JP2013023517A - Polyphenylene ether resin composition, resin varnish, prepreg, metal-clad laminate, and printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyphenylene ether resin composition excellent in heat resistance and flame retardancy of a cured product, while keeping an excellent dielectric characteristic of a polyphenylene ether.SOLUTION: The polyphenylene ether resin composition contains a modified polyphenylene ether expressed by formula (1), and a thermal crosslinking type curing agent. In the formula (1), m represents 1 or 2; L represents a polyphenylene ether chain of prescribed structure; M represents a hydrogen atom, or a group of prescribed structure containing an unsaturated double bond and phosphorus, M is not hydrogen atom when m is 1, at least either of two Ms is not hydrogen atom when m is 2, and T represents hydrogen atom when m is 1, and represents an alkylene group, or a group of prescribed structure derived from a polyphenylene ether, when m is 2.

Description

  The present invention provides a polyphenylene ether resin composition, a resin varnish containing the polyphenylene ether resin composition, a prepreg obtained using the resin varnish, a metal-clad laminate obtained using the prepreg, and the prepreg. It is related with the printed wiring board manufactured using.

  2. Description of the Related Art In recent years, various electronic devices have rapidly advanced mounting technologies such as higher integration of electronic components such as semiconductor devices to be mounted, higher density of wiring, and multilayering as the amount of information processing increases. Insulating materials such as printed wiring board base materials used in various electronic devices, in order to reduce the transmission loss of signals transmitted to the metal wiring arranged on the base material etc., and increase the signal transmission speed, A low dielectric constant and dielectric loss tangent are required.

  Polyphenylene ether (PPE) has excellent dielectric properties such as dielectric constant and dielectric loss tangent even in the high frequency band (high frequency region) from the MHz band to the GHz band, so that the printed wiring board of the electronic equipment using the high frequency band It is preferably used for an insulating material such as a base material.

  In addition, the substrate of the printed wiring board is required to have high heat resistance and flame retardancy in order to increase the reliability of the printed wiring board.

  However, since PPE is relatively poor in flame retardancy, it is conceivable to add a flame retardant to PPE when PPE is used as a substrate material for printed wiring boards. That is, it is conceivable to use a flame retardant-added resin composition containing PPE.

  In addition to the use of such a flame retardant-added polyphenylene ether resin composition, a resin composition containing modified PPE obtained by reacting a flame retardant with a hydroxyl group at the terminal of PPE, that is, a flame retardant reactive polyphenylene. It is conceivable to use an ether resin composition.

  In addition, the flame retardant compounded to increase the flame retardancy of the cured product of the resin composition includes halogen-based flame retardants such as brominated flame retardants, and halogen-containing epoxy resins such as tetrabromobisphenol A type epoxy resins. Of these, those containing halogen were often used.

  However, a resin composition containing such a halogen-containing flame retardant may generate harmful substances such as hydrogen halide when the cured product burns, which may adversely affect the human body and the environment. There are disadvantages. Under such a background, as a base material of a printed wiring board, it is required to contain no halogen, that is, to be halogen-free.

  Specific examples of such a halogen-free resin composition include the resin composition described in Patent Document 1. Patent Document 1 describes a phosphorus flame retardant having a phosphorus content of 20 to 30% by mass, a polyphenylene ether resin having a number average molecular weight of 1000 to 4000, a non-halogen-containing thermosetting resin, and a curing agent for the thermosetting resin. A resin composition containing is described.

JP 2004-315725 A

  First, in the case of a flame retardant-added polyphenylene ether resin composition, a so-called bleed out that a flame retardant exudes from a resin component such as PPE occurs, and the flame retardancy may not be sufficiently maintained. Moreover, glass transition temperature fell by adding a flame retardant, and the heat resistance of the hardened | cured material of the resin composition might fall.

  Moreover, in the case of a flame retardant reaction type polyphenylene ether resin composition, since the polarity of PPE itself is low, the solubility in a solvent and the compatibility with a flame retardant tend to be low. Therefore, the PPE and the flame retardant are separated, the reaction between the PPE and the flame retardant is difficult to proceed, and it is difficult to obtain a modified PPE in which the flame retardant is reacted with the hydroxyl group at the end of the PPE.

  Further, since general PPE has a relatively high molecular weight, the terminal hydroxyl group concentration is low, and there is a tendency that less flame retardant is introduced into the PPE. That is, there is a tendency that the flame retardant concentration cannot be sufficiently increased and sufficient flame retardancy cannot be exhibited.

  Therefore, it is conceivable to use PPE having a reduced molecular weight. Specifically, it is conceivable to use PPE having a low molecular weight by causing molecular cleavage by redistributing a high molecular weight PPE in a solvent in the presence of a phenol species and a radical initiator. . However, when PPE having a reduced molecular weight is used, there is a problem that the curability of the resin composition containing the PPE becomes insufficient and the heat resistance of the cured product is lowered.

  Moreover, according to Patent Document 1, it is disclosed that excellent heat resistance, flame retardancy, and dielectric properties can be exhibited without containing a halogen compound.

  However, as in Patent Document 1, it is difficult to achieve both the heat resistance and the flame retardancy of the cured product of the obtained resin composition only by including a phosphorus flame retardant. This is considered to be due to the problem of the flame retardant-added polyphenylene ether resin composition as described above because it becomes a flame-retardant-added polyphenylene ether resin composition.

  The present invention has been made in view of such circumstances, and provides a polyphenylene ether resin composition excellent in heat resistance and flame retardancy of a cured product while maintaining the excellent dielectric properties of polyphenylene ether. With the goal. Another object of the present invention is to provide a prepreg using the polyphenylene ether resin composition, a metal-clad laminate using the prepreg, and a printed wiring board manufactured using the prepreg.

  The polyphenylene ether resin composition according to one embodiment of the present invention includes a modified polyphenylene ether represented by the following formula (1) and a heat-crosslinking curing agent.

  In the above formula (1), m represents 1 or 2, L represents a polyphenylene ether chain represented by the following formula (2), M represents a hydrogen atom, represented by the following formula (3). Or a group represented by the following formula (4), and when m is 1, M is not a hydrogen atom, and when m is 2, at least one of the two M is T, not a hydrogen atom, represents a hydrogen atom when m is 1, and represents an alkylene group or a group represented by the following formula (5) when m is 2.

Here, in the above formula (2), n represents a positive integer of 50 or less, and R ¹ , R ² , R ³ , and R ⁴ are each independently a hydrogen atom, an alkyl group, an alkenyl group, An alkynyl group, a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group;

Here, in said formula (3), R < ⁵ > and R < ⁶ > show an alkyl group, an alkenyl group, an alkoxy group, an aryl group, or an amino group each independently, Of R < ⁵ > and R < ⁶ > At least one of them has an unsaturated double bond at the terminal.

Here, in said formula (4), R < ⁷ > and R < ⁸ > show an alkyl group, an alkenyl group, an alkoxy group, an aryl group, or an amino group each independently, Of R < ⁷ > and R < ⁸ > At least one of them has an unsaturated double bond at the terminal.

Here, in the above formula (5), R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently a hydrogen atom, alkyl group, alkenyl group, alkynyl group, formyl group, alkylcarbonyl group, alkenylcarbonyl. Group or an alkynylcarbonyl group.

  In the polyphenylene ether resin composition, the content of the modified polyphenylene ether is preferably 30 to 90% by mass with respect to the total amount of the modified polyphenylene ether and the thermally crosslinkable curing agent.

  In the polyphenylene ether resin composition, the thermally crosslinkable curing agent is a trialkenyl isocyanurate compound, a polyfunctional acrylate compound having two or more acryl groups in the molecule, and two or more methacryl groups in the molecule. It is preferably at least one selected from the group consisting of polyfunctional methacrylate compounds.

  In the polyphenylene ether resin composition, the modified polyphenylene ether preferably has a number average molecular weight of 1000 to 7000.

  The polyphenylene ether resin composition preferably further includes an inorganic filler.

  A resin varnish according to another embodiment of the present invention is a resin varnish containing the polyphenylene ether resin composition and a solvent.

  The prepreg according to another embodiment of the present invention is a prepreg obtained by impregnating a fibrous base material with the resin varnish.

  Moreover, the metal-clad laminate according to another aspect of the present invention is a metal-clad laminate obtained by laminating a metal foil on the prepreg and then heat-pressing it.

  Moreover, the printed wiring board which concerns on the other one aspect | mode of this invention is a printed wiring board manufactured using the said prepreg.

  ADVANTAGE OF THE INVENTION According to this invention, the polyphenylene ether resin composition excellent in the heat resistance and flame retardance of hardened | cured material can be provided, maintaining the outstanding dielectric property which polyphenylene ether has. Moreover, the prepreg using the said resin composition, the metal-clad laminated board using the said prepreg, and the printed wiring board manufactured using the said prepreg are provided.

  The polyphenylene ether resin composition according to an embodiment of the present invention includes a modified polyphenylene ether represented by the formula (1) and a heat crosslinkable curing agent. With such a polyphenylene ether resin composition, a cured product having excellent heat resistance and flame retardancy can be obtained while maintaining the excellent dielectric properties of polyphenylene ether.

  This is considered to be due to the fact that the modified polyphenylene ether represented by the formula (1) has in its molecule phosphorus, which is a flame retardant component, and an unsaturated double bond at the terminal. That is, since the modified polyphenylene ether has an unsaturated double bond at its terminal, a three-dimensional crosslinking can be suitably formed by causing a curing reaction between the modified polyphenylene ether and the thermally crosslinkable curing agent, It is considered that the heat resistance of the cured product can be sufficiently enhanced. In addition, since the modified polyphenylene ether contains phosphorus in the molecule, when the resin composition containing the modified polyphenylene ether is cured, the phosphorus is sufficiently incorporated into the crosslinked structure of the cured product and contains phosphorus. It is considered that the compound can be sufficiently suppressed from exuding from the cured product. That is, as in the case of a flame retardant-added polyphenylene ether resin composition, the occurrence of a decrease in flame retardant due to the bleed out of the flame retardant, which is a phenomenon in which a flame retardant containing phosphorus exudes from the resin component It is thought to be suppressed. Therefore, it is considered that flame retardancy can be increased. Moreover, even if polyphenylene ether is reduced in molecular weight in order to increase the phosphorus concentration, it is considered that the heat resistance of the cured product can be sufficiently maintained by having an unsaturated double bond at the terminal.

  The modified polyphenylene ether used in the present embodiment is not particularly limited as long as it is a modified polyphenylene ether represented by the formula (1).

  The modified polyphenylene ether represented by the formula (1) is one in which m in the formula (1) is 1 or 2. This m represents the number of -LM bonded to T. From this, the modified polyphenylene ether represented by the formula (1) is specifically a modified polyphenylene ether represented by TLMM or MLTLM.

L represents a polyphenylene ether chain represented by the formula (2). In the formula (2), n represents a positive integer of 50 or less. R ¹ , R ² , R ³ , and R ⁴ are independent of each other. That is, R ¹ , R ² , R ³ , and R ⁴ may be the same group or different groups. R ¹ , R ² , R ³ , and R ⁴ represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group. Among these, a hydrogen atom and an alkyl group are preferable.

  M represents a hydrogen atom, a group represented by Formula (3), or a group represented by Formula (4). In addition, when m is 1, that is, when the modified polyphenylene ether is TLM, M is not a hydrogen atom but a group represented by the formula (3) or a formula (4). Represents a group. In addition, when M is 2, that is, when the modified polyphenylene ether is MLTLM, at least one of the two Ms is not a hydrogen atom, and the two M are Are preferably groups represented by the formula (3) or groups represented by the formula (4).

In Formula (3), R ⁵ and R ⁶ are independent of each other. That is, R ⁵ and R ⁶ may be the same group or different groups. R ⁵ and R ⁶ represent an alkyl group, an alkenyl group, an alkoxy group, an aryl group, or an amino group. Among these, an alkoxy group and an aryl group are preferable. In addition, at least one of R ⁵ and R ⁶ is a group having an unsaturated double bond at the terminal.

In Formula (4), R ⁷ and R ⁸ are independent of each other. That is, R ⁷ and R ⁸ may be the same group or different groups. R ⁷ and R ⁸ represent an alkyl group, an alkenyl group, an alkoxy group, an aryl group, or an amino group. Among these, an alkoxy group and an aryl group are preferable. In addition, at least one of R ⁷ and R ⁸ is a group having an unsaturated double bond at the terminal.

  T represents a hydrogen atom when m is 1, that is, when the modified polyphenylene ether is TLM. The modified polyphenylene ether represented by TLM is a modified polyphenylene ether represented by HLM. T represents an alkylene group or a group represented by Formula (5) when m is 2, that is, when the modified polyphenylene ether is MLTLM. Among these, m is 2, T is preferably an alkylene group, m is 2, and T is preferably a 2,2-propylene group.

In the formula (5), R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are each independently a hydrogen atom, alkyl group, alkenyl group, alkynyl group, formyl group, alkylcarbonyl group, alkenylcarbonyl group, Or an alkynylcarbonyl group is shown. R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ may be the same group or different groups.

Specific examples of the functional groups listed in R ^{1 to} R ¹⁴ include the following.

  Although an alkyl group is not specifically limited, For example, a C1-C18 alkyl group is preferable and a C1-C10 alkyl group is more preferable. Specific examples include a methyl group, an ethyl group, a propyl group, a hexyl group, and a decyl group.

  Moreover, although an alkenyl group is not specifically limited, For example, a C2-C18 alkenyl group is preferable and a C2-C10 alkenyl group is more preferable. Specifically, a vinyl group, an allyl group, a 3-butenyl group, etc. are mentioned, for example.

  Moreover, although an alkynyl group is not specifically limited, For example, a C2-C18 alkynyl group is preferable and a C2-C10 alkynyl group is more preferable. Specific examples include an ethynyl group and a prop-2-yn-1-yl group (propargyl group).

  The alkylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkyl group. For example, an alkylcarbonyl group having 2 to 18 carbon atoms is preferable, and an alkylcarbonyl group having 2 to 10 carbon atoms is more preferable. . Specific examples include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a hexanoyl group, an octanoyl group, and a cyclohexylcarbonyl group.

  The alkenylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkenyl group. For example, an alkenylcarbonyl group having 3 to 18 carbon atoms is preferable, and an alkenylcarbonyl group having 3 to 10 carbon atoms is more preferable. . Specifically, an acryloyl group, a methacryloyl group, a crotonoyl group, etc. are mentioned, for example.

  The alkynylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkynyl group. For example, an alkynylcarbonyl group having 3 to 18 carbon atoms is preferable, and an alkynylcarbonyl group having 3 to 10 carbon atoms is more preferable. . Specifically, a propioyl group etc. are mentioned, for example.

  Moreover, although an alkoxy group is not specifically limited, For example, a C1-C12 alkoxy group is preferable and a C1-C8 alkoxy group is more preferable. Specific examples include a methoxy group, an ethoxy group, an allyloxy group, a butoxy group, a phenoxy group, and a p-vinylphenoxy group.

  The aryl group is not particularly limited, but for example, an aryl group having 6 to 14 carbon atoms is preferable, and an aryl group having 6 to 10 carbon atoms is more preferable. Specific examples include a phenyl group, a benzyl group, a p-vinylbenzyl group, a tolyl group, and a benzylphenyl group.

The amino group is not particularly limited, but for example, an amino group having 0 to 20 carbon atoms is preferable, and an amino group having 0 to 10 carbon atoms is more preferable. Specifically, for example, —NH ₂ , methylamino group, dimethylamino group, diethylamino group, dibenzylamino group, diphenylamino group, ditolylamino group, diallylamino group, di (2-ethylhexyl) amino group and the like can be mentioned. It is done.

  Moreover, although an alkylene group is not specifically limited, For example, a C1-C10 alkylene group is preferable and a C1-C5 alkylene group is more preferable. Specific examples include a methylene group, an ethylene group, a propylene group such as a 2,2-propylene group, and a butylene group.

  The number average molecular weight of the modified polyphenylene ether is not particularly limited, but is preferably 1000 to 7000, and more preferably 2000 to 4000. Further, as described above, n is a positive integer of 50 or less, and is preferably a numerical value such that the number average molecular weight of the modified polyphenylene ether falls within such a range. Specifically, it is preferably 1 to 50. In addition, the number average molecular weight should just be what was measured by the general molecular weight measuring method here, and the value etc. which were specifically measured using gel permeation chromatography (GPC) are mentioned.

  When the number average molecular weight of the modified polyphenylene ether is within such a range, the cured product of the obtained polyphenylene ether resin composition has higher flame retardancy. This is presumably because the content of phosphorus contained in the molecule increases because the number average molecular weight of the modified polyphenylene ether is within such a range. Further, when the number average molecular weight of the modified polyphenylene ether is within such a range, the polyphenylene ether has a relatively low molecular weight, so that the heat resistance of the cured product tends to be reduced in the case of ordinary polyphenylene ether. In this respect, since the modified polyphenylene ether used in this embodiment has an unsaturated double bond at the terminal, crosslinking with the modified polyphenylene ether and the thermally crosslinkable curing agent is preferable by curing together with the thermally crosslinkable curing agent. As a result, a cured product having sufficiently high heat resistance is obtained. Therefore, it is considered that the obtained polyphenylene ether resin composition is excellent in both the heat resistance and flame retardancy of the cured product.

  The modified polyphenylene ether is not particularly limited as long as it has a configuration represented by the formula (1). Specifically, for example, the modified polyphenylene ether represented by the formula (6) or the formula (7) is used. Ether is preferred.

Here, in the formula (6), ^{R 5,} and ^{R 6, R 5} in the formula (3), and the same meanings as ^{R 6.} Specifically, R ⁵ and R ⁶ each independently represent an alkyl group, an alkenyl group, an alkoxy group, an aryl group, or an amino group, and at least one of R ⁵ and R ⁶ is Have an unsaturated double bond at the end.

Here, in the formula (7), ^{R 7,} and ^{R 8, R 7} in formula (4), and the same meanings as ^{R 8.} Specifically, R ⁷ and R ⁸ each independently represent an alkyl group, an alkenyl group, an alkoxy group, an aryl group, or an amino group, and at least one of R ⁷ and R ⁸ is Have an unsaturated double bond at the end.

  The method for synthesizing the modified polyphenylene ether is not particularly limited as long as the modified polyphenylene ether represented by the formula (1) can be synthesized. Specifically, for example, at least one of a halogenated organophosphorus compound represented by formula (8) and a halogenated organophosphorus compound represented by formula (9), and polyphenylene represented by formula (10) Examples include a method of reacting with ether. Moreover, this reaction includes reaction in the presence of a catalyst such as triethylamine in a solvent such as 1,2-dichloroethane, if necessary.

Here, in the formula (8), X represents a halogen atom, ^{R 5,} and ^{R 6, R 5} in the formula (3), and the same meanings as ^{R 6.} Specifically, R ⁵ and R ⁶ each independently represent an alkyl group, an alkenyl group, an alkoxy group, an aryl group, or an amino group, and at least one of R ⁵ and R ⁶ is Have an unsaturated double bond at the end. X represents a halogen atom, and specific examples include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom. Among these, a chlorine atom is preferable.

Here, in the formula (9), X represents a halogen atom, ^{R 7,} and ^{R 8} are the same meanings as ^{R 7,} and ^{R 8} in formula (4). Specifically, R ⁷ and R ⁸ each independently represent an alkyl group, an alkenyl group, an alkoxy group, an aryl group, or an amino group, and at least one of R ⁷ and R ⁸ is Have an unsaturated double bond at the end. X represents a halogen atom, and specific examples include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom. Among these, a chlorine atom is preferable.

  Here, in Formula (10), m, L, and T are the same as m, L, and T in Formula (1). Specifically, m represents 1 or 2, L represents a polyphenylene ether chain represented by the formula (2), T represents a hydrogen atom when m is 1, and m is 2. Represents an alkylene group or a group represented by the formula (5).

  The method for synthesizing the halogenated organophosphorus compound represented by formula (8) is not particularly limited as long as the halogenated organophosphorus compound represented by formula (8) can be synthesized. Specifically, for example, a method of reacting a dihalogenated organic phosphorus compound represented by the formula (11) and an organic compound represented by the formula (12) can be used. Moreover, this reaction includes reaction in the presence of a catalyst such as triethylamine in a solvent such as 1,2-dichloroethane, if necessary.

Here, in the formula (11), X represents a halogen atom, ^{R 5} represents the same as ^{R 5} in formula (3). Specifically, R ⁵ represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, or an amino group.

Here, in formula (12), R ⁶ represents the same as R ^{6 in} formula (3). Specifically, R ⁶ represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, or an amino group.

In the dihalogenated organophosphorus compound represented by the formula (11) and the organic compound represented by the formula (12), at least one of R ⁵ and R ⁶ is terminally unsaturated. Has a double bond.

  Moreover, the halogenated organophosphorus compound represented by the formula (8) can also be synthesized by the following method. Specifically, for example, a method of reacting the organophosphorus compound represented by the formula (13) with a halogenating agent can also be mentioned. Moreover, this reaction includes reaction in the presence of a catalyst such as N, N-dimethylformamide (DMF) as necessary.

Here, in the formula (13), ^{R 5,} and ^{R 6, R 5} in the formula (3), and the same meanings as ^{R 6.} Specifically, R ⁵ and R ⁶ represent an alkyl group, an alkenyl group, an alkoxy group, an aryl group, or an amino group. R ¹⁵ is the same as R ⁶ and specifically represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, or an amino group. R ¹⁵ is a group that is easily eliminated from R ⁵ and R ⁶ with a halogenating agent and is easily substituted with halogen. At least one of R ⁵ and R ⁶ has an unsaturated double bond at the terminal.

  The method for synthesizing the halogenated organophosphorus compound represented by formula (9) is not particularly limited as long as the halogenated organophosphorus compound represented by formula (9) can be synthesized. Specifically, for example, a method of reacting a dihalogenated organic phosphorus compound represented by the formula (14) with an organic compound represented by the formula (15) can be mentioned. Moreover, this reaction includes reaction in the presence of a catalyst such as triethylamine in a solvent such as 1,2-dichloroethane, if necessary.

Here, in the formula (14), X represents a halogen atom, ^{R 7} represents the same as ^{R 7} in formula (4). Specifically, R ⁷ represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, or an amino group.

Here, in the formula (15), ^{R 8} represents the same as ^{R 8} in formula (4). Specifically, R ⁸ represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, or an amino group.

In the dihalogenated organophosphorus compound represented by the formula (14) and the organic compound represented by the formula (15), at least one of R ⁷ and R ⁸ is terminally unsaturated Has a double bond.

  The heat crosslinkable curing agent used in the present embodiment is not particularly limited as long as it can be cured by forming a crosslink by reacting with a modified polyphenylene ether. Specific examples include compounds having two or more unsaturated double bonds in the molecule. More specifically, trialkenyl isocyanurate compounds such as triallyl isocyanurate (TAIC), polyfunctional methacrylate compounds having two or more methacryl groups in the molecule, polyfunctional acrylate compounds having two or more acrylic groups in the molecule And vinylbenzyl compounds having two or more vinylbenzyl groups in the molecule. Among these, a trialkenyl isocyanurate compound, a polyfunctional acrylate compound having two or more acrylic groups in the molecule, and a polyfunctional methacrylate compound are preferable. When these are used, it is considered that the crosslinking is more suitably formed by the curing reaction, and the heat resistance of the cured product of the polyphenylene ether resin composition of the present embodiment can be further increased. Moreover, the heat-crosslinking-type hardening | curing agent may use the illustrated heat-crosslinking-type hardening | curing agent independently, and may be used in combination of 2 or more type.

  Further, the content ratio of the modified polyphenylene ether represented by the formula (1) is not particularly limited as long as it is a ratio capable of forming a cured product by reacting with a thermal crosslinking curing agent. It is preferably 30 to 90% by mass, more preferably 40 to 90% by mass, and still more preferably 50 to 90% by mass with respect to the total amount with the crosslinking type curing agent. That is, the content of the heat crosslinkable curing agent is preferably 10 to 70% by mass, and more preferably 10 to 60% by mass with respect to the total amount of the modified polyphenylene ether and the heat crosslinkable curing agent. More preferably, it is 10-50 mass%. If it is such a content rate, what was excellent in the heat resistance of a hardened | cured material and a flame retardance will be obtained, maintaining the outstanding dielectric characteristic which polyphenylene ether has. This is considered to be because crosslinking is more preferably formed by a curing reaction while maintaining the content of the polyphenylene ether component capable of exhibiting excellent dielectric properties and the content of phosphorus which is a flame retardant component. .

  In addition, the polyphenylene ether resin composition according to the present embodiment may be composed of a modified polyphenylene ether and a heat-crosslinking curing agent, but if it contains a modified polyphenylene ether and a heat-crosslinking curing agent, May be included. Examples of other components include inorganic fillers, flame retardants, additives, and reaction initiators. Among these, it is preferable to contain an inorganic filler. Even when other components are included, the total content of the modified polyphenylene ether and the thermal crosslinking curing agent is preferably 30% by mass or more based on the polyphenylene ether resin composition. More preferably, it is 90 mass%, and it is further more preferable that it is 40-80 mass%. Within such a range, while maintaining the excellent dielectric properties of polyphenylene ether, the effect of obtaining a cured product with excellent heat resistance and flame retardancy can be obtained without inhibiting other components, Can fully demonstrate.

  Moreover, as described above, the polyphenylene ether resin composition according to this embodiment may contain an inorganic filler. Examples of the inorganic filler include those added to increase the heat resistance and flame retardancy of the cured product of the resin composition, and are not particularly limited. By containing an inorganic filler, heat resistance, flame retardancy and the like can be enhanced. In addition, the resin composition containing polyphenylene ether has a low cross-linking density compared to a general epoxy resin composition for an insulating substrate, etc., and the thermal expansion coefficient of the cured product, particularly at a temperature exceeding the glass transition temperature. The thermal expansion coefficient α2 tends to increase. By including an inorganic filler, it has excellent dielectric properties and heat resistance and flame retardancy of the cured product, and the thermal expansion coefficient of the cured product, especially the glass transition temperature, has been exceeded while the viscosity when made into a varnish is low. It is possible to reduce the thermal expansion coefficient α2 at temperature and toughen the cured product. Specific examples of the inorganic filler include silica, alumina, talc, aluminum hydroxide, magnesium hydroxide, titanium oxide, mica, aluminum borate, barium sulfate, and calcium carbonate. Moreover, as an inorganic filler, although you may use as it is, what was surface-treated with the silane coupling agent of an epoxy silane type or an aminosilane type is especially preferable. A metal-clad laminate obtained by using a resin composition in which an inorganic filler surface-treated with such a silane coupling agent is blended has high heat resistance during moisture absorption, and tends to have high interlayer peel strength. There is.

  Moreover, when it contains an inorganic filler, it is preferable that the content is 5-60 mass% with respect to a polyphenylene ether resin composition, It is more preferable that it is 10-60 mass%, 15-50 More preferably, it is mass%.

  Moreover, the polyphenylene ether resin composition according to the present embodiment may contain a flame retardant as described above. By doing so, the flame retardance of the hardened | cured material of a resin composition can further be improved. The flame retardant is not particularly limited. Specifically, a phosphorus flame retardant etc. are mentioned, for example. Specific examples of the phosphorus-based flame retardant include, for example, phosphoric acid esters such as condensed phosphate esters and cyclic phosphate esters, phosphazene compounds such as cyclic phosphazene compounds, and phosphinic acid metal salts such as aluminum dialkylphosphinates. Examples thereof include salt flame retardants, melamine phosphates such as melamine phosphate, and melamine polyphosphate. Moreover, a phosphorus flame retardant is preferably used from a halogen-free viewpoint. As a flame retardant, each illustrated flame retardant may be used independently and may be used in combination of 2 or more type.

  Moreover, the polyphenylene ether resin composition according to the present embodiment may contain an additive as described above. As additives, for example, antifoaming agents such as silicone antifoaming agents and acrylic ester antifoaming agents, heat stabilizers, antistatic agents, ultraviolet absorbers, dyes and pigments, lubricants, wetting and dispersing agents, etc. A dispersing agent etc. are mentioned.

  Moreover, as described above, the polyphenylene ether resin composition according to the present embodiment may contain a reaction initiator. Even if the polyphenylene ether resin composition according to this embodiment is composed of a modified polyphenylene ether and a thermally crosslinkable curing agent, the curing reaction can proceed, but depending on the process conditions, the temperature is increased until the curing proceeds. Since it may not be possible, it is preferable to add a reaction initiator. The reaction initiator is not particularly limited as long as it can accelerate the curing reaction between the modified polyphenylene ether and the heat crosslinking curing agent. Specifically, for example, α, α′-bis (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexyne, Benzoyl oxide, 3,3 ′, 5,5′-tetramethyl-1,4-diphenoquinone, chloranil, 2,4,6-tri-t-butylphenoxyl, t-butylperoxyisopropyl monocarbonate, azobisisobuty An oxidizing agent such as ronitrile can be used. Moreover, a carboxylic acid metal salt etc. can be used together as needed. By doing so, the curing reaction can be further accelerated. Among these, α, α'-bis (t-butylperoxy-m-isopropyl) benzene is preferably used. Since α, α′-bis (t-butylperoxy-m-isopropyl) benzene has a relatively high reaction initiation temperature, it suppresses the acceleration of the curing reaction at the time when curing is not required, such as during prepreg drying. And a decrease in storage stability of the polyphenylene ether resin composition can be suppressed. Furthermore, α, α'-bis (t-butylperoxy-m-isopropyl) benzene has low volatility, and therefore does not volatilize during prepreg drying or storage, and has good stability. Moreover, a reaction initiator may be used independently or may be used in combination of 2 or more type.

  When producing a prepreg, the polyphenylene ether resin composition according to the present embodiment is often prepared and used in the form of a varnish for the purpose of impregnating the substrate (fibrous substrate) for forming the prepreg. . That is, the polyphenylene ether resin composition according to the present embodiment is usually a resin prepared in a varnish shape (resin varnish) in many cases. Such a resin varnish is prepared as follows, for example.

  First, each component that can be dissolved in an organic solvent, such as a modified polyphenylene ether and a heat-crosslinking curing agent, is introduced into the organic solvent and dissolved. At this time, heating may be performed as necessary. After that, a component that is used as necessary and does not dissolve in an organic solvent, such as an inorganic filler, is added and dispersed using a ball mill, a bead mill, a planetary mixer, a roll mill or the like until a predetermined dispersion state is obtained. Thus, a varnish-like resin composition is prepared. The organic solvent used here is not particularly limited as long as it dissolves the modified polyphenylene ether, the heat-crosslinking curing agent, and the like and does not inhibit the curing reaction. Specifically, toluene etc. are mentioned, for example.

  As a method for producing a prepreg using the obtained resin varnish, for example, a method of impregnating a fibrous base material with the obtained resin varnish and then drying it may be mentioned.

  Specific examples of the fibrous base material used when producing the prepreg include glass cloth, aramid cloth, polyester cloth, glass nonwoven fabric, aramid nonwoven fabric, polyester nonwoven fabric, pulp paper, and linter paper. . When a glass cloth is used, a laminate having excellent mechanical strength can be obtained, and a flat glass processed glass cloth is particularly preferable. Specifically, the flattening processing can be performed, for example, by continuously pressing a glass cloth with a press roll at an appropriate pressure and compressing the yarn flatly. In addition, as a thickness of a fibrous base material, the thing of 0.04-0.3 mm can generally be used, for example.

  The impregnation of the resin base material with the resin varnish is performed by dipping or coating. This impregnation can be repeated a plurality of times as necessary. At this time, it is also possible to repeat the impregnation using a plurality of resin varnishes having different compositions and concentrations, and finally adjust to a desired composition and resin amount.

  The fibrous base material impregnated with the resin varnish is heated at a desired heating condition, for example, 80 to 170 ° C. for 1 to 10 minutes to obtain a semi-cured (B stage) prepreg.

  As a method for producing a metal-clad laminate using the prepreg thus obtained, one or a plurality of prepregs are stacked, and a metal foil such as a copper foil is stacked on both upper and lower sides or one side thereof. A laminated body of double-sided metal foil tension or single-sided metal foil tension can be produced by heat and pressure forming and laminating and integrating. The heating and pressing conditions can be appropriately set depending on the thickness of the laminate to be manufactured, the type of the resin composition of the prepreg, and the like. For example, the temperature is 170 to 210 ° C., the pressure is 1.5 to 4.0 MPa, and the time For 60 to 150 minutes.

  The polyphenylene ether resin composition according to this embodiment is a polyphenylene ether resin composition having excellent dielectric properties of polyphenylene ether and excellent in heat resistance and flame retardancy of a cured product. For this reason, the metal-clad laminated board using the prepreg obtained using the polyphenylene ether resin composition can produce a printed wiring board excellent in dielectric properties, heat resistance, and flame retardancy.

  And the printed wiring board which provided the conductor pattern as a circuit on the surface of a laminated body can be obtained by carrying out the etching process etc. of the metal foil on the surface of the produced laminated body. The printed wiring board thus obtained is excellent in dielectric properties, heat resistance, and flame retardancy.

  The present invention will be described more specifically with reference to the following examples. However, the scope of the present invention is not limited to these examples.

[Synthesis of Modified Polyphenylene Ether A (Modified PPE A)]
First, a halogenated organophosphorus compound used for reacting with polyphenylene ether to form a modified polyphenylene ether was synthesized.

(Synthesis of halogenated organophosphorus compounds)
Ethylphenyl-p-vinylbenzylphosphonate as a starting material (organophosphorus compound) was reacted with oxalyl chloride as a halogenating agent. By doing so, phenyl-p-vinylbenzylphosphonochloride was obtained as a halogenated organophosphorus compound having an unsaturated double bond at the terminal. The phenyl-p-vinylbenzylphosphonochloride is a halogenated organophosphorus compound represented by the formula (8), wherein X is a chlorine atom that is a halogen atom, and R ⁵ is a phenyl group that is an aryl group. , R ⁶ is a p-vinylbenzyl group which is an aryl group.

  More specifically, it was synthesized as follows.

  After charging 22.92 g of ethylphenyl-p-vinylbenzylphosphonate into a four-necked flask, the inside of the four-necked flask was purged with nitrogen. Next, 0.4 mL of DMF was added as a catalyst in the four-necked flask. Thereafter, while the inside of the four-necked flask was replaced with nitrogen, the four-necked flask was cooled in an ice bath, and 13.68 mL of oxalyl chloride as a halogenating agent was added. Then, it heated until the temperature of the liquid in a four neck flask became 35 degreeC, and stirred for 2 hours with the liquid temperature. By doing so, ethylphenyl-p-vinylbenzylphosphonate was reacted with oxalyl chloride. The completion of this reaction was confirmed by gas chromatography (GC). The solvent and unreacted raw material were removed by concentrating the reaction liquid H1 obtained by the stirring. By doing so, 19.31 g of light yellowish white liquid was obtained. The yield was about 100%.

The obtained liquid was analyzed by ¹ H-NMR (400 MHz, CDCl ₃ , TMS). The ¹ H-NMR spectrum data of this liquid was δ: 5.2 (1H, d, 12.8), 5.7 (1H, d, 16), 7.5 (2H, t, 16). It was. This confirmed that the obtained liquid was phenyl-p-vinylbenzylphosphonochloride.

(Modification of polyphenylene ether: Synthesis of modified polyphenylene ether A)
The phenyl-p-vinylbenzylphosphonochloride thus obtained was reacted with polyphenylene ether. By doing so, a modified polyphenylene ether was obtained. The polyphenylene ether used here is a polyphenylene ether represented by the formula (10), where m is 2, T is an alkylene group dimethylmethylene group (2,2-propylene group), and L is It is a polyphenylene ether which is a polyphenylene ether chain represented by the formula (2). The polyphenylene ether chain represented by the formula (2) is a methyl group in which n is 5, R ¹ and R ³ are each a hydrogen atom, and R ² and R ⁴ are each an alkyl group. Polyphenylene ether chain.

  More specifically, it was synthesized as follows.

  In 200 mL of 1,2-dichloroethane as a solvent, 53.2 g of the polyphenylene ether (SABIC Innovative Plastics, number average molecular weight: 1500) was dissolved. 12.24 mL of triethylamine as a catalyst was added to the obtained solution. And the reaction liquid H1 obtained above was dripped at the solution which added the catalyst. Then, it heated until the temperature of the liquid became 40 degreeC, and stirred for 3 hours with the liquid temperature. Then, it stirred at room temperature overnight. The reaction solution obtained by the stirring was dropped into methanol and stirred for 1 hour to precipitate a precipitate. That is, the product contained in the obtained reaction solution was reprecipitated with methanol. Then, the precipitate was taken out by filtration, washed with 2 L of methanol, and then dried under reduced pressure. By doing so, 51.9 g of light yellow powder was obtained. The yield was about 74.3%.

The obtained powder was analyzed by ¹ H-NMR (400 MHz, CDCl ₃ , TMS). The ¹ H-NMR spectrum data of this powder is δ: 5.2 (1H, d, 12.8), 5.7 (1H, d, 16), 7.5 (2H, t, 16). there were. Thus, the obtained powder was a modified polyphenyl represented by the formula (1) (arylphenylene ether, where m is 2 and T is an alkylene group, a dimethylmethylene group (2,2-propylene group). It was confirmed that L is a polyphenylene ether which is a polyphenylene ether chain represented by the formula (2), and M is a modified polyphenylene ether which is a group represented by the formula (3). The polyphenylene ether chain represented by the formula (2) is a polyphenylene ether chain in which n is 5, R ¹ and R ³ are each a hydrogen atom, and R ² and R ⁴ are each a methyl group that is an alkyl group. also it was confirmed that. also, here, a group represented by the formula (3) is, R ⁵ is a phenyl group an aryl group, R ⁶ is, is an aryl group p- vinylbenzyl It was also confirmed that it is. That is, represented by formula (3), R ⁵ is a phenyl group an aryl group, R ⁶ has a group which is p- vinylbenzyl group is an aryl group, the terminus It was confirmed that a modified polyphenylene ether was obtained, and the number average molecular weight of the obtained modified polyphenylene ether was 2000. The number average molecular weight was determined using gel permeation chromatography (GPC). It is a measured value.

[Synthesis of Modified Polyphenylene Ether B (Modified PPE B)]
The modified polyphenylene ether B was synthesized in the same manner as the modified polyphenylene ether A except that the molecular weight of the polyphenylene ether used in the synthesis of the modified polyphenylene ether B was 3500. Since the modified polyphenylene ether B has the same functional group as the modified polyphenylene ether A, the ¹ H-NMR spectrum data was almost the same. Moreover, the number average molecular weight of the obtained modified polyphenylene ether was 4000.

[Synthesis of Modified Polyphenylene Ether C (Modified PPEC)]
First, a halogenated organophosphorus compound used for reacting with polyphenylene ether to form a modified polyphenylene ether was synthesized.

(Synthesis of halogenated organophosphorus compounds)
Diethoxy-p-vinylbenzylphosphonate as a starting material (organic phosphorus compound) was reacted with oxalyl chloride as a halogenating agent. By doing so, ethoxy-p-vinylbenzyl phosphonochloride was obtained as a halogenated organophosphorus compound having an unsaturated double bond at the terminal. Note that ethoxy-p-vinylbenzylphosphonochloride is a halogenated organophosphorus compound represented by the formula (8), wherein X is a chlorine atom which is a halogen atom, and R ⁵ is an ethoxy group which is an alkoxy group. , R ⁶ is a p-vinylbenzyl group which is an aryl group.

  More specifically, it was synthesized as follows.

  After charging 50.8 g of diethoxy-p-vinylbenzyl phosphonate into a four-necked flask, the inside of the four-necked flask was purged with nitrogen. Next, 1 mL of DMF was added as a catalyst in the four-necked flask. Thereafter, the inside of the four-necked flask was cooled while being purged with nitrogen, and 34.32 mL of oxalyl chloride as a halogenating agent was added. Then, it heated until the temperature of the liquid in a four neck flask became 35 degreeC, and stirred for 2 hours with the liquid temperature. By doing so, diethoxy-p-vinylbenzyl phosphonate was reacted with oxalyl chloride. The completion of this reaction was confirmed by gas chromatography (GC). The solvent and unreacted raw material were removed by concentrating the reaction liquid H2 obtained by the stirring. By doing so, 50.8 g of light yellowish white liquid was obtained. The yield was about 100%.

The obtained liquid was analyzed by ¹ H-NMR (400 MHz, CDCl ₃ , TMS). The ¹ H-NMR spectral data of this liquid are δ: 1.1 (3H, dd, 5.8), 5.2 (1H, d, 2.4), 5.7 (1H, d, 6. 8) and 7.3 (4H, d, 7.6). This confirmed that the resulting liquid was ethoxy-p-vinylbenzylphosphonochloride.

(Modification of polyphenylene ether: Synthesis of modified polyphenylene ether C)
The phenyl-p-vinylbenzylphosphonochloride thus obtained was reacted with the same polyphenylene ether used in the synthesis of the modified polyphenylene ether A. By doing so, a modified polyphenylene ether was obtained.

  More specifically, it was synthesized as follows.

  In 400 mL of 1,2-dichloroethane as a solvent, 130 g of the polyphenylene ether (manufactured by SABIC Innovative Plastics, number average molecular weight: 1500) was dissolved. 30.63 mL of triethylamine as a catalyst was added to the obtained solution. And the reaction liquid H2 obtained above was dripped at the solution which added the catalyst. Then, it heated until the temperature of the liquid became 40 degreeC, and stirred for 3 hours with the liquid temperature. Then, it stirred at room temperature overnight. The reaction solution obtained by the stirring was dropped into methanol and stirred for 1 hour to precipitate a precipitate. That is, the product contained in the obtained reaction solution was reprecipitated with methanol. Then, the precipitate was taken out by filtration, washed with 2 L of methanol, and then dried under reduced pressure. By doing so, 150 g of light yellow powder was obtained. The yield was about 91.0%.

The obtained powder was analyzed by ¹ H-NMR (400 MHz, CDCl ₃ , TMS). The ¹ H-NMR spectral data of this powder are δ: 1.1 (3H, dd, 5.8), 5.2 (1H, d, 2.4), 5.7 (1H, d, 6 .8), 7.3 (4H, d, 7.6). Thus, the obtained powder is a modified polyphenylene ether represented by the formula (1), where m is 2, T is an alkylene group dimethylmethylene group (2,2-propylene group), and L is It was confirmed that polyphenylene ether, which is a polyphenylene ether chain represented by the formula (2), and M is a modified polyphenylene ether which is a group represented by the formula (3). The polyphenylene ether chain represented by the formula (2) is a methyl group in which n is 5, R ¹ and R ³ are each a hydrogen atom, and R ² and R ⁴ are each an alkyl group. It was also confirmed that it was a polyphenylene ether chain. It was also confirmed that in the group represented by the formula (3), R ⁵ is an ethoxy group that is an alkoxy group, and R ⁶ is a p-vinylbenzyl group that is an aryl group. That is, a modified polyphenylene ether represented by the formula (3), in which R ⁵ is an alkoxy group, which is an alkoxy group, and R ⁶ is a p-vinylbenzyl group, which is an aryl group, is obtained. Was confirmed. Moreover, the number average molecular weight of the obtained modified polyphenylene ether was 1900.

[Synthesis of Modified Polyphenylene Ether D (Modified PPE D)]
First, a halogenated organophosphorus compound used for reacting with polyphenylene ether to form a modified polyphenylene ether was synthesized.

(Synthesis of halogenated organophosphorus compounds)
Phenyldichlorophosphine as a starting material (dihalogenated organophosphorus compound) was reacted with 1-octen-3-ol as an organic compound. By doing so, 1-ethenehexylphenylphosphine chloride was obtained as a halogenated organophosphorus compound having an unsaturated double bond at the terminal. 1-ethenehexylphenylphosphine chloride is a halogenated organophosphorus compound represented by the formula (9), wherein X is a chlorine atom that is a halogen atom, R ⁷ is a phenyl group that is an aryl group, R ⁸ is a compound which is a 1-ethenehercyloxy group which is an alkoxy group.

  More specifically, it was synthesized as follows.

  Into a nitrogen-substituted four-necked flask, 40 mL of 1,2-dichloroethane as a solvent, 5.4 mL of phenyldichlorophosphine, and 5.6 mL of triethylamine as a catalyst were added dropwise, and 6.1 mL of 1-octen-3-ol was added dropwise. did. Then, it stirred at room temperature for 2 hours. By doing so, phenyldichlorophosphine was reacted with 1-octen-3-ol. The completion of this reaction was confirmed by gas chromatography (GC). The solvent and unreacted raw material were removed by concentrating the reaction solution H3 obtained by the stirring. By doing so, 10.76 g of light yellowish white liquid was obtained. The yield was about 100%.

The obtained liquid was analyzed by ¹ H-NMR (400 MHz, CDCl ₃ , TMS). The ¹ H-NMR spectrum data of this liquid was δ: 4.3 (1H, dd, 8.8), 7.0 (1H, d, 3.4), 7.8 (1H, s). It was. This confirmed that the resulting liquid was 1-ethenehexylphenylphosphine chloride.

(Modification of polyphenylene ether: Synthesis of modified polyphenylene ether D)
The 1-ethenehexylphenylphosphine chloride thus obtained was reacted with the same polyphenylene ether used in the synthesis of the modified polyphenylene ether A. By doing so, a modified polyphenylene ether was obtained.

  More specifically, it was synthesized as follows.

  26.7 g of the polyphenylene ether (manufactured by SABIC Innovative Plastics, number average molecular weight: 1500) was dissolved in 80 mL of 1,2-dichloroethane as a solvent. And the obtained solution was dripped at the reaction liquid H3 obtained above. Then, it stirred for 2 hours. The reaction solution obtained by the stirring was dropped into 600 mL of methanol to precipitate a precipitate. That is, the product contained in the obtained reaction solution was reprecipitated with methanol. Then, the precipitate was taken out by filtration, washed with 150 mL of methanol, and then dried under reduced pressure. By doing so, 26.78 g of a pale yellow powder was obtained. The yield was about 76.3%.

The obtained powder was analyzed by ¹ H-NMR (400 MHz, CDCl ₃ , TMS). The ¹ H-NMR spectrum data of this powder is δ: 4.3 (1H, dd, 8.8), 7.0 (1H, d, 3.4), 7.8 (1H, s). there were. Thus, the obtained powder is a modified polyphenylene ether represented by the formula (1), where m is 2, T is an alkylene group dimethylmethylene group (2,2-propylene group), and L is It was confirmed that polyphenylene ether, which is a polyphenylene ether chain represented by the formula (2), and M is a modified polyphenylene ether which is a group represented by the formula (4). The polyphenylene ether chain represented by the formula (2) is a methyl group in which n is 5, R ¹ and R ³ are each a hydrogen atom, and R ² and R ⁴ are each an alkyl group. It was also confirmed that it was a polyphenylene ether chain. In addition, it was also confirmed that the group represented by the formula (4) in this case is that R ⁷ is a phenyl group that is an aryl group, and R ⁸ is a 1-ethenehelyloxy group that is an alkoxy group. . That is, a modified polyphenylene ether represented by the formula (4), in which R ⁷ is a phenyl group that is an aryl group, and R ⁸ is a 1-ethenehercyloxy group that is an alkoxy group is obtained. I was able to confirm. Moreover, the number average molecular weight of the obtained modified polyphenylene ether was 2000.

<Examples 1-9, Comparative Examples 1-3>
[Preparation of resin composition]
In this example, each component used when preparing the resin composition will be described.

(Polyphenylene ether)
Modified PPE A: a modified polyphenylene ether represented by the formula (3), wherein R ⁵ is a phenyl group which is an aryl group, and R ⁶ is a group having a p-vinylbenzyl group which is an aryl group at the terminal, number average Molecular weight 2000
Modified PPE B: a modified polyphenylene ether represented by the formula (3), wherein R ⁵ is a phenyl group which is an aryl group, and R ⁶ is a p-vinylbenzyl group which is an aryl group at the terminal, number average Molecular weight 4000
Modified PPE C: a modified polyphenylene ether represented by the formula (3), wherein R ⁵ is an ethoxy group that is an alkoxy group, and R ⁶ is a p-vinylbenzyl group that is an aryl group at the terminal, number average Molecular weight 2000
Modified PPE D: Modified polyphenylene ether represented by formula (4), wherein R ⁷ is a phenyl group that is an aryl group, and R ⁸ is a group that is a 1-ethenehercyloxy group that is an alkoxy group. PPE E: a modified polyphenylene ether synthesized by the method described in paragraph [0036] of JP-A No. 2004-339328, having no P in the molecule and having an unsaturated double bond at the end, specifically Modified polyphenylene ether synthesized as follows was used. First, 200 g of polyphenylene ether (number average molecular weight: about 2400), 14.51 g of chloromethylstyrene, tetra-n- were added to a 1 liter three-necked flask equipped with a temperature controller, a stirrer, cooling equipment and a dropping funnel. After adding 0.818 g of butylammonium bromide and 400 g of toluene, the mixture was stirred and dissolved. Thereafter, the liquid temperature was raised to 75 ° C., an aqueous sodium hydroxide solution (11 g of sodium hydroxide / 11 g of water) was added dropwise over 20 minutes, and stirring was further continued at 75 ° C. for 4 hours. Next, after neutralizing the contents of the flask with a 10% aqueous hydrochloric acid solution, a large amount of methanol was added to reprecipitate the ethenylbenzylated modified polyphenylene ether compound, followed by filtration. The filtrate was washed 3 times with a mixture of methanol 80 and water 20 and then treated under reduced pressure at 80 ° C. for 3 hours to take out ethenylbenzylated modified polyphenylene ether from which the solvent and water had been removed. This was designated as modified PPE E.

Unmodified PPE: Polyphenylene ether (SA120 manufactured by SABIC Innovative Plastics)
(Heat-crosslinking type curing agent)
TAIC: triallyl isocyanurate (manufactured by Nippon Kasei Co., Ltd.)
DCP: Tricyclodecane dimethanol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
A-DCP: Tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
(Other ingredients)
Initiator: 1,3-bis (butylperoxyisopropyl) benzene (Perbutyl P from NOF Corporation)
Filler: Surface treated silica (SC2500SVJ manufactured by Admatechs Co., Ltd.)
Flame retardant: Aromatic condensed phosphate ester (PX200 manufactured by Daihachi Chemical Industry Co., Ltd.)
[Preparation method]
First, each component was added to toluene and mixed at a blending ratio shown in Table 1 so that the solid content concentration was 60% by mass. The mixture was heated to 80 ° C. and stirred at 80 ° C. for 30 minutes to obtain a varnish-like resin composition (resin varnish).

  Next, the obtained resin varnish was impregnated into a glass cloth (# 2116 type, WEA116E, E glass manufactured by Nitto Boseki Co., Ltd.) and then heated and dried at 150 ° C. for about 3 to 8 minutes to obtain a prepreg. . In that case, it adjusted so that content (resin content) of resin components, such as polyphenylene ether and a heat-crosslinking-type hardening | curing agent, might be about 50 mass%.

  Then, a predetermined number of the obtained prepregs were stacked and laminated, and heated and pressed under the conditions of a temperature of 200 ° C., 2 hours, and a pressure of 3 MPa to obtain an evaluation substrate having a predetermined thickness.

  Specifically, for example, an evaluation board having a thickness of about 0.8 mm was obtained by stacking six obtained prepregs on top of each other.

  Each prepreg and evaluation substrate prepared as described above were evaluated by the following method.

[Dielectric properties (dielectric constant and dielectric loss tangent)]
The dielectric constant and dielectric loss tangent of the evaluation substrate at 10 GHz were measured by a cavity resonator perturbation method. Specifically, the dielectric constant and dielectric loss tangent of the evaluation substrate at 10 GHz were measured using a network analyzer (N5230A manufactured by Agilent Technologies).

[Glass transition temperature (Tg)]
The Tg of the prepreg was measured using a viscoelastic spectrometer “DMS100” manufactured by Seiko Instruments Inc. At this time, dynamic viscoelasticity measurement (DMA) was performed with a bending module at a frequency of 10 Hz, and the temperature at which tan δ was maximized when the temperature was raised from room temperature to 280 ° C. at a temperature rising rate of 5 ° C./min was Tg. did.

[Flame retardance]
A test piece having a length of 125 mm and a width of 12.5 mm was cut out from the evaluation substrate. Then, this test piece was evaluated according to "Test for Flammability of Plastic Materials-UL 94" of Underwriters Laboratories.

[Heat-resistant]
The heat resistance was measured by a method based on JIS C 6481. Specifically, the evaluation substrate was subjected to a pressure cooker test (PCT) at 121 ° C., 2 atm (0.2 MPa), and 2 hours, and was performed for each sample. It was immersed for 20 seconds, and the presence or absence of occurrence of mesling or swelling was visually observed. If the occurrence of measling or swelling could not be confirmed, it was evaluated as “◯”, and if it was confirmed, it was evaluated as “x”.

  The results in the above evaluations are shown in Table 1.

  As can be seen from Table 1, in the case of a resin composition containing a modified polyphenylene ether represented by formula (1), that is, a modified polyphenylene ether containing phosphorus in the molecule and having an unsaturated double bond at the terminal (Examples) 1 to 9) have an unsaturated double bond at the end, but use a modified polyphenylene ether containing no phosphorus in the molecule (Comparative Examples 1 and 3) or a non-modified polyphenylene ether (Comparative Example 2). ), A cured product having excellent dielectric properties, heat resistance, and flame retardancy can be obtained.

  As described above, the present specification discloses various modes of technology, of which the main technologies are summarized below.

  The polyphenylene ether resin composition according to one embodiment of the present invention includes a modified polyphenylene ether represented by the formula (1) and a heat-crosslinking curing agent.

  In the above formula (1), m represents 1 or 2, L represents a polyphenylene ether chain represented by the above formula (2), M represents a hydrogen atom, a group represented by the above formula (3) Or a group represented by the above formula (4), and when m is 1, M is not a hydrogen atom, and when m is 2, at least one of the two M is a hydrogen atom. In addition, T represents a hydrogen atom when m is 1, and represents an alkylene group or a group represented by the above formula (5) when m is 2.

In the above formula (2), n represents a positive integer of 50 or less, and R ¹ , R ² , R ³ , and R ⁴ are each independently a hydrogen atom, an alkyl group, an alkenyl group, alkynyl. A group, a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group;

In the formula (3), R ⁵ and R ⁶ each independently represent an alkyl group, an alkenyl group, an alkoxy group, an aryl group, or an amino group, and at least one of R ⁵ and R ⁶ Either one has an unsaturated double bond at the terminal.

In the formula (4), R ⁷ and R ⁸ each independently represent an alkyl group, an alkenyl group, an alkoxy group, an aryl group, or an amino group, and at least one of R ⁷ and R ⁸ Either one has an unsaturated double bond at the terminal.

In the above formula (5), R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently a hydrogen atom, alkyl group, alkenyl group, alkynyl group, formyl group, alkylcarbonyl group, alkenylcarbonyl group. Or an alkynylcarbonyl group.

  According to such a structure, the polyphenylene ether resin composition excellent in the heat resistance and flame retardance of hardened | cured material can be provided, maintaining the outstanding dielectric characteristic which polyphenylene ether has.

  In the polyphenylene ether resin composition, the content of the modified polyphenylene ether is preferably 30 to 90% by mass with respect to the total amount of the modified polyphenylene ether and the thermally crosslinkable curing agent.

  According to such a configuration, it is possible to provide a polyphenylene ether resin composition that is superior in heat resistance and flame retardancy of a cured product.

  In the polyphenylene ether resin composition, the thermally crosslinkable curing agent is a trialkenyl isocyanurate compound, a polyfunctional acrylate compound having two or more acryl groups in the molecule, and two or more methacryl groups in the molecule. It is preferably at least one selected from the group consisting of polyfunctional methacrylate compounds.

  According to such a structure, the polyphenylene ether resin composition excellent in heat resistance of hardened | cured material can be provided. This is considered due to the fact that the curability of the thermally crosslinkable curing agent and the modified polyphenylene ether can be further enhanced.

  In the polyphenylene ether resin composition, the modified polyphenylene ether preferably has a number average molecular weight of 1000 to 7000.

  According to such a structure, the polyphenylene ether resin composition excellent in the flame retardance of hardened | cured material can be provided. This is presumably because the modified polyphenylene ether has a relatively low molecular weight, so that the concentration of phosphorus, which is a flame retardant component, increases. In that case, since it has an unsaturated double bond at the terminal of the modified polyphenylene ether, it is excellent in curability, and even with a relatively low molecular weight modified polyphenylene ether, flame resistance is suppressed while suppressing a decrease in heat resistance. Can be increased.

  The polyphenylene ether resin composition preferably further includes an inorganic filler.

  According to such a configuration, performance required for those manufactured using the resin composition, for example, performance such as heat resistance, flame retardancy, low thermal expansion coefficient, and toughness required for a laminated board, etc. Can be increased.

  A resin varnish according to another embodiment of the present invention is a resin varnish containing the polyphenylene ether resin composition and a solvent.

  According to such a configuration, a resin varnish excellent in dielectric properties, heat resistance of the cured product and flame retardancy can be obtained.

  The prepreg according to another embodiment of the present invention is a prepreg obtained by impregnating a fibrous base material with the resin varnish.

  According to such a configuration, it is possible to obtain a metal-clad laminate and a printed wiring board that are excellent in dielectric properties, heat resistance, and flame retardancy.

  Moreover, the metal-clad laminate according to another aspect of the present invention is a metal-clad laminate obtained by laminating a metal foil on the prepreg and then heat-pressing it.

  According to such a configuration, a metal-clad laminate having excellent dielectric properties, heat resistance and flame retardancy can be obtained.

  Moreover, the printed wiring board which concerns on the other one aspect | mode of this invention is a printed wiring board manufactured using the said prepreg.

  According to such a configuration, a printed wiring board excellent in dielectric properties, heat resistance and flame retardancy can be obtained.

Claims (9)

A modified polyphenylene ether represented by the following formula (1);
A polyphenylene ether resin composition comprising a thermally crosslinkable curing agent.

[In the formula (1), m represents 1 or 2, L represents a polyphenylene ether chain represented by the following formula (2), M represents a hydrogen atom, a group represented by the following formula (3) Or a group represented by the following formula (4), and when m is 1, M is not a hydrogen atom, and when m is 2, at least one of the two M is a hydrogen atom. In addition, T represents a hydrogen atom when m is 1, and an alkylene group or a group represented by the following formula (5) when m is 2. ]

[In the formula (2), n represents a positive integer of 50 or less, and R ¹ , R ² , R ³ , and R ⁴ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, A formyl group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group; ]

[In Formula (3), R ⁵ and R ⁶ each independently represent an alkyl group, an alkenyl group, an alkoxy group, an aryl group, or an amino group, and at least one of R ⁵ and R ⁶ One has an unsaturated double bond at the end. ]

[In Formula (4), R ⁷ and R ⁸ each independently represent an alkyl group, an alkenyl group, an alkoxy group, an aryl group, or an amino group, and at least one of R ⁷ and R ⁸ One has an unsaturated double bond at the end. ]

[In the formula (5), R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group, or An alkynylcarbonyl group is shown. ]   2. The polyphenylene ether resin composition according to claim 1, wherein a content ratio of the modified polyphenylene ether is 30 to 90 mass% with respect to a total amount of the modified polyphenylene ether and the thermally crosslinkable curing agent.   The thermally crosslinkable curing agent is selected from the group consisting of a trialkenyl isocyanurate compound, a polyfunctional acrylate compound having two or more acrylic groups in the molecule, and a polyfunctional methacrylate compound having two or more methacryl groups in the molecule. The polyphenylene ether resin composition according to claim 1, wherein the polyphenylene ether resin composition is at least one selected from the group consisting of:   The polyphenylene ether resin composition according to any one of claims 1 to 3, wherein the number average molecular weight of the modified polyphenylene ether is 1000 to 7000.   The polyphenylene ether resin composition according to any one of claims 1 to 4, further comprising an inorganic filler.   A resin varnish containing the polyphenylene ether resin composition according to any one of claims 1 to 5 and a solvent.   A prepreg obtained by impregnating a fibrous base material with the resin varnish according to claim 6.   A metal-clad laminate obtained by laminating a metal foil on the prepreg according to claim 7 and heating and pressing.   A printed wiring board manufactured using the prepreg according to claim 7.