Flame-retardant resin composition, composition for electronic substrate, and molded article

Abstract

Provided are a flame-retardant resin composition that is excellent in flame retardancy and can be used to form a molded article having a low dielectric constant and a low dielectric loss tangent, and that can also be used to form a molded article having a high glass transition temperature; an electronic substrate composition containing the flame-retardant resin composition; and a molded article of the flame-retardant resin composition. [Solution] The flame-retardant resin composition of the present invention is a resin composition containing a resin (A) and a flame retardant (B), wherein the resin (A) is at least one selected from the group consisting of polyphenylene-based resins and aromatic vinyl-based resins, and the flame retardant (B) is a compound containing a reactive functional group.

Description

[Technical Field]

[0001] The present invention relates to a flame-retardant resin composition, a composition for electronic substrates, and a molded article. [Background technology]

[0002] In recent years, as electronic devices have become smaller and more powerful, the performance requirements for various materials used in electronic devices have also increased. A wide variety of materials can be used in electronic devices, and resin materials are widely used for electronic components such as electronic substrates. Such resin materials are required to have high flame retardancy. The use of such resins in electronic component applications makes it possible to impart excellent flame retardancy to electronic components such as electronic substrates. In addition, since electronic component applications also require low dielectric constants and low dielectric loss tangents, the development of resin materials capable of imparting low dielectric constants and low dielectric loss tangents is essential.

[0003] For example, Patent Document 1 proposes a soluble polyfunctional vinyl aromatic copolymer having a specific chemical structure. A molded article obtained using a curable composition containing the soluble polyfunctional vinyl aromatic copolymer is said to have excellent heat resistance and dielectric properties. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2018-39995 Summary of the Invention [Problem to be solved by the invention]

[0005] In recent years, with the rapid advancement in the performance of electronic components and the like, the performance requirements for resins used therein have also been increasing. For example, there is a demand for resins that can impart a lower dielectric constant and a lower dielectric loss tangent to electronic components while further improving their flame retardancy. However, increasing the flame retardancy of a resin can conversely lower the glass transition temperature of the resin, which may result in reduced heat resistance of molded resin products. Furthermore, even if a balance between flame retardancy and glass transition temperature can be maintained by adjusting the type and amount of flame retardant used, it has been difficult to adjust the dielectric constant and dielectric loss tangent to the desired range.

[0006] The present invention has been made in view of the above, and aims to provide a flame-retardant resin composition that is excellent in flame retardancy and can be used to form a molded article having a low dielectric constant and a low dielectric loss tangent, and that can also form a molded article having a high glass transition temperature. Another aim of the present invention is to provide an electronic substrate composition containing the flame-retardant resin composition, and a molded article of the flame-retardant resin composition. [Means for solving the problem]

[0007] As a result of extensive research into achieving the above object, the inventors have discovered that the above object can be achieved by using a specific resin and a specific flame retardant as essential components, and have thus completed the present invention.

[0008] That is, the present invention includes, for example, the subject matter described in the following sections. Item 1 A resin composition comprising a resin (A) and a flame retardant (B), the resin (A) is at least one selected from the group consisting of polyphenylene resins and aromatic vinyl resins, The flame-retardant resin composition, wherein the flame retardant (B) is a compound containing a reactive functional group.

[0009] Section 2 Item 2. The flame-retardant resin composition according to Item 1, wherein the compound containing a reactive functional group is a compound having a polymerizable double bond.

[0010] Section 3 The compound containing the reactive functional group is represented by the following general formula (1):

[0011] [ka] (In formula (1), Z is a monovalent group containing a polymerizable double bond, and n is a number of 1 or more.) Item 3. The flame-retardant resin composition according to item 1 or 2, wherein the compound is represented by the formula:

[0012] Section 4 Item 4. The flame-retardant resin composition according to Item 3, wherein in formula (1), Z is a group containing an allyl group, a (meth)acryloyl group, or a vinylbenzyl group.

[0013] Section 5 Item 5. The flame-retardant resin composition according to Item 3 or 4, wherein in formula (1), Z is a vinylbenzyl group.

[0014] Section 6 6. The flame-retardant resin composition according to any one of items 1 to 5, wherein the resin (A) is a resin having a polymerizable double bond.

[0015] Section 7 7. The flame-retardant resin composition according to any one of items 1 to 6, wherein the flame retardant (B) is contained in an amount of 6 parts by mass or more per 100 parts by mass of the total amount of the resin (A) and the flame retardant (B).

[0016] Section 8 An electronic substrate composition for use in an electronic substrate, comprising: Item 8. A composition for an electronic substrate, comprising the flame-retardant resin composition according to any one of Items 1 to 7.

[0017] Section 9 Item 8. A molded article of the flame-retardant resin composition according to any one of items 1 to 7. [Effects of the Invention]

[0018] The flame-retardant resin composition of the present invention is capable of forming a molded article having excellent flame retardancy, a low dielectric constant and a low dielectric loss tangent, and further capable of forming a molded article having a high glass transition temperature.

[0019] The molded article of the present invention has excellent flame retardancy, a low dielectric constant and a low dielectric loss tangent, and a high glass transition temperature, and is therefore suitable for use in electronic components, particularly as an electronic substrate. DETAILED DESCRIPTION OF THE INVENTION

[0020]

[0023] In the present specification, the terms "contain" and "comprise" include the concepts of "contain," "comprise," "consist essentially of," and "consist only of."

[0021] In the numerical ranges described in stages in this specification, the upper or lower limit of a certain numerical range can be arbitrarily combined with the upper or lower limit of another numerical range. In the numerical ranges described in this specification, the upper or lower limit of the numerical range may be replaced with a value shown in an example or a value that can be unambiguously derived from an example. In addition, in this specification, numerical values ​​connected with "to" mean a numerical range that includes the numbers before and after "to" as the lower and upper limits.

[0022] The flame-retardant resin composition of the present invention comprises a resin (A) and a flame retardant (B), wherein the resin (A) is at least one selected from the group consisting of polyphenylene resins and aromatic vinyl resins, and the flame retardant (B) is a compound containing a reactive functional group.

[0023] The flame-retardant resin composition of the present invention contains the resin (A) and the flame retardant (B), and thus can form a molded article having excellent flame retardancy, a low dielectric constant, and a low dielectric dissipation factor. Furthermore, the flame-retardant resin composition of the present invention contains the resin (A) and the flame retardant (B), and thus can form a molded article having a high glass transition temperature. That is, a molded article obtained using the flame-retardant resin composition of the present invention has excellent flame retardancy, a low dielectric constant, a low dielectric dissipation factor, and a high glass transition temperature.

[0024] Resin (A) The resin (A) contained in the flame-retardant resin composition of the present invention is at least one resin selected from the group consisting of polyphenylene-based resins and aromatic vinyl-based resins. (Polyphenylene resin) The polyphenylene resin may be a resin having a phenylene moiety in its repeating structural unit. The phenylene moiety may be present in either the main chain or the side chain, and preferably in the main chain.

[0025] The polyphenylene resin may be, for example, a wide variety of known polyphenylene resins. An example of such a polyphenylene resin is a polyphenylene ether resin. Among these, the polyphenylene ether resin is preferably curable, and specifically, a thermosetting polyphenylene ether resin is preferred. An example of a curable polyphenylene ether resin is a modified polyphenylene ether resin, which will be described later.

[0026] When the polyphenylene resin is a polyphenylene ether resin or a modified polyphenylene ether resin, a molded article obtained using the flame-retardant resin composition of the present invention will have better flame retardancy, a lower dielectric constant and dielectric dissipation factor, and will also tend to have a higher glass transition temperature.

[0027] Examples of polyphenylene ether resins include resins having a phenylene ether moiety in the main chain. More specifically, examples of polyphenylene ether resins include resins having a "-Ph-O-" moiety in the main chain. Here, "Ph" represents a phenylene moiety that may have a substituent.

[0028] A more specific example of the polyphenylene ether resin is a polyphenylene ether containing a structure represented by the following formula (2).

[0029] [ka]

[0030] Here, in formula (2), R 1 ~R 16 are the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms; A represents a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms; and m and k represent integers of 0 to 100, at least one of which is not 0.

[0031] In formula (2), R 1 ~R 16 are the same or different and preferably include a methyl group and an ethyl group.

[0032] In formula (2), A may be, for example, a divalent organic group such as methylene, ethylidene, 1-methylethylidene, 1,1-propylidene, 1,4-phenylenebis(1-methylethylidene), 1,3-phenylenebis(1-methylethylidene), cyclohexylidene, phenylmethylene, naphthylmethylene, or 1-phenylethylidene.

[0033] In formula (2), m and k are integers of 0 to 100, with at least one not being 0, and both m and k are preferably 70 or less, more preferably 50 or less, even more preferably 30 or less, still more preferably 20 or less, and particularly preferably 20 or less. In formula (2), m and k may be the same or different and are preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more.

[0034] The polyphenylene ether resin may be a resin in which both ends or one end of the polyphenylene ether resin in formula (2) have hydrogen atoms. Alternatively, the polyphenylene ether resin may be a resin in which both ends or one end of the polyphenylene ether resin in formula (2) have polymerizable double bonds as described below. In this case, the polyphenylene ether resin is a modified polyphenylene ether resin.

[0035] Specific examples of polyphenylene ethers represented by formula (2) include polycondensates of 2,2-bis(4-hydroxy-3,5-methylphenyl)propane and 2,6-dimethylphenol, polycondensates of 2,2-bis(4-hydroxy-3,5-methylphenyl)propane and 2,3,6-trimethylphenol, polycondensates of 4,4'-methylenebis(2,6-dimethylphenol) and 2,6-dimethylphenol, and polycondensates of 4,4'-methylenebis(2,6-dimethylphenol) and 2,3,6-trimethylphenol.

[0036] Another example of the polyphenylene ether resin is a polyphenylene ether containing a structure represented by the following formula (3).

[0037] [ka]

[0038] Here, in equation (3), R 17 ~R 20 are the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms; j represents an integer of 1 to 100.

[0039] In formula (3), R17 ~R 20 are the same or different and preferably include a methyl group and an ethyl group.

[0040] In formula (3), both ends or one end may be, for example, a hydrogen atom, or both ends or one end may be a polymerizable double bond as described below.

[0041] Specific examples of the polyphenylene ether represented by formula (3) include 2,6-dimethylphenol polycondensates and 2,3,6-trimethylphenol polycondensates.

[0042] When the polyphenylene resin is a modified polyphenylene ether resin, the modified polyphenylene ether resin may be, for example, a polyphenylene ether resin having a polymerizable double bond. The polymerizable double bond may be, for example, a double bond exhibiting radical polymerization, specifically, an allyl group, a (meth)acryloyl group, or a vinylbenzyl group. Among these, the polymerizable double bond is more preferably a (meth)acryloyl group or a vinylbenzyl group.

[0043] In this specification, the term "(meth)acryloyl group" refers to an acryloyl group or a methacryloyl group.

[0044] The allyl group, (meth)acryloyl group, or vinylbenzyl group can be directly bonded to the terminal of the polyphenylene ether resin without any other group therebetween, or can be bonded to the terminal of the polyphenylene ether resin via another group. It is preferable that the (meth)acryloyl group or vinylbenzyl group is directly bonded to the terminal of the polyphenylene ether resin.

[0045] In the modified polyphenylene ether resin, the number of polymerizable double bonds is not particularly limited, and is, for example, preferably 1 or more, more preferably 2 or more, and preferably 4 or less.

[0046] The modified polyphenylene ether resin may be, for example, a polyphenylene ether resin having a structure represented by the formula (2) in which the radically polymerizable double bond is bonded to both ends or one end, or a polyphenylene ether resin having a structure represented by the formula (3) in which the radically polymerizable double bond is bonded to a terminal oxygen atom.

[0047] The modified polyphenylene ether resin may be, for example, a resin in which a (meth)acryloyl group or a vinylbenzyl group is directly bonded to both ends or one end of the structure represented by the formula (2). The modified polyphenylene ether resin may also be, for example, a resin in which an allyl group is directly or indirectly bonded to both ends or one end of the structure represented by the formula (2). Specifically, a modified polyphenylene ether resin in which a group corresponding to diallyl isocyanurate is bonded to both ends or one end of the structure represented by the formula (2) is also exemplified.

[0048] The method for producing the polyphenylene ether resin and the modified polyphenylene ether resin is not particularly limited, and for example, a wide variety of known methods for producing polyphenylene ether resins and known methods for producing modified polyphenylene ether resins can be employed in the present invention.

[0049] For example, a modified polyphenylene ether resin can be produced by reacting a compound having a phenolic hydroxyl group with a compound having a polymerizable double bond. An example of a compound having a phenolic hydroxyl group is a compound of the formula (2) in which both terminals are hydrogen atoms. Alternatively, an example of a compound having a phenolic hydroxyl group is a compound of the formula (3) in which both terminals are hydrogen atoms.

[0050] An example of a compound having a polymerizable double bond is halogenated methylstyrene. Examples of halogenated methylstyrene include o-chloromethylstyrene, m-chloromethylstyrene, p-chloromethylstyrene, o-bromomethylstyrene, m-bromomethylstyrene, and p-bromomethylstyrene. When the compound having a polymerizable double bond is halogenated methylstyrene, the resulting modified polyphenylene ether resin is a polyphenylene ether resin having vinylbenzyl groups at both ends or one end (also referred to as a poly(vinylbenzyl) ether compound), and examples thereof include compounds having a structure in which vinylbenzyl groups are bonded to the ends in the formula (2) or (3).

[0051] Other examples of the compound having a polymerizable double bond include compounds having a (meth)acryloyl group, such as (meth)acryloyl chloride and (meth)acrylic acid. When the compound having a polymerizable double bond is a compound having a (meth)acryloyl group, the resulting modified polyphenylene ether resin is a polyphenylene ether resin having (meth)acryloyl groups at both ends or one end, and examples thereof include compounds having a structure in which a (meth)acryloyl group is bonded to the end in the above formula (2) or (3).

[0052] Another example of the compound having a polymerizable double bond is diallyl isocyanurate. When the compound having a polymerizable double bond is diallyl isocyanurate, the resulting modified polyphenylene ether resin is a polyphenylene ether resin having diallyl groups at both ends or one end, and examples thereof include compounds having a structure in which a group corresponding to diallyl isocyanurate is bonded to an end in the above formula (2) or (3).

[0053] The method for reacting the compound having a phenolic hydroxyl group with the compound having a polymerizable double bond is not particularly limited. For example, the two can be reacted in a solvent containing an aromatic hydrocarbon and an aprotic polar solvent in the presence of an aqueous alkali metal hydroxide solution. The aqueous alkali metal hydroxide solution is not particularly limited, and examples thereof include sodium hydroxide, potassium hydroxide, lithium hydroxide, and mixtures thereof. Examples of aromatic hydrocarbons include benzene, toluene, ethylbenzene, xylene, and ethyltoluene. Examples of aprotic polar solvents include dimethyl sulfoxide, dimethylformamide, acetonitrile, N-methylpyrrolidone, and propylene carbonate.

[0054] The polyphenylene resin is not limited to the above polyphenylene ether resin and modified polyphenylene ether resin, but may be other polyphenylenes.

[0055] The polyphenylene resin is preferably linear. The number average molecular weight (Mn) of the polyphenylene resin is not particularly limited and is, for example, 1,000 or more, preferably 1,500 or more, more preferably 1,800 or more, and even more preferably 2,000 or more, and is preferably 100,000 or less, preferably 50,000 or less, and more preferably 20,000 or less. The number average molecular weight (Mn) of the polyphenylene resin is the polystyrene-equivalent number average molecular weight (Mn) measured by gel permeation chromatography (GPC).

[0056] The weight average molecular weight (Mw) of the polyphenylene resin is not particularly limited and is, for example, 1000 or more, preferably 2000 or more, more preferably 2500 or more, and even more preferably 3000 or more, and is preferably 100,000 or less, preferably 50,000 or less, and more preferably 20,000 or less. The weight average molecular weight (Mw) of the polyphenylene resin is the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC).

[0057] (aromatic vinyl resin) The aromatic vinyl resin is a resin other than the polyphenylene resin, and includes a wide range of resins having an aromatic moiety in the repeating structural unit of the resin. The aromatic moiety may be, for example, a monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms.

[0058] The type of aromatic vinyl resin is not particularly limited as long as it has an aromatic moiety in the repeating structural unit.An example of the aromatic vinyl resin is a resin having a repeating unit corresponding to a monovinyl aromatic compound, a repeating unit corresponding to a divinyl aromatic compound, and at least one repeating unit selected from the group consisting of an aromatic ring condensed cyclic olefin compound.The structure of such a resin will be described in detail below.

[0059] As the monovinyl aromatic compound, for example, can be widely exemplified aromatic compounds having one vinyl group.Specific examples of the monovinyl aromatic compound include vinyl aromatic compounds such as styrene, vinylnaphthalene, vinylbiphenyl, etc., alkylstyrene (for example, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene), dialkylstyrene (for example, 3,5-dimethylstyrene, 2,5-dimethylstyrene, 2,5-diethylstyrene), alkylvinylbiphenyl (for example, ethylvinylbiphenyl), alkylvinylnaphthalene (for example, ethylvinylnaphthalene), etc.

[0060] Among these, the monovinyl aromatic compound is preferably at least one selected from the group consisting of styrene, vinylnaphthalene, vinylbiphenyl, alkylstyrene, dialkylstyrene, alkylvinylbiphenyl, and alkylvinylnaphthalene, and more preferably styrene.

[0061] The divinyl aromatic compound can be, for example, a wide range of aromatic compounds having two vinyl groups. Specific examples of the divinyl aromatic compound include divinylbenzene (including each positional isomer or a mixture thereof), divinylnaphthalene (including each positional isomer or a mixture thereof), and divinylbiphenyl (including each positional isomer or a mixture thereof).

[0062] Among these, the divinylaromatic compound preferably contains divinylbenzene, which may be an m-isomer, a p-isomer, or a mixture of positional isomers thereof.

[0063] The aromatic ring-fused cyclic olefin compound may be, for example, a cyclic olefin compound having a fused aromatic ring, more specifically, a compound having a fused ring of an aliphatic ring having a carbon-carbon double bond with an aromatic ring. The condensation may be ortho-condensation or ortho-peri-condensation.

[0064] Examples of the aromatic ring-fused cyclic olefin compounds include indene-based compounds, acenaphthylene-based compounds, phenalene-based compounds, acephenanthrylene-based compounds, aceanthrylene-based compounds, benzofuran-based compounds, and benzothiophene-based compounds. Among these, aromatic ring-fused cyclic olefin compounds having three or fewer rings are preferred. Specifically, aromatic ring-fused cyclic olefin compounds having two rings are preferred, such as indene-based compounds, benzofuran-based compounds, and benzothiophene-based compounds; and aromatic ring-fused cyclic olefin compounds having three rings are preferred, such as acenaphthylene-based compounds and phenalene-based compounds, and more preferably indene-based compounds and / or acenaphthylene-based compounds.

[0065] The indene-based compound may be, for example, at least one selected from the group consisting of indene, alkylindene, halogenated indene, arylindene, and alkoxyindene.

[0066] The acenaphthylene-based compound may be, for example, at least one selected from the group consisting of acenaphthylene, alkylacenaphthylene, halogenated acenaphthylene, arylacenaphthylene, and alkoxyacenaphthylene.

[0067] The phenalene-based compounds, acephenanthrylene-based compounds, aceanthrylene-based compounds, benzofuran-based compounds, and benzothiophene-based compounds include phenalene, acephenanthrylene, aceanthrylene, benzofuran, and benzothiophene, as well as compounds having the same substituents as the above-mentioned indene-based compounds.

[0068] The aromatic ring-fused cyclic olefin compound more preferably contains acenaphthylene.

[0069] The aromatic vinyl resin is preferably a resin having all of the repeating units corresponding to a monovinyl aromatic compound, a divinyl aromatic compound, and an aromatic-ring-fused cyclic olefin compound. In this case, a molded article obtained using the flame-retardant resin composition of the present invention will have better flame retardancy, a lower dielectric constant and dielectric loss tangent, and a higher glass transition temperature.

[0070] When the aromatic vinyl resin contains a repeating unit corresponding to a monovinyl aromatic compound, the aromatic vinyl resin may contain one or two types of repeating units corresponding to such monovinyl aromatic compounds.

[0071] When the aromatic vinyl resin contains a repeating unit corresponding to a divinyl aromatic compound, the aromatic vinyl resin may contain one or two types of repeating units corresponding to such divinyl aromatic compounds.

[0072] When the aromatic vinyl resin contains a repeating unit corresponding to an aromatic ring-fused cyclic olefin compound, the aromatic vinyl resin may contain one or two types of repeating units corresponding to such aromatic ring-fused cyclic olefin compound.

[0073] In the aromatic vinyl resin, the content ratio of each repeating unit is not particularly limited. For example, when the total repeating units constituting the aromatic vinyl resin is 100 mol%, the content ratio of repeating units corresponding to monovinyl aromatic compounds in this 100 mol% is preferably 15 mol% or more, more preferably 30 mol% or more, even more preferably 40 mol% or more, particularly preferably 50 mol% or more, and also preferably 90 mol% or less, more preferably 80 mol% or less, even more preferably 75 mol% or less, particularly preferably 70 mol% or less.

[0074] Furthermore, assuming that all repeating units constituting the aromatic vinyl resin are 100 mol%, the content of repeating units corresponding to the divinyl aromatic compound in this 100 mol% is preferably 3 mol% or more, more preferably 5 mol% or more, even more preferably 8 mol% or more, particularly preferably 10 mol% or more, and is preferably 30 mol% or less, more preferably 25 mol% or less, even more preferably 22 mol% or less, particularly preferably 20 mol% or less.

[0075] Furthermore, when all repeating units constituting the aromatic vinyl resin are taken as 100 mol%, the content of repeating units corresponding to the aromatic ring-fused cyclic olefin compound in this 100 mol% is preferably 5 mol% or more, more preferably 7 mol% or more, even more preferably 8 mol% or more, particularly preferably 10 mol% or more, and is preferably 80 mol% or less, more preferably 50 mol% or less, even more preferably 35 mol% or less, particularly preferably 30 mol% or less.

[0076] The aromatic vinyl resin may contain repeating units other than those corresponding to the monovinyl aromatic compound, the divinyl aromatic compound, and the aromatic-ring-fused cyclic olefin compound. Examples of monomers constituting such repeating units include trivinyl aromatic compounds, trivinyl aliphatic compounds, divinyl aliphatic compounds, and monovinyl aliphatic compounds.

[0077] The aromatic vinyl resin preferably contains repeating units corresponding to the monovinyl aromatic compound, repeating units corresponding to the divinylaromatic compound, and repeating units corresponding to the aromatic ring-fused cyclic olefin compound in total of 50 mol% or more, more preferably 80 mol% or more, even more preferably 90 mol% or more, and particularly preferably 95 mol% or more. The repeating units forming the aromatic vinyl resin may consist only of repeating units corresponding to the monovinyl aromatic compound, repeating units corresponding to the divinylaromatic compound, and repeating units corresponding to the aromatic ring-fused cyclic olefin compound.

[0078] The aromatic vinyl resin is preferably curable. When the aromatic vinyl resin is curable, a molded article obtained from the flame-retardant resin composition of the present invention has better flame retardancy, a lower dielectric constant and dielectric loss tangent, and a higher glass transition temperature. Specifically, the curable aromatic vinyl resin is preferably a thermosetting aromatic vinyl resin.

[0079] More specifically, the curable aromatic vinyl resin preferably has a polymerizable double bond. Examples of the polymerizable double bond include double bonds that exhibit radical polymerization, specifically, allyl groups, (meth)acryloyl groups, and vinylbenzyl groups. Among these, the polymerizable double bond is more preferably a (meth)acryloyl group or a vinylbenzyl group.

[0080] Examples of aromatic vinyl resins having a polymerizable double bond include aromatic vinyl resins obtained by a production method using a vinylbenzyl phosphonium salt, which will be described later. Such aromatic vinyl resins are resins having all of the repeating units corresponding to the monovinyl aromatic compound, the divinyl aromatic compound, and the aromatic-ring-fused cyclic olefin compound.

[0081] The method for producing the aromatic vinyl resin is not particularly limited, and for example, the aromatic vinyl resin can be produced by a known production method. One embodiment of the method for producing the aromatic vinyl resin, for example, includes a method of copolymerizing a vinylbenzyl phosphonium salt, a monovinyl aromatic compound, and an aromatic ring-fused cyclic olefin compound in the presence of a polymerization initiator, and then reacting the resulting copolymer with formaldehyde. The aromatic vinyl resin obtained by this method is an aromatic vinyl resin having a polymerizable double bond.

[0082] As the vinylbenzyl phosphonium salt, it is preferable to use a vinylbenzyl phosphonium halide.The phosphonium group in the vinylbenzyl phosphonium salt may be, for example, a quaternary phosphonium group such as a trialkyl phosphonium, a triaryl phosphonium, or a triaralkyl phosphonium.In addition, the halogen atom that forms a salt with the phosphonium group may be, for example, chlorine, bromine, or the like.

[0083] The vinylbenzylphosphonium salt can be copolymerized with a monovinyl aromatic compound and an aromatic ring-fused cyclic olefin compound by a known vinyl polymerization method using a polymerization initiator. During the polymerization, a chain transfer agent can be added to adjust the weight average molecular weight (Mw) of the resulting copolymer.

[0084] The copolymer obtained can be reacted with formaldehyde by the well-known Wittig reaction, in which the copolymer is treated with a base and then reacted with formaldehyde, thereby removing the phosphonium group and introducing a vinyl group.

[0085] In the method of reacting the copolymer with formaldehyde, since the vinylbenzyl phosphonium salt is monovinyl, a linear copolymer without branches is obtained, and after copolymerization, a vinyl group is introduced into the repeating unit derived from the vinylbenzyl phosphonium salt. The aromatic vinyl resin obtained in this manner has a polymerizable double bond, that is, an aromatic vinyl resin having a polymerizable double bond is obtained. When the above production method using a vinylbenzyl phosphonium salt is adopted, a vinylbenzyl group may be present in the aromatic vinyl resin having a polymerizable double bond. In this case, the aromatic vinyl resin becomes a resin containing a repeating unit corresponding to a divinyl aromatic compound, and a vinylbenzyl group is present in the repeating unit.

[0086] The weight average molecular weight (Mw) of the aromatic vinyl resin is not particularly limited and is, for example, 1000 or more, preferably 2000 or more, more preferably 2500 or more, and even more preferably 3000 or more, and is preferably 100,000 or less, preferably 70,000 or less, more preferably 50,000 or less, even more preferably 40,000 or less, and particularly preferably 30,000 or less. The weight average molecular weight (Mw) of the aromatic vinyl resin is the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC).

[0087] (Resin (A)) Resin (A) is at least one selected from the group consisting of the polyphenylene resins and the aromatic vinyl resins, and may be either the polyphenylene resin or the aromatic vinyl resin, or may contain both the polyphenylene resin and the aromatic vinyl resin.

[0088] The resin (A) contained in the flame-retardant resin composition of the present invention can contain one or more polyphenylene resins, and can also contain one or more aromatic vinyl resins.

[0089] As described above, the resin (A) is preferably a resin having a polymerizable double bond. In other words, the resin (A) is preferably at least one selected from the group consisting of polyphenylene resins having a polymerizable double bond and aromatic vinyl resins having a polymerizable double bond. In this case, a molded article obtained using the flame-retardant resin composition of the present invention has better flame retardancy, a lower dielectric constant and dielectric loss tangent, and, in particular, is likely to have a particularly high glass transition temperature. When the resin (A) is a resin having a polymerizable double bond, such a resin can exhibit, for example, thermosetting properties.

[0090] The type of polymerizable double bond is the same as described above, that is, an allyl group, a (meth)acryloyl group, or a vinylbenzyl group can be mentioned, and among these, a (meth)acryloyl group or a vinylbenzyl group is more preferable as the polymerizable double bond.

[0091] Resins Having Polymerizable Double Bonds Examples of the polyphenylene resins include the modified polyphenylene ether resins described above. Examples of aromatic vinyl resins having polymerizable double bonds include the aromatic vinyl resins having vinylbenzyl groups described above.

[0092] The resin (A) preferably contains the modified polyphenylene ether resin. In this case, a molded article obtained using the flame-retardant resin composition of the present invention has particularly excellent flame retardancy, a particularly low dielectric constant and dielectric loss tangent, and a particularly high glass transition temperature. The modified polyphenylene ether resin is more preferably a resin in which (meth)acryloyl groups or vinylbenzyl groups are directly bonded to oxygen atoms at both ends of the polyphenylene ether, and particularly preferably a resin in which vinylbenzyl groups are directly bonded.

[0093] Flame retardant (B) The flame retardant (B) contained in the flame-retardant resin composition of the present invention is a compound containing a reactive functional group. The flame retardant (B) is not particularly limited as long as it can impart flame retardancy to the resin and is a compound containing a reactive functional group. For example, a preferred example of the flame retardant (B) is a bromine-based compound containing a reactive functional group.

[0094] In the flame retardant (B), the reactive functional group is preferably, for example, a polymerizable double bond. In other words, the compound containing a reactive functional group as the flame retardant (B) is preferably a compound having a polymerizable double bond. In this case, the molded article obtained using the flame-retardant resin composition of the present invention has better flame retardancy, a lower dielectric constant and dielectric loss tangent, and is likely to have a higher glass transition temperature.

[0095] In the flame retardant (B), the polymerizable double bond may be an allyl group, a (meth)acryloyl group, or a vinylbenzyl group. Among these, the polymerizable double bond is more preferably a (meth)acryloyl group or a vinylbenzyl group, and particularly preferably a vinylbenzyl group.

[0096] In the flame retardant (B), the number of polymerizable double bonds is not particularly limited, and is, for example, preferably 1 or more, more preferably 2 or more, and preferably 4 or less.

[0097] Examples of the bromine-based compound containing a reactive functional group (that is, the flame retardant (B)) include compounds represented by the following general formula (1).

[0098] [ka]

[0099] In the formula (1), Z is a monovalent group containing a polymerizable double bond, and n is a number of 1 or more.

[0100] As can be seen from formula (1), Z is a group bonded to an oxygen atom, and examples thereof include a group containing an allyl group, a (meth)acryloyl group, or a vinylbenzyl group. Z is preferably a vinylbenzyl group.

[0101] When Z is a group containing an allyl group, an example thereof is a group corresponding to diallyl isocyanurate.

[0102] Preferred examples of the compound represented by formula (1) include a vinylbenzyl-modified brominated flame retardant in which Z is a vinylbenzyl group, and a diallyl cyanurate-modified brominated flame retardant in which Z corresponds to diallyl isocyanurate.

[0103] In formula (1), n ​​is preferably 2 or more, more preferably 3 or more, even more preferably 4 or more, and particularly preferably 5 or more, and is preferably 30 or less, more preferably 25 or less, and even more preferably 20 or less.

[0104] The method for producing the flame retardant (B) is not particularly limited, and for example, a wide variety of known methods can be employed in the present invention. The flame retardant (B) can also be obtained as a commercially available product.

[0105] For example, when producing a compound represented by formula (1) as the flame retardant (B), the compound represented by formula (1) can be obtained by a method of reacting a compound represented by formula (1) in which Z is H (hydrogen) with a compound having a polymerizable double bond. Examples of the compound having a polymerizable double bond include acrylic acid, acryloyl chloride, halogenated methylstyrene, and diallyl isocyanurate.

[0106] Flame-retardant resin composition The flame-retardant resin composition of the present invention contains, as essential components, a resin (A) and a flame retardant (B). In the flame-retardant resin composition of the present invention, the contents of the resin (A) and the flame retardant (B) are not particularly limited.

[0107] For example, the flame retardant (B) is preferably contained in an amount of 6 parts by mass or more relative to 100 parts by mass of the total amount of the resin (A) and the flame retardant (B). In this case, a molded article obtained using the flame-retardant resin composition of the present invention will have better flame retardancy, a lower dielectric constant and dielectric dissipation factor, and a higher glass transition temperature. The flame retardant (B) is preferably contained in an amount of 8 parts by mass or more, more preferably 10 parts by mass or more, even more preferably 11 parts by mass or more, particularly preferably 12 parts by mass or more, relative to 100 parts by mass of the total amount of the resin (A) and the flame retardant (B), and is preferably contained in an amount of 50 parts by mass or less, more preferably 40 parts by mass or less, even more preferably 30 parts by mass or less, and particularly preferably 25 parts by mass or less.

[0108] The flame-retardant resin composition of the present invention may contain other components as long as the effects of the present invention are not impaired. For example, the flame-retardant resin composition of the present invention may contain a resin other than resin (A) and may also contain a flame retardant other than flame retardant (B). Examples of resins other than resin (A) include known resins that can be used to form electronic substrates, etc. Examples of flame retardants other than flame retardant (B) include a wide range of known flame retardants.

[0109] In the flame-retardant resin composition of the present invention, the content of resin (A) and resin (B) is preferably 80% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, and particularly preferably 99% by mass or more, based on the total amount of components other than volatile components. Volatile components include, for example, solvents.

[0110] The flame-retardant resin composition of the present invention may contain various components other than the resin (A) and the resin (B), such as a filler, a curing accelerator, a polymerization initiator, an antifoaming agent, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a colorant such as a dye or a pigment, a lubricant, and a dispersant.

[0111] The flame-retardant resin composition of the present invention may contain an organic solvent for the purpose of adjusting viscosity, etc. In this case, the flame-retardant resin composition of the present invention may be a solution or dispersion. The organic solvent used may be one that can dissolve the resin (A), and examples thereof include ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as ethyl acetate, propyl acetate, and butyl acetate; amides such as dimethylacetamide and dimethylformamide; and aromatic hydrocarbons such as toluene and xylene. These may be used alone or in combination of two or more.

[0112] The flame-retardant resin composition of the present invention contains the resin (A) and the flame retardant (B), and thus can form a molded article that has excellent flame retardancy, a low dielectric constant, and a low dielectric loss tangent, and can also form a molded article that has a high glass transition temperature.

[0113] In addition, since the flame retardant (B) is a compound containing a reactive functional group, it can undergo a chemical reaction with the resin (A) during the molding process of the flame-retardant resin composition, and therefore the flame retardant (B) is strongly bonded to the resin (A), so that the resulting molded product can exhibit excellent flame retardancy.

[0114] In the past, adding a flame retardant to a resin could impart flame retardancy, but this had problems such as a decrease in the glass transition temperature and a decrease in the dielectric constant, etc. However, the flame-retardant resin composition of the present invention, which contains the resin (A) and the flame retardant (B), can impart flame retardancy while suppressing the decrease in the glass transition temperature, dielectric constant, etc.

[0115] In particular, when the resin (A) has a polymerizable double bond as described above and the flame retardant (B) also has a polymerizable double bond, a polymerization reaction between the two proceeds during the molding of the flame-retardant resin composition, and for example, a crosslinking reaction may occur, resulting in a molded article with particularly excellent flame retardancy, particularly low dielectric constant and dielectric loss tangent, a high glass transition temperature, and significantly reduced thermal stability.

[0116] As described above, the flame-retardant resin composition of the present invention can be used to produce a molded article having excellent flame retardancy, a low dielectric constant and dielectric dissipation factor, and a low glass transition temperature.

[0117] Molded articles of such flame-retardant resin compositions can be used in a variety of applications, particularly for electronic components, and are particularly suitable for use as electronic substrates.

[0118] Therefore, the flame-retardant resin composition of the present invention is suitable as a composition for electronic substrates for use in electronic substrates. Because the composition for electronic substrates contains the flame-retardant resin composition of the present invention, it is possible to produce a molded article having excellent flame retardancy, low dielectric constant and dielectric dissipation factor, and high glass transition temperature.

[0119] Examples of the electronic substrate include printed circuit boards, and specific examples include rigid printed circuit board materials such as single-sided boards, double-sided boards, multilayer boards, and build-up boards, as well as film- or sheet-like flexible printed circuit board materials. Furthermore, since the molded body has a low dielectric constant, suitable examples of the electronic substrate include high-frequency board materials used in high-frequency communication devices.

[0120] The method for preparing the flame retardant composition is not particularly limited, and for example, the flame retardant composition can be prepared by blending the resin (A) and the flame retardant (B) in a predetermined ratio.

[0121] The method for producing a molded article using the flame retardant composition is not particularly limited, and for example, a wide variety of known molding methods can be adopted in the present invention. For example, the flame retardant composition can be molded using a known molding machine to obtain a molded article of a desired shape. In particular, since the flame retardant resin composition of the present invention is easily cured by heat, it is preferable to produce a molded article by thermoforming.

[0122] In particular, when resin (A) is a resin having a polymerizable double bond, a curing reaction proceeds during molding (preferably during thermoforming), and as a result, the resulting molded article has particularly excellent flame retardancy, particularly low dielectric constant and dielectric loss tangent, and furthermore, a high glass transition temperature, and the decrease in thermal stability is significantly suppressed.

[0123] The temperature during molding is not particularly limited and can be, for example, 150 to 300° C. The pressure during molding is also not particularly limited and can be set appropriately, for example, the molding pressure can be the same as known molding conditions.

[0124] In specifying the inventions included in the present disclosure, the components (properties, structures, functions, etc.) described in the embodiments of the present disclosure may be combined in any manner. In other words, the present disclosure includes all subject matter consisting of all combinations of the components that can be combined as described in this specification. [Example]

[0125] The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to these examples.

[0126] (Production Example 1: Production of Resin (A)) A 2 L four-neck flask equipped with a temperature controller, a stirrer, a cooling condenser, and a dropping funnel was charged with 158 g (0.1 mol) of polyphenylene ether having a number average molecular weight (Mn) of 1580, represented by the following formula (2'). In formula (2'), R 1 , R 3 , R 5 , R 7 , R 10 , R 12 , R 14 , R 16 is a methyl group, and R 2 , R 4 , R 6 , R 8 , R 9 , R 11 , R 13 , R 15was set to hydrogen, A was set to an isopropylidene group, and m+k was set to 12.

[0127] [ka]

[0128] The flask was further charged with 221 g of toluene and 94.8 g of dimethyl sulfoxide (hereinafter referred to as DMSO) to form a homogeneous solution, followed by the addition of 0.96 g of tetra-n-butylammonium bromide and 32.7 g (0.214 mol) of chloromethylstyrene (dichloro compound content: GC area 0.0%, di(chloromethyl)styrene content: GC area 0.9%), and the temperature was raised to 65°C. 53.3 g (0.64 mol) of 48% aqueous sodium hydroxide solution was added dropwise over 30 minutes, and the reaction was carried out at 65°C for 8 hours, resulting in a reaction rate of 98% or more.

[0129] The flask was then cooled to 50°C, and 295 g of toluene, 126.4 g of isopropanol (hereinafter referred to as "IPA"), and 79 g of water were added. The mixture was then neutralized with 46.7 g of 35% by weight aqueous hydrochloric acid. The reaction solution was allowed to stand until it separated into two layers, and the lower aqueous layer was removed. The mixture was then washed five times with a mixture of 15.8 g of IPA and 63.2 g of water. The organic layer was then removed at 70°C and 50 mmHg until the moisture content was 0.05% or less. The solution was then filtered to obtain 345 g of a 50% toluene solution of vinylbenzylated polyphenylene ether compound (95% yield based on the polyphenylene ether compound, hereinafter referred to as the product). The residual chloromethylstyrene content (based on solids content) in this product was less than 0.1%, the hydrolyzable chlorine content was 76 ppm, the number average molecular weight (Mn) was 2,180, and the weight average molecular weight (Mw) was 3,680. The resulting product was designated as vinylbenzyl-modified polyphenylene ether resin (a1).

[0130] (Production Example 2: Production of Resin (A)) A reaction was carried out in the same manner as in Production Example 1, except that chloromethylstyrene was replaced with methacryloyl chloride, thereby obtaining a methacrylated polyphenylene ether compound instead of a vinylbenzylated polyphenylene ether compound. The obtained methacrylated polyphenylene ether compound was designated as methacrylic-modified polyphenylene ether resin (a2).

[0131] (Production Example 3: Production of Resin (A)) 1.5 mol (228.9 g) of vinylbenzyl chloride (trade name: CMS-14, manufactured by AGC Seimi Chemical Co., Ltd.), 1.8 mol (472.1 g) of triphenylphosphine, and 622.4 g of dimethylformamide were charged into a 2.0 L reactor and reacted at 70°C under nitrogen for 3 hours, resulting in the precipitation of a white solid. The solid was thoroughly washed with acetone and then dried under reduced pressure at 92°C, recovering 490 g of compound 1 (vinylbenzyltriphenylphosphonium chloride).

[0132] Next, 15.1 g of styrene, 13.2 g of the compound 1, 5.5 g of acenaphthylene, 1.8 g of 2,4-diphenyl-4-methyl-1-pentene, 1.28 g of 2,2'-azobis(2,4,4-trimethylpentane), and 78.8 g of dimethylformamide were added to a 500 mL reactor and reacted at 120 °C for 3.5 hours under nitrogen conditions to obtain copolymer L as a dimethylformamide solution. 115.7 g of the dimethylformamide solution of copolymer L, 115.7 g of toluene, 31.1 g of 37% by weight formalin, and 38.3 g of 28% by weight aqueous potassium hydroxide solution were added to a 500 mL reactor and reacted at room temperature for 4 hours. The reaction solution was diluted with toluene, and the organic layer was washed with distilled water and IPA. The organic layer was dehydrated and concentrated, and then 18.2 g of anhydrous magnesium chloride was added and stirred at 65 °C for 2 hours. The solid matter was removed by filtration, and the filtrate was diluted with toluene and reprecipitated in methanol. The solid was then removed by filtration and dried under reduced pressure at 60°C, recovering 14.3 g of the solid. This solid was designated as aromatic vinyl resin (a3). The aromatic vinyl resin (a3) ​​had a number average molecular weight (Mn) of 9,000 and a weight average molecular weight (Mw) of 10,900. The aromatic vinyl resin (a3) ​​contained styrene units at 60.7 mol%, divinylbenzene units at 16.9 mol%, and acenaphthylene units at 22.4 mol%.

[0133] (Production Example 4: Production of Flame Retardant (B)) A 500 mL separable flask equipped with a temperature controller, stirrer, cooling condenser, and dropping funnel was charged with 50 g (0.0185 mol) of a polyphenylene ether compound represented by the general formula (1) (Z in general formula (1) is hydrogen, number average molecular weight (Mw) 1900), 70 g of toluene, and 30 g of dimethyl sulfoxide (hereinafter referred to as "DMSO") to form a homogeneous solution. Subsequently, 0.27 g of tetra-n-butylammonium bromide and 3.75 g (0.0245 mol) of chloromethylstyrene (dichloro compound content: GC area 0.0%, di(chloromethyl)styrene content: GC area 0.9%) were added and the temperature was raised to 65 ° C. 5.42 g (0.0609 mol) of 48% aqueous sodium hydroxide solution was added dropwise over 30 minutes, and the reaction was carried out at 65 ° C. for 8 hours. The reaction rate was over 85%.

[0134] The mixture was then cooled to 50°C, and 67.63 g of toluene, 13.19 g of IPA, and 25.24 g of water were added. The mixture was then neutralized with 6.41 g of 35% by mass aqueous hydrochloric acid. The reaction solution was allowed to stand until it separated into two layers, and the lower aqueous solution layer was removed. The mixture was then washed three times with a mixture of 13.14 g of IPA and 52.74 g of water. This organic layer was reprecipitated in 279.13 g of methanol. The solid was then filtered and dried under reduced pressure at 80°C, recovering 44.8 g of the solid. This solid was designated as a vinylbenzyl group-containing flame retardant (b1) (vinylbenzyl-modified bromine-based flame retardant).

[0135] (Production Example 5: Production of Flame Retardant (B)) A 500 mL separable flask equipped with a temperature controller, stirrer, cooling condenser, and dropping funnel was charged with 14.75 g (0.08 mol) of cyanuric chloride and 160 g of methylene chloride, and the atmosphere inside the flask was replaced with nitrogen. The mixture was cooled to 0°C with stirring, and a mixture of 0.93 g (0.016 mol) of allyl alcohol and 31.0 g (0.024 mol) of N,N-diisopropylethylamine was added dropwise and stirred for 1 hour. The mixture was then warmed to room temperature and stirred for 9 hours. The reaction mixture was then washed three times with 70.90 g of water, and the organic layer was concentrated to obtain 15.11 g of compound 2 (diallyl chlorocyanurate).

[0136] Next, 25 g (0.00922 mol) of a polyphenylene ether compound represented by general formula (1) (Z in general formula (1) is hydrogen, number average molecular weight (Mn) 1900) was added to a 500 mL separable flask equipped with a temperature controller, a stirrer, a cooling condenser, and a dropping funnel. 140 g of toluene and 60 g of DMSO were added to form a homogeneous solution. 0.28 g of tetra-n-butylammonium bromide and 4.21 g (0.0187 mol) of the compound 2 were then added and the temperature was raised to 65 ° C. 8.54 g (0.0913 mol) of a 48% aqueous sodium hydroxide solution was added dropwise over 30 minutes, and the reaction was carried out at 65 ° C. for 8 hours. The reaction rate was 85% or more.

[0137] The mixture was then cooled to 50°C, and 65.36 g of toluene, 14.09 g of IPA, and 54.85 g of water were added. The mixture was then neutralized with 3.20 g of a 35% by weight aqueous hydrochloric acid solution. The reaction solution was allowed to stand until it separated into two layers, and the lower aqueous solution layer was removed. The mixture was then washed three times with a mixture of 13.11 g of IPA and 54.85 g of water. This organic layer was reprecipitated in 149.89 g of methanol. The solid was then filtered and dried under reduced pressure at 80°C, recovering 19.93 g of solid. This solid was designated as flame retardant (b2) (diallyl cyanurate-modified bromine-based flame retardant) containing an allyl group (a group corresponding to diallyl isocyanurate).

[0138] (raw materials) Raw materials were selected from those shown below to prepare flame-retardant resin compositions of the examples and comparative examples described below.

[0139] (Resin (A)) The following three types of resin (A) were prepared. Polyphenylene resin (a1): The vinylbenzyl-modified polyphenylene ether resin (a1) obtained in Production Example 1 was used. Polyphenylene resin (a2): The methacrylic-modified polyphenylene ether resin (a2) obtained in Production Example 2 was used. Aromatic vinyl resin (a3): This was used as the aromatic vinyl resin (a3) ​​in Production Example 3.

[0140] (Flame retardant (B)) The following two types of flame retardant (B) were prepared. Flame retardant (b1): The flame retardant (vinylbenzyl-modified) obtained in Production Example 4 was used (referred to as "flame retardant (b1) (vinylbenzyl-modified)" in Table 1 below). Flame retardant (b2): The flame retardant (modified with diallyl cyanurate) obtained in Production Example 5 was used (referred to as "flame retardant (b1) (modified with diallyl cyanurate)" in Table 1 below).

[0141] (comparison flame retardant) The following three types of comparative flame retardants, that is, flame retardants having no polymerizable double bonds, were prepared. Comparative flame retardant (1): Pyroguard (registered trademark) "SR-245" (Dai-ichi Kogyo Seiyaku Co., Ltd.) Comparative flame retardant (2): Rabitol (registered trademark) "FP-110" (Mitsui Chemicals Fine Chemicals, Inc.) Comparative flame retardant (3): "PX-200" (Daihachi Chemical Industry)

[0142] Example 1 A flame-retardant resin composition was prepared by mixing 85 parts by mass of the polyphenylene resin (a1) and 15 parts by mass of the flame retardant (b1).

[0143] Example 2 A flame-retardant resin composition was prepared by mixing 80 parts by mass of the polyphenylene resin (a1) and 20 parts by mass of the flame retardant (b1).

[0144] Example 3 A flame-retardant resin composition was prepared by mixing 85 parts by mass of the polyphenylene resin (a1) and 15 parts by mass of the flame retardant (b2).

[0145] Example 4 A flame-retardant resin composition was prepared by mixing 80 parts by mass of the polyphenylene resin (a1) and 20 parts by mass of the flame retardant (b2).

[0146] Example 5 A flame-retardant resin composition was prepared by mixing 80 parts by mass of the polyphenylene resin (a2) and 20 parts by mass of the flame retardant (b1).

[0147] Example 6 A flame-retardant resin composition was prepared by mixing 80 parts by mass of the polyphenylene resin (a2) and 20 parts by mass of the flame retardant (b2).

[0148] Example 7 A flame-retardant resin composition was prepared by mixing 80 parts by mass of the aromatic vinyl resin (a3) ​​and 20 parts by mass of the flame retardant (b1).

[0149] Example 8 A flame-retardant resin composition was prepared by mixing 80 parts by mass of the aromatic vinyl resin (a3) ​​and 20 parts by mass of the flame retardant (b2).

[0150] (Comparative Example 1) A flame-retardant resin composition consisting of 100 parts by mass of polyphenylene resin (a1) alone was prepared.

[0151] (Comparative Example 2) A flame-retardant resin composition was prepared by mixing 85 parts by mass of the polyphenylene resin (a1) and 15 parts by mass of the comparative flame retardant (2).

[0152] (Comparative Example 3) A flame-retardant resin composition was prepared by mixing 85 parts by mass of the polyphenylene resin (a1) and 15 parts by mass of the comparative flame retardant (3).

[0153] Comparative Example 4 A flame-retardant resin composition consisting of 100 parts by mass of polyphenylene resin (a2) alone was prepared.

[0154] (Comparative Example 5) A flame-retardant resin composition was prepared by mixing 80 parts by mass of the polyphenylene resin (a2) and 20 parts by mass of the comparative flame retardant (2).

[0155] (Comparative Example 6) A flame-retardant resin composition was prepared by mixing 80 parts by mass of the polyphenylene resin (a2) and 20 parts by mass of the comparative flame retardant (3).

[0156] (Comparative Example 7) A flame-retardant resin composition consisting of 100 parts by mass of the aromatic vinyl resin (a3) ​​alone was prepared.

[0157] (Comparative Example 8) A flame-retardant resin composition was prepared by mixing 80 parts by mass of the aromatic vinyl resin (a3) ​​and 20 parts by mass of the comparative flame retardant (1).

[0158] (Comparative Example 9) A flame-retardant resin composition was prepared by mixing 80 parts by mass of the aromatic vinyl resin (a3) ​​and 20 parts by mass of the comparative flame retardant (2).

[0159] (Comparative Example 10) A flame-retardant resin composition was prepared by mixing 80 parts by mass of the aromatic vinyl resin (a3) ​​and 20 parts by mass of the comparative flame retardant (3).

[0160] (Test Example 1: Production of Molded Body) Molded articles of the flame-retardant resin compositions obtained in each Example and Comparative Example were produced using a test single-action compression molding machine (manufactured by Yasuda Seiki Seisakusho Co., Ltd.). Specifically, 23 g of the flame-retardant resin composition was press-molded for 15 minutes under conditions of a pressure of 10 MPa and a temperature of 200°C. This resulted in a molded plate-like article measuring 162 mm x 162 mm x 0.8 mm thick.

[0161] (Evaluation method) The molded article obtained in Test Example 1 above was evaluated for glass transition temperature (Tg), dielectric constant, dielectric loss tangent, and flame retardancy.

[0162] [Glass transition temperature (Tg)] A test piece measuring 5 mm in width, approximately 0.8 mm in thickness, and 30 mm in length was cut out from the molded article obtained in Test Example 1. The glass transition temperature (Tg) of this test piece was measured using a dynamic viscoelasticity measuring apparatus "Rheogel-E4000" (manufactured by UBM Corporation). Specifically, the test piece was measured under conditions of a tensile sine wave, a dynamic strain of 5 m, a frequency of 1 Hz, and a temperature rise rate of 3°C / min. The temperature at which the loss tangent (tan δ) reached a maximum value was determined as the glass transition temperature of the molded article, and the glass transition temperature was evaluated according to the following criteria. However, when the molded article contained a polyphenylene-based resin (e.g., the polyphenylene-based resin (a1) and the polyphenylene-based resin (a2)), the following criteria 1 was adopted, and when the molded article contained an aromatic vinyl-based resin (e.g., the aromatic vinyl-based resin (a3)), the following criteria 2 was adopted. <Judgment criteria 1> A: The Tg was 200°C or higher, which was an extremely high Tg. B: The Tg was high, 190°C or higher and less than 200°C. C: Tg was low, less than 190°C. <Judgment Criteria 2> A: The Tg was 180°C or higher, which was an extremely high Tg. B: The Tg was high, 170°C or higher and lower than 180°C. C: Tg was lower than 170°C, which was a low Tg.

[0163] Dielectric constant (Dk) A test piece measuring 54 mm in width, 0.8 mm in thickness, and 125 mm in length was prepared from the molded body obtained in Test Example 1. The dielectric constant of this test piece was measured using a spread cylinder resonator method dielectric constant measuring device (manufactured by EM Lab), and the dielectric constant was evaluated according to the following criteria. <Judgment criteria> A: The dielectric constant was less than 2.7, which was an extremely low dielectric constant. B: The dielectric constant was low, ie, not less than 2.7 and less than 2.8. C: The dielectric constant was 2.8 or more, which was a high dielectric constant.

[0164] Dissipation Factor (Df) A test piece measuring 54 mm in width, 0.8 mm in thickness, and 125 mm in length was prepared from the molded article obtained in Test Example 1. The dielectric loss tangent of this test piece was measured using a spread cylinder resonator method dielectric constant measuring device (manufactured by EM Labo), and the dielectric loss tangent was evaluated according to the following criteria. <Judgment criteria> A: The dielectric loss tangent was less than 0.002, which was an extremely low dielectric loss tangent. B: The dielectric loss tangent was 0.002 or more and less than 0.003, that is, the dielectric loss tangent was low. C: The dielectric loss tangent was 0.003 or more, which was a high dielectric loss tangent.

[0165] [Flame retardant (UL94V)] A test specimen measuring 127 mm in length, 12.7 mm in width, and 1.6 mm in thickness was prepared from the molded article obtained in Test Example 1. Using this test specimen, a flame retardancy test was carried out in accordance with UL94V (flame retardancy of plastic materials) of the UL standard, and the flame retardancy performance was evaluated according to the following criteria. <Judgment criteria> V-0: Met UL94V V-0 and had extremely excellent flame retardancy. V-1: Meets UL94V V-1 and has excellent flame retardancy. NOT V: Did not satisfy any of the UL94V standards and had poor flame retardancy.

[0166] (Evaluation results) Table 1 shows the compounding conditions for the flame-retardant resin compositions obtained in each example and the evaluation results (glass transition temperature (Tg), dielectric constant, dielectric dissipation factor, and flame retardancy) of the molded articles obtained using the flame-retardant resin compositions.

[0167] Table 2 shows the compounding conditions for the flame-retardant resin compositions obtained in each comparative example and the evaluation results (glass transition temperature (Tg), dielectric constant, dielectric dissipation factor, and flame retardancy) of the molded articles obtained using the flame-retardant resin compositions. In Tables 1 and 2, blank cells indicate that the raw material was not used.

[0168] The results in Tables 1 and 2 show that the molded articles of the flame-retardant resin compositions obtained in the examples have excellent flame retardancy, low dielectric constant and low dielectric loss tangent, and also have a high glass transition temperature.

[0169] Therefore, it has been demonstrated that a resin composition containing at least one resin (resin (A)) selected from the group consisting of polyphenylene-based resins and aromatic vinyl-based resins, and a compound containing a reactive functional group (flame retardant (B)), can form a molded article that has excellent flame retardancy, a low dielectric constant, and a low dielectric dissipation factor, and can also form a molded article that has a high glass transition temperature.

[0170] [Table 1]

[0171] [Table 2]

Claims

1. A resin composition comprising a resin (A) and a flame retardant (B), the resin (A) is at least one selected from the group consisting of polyphenylene-based resins and aromatic vinyl-based resins, The flame retardant (B) is a compound containing a reactive functional group, The compound containing the reactive functional group is represented by the following general formula (1): 【Chemistry 1】 (in formula (1), Z is a group corresponding to a vinylbenzyl group or diallyl isocyanurate, and n is a number of 1 or more), The flame-retardant resin composition, wherein the resin (A) is a resin having a polymerizable double bond.

2. 2. The flame-retardant resin composition according to claim 1, wherein Z in formula (1) is a vinylbenzyl group.

3. 2. The flame-retardant resin composition according to claim 1, wherein the flame retardant (B) is contained in an amount of 6 parts by mass or more per 100 parts by mass of the total amount of the resin (A) and the flame retardant (B).

4. An electronic substrate composition for use in an electronic substrate, comprising: An electronic substrate composition comprising the flame-retardant resin composition according to any one of claims 1 to 3.

5. A molded article of the flame-retardant resin composition according to any one of claims 1 to 3.

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