 ± 2°C) and relative humidity of 45 to 55% using the cavity resonator perturbation method with a vector network analyzer (Keysight Technologies, product name "N5290A") and a split cylinder resonator. The following evaluation criteria were used: Excellent: Dielectric loss tangent was less than 0.001. Good: Dielectric loss tangent was 0.001 or more and less than 0.0015. Acceptable: Dielectric loss tangent was 0.0015 or more and less than 0.002. Unacceptable: Dielectric loss tangent was 0.002 or more.

[0090] [Preparation of Precursors] Precursors P1-1, P1-2, and P2-1 having the iodine content shown in Table 1 were prepared.

[0091]

[0092] [Preparation of Compound (I) and Production of PAS Resin (II) Using the Same] [Example 1] Precursor P1-1 was dissolved in ethanol at room temperature and allowed to stand for 24 hours at 0°C to recrystallize, obtaining compound (I-1-1) with an iodine content of 150 ppb. Next, 2,3-dichloro-5,6-dicyano-parabenzoquinone (DDQ) (0.4149 g, 1.8 mmol) as an oxidizing agent and trifluoroacetic acid (0.0312 g, 0.3 mmol) as an acid component were mixed with dichloromethane (2.6792 g) and set in the reactor of a calorimeter. Next, with the reaction temperature controlled to 0°C, a mixed solution of compound (I-1-1) (0.4914 g, 1.8 mmol) and dichloromethane (0.6605 g) was added to the reactor, and the exothermic curve of the reaction heat was measured to calculate the induction period, which was found to be 75 minutes. Subsequently, oxidative polymerization was carried out until no reaction heat was detected. The reaction solution was added dropwise to hydrochloric acid-acidified methanol, and the powder was collected by filtration. The powder was then washed with potassium hydroxide aqueous solution (0.1 M) and pure water, and vacuum dried to obtain PAS resin. The Mw, dielectric loss tangent, and moldability of the obtained PAS resin were evaluated by the method described above. The results are shown in Table 2.

[0093] [Example 2] Precursor P1-2 was dissolved in ethanol at room temperature and allowed to stand for 24 hours at 0°C to recrystallize, yielding compound (I-1-2) with an iodine content of 870 ppb. Next, 2,3-dichloro-5,6-dicyano-parabenzoquinone (DDQ) (0.4143 g, 1.8 mmol) as an oxidizing agent and trifluoroacetic acid (0.0312 g, 0.3 mmol) as an acid component were mixed with dichloromethane (2.6734 g) and set in the reactor of a calorimeter. Next, with the reaction temperature controlled to 0°C, a mixed solution of compound (I-1-2) (0.4364 g, 1.6 mmol) and dichloromethane (0.5916 g) was added to the reactor, and the exothermic curve of the reaction heat was measured to calculate the induction period, which was 104 minutes. After that, oxidative polymerization was carried out until no reaction heat was detected. The reaction solution was added dropwise to hydrochloric acid-acidified methanol, and the powder was recovered by filtration. The powder was then washed with potassium hydroxide aqueous solution (0.1 M) and pure water, and vacuum-dried to obtain PAS resin. The Mw, dielectric loss tangent, and moldability of the obtained PAS resin were evaluated by the method described above. The results are shown in Table 2.

[0094] [Example 3] Compound (I-1-2) prepared in Example 2 was given an iodine source (iodine content: 44,000 ppb) to obtain compound (I-1-3) with an iodine content of 2,440 ppb. Next, 2,3-dichloro-5,6-dicyano-parabenzoquinone (DDQ) (0.4140 g, 1.8 mmol) as an oxidizing agent and trifluoroacetic acid (0.0309 g, 0.3 mmol) as an acid component were mixed with dichloromethane (2.6549 g) and set in the reactor of a calorimeter. Next, with the reaction temperature controlled to 0°C, a mixed solution of compound (I-1-3) (0.4852 g, 1.8 mmol) and dichloromethane (0.6621 g) was added to the reactor, and the exothermic curve of the reaction heat was measured to calculate the induction period, which was 132 minutes. Subsequently, oxidative polymerization was carried out until no reaction heat was detected. The reaction solution was added dropwise to hydrochloric acid-acidified methanol, and the powder was collected by filtration. The powder was then washed with potassium hydroxide aqueous solution (0.1 M) and pure water, and vacuum dried to obtain PAS resin. The Mw, dielectric loss tangent, and moldability of the obtained PAS resin were evaluated by the method described above. The results are shown in Table 2.

[0095] [Example 4] Compound (I-1-2) prepared in Example 2 was given an iodine source (iodine content: 44,000 ppb) to obtain compound (I-1-4) with an iodine content of 4,410 ppb. Next, 2,3-dichloro-5,6-dicyano-parabenzoquinone (DDQ) (0.4143 g, 1.8 mmol) as an oxidizing agent and trifluoroacetic acid (0.0311 g, 0.3 mmol) as an acid component were mixed with dichloromethane (2.6596 g) and set in the reactor of a calorimeter. Next, with the reaction temperature controlled to 0°C, a mixed solution of compound (I-1-4) (0.4689 g, 1.7 mmol) and dichloromethane (0.6656 g) was added to the reactor, and the exothermic curve of the reaction heat was measured to calculate the induction period, which was 161 minutes. Subsequently, oxidative polymerization was carried out until no reaction heat was detected. The reaction solution was added dropwise to hydrochloric acid-acidified methanol, and the powder was collected by filtration. The powder was then washed with potassium hydroxide aqueous solution (0.1 M) and pure water, and vacuum dried to obtain PAS resin. The Mw, dielectric loss tangent, and moldability of the obtained PAS resin were evaluated by the method described above. The results are shown in Table 2.

[0096] [Comparative Example 1] PAS resin was produced using precursor P1-1 as a monomer raw material. Specifically, 2,3-dichloro-5,6-dicyano-parabenzoquinone (DDQ) (0.4143 g, 1.8 mmol) was used as an oxidizing agent, and trifluoroacetic acid (0.0312 g, 0.3 mmol) was used as an acid component. These were mixed with dichloromethane (2.6705 g) and set in the reactor of a calorimeter. With the reaction temperature controlled to 0°C, the mixed solution of precursor P1-1 (0.5068 g, 1.8 mmol) and dichloromethane (0.6734 g) was added to the reactor, and the exothermic curve of the reaction heat was measured to calculate the induction period, which was found to be over 360 minutes. After that, oxidative polymerization was carried out until no reaction heat was detected. The reaction solution was added dropwise to hydrochloric acid-acidified methanol, and the powder was recovered by filtration. Subsequently, the powder was washed with a potassium hydroxide aqueous solution (0.1 M) and pure water, and then vacuum-dried to obtain PAS resin. The Mw, dielectric loss tangent, and moldability of the obtained PAS resin were evaluated by the method described above. The results are shown in Table 2.

[0097] [Comparative Example 2] PAS resin was produced using precursor P1-2 as a monomer raw material. Specifically, 2,3-dichloro-5,6-dicyano-parabenzoquinone (DDQ) (0.4153 g, 1.8 mmol) was used as an oxidizing agent, and trifluoroacetic acid (0.0311 g, 0.3 mmol) was used as an acid component. These were mixed with dichloromethane (2.6607 g) and set in the reactor of a calorimeter. With the reaction temperature controlled to 0°C, a mixed solution of precursor P1-2 (0.5043 g, 1.8 mmol) and dichloromethane (0.6739 g) was added, and the induction period was calculated by measuring the exothermic curve of the reaction heat. The induction period was found to be over 360 minutes. After that, oxidative polymerization was carried out until no reaction heat was detected. The reaction solution was added dropwise to hydrochloric acid-acidified methanol, and the powder was recovered by filtration. Subsequently, the powder was washed with a potassium hydroxide aqueous solution (0.1 M) and pure water, and then vacuum-dried to obtain PAS resin. The Mw, dielectric loss tangent, and moldability of the obtained PAS resin were evaluated by the method described above. The results are shown in Table 2.

[0098] [Comparative Example 3] PAS resin was produced using precursor P2-1 as a monomer raw material. Specifically, 2,3-dichloro-5,6-dicyano-parabenzoquinone (DDQ) (0.4541 g, 2.0 mmol) was used as an oxidizing agent, and trifluoroacetic acid (0.2070 g, 1.8 mmol) was used as an acid component. These were mixed with dichloromethane (2.6679 g) and set in the reactor of a calorimeter. With the reaction temperature controlled to 0°C, the mixed solution of precursor P2-1 (0.4955 g, 2.3 mmol) and dichloromethane (0.6600 g) was added to the reactor, and the exothermic curve of the reaction heat was measured to calculate the induction period, which was 1 minute. After that, oxidative polymerization was carried out until no reaction heat was detected. The reaction solution was added dropwise to hydrochloric acid-acidified methanol, and the powder was recovered by filtration. Subsequently, the powder was washed with a potassium hydroxide aqueous solution (0.1 M) and pure water, and then vacuum-dried to obtain PAS resin. The Mw, dielectric loss tangent, and moldability of the obtained PAS resin were measured by the method described above. The results are shown in Table 2.

[0099]

[0100] As shown in Table 2, the PAS resins of Examples 1 to 4, which used compound (I) according to the first embodiment as a monomer raw material, were able to control the reaction induction period during resin production within an appropriate range. Furthermore, the PAS resins (II) of Examples 1 to 2 had a low dielectric loss tangent and also exhibited good film moldability. Although Examples 3 to 4 had a higher iodine content than Examples 1 to 2, the molecular weight was sufficiently extended, resulting in a smaller dipole moment for the entire molecular chain compared to low molecular weight compounds, and it is presumed that the dielectric loss tangent value was within the good or acceptable range. On the other hand, the PAS resins of Comparative Examples 1 to 2, which used compounds with an iodine content of 5500 ppb or more as monomer raw materials, had a reaction induction period exceeding 360 minutes. In addition, the Mw after 6 hours of reaction was less than 1000. The PAS resins of Comparative Examples 1 to 2 also had poor film moldability, indicating that they are not suitable for application to wiring boards such as printed circuit boards. Furthermore, the PAS resin of Comparative Example 3, which used a compound with zero iodine content as a monomer raw material, had a very short reaction induction period of 1 minute, making it difficult to control the reaction during resin production. From these results, it was confirmed that the compound in this disclosure can solve the first problem. In addition, it was confirmed that the PAS resin containing monomer units of the compound can solve the second problem.

[0101] Compound (I) according to the first embodiment has industrial applicability as a raw material (monomer) for producing polyarylene sulfide resin because it allows for easy control of the reaction induction period during resin production and enables the stable production of polyarylene sulfide resin having a low dielectric loss tangent. PAS resin (II) according to the second embodiment has good moldability and can be applied to wiring substrates such as printed circuit boards, and therefore has industrial applicability.

Claims

1. The following formula (1): (In formula (1), R １ ~R １０ Compound (I) is represented as (where each independently represents H, an alkyl group, an alkoxy group, an alkenyl group, or a phenyl group, and n is an integer from 1 to 8), and has an iodine content of 1 ppb or more and less than 5500 ppb.

2. A method for producing compound (I) as described in claim 1, comprising: (A1) preparing a precursor of compound (I); and (A2) adjusting the iodine content in the precursor to 1 ppb or more and less than 5500 ppb.

3. The compound (I) is a diaryl disulfide in which n in the formula (1) is 2, and the (A1) is: (a1) oxidizing a substrate represented by the following formula (2) using iodine or an iodide: (In the formula (2), R １ to R ５ each independently represents H, an alkyl group, an alkoxy group, an alkenyl group, or a phenyl group, and L represents H, an alkali metal element, or an alkaline earth metal element) to obtain the precursor, and the (A2) includes purifying the precursor obtained by the (a1). The method for producing the compound (I) according to claim 2.

4. A polyarylene sulfide resin (II) comprising monomer units of compound (I) described in claim 1, wherein the iodine content is 1 ppb or more and less than 5500 ppb.

5. A method for producing polyarylene sulfide resin (II) according to claim 4, comprising polymerizing a raw material containing compound (I) according to claim 1.

6. A method for producing polyarylene sulfide resin (II) according to claim 5, comprising polymerizing the raw materials in the presence of an oxidizing agent.

7. The method for producing polyarylene sulfide resin (II) according to claim 6, wherein the oxidizing agent comprises one or more selected from quinone-based oxidizing agents and vanadium-based oxidizing agents.

8. A molded article comprising the polyarylene sulfide resin (II) described in claim 4.

Images