JP6025129B2 - Resin composition, resin varnish, prepreg, metal-clad laminate, and printed wiring board - Google Patents

Description

  The present invention relates to a resin composition suitably used for an insulating material of a printed wiring board, a resin varnish containing the resin composition, a prepreg obtained using the resin varnish, and a metal obtained using the prepreg The present invention relates to a tension laminate and a printed wiring board manufactured using the prepreg.

  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. Insulating materials such as printed wiring boards 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. That is, in order to realize high-speed communication, an insulating material such as a printed wiring board is required to have a low dielectric constant and a low dielectric loss tangent.

  Polyarylene ether copolymers (PAE) such as polyphenylene ether (PPE) have excellent dielectric properties such as dielectric constant and dielectric loss tangent even in the high frequency band (high frequency region) from MHz band to GHz band. It is preferably used for an insulating material such as a printed wiring board of an electronic device using a band.

  As a composition containing a polyarylene ether copolymer, the curable composition of patent document 1 is mentioned, for example.

  Patent Document 1 includes about 5 to 50 parts by weight of polyarylene ether, about 25 to 90 parts by weight of a thermosetting resin such as benzoxazine resin, about 0.5 to 15 parts by weight of a compatibilizing agent, and thermosetting. A curable composition is described comprising about 3 to 150 parts by weight of amine curing agent per 100 parts by weight of resin.

JP-T-2004-53634

  According to Patent Document 1, it is disclosed that polyarylene ether can be present in a thermosetting resin in a state where it can be processed at a temperature suitable for addition of a low-temperature curing agent.

  However, a general polyarylene ether copolymer has a relatively high molecular weight and a high softening point, and therefore tends to have high viscosity and low fluidity. And, using the resin composition containing such a polyarylene ether copolymer, a prepreg used for producing a multilayer printed wiring board or the like is formed, and the printed wiring board is formed using the formed prepreg. When manufactured, molding defects such as generation of voids at the time of manufacturing, for example, multi-layer molding may occur, and there may be a problem of moldability that it is difficult to obtain a highly reliable printed wiring board.

  Therefore, in order to suppress the occurrence of such a problem, the use of a polyarylene ether copolymer having a relatively low molecular weight was examined. Specifically, for example, a high molecular weight polyphenylene ether is subjected to a redistribution reaction in a solvent in the presence of a phenol species and a radical initiator, thereby causing molecular cleavage, and thereby reducing the molecular weight of the polyphenylene ether. The use of was considered. That is, the polyarylene ether copolymer was reduced in molecular weight, and the use of the reduced molecular weight polyarylene ether copolymer was examined.

  However, according to the study by the present inventors, curing is insufficient only by using such a relatively low molecular weight polyarylene ether copolymer in place of a general polyarylene ether copolymer. There was a tendency for the heat resistance of the cured product to decrease.

  The present invention has been made in view of such circumstances, has excellent dielectric properties possessed by a polyarylene ether copolymer, is excellent in heat resistance and dimensional stability of a cured product, and further in moldability. The object is to provide an excellent resin composition. Moreover, it aims at providing the prepreg using the said resin composition, the metal-clad laminated board using the said prepreg, and the printed wiring board manufactured using the said prepreg.

  The resin composition according to one embodiment of the present invention has an intrinsic viscosity of 0.03 to 0.12 dl / g measured in methylene chloride at 25 ° C., and an average of 1. 5 to 3 polyarylene ether copolymer and a thermosetting compound containing a benzoxazine compound, and the total content of the polyarylene ether copolymer and the benzoxazine compound is the polyarylene ether copolymer. It is 70-100 mass parts with respect to a total of 100 mass parts of a polymer and the said thermosetting compound, It is characterized by the above-mentioned.

  In the resin composition, the benzoxazine compound preferably has a phenolphthalein structure in the molecule.

  In the resin composition, the benzoxazine compound is preferably a compound represented by the following formula (1).

In formula (1), R ¹ and R ² each independently represent an alkyl group having 1 to 10 carbon atoms or a phenyl group.

  In the resin composition, it is preferable that the polyarylene ether copolymer is composed of 2,6-dimethylphenol and at least one of bifunctional phenol and trifunctional phenol.

  In the resin composition, the content of the polyarylene ether copolymer is 40 to 80 parts by mass with respect to 100 parts by mass of the resin composition, and the content of the benzoxazine compound is the resin. It is preferable that it is 10-60 mass parts with respect to 100 mass parts of compositions.

  In the resin composition, the thermosetting compound preferably includes an epoxy compound that can react with the polyarylene ether copolymer and the benzoxazine compound.

  In the resin composition, the epoxy compound is preferably an epoxy resin having a solubility in toluene of 10% by mass or more at 25 ° C.

  Moreover, in the said resin composition, it is preferable to further contain an inorganic filler, a flame retardant, and an additive.

  Moreover, the resin varnish which concerns on the other one aspect | mode of this invention is a resin varnish containing the said resin composition and a solvent.

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

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

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

  According to the present invention, it is possible to provide a resin composition having excellent dielectric properties possessed by a polyarylene ether copolymer, excellent in heat resistance and dimensional stability of a cured product, and excellent in moldability. it can. Moreover, the prepreg using the said resin composition, the metal-clad laminated board using the said prepreg, and the printed wiring board manufactured using the said prepreg are provided.

  The present inventors first noticed that when a relatively low molecular weight polyarylene ether copolymer as described above is used, the heat resistance of the cured product tends to be low. In order to increase the heat resistance of the cured product, it is possible to use a resin other than the polyarylene ether copolymer instead of the polyarylene ether copolymer, but a polyarylene ether copolymer having excellent dielectric properties is used. It was decided. At that time, the use of a thermosetting compound in combination with a polyarylene ether copolymer having a relatively low molecular weight was examined. By doing so, it is speculated that the heat resistance of the obtained cured product can be increased by advancing the curing reaction between the polyarylene copolymer and the thermosetting compound to form a three-dimensional cross-link. did. Further, according to the study by the present inventors, the heat resistance of the cured product may not be sufficiently improved depending on the type of the thermosetting compound used.

  From the above, the present inventors have come up with the present invention as a result of various studies based on such knowledge.

  The resin composition according to the embodiment of the present invention has an intrinsic viscosity of 0.03 to 0.12 dl / g measured in methylene chloride at 25 ° C., and an average of 1. 5 to 3 polyarylene ether copolymer and a thermosetting compound containing a benzoxazine compound, and the total content of the polyarylene ether copolymer and the benzoxazine compound is the polyarylene ether copolymer. It is 70-100 mass parts with respect to a total of 100 mass parts of a polymer and the said thermosetting compound.

  Such a resin composition is a resin composition having the excellent dielectric properties of the polyarylene ether copolymer, excellent in heat resistance and dimensional stability of the cured product, and excellent in moldability.

  This is considered to be due to the following.

  First, since the benzoxazine compound can be dissolved in toluene, it is considered that the compatibility with the polyarylene ether copolymer having high solubility in toluene is high. From this, when a polyarylene ether copolymer and a benzoxazine compound are subjected to a curing reaction, three-dimensional crosslinking can be suitably formed, and the heat resistance of the obtained cured product can be increased. Conceivable.

  Further, the obtained cured product has a low coefficient of thermal expansion (CTE) and excellent dimensional stability. This is considered to be due to the high density of the three-dimensional crosslinking formed by the curing reaction between the polyarylene ether copolymer and the benzoxazine compound.

  In addition, the polyarylene ether copolymer has an intrinsic viscosity of 0.03 to 0.12 dl / g measured in methylene chloride at 25 ° C., and has a relatively low viscosity in solution, and is compatible with the benzoxazine compound. Since it is high, it is thought that the viscosity when a solvent is added to the obtained resin composition to form a resin varnish becomes low. From this, it is thought that the obtained resin composition is excellent in the moldability of the cured product.

  From the above, it is considered that the polyarylene ether copolymer has the excellent dielectric properties, the cured product is excellent in heat resistance and dimensional stability, and is further excellent in moldability.

  Hereinafter, each component of the resin composition will be described in detail.

  The polyarylene ether copolymer used in the present embodiment has an intrinsic viscosity of 0.03 to 0.12 dl / g measured in methylene chloride at 25 ° C., and an average of phenolic hydroxyl groups per molecule at the molecular terminals. The polyarylene ether copolymer having 1.5 to 3 is not particularly limited.

  The intrinsic viscosity of the polyarylene ether copolymer may be 0.03 to 0.12 dl / g, but is preferably 0.06 to 0.095 dl / g. If this intrinsic viscosity is too low, the molecular weight tends to be low, and a sufficient heat resistance of the cured product tends to be difficult to obtain. Moreover, when intrinsic viscosity is too high, there exists a tendency for viscosity to be high and sufficient fluidity | liquidity not to be obtained and to prevent a molding defect. Therefore, if the intrinsic viscosity of the polyarylene ether copolymer is within the above range, excellent heat resistance and moldability of the cured product can be realized.

  In addition, the intrinsic viscosity here can be found from the standard value of the product of the polyarylene ether copolymer used. 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.

  Moreover, as a polyarylene ether copolymer used by this embodiment, the average number (number of terminal hydroxyl groups) per molecule | numerator of the phenolic hydroxyl group of a molecule terminal should just be 1.5-3, but 1.8. It is preferable that it is -2.4 pieces. When the number of terminal hydroxyl groups is too small, the reactivity with the benzoxazine compound is lowered, and there is a tendency that it is difficult to obtain a cured product having sufficient heat resistance. Further, when the number of terminal hydroxyl groups is too large, the reactivity with the benzoxazine compound becomes too high, for example, the storage stability of the resin composition may be lowered, or problems such as an increase in dielectric constant and dielectric loss tangent may occur. There is.

  Here, the number of hydroxyl groups of the polyarylene ether copolymer can be understood from the standard value of the product of the low molecular weight polyphenylene ether used. In addition, as the number of terminal hydroxyl groups here, specifically, for example, an average value of hydroxyl groups per molecule of all the polyarylene ether copolymers present in 1 mol of the polyarylene ether copolymer was expressed. Examples include numerical values.

  Therefore, since the polyarylene ether copolymer used in the present embodiment has a relatively low molecular weight and a relatively large number of terminal hydroxyl groups, it is considered that the polyarylene ether copolymer is likely to form a three-dimensional bridge with a benzoxazine compound described later. Therefore, by using such a polyarylene ether copolymer, it has not only good dielectric properties in a wide frequency range, but also has sufficient fluidity to suppress molding defects, and further the heat resistance of the cured product. It is thought that it can be raised sufficiently.

  Moreover, as a polyarylene ether copolymer used by this embodiment, it is preferable that a number average molecular weight (Mn) is 500-3000, and it is more preferable that it is 650-1500. Moreover, when molecular weight is too low, there exists a tendency for sufficient thing as heat resistance of hardened | cured material not to be obtained. On the other hand, if the molecular weight is too high, the melt viscosity becomes high, sufficient fluidity cannot be obtained, and molding defects tend not to be suppressed. Therefore, if the intrinsic viscosity of the polyarylene ether copolymer is within the above range, more excellent heat resistance and moldability of the cured product can be realized.

  The number average molecular weight here can be specifically measured using, for example, gel permeation chromatography.

  Specifically, as the polyarylene ether copolymer used in the present embodiment, for example, a polyarylene ether copolymer composed of 2,6-dimethylphenol and at least one of a bifunctional phenol and a trifunctional phenol, Examples thereof include those containing polyphenylene ether such as poly (2,6-dimethyl-1,4-phenylene oxide) as a main component. Examples of the bifunctional phenol include tetramethylbisphenol A. More specific examples of such a polyarylene ether copolymer include a polyarylene ether copolymer having a structure represented by the general formula (2).

  In the formula (2), s and t may have a polymerization degree such that the above-described intrinsic viscosity is in the range of 0.03 to 0.12 dl / g. Specifically, the total value of s and t is preferably 1-30. Moreover, it is preferable that s is 0-20, and it is preferable that t is 0-20.

  The thermosetting compound used in the present embodiment only needs to contain a benzoxazine compound, and may contain other thermosetting compounds. That is, the thermosetting compound may be a benzoxazine compound alone or a mixture of a benzoxazine compound and a thermosetting compound other than the benzoxazine compound.

  Moreover, a benzoxazine compound will not be specifically limited if it is a compound which has a benzoxazine ring in a molecule | numerator. Specifically, a benzoxazine resin or the like may be used as long as it is a compound having a benzoxazine ring in the molecule.

  Specific examples of the benzoxazine compound include, for example, a benzoxazine compound having a phenolphthalein structure in the molecule, that is, a compound represented by the following formula (1) (phenolphthalein-type benzoxazine compound), Examples thereof include compounds represented by (3) (bisphenol F-type benzoxazine compounds) and compounds represented by the following formula (4) (diaminodiphenylmethane (DDM) -type benzoxazine compounds).

Here, in Formula (1), R ¹ and R ² each independently represent an alkyl group having 1 to 10 carbon atoms or a phenyl group, and both R ¹ and R ² are phenyl groups. preferable.

  As described above, the benzoxazine compound is not particularly limited, but a benzoxazine compound having a phenolphthalein structure in the molecule (phenolphthalein-type benzoxazine compound) is preferable. That is, specifically, a compound represented by the above formula (1) is preferable. By using such a benzoxazine compound, the heat resistance of the cured product can be further increased.

  The total content of the polyarylene ether copolymer and the benzoxazine compound is 70 to 100 parts by mass, and 75 to 100 parts by mass with respect to 100 parts by mass in total of the polyarylene ether copolymer and the thermosetting compound. Part is preferable, and 80 to 100 parts by mass is more preferable. In addition, the resin composition according to the present embodiment may be such that the total content of the polyarylene ether copolymer and the benzoxazine compound is within the above range, a thermosetting compound other than the benzoxazine compound, an inorganic filler, You may contain components, such as a flame retardant and an additive. Moreover, the resin composition according to this embodiment may be composed of a polyarylene ether copolymer and a benzoxazine compound. Moreover, when there is too little total content of a polyarylene ether copolymer and a benzoxazine compound, there exists a tendency which cannot fully improve the heat resistance of hardened | cured material. Therefore, by setting the total content of the polyarylene ether copolymer and the benzoxazine compound so as to be within the above-described range, the polyarylene ether copolymer has excellent dielectric properties, Furthermore, the heat resistance of the cured product can be sufficiently increased.

  Moreover, each content of the polyarylene ether copolymer and the benzoxazine compound may satisfy the range of the total content of the polyarylene ether copolymer and the benzoxazine compound described above, but may be in the following range: preferable. Specifically, the content of the polyarylene ether copolymer is preferably 40 to 80 parts by mass, more preferably 40 to 70 parts by mass with respect to 100 parts by mass of the resin composition, and 50 More preferably, it is -70 mass parts. Moreover, it is preferable that content of a benzoxazine compound is 10-60 mass parts with respect to 100 mass parts of resin compositions, It is more preferable that it is 20-60 mass parts, It is 20-50 mass parts. More preferably. Moreover, the content ratio of the polyarylene ether copolymer and the benzoxazine compound is preferably 9: 1 to 1: 9, more preferably 8: 2 to 2: 8, in terms of mass ratio. Moreover, it is preferable that content of a polyarylene ether copolymer is more than content of a benzoxazine compound. Therefore, it is more preferable that it is 8: 2-5: 5. If each content of the polyarylene ether copolymer and the benzoxazine compound is within the above ranges, the heat resistance of the cured product is maintained while maintaining the excellent dielectric properties of the polyarylene ether copolymer. And moldability can be improved.

  In addition, as described above, the resin composition according to the present embodiment may contain other components as long as the total content of the polyarylene ether copolymer and the benzoxazine compound is within the above range. Examples of other components include thermosetting compounds other than benzoxazine compounds, inorganic fillers, flame retardants, and additives.

  The thermosetting compound other than the benzoxazine compound is not particularly limited as long as it does not inhibit the curing reaction between the polyarylene ether copolymer and the benzoxazine compound. Specifically, for example, an epoxy compound such as an epoxy resin, a phenol resin, or the like can be given. Moreover, as a thermosetting compound other than a benzoxazine compound, it is preferable that it is an epoxy compound which can react with a polyarylene ether copolymer and a benzoxazine compound. By doing so, the hardened | cured material with higher heat resistance is obtained. This is considered to be due to not only the curing reaction of the polyarylene ether copolymer and the benzoxazine compound but also the curing reaction of the polyarylene ether copolymer and the benzoxazine compound and the epoxy compound. Moreover, as this epoxy compound, it is preferable that it is an epoxy resin whose solubility with respect to toluene is 10 mass% or more at 25 degreeC. By doing so, the heat resistance of hardened | cured material can be improved more. This is considered to be due to the following. First, since the epoxy resin has a solubility in toluene of 10% by mass or more at 25 ° C., it is considered that the compatibility with a polyarylene ether copolymer or a benzoxazine compound having a high affinity with toluene is high. From this, it is considered that a three-dimensional crosslinking can be suitably formed by curing reaction of the polyarylene ether copolymer, the benzoxazine compound and the epoxy compound. From this, it is thought that the heat resistance of the obtained hardened | cured material can be improved more.

  In addition, the content of the thermosetting compound other than the benzoxazine compound, for example, the epoxy compound is 0 to 20 parts by mass with respect to 100 parts by mass in total of the polyarylene ether copolymer and the thermosetting compound, and contained. You don't have to.

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

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

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

  Moreover, the resin composition according to the present embodiment may contain a curing accelerator. The curing accelerator) is not particularly limited as long as it can accelerate the curing reaction between the polyarylene ether copolymer and the benzoxazine compound. Specifically, for example, imidazole compounds such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, Organic phosphine compounds such as phenylphosphine, tributylphosphine, trimethylphosphine, etc., tertiary amine compounds such as 1,8-diaza-bicyclo (5,4,0) undecene-7 (DBU), triethanolamine, benzyldimethylamine, etc. And metal soaps. The exemplified metal soap refers to a fatty acid metal salt, and may be a linear fatty acid metal salt or a cyclic fatty acid metal salt. Specific examples include linear aliphatic metal salts and cyclic aliphatic metal salts having 6 to 10 carbon atoms. More specifically, for example, linear fatty acids such as stearic acid, lauric acid, ricinoleic acid, and octylic acid, cyclic fatty acids such as naphthenic acid, lithium, magnesium, calcium, barium, copper, and zinc Aliphatic metal salts composed of these metals. Among these, zinc octylate is preferably used. A hardening accelerator 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 is often prepared and used in the form of a varnish for the purpose of impregnating a base material (fibrous base material) for forming the prepreg. That is, the resin composition according to the present embodiment is usually a resin composition prepared in a varnish shape (resin varnish) in many cases. Such a resin varnish is prepared as follows, for example.

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

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

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

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

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

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

  The resin composition according to the present embodiment is a resin composition having excellent dielectric properties of the polyarylene ether copolymer and excellent in heat resistance and moldability of the cured product. For this reason, the metal-clad laminate using the prepreg obtained using the resin composition can produce a printed wiring board excellent in dielectric properties and heat resistance while suppressing the occurrence of molding defects, Is high.

  And the printed wiring board which provided the conductor pattern as a circuit on the surface of a laminated body can be obtained by carrying out the etching process etc. of the metal foil on the surface of the produced laminated body. The printed wiring board thus obtained has excellent dielectric characteristics and heat resistance, and further suppresses the occurrence of molding defects.

  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, Comparative Examples 1-5>
[Preparation of resin composition]
In this example, each component used when preparing the resin composition will be described. Here, the intrinsic viscosity (IV) measured in methylene chloride at 25 ° C. is shown. Moreover, the solubility in toluene at 25 ° C. is referred to as toluene solubility. Moreover, the average number per molecule of the phenolic hydroxyl group at the molecular end of the polyarylene ether copolymer is shown as the number of terminal hydroxyl groups.

(Polyarylene ether copolymer: PAE)
PAE 1: Polyarylene ether copolymer (MX-90 manufactured by SABIC Innovative Plastics, intrinsic viscosity (IV) 0.085 dl / g, number of terminal hydroxyl groups 1.9, number average molecular weight Mn1050)
PAE 2: Polyarylene ether copolymer synthesized by the method described in International Publication No. 2007/066769 (Intrinsic viscosity (IV) 0.06 dl / g, number of terminal hydroxyl groups 1.8, number average molecular weight Mn800)
PAE 3: Polyarylene ether copolymer synthesized by the method described in International Publication No. 2007/0667669 (Intrinsic viscosity (IV) 0.09 dl / g, terminal hydroxyl number 2.8, number average molecular weight Mn 1150)
PAE 4: Polyarylene ether copolymer (SA-120 manufactured by SABIC Innovative Plastics, intrinsic viscosity (IV) 0.13 dl / g, number of terminal hydroxyl groups 0.9, number average molecular weight Mn 3200)
PAE 5: polyarylene ether copolymer synthesized by the method described in International Publication No. 2007/0667669 (Inherent viscosity (IV) 0.15 dl / g, number of terminal hydroxyl groups 2.5, number average molecular weight Mn5000)
(Benzoxazine compound)
Phenolphthalein type benzoxazine compound: a compound represented by the above formula (1), wherein R ¹ and R ² are both phenyl groups (manufactured by Huntsman)
Bisphenol F-type benzoxazine compound: Compound represented by the above formula (3) (manufactured by Huntsman)
DDM-type benzoxazine compound: Compound represented by the above formula (4) (manufactured by Shikoku Kasei Kogyo Co., Ltd.)
(Thermosetting compounds other than benzoxazine compounds)
Epoxy resin: Cresol novolac type epoxy resin (Epiclon N690 manufactured by DIC Corporation, toluene solubility 80 mass%)
Phenol resin: TD-2090 manufactured by DIC Corporation
[Preparation method]
First, each component was added to toluene and mixed at a blending ratio shown in Table 1 so that the solid content concentration was 60% by mass. The mixture was heated to 80 ° C. and stirred at 80 ° C. for 30 minutes to obtain a varnish-like resin composition (resin varnish).

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

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

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

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

[Dielectric properties (dielectric constant and dielectric loss tangent)]
The dielectric constant and dielectric loss tangent of the evaluation 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).

[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.

[Solder heat resistance]
The 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.

[Coefficient of thermal expansion (CTE)]
The thermal expansion coefficient in the Z-axis direction of the evaluation substrate was measured by a method based on JIS C 6481. The measurement conditions were a temperature increase rate of 10 ° C./min, and the temperature range was a temperature range below Tg, specifically, 75 to 125 ° C.

[Formability]
The obtained evaluation substrate was visually evaluated.

  At that time, when no void, for example, a void due to insufficient fluidity of the resin varnish was confirmed, it was evaluated as “◯”. When the number of voids confirmed per 10 cm × 10 cm region was less than 3, it was evaluated as “Δ”, and when the number was 3 or more, it was evaluated as “x”.

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

  As can be seen from Table 1, the intrinsic viscosity measured in methylene chloride at 25 ° C. is 0.03 to 0.12 dl / g and has an average of 1.5 to 3 phenolic hydroxyl groups per molecule at the molecular terminals. A polyarylene ether copolymer and a thermosetting compound containing a benzoxazine compound, and the total content of the polyarylene ether copolymer and the benzoxazine compound is a polyarylene ether copolymer and a thermosetting compound. When the resin composition which is 70-100 mass parts is used with respect to a total of 100 mass parts (Examples 1-9), it compares with the case where other resin compositions are used (Comparative Examples 1-5). Thus, a cured product having excellent dielectric properties, moldability, and dimensional stability can be obtained, and furthermore, since the moldability is excellent, a suitable laminate can be manufactured.

  Specifically, when PAE having a high viscosity and a small number of terminal hydroxyl groups was used (Comparative Example 1), the solder heat resistance tended to be lower than that of the Examples. Moreover, when the benzoxazine compound is not included (Comparative Example 2), the thermal expansion coefficient is larger than that of the Example, so that it is considered that the dimensional stability tends to be low. Further, Comparative Example 2 tended to have a high dielectric constant, and had a tendency to be somewhat inferior in dielectric characteristics. Moreover, when it did not contain PAE (comparative example 3), since the dielectric constant was high compared with the Example, there existed a tendency for the dielectric constant to be inferior. When PAE having a high viscosity and a large number of terminal hydroxyl groups was used (Comparative Example 4), it was inferior in moldability as compared with the Examples. In addition, a resin composition in which the total content of the polyarylene ether copolymer and the benzoxazine compound is less than 70 parts by mass with respect to 100 parts by mass in total of the polyarylene ether copolymer and the thermosetting compound was used. In the case (Comparative Example 5), since the dielectric constant is higher than that of the Example, the dielectric properties are inferior and the heat resistance is also low. Moreover, since the thermal expansion coefficient is larger than that of the example, it is considered that the dimensional stability tends to be low.

  Further, from comparison between Example 1 and Example 4 and the like, it is found that a phenolphthalein type compound is preferable as the benzoxazine compound from the viewpoint of Tg.

  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 has an intrinsic viscosity of 0.03 to 0.12 dl / g measured in methylene chloride at 25 ° C., and an average of 1. 5 to 3 polyarylene ether copolymer and a thermosetting compound containing a benzoxazine compound, and the total content of the polyarylene ether copolymer and the benzoxazine compound is the polyarylene ether copolymer. It is 70-100 mass parts with respect to a total of 100 mass parts of a polymer and the said thermosetting compound, It is characterized by the above-mentioned.

  According to such a configuration, a resin composition having excellent dielectric properties of the polyarylene ether copolymer, excellent heat resistance and dimensional stability of the cured product, and excellent moldability is provided. be able to.

  In the resin composition, the benzoxazine compound preferably has a phenolphthalein structure in the molecule.

  According to such a configuration, it is possible to provide a resin composition that is more excellent in heat resistance and dimensional stability of the cured product.

  In the resin composition, the benzoxazine compound is preferably a compound represented by the above formula (1).

  According to such a configuration, it is possible to provide a resin composition that is more excellent in heat resistance and dimensional stability of the cured product.

  In the resin composition, it is preferable that the polyarylene ether copolymer is composed of 2,6-dimethylphenol and at least one of bifunctional phenol and trifunctional phenol.

  According to such a configuration, a resin composition excellent in the dielectric properties, heat resistance, and dimensional stability of the cured product can be obtained. This is suitable for three-dimensional crosslinking between the polyarylene ether copolymer and the benzoxazine compound while maintaining the excellent dielectric properties of the polyarylene ether copolymer composed of 2,6-dimethylphenol. It is thought that it can be formed.

  In the resin composition, the content of the polyarylene ether copolymer is 40 to 80 parts by mass with respect to 100 parts by mass of the resin composition, and the content of the benzoxazine compound is the resin. It is preferable that it is 10-60 mass parts with respect to 100 mass parts of compositions.

  According to such a configuration, it is possible to provide a resin composition having excellent dielectric properties of a polyarylene ether copolymer, excellent in heat resistance and dimensional stability of a cured product, and excellent in moldability. it can.

  In the resin composition, the thermosetting compound preferably includes an epoxy compound that can react with the polyarylene ether copolymer and the benzoxazine compound.

  According to such a structure, the resin composition with higher heat resistance of hardened | cured material can be provided. This is considered to be due to not only the curing reaction of the polyarylene ether copolymer and the benzoxazine compound but also the curing reaction of the polyarylene ether copolymer and the benzoxazine compound and the epoxy compound.

  In the resin composition, the epoxy compound is preferably an epoxy resin having a solubility in toluene of 10% by mass or more at 25 ° C.

  According to such a structure, the heat resistance of hardened | cured material can be improved more. This is considered to be due to the following. First, since the epoxy resin has a solubility in toluene of 10% by mass or more at 25 ° C., it is considered that the compatibility with a polyarylene ether copolymer or a benzoxazine compound having a high affinity with toluene is high. From this, it is considered that a three-dimensional crosslinking can be suitably formed by curing reaction of the polyarylene ether copolymer, the benzoxazine compound and the epoxy compound. From this, it is thought that the heat resistance of the obtained hardened | cured material can be improved more.

  Moreover, in the said resin composition, it is preferable to further contain an inorganic filler, a flame retardant, and an additive.

  According to such a structure, the performance required by what is manufactured using a resin composition, for example, performance, such as heat resistance and a flame retardance required by a laminated board, can be improved.

  Moreover, the resin varnish which concerns on the other one aspect | mode of this invention is a resin varnish containing the said resin composition and a solvent.

  According to such a configuration, a resin varnish having excellent dielectric properties, heat resistance of a cured product, dimensional stability, low viscosity, and high fluidity can be obtained. And the prepreg obtained using this resin varnish can manufacture electronic components, such as a printed wiring board, suppressing generation | occurrence | production of a molding defect.

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

  According to such a configuration, the metal-clad laminate is suitable for manufacturing a metal-clad laminate having excellent dielectric properties, cured products, formability, heat resistance, and dimensional stability. In addition, it is possible to obtain a highly reliable product that can suppress the occurrence of molding defects when manufacturing printed wiring boards.

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

  According to such a configuration, it is possible to obtain a highly reliable metal-clad laminate that can produce a printed wiring board having excellent dielectric characteristics, heat resistance, and dimensional stability while suppressing the occurrence of molding defects.

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

  According to such a configuration, it is possible to obtain a product having excellent dielectric characteristics, heat resistance, and dimensional stability, and further suppressing the occurrence of molding defects.

Claims (8)

A polyarylene ether copolymer having an intrinsic viscosity of 0.03 to 0.12 dl / g measured in methylene chloride at 25 ° C. and having an average of 1.5 to 3 phenolic hydroxyl groups per molecule at the molecular ends; ,
A resin composition comprising a thermosetting compound comprising a benzoxazine compound ,
Before SL content of benzoxazine compounds, relative to the resin composition 100 parts by weight, the resin composition characterized in that from 20 to 60 parts by weight.   The resin composition according to claim 1, wherein the polyarylene ether copolymer comprises 2,6-dimethylphenol and at least one of a bifunctional phenol and a trifunctional phenol.   The resin composition according to claim 1 or 2, wherein a content of the polyarylene ether copolymer is 40 to 80 parts by mass with respect to 100 parts by mass of the resin composition. The resin composition according to any one of claims 1 to 3 , further comprising an inorganic filler, a flame retardant, and an additive. A resin varnish containing the resin composition according to any one of claims 1 to 4 and a solvent. A prepreg obtained by impregnating a fibrous base material with the resin varnish according to claim 5 . A metal-clad laminate obtained by laminating a metal foil on the prepreg according to claim 6 and molding by heating and pressing. A printed wiring board manufactured using the prepreg according to claim 6 .