JP2019023263A - Resin composition, prepreg, film with resin, metal foil with resin, metal-clad laminate, and wiring board - Google Patents

Abstract

An object of the present invention is to provide a resin composition from which a cured product having excellent dielectric properties, heat resistance, flame retardancy, moldability, interlayer adhesion, chemical resistance, and desmear properties can be obtained. A modified polyphenylene ether compound terminal-modified with a substituent having a carbon-carbon unsaturated double bond, a cross-linkable curing agent having a carbon-carbon unsaturated double bond in the molecule, and the modified polyphenylene ether. And 50 to 80 parts by mass of silica with respect to a total of 100 parts by mass of the crosslinkable curing agent, 25 to 60 parts by mass of diphenylphosphine oxide, and 100 parts by mass with respect to the total of 100 parts by mass. On the other hand, it is a resin composition containing 0.5 to 15 parts by mass of an incompatible phosphorus compound other than diphenylphosphine oxide. [Selection figure] None

Description

  The present invention relates to a resin composition, a prepreg, a film with a resin, a metal foil with a resin, a metal-clad laminate, and a wiring board.

  In various electronic devices, as the amount of information processing increases, mounting technologies such as higher integration of semiconductor devices to be mounted, higher wiring density, and multilayering are rapidly progressing. Moreover, as a wiring board used for various electronic devices, it is calculated | required that it is a wiring board corresponding to high frequency, such as a millimeter wave radar board | substrate in a vehicle-mounted use, for example.

  When a signal is transmitted to the wiring provided on the wiring board, transmission loss occurs. It is known that such transmission loss is particularly likely to occur when the signal transmitted to the wiring provided on the wiring board is a high-frequency signal. For this reason, the wiring board is required to reduce the loss during signal transmission in order to increase the signal transmission speed, and particularly to a high-frequency wiring board. In order to satisfy this requirement, it is conceivable to use a material having a low dielectric constant and dielectric loss tangent and excellent dielectric characteristics as a substrate material for manufacturing an insulating layer constituting a wiring board.

  The wiring board is also required to have excellent flame retardancy. In this respect, the resin composition used as the substrate material often contains a halogen-containing flame retardant such as a brominated flame retardant and a halogen-containing compound such as a halogen-containing epoxy resin.

  However, a resin composition containing such a halogen-containing compound contains halogen in the cured product and may generate harmful substances such as hydrogen halide during combustion. Concerns have been pointed out that adversely affect the environment. Against this background, molding materials such as substrate materials are required to be free of halogen, so-called halogen-free.

  Examples of the composition containing a flame retardant that does not contain halogen so as to realize such halogen-free include the composition described in Patent Document 1.

  Patent Document 1 includes a radical polymerizable compound having a carbon-carbon unsaturated double bond in the molecule and an incompatible phosphorus compound that is incompatible with the radical polymerizable compound, and the incompatible phosphorus compound is Describes a curable composition containing a phosphine oxide compound having two or more diphenylphosphine oxide groups in the molecule.

JP 2017-14475 A

  The resin composition described in Patent Document 1 can be made halogen-free by using a phosphorus-based flame retardant such as the phosphine oxide compound instead of a halogen-based flame retardant as a flame retardant. According to Patent Document 1, it is disclosed that a resin composition excellent in dielectric properties, heat resistance, flame retardancy, adhesive strength, and chemical resistance of a cured product can be obtained.

  In addition, the substrate material for constituting the substrate of the wiring board is required to have various characteristics in order to cope with further progress in 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 suppressing deterioration of properties such as dielectric properties, etc., while having excellent moldability, and an insulating layer It is also required that the adhesive strength between the layers constituting the layer and the circuit be high. Further, for example, during desmear treatment or repair, the substrate may be whitened due to alkali treatment under high temperature and high concentration conditions. In order to prevent this from happening, the substrate material is also required to have high chemical resistance. In addition, when a substrate is drilled with a drill or a laser, the substrate material is also required to easily remove debris generated by the drilling, that is, to have a high desmear property. For these reasons, it is required to further improve the heat resistance and flame retardancy of the cured product while maintaining excellent dielectric properties and other properties, and to be excellent in moldability, interlayer adhesion, chemical resistance, and desmearability. ing.

  The present invention has been made in view of such circumstances, and a resin composition from which a cured product excellent in dielectric properties, heat resistance, flame retardancy, moldability, interlayer adhesion, chemical resistance, and desmear properties can be obtained. The purpose is to provide goods. Another object of the present invention is to provide a prepreg, a film with a resin, a metal foil with a resin, a metal-clad laminate, and a wiring board obtained using the resin composition.

  As a result of various studies, the present inventor has found that the above object is 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. The flame retardant contains a curing agent, a flame retardant, and silica, and the content of the silica is 50 to 80 parts by mass with respect to a total of 100 parts by mass of the modified polyphenylene ether and the crosslinkable curing agent. Contains two or more incompatible phosphorus compounds that are incompatible with the mixture of the modified polyphenylene ether and the cross-linking curing agent, the incompatible phosphorus compound contains diphenylphosphine oxide, and the content of diphenylphosphine oxide Is 25-60 parts by mass with respect to a total of 100 parts by mass of the modified polyphenylene ether and the cross-linking curing agent, The content of the incompatible phosphorus compound other than nil phosphine oxide is, per 100 parts by weight of the modified polyphenylene ether and the crosslinking curing agent, characterized in that 0.5 to 15 parts by weight.

  According to such a configuration, it is possible to provide a resin composition from which a cured product having excellent dielectric properties, heat resistance, flame retardancy, moldability, interlayer adhesion, chemical resistance, and desmear properties can be obtained.

  In the resin composition, it is preferable that the incompatible phosphorus compound other than the diphenylphosphine oxide is at least one selected from the group consisting of a phosphinate compound, a polyphosphate compound, and a phosphonium salt compound.

  According to such a configuration, it is possible to provide a resin composition from which a cured product having excellent dielectric properties, heat resistance, flame retardancy, moldability, interlayer adhesion, chemical resistance, and desmear properties can be obtained.

  In the resin composition, the substituent 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, a cured product excellent in dielectric properties, heat resistance, flame retardancy, moldability, interlayer adhesion, chemical resistance, and desmear properties can be obtained.

  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, a cured product excellent in dielectric properties, heat resistance, flame retardancy, moldability, interlayer adhesion, chemical resistance, and desmear properties can be obtained.

  In the resin composition, the silica is preferably silica particles.

  According to such a configuration, a cured product excellent in dielectric properties, heat resistance, flame retardancy, moldability, interlayer adhesion, chemical resistance, and desmear properties can be obtained.

  Moreover, the prepreg which concerns on the other one aspect | mode of this invention is equipped with the said resin composition or the semi-hardened | cured material of the said resin composition, and a fibrous base material, It is characterized by the above-mentioned.

  According to such a configuration, a prepreg excellent in dielectric properties, heat resistance, flame retardancy, moldability, interlayer adhesion, chemical resistance, and desmear properties can be obtained.

  Moreover, the film with resin which concerns on another one aspect | mode of this invention is equipped with the resin layer containing the said resin composition or the semi-hardened | cured material of the said resin composition, and a support film, It is characterized by the above-mentioned.

  According to such a configuration, a film with a resin excellent in dielectric properties, heat resistance, flame retardancy, moldability, interlayer adhesion, chemical resistance, and desmear properties can be obtained.

  Moreover, the metal foil with resin which concerns on another one aspect | mode of this invention is equipped with the resin layer containing the said resin composition or the semi-hardened material of the said resin composition, and metal foil, It is characterized by the above-mentioned.

  According to such a configuration, a metal foil with resin excellent in dielectric properties, heat resistance, flame retardancy, moldability, interlayer adhesion, chemical resistance, and desmear properties can be obtained.

  In addition, a metal-clad laminate according to another embodiment of the present invention includes an insulating layer containing a cured product of the resin composition and a metal foil.

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

  Moreover, the wiring board which concerns on the other one aspect | mode of this invention is equipped with the insulating layer containing the hardened | cured material of the said resin composition, and wiring.

  According to such a configuration, a wiring board having excellent dielectric properties, heat resistance, flame retardancy, moldability, interlayer adhesion, chemical resistance, and desmear properties can be obtained.

  ADVANTAGE OF THE INVENTION According to this invention, the resin composition from which the hardened | cured material excellent in the dielectric property, heat resistance, a flame retardance, a moldability, interlayer adhesiveness, chemical resistance, and desmear property can be obtained can be provided. Moreover, according to this invention, the prepreg obtained using the said resin composition, the film with resin, metal foil with resin, a metal-clad laminated board, and a wiring board can be provided.

FIG. 1 is a schematic cross-sectional view showing a configuration of a prepreg according to an embodiment of the present invention. FIG. 2 is a schematic cross-sectional view showing a configuration of a metal-clad laminate according to an embodiment of the present invention. FIG. 3 is a schematic cross-sectional view showing a configuration of a wiring board according to an embodiment of the present invention. FIG. 4 is a schematic cross-sectional view illustrating a configuration of a resin-coated metal foil according to an embodiment of the present invention. FIG. 5 is a schematic cross-sectional view showing a configuration of a film with resin according to an embodiment of the present invention.

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

  The resin composition according to this embodiment includes a modified polyphenylene ether compound terminal-modified with a substituent having a carbon-carbon unsaturated double bond, and a cross-linkable curing agent having a carbon-carbon unsaturated double bond in the molecule. And a flame retardant and silica.

  The modified polyphenylene ether compound used in the present embodiment is not particularly limited as long as it is a modified polyphenylene ether compound 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 of the arylene group 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. It is done.

  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.

  The modified polyphenylene ether compound 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.

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.

  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.

  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 ,. When the modified polyphenylene ether compound has a repeating unit represented by the formula (5) 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 respect, it is considered that the modified polyphenylene ether compound has an unsaturated double bond at the terminal, and thus a 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.

  In the modified polyphenylene ether compound used in the present embodiment, the average number of substituents (number of terminal functional groups) at the molecular end per molecule of the modified polyphenylene ether compound 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 compound is used, due to lack of fluidity and the like, for example, molding defects such as generation of voids during multilayer molding occur, and it is difficult to obtain a highly reliable 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.

  The intrinsic viscosity of the modified polyphenylene ether compound used in the present embodiment is not particularly limited. Specifically, it is preferably 0.03 to 0.12 dl / g, more preferably 0.04 to 0.11 dl / g, and further preferably 0.06 to 0.095 dl / g. preferable. 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.

  The method for synthesizing the modified polyphenylene ether compound used in the present embodiment is not particularly limited as long as it can synthesize a modified polyphenylene ether compound terminal-modified with a substituent having a carbon-carbon unsaturated double bond. 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.

  As the compound represented by the formula (6), those exemplified above may be used alone, or two or more kinds may be used in combination.

  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 raw material polyphenylene ether is not particularly limited as long as it can finally synthesize a predetermined modified polyphenylene ether compound. 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 specific examples of such polyphenylene ether include polyphenylene ether having a structure represented by the following formula (7) or the following formula (9).

  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 a linear, branched, or cyclic hydrocarbon group. Y represents, for example, a group represented by the following formula (8).

In formula (8), R ⁹ and R ¹⁰ each independently represent a hydrogen atom or an alkyl group. Examples of the alkyl group include a methyl group. Moreover, as a functional group represented by Formula (8), a methylene group, a methylmethylene group, a dimethylmethylene group etc. are mentioned, for example.

  In Expression (9), s and t are the same as s and t in Expression (7).

  As the modified polyphenylene ether compound, a polyphenylene ether having a structure represented by formula (7) or formula (9) is terminal-modified with a substituent having a carbon-carbon unsaturated double bond as described above. preferable. Examples of the modified polyphenylene ether compound include those having a group represented by the formula (1) or the formula (4) at the terminal of the polyphenylene ether represented by the formula (7) or the formula (9). More specifically, modified polyphenylene ether compounds represented by the following formula (10) to the following formula (13) are mentioned.

In formula (10), s and t are the same as s and t in formula (7), and Y is the same as Y in formula (7). In Formula (10), R ^{1 to} R ³ are the same as R ^{1 to} R ^{3 in} Formula (1), Z is the same as Z in Formula (1), and n is This is the same as n in formula (1).

In Expression (11), s and t are the same as s and t in Expression (7). In Formula (11), R ^{1 to} R ³ are the same as R ^{1 to} R ^{3 in} Formula (1), Z is the same as Z in Formula (1), and n is This is the same as n in formula (1).

In Expression (12), s and t are the same as s and t in Expression (7), and Y is the same as Y in Expression (7). In the formula (12), ^{R 8} is the same as ^{R 8} in the formula (4).

In Expression (13), s and t are the same as s and t in Expression (7). In the formula (13), ^{R 8} is the same as ^{R 8} in the formula (4).

  Examples of the method for synthesizing the modified polyphenylene ether compound include the methods 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 compound used in this embodiment.

  The reaction is preferably performed 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.

  The reaction conditions such as reaction time and reaction temperature vary 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 is not particularly limited as long as it 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). There is no particular limitation. Specifically, toluene etc. are mentioned.

  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 used in the present embodiment preferably contains the modified polyphenylene ether compound obtained as described above as the modified polyphenylene ether compound.

  The crosslinkable 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 crosslinkable curing agent may be any one that can cure the resin composition by forming a crosslink in the resin composition by reacting with the modified polyphenylene ether compound. The cross-linking curing agent is preferably a compound having two or more carbon-carbon unsaturated double bonds in the molecule.

  The cross-linking curing agent used in the present embodiment preferably has a weight average molecular weight of 100 to 5000, more preferably 100 to 4000, and still more 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 the crosslinking type curing agent used in the present embodiment, the average number of carbon-carbon unsaturated double bonds (number of terminal double bonds) per molecule of the crosslinking type curing agent depends on the weight average molecular weight of the crosslinking type curing agent. Although it is different, for example, 1 to 20 is preferable, and 2 to 18 is more preferable. 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.

  As the number of terminal double bonds of the crosslinking type curing agent, in consideration of the weight average molecular weight of the crosslinking type curing agent, when the weight average molecular weight of the crosslinking type curing agent is less than 500 (for example, 100 or more and less than 500), 1 to It is preferable that there are four. 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.

  Specifically, the crosslinkable curing agent used in the present embodiment is a trialkenyl isocyanurate compound such as triallyl isocyanurate (TAIC), a polyfunctional methacrylate compound having two or more methacryl groups in the molecule, Polyfunctional acrylate compounds having 2 or more acrylic groups, vinyl compounds having 2 or more vinyl groups in the molecule such as polybutadiene (polyfunctional vinyl compounds), styrene having a vinylbenzyl group in the molecule, divinylbenzene, etc. And vinylbenzyl compounds. 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 used in 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).

  The content of the modified polyphenylene ether compound is preferably 30 to 90 parts by mass, and preferably 50 to 90 parts by mass with respect to 100 parts by mass in total of the modified polyphenylene ether compound and the crosslinkable curing agent. Is more preferable. 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.

  As described above, the resin composition contains the flame retardant and the silica in addition to the modified polyphenylene ether compound and the crosslinkable curing agent.

  The flame retardant used in the present embodiment includes two or more incompatible phosphorus compounds that are incompatible with the mixture of the modified polyphenylene ether compound and the cross-linking curing agent, and one of them is diphenylphosphine oxide. The incompatible phosphorus compound other than diphenylphosphine oxide (other 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. Further, incompatible, that is, incompatible, in this case, is not compatible in the mixture of the modified polyphenylene ether compound and the cross-linking curing agent, and the object (phosphorus compound) is island-shaped in the mixture. It means being in a distributed state. Examples of the other incompatible phosphorus compounds include compounds containing phosphorus and forming salts such as 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 other incompatible phosphorus compound may be used individually by 1 type, and may be used in combination of 2 or more type. Moreover, as said incompatible phosphorus compound, a phosphinate compound and a polyphosphate compound are preferable among the said illustration. Examples of diphenylphosphine oxide include paraxylylene bisdiphenylphosphine oxide.

  The content of diphenylphosphine oxide is 25 to 60 parts by mass, preferably 30 to 55 parts by mass with respect to a total of 100 parts by mass of the modified polyphenylene ether compound and the crosslinkable curing agent, and preferably 35 to 50 parts. More preferably, it is part by mass. When the content of diphenylphosphine oxide is too small, chemical resistance such as flame retardancy and alkali resistance tends to be insufficient. In addition, when a phosphorus compound other than diphenylphosphine oxide is contained so that sufficient flame retardancy can be achieved, chemical resistance such as alkali resistance tends to be further lowered. Moreover, when there is too much content of diphenylphosphine oxide, there exists a tendency for a moldability and desmear property to fall. Therefore, by making the content of diphenylphosphine oxide within the above range, not only is it excellent in dielectric properties, heat resistance, and interlayer adhesion, but it is also excellent in flame retardancy, moldability, chemical resistance, and desmear properties. A resin composition to be a cured product is obtained.

  The content of incompatible phosphorus compounds other than diphenylphosphine oxide (other incompatible phosphorus compounds) is 0.5 to 15 masses with respect to a total of 100 parts by mass of the modified polyphenylene ether compound and the crosslinkable curing agent. Part, preferably 1 to 15 parts by mass, and more preferably 2 to 15 parts by mass. When there is too little content of the said other incompatible phosphorus compound, there exists a tendency for a flame retardance and desmear property to fall. Moreover, when there is too much content of the said other incompatible phosphorus compound, there exists a tendency for a moldability to fall and for chemical resistance, such as alkali resistance, also to fall. Therefore, by setting the content of the other incompatible phosphorus compound within the above range, not only is it excellent in dielectric properties, heat resistance, and interlayer adhesion, but also flame retardancy, moldability, chemical resistance, and A resin composition that is a cured product having excellent desmear properties is obtained.

  In addition to the incompatible phosphorus compound, the flame retardant may contain a compatible phosphorus compound that is compatible with the mixture of the modified polyphenylene ether compound and the cross-linking curing agent.

  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 a phosphoric acid ester compound, a phosphazene compound, a phosphite compound, and a phosphine compound that contain phosphorus and do not form a salt. 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. Moreover, as said compatible phosphorus compound, among the above examples, a phosphazene compound is preferable.

  The silica used in this embodiment is not particularly limited. Examples of the silica include crushed silica and silica particles, and silica particles are preferable. The silica may be surface-treated silica or silica that has not been surface-treated. Examples of the surface treatment include treatment with a silane coupling agent.

  Moreover, content of the said silica is 50-80 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, and it is preferable that it is 50-70 mass parts. When there is too little content of the said silica, there exists a tendency for a flame retardance to fall. Moreover, when there is too much content of the said silica, there exists a tendency for the malfunction by containing a silica to generate | occur | produce easily. Specifically, formability and the like tend to decrease. Therefore, by setting the content of the silica within the above range, not only excellent dielectric properties, heat resistance, interlayer adhesion, chemical resistance, and desmear properties, but also excellent flame retardancy and moldability are cured. A resin composition is obtained.

  When the resin composition is produced, the silica previously surface-treated with a silane coupling agent may be added, or the silica and the silane coupling agent may be added by an integral blend method.

  The resin composition may contain a filler other than the silica. Examples of the filler include those added to increase the heat resistance and flame retardancy of the cured product of the curable composition, and to increase the dimensional stability during heating, and are not particularly limited. That is, by containing a filler, heat resistance and flame retardancy can be increased, and dimensional stability during heating can be increased. Specific examples of the filler include metal oxides such as alumina, titanium oxide, and mica, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, talc, aluminum borate, barium sulfate, and calcium carbonate. Etc.

  The resin composition according to the present embodiment is, for example, a silane coupling agent, an antifoaming agent, an antioxidant, a heat stabilizer, an antistatic agent, and an ultraviolet absorber as long as the effects of the present invention are not impaired. An additive such as an agent, a dye or pigment, a lubricant, and an inorganic filler may be further included. Especially about a silane coupling agent, it is used suitably for the improvement of adhesion | attachment with metal foil or adhesion | attachment between resin, and the coupling agent which has a carbon-carbon unsaturated double bond is preferable. Examples of the silane coupling agent include a silane coupling agent having a methacryl group in the molecule and a silane coupling agent having a vinyl group in the molecule.

  Moreover, by using the resin composition according to the present embodiment, a prepreg, a metal-clad laminate, a wiring board, a metal foil with resin, and a film with resin can be obtained as follows.

  FIG. 1 is a schematic cross-sectional view showing an example of a prepreg 1 according to an embodiment of the present invention.

  As shown in FIG. 1, the prepreg 1 according to this embodiment includes the resin composition or a semi-cured product 2 of the resin composition, and a fibrous base material 3. As this prepreg 1, the thing in which the fibrous base material 3 exists in the said resin composition or the said semi-hardened | cured material 2 is mentioned. That is, the prepreg 1 includes the resin composition or the semi-cured product 2 and the fibrous base material 3 present in the resin composition or the semi-cured product 2.

  In the present embodiment, the semi-cured product is a product obtained by curing the resin composition halfway to such an extent that the resin composition can be further cured. That is, the semi-cured product is a product obtained by semi-curing the resin composition (B-staged). For example, when heated, when the resin composition is heated, the viscosity gradually decreases, and thereafter, curing starts and the viscosity gradually increases. In such a case, the semi-curing includes a state before the viscosity is completely cured after the viscosity starts to increase.

  The prepreg obtained by using the resin composition according to the present embodiment may include a semi-cured product of the resin composition as described above, or the resin composition before curing. It may be provided. That is, it may be a prepreg comprising a semi-cured product of the resin composition (the resin composition of the B stage) and a fibrous base material, or the resin composition before curing (the resin composition of the A stage) And a prepreg provided with a fibrous base material. Specifically, for example, those in which a fibrous base material is present in the resin composition can be mentioned.

  When manufacturing a prepreg, the resin composition 2 is often prepared and used in the form of a varnish in order to impregnate the fibrous base material 3 which is a base material for forming the prepreg. That is, the resin composition 2 is usually a resin varnish prepared in a varnish shape. 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 compound and a cross-linkable curing agent, is introduced into an organic solvent and dissolved. At this time, heating may be performed as necessary. After that, by adding a component that is not dissolved in an organic solvent, for example, silica or the like, which is used as necessary, and using a ball mill, a bead mill, a planetary mixer, a roll mill or the like, it is dispersed until a predetermined dispersion state is obtained. A varnish-like composition is prepared. The organic solvent used here is not particularly limited as long as it dissolves the modified polyphenylene ether compound, the crosslinking type curing agent, and the like and does not inhibit the curing reaction. Specifically, toluene, methyl ethyl ketone (MEK), etc. are mentioned, for example.

  Examples of the method for producing the prepreg 1 include a method in which the fibrous base material 3 is impregnated with the resin composition 2, for example, the resin composition 2 prepared in a varnish form, and then dried.

  Specific examples of the fibrous base material 3 used when producing the prepreg 1 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. Specific examples of the flattening processing include a method in which a glass cloth is continuously pressed with a press roll at an appropriate pressure to compress the yarn flatly. In addition, as a fibrous base material, the thickness is 0.04-0.3 mm, for example.

  The resin composition 2 is impregnated into the fibrous base material 3 by dipping and coating. If necessary, the impregnation can be repeated several times. At this time, it is also possible to finally adjust to a desired composition and impregnation amount by repeating impregnation using a plurality of resin compositions having different compositions and concentrations.

  The fibrous base material 3 impregnated with the resin composition 2 is heated at a desired heating condition, for example, 80 ° C. or higher and 180 ° C. or lower for 1 minute or longer and 10 minutes or shorter. The prepreg 1 before curing (A stage) or semi-cured state (B stage) is obtained by heating.

  The resin composition according to this embodiment is a resin composition from which a cured product having excellent dielectric properties, heat resistance, flame retardancy, moldability, interlayer adhesion, chemical resistance, and desmear properties can be obtained. For this reason, the prepreg obtained using this resin composition can exhibit excellent dielectric properties, heat resistance, flame retardancy, moldability, interlayer adhesion, chemical resistance, and desmear properties. This prepreg can produce metal-clad laminates and wiring boards having excellent dielectric properties, heat resistance, flame retardancy, moldability, interlayer adhesion, chemical resistance, and desmear properties.

  FIG. 2 is a schematic cross-sectional view showing an example of the metal-clad laminate 11 according to the embodiment of the present invention.

  As shown in FIG. 2, the metal-clad laminate 11 includes an insulating layer 12 containing a cured product of the prepreg 1 shown in FIG. 1 and a metal foil 13 laminated together with the insulating layer 12. That is, the metal-clad laminate 11 has a metal foil 13 on an insulating layer 12 containing a cured product of the resin composition. The metal-clad laminate 11 includes an insulating layer 12 containing a cured product of the resin composition and a metal foil 13 bonded to the insulating layer 12.

  As a method of producing the metal-clad laminate 11 using the prepreg 1, one or a plurality of prepregs 1 are stacked, and a metal foil 13 such as a copper foil is stacked on both upper and lower surfaces or one surface of the prepreg 1. There is a method of producing a laminated plate 11 having a double-sided metal foil or a single-sided metal foil, by subjecting 1 to heat and pressure forming and laminating and integrating. That is, the metal-clad laminate 11 is obtained by laminating the metal foil 13 on the prepreg 1 and heating and pressing. The heating and pressing conditions can be appropriately set depending on the thickness of the metal-clad laminate 11 to be manufactured, the type of the composition of the prepreg 1, and the like. For example, the temperature may be 170 to 210 ° C., the pressure may be 3.5 to 4 MPa, and the time may be 60 to 150 minutes. Moreover, you may manufacture a metal-clad laminated board, without using a prepreg. For example, a method in which a varnish-like resin composition or the like is applied onto a metal foil, a layer containing the resin composition is formed on the metal foil, and then heated and pressurized is exemplified.

  Further, the metal-clad laminate 11 may be produced by forming a varnish-like resin composition on the metal foil 13 without using the prepreg 1 and heating and pressing.

  The resin composition according to this embodiment is a resin composition from which a cured product having excellent dielectric properties, heat resistance, flame retardancy, moldability, interlayer adhesion, chemical resistance, and desmear properties can be obtained. For this reason, the metal-clad laminate obtained using this resin composition exhibits excellent dielectric properties, heat resistance, flame retardancy, moldability, interlayer adhesion, chemical resistance, and desmear properties. Can do. This metal-clad laminate can produce a wiring board that exhibits excellent dielectric properties, heat resistance, flame retardancy, moldability, interlayer adhesion, chemical resistance, and desmear properties.

  FIG. 3 is a schematic sectional view showing an example of the wiring board 21 according to the embodiment of the present invention.

  As shown in FIG. 3, the wiring board 21 according to the present embodiment is laminated together with the insulating layer 12 used by curing the prepreg 1 shown in FIG. 1 and the insulating layer 12, and the metal foil 13 is partially removed. And the wiring 14 formed in this manner. That is, the wiring board 21 has the wiring 14 on the insulating layer 12 containing a cured product of the resin composition. The wiring board 21 includes an insulating layer 12 containing a cured product of the resin composition and a wiring 14 bonded to the insulating layer 12.

  Then, by forming a wiring by etching the metal foil 13 on the surface of the produced metal-clad laminate 11, a wiring board 21 in which wiring is provided as a circuit on the surface of the insulating layer 12 is obtained. That is, the wiring board 21 is obtained by forming a circuit by partially removing the metal foil 13 on the surface of the metal-clad laminate 11. The wiring board 21 has the insulating layer 12 excellent in dielectric properties, heat resistance, flame retardancy, moldability, interlayer adhesion, chemical resistance, and desmear properties.

  Such a wiring board is a wiring board that exhibits excellent dielectric properties, heat resistance, flame retardancy, moldability, interlayer adhesion, chemical resistance, and desmear properties.

  FIG. 4 is a schematic cross-sectional view showing an example of the metal foil 31 with resin according to the present embodiment.

  As shown in FIG. 4, the metal foil with resin 31 according to this embodiment includes a resin layer 32 including the resin composition or a semi-cured product of the resin composition, and the metal foil 13. The metal foil 31 with resin has the metal foil 13 on the surface of the resin layer 32. That is, the metal foil with resin 31 includes the resin layer 32 and the metal foil 13 laminated together with the resin layer 32. Further, the resin-attached metal foil 31 may include another layer between the resin layer 32 and the metal foil 13.

  Moreover, as the said resin layer 32, the above-mentioned semi-hardened | cured material of the said resin composition may be included, and the said resin composition before hardening may be included. That is, the metal foil with resin may include a semi-cured product of the resin composition (the resin composition of the B stage) and a metal foil, or the resin composition before curing (of the A stage). A resin-attached metal foil comprising a resin layer containing the resin composition) and a metal foil may be used. Moreover, as the said resin layer, the semi-cured material of the said resin composition or the said resin composition should just be included, and even if it contains the fibrous base material, it does not need to be included. Moreover, as a fibrous base material, the thing similar to the fibrous base material of a prepreg can be used. In addition, the said resin layer becomes an insulating layer by hardening, for example, becomes an insulating layer of a wiring board.

  Moreover, as metal foil, the metal foil used for a metal foil with resin and a metal-clad laminate can be used without limitation. Examples of the metal foil include copper foil and aluminum foil.

  The metal foil with resin 31 is manufactured, for example, by applying the varnish-like resin composition onto the metal foil 13 and heating. The varnish-like resin composition is applied onto the metal foil 13 by using, for example, a bar coater. The applied resin composition is heated, for example, under conditions of 80 ° C. or higher and 180 ° C. or lower, 1 minute or longer and 10 minutes or shorter. The heated resin composition is formed on the metal foil 13 as an uncured resin layer 32.

  The resin composition according to this embodiment is a resin composition from which a cured product having excellent dielectric properties, heat resistance, flame retardancy, moldability, interlayer adhesion, chemical resistance, and desmear properties can be obtained. Therefore, the resin-coated metal foil obtained using this resin composition exhibits excellent dielectric properties, heat resistance, flame retardancy, moldability, interlayer adhesion, chemical resistance, and desmear properties. Can do. That is, the metal foil with resin can realize excellent dielectric properties, heat resistance, flame retardancy, moldability, interlayer adhesion, chemical resistance, and desmear properties. Moreover, such a metal foil with a resin can be used when manufacturing a wiring board. Therefore, by using this metal foil with resin, it is possible to produce a wiring board having excellent dielectric properties, heat resistance, flame retardancy, moldability, interlayer adhesion, chemical resistance, and desmear properties.

  FIG. 5 is a schematic cross-sectional view showing an example of the resin-coated film 41 according to the present embodiment.

  As shown in FIG. 5, the resin-coated film 41 according to this embodiment includes a resin layer 42 including the resin composition or a semi-cured product of the resin composition, and a support film 43. This resin-equipped film 41 has a support film 43 on the surface of the resin layer 42. That is, the film 41 with resin includes the resin layer 42 and a support film 43 laminated together with the resin layer 42. Moreover, the film 41 with resin may include another layer between the resin layer 42 and the support film 43.

  Moreover, as the said resin layer 42, the above-mentioned semi-hardened | cured material of the said resin composition may be included, and the said resin composition before hardening may be included. That is, the resin composition may be provided with a semi-cured product (the resin composition of the B stage) and a support film, or the resin composition before curing (the resin composition of the A stage). The film with resin provided with the resin layer to contain and a support film may be sufficient. Moreover, as the said resin layer, the semi-cured material of the said resin composition or the said resin composition should just be included, and even if it contains the fibrous base material, it does not need to be included. Moreover, as a fibrous base material, the thing similar to the fibrous base material of a prepreg can be used. In addition, the said resin layer becomes an insulating layer by hardening, for example, becomes an insulating layer of a wiring board.

  Moreover, as the support film 43, the support film used for a film with resin can be used without limitation. As a support film, a polyester film, a polyethylene terephthalate film, etc. are mentioned, for example.

  The film 41 with resin is manufactured by, for example, applying the varnish-like resin composition on the support film 43 and heating. The varnish-like resin composition is applied onto the support film 43 by using, for example, a bar coater. The applied resin composition is heated, for example, under conditions of 80 ° C. or higher and 180 ° C. or lower, 1 minute or longer and 10 minutes or shorter. The heated resin composition is formed on the support film 43 as an uncured resin layer 42.

  The resin composition according to this embodiment is a resin composition from which a cured product having excellent dielectric properties, heat resistance, flame retardancy, moldability, interlayer adhesion, chemical resistance, and desmear properties can be obtained. For this reason, the resin-coated film obtained using this resin composition can exhibit excellent dielectric properties, heat resistance, flame retardancy, moldability, interlayer adhesion, chemical resistance, and desmear properties. it can. Moreover, such a film with a resin can be used when manufacturing a wiring board. For example, after laminating on a wiring board, a multi-layer wiring board can be manufactured by peeling the support film or peeling the support film and then laminating on the wiring board. As a wiring board obtained using such a film with resin, a wiring board having excellent dielectric properties, heat resistance, flame retardancy, moldability, interlayer adhesion, chemical resistance, and desmearing properties is manufactured. can do.

  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 1-9 and Comparative Examples 1-13]
In this example, each component used when preparing the resin composition will be described.

(Modified polyphenylene ether compound)
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, this 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 ¹ H-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.

(Crosslinking curing agent)
TAIC: triallyl isocyanurate (TAIC manufactured by Nippon Kasei Co., Ltd., molecular weight 249, number of terminal double bonds 3)
(Reaction initiator)
Peroxide: 1,3-bis (butylperoxyisopropyl) benzene (Perbutyl P manufactured by NOF Corporation)
(Silane coupling agent)
Vinyl group: Silane coupling agent having a vinyl group in the molecule (vinyl triethoxysilane, KBM-1003 manufactured by Shin-Etsu Chemical Co., Ltd.)
Glycidoxy group: Silane coupling agent having a glycidoxy group in the molecule (3-glycidoxypropyltriethoxysilane, KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.)
Methacryloxy group: Silane coupling agent having a methacryloxy group in the molecule (3-methacryloxypropyltrimethoxysilane, KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.)
Amino group: Silane coupling agent having an amino group in the molecule (3-aminopropyltriethoxysilane, KBM-903 manufactured by Shin-Etsu Chemical Co., Ltd.)
Phenylamino group: Silane coupling agent having a phenylamino group in the molecule (N-phenyl-3-aminopropyltrimethoxysilane, KBM-573 manufactured by Shin-Etsu Chemical Co., Ltd.)
Ureido group: Silane coupling agent having a ureido group in the molecule (3-ureidopropyltriethoxysilane, KBE-585 manufactured by Shin-Etsu Chemical Co., Ltd.)
(Flame retardant: Incompatible phosphorus compound)
Phosphinate compound: Trisdiethylphosphinate aluminum (Exorit OP-935 manufactured by Clariant Japan KK, phosphorus concentration 24 mass%)
Diphenylphosphine oxide: paraxylylene bisdiphenylphosphine oxide (PQ60 manufactured by Soichi Kako Co., Ltd., phosphorus concentration 12 mass%)
Polyphosphate compound: Melamine polyphosphate (Melapore 200 manufactured by BASF, phosphorus concentration 13% by mass)
(Flame retardant: compatible phosphorus compound)
Phosphate ester compound: aromatic condensed phosphate ester compound (PX-200 manufactured by Daihachi Chemical Industry Co., Ltd., phosphorus concentration 9% by mass)
Phosphazene compound: Cyclic phosphazene compound (SPB-100 manufactured by Otsuka Chemical Co., Ltd., phosphorus concentration 13% by mass)
(silica)
Silica particles: SC2500-SVJ manufactured by Admatechs Corporation
[Preparation method]
First, each component was added to toluene at a blending ratio (parts by mass) described in Tables 1 and 2 so that the solid content concentration was 60% by mass, and the mixture was 80 ° C. And stirred for 60 minutes at 80 ° C. to obtain a varnish-like resin composition (varnish).

  Next, after impregnating the obtained varnish into a glass cloth, a prepreg was produced by heating and drying at 100 to 170 ° C. for about 3 to 6 minutes. Specifically, this glass cloth is # 2116 type, E glass manufactured by Nitto Boseki Co., Ltd. In that case, it adjusts so that content (resin content) of the component which comprises resin by hardening reaction, such as a modified polyphenylene ether compound and a crosslinking type hardening | curing agent, may be about 50 mass%.

  And 4 sheets of each obtained prepreg were piled up, and the evaluation board | substrate was obtained by heat-pressing on the conditions of temperature 200 degreeC, 2 hours, and pressure 3MPa.

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

[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 in accordance with “Test for Flammability of Plastic Materials-UL 94” by Underwriters Laboratories. As a result, if the combustibility is “V-0” level, it is evaluated as “◯”, and if it is “V−1” level, it is evaluated as “△”, and the level is less than “V-1”. If so, it was evaluated as “×”.

[Formability-1]
When creating the evaluation substrate, after stacking four obtained prepregs, sandwiched between 18 μm thick copper foil, and heated and pressurized under the conditions of a temperature of 200 ° C., 2 hours, and a pressure of 3 MPa, A metal-clad laminate (copper-clad laminate) was obtained. A grid-like pattern was formed so that the remaining copper ratio was 50% with respect to the copper foils on both sides of the copper-clad laminate. The prepregs were laminated one by one on both sides of the substrate on which the lattice pattern was formed, and heating and pressurization were performed under the same conditions as when the copper-clad laminate was manufactured. It was evaluated whether or not prepreg-derived resin or the like sufficiently entered between the lattice-like patterns in the formed laminate, and voids were formed.

  The formation of this void was confirmed as follows. First, the laminate was boiled in ion exchange water for 2 hours, and then immersed in a solder bath at 260 ° C. for 20 seconds. The presence or absence of blistering in the soaked laminate was visually observed. If the swelling was confirmed, it was judged that a void was formed.

  As a result, if it was determined that no void was formed, it was evaluated as “◯”, and if it was determined that a void was formed, it was evaluated as “x”.

[Formability-2]
Evaluation was performed in the same manner as in the above “Formability-1” except that a copper foil having a thickness of 35 μm was used.

[Formability-3]
Evaluation was performed in the same manner as in the above “Formability-1” except that a copper foil having a thickness of 70 μm was used.

[Interlayer adhesion: Interlayer adhesion strength]
The evaluation substrate was peeled off between the prepregs, and the strength (interlayer adhesion strength) at that time was measured according to JIS C 6481. Specifically, the insulating layer (prepreg) on the uppermost surface of the evaluation substrate was peeled off at a speed of 50 mm / min with a tensile tester, and the peeling strength (N / mm) at that time was measured.

[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.

[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).

[Alkali resistance-1]
The evaluation substrate was immersed in a chemical solution (3 mass% NaOH aqueous solution) at 40 ° C. for 3 minutes, and then the evaluation substrate was visually confirmed. As a result, when the color change cannot be confirmed, it is evaluated as “◯”, when a slight color change is confirmed, it is evaluated as “△”, and when the clear color change is confirmed, “×”. It was evaluated.

[Alkali resistance-2]
Evaluation board | substrate was evaluated similarly to said "alkali resistance-1" except being immersed for 15 minutes in a 70 degreeC chemical | medical solution (15 mass% NaOH aqueous solution).

[Desmear property (Desmear solubility)]
The evaluation board | substrate was desmeared once on FR4 conditions using the desmear process liquid (MLB213 by the Rohm and Haas company). Then, the weight of the evaluation substrate after the desmear treatment is measured, and the weight reduction amount (mg / dm ² ) due to the desmear treatment is calculated from the weight of the evaluation substrate after the desmear treatment and the weight of the evaluation substrate before the desmear treatment. did. Specifically, if the weight loss is 5 mg / dm ² or more, it is evaluated as “◯”, and if it is 1 mg / dm ² or more and less than 5 mg / dm ² , it is evaluated as “Δ”, and 1 mg / dm. If it was less than ² , it was evaluated as “x”.

  The results in the above evaluations are shown in Tables 1 and 2.

  As can be seen from Tables 1 and 2, a modified polyphenylene ether compound terminal-modified with a substituent having a carbon-carbon unsaturated double bond, and a cross-linkable curing agent having a carbon-carbon unsaturated double bond in the molecule. And 50 to 80 parts by mass of silica with respect to a total of 100 parts by mass of the modified polyphenylene ether and the crosslinkable curing agent, and 25 to 60 parts by mass of diphenylphosphine oxide with respect to the total of 100 parts by mass, When the resin composition containing 0.5 to 15 parts by mass of an incompatible phosphorus compound other than diphenylphosphine oxide is used with respect to 100 parts by mass in total (Examples 1 to 9), the resin is not so. Compared to the case of using the composition (Comparative Examples 1 to 13), the dielectric properties, heat resistance, flame retardancy, moldability, interlayer adhesion, chemical resistance, and desmear properties are excellent. .

  Specifically, Examples 1 to 9 are found to be superior in flame retardancy and desmear solubility as compared with the case of not containing incompatible phosphorus compounds other than diphenylphosphine oxide (Comparative Example 1). It was.

  In Examples 1 to 9, when diphenylphosphine oxide is not included (Comparative Example 2) and when the content of diphenylphosphine oxide is less than 25 parts by mass with respect to the total of 100 parts by mass (Comparative Example 5) Compared to the case, it was found that there is a tendency to be excellent in flame retardancy and alkali resistance.

  Furthermore, when it is a case where diphenylphosphine oxide is not included and the flame retardant property is increased by increasing the content of the incompatible phosphorus compound in addition to diphenylphosphine oxide (Comparative Example 3), the alkali resistance is further reduced. I understood it. Moreover, even if it did not contain diphenylphosphine oxide and contained a compatible phosphorus compound (Comparative Example 7), it was found that flame retardancy and alkali resistance were not sufficient.

  Moreover, Examples 1-9 are moldability compared with the case where the content of incompatible phosphorus compounds other than diphenylphosphine oxide exceeds 15 parts by mass with respect to 100 parts by mass in total (Comparative Example 4). It was found that there was a tendency to be excellent in alkali resistance.

  Moreover, compared with the case where Examples 1-9 have content of diphenylphosphine oxide exceeding 60 mass parts with respect to the said total 100 mass parts (comparative example 6), a moldability and a desmear solubility. It was found to be excellent.

  Moreover, Examples 1-9 are compared with the case (Comparative Example 8) which does not contain an incompatible phosphorus compound, but contains the phosphorus ester compound which is a compatible compound in the quantity which fully exhibits a flame retardance. And since it was excellent in interlayer adhesiveness and the glass transition temperature was high, it turned out that it is excellent in heat resistance. Moreover, Examples 1-9 compared with the case (Comparative Example 9) which does not contain an incompatible phosphorus compound but contains the phosphazene compound, which is a compatible compound, in an amount that sufficiently exhibits flame retardancy. It was found that the dielectric properties were excellent.

  Moreover, it turned out that Examples 1-9 are excellent in a flame retardance compared with the case where the content of silica is less than 50 parts by mass with respect to the total of 100 parts by mass (Comparative Examples 10 and 11). .

  Moreover, it turned out that Examples 1-9 are excellent in a moldability compared with the case where the content of silica exceeds 80 parts by mass with respect to the total of 100 parts by mass (Comparative Examples 12 and 13).

DESCRIPTION OF SYMBOLS 1 Prepreg 2 Resin composition or semi-cured product of resin composition 3 Fibrous substrate 11 Metal-clad laminate 12 Insulating layer 13 Metal foil 14 Wiring 21 Wiring board 31 Metal foil with resin 32, 42 Resin layer 41 Film with resin 43 Support film

Claims (10)

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;
Flame retardants,
Silica and
The content of the silica is 50 to 80 parts by mass with respect to a total of 100 parts by mass of the modified polyphenylene ether and the crosslinkable curing agent,
The flame retardant contains two or more incompatible phosphorus compounds that are incompatible with the mixture of the modified polyphenylene ether and the cross-linking curing agent,
The incompatible phosphorus compound includes diphenylphosphine oxide,
The content of diphenylphosphine oxide is 25 to 60 parts by mass with respect to 100 parts by mass in total of the modified polyphenylene ether and the crosslinkable curing agent,
Content of incompatible phosphorus compounds other than diphenylphosphine oxide is 0.5 to 15 parts by mass with respect to a total of 100 parts by mass of the modified polyphenylene ether and the cross-linking curing agent. object.   The resin composition according to claim 1, wherein the incompatible phosphorus compound other than the diphenylphosphine oxide is at least one selected from the group consisting of a phosphinate compound, a polyphosphate compound, and a phosphonium salt compound.   The resin composition according to claim 1, wherein the substituent is a substituent having at least one selected from the group consisting of a vinylbenzyl group, an acrylate group, and a methacrylate group.   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 3, wherein the resin composition 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 4, wherein the silica is silica particles.   A prepreg comprising the resin composition according to any one of claims 1 to 5 or a semi-cured product of the resin composition, and a fibrous base material.   A resin-coated film comprising the resin composition according to any one of claims 1 to 5 or a resin layer containing a semi-cured product of the resin composition, and a support film.   A resin-coated metal foil comprising the resin composition according to any one of claims 1 to 5 or a resin layer containing a semi-cured product of the resin composition, and a metal foil.   A metal-clad laminate comprising an insulating layer containing a cured product of the resin composition according to any one of claims 1 to 5, and a metal foil.   A wiring board comprising: an insulating layer containing a cured product of the resin composition according to claim 1; and wiring.

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