JP6282134B2 - Laminate containing PPE - Google Patents

Description

  The present invention relates to a laminate including polyphenylene ether (PPE) and a method for producing the same.

  In recent years, due to remarkable progress in information network technology and expansion of services utilizing information networks, electronic devices are required to have a large amount of information and a high processing speed. In order to transmit a large amount of digital signal at high speed, it is effective to shorten the wavelength of the signal, and the frequency of the signal is increasing. However, electric signals in the high frequency region are easily attenuated by the wiring circuit. Therefore, a printed wiring board with good transmission characteristics is required.

  Polyphenylene ether (PPE) has a dielectric property that the dielectric constant and dielectric loss tangent are low, and is excellent in high-frequency properties, so that it is suitable as a material for a printed wiring board of an electronic device using a high frequency band. Since PPE is a thermoplastic resin, when used as a substrate material, it is generally used in combination with a crosslinking agent for the purpose of imparting dimensional stability and heat resistance. Furthermore, in order to impart flame retardancy and mechanical properties desired for printed wiring board applications, it is used in combination with flame retardants and inorganic fillers.

  For example, in Patent Documents 1 and 2 below, a thermoplastic resin PPE is combined with a crosslinkable monomer such as triallyl isocyanurate, triallyl cyanurate, or a cyanate ester to obtain a curable resin composition. And a technique for producing a laminate having good electrical properties derived from PPE is disclosed. In addition, for example, Patent Documents 3 and 4 below describe techniques related to a laminate in which a flame retardant or an inorganic filler is used in combination with PPE in order to impart flame retardancy and mechanical properties.

  As a material for such a laminate, a material excellent in water absorption resistance is selected and used in order to maintain good electrical characteristics. This is because, in the high-frequency region, even with slight water absorption deterioration, the laminated plate is remarkably deteriorated in electrical characteristics, and the characteristics are greatly impaired.

JP-A 61-287739 Japanese Patent Publication No. 61-018937 Japanese Unexamined Patent Publication No. 63-25035 JP-A-8-231847

  However, in the prior art, the current situation is that the deterioration of electrical characteristics over time cannot be prevented. The cause of this is not clear, but it is expected that the slight water absorption deterioration that occurs at the interface between the materials, the uncrosslinked portion of the crosslinking agent, the strained portion, etc. in the laminate is one of the causes. In the techniques described in Patent Documents 1 to 4, there is still room for improvement with respect to such a viewpoint.

  Under such circumstances, the problem to be solved by the present invention is to prevent the deterioration of electrical characteristics over time, and to maintain the good electrical characteristics inherent in PPE, and to be suitably used as a material for high-frequency printed circuit boards, and its laminate It is to provide a manufacturing method.

As a result of intensive studies and experiments to solve the above-mentioned problems, the present inventors have found that a laminated board that solves the above-described problems can be realized by controlling the presence of the solvent in the laminated board, Based on this knowledge, the present invention has been completed.
That is, the present invention is as follows.

[1] A laminate comprising polyphenylene ether (A) and an organic solvent (B),
The organic solvent (B) is the following (a) to (c):
(A) the boiling point at 1 atmosphere is 120 ° C. or higher,
(B) The octanol / water partition coefficient LogP _OW is 0.04 or more and 4.00 or less, and (c) the amount contained in the laminate is 0.01% by mass or more and 1% by mass or less. Being
Satisfying the laminated board.
[2] The laminate according to [1], wherein the organic solvent (B) is cyclohexanone and / or cyclopentanone.
[3] The laminate plate according to [1] or [2], including a crosslinked product of a crosslinkable compound.
[4] The laminate according to [3], wherein the crosslinkable compound is a compound having two or more vinyl groups in the molecule.
[5] The laminated board according to [4], wherein the crosslinkable compound is triallyl isocyanurate.
[6] The laminate according to any one of [1] to [5], wherein the polyphenylene ether (A) has a number average molecular weight of 8000 or more.
[7] A method for producing a laminated board according to any one of [1] to [6],
(1) a step of preparing a laminate precursor containing the polyphenylene ether (A), the organic solvent (B), and a crosslinkable compound; and (2) the laminate precursor is heated and cured to obtain a laminate. The manufacturing method of a laminated board including the process of obtaining.

  ADVANTAGE OF THE INVENTION According to this invention, the laminated board which can maintain a favorable electrical property with time is provided.

  Hereinafter, exemplary modes for carrying out the present invention (hereinafter abbreviated as “embodiments”) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

  The laminated board of this embodiment contains polyphenylene ether (A) (hereinafter also referred to as PPE (A) or simply PPE). PPE is preferably the following general formula (1):

{Wherein R1, R2, R3 and R4 each independently have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a substituent. An aryl group that may be substituted, an amino group that may have a substituent, a nitro group, or a carboxyl group. } Is included.

  Specific examples of PPE include poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), and poly (2-methyl-6). -Phenyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether) and the like, and 2,6-dimethylphenol and other phenols (for example, 2,3,6-phenylene ether) And a polyphenylene ether copolymer obtained by coupling 2,6-dimethylphenol and biphenols or bisphenols, and the like. A preferred example is poly (2,6-dimethyl-1,4-phenylene ether).

  In the present disclosure, PPE means a polymer composed of a substituted or unsubstituted phenylene ether unit structure, but may further contain other copolymerization components. Moreover, the terminal is not limited to a hydroxyl group, but may be modified by a known method.

As a compounding quantity of PPE, 25 mass% or more is preferable among 100 mass% of organic substance components of a laminated board. More preferably, it is 30 mass% or more, More preferably, it is 35 mass% or more. Moreover, as an upper limit, Preferably it is 80 mass% or less, More preferably, it is 75 mass% or less, More preferably, it is 70 mass% or less. If it is 25 mass% or more, it tends to provide good electrical characteristics, which is preferable. Moreover, if it is 80 mass% or less, since it becomes the tendency for favorable heat resistance and mechanical characteristics to be acquired, it is preferable.
In addition, the organic substance component here means the whole organic substance contained in a laminated board. Therefore, for example, when an inorganic filler and an inorganic base material are contained in a laminated board, it is a component except those.

  The number average molecular weight of PPE is not particularly limited, but is preferably 8000 or more, more preferably 8500 or more, and still more preferably 9000 or more. As an upper limit, Preferably it is 40000 or less, More preferably, it is 30000 or less.

  If the number average molecular weight of PPE is 8000 or more, the peel strength of the laminate (for example, the copper foil peel strength when the laminate and the copper foil are laminated) tends to be good, which is preferable. On the other hand, if the number average molecular weight of PPE is 40000 or less, the melt viscosity at the time of shaping | molding is small, and it is desirable at the point from which favorable moldability is obtained. The molecular weight is a value measured by gel permeation chromatography in terms of standard polystyrene.

The laminated board of this embodiment contains an organic solvent (B). The organic solvent (B) is the following (a) to (c):
(A) the boiling point at 1 atmosphere is 120 ° C. or higher,
(B) The octanol / water partition coefficient LogP _OW is 0.04 or more and 4.00 or less, and (c) the amount contained in the laminate is 0.01% by mass or more and 1% by mass or less. Being
Satisfied. By including such an organic solvent (B), deterioration of electrical characteristics over time can be prevented, and the laminate can continuously retain good electrical characteristics. The cause of this is not clear, but by controlling a specific organic solvent with high hydrophobicity to be present in a specific amount in the laminate, the interface between materials, the uncrosslinked part and the distorted part of the crosslinking agent, etc. This is considered to prevent water absorption deterioration that is expected to occur at the time.

  The organic solvent (B) has a boiling point of 120 ° C. or higher at 1 atm. Preferably, it is 125 ° C. or higher, more preferably 130 ° C. or higher. If the boiling point at 1 atm is 120 ° C. or higher, it is preferable because the above-described effect of preventing water absorption deterioration can be sustained. If the boiling point is 120 ° C. or higher, it is expected that the solvent will not volatilize excessively and the effect will continue. The upper limit of the boiling point is not particularly limited, but is preferably 180 ° C. or lower. When the boiling point is 180 ° C. or lower, it is preferable that the solvent is hardly left excessively, and therefore, the electric characteristics and the heat resistance due to the organic solvent (B) itself are not exhibited.

The organic solvent (B) has an octanol / water partition coefficient (LogP _ow ) of 0.04 to 4.00. Preferably, it is 0.04 or more and 3.50 or less, More preferably, it is 0.08 or more and 3.30 or less, More preferably, it is 0.10 or more and 3.00 or less. If the distribution coefficient is 0.04 or more, the effect of preventing water absorption deterioration as described above tends to be good, which is preferable. This is presumably because an organic solvent having a partition coefficient in the above range has hydrophobicity that can well prevent water absorption deterioration. Further, if the distribution coefficient is 4.00 or less, the affinity with PPE tends to be improved, and therefore, it tends to be easy to produce a varnish for use in producing a laminate, which is preferable.

  The amount of the organic solvent (B) contained in the laminate is 0.01% by mass or more and 1% by mass or less. Preferably, they are 0.05 mass% or more and 0.9 mass% or less, More preferably, they are 0.1 mass% or more and 0.8 mass% or less.

  If the amount of the organic solvent (B) in the laminate is 0.01% by mass or more, the effect of preventing water absorption deterioration as described above tends to be good, which is preferable. Moreover, if it is 1 mass% or less, it becomes the tendency for the deterioration of an electrical property or heat resistance resulting from this organic solvent (B) itself not to express, and it is preferable.

  The amount of the organic solvent (B) in the laminated plate can be controlled relatively easily by selecting a solvent satisfying the above characteristics (a) and (b) and incorporating it into a normal production method of the laminated plate. For example, when manufacturing a laminated board by coating using a varnish, the organic solvent (B) is used as the solvent or a part of the solvent, and the drying conditions can be adjusted and controlled. Moreover, when manufacturing a laminated board through a press molding process, it can control by adjusting molding conditions, such as a pressure, heating temperature, and a temperature increase rate.

  The organic solvent (B) is not particularly limited as long as it has the above characteristics, but is preferably a nonpolar solvent from the viewpoint of affinity with PPE, and examples thereof include cyclohexanone, cyclopentanone, and xylene. Of these, cyclohexanone and / or cyclopentanone are particularly preferable. The type of organic solvent (B) contained in the laminate may be single or plural.

  The laminated board of this embodiment can contain various components according to the objective other than PPE (A) and the organic solvent (B).

The laminated board of this embodiment can contain the crosslinked body of a crosslinkable compound. Although there is no restriction | limiting in particular as a crosslinkable compound, From a viewpoint of an electrical property, the monomer which has a 2 or more vinyl group in a molecule | numerator, the compound which has a 2 or more cyanate group in a molecule | numerator, etc. are mentioned.
Examples of the compound having two or more cyanate groups in the molecule include 2,2-bis (4-cyanatophenyl) propane, bis (3,5-dimethyl-4-cyanatophenyl) methane, 2,2 -Aromatic cyanate ester compounds such as bis (4-cyanatophenyl) ethane or derivatives thereof.
Examples of monomers having two or more vinyl groups in the molecule include triallyl isocyanurate (TAIC), trimethallyl isocyanurate, triallyl cyanurate, triallylamine, triallyl mesate, divinylbenzene, divinylnaphthalene, divinyl. Biphenyl and derivatives thereof may be mentioned.
As the crosslinked compound, those having two or more vinyl groups in the molecule are preferable from the viewpoint of heat resistance and water absorption after crosslinking, and among them, TAIC having good compatibility with PPE is preferable.

  As a compounding quantity of a crosslinked body, as a ratio which occupies in the total amount of PPE and a crosslinked body, Preferably it is 5-50 mass%, More preferably, it is 10-45 mass%, More preferably, it is 15-40 mass%. The content of 5% by mass or more is preferable from the viewpoint of heat resistance, and the content of 50% by mass or less is preferable from the viewpoint of electrical characteristics.

  The laminated board of this embodiment can further contain an appropriate additive. Examples of the additive include a flame retardant, a heat stabilizer, an antioxidant, a UV absorber, a surfactant, a lubricant, a filler, and a polymer additive.

  For example, the flame retardant is not particularly limited as long as it has a function of hindering the combustion mechanism. Inorganic flame retardants such as antimony trioxide, aluminum hydroxide, magnesium hydroxide, zinc borate, hexabromobenzene, deca And aromatic bromine compounds such as bromodiphenylethane, 4,4-dibromobiphenyl, and ethylenebistetrabromophthalimide. Among these, decabromodiphenylethane and the like are preferable from the viewpoint of keeping the dielectric constant and dielectric loss tangent of the obtained laminated plate low.

  The amount of the additive used is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and still more preferably 15 parts by mass or more with respect to 100 parts by mass in total of the PPE and the crosslinked product of the crosslinkable compound. Further, from the viewpoint of keeping the dielectric constant and dielectric loss tangent of the obtained laminated plate small, the amount of the additive used is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, and still more preferably 40 parts by mass or less. .

The laminate may further contain an additional solvent other than the organic solvent (B), but when an additional solvent is present in the laminate, the total amount of the organic solvent (B) and the additional solvent is 100 mass. %, The amount of the additional solvent is preferably 70% by mass or less, more preferably 50% by mass or less, still more preferably 30% by mass or less, and most preferably 10% by mass or less. If the amount of the additional solvent is 70% by mass or less, the effect of the organic solvent (B) tends to be obtained, which is preferable.
From the viewpoint of heat resistance and electrical properties of the laminate, the total of the organic solvent (B) and the additional solvent contained in the laminate is preferably 1.2% by mass or less, more preferably 1.1% by mass. Hereinafter, it is more preferably 1.0% by mass or less.

  The laminate of the present embodiment typically includes an insulating layer containing PPE (A) and an organic solvent (B) and a conductive layer such as a copper foil or a metal foil with resin. A laminated board can be manufactured by the following methods, for example.

Another embodiment of the present invention comprises the following steps:
(1) a step of preparing a laminate precursor containing polyphenylene ether (A), an organic solvent (B), and a crosslinkable compound; and (2) heat-curing the laminate precursor to obtain a laminate. It is a manufacturing method of a laminated board including a process. The details of polyphenylene ether (A), organic solvent (B) and crosslinkable compound are as described above.

  The laminate precursor in such an embodiment is prepared from a varnish containing PPE (A), an organic solvent (B), and a crosslinkable compound. The varnish can contain a solid content containing PPE (A) and a crosslinkable compound (hereinafter, the solid content in the varnish is also referred to as a resin composition) and a solvent or dispersion medium containing an organic solvent (B). . Laminate precursors can be obtained by coating the varnish on a base material using a support film as a base material, and by removing the solvent in the varnish substantially, or by using the varnish as a porous base material. A prepreg obtained by impregnating and substantially removing the dispersion medium in the varnish is included.

  Examples of the support film include polyolefin such as polyethylene and polypropylene; polyvinyl chloride; polyester such as polyethylene terephthalate and polyethylene naphthalate; polycarbonate; polyimide; metal foil such as copper foil and aluminum foil; . In addition, the support film may be subjected to chemical and / or physical treatment such as mud treatment, corona treatment, and release treatment in advance.

  Examples of the porous substrate include various glass cloths such as roving cloth, cloth, chopped mat, and surfacing mat, asbestos cloth, metal fiber cloth, and other synthetic or natural inorganic fiber cloth; wholly aromatic polyamide fiber, Woven or non-woven fabrics obtained from liquid crystal fibers such as wholly aromatic polyester fibers and polybenzoxazole fibers; natural fiber fabrics such as cotton cloth, linen and felt; carbon fiber cloth, kraft paper, cotton paper, paper-glass mixed paper Examples thereof include natural cellulose-based substrates such as cloth, polytetrafluoroethylene porous film, and the like, and these can be used alone or in combination of two or more.

  In addition, it is preferable that the ratio of the resin composition which occupies for a prepreg (after dispersion medium removal) is 30-80 mass parts with respect to 100 mass parts of prepreg whole quantity, More preferably, it is 40-70 mass parts. When the ratio of the resin composition is 30 parts by mass or more, for example, when a prepreg is used as an insulating material for molding an electronic circuit board, it is preferable because excellent insulation reliability and electrical characteristics are obtained. Moreover, when the ratio of a resin composition is 80 mass parts or less, since the obtained electronic circuit board tends to be excellent in mechanical characteristics, such as a bending elasticity, it is preferable, for example.

  A laminated board can be manufactured by, for example, laminating one or more of the above-mentioned laminated board precursors with a copper foil and then curing the resin component by press molding to form an insulating layer. For example, a metal foil with resin can be used instead of the copper foil.

  Hereinafter, the present embodiment will be described more specifically with reference to examples and comparative examples. However, the present embodiment is not limited to the following examples as long as the gist of the present embodiment is not exceeded.

Low molecular weight PPE was prepared according to the following production example and used in the examples.
In addition, the number average molecular weight of PPE in an Example was calculated | required by the comparison with the elution time of the standard polystyrene of molecular weight known by gel permeation chromatography (GPC). HLC-8220GPC (manufactured by Tosoh Corporation) is used as a measuring device, and measurement is performed under the conditions of column: Shodex LF-804 × 2 (manufactured by Showa Denko KK), eluent: chloroform at 50 ° C., detector: RI. It was.

<Production Example 1: Low molecular weight PPE>
A 10 L flask was placed in an oil bath heated to 90 ° C., and nitrogen gas was introduced into the flask at a rate of 30 ml per minute. Thereafter, the operation was always performed under a nitrogen gas stream. PPE (S202A, manufactured by Asahi Kasei Chemicals Corporation, number average molecular weight 18000), 1 kg, and 3 kg of toluene were added and dissolved by stirring. Further, a solution obtained by dissolving 80 g of bisphenol A in 350 g of methanol was added to the flask with stirring. After stirring for 5 minutes, 3 ml of 6 mass% cobalt naphthenate mineral spirit solution was added with a syringe, and stirring was continued for 5 minutes. Subsequently, 1125 g of toluene was added to 375 g of the benzoyl peroxide solution, and a solution diluted so that the benzoyl peroxide concentration was 10% by mass was placed in a dropping funnel and dropped into the flask over 2 hours. After completion of the dropping, heating and stirring were further continued for 2 hours to obtain a reaction liquid containing low molecular weight PPE. A large amount of methanol was added thereto to precipitate low molecular weight PPE, and after filtration, dried, low molecular weight PPE was obtained. The number average molecular weight of the obtained low molecular weight PPE was 2,800.

<Production Example 2: Low molecular weight / benzylated PPE>
By the same method as in Production Example 1, the process up to the step before precipitation of PPE by adding methanol was carried out to obtain a reaction solution containing low molecular weight PPE. The temperature of the reaction solution was lowered to 50 ° C., an aqueous solution in which 340 g of sodium hydroxide was dissolved in 3050 g of ion-exchanged water and 31 g of tetrabutylammonium iodide were added and stirred for 5 minutes. Subsequently, after adding 1070 g of benzyl chloride, stirring was continued for 4 hours at a temperature of 50 ° C. to obtain a reaction solution containing a low molecular weight / benzylated polyphenylene ether. A large amount of methanol was added thereto to precipitate a low molecular weight / benzylated polyphenylene ether, filtered and dried to obtain a low molecular weight / benzylated PPE.
The number average molecular weight of the obtained low molecular weight / benzylated PPE was 3,000.

<Production Example 3: Low molecular weight / vinylbenzylated PPE>
A low molecular weight vinylbenzylated PPE was obtained in the same manner as in Production Example 2, except that 1070 g of benzyl chloride was changed to 1290 g of chloromethylstyrene.
The number average molecular weight of the obtained low molecular weight vinylbenzylated PPE was 3,100.

[Examples 1-16, Comparative Examples 1-5]
A coating varnish for PPE containing the composition shown in Table 1 is prepared, impregnated with an E glass glass cloth (2116 style, manufactured by Asahi Schwer) with a thickness of about 0.1 mm, and the excess varnish is scraped off with a slit. After dropping, it was dried under various conditions in a drier to obtain a prepreg in which a necessary amount of the solvent remained. Using the prepreg as a laminate precursor, a laminate was produced by the following method, and the physical properties in the examples were measured.

(1) Solvent content The solvent content of the laminate was measured by gas chromatography by the following method.

Two prepregs are stacked, and 35 μm copper foil (GTS-MP foil, Furukawa Electric Co., Ltd.) is stacked on top and bottom of the prepreg so that the profile surface is on the prepreg side, and heated from room temperature at a heating rate of 3 ° C./min. While pressing at a pressure of 10 kg / cm ² and reaching 130 ° C., heating at a rate of temperature increase of 3 ° C./min and vacuum pressing at a pressure of 40 kg / cm ² and reaching 200 ° C. A laminate was produced by performing vacuum pressing under the conditions of a pressure of 40 kg / cm ² and a time of 60 minutes while maintaining the temperature at 200 ° C.

  The laminate was etched by a known method using iron chloride, and after removing the copper foil completely, 3 g was accurately cut out. The cut 3 g laminated plate is further finely cut to about 5 mm square, put into 60 g of chloroform (Sigma Aldrich ≧ 99.5%), stirred for 3 hours, and allowed to stand for 24 hours to obtain a residual solvent contained in the laminated plate. Was extracted into chloroform. Next, the solid content was removed by filtration operation, 0.1 g of precisely weighed n-hexadecane (Sigma Aldrich ≧ 99%) was added, and chloroform was further added to prepare a sample solution having a total amount of 100 g. The sample solution was measured with a capillary gas chromatograph (GC-2010, Shimadzu Corporation), and the solvent content was quantified using hexadecane as an internal standard substance.

(2) Boiling point of contained solvent About the containing solvent of the laminated board identified by the gas chromatography by the above-mentioned method, the same solvent was obtained as a reagent and measured based on the average reflux boiling point test as described in JISK2233.

(3) 1-Octanol / water partition coefficient of the solvent (LogP _ow )
About the solvent of the laminated board identified by the gas chromatography by the above-mentioned method, the same solvent was obtained as a reagent and it measured based on the flask shaking method as described in JISZ7260-107.

(4) Dielectric loss tangent The change with time of the dielectric loss tangent of the laminate was measured by the following method.
Except for stacking 10 prepregs, vacuum press molding was performed under the same conditions as described above to produce a laminate. The laminated plate is etched using iron chloride by a known method to completely remove the copper foil, and then five test pieces having a length of about 50 mm and a width of about 1.5 mm are cut out and dried at 105 ° C. for 2 hours. Then, the dielectric loss tangent of 10 GHz was measured under the following conditions.

Measurement 1: Measured immediately after drying Measurement 2: Measured after standing in a constant temperature room at 23 ° C. and 50% RH for 24 hours Measurement 3: Measured after standing in a constant temperature room at 23 ° C. and 50% RH for 240 hours Using a network analyzer (manufactured by E8362B Agilent Technologies), measurement was performed using a cavity resonator (manufactured by Kanto Electronics Application Development Co., Ltd., CP531) under conditions of a frequency of 10 GHz. The measurement was performed on five cut out test pieces, and the average value was taken as the value of dielectric loss tangent.

(5) Copper foil peel strength Two of the above prepregs were stacked and vacuum press molded under the same conditions as described above. The obtained laminate was cut into a size of 15 mm in width x 150 mm in length, and using an autograph (AG-5000D, manufactured by Shimadzu Corporation), the copper foil was removed at an angle of 90 ° C with respect to the removal surface at 50 mm / min. The average value of the load when peeled off at a speed was measured, the average value of five measurements was obtained, and the following evaluation was performed.

○: Copper foil peel strength is 1.4 kN / m or more ×: Copper foil peel strength is less than 1.4 kN / m

Details of the materials are as follows.

The partition coefficient and boiling point of the solvent are as follows.

As shown in Table 1, in Examples 1-16, the laminated board which has a favorable electrical property continuously could be obtained.
In Comparative Example 1, the content of the organic solvent was insufficient, and it was not possible to prevent deterioration of electrical characteristics over time.
In Comparative Example 2, the content of the organic solvent was excessive, and good electrical characteristics could not be obtained.
In Comparative Examples 3 and 5, the boiling point of the organic solvent was low, and the electrical characteristics over time could not be sufficiently prevented.
In Comparative Example 4, the partition coefficient of the organic solvent was low, and good electrical characteristics could not be obtained. This is presumably because the hydrophobicity of the organic solvent was insufficient.

Claims (5)

A laminate comprising a polyphenylene ether (A), an organic solvent (B), and a crosslinked product of a crosslinkable compound ,
The organic solvent (B) is the following (a) to ( d ):
(A) the boiling point at 1 atmosphere is 120 ° C. or higher,
(B) The octanol / water partition coefficient LogP _OW is 0.04 or more and 4.00 or less ,
(C) The amount contained in the laminate is 0.01% by mass or more and 1% by mass or less, and
(D) being cyclohexanone and / or cyclopentanone,
Satisfying the laminated board. The crosslinking compound is a compound having two or more vinyl groups in the molecule, the laminate of claim 1. The laminated board of Claim 2 whose said crosslinkable compound is triallyl isocyanurate. The laminated board as described in any one of Claims 1-3 whose number average molecular weights of the said polyphenylene ether (A) are 8000 or more. It is a manufacturing method of the laminated board as described in any one of Claims 1-4 ,
(1) a step of preparing a laminate precursor containing the polyphenylene ether (A), the organic solvent (B), and a crosslinkable compound; and (2) the laminate precursor is heated and cured to obtain a laminate. The manufacturing method of a laminated board including the process of obtaining.