JP2010275342A - Polyphenylene ether resin composition, prepreg, metal-clad laminate and printed-wiring board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyphenylene ether resin composition which excels in the heat resistance and the flame retardance of a cured product while maintaining excellent dielectric properties possessed by PPE and further obtains a prepreg excellent in adhesion to a metal foil and the like. <P>SOLUTION: The polyphenylene ether resin composition includes a low-molecular weight polyphenylene ether having a number average molecular weight of 800-2,000 and averaging 1.5 to 2 hydroxyl groups per molecule, an epoxy resin having averaging 2 or more epoxy groups per molecule, and a polyphosphate having a triazine skeleton and a pH of 4-7 and the contents of the low-molecular weight polyphenylene ether, the epoxy resin, and the polyphosphate are, on the basis of 100 pts.mass sum of the low-molecular weight polyphenylene ether and the epoxy resin, 60-75 pts.mass, 25-40 pts.mass, and 10-30 pts.mass, respectively. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention provides a polyphenylene ether resin composition suitably used as an insulating material for a printed wiring board, a prepreg using the polyphenylene ether resin composition, a metal-clad laminate using the prepreg, and the metal-clad laminate It relates to the printed wiring board used.

  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.

  Polyphenylene ether (PPE) has excellent dielectric properties such as dielectric constant and dielectric loss tangent even in the high frequency band (high frequency region) from the MHz band to the GHz band, so printed wiring boards for electronic devices using the high frequency band The insulating material is preferably used. However, since high molecular weight PPE generally has a high melting point, it tends to have high viscosity and low fluidity. And when a prepreg used for manufacturing a multilayer printed wiring board etc. is formed using such PPE, and a printed wiring board is manufactured using the formed prepreg, at the time of manufacturing, for example, multilayer molding Forming defects such as generation of voids occurred, and there was a problem of formability that it was difficult to obtain a highly reliable printed wiring board. In order to solve such a problem, for example, a technique of causing molecular cleavage by redistributing a high molecular weight PPE in a solvent in the presence of a phenol species and a radical initiator to lower the molecular weight of PPE. It has been known. However, when the molecular weight of PPE is lowered, there is a problem that the curing becomes insufficient and the heat resistance of the cured product is lowered.

  In addition, since PPE is relatively poor in flame retardancy, resin compositions used as insulating materials such as printed wiring boards generally include halogen flame retardants such as brominated flame retardants and tetrabromobisphenol. In many cases, a halogen-containing compound such as a halogen-containing epoxy resin such as an A-type epoxy resin is blended. However, a cured product of such a halogen-containing resin composition may generate harmful substances such as hydrogen halide during combustion, and has a drawback of adversely affecting the human body and the natural environment. Against this background, non-halogenated materials are required as insulating materials for printed wiring boards and the like.

  Thus, specific examples of the non-halogenated resin composition include the composition described in Patent Document 1 below. Patent Document 1 contains PPE, an epoxy resin, and melamine polyphosphate, and 10 to 98 parts by weight of the PPE and 90 to 90 parts by weight of the epoxy resin with respect to 100 parts by weight of the total amount of the PPE and the epoxy resin. A curable resin composition containing 2 parts by weight and 10 to 80 parts by weight of the melamine polyphosphate is described. According to Patent Document 1, it is disclosed that while being halogen-free, it maintains heat resistance, which is a characteristic of PPE, and has flame retardancy.

Japanese Patent No. 4007911

  However, in order to fully exhibit the heat resistance characteristic of PPE, it is necessary to be a high molecular weight PPE, and if a high molecular weight PPE is used, problems that may occur with the above high molecular weight PPE, For example, the problem of formability due to the viscosity being too high cannot be solved. Moreover, it is difficult to maintain heat resistance, flame retardancy and the like simply by using low molecular weight PPE. Specifically, a phosphate having a triazine skeleton such as melamine polyphosphate is used, and even when each component is within the above ranges, for example, when the content ratio of PPE is low, flame retardancy is achieved. There was a problem that it could not be fully demonstrated. Further, depending on the properties of the phosphate, for example, the pH of the phosphate, the flame retardancy cannot be sufficiently exhibited, and further, obtained by laminating a metal foil on the obtained prepreg and heating and pressing. A phenomenon that the adhesion of the metal foil of the metal-clad laminate becomes poor occurred.

  The present invention has been made in view of such circumstances, while maintaining the excellent dielectric properties possessed by PPE, it is excellent in heat resistance and flame retardancy of a cured product, and further excellent in adhesion to a metal foil or the like. Another object of the present invention is to provide a polyphenylene ether resin composition from which a prepreg can be obtained. It is another object of the present invention to provide a prepreg using the polyphenylene ether resin composition, a metal-clad laminate using the prepreg, and a printed wiring board using the metal-clad laminate.

  The polyphenylene ether resin composition of the present invention comprises a low molecular weight polyphenylene ether having a number average molecular weight of 800 to 2000 and an average of 1.5 to 2 hydroxyl groups in one molecule, and an average of two or more epoxy in one molecule. An epoxy resin having a group and a polyphosphate having a triazine skeleton having a pH of 4 to 7, and each of the low molecular weight polyphenylene ether, the epoxy resin, and the polyphosphate has a content of the low molecular weight polyphenylene It is 60-75 mass parts, 25-40 mass parts, and 10-30 mass parts, respectively with respect to a total of 100 mass parts of ether and the said epoxy resin.

  According to the said structure, the polyphenylene ether resin composition from which the prepreg excellent in the heat resistance and flame retardance of hardened | cured material, and the adhesiveness with metal foil etc. is obtained, maintaining the outstanding dielectric characteristic which PPE has. Things can be provided.

  This is considered to be that inhibition of the curing reaction between the low molecular weight polyphenylene ether and the epoxy resin is suppressed by using the polyphosphate having the structure and pH range as described above. . The polyphosphate is contained as a flame retardant so as to be in the respective content ranges together with the low molecular weight polyphenylene ether and the epoxy resin, so that the polyphosphate becomes the low molecular weight polyphenylene ether and the epoxy resin. This is thought to be because the flame retardancy of the cured product obtained by the curing reaction can be improved and the curing reaction can be suitably advanced. Therefore, even if the polyphosphate that can increase the flame retardancy is contained, the curing reaction of the low molecular weight polyphenylene ether and the epoxy resin proceeds suitably, so that the obtained cured product has flame retardancy. It is considered that a polyphenylene ether resin composition having not only excellent heat resistance but also excellent heat resistance can be obtained. And it is thought that the obtained polyphenylene ether resin composition can manufacture the prepreg excellent in adhesiveness with metal foil etc. by making the base material which comprises a prepreg impregnate.

  The polyphosphate is preferably melamine polyphosphate. According to this configuration, it is possible to provide a polyphenylene ether resin composition that is excellent in the heat resistance and flame retardancy of a cured product, and further capable of obtaining a prepreg superior in adhesiveness with a metal foil or the like.

  The epoxy resin preferably has at least one of a bisphenol F skeleton and a naphthalene skeleton. According to this configuration, it is possible to provide a polyphenylene ether resin composition that is excellent in the heat resistance and flame retardancy of a cured product, and further capable of obtaining a prepreg superior in adhesiveness with a metal foil or the like.

  The prepreg of the present invention is obtained by impregnating a fibrous base material with the polyphenylene ether resin composition. According to this configuration, it is possible to obtain a metal-clad laminate that is excellent in dielectric properties, heat resistance, and flame retardancy, and has excellent adhesion to a metal foil or the like. Furthermore, since the polyphenylene ether contained in the polyphenylene ether resin composition has a low molecular weight, the polyphenylene ether resin composition has low viscosity and high fluidity. Therefore, the obtained prepreg is excellent in reliability capable of suppressing the occurrence of molding defects when manufacturing a metal-clad laminate or a printed wiring board using the metal-clad laminate.

  The metal-clad laminate according to the present invention is obtained by laminating a metal foil on the prepreg and heating and pressing. According to this configuration, it is possible to obtain a printed wiring board that is excellent in dielectric properties, heat resistance, and flame retardancy, and can be manufactured with excellent adhesion to a circuit formed from a metal foil.

  The printed wiring board of the present invention is obtained by forming a circuit by partially removing the metal foil on the surface of the metal-clad laminate. According to this structure, what is excellent in dielectric characteristics, heat resistance, and flame retardancy and in which peeling of a circuit formed from the metal foil is suppressed can be obtained.

  According to the present invention, a polyphenylene ether resin composition capable of obtaining a prepreg having excellent heat resistance and flame retardancy of a cured product and excellent adhesion to a metal foil or the like while maintaining excellent dielectric properties of PPE. Things can be provided. Also provided are a prepreg using the polyphenylene ether resin composition, a metal-clad laminate using the prepreg, and a printed wiring board using the metal-clad laminate.

  The polyphenylene ether resin composition according to an embodiment of the present invention includes a low molecular weight polyphenylene ether having a number average molecular weight of 800 to 2000 and an average of 1.5 to 2 hydroxyl groups in one molecule, and an average of 2 in one molecule. Including an epoxy resin having one or more epoxy groups and a polyphosphate having a triazine skeleton having a pH of 4 to 7, each content of the low molecular weight polyphenylene ether, the epoxy resin, and the polyphosphate, It is 60-75 mass parts, 25-40 mass parts, and 10-30 mass parts, respectively with respect to a total of 100 mass parts of the said low molecular weight polyphenylene ether and the said epoxy resin.

  The low molecular weight polyphenylene ether is not particularly limited as long as it is a polyphenylene ether having a number average molecular weight (Mn) of 800 to 2000 and an average of 1.5 to 2 hydroxyl groups in one molecule. Specific examples include those having a number average molecular weight of 800 to 2000 directly obtained by a polymerization reaction. Moreover, when the number average molecular weight is less than 800, sufficient heat resistance of the cured product cannot be obtained, and when the number average molecular weight exceeds 2000, the melt viscosity becomes high and sufficient fluidity cannot be obtained. , Molding defects cannot be suppressed. Therefore, by using the low molecular weight polyphenylene ether, the dielectric properties are not only good in a wide frequency range, but also have sufficient fluidity to suppress molding defects. Moreover, when the number of hydroxyl groups in one molecule is less than 1.5 on average, the reactivity with the epoxy group of the epoxy resin is lowered, and sufficient heat resistance of the cured product cannot be obtained. If the number of hydroxyl groups exceeds 2 on average, the reactivity of the epoxy resin with the epoxy group becomes too high, and there is a possibility that problems such as a decrease in storage stability of the resin composition may occur.

  Specific examples of the low molecular weight polyphenylene ether include poly (2,6-dimethyl-1,4-phenylene oxide).

  Here, the number of hydroxyl groups of the low molecular weight polyphenylene ether can be determined from the standard value of the low molecular weight polyphenylene ether used. Specific examples of the number of hydroxyl groups of the low molecular weight polyphenylene ether include, for example, a numerical value representing an average value of hydroxyl groups per molecule of all the low molecular weight polyphenylene ethers present in 1 mol of the low molecular weight polyphenylene ether. Can be mentioned.

  Moreover, content of the said low molecular weight polyphenylene ether is 60-75 mass parts with respect to a total of 100 mass parts of the said low molecular weight polyphenylene ether and the said epoxy resin, and it is preferable that it is 65-70 mass parts. If the amount of the low molecular weight polyphenylene ether is too small, the excellent dielectric properties of the polyphenylene ether tend not to be maintained. If the amount is too large, the heat resistance of the cured product tends to be insufficient. That is, when the content of the low molecular weight polyphenylene ether is within the above range, the heat resistance of the cured product is sufficiently high, and the excellent dielectric properties of the polyphenylene ether can be exhibited.

  The epoxy resin is not particularly limited as long as the epoxy group has an average of two or more epoxy resins in one molecule. Specifically, for example, dicyclopentadiene type epoxy resin, bisphenol A type epoxy resin having bisphenol A skeleton, bisphenol F type epoxy resin having bisphenol F skeleton, phenol novolac type epoxy resin, naphthalene type epoxy resin having naphthalene skeleton And biphenyl type epoxy resin. These may be used alone or in combination of two or more. Among these, bisphenol A type epoxy resin, bisphenol F type epoxy resin, and naphthalene type epoxy resin are preferable from the viewpoint of good compatibility with the low molecular weight polyphenylene ether, and bisphenol F type epoxy resin and naphthalene type epoxy resin are preferable. Is more preferably used. In addition, although it is preferable not to contain a halogenated epoxy resin in the said polyphenylene ether resin composition, as long as the effect of this invention is not impaired, you may mix | blend as needed.

  Moreover, the said epoxy resin is preferable from the point which the heat resistance of the hardened | cured material of the obtained epoxy resin composition increases if the epoxy group in 1 molecule is 2 or more on average.

  In addition, the number of epoxy groups of the said epoxy resin here can be known from the specification value of the product of the said epoxy resin to be used. Specific examples of the number of epoxy groups in the epoxy resin include a numerical value representing an average value of epoxy groups per molecule of all the epoxy resins present in 1 mol of the epoxy resin.

  Moreover, content of the said epoxy resin is 25-40 mass parts with respect to a total of 100 mass parts of the said low molecular weight polyphenylene ether and the said epoxy resin, and it is preferable that it is 30-35 mass parts. If the amount of the epoxy resin is too small, the heat resistance of the cured product tends to be insufficient. If the amount is too large, the influence of the epoxy resin increases, and the excellent dielectric properties of polyphenylene ether tend not to be maintained. is there. That is, when the content of the epoxy resin is within the above range, the heat resistance of the cured product is sufficiently high, and the excellent dielectric properties of polyphenylene ether can be exhibited.

  The polyphosphate is not particularly limited as long as it is a polyphosphate having a triazine skeleton having a pH of 4 to 7, and is used for enhancing flame retardancy. Since this polyphosphate is a polymer, it is considered that not only the flame retardancy can be improved, but also hydrolysis resistance, heat resistance, and the like can be improved. In addition, the polyphosphate can exert a carbonization promoting effect on the polyphenylene ether resin more significantly than the epoxy resin. And the carbonization layer formed by exhibiting the carbonization promotion effect can suppress the spread of combustible gas and heat, and can fully raise a flame retardance. Therefore, the flame retardancy of the cured product of the obtained resin composition can be sufficiently enhanced by using the polyphosphate in combination with a predetermined amount or more of the polyphenylene ether resin.

  Specific examples of the polyphosphate include melamine polyphosphate, melam polyphosphate, melem polyphosphate, and complex salts thereof. Among these, melamine polyphosphate is preferably used. Examples of the complex salt include those described in JP-A-10-306081.

  If the pH of the polyphosphate is too low, the curing reaction between the low molecular weight polyphenylene ether and the epoxy resin tends to be inhibited, and the heat resistance of the cured product tends to decrease, and the pH of the polyphosphate is high. If it is too much, it tends to be unstable as a material or a large amount of by-products are mixed.

  The melamine polyphosphate specifically has, for example, an average particle size of preferably 10 μm or less, and more preferably 5 μm or less.

  As the polyphosphate, as described above, any polyphosphate having a triazine skeleton having a pH of 4 to 7 can be used without particular limitation. What was prepared by the method etc. which are described in -306081 gazette can be used. Examples of the method for adjusting the pH of the polyphosphate include a method for adjusting the mixing ratio of polyphosphoric acid and melamine, melam, melem and the like in the method for producing polyphosphate.

  The pH of the polyphosphate can be measured with a general pH meter.

  Moreover, content of the said polyphosphate is 10-30 mass parts with respect to a total of 100 mass parts of the said low molecular weight polyphenylene ether and the said epoxy resin, and it is preferable that it is 10-20 mass parts. If the amount of the polyphosphate is too small, there is a tendency that the flame retardancy of the cured product cannot be sufficiently increased, and if it is too large, the dielectric constant of the cured product of the obtained epoxy resin composition becomes too high, There exists a tendency for adhesiveness and heat resistance with metal foils, such as copper foil, to also fall. That is, when the content of the polyphosphate is within the above range, the flame retardancy of a cured product obtained by a curing reaction between the low molecular weight polyphenylene ether and the epoxy resin is increased, and the curing reaction is preferably performed. Can proceed to.

  Moreover, it is preferable to mix | blend a hardening | curing agent with the said polyphenylene ether resin composition. As said hardening | curing agent, what was generally used conventionally can be used, For example, if it can be used as a hardening | curing agent of the said epoxy resin, it will not specifically limit. Specific examples include amine curing agents such as primary amines and secondary amines, phenolic curing agents such as bisphenol A and bisphenol F, and acid anhydride curing agents. Among these, an amine curing agent is preferable from the viewpoint of improving curability, and specifically, diethyltoluenediamine is more preferable among the amine curing agents. The curing agent is preferably blended in an equivalent ratio of 0.1 to 0.5 equivalent with respect to the epoxy resin.

  The polyphenylene ether resin composition is blended with a curing accelerator (curing catalyst) in order to promote a crosslinking reaction (curing reaction) between the low molecular weight polyphenyl ether and the epoxy resin together with the curing agent. Is preferred. Even if the curing accelerator is not blended, the reaction can proceed if the temperature is raised, but depending on the process conditions, it may not be possible to raise the temperature. Therefore, it is preferable to blend the curing catalyst. Specific examples of such curing catalysts include, for example, organic metal salts such as octanoic acid, stearic acid, acetylacetonate, naphthenic acid, and salicylic acid, such as Zn, Cu, and Fe, triethylamine, and triethanol. Examples include tertiary amines such as amines, imidazoles such as 2-ethyl-4-imidazole, and 4-methylimidazole. These may be used alone or in combination of two or more. Among these, an organic metal salt, particularly zinc octoate, is particularly preferably used because high heat resistance can be obtained.

  The blending ratio of the curing catalyst is not particularly limited. For example, when using an organic metal salt, 0.005 to 5 parts by mass with respect to a total of 100 parts by mass of the low molecular weight polyphenylene ether and the epoxy resin. Preferably, when imidazoles are used, the amount is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass in total of the low molecular weight polyphenylene ether and the epoxy resin.

  It is preferable that a flame retardant other than the polyphosphate is further added to the polyphenylene ether resin composition as a flame retardant. The flame retardant can be used without any particular limitation. Specific examples include phosphinate flame retardants. Specific examples of the phosphinate flame retardant include phosphinic acid metal salts such as dialkylphosphinic acid aluminum salts. As said flame retardant, the said flame retardant may be used independently and may be used in combination of 2 or more type.

  The polyphenylene ether resin composition may further contain an inorganic filler as necessary for the purpose of increasing dimensional stability during heating or increasing flame retardancy.

  Specific examples of the inorganic filler include silica, alumina, talc, aluminum hydroxide, magnesium hydroxide, titanium oxide, mica, aluminum borate, barium sulfate, and calcium carbonate. In addition, the inorganic filler may be used as it is, but it is particularly preferable that the surface is treated with an epoxy silane type or amino silane type silane coupling agent. A metal-clad laminate obtained by using a polyphenylene ether resin composition containing an inorganic filler surface-treated with a silane coupling agent as described above has high heat resistance during moisture absorption and also has an interlayer peel strength. Tend to be higher.

  The polyphenylene ether resin composition is blended with additives such as heat stabilizers, antistatic agents, ultraviolet absorbers, dyes, pigments, lubricants, etc., as necessary, as long as the effects of the present invention are not impaired. Also good.

  In addition, the number average molecular weight of the said low molecular weight polyphenylene ether and the said epoxy resin in this invention can be specifically measured using a gel permeation chromatography etc., for example.

  When the prepreg is produced, the polyphenylene ether resin composition 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 polyphenylene ether resin composition is usually prepared in a varnish form in many cases. Such a varnish is prepared as follows, for example.

  First, the low molecular weight polyphenyl ether, the epoxy resin, and the like are introduced into an organic solvent and dissolved. At this time, heating may be performed as necessary. Furthermore, add curing agents, curing catalysts, flame retardants and inorganic fillers used as necessary, and use a ball mill, bead mill, planetary mixer, roll mill, etc. to disperse until a predetermined dispersion state is achieved. Thus, a varnish-like resin composition is prepared. The organic solvent is not particularly limited as long as it dissolves the low molecular weight polyphenyl ether and the epoxy resin and does not inhibit the curing reaction. Specifically, toluene etc. are mentioned, for example.

  Examples of a method for producing a prepreg using the obtained varnish-like resin composition include a method in which a fibrous base material is impregnated with the polyphenylene ether resin composition and then dried.

  Specific examples of the fibrous base material 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 the said fibrous base material, the thing of 0.04-0.3 mm can generally be used, for example.

  The impregnation is performed by dipping or coating. The 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 solutions having different compositions and concentrations, and finally adjust to a desired composition and resin amount.

  The fibrous base material impregnated with the polyphenylene ether resin composition is heated at a desired heating condition, for example, at 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 the prepregs are stacked, and a metal foil such as a copper foil is stacked on both upper and lower surfaces or one surface thereof. By heating and pressing to laminate and integrate, a double-sided metal foil-clad laminate or a single-sided metal foil-clad laminate can be produced. The heating and pressing conditions can be appropriately set depending on the thickness of the laminate to be produced, the type of the polyphenylene ether resin composition of the prepreg, etc. For example, the temperature is 170 to 210 ° C. and the pressure is 3.5 to 4.0 Pa. The time can be 60-150 minutes.

  The polyphenylene ether resin composition includes the low molecular weight polyphenylene ether, the epoxy resin, and the polyphosphate, and defines the respective contents, so that the excellent dielectric properties of the polyphenylene ether are maintained. As it is, a polyphenylene ether resin composition is obtained in which a prepreg excellent in heat resistance and flame retardancy of the cured product and in excellent adhesion to a metal foil or the like is obtained.

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

  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.

[Preparation of resin composition]
In this example, each component used when preparing the resin composition will be described.

(Polyphenylene ether)
PPE 1: Polyphenylene ether (MX90 manufactured by SABIC, number average molecular weight Mn1000, average number of hydroxyl groups in molecule 1.7)
PPE 2: Polyphenylene ether obtained by reducing the molecular weight of a high molecular weight polyphenylene ether by a known molecular weight reduction method (molecular cutting method) (number average molecular weight Mn1000, average number of hydroxyl groups in one molecule 1.1)
(Epoxy resin)
Bisphenol A type epoxy resin: Bisphenol A type epoxy resin (Epiclon 850S manufactured by DIC Corporation, number average molecular weight Mn380, average number of epoxy groups 2 in one molecule)
Bisphenol F type epoxy resin: Bisphenol F type epoxy resin (Epiclon 830S manufactured by DIC Corporation, number average molecular weight Mn340, average number of epoxy groups 2 in one molecule)
Naphthalene type epoxy resin: Naphthalene type epoxy resin (Epiclon HP5000 manufactured by DIC Corporation, number average molecular weight Mn780, average number of epoxy groups in molecule 2.5)
(Curing agent)
Amine-based curing agent: diethyltoluenediamine (Etacure 100 manufactured by Albemarle)
(Polyphosphate: flame retardant)
Melamine polyphosphate 1: Melamine polyphosphate (melapur200, pH 5 manufactured by Ciba Japan Co., Ltd.)
Melamine polyphosphate 2: Melamine polyphosphate (Fosmel 200, pH 6 manufactured by Nissan Chemical Industries, Ltd.)
Melamine polyphosphate 3: Melamine polyphosphate (Fosmel 100, pH 3.5 manufactured by Nissan Chemical Industries, Ltd.)
Condensed phosphate ester: 1,3-phenylenebis (di-2,6-xylenyl phosphate) (PX200 manufactured by Daihachi Chemical Industry Co., Ltd.)
(Curing accelerator)
2E4MZ: 2-ethyl-4-imidazole zinc octoate: manufactured by DIC Corporation [Preparation method]
The toluene solution of polyphenylene ether was heated to 90 ° C., and the epoxy resin was added so that the blending ratios shown in Tables 1 and 2 were obtained, and then the mixture was completely dissolved by stirring for 30 minutes. Further, a varnish-like resin composition (resin varnish) was obtained by adding a curing agent, a polyphosphate, a curing accelerator, and an inorganic filler and dispersing them with a ball mill.

  Next, after impregnating the obtained resin varnish into a glass cloth (WEA116E manufactured by Nitto Boseki Co., Ltd.), prepreg was obtained by heating and drying at 150 ° C. for 3 to 5 minutes.

  Then, each of the obtained prepregs was laminated and laminated, and copper foils (GT-MP manufactured by Furukawa Circuit Foil Co., Ltd., thickness 18 μm) were disposed on both outer layers, and the temperature was 180 ° C. for 2 hours. The copper-clad laminate having a thickness of 0.75 mm was obtained by heating and pressing under the condition of a pressure of 3 MPa.

  Each prepreg and copper clad laminate prepared as described above were evaluated by the method shown below.

[Average burning time]
After removing the copper foil on the surface of the copper clad laminate, a test piece having a length of 125 mm and a width of 12.5 mm was cut out. Then, the test piece was subjected to a combustion test in accordance with “Test for Flammability of Plastic Materials-UL 94” of Underwriters Laboratories, and evaluated using an average combustion time (seconds) at that time. In addition, when the flame was not extinguished, it was evaluated as “whole burning”.

[Dielectric constant]
Using a cavity resonator “CP461” manufactured by Kanto Electronics Application Development Co., Ltd., the dielectric constant of a copper clad laminate at 2 GHz was measured.

[Copper foil peel strength]
The peel strength (copper foil peel strength) of the copper foil on the surface of the copper clad laminate was measured in accordance with JIS C 6481. At this time, a pattern having a width of 10 mm and a length of 100 mm is formed on a test piece having a width of 20 mm and a length of 100 mm, and the copper foil is peeled off at a speed of 50 mm / min by a tensile tester. cm).

[Tensile elongation]
Instead of glass cloth (WEA116E manufactured by Nitto Boseki Co., Ltd.), two prepregs made using glass cloth (WEA1078 manufactured by Nitto Boseki Co., Ltd.) are stacked and laminated, and copper foil ( A copper-clad laminate was obtained by arranging GT-MP manufactured by Furukawa Circuit Foil Co., Ltd., having a thickness of 18 μm, and heating and pressing under conditions of a temperature of 180 ° C., a time of 2 hours, and a pressure of 3 MPa. Thereafter, a test piece having a width of 10 mm and a length of 8 cm was cut out from a laminate having a thickness of 0.18 mm obtained by peeling off the copper foil, and the test piece was used in a method according to JPCA-BU01. Tensile elongation (%) was measured.

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

[PCT solder heat resistance]
PCT solder heat resistance was measured by the following method.

  First, after removing the copper foil on the surface from the obtained 6 mm copper clad laminate of 50 mm × 50 mm, the laminate from which the copper foil was removed was subjected to pressure at 121 ° C., 2 atm (0.2 MPa), 2 hours. A cooker test (PCT) was performed on each sample, and the number of samples was 5 and immersed in a solder bath at 260 ° C. for 20 seconds. The presence or absence of occurrence of measling or swelling was visually observed. If the occurrence of measling or swelling was not confirmed, it was evaluated as “OK”, and if the occurrence was confirmed, it was evaluated as “NG”.

  As can be seen from Tables 1 and 2, a low molecular weight polyphenylene ether having an average of 1.5 to 2 hydroxyl groups in one molecule having an Mn of 800 to 2000 and an average of two or more epoxy groups in one molecule. An epoxy resin having a pH of 4 to 7 and a polyphosphate having a triazine skeleton, and the contents of the low molecular weight polyphenylene ether, the epoxy resin, and the polyphosphate are the low molecular weight polyphenylene ether and When using the polyphenylene ether resin composition which is 60-75 mass parts, 25-40 mass parts, and 10-30 mass parts, respectively with respect to a total of 100 mass parts of the said epoxy resins (Examples 1-6) Compared to the other cases (Comparative Examples 1 to 8), the average dielectric properties of polyphenylene ether (PPE) are maintained while maintaining the excellent dielectric properties. Long burn time, PCT solder heat resistance and high Tg, further the copper foil peel strength is high prepreg was obtained. And the tensile elongation of the hardened | cured material of the polyphenylene ether resin composition was also high.

Claims (6)

A low molecular weight polyphenylene ether having a number average molecular weight of 800 to 2000 and having an average of 1.5 to 2 hydroxyl groups in one molecule;
An epoxy resin having an average of two or more epoxy groups in one molecule;
a polyphosphate having a triazine skeleton having a pH of 4 to 7,
Each content of the said low molecular weight polyphenylene ether, the said epoxy resin, and the said polyphosphate is 60-75 mass parts, 25-40 respectively with respect to a total of 100 mass parts of the said low molecular weight polyphenylene ether and the said epoxy resin. A polyphenylene ether resin composition, characterized by being 10 parts by mass and 10 to 30 parts by mass.   The polyphenylene ether resin composition according to claim 1, wherein the polyphosphate is melamine polyphosphate.   The polyphenylene ether resin composition according to claim 1 or 2, wherein the epoxy resin has at least one of a bisphenol F skeleton and a naphthalene skeleton.   A prepreg obtained by impregnating a fibrous base material with the polyphenylene ether resin composition according to any one of claims 1 to 3.   A metal-clad laminate obtained by laminating a metal foil on the prepreg according to claim 4 and heating and pressing.   A printed wiring board obtained by forming a circuit by partially removing the metal foil on the surface of the metal-clad laminate according to claim 5.