JP6172520B2 - Resin composition, prepreg, metal-clad laminate, and printed wiring board - Google Patents

Description

  The present invention relates to a resin composition, a prepreg using the resin composition, a metal-clad laminate using the prepreg, and a printed wiring board using the metal-clad laminate.

  2. Description of the Related Art In recent years, with various types of electronic equipment, mounting techniques such as higher integration of semiconductor devices to be mounted, higher density of wiring, and multilayering have rapidly progressed as the amount of information processing has increased. Substrate materials used to construct printed wiring board base materials used in various electronic devices are required to have a low dielectric constant and dielectric loss tangent in order to increase signal transmission speed and reduce loss during signal transmission. It is done.

  Polyphenylene ether (PPE) has excellent dielectric properties such as dielectric constant and dielectric loss tangent, and is also known to have excellent dielectric properties such as dielectric constant and dielectric loss tangent even in the high frequency band (high frequency region) from MHz to GHz. It has been. For this reason, use of polyphenylene ether as, for example, a molding material for high frequency has been studied. More specifically, it is preferably used as a substrate material for constituting a substrate of a printed wiring board provided in an electronic device using a high frequency band.

  On the other hand, when used as a molding material such as a substrate material, it is required not only to have excellent dielectric properties but also to have excellent flame retardancy. In this regard, resin compositions used as molding materials such as substrate materials generally include halogen flame retardants such as brominated flame retardants and halogen-containing epoxy resins such as tetrabromobisphenol A type epoxy resins. In many cases, a compound containing was added.

  However, a resin composition containing such a halogen-containing compound will contain halogen in its fallout, and may generate harmful substances such as hydrogen halide during combustion. Concerns have been pointed out. Against this background, molding materials such as substrate materials are required to be free of halogen, so-called halogen-free.

  Examples of such a halogen-free resin composition include the resin composition described in Patent Document 1.

  Patent Document 1 describes a polyphenylene ether resin composition in which a polyphenylene ether resin having a predetermined terminal structure, a crosslinkable curing agent, a phosphinate flame retardant, and a curing catalyst are blended.

JP 2010-53178 A

  The resin composition described in Patent Document 1 achieves halogen-free by using not a halogen flame retardant but a phosphorus flame retardant as a flame retardant. Patent Document 1 discloses that the resin compositions described therein are excellent in heat resistance and flame retardancy of a cured product and have excellent dielectric properties.

  In addition, the substrate material for constituting the substrate of the printed wiring board is required to have various characteristics in order to cope with the progress of mounting technology such as higher integration of semiconductor devices, higher density of wiring, and multilayering. It is growing. Specifically, it is required to further improve the heat resistance and flame retardancy of the cured product while maintaining the excellent dielectric properties of polyphenylene ether.

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

  In order to increase the flame retardancy of the cured resin composition, it is conceivable to increase the content of the flame retardant in the resin composition. However, according to studies by the present inventors, merely increasing the content of the flame retardant sometimes reduces the dielectric properties and the heat resistance of the cured product. As a result of various studies, the present inventors have found that the composition of the flame retardant is influenced by the flame retardancy of the cured product. As a result of further examination of this influence, it has been found that the above object can be achieved by the present invention described below.

  The resin composition according to one embodiment of the present invention includes a modified polyphenylene ether compound terminal-modified with a substituent having a carbon-carbon unsaturated double bond, and a crosslinked type having a carbon-carbon unsaturated double bond in the molecule. Contains a curing agent and a flame retardant. The flame retardant contains a compatible phosphorus compound that is compatible with the mixture of the modified polyphenylene ether compound and the crosslinkable curing agent, and an incompatible phosphorus compound that is not compatible with the mixture.

  In the resin composition, the content ratio of the compatible phosphorus compound and the incompatible phosphorus compound is preferably 20:80 to 80:20 by mass ratio.

  Moreover, in the said resin composition, content of a phosphorus atom is 1.8-5.2 mass parts with respect to a total of 100 mass parts of an organic component (except the said flame retardant) and the said flame retardant. Is preferred.

  In the resin composition, the compatible phosphorus compound is preferably at least one selected from the group consisting of a phosphate ester compound, a phosphazene compound, a phosphite compound, and a phosphine compound. The incompatible phosphorus compound is preferably at least one selected from the group consisting of phosphinate compounds, polyphosphate compounds, and phosphonium salt compounds.

  In the resin composition, the cross-linking curing agent preferably has a weight average molecular weight of 100 to 5000 and has an average of 1 to 20 carbon-carbon unsaturated double bonds in one molecule.

  In the resin composition, the crosslinking curing agent is 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. And at least one selected from the group consisting of polyfunctional vinyl compounds having two or more vinyl groups in the molecule.

  In the resin composition, the modified polyphenylene ether compound preferably has a weight average molecular weight of 500 to 5000 and has an average of 1 to 5 substituents per molecule.

  In the resin composition, the substituent at the terminal of the modified polyphenylene ether compound is preferably a substituent having at least one selected from the group consisting of a vinylbenzyl group, an acrylate group, and a methacrylate group.

  In the resin composition, the content ratio of the modified polyphenylene ether compound and the cross-linking curing agent is preferably 90:10 to 30:70 by mass ratio.

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

  In addition, the metal-clad laminate according to another aspect of the present invention is obtained by laminating a metal foil on the prepreg and heating and pressing.

  The printed wiring board according to another aspect of the present invention is obtained by forming a circuit by partially removing the metal foil on the surface of the metal-clad laminate.

  ADVANTAGE OF THE INVENTION According to this invention, the 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, according to this invention, the prepreg using the said resin composition, the metal-clad laminated board using the said prepreg, and the printed wiring board using the said metal-clad laminated board are provided.

  Hereinafter, although the embodiment concerning the present invention is described, the present invention is not limited to these.

  The resin composition according to one embodiment of the present invention includes a modified polyphenylene ether compound terminal-modified with a substituent having a carbon-carbon unsaturated double bond, and a crosslinked type having a carbon-carbon unsaturated double bond in the molecule. Contains a curing agent and a flame retardant.

  First, the modified polyphenylene ether compound used in the present embodiment is not particularly limited as long as it is a polyphenylene ether that is terminal-modified with a substituent having a carbon-carbon unsaturated double bond.

  The substituent having a carbon-carbon unsaturated double bond is not particularly limited. Examples of the substituent include a substituent represented by the following formula (1).

In formula (1), n shows 0-10. Z represents an arylene group. R ^{1 to} R ³ are independent of each other. That is, R ^{1 to} R ³ may be the same group or different groups. R ^{1 to} R ³ represent a hydrogen atom or an alkyl group.

  In the formula (1), when n is 0, Z is directly bonded to the terminal of the polyphenylene ether.

  This arylene group is not particularly limited. Specific examples include a monocyclic aromatic group such as a phenylene group and a polycyclic aromatic group in which the aromatic is not a monocyclic but a polycyclic aromatic such as a naphthalene ring. The arylene group also includes derivatives in which a hydrogen atom bonded to an aromatic ring is substituted with a functional group such as an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group. Moreover, the said 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.

  More specifically, examples of the substituent include vinylbenzyl groups (ethenylbenzyl group) such as p-ethenylbenzyl group and m-ethenylbenzyl group, vinylphenyl group, acrylate group, and methacrylate group. Is mentioned.

  Preferable specific examples of the substituent represented by the above formula (1) include a functional group containing a vinylbenzyl group. Specific examples include at least one substituent selected from the following formula (2) or formula (3).

  Examples of the other substituent having a carbon-carbon unsaturated double bond that is terminally modified in the modified polyphenylene ether used in the present embodiment include a (meth) acrylate group, and is represented by the following formula (4), for example. .

In formula (4), R ⁸ represents a hydrogen atom or an alkyl group. The alkyl group is not particularly limited, and for example, an alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 10 carbon atoms is more preferable. Specific examples include a methyl group, an ethyl group, a propyl group, a hexyl group, and a decyl group.

  Moreover, the modified polyphenylene ether according to the present embodiment has a polyphenylene ether chain in the molecule, and preferably has, for example, a repeating unit represented by the following formula (5) in the molecule.

Moreover, in Formula (5), m shows 1-50. R ^{4 to} R ⁷ are independent of each other. That is, R ^{4 to} R ⁷ may be the same group or different groups. R ^{4 to} R ⁷ 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.

Specific examples of the functional groups listed in R ^{4 to} R ⁷ 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.

  The weight average molecular weight (Mw) of the modified polyphenylene ether compound used in the present embodiment is not particularly limited. Specifically, it is preferably 500 to 5000, more preferably 800 to 4000, and still more preferably 1000 to 3000. In addition, here, the weight average molecular weight should just be measured by the general molecular weight measuring method, and the value measured using gel permeation chromatography (GPC) etc. are mentioned specifically ,. Further, when the modified polyphenylene ether compound has a repeating unit represented by the formula (2) in the molecule, m is a numerical value such that the weight average molecular weight of the modified polyphenylene ether compound is within such a range. It is preferable that Specifically, m is preferably 1 to 50.

  When the weight average molecular weight of the modified polyphenylene ether compound is within such a range, the polyphenylene ether has excellent dielectric properties and not only is excellent in the heat resistance of the cured product, but also is excellent in moldability. . This is considered to be due to the following. In the case of ordinary polyphenylene ether, if the weight average molecular weight is within such a range, the heat resistance of the cured product tends to be lowered because it has a relatively low molecular weight. In this regard, the modified polyphenylene ether compound according to the present embodiment has an unsaturated double bond at the terminal, so that it is considered that a cured product having sufficiently high heat resistance can be obtained. Further, when the weight average molecular weight of the modified polyphenylene ether compound is within such a range, it is considered that the moldability is excellent because it has a relatively low molecular weight. Therefore, it is considered that such a modified polyphenylene ether compound is excellent not only in the heat resistance of the cured product but also excellent in moldability.

  Further, the average number of substituents (number of terminal functional groups) at the molecular end per molecule of the modified polyphenylene ether in the modified polyphenylene ether compound used in the present embodiment is not particularly limited. Specifically, the number is preferably 1 to 5, more preferably 1 to 3, and still more preferably 1.5 to 3. When the number of terminal functional groups is too small, it is difficult to obtain a cured product having sufficient heat resistance. Moreover, when there are too many terminal functional groups, reactivity will become high too much, for example, the preservability of a resin composition may fall, or malfunctions, such as the fluidity | liquidity of a resin composition falling, may generate | occur | produce. . That is, when such a modified polyphenylene ether is used, due to insufficient fluidity, for example, molding defects such as generation of voids during multilayer molding occur, and it is difficult to obtain a highly reliable printed wiring board. There was a risk of problems.

  In addition, the number of terminal functional groups of the modified polyphenylene ether compound includes a numerical value representing an average value of the substituents per molecule of all the modified polyphenylene ether compounds present in 1 mol of the modified polyphenylene ether compound. The number of terminal functional groups can be measured, for example, by measuring the number of hydroxyl groups remaining in the obtained modified polyphenylene ether compound and calculating the amount of decrease from the number of hydroxyl groups of the polyphenylene ether before modification. The decrease from the number of hydroxyl groups in the polyphenylene ether before modification is the number of terminal functional groups. The method for measuring the number of hydroxyl groups remaining in the modified polyphenylene ether compound is to add a quaternary ammonium salt (tetraethylammonium hydroxide) associated with hydroxyl groups to the solution of the modified polyphenylene ether compound and measure the UV absorbance of the mixed solution. It can be obtained by doing.

  Moreover, the intrinsic viscosity of the modified polyphenylene ether compound used in the present embodiment is not particularly limited. Specifically, it may be 0.03 to 0.12 dl / g, preferably 0.04 to 0.11 dl / g, and more preferably 0.06 to 0.095 dl / g. . If the intrinsic viscosity is too low, the molecular weight tends to be low, and low dielectric properties such as low dielectric constant and low dielectric loss tangent tend to be difficult to obtain. On the other hand, if the intrinsic viscosity is too high, the viscosity is high, sufficient fluidity cannot be obtained, and the moldability of the cured product tends to decrease. Therefore, if the intrinsic viscosity of the modified polyphenylene ether compound is within the above range, excellent heat resistance and moldability of the cured product can be realized.

  The intrinsic viscosity here is an intrinsic viscosity measured in methylene chloride at 25 ° C. More specifically, for example, a 0.18 g / 45 ml methylene chloride solution (liquid temperature 25 ° C.) is used as a viscometer. It is the value measured by. Examples of the viscometer include AVS500 Visco System manufactured by Schott.

  In addition, the method for synthesizing the modified polyphenylene ether compound used in the present embodiment is not particularly limited as long as the modified polyphenylene ether compound terminal-modified with a substituent having a carbon-carbon unsaturated double bond can be synthesized. Specifically, a method of reacting a compound in which a substituent having a carbon-carbon unsaturated double bond and a halogen atom are reacted with polyphenylene ether can be used.

  Examples of the compound in which a substituent having a carbon-carbon unsaturated double bond and a halogen atom are bonded include a compound represented by the formula (6).

Wherein ^{(6), n, Z,} R 1 ~R 3 shows n in formula (1), ^Z, the same as R 1 to R ^3. Specifically, n represents 0-10. Z represents an arylene group. R ^{1 to} R ³ are independent of each other. That is, R ^{1 to} R ³ may be the same group or different groups. R ^{1 to} R ³ represent a hydrogen atom or an alkyl group. 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.

  Moreover, the compound represented by Formula (6) may use what was illustrated above independently, and may be used in combination of 2 or more type.

  Examples of the compound in which a substituent having a carbon-carbon unsaturated double bond and a halogen atom are bonded include p-chloromethylstyrene and m-chloromethylstyrene.

  The polyphenylene ether as a raw material is not particularly limited as long as it can finally synthesize a predetermined modified polyphenylene ether. Specifically, polyphenylene ethers such as polyphenylene ether and poly (2,6-dimethyl-1,4-phenylene oxide) composed of 2,6-dimethylphenol and at least one of bifunctional phenol and trifunctional phenol are used. The thing etc. which are made into a main component are mentioned. Bifunctional phenol is a phenol compound having two phenolic hydroxyl groups in the molecule, and examples thereof include tetramethylbisphenol A. Trifunctional phenol is a phenol compound having three phenolic hydroxyl groups in the molecule. More specifically, examples of such polyphenylene ether include polyphenylene ether having a structure represented by the formula (7).

  In formula (7), it is preferable that s and t are those in which the total value of s and t is 1 to 30, for example. Moreover, it is preferable that s is 0-20, and it is preferable that t is 0-20. That is, s represents 0 to 20, t represents 0 to 20, and the sum of s and t preferably represents 1 to 30. Y represents an alkylene group having 1 to 3 carbon atoms or a direct bond. Examples of the alkylene group include a dimethylmethylene group.

  Examples of the method for synthesizing the modified polyphenylene ether compound include those described above. Specifically, the polyphenylene ether as described above and the compound represented by the formula (6) are dissolved in a solvent and stirred. By doing so, the polyphenylene ether and the compound represented by the formula (6) react to obtain the modified polyphenylene ether used in the present embodiment.

  In this reaction, it is preferably carried out in the presence of an alkali metal hydroxide. By doing so, this reaction is considered to proceed suitably. This is presumably because the alkali metal hydroxide functions as a dehydrohalogenating agent, specifically, a dehydrochlorinating agent. That is, the alkali metal hydroxide desorbs the hydrogen halide from the phenol group of polyphenylene ether and the compound represented by formula (6), thereby replacing the hydrogen atom of the phenol group of polyphenylene ether. In addition, it is considered that the substituent represented by the formula (1) is bonded to the oxygen atom of the phenol group.

  The alkali metal hydroxide is not particularly limited as long as it can function as a dehalogenating agent, and examples thereof include sodium hydroxide. Moreover, alkali metal hydroxide is normally used in the state of aqueous solution, and specifically, it is used as sodium hydroxide aqueous solution.

  Moreover, reaction conditions, such as reaction time and reaction temperature, are different depending on the compound represented by the formula (6) and the like, and are not particularly limited as long as the above reaction proceeds favorably. Specifically, the reaction temperature is preferably room temperature to 100 ° C, and more preferably 30 to 100 ° C. Moreover, it is preferable that reaction time is 0.5 to 20 hours, and it is more preferable that it is 0.5 to 10 hours.

  The solvent used in the reaction can dissolve the polyphenylene ether and the compound represented by the formula (6), and does not inhibit the reaction between the polyphenylene ether and the compound represented by the formula (6). If there is, it will not be specifically limited. Specifically, toluene etc. are mentioned.

  In addition, the above reaction is preferably performed in a state where not only the alkali metal hydroxide but also the phase transfer catalyst is present. That is, the above reaction is preferably performed in the presence of an alkali metal hydroxide and a phase transfer catalyst. By doing so, it is considered that the above reaction proceeds more suitably. This is considered to be due to the following. The phase transfer catalyst has a function of incorporating an alkali metal hydroxide and is soluble in both a polar solvent phase such as water and a nonpolar solvent phase such as an organic solvent. This is considered to be due to the fact that it is a catalyst that can move. Specifically, when an aqueous solution of sodium hydroxide is used as the alkali metal hydroxide and an organic solvent such as toluene that is incompatible with water is used as the solvent, the aqueous solution of sodium hydroxide is used for the reaction. Even if it is added dropwise to the solvent, it is considered that the solvent and the aqueous sodium hydroxide solution are separated, and the sodium hydroxide is difficult to transfer to the solvent. In this case, it is considered that the aqueous sodium hydroxide solution added as the alkali metal hydroxide hardly contributes to the promotion of the reaction. In contrast, when the reaction is carried out in the presence of an alkali metal hydroxide and a phase transfer catalyst, the alkali metal hydroxide is transferred to the solvent in a state of being taken into the phase transfer catalyst, and the aqueous sodium hydroxide solution is reacted. It is likely to contribute to promotion. For this reason, when it is made to react in presence of an alkali metal hydroxide and a phase transfer catalyst, it is thought that the said reaction advances more suitably.

  The phase transfer catalyst is not particularly limited, and examples thereof include quaternary ammonium salts such as tetra-n-butylammonium bromide.

  The resin composition according to this embodiment preferably contains the modified polyphenylene ether obtained as described above as the modified polyphenylene ether.

  Moreover, the crosslinking type curing agent used in the present embodiment is not particularly limited as long as it has a carbon-carbon unsaturated double bond in the molecule. That is, the cross-linking curing agent may be any one that can be cured by forming a cross-link by reacting with the modified polyphenylene ether compound. The crosslinkable curing agent is preferably a compound having two or more carbon-carbon unsaturated double bonds in the molecule.

  Moreover, it is preferable that the weight average molecular weights of the crosslinkable curing agent used in this embodiment are 100 to 5000, more preferably 100 to 4000, and further preferably 100 to 3000. If the weight average molecular weight of the crosslinkable curing agent is too low, the crosslinkable curing agent may easily volatilize from the compounding component system of the resin composition. Moreover, when the weight average molecular weight of a crosslinking type hardening | curing agent is too high, there exists a possibility that the viscosity of the varnish of a resin composition and the melt viscosity at the time of thermoforming may become high too much. Therefore, when the weight average molecular weight of the crosslinkable curing agent is within such a range, a resin composition superior in heat resistance of the cured product can be obtained. This is considered to be because a crosslink can be suitably formed by reaction with the modified polyphenylene ether compound. In addition, here, the weight average molecular weight should just be measured by the general molecular weight measuring method, and the value measured using gel permeation chromatography (GPC) etc. are mentioned specifically ,.

  In addition, the crosslinking type curing agent used in the present embodiment is an average number of carbon-carbon unsaturated double bonds (number of terminal double bonds) per molecule of the crosslinking type curing agent. Although it varies depending on the molecular weight, for example, it is preferably 1-20, more preferably 2-18. When the number of terminal double bonds is too small, it is difficult to obtain a cured product having sufficient heat resistance. In addition, when the number of terminal double bonds is too large, the reactivity becomes too high, and, for example, there is a risk that problems such as deterioration of the storage stability of the resin composition or deterioration of the fluidity of the resin composition may occur. There is.

  In addition, as the number of terminal double bonds of the crosslinkable curing agent, in consideration of the weight average molecular weight of the crosslinkable curing agent, the weight average molecular weight of the crosslinkable curing agent is less than 500 (for example, 100 or more and less than 500). It is preferable that it is 1-4. The number of terminal double bonds of the crosslinkable curing agent is preferably 3 to 20 when the weight average molecular weight of the crosslinkable curing agent is 500 or more (for example, 500 or more and 5000 or less). In each case, if the number of terminal double bonds is less than the lower limit of the above range, the reactivity of the crosslinkable curing agent decreases, the crosslink density of the cured product of the resin composition decreases, and heat resistance and Tg May not be sufficiently improved. On the other hand, when the number of terminal double bonds is larger than the upper limit of the above range, the resin composition may be easily gelled.

  In addition, the number of terminal double bonds here can be found from the standard value of the product of the crosslinking type curing agent to be used. As the number of terminal double bonds here, specifically, for example, a numerical value representing an average value of the number of double bonds per molecule of all the crosslinking type curing agents present in 1 mol of the crosslinking type curing agent. Etc.

  The crosslinking type curing agent used in the present embodiment is specifically a trialkenyl isocyanurate compound such as triallyl isocyanurate (TAIC), a polyfunctional methacrylate compound having two or more methacryl groups in the molecule, a molecule Polyfunctional acrylate compound having two or more acrylic groups in it, vinyl compound having two or more vinyl groups in the molecule such as polybutadiene (polyfunctional vinyl compound), and styrene or divinyl having vinylbenzyl group in the molecule Examples thereof include vinylbenzyl compounds such as benzene. Among these, those having two or more carbon-carbon double bonds in the molecule are preferable. Specific examples include a trialkenyl isocyanurate compound, a polyfunctional acrylate compound, a polyfunctional methacrylate compound, a polyfunctional vinyl compound, and a divinylbenzene compound. 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 resin composition according to the present embodiment can be further increased. In addition, as the crosslinking type curing agent, the exemplified crosslinking type curing agent may be used alone, or two or more types may be used in combination. Further, as the crosslinking type curing agent, a compound having two or more carbon-carbon unsaturated double bonds in the molecule and a compound having one carbon-carbon unsaturated double bond in the molecule may be used in combination. Good. Specific examples of the compound having one carbon-carbon unsaturated double bond in the molecule include compounds having one vinyl group in the molecule (monovinyl compound).

  Moreover, it is preferable that content of the said modified polyphenylene ether compound is 30-90 mass parts with respect to a total of 100 mass parts of the said modified polyphenylene ether compound and the said crosslinking-type hardening | curing agent, 50-90 mass parts More preferably. Moreover, it is preferable that content of the said crosslinking type hardening | curing agent is 10-70 mass parts with respect to a total of 100 mass parts of the said modified | denatured polyphenylene ether compound and the said crosslinking type curing agent, More preferably. That is, the content ratio of the modified polyphenylene ether compound and the cross-linking curing agent is preferably 90:10 to 30:70, and preferably 90:10 to 50:50 in terms of mass ratio. If each content of the modified polyphenylene ether compound and the crosslinkable curing agent satisfies the above ratio, the resin composition is more excellent in the heat resistance and flame retardancy of the cured product. This is presumably because the curing reaction between the modified polyphenylene ether compound and the crosslinkable curing agent suitably proceeds.

  Further, the flame retardant used in the present embodiment contains a compatible phosphorus compound that is compatible with the mixture of the modified polyphenylene ether compound and the cross-linking curing agent, and an incompatible phosphorus compound that is not compatible with the mixture. .

  The compatible phosphorus compound is not particularly limited as long as it is a phosphorus compound that acts as a flame retardant and is compatible with the mixture. In addition, in this case, “compatible” means that the mixture is finely dispersed, for example, at the molecular level in the mixture of the modified polyphenylene ether compound and the cross-linking curing agent. Examples of the compatible phosphorus compound include phosphate ester compounds, phosphazene compounds, phosphite ester compounds, and phosphine compounds. Examples of the phosphazene compound include cyclic or chain phosphazene compounds. The cyclic phosphazene compound is also called cyclophosphazene, and is a compound having in its molecule a double bond having phosphorus and nitrogen as constituent elements, and has a cyclic structure. Examples of the phosphoric acid ester compound include triphenyl phosphate, tricresyl phosphate, xylenyl diphenyl phosphate, cresyl diphenyl phosphate, 1,3-phenylenebis (di2,6-xylenyl phosphate), 9 , 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), condensed phosphoric acid ester compounds such as aromatic condensed phosphoric acid ester compounds, and cyclic phosphoric acid ester compounds. Examples of the phosphite compound include trimethyl phosphite and triethyl phosphite. Examples of the phosphine compound include tris- (4-methoxyphenyl) phosphine and triphenylphosphine. Moreover, the said compatible phosphorus compound may be used individually by 1 type, and may be used in combination of 2 or more type.

  The incompatible phosphorus compound is not particularly limited as long as it is an incompatible phosphorus compound that acts as a flame retardant and is incompatible with the mixture. Incompatible with this case means that the object (phosphorus compound) is dispersed in islands in the mixture without being compatible in the mixture of the modified polyphenylene ether compound and the crosslinkable curing agent. Say. Examples of the incompatible phosphorus compound include phosphinate compounds, polyphosphate compounds, and phosphonium salt compounds. Examples of the phosphinate compound include aluminum dialkylphosphinate, aluminum trisdiethylphosphinate, aluminum trismethylethylphosphinate, aluminum trisdiphenylphosphinate, zinc bisdiethylphosphinate, zinc bismethylethylphosphinate, bisdiphenyl. Examples thereof include zinc phosphinate, titanyl bisdiethylphosphinate, titanyl bismethylethylphosphinate, and titanyl bisdiphenylphosphinate. Examples of the polyphosphate compound include melamine polyphosphate, melam polyphosphate, melem polyphosphate, and the like. Examples of the phosphonium salt compound include tetraphenylphosphonium tetraphenylborate and tetraphenylphosphonium bromide. Moreover, the said incompatible phosphorus compound may be used individually by 1 type, and may be used in combination of 2 or more type.

  As described above, the resin composition according to the present embodiment uses the compatible phosphorus compound and the incompatible phosphorus compound in combination as the flame retardant, so that the compatible phosphorus compound and the incompatible phosphorus compound are combined. The flame retardancy of the obtained cured product can be increased compared with the case where only one of the above is used. The combined use of the compatible phosphorus compound and the incompatible phosphorus compound sufficiently suppresses the inhibition of the curing reaction between the modified polyphenylene ether compound and the crosslinkable curing agent, and the flame retardancy of the obtained cured product. It is thought that it can raise. Furthermore, since inhibition of the curing reaction is sufficiently suppressed, it is considered that a decrease in heat resistance of the cured product can be sufficiently suppressed. From these things, it is thought that the said resin composition becomes the thing excellent by the heat resistance and flame retardance of hardened | cured material. In addition, when any of the compatible phosphorus compound and the incompatible phosphorus compound is used as a flame retardant, when trying to ensure the same level of flame retardancy as in the case of the combined use, the compatible phosphorus compound or It is necessary to contain a large amount of the incompatible phosphorus compound. That is, the compatible phosphorus compound or the incompatible phosphorus compound needs to be contained in a larger amount than the total content of the compatible phosphorus compound and the incompatible phosphorus compound in the present embodiment. Thus, it is conceivable that the dielectric properties, the heat resistance of the cured product, and the like are lowered only by increasing the content of the flame retardant instead of using the above-mentioned combination. From this, when the said combined use is employ | adopted as a flame retardant, a flame retardance can be improved, suppressing the fall of a dielectric property, the heat resistance of hardened | cured material, etc. with content as mentioned later. From the above, the resin composition is considered to be excellent in the heat resistance and flame retardancy of the cured product while maintaining the excellent dielectric properties of polyphenylene ether.

  The content ratio of the compatible phosphorus compound and the incompatible phosphorus compound is preferably 20:80 to 80:20, more preferably 20:80 to 50:50, in terms of mass ratio. If it is such a content ratio, it will become the resin composition which was excellent with the heat resistance and flame retardance of hardened | cured material, maintaining the outstanding dielectric characteristic which polyphenylene ether has. This is considered because the said effect which uses a compatible phosphorus compound and an incompatible phosphorus compound together as a flame retardant can be exhibited more.

  The resin composition has a phosphorus atom content of 1.8 to 5.2 parts by mass with respect to 100 parts by mass in total of the organic component (excluding the flame retardant) and the flame retardant. Is preferably 1.8 to 5 parts by mass, and more preferably 1.8 to 4.8 parts by mass. Further, the content of the flame retardant is preferably such that the content of phosphorus atoms in the resin composition falls within the above range. If it is such content, it will become the resin composition which was excellent by the heat resistance and flame retardance of hardened | cured material, maintaining the outstanding dielectric characteristic which polyphenylene ether has. This is considered to be due to the fact that the flame retardancy can be sufficiently enhanced while sufficiently suppressing the decrease in dielectric properties and the heat resistance of the cured product due to the inclusion of the flame retardant. The organic component (excluding the flame retardant) includes an organic component such as the modified polyphenylene ether compound and the cross-linking type curing agent, and when other organic components are added additionally, Additional organic components added are also included.

  Further, the resin composition according to the present embodiment may be composed of the compatible phosphorus compound and the incompatible phosphorus compound as a flame retardant, and also contains a flame retardant other than these two types. May be. Moreover, although flame retardants other than the said compatible phosphorus compound and the said incompatible phosphorus compound may be contained as a flame retardant, it is preferable not to contain a halogen flame retardant from a halogen-free viewpoint.

  Further, the resin composition according to the present embodiment may be composed of the modified polyphenylene ether compound, the thermosetting curing agent, and the flame retardant, but if these are included, other components are included. Further, it may be included. Examples of other components include fillers, additives, and reaction initiators.

  Moreover, as mentioned above, the resin composition according to the present embodiment may contain a filler. As a filler, what is added in order to improve the heat resistance and flame retardance of the hardened | cured material of a resin composition is mentioned, It does not specifically limit. Moreover, heat resistance, a flame retardance, etc. can further be improved by containing a filler. Specific examples of the filler include silica such as spherical silica, metal oxides such as alumina, titanium oxide, and mica, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, talc, aluminum borate, and sulfuric acid. Examples include barium and calcium carbonate. Of these, silica, mica, and talc are preferable as the filler, and spherical silica is more preferable. Moreover, a filler may be used individually by 1 type and may be used in combination of 2 or more type. Moreover, as a filler, you may use as it is, but you may use what was surface-treated with the silane coupling agent of an epoxy silane type or an aminosilane type.

  Moreover, when containing a filler, it is preferable that the content is 10-200 mass parts with respect to a total of 100 mass parts of an organic component (except the said flame retardant) and the said flame retardant, 30- It is preferable that it is 150 mass parts.

  Moreover, the resin composition according to the present embodiment may contain an additive as described above. Examples of additives include antifoaming agents such as silicone-based antifoaming agents and acrylic acid ester-based antifoaming agents, thermal stabilizers, antistatic agents, ultraviolet absorbers, dyes and pigments, lubricants, wetting and dispersing agents, etc. Agents and the like.

  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 is composed of a modified polyphenylene ether and a thermosetting curing agent, the curing reaction can proceed. Moreover, even with only the modified polyphenylene ether, the curing reaction can proceed. However, depending on the process conditions, it may be difficult to increase the temperature until curing proceeds, so a reaction initiator may be added. The reaction initiator is not particularly limited as long as it can accelerate the curing reaction between the modified polyphenylene ether and the thermosetting 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 the prepreg is produced, the resin composition according to the present embodiment may be prepared and used in a varnish for the purpose of impregnating a base material (fibrous base material) for forming the prepreg. That is, the resin composition may be usually prepared in a varnish shape. Such a varnish-like resin composition is prepared as follows, for example.

  First, each component that can be dissolved in an organic solvent, such as a modified polyphenylene ether compound, a cross-linkable curing agent, and a compatible flame retardant, is charged into the organic solvent and dissolved. At this time, heating may be performed as necessary. Thereafter, components that are used as necessary and not dissolved in an organic solvent, for example, an inorganic filler, an incompatible flame retardant, and the like are added, using a ball mill, a bead mill, a planetary mixer, a roll mill, etc. A varnish-like composition is prepared by dispersing until a predetermined dispersion state is obtained. The organic solvent used here is not particularly limited as long as it can dissolve the modified polyphenylene ether compound, the crosslinking curing agent, the flame retardant, and the like and does not inhibit the curing reaction. Specifically, toluene, methyl ethyl ketone (MEK), etc. are mentioned, for example.

  Moreover, it is good also as a prepreg by impregnating the fiber base material with the resin composition which concerns on this embodiment. That is, the prepreg according to the embodiment of the present invention is obtained by impregnating a fibrous base material with the resin composition. Examples of the method for producing such a prepreg include a method in which a fibrous base material is impregnated with the resin composition, for example, a resin composition prepared in a varnish form, and then dried.

  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 0.02-0.3 mm can generally be used, for example.

  The impregnation of the resin composition into the fibrous base material is performed by dipping and 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 compositions having different compositions and concentrations, and finally adjust to a desired composition and impregnation amount.

  The fibrous base material impregnated with the resin composition is heated at a desired heating condition, for example, at 80 to 180 ° C. for 1 to 10 minutes, whereby a semi-cured (B stage) prepreg is obtained.

  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. That is, the metal-clad laminate according to the embodiment of the present invention is obtained by laminating a metal foil on the above-described prepreg and then heating and pressing. The heating and pressing conditions can be appropriately set depending on the thickness of the laminate to be produced, the type of the prepreg resin composition, and the like. For example, the temperature can be set to 170 to 210 ° C., the pressure can be set to 1.5 to 4.0 MPa, and the time can be set to 60 to 150 minutes.

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

  Then, by forming a circuit by etching the metal foil on the surface of the produced metal-clad laminate, a printed wiring board provided with a conductor pattern as a circuit on the surface of the metal-clad laminate can be obtained. It is. That is, the printed wiring board according to the embodiment of the present invention is obtained by forming a circuit by partially removing the metal foil on the surface of the metal-clad laminate. The printed wiring board thus obtained has excellent dielectric properties, heat resistance and flame retardancy.

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

  The resin composition according to one embodiment of the present invention includes a modified polyphenylene ether compound terminal-modified with a substituent having a carbon-carbon unsaturated double bond, and a crosslinked type having a carbon-carbon unsaturated double bond in the molecule. Contains a curing agent and a flame retardant. The flame retardant contains a compatible phosphorus compound that is compatible with the mixture of the modified polyphenylene ether compound and the crosslinkable curing agent, and an incompatible phosphorus compound that is not compatible with the mixture.

  According to such a structure, the 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. The present inventors have found that the flame retardancy of the obtained cured product can be further enhanced by using a compatible phosphorus compound and an incompatible phosphorus compound in combination as a flame retardant. That was done. That is, by using a compatible phosphorus compound and an incompatible phosphorus compound in combination as a flame retardant, the flame retardant of the obtained cured product is more than when using either a compatible phosphorus compound or an incompatible phosphorus compound. By being able to enhance the nature. The combined use of the compatible phosphorus compound and the incompatible phosphorus compound increases the flame retardancy of the obtained cured product while sufficiently suppressing the inhibition of the curing reaction between the modified polyphenylene ether compound and the cross-linking curing agent. It is considered possible. And since inhibition of the said hardening reaction is fully suppressed, it is thought that the fall of the heat resistance of hardened | cured material can also be fully suppressed. From these things, it is thought that the said resin composition becomes the thing excellent in the heat resistance and flame retardance of hardened | cured material, maintaining the outstanding dielectric characteristic which polyphenylene ether has.

  From the above, according to the above configuration, a resin composition excellent in heat resistance and flame retardancy of a cured product can be obtained while maintaining the excellent dielectric properties of polyphenylene ether.

  In the resin composition, the content ratio of the compatible phosphorus compound and the incompatible phosphorus compound is preferably 20:80 to 80:20 by mass ratio.

  According to such a configuration, it is possible to provide a resin composition that is more excellent in the heat resistance and flame retardancy of the cured product while maintaining the excellent dielectric properties of polyphenylene ether. This is considered because the said effect which uses a compatible phosphorus compound and an incompatible phosphorus compound together as a flame retardant can be exhibited more.

  Moreover, in the said resin composition, content of a phosphorus atom is 1.8-5.2 mass parts with respect to a total of 100 mass parts of an organic component (except the said flame retardant) and the said flame retardant. Is preferred.

  According to such a configuration, it is possible to provide a resin composition that is more excellent in the heat resistance and flame retardancy of the cured product while maintaining the excellent dielectric properties of polyphenylene ether. This is considered to be due to the fact that the flame retardancy can be sufficiently enhanced while sufficiently suppressing the decrease in dielectric properties and the heat resistance of the cured product due to the inclusion of the flame retardant.

  In the resin composition, the compatible phosphorus compound is preferably at least one selected from the group consisting of a phosphate ester compound, a phosphazene compound, a phosphite compound, and a phosphine compound. The incompatible phosphorus compound is preferably at least one selected from the group consisting of phosphinate compounds, polyphosphate compounds, and phosphonium salt compounds.

  According to such a configuration, it is possible to provide a resin composition that is more excellent in the heat resistance and flame retardancy of the cured product while maintaining the excellent dielectric properties of polyphenylene ether.

  In the resin composition, the cross-linking curing agent preferably has a weight average molecular weight of 100 to 5000 and has an average of 1 to 20 carbon-carbon unsaturated double bonds in one molecule.

  According to such a configuration, it is possible to provide a resin composition that is more excellent in the heat resistance and flame retardancy of the cured product while maintaining the excellent dielectric properties of polyphenylene ether.

  In the resin composition, the crosslinking curing agent is 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. And at least one selected from the group consisting of polyfunctional vinyl compounds having two or more vinyl groups in the molecule.

  According to such a configuration, it is possible to provide a resin composition that is more excellent in the heat resistance and flame retardancy of the cured product while maintaining the excellent dielectric properties of polyphenylene ether.

  In the resin composition, the modified polyphenylene ether compound preferably has a weight average molecular weight of 500 to 5000 and has an average of 1 to 5 substituents per molecule.

  According to such a configuration, it is possible to provide a resin composition that is more excellent in the heat resistance and flame retardancy of the cured product while maintaining the excellent dielectric properties of polyphenylene ether.

  In the resin composition, the substituent at the terminal of the modified polyphenylene ether compound is preferably a substituent having at least one selected from the group consisting of a vinylbenzyl group, an acrylate group, and a methacrylate group.

  According to such a configuration, it is possible to provide a resin composition that is more excellent in the heat resistance and flame retardancy of the cured product while maintaining the excellent dielectric properties of polyphenylene ether.

  In the resin composition, the content ratio of the modified polyphenylene ether compound and the cross-linking curing agent is preferably 90:10 to 30:70 by mass ratio.

  According to such a configuration, it is possible to provide a resin composition that is more excellent in the heat resistance and flame retardancy of the cured product while maintaining the excellent dielectric properties of polyphenylene ether.

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

  According to such a structure, the prepreg which can manufacture the metal-clad laminated board excellent in the dielectric property, heat resistance, and a flame retardance is obtained.

  In addition, the metal-clad laminate according to another aspect of the present invention is obtained by laminating a metal foil on the prepreg and heating and pressing.

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

  The printed wiring board according to another aspect of the present invention is obtained by forming a circuit by partially removing the metal foil on the surface of the metal-clad laminate.

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

  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.

[Examples 1 to 17 and Comparative Examples 1 to 4]
In this example, each component used when preparing the resin composition will be described.

(Polyphenylene ether compound: PPE component)
Modified PPE-1: Modified polyphenylene ether obtained by modifying the terminal hydroxyl group of polyphenylene ether with methacrylic group (SA9000 manufactured by SABIC Innovative Plastics, weight average molecular weight Mw 1700, number of terminal functional groups 2)
Modified PPE-2:
It is a modified polyphenylene ether obtained by reacting polyphenylene ether and chloromethylstyrene.

  Specifically, it is a modified polyphenylene ether obtained by reacting as follows.

  First, polyphenylene ether (SA90 manufactured by SABIC Innovative Plastics, 2 terminal hydroxyl groups, weight average molecular weight Mw1700) was added to a 1 liter three-necked flask equipped with a temperature controller, a stirrer, cooling equipment, and a dropping funnel. 200 g, 30 g of a 50:50 mixture of p-chloromethylstyrene and m-chloromethylstyrene (Tokyo Chemical Industry Co., Ltd., chloromethylstyrene: CMS), tetra-n-butylammonium as a phase transfer catalyst 1.227 g of bromide and 400 g of toluene were charged and stirred. And it stirred until polyphenylene ether, chloromethyl styrene, and tetra-n-butylammonium bromide melt | dissolved in toluene. At that time, it was gradually heated and finally heated until the liquid temperature reached 75 ° C. And the sodium hydroxide aqueous solution (sodium hydroxide 20g / water 20g) was dripped at the solution over 20 minutes as an alkali metal hydroxide. Thereafter, the mixture was further stirred at 75 ° C. for 4 hours. Next, after neutralizing the contents of the flask with 10% by mass hydrochloric acid, a large amount of methanol was added. By doing so, a precipitate was produced in the liquid in the flask. That is, the product contained in the reaction solution in the flask was reprecipitated. Then, the precipitate was taken out by filtration, washed three times with a mixed solution having a mass ratio of methanol and water of 80:20, and then dried at 80 ° C. under reduced pressure for 3 hours.

  The obtained solid was analyzed by 1H-NMR (400 MHz, CDCl 3, TMS). As a result of measuring NMR, a peak derived from a vinylbenzyl group (ethenylbenzyl group) was confirmed at 5 to 7 ppm. Thereby, it was confirmed that the obtained solid was a modified polyphenylene ether having a vinylbenzyl group as a substituent at the molecular end. Specifically, it was confirmed that the polyphenylene ether was ethenylbenzylated.

  Moreover, the number of terminal functional groups of the modified polyphenylene ether was measured as follows.

  First, the modified polyphenylene ether was accurately weighed. The weight at that time is X (mg). Then, the weighed modified polyphenylene ether was dissolved in 25 mL of methylene chloride, and an ethanol solution of 10% by mass of tetraethylammonium hydroxide (TEAH) (TEAH: ethanol (volume ratio) = 15: 85) was added to the solution. After adding 100 μL, the absorbance (Abs) at 318 nm was measured using a UV spectrophotometer (UV-1600 manufactured by Shimadzu Corporation). And from the measurement result, the number of terminal hydroxyl groups of the modified polyphenylene ether was calculated using the following formula.

Residual OH amount (μmol / g) = [(25 × Abs) / (ε × OPL × X)] × 10 ⁶
Here, ε represents an extinction coefficient and is 4700 L / mol · cm. OPL is the cell optical path length, which is 1 cm.

  The calculated amount of residual OH (number of terminal hydroxyl groups) of the modified polyphenylene ether was almost zero, indicating that the hydroxyl groups of the polyphenylene ether before modification were substantially modified. From this, it was found that the decrease from the number of terminal hydroxyl groups of polyphenylene ether before modification was the number of terminal hydroxyl groups of polyphenylene ether before modification. That is, it was found that the number of terminal hydroxyl groups of the polyphenylene ether before modification was the number of terminal functional groups of the modified polyphenylene ether. That is, the number of terminal functional groups was two.

  In addition, the intrinsic viscosity (IV) of the modified polyphenylene ether was measured in methylene chloride at 25 ° C. Specifically, the intrinsic viscosity (IV) of the modified polyphenylene ether was measured using a 0.18 g / 45 ml methylene chloride solution (liquid temperature: 25 ° C.) of the modified polyphenylene ether using a viscometer (AVS500 Visco System manufactured by Schott). It was measured. As a result, the intrinsic viscosity (IV) of the modified polyphenylene ether was 0.086 dl / g.

  The molecular weight distribution of the modified polyphenylene ether was measured using GPC. And the weight average molecular weight (Mw) was computed from the obtained molecular weight distribution. As a result, Mw was 1900.

Modified PPE-3:
The polyphenylene ether was synthesized by the same method as the synthesis of the modified PPE-2 except that polyphenylene ether described later was used and the conditions described later were used.

  The polyphenylene ether used was polyphenylene ether (SA120 manufactured by SABIC Innovative Plastics, intrinsic viscosity (IV) 0.125 dl / g, one terminal hydroxyl group, weight average molecular weight Mw 2400).

  Next, the reaction between polyphenylene ether and chloromethylstyrene is carried out by using 200 g of the polyphenylene ether (SA120), 15 g of CMS, and 0.92 g of a phase transfer catalyst (tetra-n-butylammonium bromide). Synthesis was performed in the same manner as the synthesis of modified PPE-2 except that an aqueous sodium hydroxide solution (10 g of sodium hydroxide / 10 g of water) was used instead of (sodium hydroxide 20 g / water 20 g).

  The obtained solid was analyzed by 1H-NMR (400 MHz, CDCl 3, TMS). As a result of measuring NMR, a peak derived from an ethenylbenzyl group was confirmed at 5 to 7 ppm. Thereby, it was confirmed that the obtained solid was a modified polyphenylene ether having a vinylbenzyl group in the molecule as the substituent. Specifically, it was confirmed that the polyphenylene ether was ethenylbenzylated.

  Moreover, the terminal functional number of the modified polyphenylene ether was measured by the same method as described above. As a result, the number of terminal functionalities was one.

  The intrinsic viscosity (IV) of the modified polyphenylene ether in methylene chloride at 25 ° C. was measured by the same method as described above. As a result, the intrinsic viscosity (IV) of the modified polyphenylene ether was 0.125 dl / g.

  Further, the Mw of the modified polyphenylene ether was measured by the same method as described above. As a result, Mw was 2800.

Modified PPE-4:
The polyphenylene ether was synthesized by the same method as the synthesis of the modified PPE-2 except that polyphenylene ether described later was used and the conditions described later were used.

  The polyphenylene ether used was obtained by partitioning and rearranging polyphenylene ether (noryl 640-111 manufactured by SABIC Innovative Plastics, intrinsic viscosity (IV) 0.45 dl / g, one terminal hydroxyl group, weight average molecular weight Mw 47000). . Specifically, partition rearrangement was performed as follows.

  200 g of the polyphenylene ether (noryl 640-111), 65 g of bisphenol A as a phenol species, and 65 g of benzoyl peroxide (Niper BW manufactured by NOF Corporation) as an initiator were added, respectively, and 400 g of toluene as a solvent was added thereto. Mix for 1 hour at ° C. By doing so, partition rearranged polyphenylene ether (5 hydroxyl groups at the end, weight average molecular weight Mw2000) was obtained.

  Next, the reaction between polyphenylene ether and chloromethylstyrene is carried out using 200 g of the above-mentioned rearranged polyphenylene ether, 65 g of CMS, 1.92 g of phase transfer catalyst (tetra-n-butylammonium bromide), and water. Synthesis was performed in the same manner as the synthesis of modified PPE-2 except that an aqueous sodium hydroxide solution (sodium hydroxide 40 g / water 40 g) was used instead of the aqueous sodium oxide solution (sodium hydroxide 20 g / water 20 g).

  The solid obtained as described above was analyzed by 1H-NMR (400 MHz, CDCl 3, TMS). As a result of measuring NMR, a peak derived from an ethenylbenzyl group was confirmed at 5 to 7 ppm. Thereby, it was confirmed that the obtained solid was a modified polyphenylene ether having a vinylbenzyl group in the molecule as the substituent. Specifically, it was confirmed that the polyphenylene ether was ethenylbenzylated.

  Moreover, the terminal functional number of the modified polyphenylene ether was measured by the same method as described above. As a result, the number of terminal functionalities was 5.

  The intrinsic viscosity (IV) of the modified polyphenylene ether in methylene chloride at 25 ° C. was measured by the same method as described above. As a result, the intrinsic viscosity (IV) of the modified polyphenylene ether was 0.068 dl / g.

  Further, Mn of the modified polyphenylene ether was measured by the same method as described above. As a result, Mw was 2000.

Unmodified PPE-1: Polyphenylene ether having a hydroxyl group at the end (SA120 manufactured by SABIC Innovative Plastics, intrinsic viscosity (IV) 0.125 dl / g, number of terminal hydroxyl groups, weight average molecular weight Mw 2600)
Unmodified PPE-2: Polyphenylene ether having a hydroxyl group at the terminal (norb 640-111 manufactured by SABIC Innovative Plastics, intrinsic viscosity (IV) 0.45 dl / g, one terminal hydroxyl group, weight average molecular weight Mw 47000)
(Crosslinking curing agent)
TAIC: triallyl isocyanurate (TAIC manufactured by Nippon Kasei Co., Ltd., weight average molecular weight Mw249, number of terminal double bonds 3)
Styrene: Styrene monomer (molecular weight 104, number of terminal double bonds 1)
DCP: Dicyclopentadiene type methacrylate (DCP methacrylate manufactured by Shin-Nakamura Chemical Co., Ltd., weight average molecular weight Mw332, number of terminal double bonds 2)
DVB: divinylbenzene (DVB810 manufactured by Nippon Steel & Sumitomo Metal Corporation, molecular weight 130, number of terminal double bonds 2)
Polybutadiene oligomer: Polybutadiene oligomer (B1000 manufactured by Nippon Soda Co., Ltd., weight average molecular weight Mw 1100, number of terminal double bonds 15)
(Compatible phosphorus compound)
Phosphate ester compound: aromatic condensed phosphate ester compound (PX-200 manufactured by Daihachi Chemical Industry Co., Ltd .: phosphorus concentration 9 mass%)
Phosphazene compound: Cyclic phosphazene compound (SPB-100 manufactured by Otsuka Chemical Co., Ltd .: phosphorus concentration 13% by mass)
(Incompatible phosphorus compound)
Phosphinate compound: Aluminum trisdiethylphosphinate (Exorit OP-935 manufactured by Clariant Japan KK: Phosphorus concentration: 23% by mass)
Polyphosphate compound: Melamine polyphosphate (Melapur 200 manufactured by BASF: Phosphorus concentration 13% by mass)
(Reaction initiator)
Initiator: 1,3-bis (butylperoxyisopropyl) benzene (Perbutyl P manufactured by NOF Corporation)
[Preparation method]
First, each component was added to toluene and mixed at a blending ratio shown in Tables 1 to 3 so that the solid concentration was 60% by mass. By stirring the mixture for 60 minutes, a varnish-like resin composition (varnish) was obtained.

  Next, the obtained varnish was impregnated into glass cloth (# 7628 type, E glass manufactured by Nitto Boseki Co., Ltd.), and then heated and dried at 100 to 170 ° C. for about 3 to 6 minutes to obtain a prepreg. In that case, it adjusted so that content (resin content) of the component which comprises resin by hardening reaction, such as polyphenylene ether compounds, such as a modified | denatured polyphenylene ether compound, and a crosslinking type hardening | curing agent might be about 40 mass%.

  And 4 sheets of each obtained prepreg were laminated | stacked and laminated | stacked, and the evaluation board | substrate of predetermined thickness was obtained by heat-pressing on the conditions of temperature 200 degreeC, 2 hours, and pressure 3MPa. Specifically, for example, an evaluation board having a thickness of about 0.8 mm was obtained by laminating and stacking four obtained prepregs.

  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 board | substrate in 1 GHz were measured by the method based on IPC-TM650-2.5.5.9. Specifically, the dielectric constant and dielectric loss tangent of the evaluation board | substrate in 1 GHz were measured using the impedance analyzer (RF impedance analyzer HP4291B by Agilent Technologies).

[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. The test piece was subjected to a combustion test 10 times according to “Test for Flammability of Plastic Materials-UL 94” of Underwriters Laboratories. Specifically, a combustion test was performed twice for each of five test peels. The combustibility was evaluated by the total time of the combustion duration during the combustion test.

[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.

[Hygroscopic solder heat resistance]
The hygroscopic solder heat resistance was measured by a method according to 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 blistering could not be confirmed, it was evaluated as “◯”, and if the occurrence was confirmed, it was evaluated as “x”. Separately, a similar evaluation was performed using a solder bath at 288 ° C. instead of a solder bath at 260 ° C.

  The result in each said evaluation is shown to Tables 1-3.

  As can be seen from Tables 1 to 3, when a resin composition containing a modified polyphenylene ether compound and a crosslinkable curing agent and using a compatible phosphorus compound and an incompatible phosphorus compound as a flame retardant is used (Example 1). -17) is a laminate superior in flame retardancy compared to the case where a resin composition containing only one of a compatible phosphorus compound and an incompatible phosphorus compound is used as the flame retardant (Comparative Examples 1 and 2). A board could be manufactured. Moreover, when the modified polyphenylene ether compound terminal-modified with a substituent having a carbon-carbon unsaturated double bond is used as the polyphenylene ether compound (Examples 1 to 17), an unmodified polyphenylene ether compound is used. From the case (Comparative Examples 3 and 4), a laminate having excellent heat resistance and flame retardancy could be produced. In addition, in the case where only one of a compatible phosphorus compound and an incompatible phosphorus compound is included as a flame retardant, in order to increase the flame retardancy, if the content of the flame retardant is increased, the dielectric properties and the cured product Heat resistance and the like are reduced. Therefore, in a resin composition containing a modified polyphenylene ether compound and a crosslinkable curing agent, a combination of a compatible phosphorus compound and an incompatible phosphorus compound as a flame retardant provides excellent dielectric properties and curing. It turns out that the composition excellent in the heat resistance of a thing and a flame retardance is obtained.

Claims (11)

A modified polyphenylene ether compound terminal-modified with a substituent having a carbon-carbon unsaturated double bond;
A crosslinkable curing agent having a carbon-carbon unsaturated double bond in the molecule;
Containing flame retardants,
The flame retardant contains a compatible phosphorus compound that is compatible with the mixture of the modified polyphenylene ether compound and the crosslinkable curing agent, and an incompatible phosphorus compound that is not compatible with the mixture ;
The compatible phosphorus compound is at least one selected from the group consisting of a phosphate ester compound and a phosphazene compound,
The resin composition, wherein the incompatible phosphorus compound is at least one selected from the group consisting of a phosphinate compound and a polyphosphate compound .   2. The resin composition according to claim 1, wherein a content ratio of the compatible phosphorus compound and the incompatible phosphorus compound is 20:80 to 80:20 by mass ratio.   The content of phosphorus atoms is 1.8 to 5.2 parts by mass with respect to a total of 100 parts by mass of an organic component (excluding the flame retardant) and the flame retardant. Resin composition. The crosslinking curing agent has a weight average molecular weight of 100 to 5,000, an average 1-20 the carbon in the molecule - according to any one of claims 1 to 3 carbon unsaturated double bond Resin composition. The crosslinkable curing agent is a trialkenyl isocyanurate compound, a polyfunctional acrylate compound having two or more acrylic groups in the molecule, a polyfunctional methacrylate compound having two or more methacryl groups in the molecule, and a vinyl group in the molecule. The resin composition according to any one of claims 1 to 4 , which is at least one selected from the group consisting of two or more polyfunctional vinyl compounds. The resin composition according to any one of claims 1 to 5 , wherein the modified polyphenylene ether compound has a weight average molecular weight of 500 to 5,000 and an average of 1 to 5 substituents per molecule. Wherein the substituent at the end of the modified polyphenylene ether compounds, vinyl benzyl group, according to any one of claim 1 to 6 which is a substituent group having at least one selected from the group consisting of acrylate group and a methacrylate group, Resin composition. The resin composition according to any one of claims 1 to 7 , wherein a content ratio of the modified polyphenylene ether compound and the cross-linking curing agent is 90:10 to 30:70 by mass ratio. A prepreg obtained by impregnating a fibrous base material with the resin composition according to any one of claims 1 to 8 . A metal-clad laminate obtained by laminating a metal foil on the prepreg according to claim 9 and heating and pressing. A printed wiring board obtained by forming a circuit by partially removing the metal foil on the surface of the metal-clad laminate according to claim 10 .