JPH0726013B2 - Curable polyphenylene ether resin composition, and composite material and laminate using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention relates to a curable polyphenylene ether resin composition,
And a cured polyphenylene ether resin composition obtained by curing the resin composition. Furthermore, the present invention provides a curable composite material comprising the curable polyphenylene ether resin composition and a substrate, a cured composite material obtained by curing the curable composite material, and the cured composite material and a metal foil. And a laminated body.

[Conventional technology]

In recent years, there has been a remarkable trend toward miniaturization and high density of mounting methods in the field of electronic devices for communication, consumer use, industrial use, etc., and accordingly, better heat resistance in terms of materials,
Dimensional stability and electrical characteristics are being demanded. For example, as a printed wiring board, a copper-clad laminate having a thermosetting resin such as a phenol resin or an epoxy resin as a base material has been conventionally used. Although these have various performances in a well-balanced manner, they have the drawback of poor electrical characteristics, especially dielectric characteristics in the high frequency region. Polyphenylene ether has recently attracted attention as a new material for solving this problem, and its application to copper-clad laminates has been attempted.

Polyphenylene ether is an engineering plastic with excellent mechanical and electrical properties, and has relatively high heat resistance. However, when it is intended to be used as a printed circuit board material, extremely high heat resistance of solder is required, so that the heat resistance inherent to polyphenylene ether cannot be said to be sufficient. That is, polyphenylene ether is 20
When it is exposed to a high temperature of 0 ° C or higher, it deforms, causing a significant decrease in mechanical strength and peeling of the copper foil formed on the resin surface for circuits. Further, polyphenylene ether has strong resistance to acids, alkalis and hot water, but has extremely weak resistance to aromatic hydrocarbon compounds and halogen-substituted hydrocarbon compounds and is soluble in these solvents.

As one of the methods for improving the heat resistance and chemical resistance of polyphenylene ether, a method of introducing a crosslinkable functional group into the chain of polyphenylene ether and further curing it to utilize it as a cured polyphenylene ether has been proposed,
So far, no satisfactory solution has been obtained.

Kurian et al., As a curable polyphenylene ether,
Polymers of 2-allyl-6-methylphenol or 2,6-diallylphenol are described in Journal of Polymer Science, 49th.
Volume, 267 (1961). However, these homopolymerizations only give low molecular weight products, and when the obtained polymers are left in the air, they cure in a few weeks and become unusable.

U.S. Pat.Nos. 3,281,393 and 34,2062 describe 2,6-dimethylphenol and 2-allyl-6-methylphenol or
Copolymers with 2,6-diallylphenol are disclosed. Although this copolymer has a high molecular weight, its melting temperature is higher than the curing temperature, so that it cannot be thermoformed. As a method for improving such moldability, US Pat.
In this issue, the use of a large amount of plasticizers has been tried,
This not only impairs the excellent dielectric properties (low dielectric constant, low dielectric loss tangent) of polyphenylene ether, but also leads to deterioration in heat resistance and chemical resistance. Further, the tensile strength of this cured product is 28 kg / cm ² , which is an extremely low value as shown in Example 7, and it cannot be said that it can be practically used.

On the other hand, US Pat. No. 4,634,742 discloses vinyl group-substituted polyphenylene ether. This is obtained by using a polymer of 2,6-dimethylphenol to convert a methyl group of the polymer into a vinyl group, or by introducing a vinyl group into the 3,5 position of a phenyl group. . That is, the vinyl group thus introduced is directly bonded to the aromatic ring of the polyphenylene ether without passing through a flexible carbon chain or an ether bond, and thus lacks flexibility after curing,
It becomes an extremely brittle material and cannot be put to practical use. Further, this polymer has a low crosslinking reactivity and has a drawback that a high temperature of 300 ° C. or higher is required for crosslinking.

In order to solve the above problems, the present inventors previously invented a polyphenylene ether substituted with a propargyl group or an allyl group, and a polyphenylene ether containing a triple bond or a double bond, which can be cured. It was found that the obtained cured product was insoluble in aromatic hydrocarbon solvents and halogen-substituted hydrocarbon solvents and had excellent dielectric properties (Japanese Patent Application No. 62-224146,
62-224147, 62-269459, 62-269460, 63-
See 271983). However, these cured products have swelling and warping although they are insoluble when they are boiled with trichloroethylene, so that there is a problem that the chemical resistance is still insufficient to be used as a printed circuit board material.

[Problems to be Solved by the Invention]

In view of the above circumstances, the present invention intends to provide a novel curable polyphenylene ether resin composition having further improved chemical resistance while retaining the excellent dielectric properties of polyphenylene ether.

[Means for Solving the Problems]

The present inventors have accomplished the present invention as a result of solving the above problems and earnestly studying to obtain a material suitable as a laminated material. The present invention comprises the following five inventions.

That is, the first aspect of the present invention is: (a) a curable polyphenylene ether resin substantially composed of the following general formula (I), wherein the average substitution rate of the allyl group and / or propargyl group defined by the following formula: Is 0.1 mol% or more and 100 mol% or less, and a curable polyphenylene ether resin (B) A resin composition containing triallyl isocyanurate and / or triallyl cyanurate, wherein the component (a) is 98 to 40% by weight based on the sum of (a) and (b), ) Provided is a curable polyphenylene ether resin composition containing 2 to 60% by weight.

Q′J′-H] _m (I) [wherein, m is an integer of 1 or 2, and J ′ is a general formula. [Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom,
An allyl group or a propargyl group, at least one of R ₁ to R ₄ is other than hydrogen, and R ₁ to R ₄ may be the same or different. ] When m is 1, Q'represents a hydrogen atom, when m is 2, Q'has two phenolic hydroxyl groups in one molecule,
Residue Q of a bifunctional phenol compound having a polymerization-inert substituent at the ortho and para positions of the phenolic hydroxyl group
And / or two polyphenylene ether chains, which represent Q substituted with an allyl group and / or a propargyl group and are linked to Q ', may be the same or different. When the above composition of the present invention is cured, it is a cured polyphenylene ether resin composition comprising a chloroform non-extractable polyphenylene ether resin and a chloroform extractable polyphenylene ether resin composition, and the cured polyphenylene ether resin composition is thermally decomposed. Gas chromatographic analysis showed 2-methylphenol, 2,6-dimethylphenol, 2,4-dimethylphenol, 2,4,6-
Trimethylphenol, and triallyl isocyanurate and / or triallyl cyanurate are produced as thermal decomposition products, and the peak area ratios of these satisfy the following inequalities: [Where [1], [2], [3], [4] and [5]
Represents the peak area of the pyrolysis gas chromatogram resulting from the pyrolysis components ,,, and, respectively. ] The amount of the chloroform-extractable polyphenylene ether resin composition determined from the chloroform extraction rate when the cured polyphenylene ether resin composition is treated with chloroform at 23 ° C. for 12 hours is 0.01 based on the cured polyphenylene ether resin composition. % Or more and 5% by weight or less, and the chloroform-extractable polyphenylene ether resin composition contains a unit represented by the general formula (II) and triallyl isocyanurate and / or triallyl cyanurate. A cured polyphenylene ether resin composition is provided.

A second aspect of the present invention is a curable composite material comprising a curable polyphenylene ether resin composition and a substrate, wherein the curable polyphenylene ether resin composition is (a) substantially represented by the general formula (I). Which is a curable polyphenylene ether resin having an average substitution rate of 0.1 mol% of allyl groups and / or propargyl groups defined by the following formula:
A curable polyphenylene ether resin that is not less than 100 mol% and not more than (B) containing triallyl isocyanurate and / or triallyl cyanurate, (a) and (b)
The curable composite material is characterized in that the component (a) is 98 to 40% by weight and the component (b) is 2 to 60% by weight based on the sum of the above.

A third aspect of the present invention is a cured composite material comprising a cured polyphenylene ether resin composition and a substrate, wherein the cured polyphenylene ether resin composition is a chloroform non-extractable polyphenylene ether resin and a chloroform extractable polyphenylene ether resin composition. And by pyrolysis gas chromatography, 2-methylphenol, 2,6-dimethylphenol, 2,4-dimethylphenol, 2,4,6-trimethylphenol, and triallyl isocyanurate and / Or triallyl cyanurate is produced as a thermal decomposition product, and the peak area ratio of these ~ satisfies the following inequality: [Where [1], [2], [3], [4] and [5]
Represents the peak area of the pyrolysis gas chromatogram resulting from the pyrolysis components ,,, and, respectively. ] The amount of the chloroform-extractable polyphenylene ether resin composition obtained by treating the cured composite material with chloroform at 23 ° C. for 12 hours is 0.01% by weight or more based on the cured polyphenylene ether resin composition.
And the chloroform-extractable polyphenylene ether resin composition has a unit represented by the general formula (II), triallyl isocyanurate and / or
Alternatively, a cured composite material comprising triallyl cyanurate is provided.

Finally, a fourth aspect of the present invention is a laminate comprising a cured composite material in which a cured polyphenylene ether resin composition and a base material are composited, and a metal foil, wherein the cured polyphenylene ether resin composition is chloroform non-extractable. It consists of a polyphenylene ether resin and a chloroform-extractable polyphenylene ether resin composition, and is 2-methylphenol by analysis by pyrolysis gas chromatography, 2,
6-dimethylphenol, 2,4-dimethylphenol,
2,4,6-trimethylphenol, and triallyl isocyanurate and / or triallyl cyanurate are produced as thermal decomposition products, and the peak area ratio of these satisfies the following inequality: [Where [1], [2], [3], [4] and [5]
Represents the peak area of the pyrolysis gas chromatogram resulting from the pyrolysis components ,,, and, respectively.

The amount of the chloroform-extractable polyphenylene ether resin composition obtained by treating the laminate with chloroform at 23 ° C. for 12 hours is 0.01 wt% or more and 5 wt% or more based on the cured polyphenylene ether resin composition.
And a chloroform-extractable polyphenylene ether resin composition containing a unit represented by the general formula (II) and triallyl isocyanurate and / or triallyl cyanurate. .

The above four inventions will be described in detail below.

The curable polyphenylene ether resin used as the component (a) of the curable polyphenylene ether resin composition of the first aspect of the present invention means an allyl group and / or propargyl group substantially composed of the following general formula (I). A polyphenylene ether substituted with a compound having an average substitution rate of allyl group and / or propargyl group defined by the following formula of 0.1 mol% or more and 100 mol% or less.

In the general formula (I), m represents an integer of 1 or 2.
J'is a general formula Shows a polyphenylene ether chain containing a unit represented by, wherein R _{1 to} R ₄ are each independently a hydrogen atom, an allyl group, or a propargyl group, at least one of R _{1 to} R ₄ is other than hydrogen, And R _{1 to} R ₄ may be the same or different. Q'represents a hydrogen atom when m is 1,
When m is 2, it has two phenolic hydroxyl groups in one molecule and has a residue Q of a bifunctional phenol compound having a polymerization-inactive substituent at the ortho-position and para-position of the phenolic hydroxyl group and / or Represents Q substituted with an allyl group and / or a propargyl group. When m is 2,
The two polyphenylene ether chains linked to Q'may be the same or different.

Typical examples of the bifunctional phenol compound represented by Q include the compounds represented by the following two types of general formulas.

[In the formula, A ₁ and A ₂ represent the same or different linear alkyl groups having 1 to 4 carbon atoms, X represents an aliphatic hydrocarbon residue and a substituted derivative thereof, an aromatic hydrocarbon residue and an aromatic hydrocarbon residue thereof, and It represents a substituted derivative, an aralkyl group and their substituted derivatives, oxygen, sulfur, a sulfonyl group, and a carbonyl group.
Two phenyl groups attached directly A _2, the bonding position of A ₂ and X represents ortho and para positions of all the phenolic hydroxyl group. ] As a specific example, Etc.

Specific examples of the curable polyphenylene ether resin of the general formula (I) include resins obtained by substituting poly (2,6-dimethyl-1,4-phenylene ether) with an allyl group and / or a propargyl group, or A resin obtained by further substituting a bifunctional polyphenylene ether obtained by polymerizing 2,6-dimethylphenol in the presence of the above bifunctional phenol compound QH) _{2 with} an allyl group and / or a propargyl group, Can be mentioned.

The method for producing the curable polyphenylene ether resin of the general formula (I) is not particularly limited,
For example, the methods disclosed in Japanese Patent Application Nos. 62-224146 and 62-224147 can be mentioned. That is, as a first method, the general formula QJ-H] _m [wherein, m is an integer of 1 or 2, and J is a polyphenylene ether chain consisting of units represented by the following general formula, When m is 1, Q represents a hydrogen atom, and when m is 2, Q represents a residue of the bifunctional phenol compound represented by the general formula (III-a) or (III-b). ] A method comprising a step of metallizing the polyphenylene ether represented by the formula with an organic metal and a step of performing a substitution reaction with allyl halide and / or propargyl halide. In addition, as a second manufacturing method, a general formula Q ″ J ″ -H] _m [wherein, m is an integer of 1 or 2 and J ″ is a general formula (Here, R ₅ , R ₆ , R ₇ and R ₈ are each independently a hydrogen atom or an allyl group, at least one of R _{5 to} R ₈ is an allyl group, and R _{5 to} R ₈ are the same. A polyphenylene ether chain containing a unit represented by the following formula, wherein when m is 1, Q ″ represents a hydrogen atom, and when m is 2, Q ″ represents the above general formula (III-a), (III-b) represents Q substituted with a residue of a bifunctional phenol compound and / or an allyl group. ] A method comprising a step of adding a halogen to a double bond of an allyl group of an allyl group-substituted polyphenylene ether substantially composed of and a step of dehydrohalogenating with a metal amide.

The molecular weight of the curable polyphenylene ether resin of the general formula (I) is not particularly limited, and low molecular weight to high molecular weight can be used. In particular, the viscosity number η _sp measured at 30 ° C. in a 0.5 g / dl chloroform solution is η _sp. Those with / C in the range of 0.2 to 1.0 can be used satisfactorily.

In obtaining the resin composition of the present invention, the average substitution rate of allyl groups and / or propargyl groups of the curable polyphenylene ether resin of general formula (I) is in the range of 0.1 mol% or more and 100 mol% or less. Is preferable, and more preferably in the range of 0.5 mol% or more and 50 mol% or less.
The average substitution rate here is defined as the ratio of the total number of moles of allyl groups and / or propargyl groups to the total number of moles of phenyl groups, and is at most 400 mole%. If the average substitution rate is less than 0.1 mol%, the film-forming property by the casting method described below is deteriorated and the chemical resistance after curing is insufficiently improved, which is not preferable. If it exceeds 100 mol%, it becomes very brittle after curing, which is also not preferable.

The triallyl isocyanurate and / or triallyl cyanurate used as the component (b) of the curable polyphenylene ether resin composition according to the first aspect of the present invention is a trifunctional monomer represented by the following structural formula. .

In carrying out the present invention, triallyl isocyanurate (IV) and triallyl cyanurate (V) are not only used alone, but both may be used in a mixture at an arbitrary ratio. .

The blending ratio of the above two components is 98-40% by weight of the component (a) and 2-60% by weight of the component (b) based on the sum of the two.
Is preferred. If the amount of the component (b) is less than 2% by weight, the chemical resistance is not sufficiently improved, which is not preferable. On the other hand, when it exceeds 60% by weight, the dielectric properties are deteriorated and the material becomes very brittle after curing, which is not preferable. Furthermore, it is not preferable to form a film by a casting method described later or to form a composite with a base material as described in the third aspect of the present invention, since the material becomes brittle and has a sticky surface.

The method for obtaining the first resin composition of the present invention from the above two components (a) and (b) is not particularly limited, but a usual melt blending or solution mixing method is used. In this case, in addition to these components, an amount of a filler or an additive may be blended in a range that does not impair the original properties for the purpose of imparting desired performance depending on the application. The filler may be fibrous or powdery, and glass fiber, aramid fiber, carbon fiber, boron fiber, ceramic fiber, asbestos fiber, carbon black, silica, alumina, talc, mica, glass beads, glass A hollow sphere etc. can be mentioned. Further, as the additive, an antioxidant, a heat stabilizer, a flame retardant, an antistatic agent, a plasticizer, a pigment, a dye, a colorant, or the like can be blended.

Further, this resin composition is cured by causing a crosslinking reaction by means of heat or the like as described later, and is used by containing a radical initiator as a catalyst for the purpose of lowering the temperature at that time or promoting the crosslinking reaction. You may. The preferred amount of the initiator is 0.1 based on 100 parts by weight of the sum of the components (a) and (b).
To 10 parts by weight, more preferably 0.1 to 5 parts by weight. When the amount of the initiator is less than 0.1% by weight, the curing is not sufficiently performed and the chemical resistance becomes insufficient, which is not preferable. On the contrary, if it exceeds 10% by weight, the initiator remains and the dielectric properties are deteriorated or the material becomes brittle, which is not preferable. Representative examples of radical initiators include benzoyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, and 2,5-dimethyl-2,5-di (t -Butylperoxy) hexyne-3,
Di-t-butyl peroxide, t-butyl cumyl peroxide, α, α'-bis (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxide) (Oxy) hexane, dicumyl peroxide, di-
t-butylperoxyisophthalate, t-butylperoxybenzoate, 2,2-bis (t-butylperoxy) butane, 2,2-bis (t-butylperoxy) octane, 2,5-dimethyl-2 There are peroxides such as, but not limited to, 5,5-di (benzoylperoxy) hexane, di (trimethylsilyl) peroxide, and trimethylsilyltriphenylsilylperoxide. Also not a peroxide,
2,3-Dimethyl-2,3-diphenylbutane can also be used as a radical initiator.

As the solvent used when mixing the above components in a solution,
Specific examples thereof include halogen-substituted hydrocarbons such as dichloromethane, chloroform and trichloroethylene, aromatic hydrocarbons such as benzene, toluene and xylene, and a single solvent or a mixed solvent thereof. The above resin composition dissolved or dispersed in these solvents can be formed into a film by the casting method.

As a shaping method other than the casting method, a usual method by heating and melting can be mentioned, and methods such as injection molding, transfer molding, extrusion molding and press molding can be used. The temperature at the time of heating and melting is selected in the range of not less than the glass transition temperature of the resin composition and not more than the curing start temperature. In the case of the curable polyphenylene ether resin represented by the general formula (I), the glass transition temperature is about 140 as compared with that of the polyphenylene ether having no functional group due to the effect of the allyl group and / or the propargyl group.
The temperature is as low as ℃ to about 210 ℃, which is advantageous for thermoforming. Furthermore, in the resin composition of the present invention, since the triallyl isocyanurate and / or triallyl cyanurate also exerts the effect as a plasticizer, the glass transition temperature is 80 to
In the range of 160 ° C, remarkable fluidity is recognized even at low temperatures, which is more advantageous for thermoforming.

The method of curing the resin composition of the present invention is optional,
A method using heat, light, an electron beam or the like can be adopted.
When heated, the temperature is not particularly limited, but the temperature is 10
It is in the range of 0 ° C to 350 ° C, more preferably 150 ° C to 300 ° C, and is selected according to the decomposition temperature of the initiator. Time is 1
Minutes to 5 hours, more preferably 1 minute to 3 hours.
The degree of this curing reaction depends on the differential scanning calorimeter and infrared absorption (hereinafter
It can be traced by a spectral method.

Summarizing the characteristics of the curable polyphenylene ether resin composition according to the first aspect of the present invention described above, firstly, the film forming property by the casting method is excellent.
Almost no solvent film-forming property is observed with ordinary polyphenylene ether, whereas the resin composition of the present invention gives a film which is smooth and has no surface stickiness and is easy to handle. The second characteristic is that it is excellent in storage stability and can be stored for a long period of time in the form of a solution or film without gelation. The third characteristic is that the glass transition temperature is low and the fluidity is excellent, so that thermoforming is easy.

Next, a cured polyphenylene ether resin composition obtained by curing the above composition of the present invention will be described. This cured polyphenylene ether resin composition is obtained by curing the curable polyphenylene ether resin composition described as the first aspect of the present invention by a method such as heating.

The fact that the cured polyphenylene ether resin composition is obtained by curing a composition composed of polyphenylene ether and triallyl isocyanurate and / or triallyl cyanurate is, for example, IR spectroscopy, solid high resolution nuclear magnetic field. It can be verified by analysis methods such as resonance (hereinafter abbreviated as NMR) spectrum method (so-called CP-MAS), pyrolysis gas chromatography and the like. In particular, pyrolysis gas chromatography is a very effective analysis means, and can be easily distinguished from similar cured products using polyphenylene ether.

That is, when the cured polyphenylene ether resin composition of the present invention is pyrolyzed at 590 ° C. for 4 seconds in an inert gas atmosphere, 2-methylphenol, 2,6-dimethylphenol, 2,4-dimethylphenol, 2,4, 5 to 6 characteristic thermal decomposition products of 6-trimethylphenol and triallyl isocyanurate and / or triallyl cyanurate are formed, and between these production amounts, The relationship always holds. Here, [1] to [5] represent the peak areas of the pyrolysis gas chromatograms caused by the pyrolysis components. Among the above thermal decomposition products, ~ is a product derived from polyphenylene ether, and its generation mechanism is described in, for example, Journal of App.
It is reported in detail in lied Polymer Science, Vol. 22, p. 2891 (1978).

When the proportion of triallyl isocyanurate and / or triallyl cyanurate in the curable polyphenylene ether resin composition described as the first aspect of the present invention becomes large, the production amount of to correspondingly increases with respect to the production amount of. . If the value calculated by the above inequality is less than 0.05, the amount of triallyl isocyanurate and / or triallyl cyanurate will be insufficient and the chemical resistance will not be sufficiently improved, which is not preferable. Conversely, if the value of the inequality is
When it exceeds 40, the dielectric properties are deteriorated or the material becomes brittle, which is not preferable.

The method of pyrolysis used in this pyrolysis gas chromatography is not particularly limited in carrying out the present invention, and any method such as a heating filament method, a heating furnace method, a high frequency induction heating method, a laser heating method, etc. can be used. Available. In particular, the high-frequency induction heating method (Curie Point Pyrolyzer) is suitable for this analysis because it enables extremely rapid heating and the obtained temperature is accurate and reproducible.

The thermal decomposition conditions are not particularly limited, but for example, heating at 590 ° C. for 4 seconds in an inert gas atmosphere is sufficient for performing this analysis. Helium or nitrogen can be used as the inert gas in common with the carrier gas of the gas chromatograph. The shape of the sample when pyrolyzed is preferably pulverized for the purpose of improving reproducibility.

For the separation column of the gas chromatograph, it is sufficient if the above-mentioned 5 or 6 thermal decomposition products can be completely decomposed,
Although not particularly limited, a methylsilicone-based non-polar column or a column having a non-polarity equivalent to this is most preferably used. The shape of the column may be a packed column or a capillary column, and the latter is particularly excellent in separation ability and can be used favorably.
Also, there is no particular limitation on the column temperature,
It is effective to raise the temperature from around room temperature by 10 to 20 ℃ per minute because the analysis time can be shortened.

The thermal conductivity type detector (TCD) and hydrogen flame ionization type detector (FID) can be used as the detectors of the gas chromatograph in this analysis, and can be connected to the mass spectrometer (MS) as a pyrolysis GCMS. It is also possible to use. A Fourier transform type IR (FT-IR) can be used instead of the detector for the purpose of qualitative analysis.

As a method for analyzing the structure of the cured polyphenylene ether resin composition of the present invention, a method as effective as pyrolysis gas chromatography is analysis of a chloroform extract. The cured polyphenylene ether resin composition of the present invention comprises a chloroform non-extractable polyphenylene ether resin composition and a chloroform extractable polyphenylene ether resin composition, of which the chloroform extractable polyphenylene ether resin composition is extracted with chloroform. It can be determined from the rate. The chloroform extraction rate here is a value obtained by immersing the cured polyphenylene ether resin composition in chloroform at 23 ° C. for 12 hours, and the following formula is based on the weight of the resin composition before immersing in chloroform. Calculated according to.

The preferred range of the chloroform extraction rate is 0.01% by weight or more and 5% by weight or less. If it is less than 0.01% by weight, the cured product becomes brittle, which is not preferable. On the other hand, when it exceeds 5% by weight, the chemical resistance is insufficient, which is also unfavorable. The cured polyphenylene ether resin composition to be dipped in chloroform is most preferably in the form of film or powder in consideration of the ease of removing chloroform.

The chloroform extraction rate can be measured using deuterated chloroform instead of chloroform, but in this case, by measuring the NMR spectrum of the deuterated chloroform solution of the extract, the components of the chloroform-extractable polyphenylene ether resin composition and It is possible to know its structure. The chloroform-extractable polyphenylene ether resin composition according to the present invention contains a unit represented by the following general formula (II) and triallyl isocyanurate and / or triallyl cyanurate.

[Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom,
An allyl group or a propargyl group, at least one of R ₁ to R ₄ is other than hydrogen, and R ₁ to R ₄ may be the same or different. The chloroform-extractable polyphenylene ether resin composition of the present invention is the curable polyphenylene ether resin composition described in the first aspect of the present invention in which components that could not sufficiently contribute to the curing reaction in the curing process were extracted. . However, the composition of the chloroform-extractable polyphenylene ether resin composition does not always match the composition of the original curable polyphenylene ether resin composition, and the polyphenylene ether represented by the general formula (II) and triallyl isocyanurate and The ratio of the / or triallyl cyanurate does not matter. The general formula (II)
The average substitution rate of the polyphenylene ether represented by the above does not match the average substitution rate of the curable polyphenylene ether resin of the component (a) shown in the first of the present invention. Further, the hydrogen or the residue of the bifunctional phenol compound represented by Q'in the component (a) may or may not be confirmed in the extract.
As a means for confirming the structure of these chloroform-extractable polyphenylene ether resin compositions, the NMR spectrum method is effective as described above, and among them, ¹ H-NMR is particularly effective. The IR spectrum method can also be used.

Summarizing the characteristics of the cured polyphenylene ether resin composition described above, the first is its excellent chemical resistance. A cured product of only polyphenylene ether that does not contain triallyl isocyanurate and / or triallyl cyanurate swells remarkably by boiling in trichloroethylene, and the change in appearance is remarkable, whereas the cured polyphenylene ether resin composition of the present invention The swelling was small even after the same treatment, and no change in appearance was observed. The second characteristic is that the excellent dielectric properties (low dielectric constant, low dielectric loss tangent) of polyphenylene ether are not impaired, and it is useful as a material for printed circuit boards and the like.
Further, the curing reaction in the present invention, an allyl group and a propargyl group in the curable polyphenylene ether resin,
Since it occurs by the addition reaction of allyl groups in triallyl isocyanurate and / or triallyl cyanurate, by-products such as water and gas due to the condensation reaction, unlike polyimide resin, are not generated, and a uniform and void-free film ,
It also has a feature that a sheet or a molded product can be obtained.

Next, the curable composite material which is the second aspect of the present invention will be described. This curable composite material is a composite material comprising the curable polyphenylene ether resin composition described as the first aspect of the present invention and a substrate. As the substrate used in the present invention, various glass cloths such as roving cloth, cloth, chopped mat, surfacing mat; ceramic fiber cloth, asbestos cloth, metal fiber cloth and other synthetic or natural inorganic fiber cloth; polyvinyl alcohol fiber Woven or non-woven fabrics made from synthetic fibers such as polyester fiber, acrylic fiber, wholly aromatic polyamide fiber; natural fiber cloth such as cotton cloth, linen cloth and felt; carbon fiber cloth; kraft paper, cotton paper, paper-glass mixed weave Natural cellulose-based cloths such as paper may be used alone or in combination of two or more.

As a method for compounding the curable polyphenylene ether resin composition shown in the first of the present invention and the above-mentioned substrate, the resin composition is selected from the halogen-substituted hydrocarbons and aromatic hydrocarbons described above. A method is employed in which the substrate is dissolved alone or in a mixed solvent, the substrate is impregnated, and then dried. Impregnation is usually done by dipping or coating. Impregnation can be repeated multiple times as needed, and in this case it is also possible to repeat impregnation using multiple solutions with different compositions and concentrations to finally adjust the desired resin composition and amount. Is.

As for the resin composition suitable for the curable composite material of the present invention, the curable polyphenylene ether resin of the component (a) is the same as the curable polyphenylene ether resin composition of the first present invention.
98-40% by weight, the proportion of triallyl isocyanurate and / or triallyl cyanurate as the component (b) is 2-60% by weight, and the above-mentioned initiator may be further added as a third component. The preferred amount of initiator is the first of the present invention.
Same as above, with the sum of the (a) component and the (b) component as the reference.
It is 1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight. In addition to the initiator, the above-mentioned fillers and additives can be blended according to the purpose.

The mixing ratio of the base material and the resin component in the curable composite material of the present invention is not particularly limited, but the base material is 5 to 90% by weight, more preferably 10 to 80% by weight, and further preferably 20.
The resin component is preferably 95 to 10% by weight, more preferably 90 to 20% by weight, still more preferably 80 to 30% by weight with respect to 70% by weight. If the amount of the base material is less than 5% by weight, the dimensional stability and strength of the composite material after curing will be insufficient, and if the amount of the base material is more than 90% by weight, the electrical properties of the composite material will be inferior.

As the characteristics of the curable composite material which is the second aspect of the present invention described above, the characteristics of the curable polyphenylene ether resin composition described in the first aspect of the present invention are directly applied. That is, the first feature is excellent film-forming property, smoothness of surface cotton, good handleability without stickiness, secondly storage stability, and thirdly excellent thermoformability.

Next, the cured composite material of the third aspect of the present invention will be described. This curable composite material is a composite material composed of the cured polyphenylene ether resin composition and the substrate described as the second of the present invention, and is not particularly limited, but the second curable composite material of the present invention is It can be obtained by curing by a method such as heating. For example, it is possible to obtain a cured composite material having a desired thickness by stacking a plurality of the curable composite materials, adhering the layers together under heat and pressure, and at the same time performing thermal curing. When laminating, the curable polyphenylene ether resin composition described as the first aspect of the present invention, which is formed into a film, may be used in combination with the curable composite material described above. It is also possible to obtain a cured composite material having a new layer structure by combining the cured composite material that has been adhesively cured once with the curable composite material and / or the curable polyphenylene ether resin composition.

The lamination molding and curing are usually performed simultaneously by using a hot press or the like, but both may be performed independently. That is,
The uncured or semi-cured composite material obtained by laminating in advance can be cured by heat treatment or by another method. Mold and cure at a temperature of 10
0-350 ° C, pressure 0.1-1000kg / cm ² , time 1 minute-5 hours, more preferably temperature 150-300 ° C, pressure 1-500k
It may be carried out in the range of g / cm ² and time of 1 minute to 3 hours.

The mixing ratio of the base material and the resin component in the cured composite material of the present invention is not limited, but the base material is 5 to 90% by weight, more preferably 10 to 80% by weight, and further preferably 20 to 70% by weight. On the other hand, the resin component is 95 to 10% by weight, more preferably 90
It is good to set it to 20% by weight, more preferably 80 to 30% by weight. When the amount of the base material is less than 5%, the dimensional stability and strength of the cured composite material are insufficient, and when the amount of the base material is more than 90% by weight, the electrical properties of the cured composite material are poor, which is not preferable.

Since the cured composite material of the present invention is a composite material of the cured polyphenylene ether resin composition and the base material already described, the characteristics of the cured polyphenylene ether resin composition described above can be applied as they are. That is, the resin component of the cured composite material of the present invention is a cured polyphenylene ether resin composition comprising a chloroform non-extractable polyphenylene ether resin and a chloroform extractable polyphenylene ether resin composition, and the cured polyphenylene ether resin composition is 2-methylphenol, 2, by analysis by decomposition gas chromatography
6-dimethylphenol, 2,4-dimethylphenol,
2,4,6-trimethylphenol, and triallyl isocyanurate and / or triallyl cyanurate are produced as thermal decomposition products, and the peak area ratio of these satisfies the following inequality: [Where [1], [2], [3], [4] and [5]
Represents the peak area of the pyrolysis gas chromatogram resulting from the pyrolysis components ,,, and, respectively. ] The amount of the chloroform-extractable polyphenylene ether resin composition obtained by treating the cured composite material with chloroform at 23 ° C. for 12 hours is 0.01% by weight or more based on the cured polyphenylene ether resin composition.
And the chloroform-extractable polyphenylene ether resin composition has a unit represented by the following general formula (II), triallyl isocyanurate and / or
Alternatively, it is characterized by containing triallyl cyanurate.

[Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom,
An allyl group or a propargyl group, at least one of R ₁ to R ₄ is other than hydrogen, and R ₁ to R ₄ may be the same or different. The method of analysis by thermal decomposition gas chromatography, the method of analyzing the chloroform-extractable polyphenylene ether resin composition, etc. are as described above.

The characteristics of the cured polyphenylene ether resin composition described above are directly applied to the characteristics of the cured composite material of the third aspect of the present invention described above. That is, the first feature is excellent chemical resistance, the second feature is excellent dielectric properties, and the third is that a uniform and void-free molded product can be obtained. In addition to this, the cured composite material of the present invention was excellent in solder heat resistance, and no change in appearance was observed even when heating was continued for 120 seconds on a solder bath at 260 ° C. It was also excellent in mechanical strength and dimensional stability (XY and Z directions). All of these characteristics show that the cured composite material can be advantageously used as a printed circuit board material, especially as a material for multilayer boards.

Finally, the fourth embodiment of the present invention will be described. This laminate is a laminate composed of the cured composite material and the metal foil described above as the fourth aspect of the present invention. Examples of the metal foil used in the present invention include copper foil and aluminum foil. The thickness is not particularly limited, but is 5 to 200 μm,
The range is more preferably 5 to 100 μm.

The method for obtaining the laminate of the present invention is not particularly limited, but, for example, a plurality of the second curable composite material of the present invention and a metal foil are laminated in a layered structure according to the purpose, and each is subjected to heating and pressurization. It can be obtained by bonding the layers together and at the same time performing heat curing. At this time, the metal foil can be attached to the surface layer or can be used as an intermediate layer.
The curable polyphenylene ether resin composition described as the first aspect of the present invention, which is formed into a film, may be used in combination with the curable composite material described above. Moreover,
It is also possible to obtain a laminate having a new layer structure by laminating the laminates once adhered and cured, or by laminating the laminate and the metal foil via the curable polyphenylene ether resin composition or the curable composite material. An adhesive may be used to bond the metal foil. Examples of the adhesive include epoxy-based, acrylic-based, phenol-based, and cyanoacrylate-based adhesives, but are not particularly limited thereto.

The lamination molding and curing are usually performed simultaneously by using a hot press or the like, but both may be performed independently. That is,
The uncured or semi-cured laminate obtained by laminating in advance can be cured by heat treatment or another method. Mold and cure at a temperature of 100
To 350 ° C, pressure 0.1 to 1000 kg / cm ² , time 1 minute to 5 hours, more preferably temperature 150 to 300 ° C, pressure 1 to 500 kg /
It may be carried out in the range of cm ² and time of 1 minute to 3 hours.

The mixing ratio of the base material and the resin component in the laminate of the present invention is not particularly limited, but the base material is 5 to 90% by weight, more preferably 10 to 80% by weight, further preferably 20 to 70% by weight.
On the other hand, the resin component is 95 to 10% by weight, more preferably 90 to
The amount is preferably 20% by weight, more preferably 80 to 30% by weight. When the amount of the base material is less than 5%, the dimensional stability and strength of the laminate are insufficient, and when the amount of the base material is more than 90% by weight, the electrical properties of the laminate are poor, which is not preferable.

Since the laminated body of the present invention is a laminated body composed of the cured composite material and the metal foil described as the third of the present invention, the characteristics and the analysis method are as described in the third section of the present invention.

As the characteristics of the laminate according to the fourth aspect of the present invention described above, the characteristics of the aforementioned cured polyphenylene ether resin composition and the characteristics of the aforementioned cured composite material of the third aspect of the present invention are directly applicable. That is, the first characteristic is excellent chemical resistance, the second is excellent dielectric characteristics, and the third is that a uniform and void-free molded product can be obtained.
Examples include solder heat resistance, mechanical strength, and dimensional stability.
In addition to these, the laminate of the present invention was also excellent in adhesiveness to the metal foil. All of the above features show that this laminate can be advantageously used as a printed circuit board material, especially as a material for multilayer boards.

〔Example〕

Hereinafter, the present invention will be described with reference to examples in order to further clarify the present invention, but the scope of the present invention is not limited to these examples.

Examples 1 to 7 Synthesis of curable polyphenylene ether resin As a typical example of the curable polyphenylene ether resin represented by the general formula (I), an allyl group-substituted polyphenylene ether shown in Table 1 was synthesized. Although the synthesizing methods are the same, Example 3 will be described as a representative example.

Viscosity number η _sp measured at 30 ℃ in 0.5g / dl chloroform solution
350 g of poly (2,6-dimethyl-1,4-phenylene ether) (hereinafter abbreviated as PPE-1) having / C of 0.57 was dissolved in 7.0 l of tetrahydrofuran (hereinafter abbreviated as THF), and n-
Butyl lithium (1.5 mol / l, hexane solution) (390 ml) was added, and the mixture was reacted at 40 ° C. for 1 hour under a nitrogen atmosphere. Subsequently, 30 ml of allyl bromide was added, and the mixture was stirred at 40 ° C. for another 30 minutes. Finally, a mixed solution of 2.8 l of water and 2.8 l of methanol was added to precipitate a polymer. 5 filtration and washing with methanol
After repeating the operation once, it was vacuum dried at 80 ° C. for 14 hours to obtain an allyl group-substituted PPE-1 in the form of white powder. The average substitution rate of allyl group determined by ¹ H-NMR was 10%. Also at 30 ℃, 0.5g / dl
The viscosity number η _sp / C measured with the chloroform solution was 0.61.

Also in Examples 1, 2 and 4 to 7, polyphenylene ethers having different average substitution rates of allyl groups were synthesized by changing the amounts of n-butyllithium and allyl bromide.

Curable polyphenylene ether resin composition A resin composition having the composition shown in Table 1 was prepared. The method will be described by taking the third embodiment as an example.

Allyl group-substituted PPE-1 with an average substitution rate of 10% 5.4 g, triallyl isocyanurate (TAIC) 0.6 g, and 2,5-dimethyl-2,5-di (t-butylperoxy) as an initiator )
Hexin-3 (Perhexin 25B manufactured by NOF CORPORATION) 0.1
8 g was dissolved in 120 ml of trichloroethylene and a film was formed at 23 ° C. by a casting method. The thickness of this film is about
It had a surface smoothness of 100 μm and was not sticky. Also, a part of the film was cut into a width of 3 mm and a length of 20 mm, and a thermomechanical analyzer (hereinafter abbreviated as TMA).
The glass transition temperature was 145 ° C.

Similarly in other examples, a film-shaped resin composition was obtained by a casting method using Perhexin 25B manufactured by NOF CORPORATION as an initiator. All of them were excellent in film forming property, and a smooth and non-sticky film was obtained. The glass transition temperatures determined by TMA are summarized in Table 1.

The above films did not gel even after being left at room temperature for 3 months, and were excellent in long-term storage stability.

Cured polyphenylene ether resin composition 12 films of the resin composition obtained by the above method are superposed, heated and compressed from room temperature to 280 ° C. by a vacuum press, and 2
After holding at 80 ° C. for 30 minutes, it was cooled to obtain a sheet-shaped cured polyphenylene ether resin composition having a thickness of about 1 mm. In each of the examples, the glass transition temperature of the film was low and the flowability was excellent, so that press molding was easy. Table 2 shows the physical properties of the obtained sheet-shaped cured product. The measurement of each physical property was performed by the method described below.

1. Amount of chloroform-extractable polyphenylene ether resin composition A part of the sheet was ground with a file to make a fine powder, immersed in chloroform at 23 ° C for 12 hours, and the weight before and after that was calculated according to the following formula.

2. Pyrolysis generation ratio of phenols and TAIC It was calculated by analyzing pyrolysis gas chromatography of fine powder of sheet-shaped cured product. The measurement conditions of the pyrolysis gas chromatography are as follows.

(Pyrolysis device) Nihon Analytical Industry Curie Point Pyrolyzer JHP-3S Oven temperature
300 ℃ Pyrolysis condition 590 ℃, 4 seconds (gas chromatograph) Hewlett Packard 5890A column J & W company DB-1 0.25mm I.D. × 30m Column temperature rises from 50 ℃ to 10 ℃ / min Carrier gas He detector FID gas chromatogram The peaks were identified using retention times, mass spectra and FT-IR using commercially available reagents as standards.
This was done by comparing the spectra.

The pyrolysis generation ratio of phenols and TAIC was calculated according to the following formula.

(In the formula, [1] is 2-methylphenol and [2] is 2,6-
Dimethylphenol, [3] is 2,4-dimethylphenol, [4] is 2,4,6-trimethylphenol, [5]
Indicates the peak area of TAIC. ) 3. Glass transition temperature It was determined by a differential scanning calorimeter (DSC).

4. Trichlorethylene resistance A sheet-like cured product was cut into about 15 mm square pieces, boiled in trichlorethylene for 5 minutes, and the weight increase 5 minutes after removal was calculated from the following formula. Further, the change in appearance was visually observed.

5. Dielectric constant and dielectric loss tangent were measured at 1MHz.

In each of the examples, the trichloroethylene resistance was good and the dielectric properties were excellent.

On the other hand, the following analysis was performed to confirm the structure of the cured polyphenylene ether resin composition. First, FT-IR (diffuse reflection method) of the finely powdered cured product was measured, and the presence of the polyphenylene ether skeleton was confirmed in each of the examples. The attribution of the main peak was as follows.

At the same time, the absorption of the carbonyl group due to TAIC was confirmed at 1700 cm ^-1 .

Then, a fine powder of the cured product was added to deuterated chloroform (CDCl ₃ ) to remove the powder.
It was immersed for 12 hours at 0 ° C. to extract the chloroform-extractable polyphenylene ether resin composition. This deuterated chloroform solution was transferred to an NMR sample tube and ¹ H-NMR was measured. As a result, polyphenylene ether chain and 2
A variety of allyl groups were identified. One of these allyl groups had the same chemical shift as the allyl group of the curable polyphenylene ether resin used as the raw material of the resin composition. The other allyl group was that of TAIC. The attributions of the main peaks are as follows.

Comparative Examples 1 to 3 As shown in Table 1, in Comparative Example 1, PPE-1 was used as it was to prepare a resin composition. In Comparative Examples 2 and 3, PP
E-1 in which an allyl group was introduced by 0.05% in the same manner as in Example 3 was used.

Attempts were made to form a film of the resin composition by the same method as in Examples 1 to 7, but in each case, many fine cracks were formed and the film was not formed. Film formation became possible by changing the drying temperature from 23 ℃ to 50 ℃, but a film with a smooth surface was not obtained.

Using this film, thermosetting and physical property measurement of the cured product were performed in the same manner as in Examples 1 to 7. The results are summarized in Table 2.
In all cases, the effect of the allyl group was either absent or insufficient, so that the trichlorethylene resistance was poor as compared with the examples.

Examples 8 to 14 Synthesis of curable polyphenylene ether resin Using PPE-1 as a raw material, an allyl group-substituted PPE-1 having an average substitution rate of 10% and a viscosity number η _sp / C of 0.62 was synthesized in the same manner as in Example 3. .

Curable polyphenylene ether resin composition As shown in Table 3, the ratio of TAIC of the curable polyphenylene ether resin was variously changed, and film formation was performed in the same manner as in Examples 1 to 7. Perhexin 25B manufactured by NOF CORPORATION was used as an initiator. A film with a smooth surface was obtained without any stickiness. Further, these films were excellent in long-term storability without causing gelation even when left at room temperature for 3 months.

Cured polyphenylene ether resin composition The same procedure as in Examples 1 to 7 was carried out using the film prepared above. However, in Examples 8 to 10, the curing condition was set to 20.
The temperature was changed to 0 ° C x 30 minutes. The physical properties of the cured product are summarized in Table 4.

Since the film of the resin composition had a low glass transition temperature and excellent fluidity, press molding was easy. The cured product had good trichlorethylene resistance and good dielectric properties. In Examples 8 to 9, good moldability and trichlorethylene resistance were exhibited despite the low press temperature.

Then, in order to confirm the structure of the cured product, FT-IR (diffuse reflection method) and ^{1 of} deuterated chloroform extract were conducted as in Examples 1 to 7.
1 H-NMR was measured. The skeleton of polyphenylene ether was confirmed from the FT-IR measurement. On the other hand, ¹ H-NMR measurement confirmed the same structure and TAIC as the original curable polyphenylene ether resin.

Comparative Examples 4 to 7 As Comparative Examples 4 to 7, Examples 8 to 14 having the compositions shown in Table 3 were used.
The same experiment was repeated. Table 4 shows the physical properties of the obtained cured polyphenylene ether resin composition. In Comparative Examples 4 and 5, the effect of TAIC was insufficient and the trichlorethylene resistance was poor. In Comparative Example 6, the amount of the chloroform-extractable polyphenylene ether resin composition was large and the trichlorethylene resistance was insufficient. In Comparative Example 7, a film having no stickiness and excellent handleability could not be obtained.

Comparative Example 8 In Example 10, heat curing was performed under the pressing condition of 320 ° C. for 2 hours. The obtained cured product had a chloroform-extractable polyphenylene ether resin composition amount of 0%, but was very brittle and could not be put to practical use.

Examples 15-23 Synthesis of Curable Polyphenylene Ether Resin In Examples 15-20, 2,6-dimethylphenol was oxidatively polymerized in the presence of 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane. Using the bifunctional polyphenylene ether thus obtained (hereinafter referred to as PPE-2), polyphenylene ethers having an average substitution rate of allyl groups of 6% and 18% were synthesized in the same manner as in Examples 1 to 7.

In Examples 21 to 23, difunctional polyphenylene ethers obtained by oxidative polymerization of 2,6-dimethylphenol in the presence of 3,3 ', 5,5'-tetramethylbiphenyl-4,4'-diol were used. Using the same method as in Examples 1 to 7, polyphenylene ether having an average substitution rate of allyl groups of 12% was synthesized.

Curable Polyphenylene Ether Resin Composition The curable polyphenylene ether resin synthesized above and triallyl cyanurate (hereinafter abbreviated as TAC) and Perhexin 25B manufactured by NOF CORPORATION as an initiator are shown in Table 5. A film was formed with the same composition as in Examples 1 to 7. A film with a smooth surface was obtained without any stickiness. Further, these films were excellent in long-term storability without causing gelation even when left at room temperature for 3 months.

Cured polyphenylene ether resin composition It carried out exactly like Examples 1-7. The curing conditions were 200 ° C. × 30 minutes in Examples 18 to 20, and 280 ° C. × 30 minutes in other cases. The measurement results of physical properties are summarized in Table 6. In all cases, the press moldability was good, and the trichloroethylene resistance after curing and the dielectric properties also showed excellent values.

In addition, in order to confirm the structure of the cured product, FT-IR (diffuse reflection method) and ^{1 of} deuterated chloroform extract were used as in Examples 1 to 7.
1 H-NMR was measured. The skeleton of polyphenylene ether was confirmed from the FT-IR measurement. On the other hand, ¹ H-NMR measurement confirmed the same structure and TAC as the original curable polyphenylene ether resin.

Comparative Examples 9 and 10 As shown in Table 5, in Comparative Example 9, Examples 15 to 2 were performed without using TAC.
The same operation as in 3 was performed. In Comparative Example 10, PPE-2 not substituted with an allyl group was used. As a result, in Comparative Example 10, the film forming property was poor, and as shown in Table 6, both of them had poor trichlorethylene resistance.

Examples 24 to 30 Synthesis of Curable Polyphenylene Ether Resin As a typical example of the curable polyphenylene ether resin represented by the general formula (I), propargyl group-substituted polyphenylene ethers shown in Table 7 were synthesized. Example 25 and Example 26 will be described as typical examples of the synthesis method.

In Example 25, poly (2,6-dimethyl-) having a viscosity number η _sp / C of 0.90 measured at 30 ° C. in a 0.5 g / dl chloroform solution was used.
1,4-phenylene ether) (hereinafter abbreviated as PPE-3) 3
Dissolve 50 g in 7.0 l THF and n-butyllithium (1.5 mol /
580 ml of hexane solution) was added, and the mixture was reacted at 40 ° C. for 1 hour under a nitrogen atmosphere. Then 103g of propargyl bromide
Was added, and the mixture was stirred at 40 ° C. for 20 minutes. Finally 2.8 liters of water
A mixed solution of 2.8 l of methanol and methanol was added to precipitate a polymer. After repeating filtration and washing with methanol 4 times, 80 ℃
After vacuum drying for 14 hours, a white powdery propargyl group-substituted PPE-3 was obtained. The average substitution rate of the propargyl group determined by ¹ H-NMR was 6%. The viscosity number η _sp / C measured with a chloroform solution of 0.5 g / dl at 30 ° C. was 0.93.

In Example 26, an allyl group was added to PPE-3 in the same manner as in Example 3.
1% introduced. 220 g of this allyl group-substituted PPE-3 was dissolved in 5.0 l of chloroform, 12 ml of bromine was added, and the mixture was stirred at room temperature for 30 minutes. The reaction mixture was poured into 10 l of methanol to precipitate a polymer, and filtration and washing with methanol were repeated 3 times to obtain a polymer.
It was vacuum dried at 14 ° C for 14 hours. The whole amount of the obtained white powdery product was dissolved in 8.0 l of THF and cooled to -15 ° C. THF of lithium diisopropylamide under nitrogen atmosphere
400 ml of the solution (1.2 mol / l) was added and stirred for 20 minutes. Finally, the reaction mixture was poured into 10 l of methanol to precipitate a polymer, and filtration and washing with methanol were repeated 4 times to obtain a polymer at 80 ° C.
Vacuum dried for 14 hours. ¹ H-NMR of the obtained polymer
When all of the original allyl groups were converted to propargyl groups, the substitution rate was 11%. 30
The viscosity number measured with a 0.5 g / dl chloroform solution at ℃ is 0.9.
Was 5.

In Example 24, polyphenylene ether was synthesized by the same method as in Example 25. In Examples 27 to 30, polyphenylene ether was synthesized by the same method as in Example 26.

Curable polyphenylene ether resin composition As shown in Table 7, a propargyl group-substituted polyphenylene ether, TAIC, and Perhexin 25B manufactured by NOF CORPORATION were used as an initiator to form a film in exactly the same manner as in Examples 1 to 7. It was In all cases, a film having a smooth surface without stickiness was obtained. Further, these films were excellent in long-term storability without causing gelation even when left at room temperature for 3 months.

Cured Polyphenylene Ether Resin Composition The film prepared above was pressed in the same manner as in Examples 1-7. The curing conditions were 200 ° C. × 1 hour in Examples 26 to 28, and 280 ° C. × 30 minutes in other cases. The physical properties of the cured product were measured in the same manner as in Examples 1-7. The results are summarized in Table 8. In all cases, the press moldability was good, and the trichloroethylene resistance after curing and the dielectric properties also showed excellent values.

In addition, in order to confirm the structure of the cured product, FT-IR (diffuse reflection method) and ^{1 of} deuterated chloroform extract were used as in Examples 1 to 7.
1 H-NMR was measured. The skeleton of polyphenylene ether was confirmed from the FT-IR measurement. On the other hand, ¹ H-NMR measurement confirmed the same structure and TAIC as the original curable polyphenylene ether resin.

Comparative Examples 11 and 12 As shown in Table 7, as Comparative Example 11, polyphenylene ether having an average substitution rate of propargyl groups of 0.05% (Example 25
The same operation as in Examples 24 to 30 was performed using (synthesized by the same method as). However, the film-forming property of the film and the resistance to trichlorethylene after curing were not good.

As Comparative Example 12, the pressing condition in Example 27 was set to 32.
The temperature was changed to 0 ° C. for 2 hours, and heat curing was performed. The obtained cured product had a chloroform-extractable polyphenylene ether resin composition amount of 0%, but was extremely brittle and could not be put to practical use.

Examples 31 to 36 Synthesis of curable polyphenylene ether resin Bifunctional polyphenylene ether (obtained by oxidative polymerization of 2,6-dimethylphenol in the presence of bis- (3,5-dimethyl-4-hydroxyphenyl) sulfone ( Hereinafter, abbreviated as PPE-4) was converted to propargyl by the same method as in Example 26 to obtain polyphenylene ether having an average substitution rate of 16%.

Curable Polyphenylene Ether Resin Composition As shown in Table 9, the ratio of propargyl group-substituted polyphenylene ether and TAC was changed variously to form a film by the same method as in Examples 1 to 7. Perhexin 25B manufactured by NOF CORPORATION was used as an initiator. A film with a smooth surface was obtained without any stickiness. Further, these films were excellent in long-term storability without causing gelation even when left at room temperature for 3 months.

Cured Polyphenylene Ether Resin Composition The film prepared above was pressed in the same manner as in Examples 1-7. The curing conditions are as follows: Examples 31 to 33 are 280 ° C. × 30.
Min., Examples 34 to 36 were 200 ° C. × 1 hour. The physical properties of the cured product were measured in the same manner as in Examples 1-7. The results are shown in Table 10
Summarized in. In all cases, the press moldability was good, and the trichloroethylene resistance after curing and the dielectric properties also showed excellent values.

In addition, in order to confirm the structure of the cured product, FT-IR (diffuse reflection method) and ^{1 of} deuterated chloroform extract were used as in Examples 1 to 7.
1 H-NMR was measured. The skeleton of polyphenylene ether was confirmed from the FT-IR measurement. On the other hand, ¹ H-NMR measurement confirmed the same structure and TAC as the original curable polyphenylene ether resin.

Comparative Examples 13 to 15 As Comparative Examples 13 to 15, Examples 31 to 36 having the compositions shown in Table 9 were used.
The same experiment was repeated. Table 10 shows the physical properties of the obtained cured polyphenylene ether resin composition. In Comparative Example 13
The resistance to trichlorethylene was poor because TAC was not used. In Comparative Example 14, the amount of chloroform-extractable polyphenylene ether resin composition was large, and the trichlorethylene resistance was insufficient. In Comparative Example 15, a film having no stickiness and excellent handleability could not be obtained.

Examples 37 to 45 Curable composite material As shown in Table 11, composite of an allyl group-substituted polyphenylene ether and a substrate was performed. In Examples 37 to 41, the same curable polyphenylene ether resin as in Examples 2 to 6 was used and the same resin composition was used. In Examples 42 to 45, the same curable polyphenylene ether resin as in Examples 9, 10, 12, and 14 was used, and the same resin composition was used. The method of compounding will be described by taking Example 38 as a representative example.

Allyl group-substituted PPE-1 with an average allyl group substitution rate of 10% and a viscosity number η _sp / C of 0.61 200 g, TAIC 22.2 g, as an initiator
6.7 g of 2,5-dimethyl-2,5-di (t-butylperoxy) hexin-3 (Perhexin 25B manufactured by NOF CORPORATION) was dissolved in 1.0 l of trichloroethylene. The weight of this solution is 10
Dip 5g / m ² of glass cloth for impregnation and
It was air dried for an hour, and further vacuum dried at 80 ° C. for 8 hours. The weight fraction of the glass cloth of the obtained curable composite material was 50%. This curable composite material was excellent in surface smoothness and had no stickiness. Further, even when left at room temperature for 3 months, gelation did not occur, and it was excellent in long-term storage stability.

The same procedure was performed for Examples 37 and 39 to 41. In Examples 42 and 43, a glass cloth having a basis weight of 48 g / m ² was used to obtain a curable composite material in which the weight fraction of the substrate was 30%. Examples 44,4
In 5, a quartz cloth with a basis weight of 48 g / m ² was used instead of the glass cloth. All were excellent in film-forming property and storage stability.

Cured composite material and laminated body Twelve curable composite materials obtained by the above method are stacked, 35 μm copper foil is placed on both surfaces, and the mixture is heated and compressed by a press molding machine from room temperature to 200 ° C. at a pressure of 100 kg / cm ^2. And then at 200 ℃ 3
After holding for 0 minutes, it was cooled to obtain a laminate having a thickness of about 1.6 mm. However, in Example 37, the curing condition was 220 ° C. × 30 minutes. Further, in Examples 40 and 41, curing was performed without using a copper foil. Table 12 shows the physical properties of the obtained laminate and the cured composite material. The measurement of each physical property was performed by the method described below.

1. Trichlorethylene resistance The laminate from which the copper foil was removed or the cured composite material was cut into 25 mm square pieces, boiled in trichlorethylene for 5 minutes, and the weight increase 5 minutes after being taken out was calculated from the following formula. Further, the change in appearance was visually observed.

2. Dielectric constant and dielectric loss tangent were measured at 1MHz.

3. Solder heat resistance The laminate from which the copper foil was removed or the cured composite material was cut into 25 mm square pieces, floated in a solder bath at 260 ° C for 120 seconds, and the change in appearance was visually observed.

4. Copper foil peeling strength A test piece with a width of 25 mm and a length of 100 mm was cut out from the laminate, and after making a parallel cut with a width of 10 mm on the copper foil surface, 50 mm / min in the direction perpendicular to the surface. The copper foil was continuously peeled off at the speed of, and the stress at that time was measured by a tensile tester, and the minimum value of the stress was shown. All the examples showed good trichlorethylene resistance, dielectric properties, solder heat resistance, and copper foil adhesive strength.

Examples 46 to 49 Curable composite material The resin composition and the base material were composited with the composition shown in Table 13. Examples 46 to 49 were carried out with the same resin composition using the same curable polyphenylene ether resin as in Examples 17, 19, 22, and 23, respectively.

The method of conjugation follows the method described in Examples 37 to 45 above,
In Examples 46 and 47, a glass cloth having a basis weight of 48 g / m ² was used, and polyphenylene ether / trichloroethylene = 200 g / 1
The solution was used after adding a predetermined amount of TAC and an initiator.
In Example 48, using a glass cloth having a basis weight of 48 g / m ² was 300 g / 1.
Was used. In Example 49, a glass cloth having a basis weight of 205 g / m ² was used for impregnation with a solution of 200 g / 1.

All the curable composite materials had good film-forming properties and storage stability.

Cured Composite Material and Laminate The curable composite material obtained above was press molded and cured in the same manner as in Examples 37-45. In Example 46, heat compression was performed at 240 ° C. for 30 minutes at a pressure of 50 kg / cm ² without using a copper foil. In Examples 47 to 49, 35 μm copper foil was used for the surface layer, and the pressure was 100 kg /
It was heat-compressed in cm ² at 200 ° C. for 1 hour. Physical properties were measured according to the same methods as in Examples 37 to 45, and good values were obtained as shown in Table 14.

Examples 50 to 57 Curable composite material As shown in Table 15, a composite of a propargyl group-substituted polyphenylene ether and a substrate was performed. In Examples 50-53,
The same resin composition was used as in Examples 25, 26, 27 and 29, using the same curable polyphenylene ether resin. Example 54
In Examples 57 to 57, the same curable polyphenylene ether resin as in Examples 32, 34, 35 and 36 was used, and the same resin composition was used.

The method of compounding was in accordance with the method described in Examples 37 to 45 above. In Examples 50 and 51, a glass cloth having a basis weight of 105 g / m ² was used, and polyphenylene ether / trichloroethylene = 15.
Impregnation was carried out with 0 g / 1 solution. In Examples 52 and 53, a quartz cloth having a basis weight of 105 g / m ² was used instead of the above glass cloth. In Examples 54 to 57, glass cloth having a basis weight of 48 g / m ² was used and impregnation was performed using a solution of 500 g / 1.

All the curable composite materials had good film-forming properties and storage stability.

Cured Composite Material and Laminate The curable composite material obtained above was press molded and cured in the same manner as in Examples 37-45. The pressure was 100 kg / cm ² , and the time was 30 minutes. Table 16 shows the temperature, the presence or absence of copper foil, and the physical properties at this time. Physical properties were measured in the same manner as in Examples 37 to 45. All the examples showed good trichlorethylene resistance, dielectric properties, solder heat resistance, and copper foil adhesive strength.

Among the laminates obtained in the above Examples 37 to 57, Examples 37, 43,
Tensile strength, bending strength, and linear expansion coefficient (XY direction and Z direction) were measured for five types of 49, 52, and 56. The results are summarized in Table 17. All had sufficient strength and were excellent in dimensional stability.

[Operation and Effect of the Invention] When the features of the curable polyphenylene ether resin composition according to the first aspect of the present invention are summarized, firstly, the film forming property by the casting method is excellent. For example, poly (2,
6-Dimethyl-1,4-phenylene ether), which is widely used in general, has almost no solvent film-forming property, so even if it is mixed with triallyl isocyanurate and / or triallyl cyanurate, its strength is high. It is not possible to obtain a film with a smooth surface.
On the other hand, the polyphenylene ether substituted with an allyl group and / or a propargyl group used in the present invention has extremely excellent film-forming property by itself, and therefore, strength and surface properties are obtained even when used in the resin composition of the present invention. An excellent film could be obtained. Moreover, there was no stickiness on the surface and it was easy to handle. The following second feature is that it is excellent in storage stability and can be stored at room temperature for 3 months without gelation in the form of a solution or film. The third feature is that the glass transition temperature is low and the fluidity is excellent, so that thermoforming is easy to perform. This is because triallyl isocyanurate and / or triallyl cyanurate exerts an effect as a plasticizer, and a glass transition temperature as low as 80 to 160 ° C. can be realized by appropriately selecting the composition.

The second feature of the cured polyphenylene ether resin composition of the present invention is, firstly, that it has excellent chemical resistance. This is due to the effects of both triallyl isocyanurate and / or triallyl cyanurate and the effect of the allyl group and / or propargyl group introduced into the polyphenylene ether. When it was lacking, remarkable swelling and change in appearance were observed by boiling in trichlorethylene. The second feature is the excellent dielectric properties of polyphenylene ether (low dielectric constant,
Low dielectric loss tangent) is not impaired. Further, since the curing reaction in the present invention occurs by the addition reaction of the allyl group or propargyl group in the curable polyphenylene ether resin and the allyl group in triallyl isocyanurate and / or triallyl cyanurate, the curing reaction is similar to that of the polyimide resin. A uniform, void-free film or sheet that does not produce water, gas, or other by-products resulting from the condensation reaction.
Another feature is that molded products can be obtained.

As the characteristic of the curable composite material which is the third aspect of the present invention, the characteristic of the curable polyphenylene ether resin composition described in the first aspect of the present invention is directly applied. That is, the first feature is excellent film-forming property, surface smoothness, good handleability without stickiness, and secondly storage stability.
Thirdly, it has excellent thermoformability.

As the characteristics of the cured composite material which is the fourth aspect of the present invention, the characteristics of the cured polyphenylene ether resin composition described in the second aspect of the present invention apply as they are. That is, the first feature is excellent chemical resistance, the second feature is excellent dielectric characteristics, and the third is that a uniform and void-free molded product can be obtained. In addition to this, the cured composite material of the present invention was excellent in solder heat resistance, and no change in appearance was observed even when heating was continued for 120 seconds on a solder bath at 260 ° C. It was also excellent in mechanical strength and dimensional stability (XY and Z directions).

Finally, as the fifth feature of the laminated body of the present invention, the feature of the cured polyphenylene ether resin composition described in the second aspect of the present invention and the feature of the fourth cured composite material of the present invention are directly applied. That is, the first feature is excellent chemical resistance, the second is excellent dielectric properties, and the third is
Is that a molded product that is uniform and has no voids can be obtained. Fourthly, solder heat resistance, mechanical strength, and dimensional stability are listed. In addition to these, the laminate of the present invention was also excellent in adhesiveness to the metal foil.

All of the features of the present invention described above indicate that the present invention can be advantageously used as a low dielectric constant printed circuit board material. In particular, since it has excellent film forming properties, moldability, and dimensional stability in the Z direction, it can be advantageously used as a material for flexible substrates, three-dimensional printed substrates by injection molding, single-sided or double-sided copper-clad laminates, prepregs for multilayer substrates, and the like. . Other applications include semiconductor encapsulation materials, satellite broadcast antenna substrates, VLSI insulating films, microwave oven materials, heat-resistant adhesives, and the like.

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Claims (6)

[Claims] 1. A curable polyphenylene ether resin consisting essentially of the following general formula (I), wherein the average substitution rate of allyl groups and / or propargyl groups defined by the following formula is 0.1 mol. % To 100 mol% and less of curable polyphenylene ether resin (B) A resin composition containing triallyl isocyanurate and / or triallyl cyanurate,
Based on the sum of (a) and (b), the component (a) is 98-40
Curable polyphenylene ether resin composition whose weight% and (b) component are 2 to 60 weight%. Q′J′-H] _m (I) [wherein, m is an integer of 1 or 2, and J ′ is a general formula. (Here, R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom,
An allyl group or a propargyl group, at least one of R ₁ to R ₄ is other than hydrogen, and R ₁ to R ₄ may be the same or different. ) Is a polyphenylene ether chain containing units, Q'represents a hydrogen atom when m is 1, Q'has two phenolic hydroxyl groups in one molecule when m is 2,
Residue Q of a bifunctional phenol compound having a polymerization-inert substituent at the ortho and para positions of the phenolic hydroxyl group
And / or two polyphenylene ether chains, which represent Q substituted with an allyl group and / or a propargyl group and are linked to Q ', may be the same or different. ] 2. The average substitution rate of allyl groups and / or propargyl groups of the curable polyphenylene ether resin is 0.5.
The curable polyphenylene ether resin composition according to claim 1, which is in the range of mol% to 50 mol%. 3. A curable composite material comprising a curable polyphenylene ether resin composition and a substrate, wherein the curable polyphenylene ether resin composition is substantially composed of (a) the following general formula (I). Curable polyphenylene ether resin, wherein the average substitution rate of allyl group and / or propargyl group defined by the following formula is 0.1 mol% or more 1
With a curable polyphenylene ether resin that is less than 00 mol% (B) containing triallyl isocyanurate and / or triallyl cyanurate, (a) and (b)
98-40% by weight of component (a), based on the sum of (b)
A curable composite material, which comprises 2 to 60% by weight of components. Q′J′-H] _m (I) [wherein, m is an integer of 1 or 2, and J ′ is a general formula. (Here, R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom,
An allyl group or a propargyl group, at least one of R ₁ to R ₄ is other than hydrogen, and R ₁ to R ₄ may be the same or different. ) Is a polyphenylene ether chain containing units, Q'represents a hydrogen atom when m is 1, Q'has two phenolic hydroxyl groups in one molecule when m is 2,
Residue Q of a bifunctional phenol compound having a polymerization-inert substituent at the ortho and para positions of the phenolic hydroxyl group
And / or two polyphenylene ether chains, which represent Q substituted with an allyl group and / or a propargyl group and are linked to Q ', may be the same or different. ] 4. The average substitution rate of allyl groups and / or propargyl groups of the curable polyphenylene ether resin is 0.5.
The curable composite material according to claim 3, wherein the content is not less than mol% and not more than 50 mol%. 5. A cured composite material comprising a cured polyphenylene ether resin composition and a substrate, wherein the cured polyphenylene ether resin composition comprises a chloroform non-extractable polyphenylene ether resin and a chloroform extractable polyphenylene ether resin composition. 2-methylphenol, 2,6-dimethylphenol, 2,4-dimethylphenol, 2,4,6-trimethylphenol, and triallyl isocyanurate and / or by analysis by pyrolysis gas chromatography Triallyl cyanurate is produced as a thermal decomposition product, and the peak area ratio of these ~ satisfies the following inequality, [Where [1], [2], [3], [4] and [5]
Represents the peak area of the pyrolysis gas chromatogram resulting from the pyrolysis components ,,, and, respectively. ] The amount of the chloroform-extractable polyphenylene ether resin composition obtained by treating the cured composite material with chloroform at 23 ° C. for 12 hours is 0.01% by weight or more based on the cured polyphenylene ether resin composition.
And the chloroform-extractable polyphenylene ether resin composition has a unit represented by the following general formula (II), triallyl isocyanurate and / or
Alternatively, a cured composite material containing triallyl cyanurate. [Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom,
An allyl group or a propargyl group, at least one of R ₁ to R ₄ is other than hydrogen, and R ₁ to R ₄ may be the same or different. ] 6. A laminate comprising a cured composite material, which is a composite of a cured polyphenylene ether resin composition and a substrate, and a metal foil, wherein the cured polyphenylene ether resin composition comprises a chloroform non-extractable polyphenylene ether resin. Chloroform extractable polyphenylene ether resin composition, and by pyrolysis gas chromatography analysis, 2-methylphenol, 2,6-dimethylphenol, 2,4-dimethylphenol, 2,4,6-trimethyl Phenol, and triallyl isocyanurate and / or triallyl cyanurate are produced as thermal decomposition products, and the peak area ratios of these satisfy the following inequalities: [Where [1], [2], [3], [4] and [5]
Represents the peak area of the pyrolysis gas chromatogram resulting from the pyrolysis components ,,, and, respectively. ] The amount of the chloroform-extractable polyphenylene ether resin composition obtained by treating the laminate with chloroform at 23 ° C. for 12 hours is 0.01 wt% or more and 5 wt% or more based on the cured polyphenylene ether resin composition.
A laminate having the following structure, wherein the chloroform-extractable polyphenylene ether resin composition contains a unit represented by the following general formula (II) and triallyl isocyanurate and / or triallyl cyanurate. [Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom,
An allyl group or a propargyl group, at least one of R ₁ to R ₄ is other than hydrogen, and R ₁ to R ₄ may be the same or different. ]