JPH0488055A - Curable polyfunctioal polyphenylene ether resin composition and composite material and laminated material using same composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a curable multifunctional polyphenylene ether resin composition and a cured polyphenylene needle resin composition obtained by curing the resin composition.

The present invention relates to a curable composite material comprising the curable polyfunctional poly-1-nylene ether resin composition and a base material, a cured composite material obtained by curing the curable composite material, and a cured composite material comprising the curable polyfunctional polynylene ether resin composition and a base material. The present invention relates to a laminate comprising metal foil.

[Conventional technology]

In recent years, there has been a remarkable trend towards miniaturization and higher density packaging methods in the field of electronic equipment for communications, consumer use, industrial use, etc. Dimensional stability and electrical properties are increasingly required. For example, as printed wiring boards, copper-clad laminates made of thermosetting resins such as phenol resins and epoxy resins have been conventionally used. Although these have a good balance of various performances, they have the disadvantage of poor electrical properties, especially dielectric properties in the high frequency range. Recently, attempts have been made to apply polyphenylene I-del to copper-clad laminates as a new material to solve this problem.

Polyphenylene ether is an engineering plastic with excellent mechanical and electrical properties, and has relatively high heat resistance. However, when trying to use it as a printed circuit board+, J14, extremely high solder heat resistance is required, so the heat resistance inherent to polyferene ether is by no means sufficient. That is, when polyphenylene ether is heated to a high temperature of 200°C or higher, it deforms.
This causes a significant decrease in mechanical strength and peeling of the copper foil formed on the resin surface for circuit use. Although polyphenylene ether has strong resistance to acids, alkalis, and hot water, it has extremely low resistance to aromatic hydrocarbon compounds and halogen-substituted hydrocarbon compounds, and dissolves in these solvents.

As one method to improve the heat resistance and chemical resistance of polyphenylene needles, a method has been proposed in which a crosslinking functional group is introduced into the polyphenylene ether chain, which is further cured and used as cured polyphenylene needles. but,
No satisfactory solution has been obtained so far.

Kurian et al. used 2-allyl-6-methylphenol or 26-methylphenol as a curable polyphenylene ether.
Journal of diarylph] ninol polymer
Polymer 5science magazine, Volume 49, 267
(1961). However, these homopolymerizations yield only low-molecular-weight polymers, and if the resulting polymers are left in the air, they will harden in a few weeks and become unusable.

US Special W] No. 3281393 @ and 3/1220
No. 62 discloses a monomer of 2,6-dimebruphenol and 2-allyl-6-methylphenol or 2,6-diallylno-1-nol. Although this copolymer has a high molecular weight, it is impossible to thermoform it because its melting temperature is higher than its curing temperature. As a method for improving moldability, U.S. Special Edition No. 3,422,062 attempts to use a large amount of plasticizer, but this impairs the excellent dielectric properties (low dielectric constant, low dielectric loss tangent) of polyphenylene ether ( In addition, the tensile strength of this cured product is extremely low at 28 Kl/ci, as shown in Example 7, and it is difficult to imagine that it can withstand practical use. Bitter and difficult.

On the other hand, US Pat. No. 463/1742 @ discloses vinyl group-substituted polyphenylene needles. This can be obtained by using a polymer of 2,6-dimethylphenol and converting the methyl group of the polymer into a vinyl group, or by introducing a vinyl group into the 3.5-position of the phenyl group. be. 1. In other words, the vinyl group introduced in this way is directly bonded to the aromatic ring of polyphenylene ether via a flexible carbon chain or ether bond, so after curing, it lacks flexibility and is extremely brittle. It becomes a material that cannot be put to practical use.

Additionally, this polymer has low crosslinking reactivity and requires 300°C for crosslinking.
It has the disadvantage of requiring higher temperatures.

In order to solve the above problems, the present inventors first 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. Patent application No. 62-22 to find out that this is possible, and that the resulting cured product is insoluble in aromatic hydrocarbon solvents and H1-substituted hydrocarbon solvents and has excellent dielectric properties.
No. 4146, No. 62-224147, No. 62-269
No. 459, No. 62-269460, No. 63-2719
(See No. 83). However, these cured bodies have i~
When boiled with dichloroethylene, although it is insoluble, it swells and warps, so there is still a problem in that the chemical resistance has not been sufficiently improved for use as a printed circuit board material.

[Problem to be solved by the invention]

In view of the above circumstances, the present invention aims to provide a novel cured polyphelene needle resin composition that maintains the excellent dielectric properties of polyphenylene ether and has further improved chemical resistance.

(Means for Solving the Problems) The present inventors solved the above-mentioned problems, and the laminated layer 4-,
As a result of intensive studies to obtain a material suitable for material A, the present invention was arrived at. This invention is next) 5 inventions in 1 J
, is composed of

That is, the first aspect of the present invention is (a) a curable polyfunctional polyphenylene resin consisting essentially of the following general formula (i), which comprises an allyl group and/or a propargyl group defined by the following formula: A curable polyfunctional polyphenylene ether resin having an average substitution rate of 0.1 mol% or more and 100 mol% or less, and an average substitution rate - / or triallyl cyanuride-1~ A resin composition containing 98~40% by weight of component (a) and 2~40% by weight of component (b) based on the sum of (a) and (b). Curable polyfunctional pop-enile that is 60% by weight
The present invention provides an ether resin composition.

Q'-+J'-1-16 (I) [wherein m is 3
is an integer of ~6, and Q' is the general formula (where R1, R2
, R3 and R4 are each independently a hydrogen atom, an allyl group or a p[1pargyl group, and at least one of R1 to R4 is
1 is other than hydrogen, and R1-R4 may be the same or different. ) is a polyphenylene ether chain containing a unit represented by represents a residue Q of a 3- to 6-functional phenol compound having Q and/or Q substituted with an allyl group and/or a propargyl group, and 3 to 6 polyphenylene ether chains bonded to Q' may be the same or different. It's okay. ] The second aspect of the present invention is a cured polyphenylene ether resin composition comprising a chloroform-nonextractable polyphenylene p-thyl resin and a chloroform-extractable polyphenylene ether resin composition, and the cured polyphenylene ether resin composition is Analysis by Decomposition Kaschroma 1-Graphie showed ■2B Methylphenol, ■2,6-dimedylphenol, ■
2,4-dimethylphenol, ■2. /l, e-trimedelphenol, and (1) Realyl isocyanurate (1) and/or triallyl cyanurate are synthesized as thermal decomposition products, and the ratios of these (2) to (3) are as follows. Satisfies the inequality, (1) ten (2) + (3) + (4) 100 ≦ 40 [where (1), (2), (3), (4) and [5]
represent the peak areas of the pyrolysis gas chromatogram caused by the pyrolysis components (1), (2), (2), (2) and (2), respectively. ] And when the cured polyphenylene needle resin composition is treated with chloroborm at 23°C for 12 hours, the adhesive If
The amount of the chloroform-extractable polyphenylene ether resin composition determined from the D-form extraction rate is 0.01% by weight or more and 5% by weight or less based on the cured polyphenylene ether resin composition, and the chloroform-extractable polyphenylene The present invention provides a cured polyphenylene ether resin composition characterized in that the ether resin composition contains a unit represented by the general formula (n) and 1-allylylisocyanurate-1- and/or triallyl cyanurate.

The third aspect of the present invention is a curable composite material comprising a curable polyfunctional polyphenylene ether resin composition and a base material,
The curable polyfunctional polyphenylene edel resin composition is
(a) A curable polyfunctional polyphenylene ether resin substantially composed of the general formula (i), wherein the average substitution rate of allyl groups, J, and/or propargyl groups defined by the following formula is 0. Curable polyfunctional polyphenylene ether resin of 1 mol % or more and 100 mol % or less and average substitution rate - number of allyl groups and/or phenyl groups (b) 1 to realyl isocyanurate] and/or 1 - realyl cyanuride-1 - (a)
The present invention provides a curable composite material characterized by having component (a) in an amount of 98 to 40% by weight and component (b) in an amount of 2 to 60% by weight, based on the sum of components (a) and (b).

A fourth aspect of the present invention is a cured composite material comprising a curable multifunctional polyphenylene ether resin composition and a base material, the cured polyphenylene needle resin composition comprising a chloroform non-extractable polyphenylene ether resin and a chloroform extractable polyphenylene ether resin. It consists of an ether resin composition, and when analyzed by pyrolysis gasket graphography,
■2-methylphenol, ■2,6-dimethylphenol, ■2,4-dimedylphenol, ■2.4.6-1~
Limethylphenol, J, and 1-realyl isocyanurate 1- and/or triallyl cyanurate are produced as thermal decomposition products, and the peak area of these 1 to 2 satisfies the following inequality, [5] 0.05≦(1)”-(2)+(3)+(4) 10()≦40 [Here, [1], (2), (3), (4) [5
] represents the pic area of the pyrolysis gas chroma j-gram caused by the pyrolysis components (■, ■, ■, ■, J, and ■), respectively. ] and the cured composite material was heated with chloroform at 23°C for 1
The amount of the chloroform-extractable polyphenylene ether resin composition obtained by the 2-hour treatment is 0.01% by weight or more and 5% by weight or less based on the cured polyphenylene ether resin composition, and the chloroform-extractable polyphenylene needle The resin composition has the following general formula (I
The present invention provides a cured composite material comprising a unit represented by I) and 1 to realyl isocyanurate and/or 1 to realyl cyanurate.

Finally, the fifth aspect of the present invention is a laminate comprising a cured composite material in which a curable multifunctional polyphelene ether resin composition and a base material are combined and a metal foil, the laminate comprising a cured composite material in which a curable polyphenylene needle resin composition is combined with a base material, and a metal foil. is composed of a chloroform-nonextractable polyphenylene ether resin and a chloroform-extractable polyphenylene ether resin composition, and when analyzed by pyrolysis gask 1 frame 1~graph, 2-methylphenol, enol, ■2,6-dimethylphenol, ■2,4-dimethylphenol, ■2,4.6-1~
Limethylphenol and (1) l-lylyl isocyanurate and/or 1~lylyl cyanure-1~ are produced as thermal decomposition products, and the peak area ratio of these (1) to (2) satisfies the following inequality, [5] 0.05≦
X(1) +(2) +(3) + C4)100
≦ 40 [where (1), (2), (3), (4) and [5]
represent the peak area of pyrolysis gas [1 madogram] caused by pyrolysis components ■, ■, ■, ■, and ■, respectively.

] The amount of the chloroform-extractable polyphenylene ether resin composition obtained by treating the laminate with a Roborum at 23°C for 12 hours is the amount of the cured polyphenylene ether resin composition.
0.01% by weight or more and 5% by weight or less based on the nylene L-chill resin composition, and the chloroform-extractable polyphenylene ether resin composition has the general formula (II
) and triallylisocyanurate
The present invention provides a laminate characterized by containing 1 to 1 and/or 1 to realyl cyanurate.

The above five inventions will be explained in detail below.

The curable multifunctional polyphenylene needle resin used as the component (a) of the curable multifunctional polyphenylene needle resin composition, which is the first aspect of the present invention, has the following general formula (i>
A polyphenylene ether substituted with an allyl group and/or a propargyl group consisting essentially of Refers to 100 mol% or less.

2/4 Q'→J'-II) II, (I) General formula (
In i), m represents an integer of 3 to 6. Also, J' is
Representative examples of the general formula Q include compounds represented by the following three general formulas.

represents a polyphenylene chain containing a unit represented by R1-R4 may be the same or different. Q' has 3 to 6 phenolic hydroxyl groups in one molecule, and A of the phenolic hydroxyl group
3-3 having polymerization-inactive substituents at the root and para positions
Residue Q of a hexafunctional phenol compound and/or Q substituted with an allyl group and/or a propargyl group
and the 3 to 6 polyph-[nylene ether chains bonded to Q' may be the same or different. ] [In the formula, △1. A2 represents the same or different linear alkyl group having 1 to 4 carbon atoms, X represents an aliphatic hydrocarbon residue and substituted derivatives thereof, an aral 4-l group and substituted derivatives thereof, oxygen, sulfur, a sulfonyl group, represents a carbonyl group, Y represents an aliphatic hydrocarbon residue and their substituted derivatives, an aromatic hydrocarbon residue and their substituted derivatives, an aralkyl group J3 and their substituted derivatives, Z represents oxygen, sulfur, a sulfonyl group, Two phenyl groups representing a carbonyl group and directly bonded to A, A2 and X,
The bonding positions of A and Y, A2 and 7 are the A- and para-positions of the phenolic hydroxyl group, p is 1 to 4, and q
fJ Represents an integer from 3 to 6. ] As a specific example, (hereinafter blank)
2/1147, 269459, 2f394BO
I can list the method disclosed in @.

That is, as a first method, the general formula % formula %) [In the formula, l'T1 is an integer of 3 to 6 -C and 1. ) is a polyphenylene edel chain consisting of units represented by the following general formula, and so on.

A specific example of the polyphenylene ether resin of the general formula (i>) is 2,6-dimethylphenol as Q (Ei).
Examples include resins obtained by polymerization in the presence of m (m is an integer of 3 to 6) and substituted with an alkynyl group and/or an alkynyl group.

As a method for producing a polyphenylene ether resin of the general formula (i) (with no particular restrictions, 1-I
Cl-13Q represents the remainder of the tri- to hexa-functional phenol compound. ] A method comprising a step of metalating a polynylene ether represented by the following with an organic metal and a step of subjecting it to a substitution reaction with an allyl halide and/or a propargyl halide can be mentioned. In addition, as a second manufacturing method, the general formula Qn→J''l-16 (where m is an integer of 3 to 6, and JIT is the general formula (where R5, R6, Frio J, and R8 is each independently a hydrogen atom or an allyl group, at least one of R5-R8 is an allyl group, and R5-R8 may be the same or different.) A polyphenylene ether chain containing a unit represented by and OIL represents the residue of the tri- to hexafunctional phenol compound and/or Q substituted with an allyl group.] Examples include a process of adding a halogen to a double bond, and a process of dehydrogenation with a metal amide.

There are no particular restrictions on the molecular weight of the curable polyfunctional borine-1-nylene ether resin of the general formula (i>), but it is possible to use it from low molecular weight to high molecular weight, especially at 30°C, 0.5y
/di glue L1071\Viscosity number η8 measured with Lum solution
．． Those having /C in the range of 0.2 to 10 can be used satisfactorily.

In order to obtain the resin composition of the present invention, the formula 1>
The average substitution rate of allyl groups and/or propargyl groups in the curable polyfunctional borif-1 nylene ether resin is preferably in the range of O, tosyl% to 1()0%, more preferably 0. The range is .5% to 50%. The average substitution rate here is defined as the ratio of the total number of allyl groups and/or propargyl groups to the total number of moles of phenyl groups, and is up to 400 mol%.
It is.

If the average substitution rate is less than 0.1 mol %, it is not preferable because the film formation rate (14) by the casting method (during the subsequent step) will be low or the chemical resistance of the cured tablet will not be sufficiently improved. Moreover, if it exceeds 100 mol%, it becomes extremely brittle after curing, which is also not preferable.

The 1-realyl isocyanure-1 and/or 1-realyl cyanurate-1 used as the component (b) of the curable polyfunctional polyphenylene ether resin composition, which is the first aspect of the present invention, is represented by the following structural formula. It is a trifunctional monomer represented.

In carrying out the present invention, 1-realyl isocyanurate-1-(IV) and 1-realyl cyanurate (v) are each used alone. It is also possible to use them in a mixed manner.

The blending ratio of the above two components is 98 to 40% by weight for component (a) and 2 to 60% by weight for component (b) based on the sum of both.
Weight % ranges are preferred. If component (b) is less than 2% by weight, the improvement in chemical resistance will be insufficient, which is not preferable. On the other hand, if it exceeds 60% by weight, the dielectric properties deteriorate and the material becomes extremely brittle after curing, which is not preferable. Furthermore, it is not preferable to form a film by a casting method, which will be described later, or to combine it with a base material, as described in the third aspect of the present invention, because the material will be brittle and have a sticky surface.

From the above two components (a) and (b), the first of the present invention
The method for obtaining the resin composition is not particularly limited, but may be a conventional melt blending or solution mixing method.

At this time, in addition to these components, fillers and additives may be added in amounts within a range that does not impair the original properties in order to impart desired performance depending on the intended use. The filler may be in the form of fibers or powder, and includes glass fibers, aramid fibers, carbon fibers, bone fibers, ceramic fibers, asbestos fibers, carbon black, silica, alumina, talc, mica, and glass. Examples include peas, glass hollow spheres, etc. Further, as additives, antioxidants, heat stabilizers, flame retardants, antistatic agents, plasticizers, pigments, dyes, colorants, etc. can be used.

In addition, this resin composition is cured by causing a crosslinking reaction by heat or other means as described below, but it may contain a radical initiator as a catalyst to lower the temperature at that time or to promote the crosslinking reaction. May be used. The preferred amount of the initiator is in the range of 0.1 to 10 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the sum of components (a) and (b).
It ranges from 1 to 5 parts by weight. If 0.1% by weight of the initiator is not mixed, curing will not be sufficient and chemical resistance will be insufficient, which is not preferable. On the other hand, if it exceeds 10% by weight, the initiator remains and deteriorates the dielectric properties or makes the material brittle, which is not preferable. Typical examples of radical initiators are:
Benzoyl peroxyloid, cumene hydroperoxide, 2,5-dimethylhex]non 2,5-cybideroba-7j-P+J-ide, 2,5-dimethyl 2,5-di(↑-butylperΔxy)hexine-3, Di1, -butyl peroxy 4oid, ↑-butyl cumyl per A kylide, α, α'-bis(t-butyl per A xy m~isopropyl)benvin, 2,5-dimethyl-2,5-di(t-butyl peroxy) Hekilin, dicumylpar A keylid, dicumylpar A xysophthalate]~
, t-butylperoxybenzoe-1-,22-bis(
t-butylperoxy)butane, 2,2-bis(↑-
Bubluper quaternary di)octane, 2,5-dimethyl-2
,5-di(benzoylbaroxy)hekirin,di(1-
Examples include, but are not limited to, peroxides such as limable silyl peroxide, trimethylsilyltriphenylsilyl peroxide, and the like. Although it is not a peroxide, 2
．． 3-dimethyl-2,3-diphenylbutane can also be used as a radical initiator.

The solvent used when mixing the above components in solution is:
Examples include single or mixed solvents selected from halogen-substituted hydrocarbons such as dichloromethane, chloroform, and trichloroethylene, and aromatic hydrocarbons such as benzene, toluene, and xylene. The above-mentioned resin composition dissolved or dispersed in these solvents can be shaped into a film by the kissing method.

Examples of shaping methods other than the J and Eel chelesting methods include conventional heating and melting methods, and methods such as injection molding, 1-transfer molding, extrusion molding, and press molding can be used. The temperature during heating and melting is selected within the range from the glass transition temperature to the curing start temperature of the resin composition. - In the case of the curable polyfunctional polyphenylene needle resin represented by the formula (I), due to the effect of allyl groups and/or propargyl groups, the glass transition humidity is lower than that of bolev nylene needle which does not have these functional groups. The temperature is approximately 140°C to 210°C, which is relatively low, which is advantageous for thermoforming. Furthermore, in the resin composition of the present invention,
Since triallyl isocyanurate and/or 1-allylyl cyanurate also exhibits the effect as a plasticizer,
The glass transition temperature is in the range of 80 to 160°C, and remarkable fluidity is observed even at low temperatures, making it even more useful for thermoforming.

Any method can be used to cure the resin composition of the present invention, and methods using heat, light, electron beams, etc. can be employed. In the case of heating, there is no particular limitation, but the temperature is 10
0°C to 350'C, more preferably 150°C to 300'C
℃ range, and is selected depending on the decomposition temperature of the initiator.

Also, the time is about 1 minute to 5 hours, more preferably 1 minute to 3 hours.
It's time. The degree of this curing reaction can be monitored by differential scanning calorimetry or infrared absorption (hereinafter abbreviated as FIR) spectroscopy.

To summarize the features of the first curable polyfunctional nylene ether resin composition of the present invention described above, first of all, it is excellent in film formability by a casting method. In the case of ordinary borinoenylene ether, solvent film formation is hardly observed, whereas with the resin composition of the present invention, a smooth film without stickiness on the surface can be obtained, and it is easy to handle. The second feature is that it has excellent storage stability, and can be stored for a long period of time without gelation in the form of a solution or film. The third feature is that it has low glass transition humidity and excellent fluidity, making it easy to thermoform.

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

Regarding the fact that the cured polyphenylene ether resin composition is obtained by curing a composition consisting of polyphenylene needle and 1-lylyl isocyanurate and/or triallyl cyanurate, see, for example, I
R spectroscopy, high-resolution nuclear magnetic resonance of solids (hereinafter NM
Spectral method (abbreviated as R) (so-called CP-MAS)
, can be demonstrated by analytical techniques such as pyrolysis gas chromatography. In particular, pyrolysis gas chromatography is a very effective means of analysis, and polyphenylene l-
It can also be easily distinguished from similar cured products using full.

That is, when the cured polyph]-nylene edel resin composition of the present invention is thermally decomposed at 590°C for 4 seconds in an inert gas atmosphere, it produces (1) 2-methylphenol, (2) 2,6-dimethylphenol, and (2) 2,4. -dimethylphenol, ■2,
4. 5 or 6 characteristic thermal decomposition products of 6-dorimedylphenol, and i~lylylisocyanure 1~ and/or trino7lyl cyanuré 1~ are produced, and the amount of these products produced. The relationship (1)+(2)+(3)+(/1) 100≦40 always holds between them. Here, [1] to [5] represent the peak areas of the pyrolysis gas chromatograph caused by the pyrolysis components 1 to 2, respectively. The other side of the above thermal decomposition products ■ to ■ are products caused by polyphenylene needles, and their generation mechanism can be found in, for example, Journal
of Applied PolymerScience
It is reported in detail in e magazine, vol. 22, p. 2891 (1978).

Triallyl isocyanurate-1 in the curable polyfunctional polyphenylene needle resin composition described as the first aspect of the present invention
- When the ratio of 1 to 1-realyl cyanurate increases, the amount of ``■'' produced relative to the amount of ``■'' to ``■'' increases correspondingly. If the value subtracted by the above inequality is less than 0.05, the amount of 1~realyl isocyanurate-1~ and/or triallyl cyanurate■ is insufficient, and the improvement in chemical resistance is insufficient. This is not desirable. On the other hand, if the value of the inequality exceeds 40, it is not preferable because the dielectric properties deteriorate or the material becomes brittle.

The pyrolysis method used in this pyrolysis gas chromatography is not particularly limited in carrying out the present invention, and all methods such as heated filament method, heating furnace method, high frequency induction heating method, laser heating method, etc. can be used. Available. In particular, the high-frequency induction heating method (Curie Point 1 to Pyrolyzer) is ideal for this analysis because it allows very rapid heating and the obtained temperature is accurate and reproducible.

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 this analysis. As the inert gas, helium or nitrogen can be used as a carrier gas for gas chromatographs.

Regarding the shape of the sample during thermal decomposition, it is preferable to pulverize it for the purpose of improving reproducibility.

As a separation column for gas chromatography, it is sufficient that the above-mentioned five or six thermal decomposition products can be completely decomposed.
Although not particularly limited, a methyl silicone-based nonpolar column or a column with an equivalent degree of nonpolarity can be most preferably used. The shape of the column may be a packed column or a capillary column, and the latter particularly has excellent separation ability and can be used favorably.

There is also no particular limitation on the column temperature;
It is effective to increase the arm temperature by 10°C to 20°C every minute from the room temperature f' to shorten the analysis time.

In this analysis, the thermal conductivity detector (CD) and flame ionization detector (FID) can be used as detectors for gas
It is also possible to connect it with S) and use it as a pyrolysis GCMS. In addition, for qualitative purposes, Fourier transform type IR (
FT-IR) can also be used instead of the detector.

As a method for analyzing the structure of the cured polyphenylene ether resin composition of the present invention, analysis of chloroform extract is an effective method along with pyrolysis gas chroma 1-graphie. The cured polyphelene ether resin composition of the present invention is
It consists of a chloroform non-extractable polyphenylene ether resin composition and a [10 vol extractable polyphenylene ether resin composition], and the ratio of the chloroform extractable polyphenylene ether resin composition can be determined from the chloroform extractability. The chloroform extraction rate referred to here is the value obtained by immersing the cured polyphenylene acyl resin composition in chloroform at 23°C for 12 hours, It is sifted according to the following formula based on weight.

Chlo[] Small lum extraction rate = Weight before immersion in chloroform Chloro 71\The preferred value range for the lum extraction rate is 0.01
It is at least 5% by weight and not more than 5% by weight. If 0.01% by weight is not swirled, the cured product becomes brittle, which is not preferable. Conversely, 5% by weight
A knife exceeding 10% has insufficient chemical resistance and is also undesirable. When fixing the shape of the cured polyphenylene ether resin composition by immersing it in chloroform, it is most preferable to use a film or powder form in view of ease of removing chloroform.

The extraction rate can also be measured using deuterium chloroform instead of chloroform. ■Nylene I - It is possible to know the components and structures of the full resin composition.

In the Roborum-extractable polyphenylene needle resin composition according to the present invention, a unit represented by the following general formula <m> and 1 to realyl isocyanurate and/or triallyl cyanurate to 1 are present. included.

(Here, R1, R2, R3 and R4 are each independently a hydrogen atom, an allyl group or a propargyl group, and R1-
At least one of R4 must be other than hydrogen, and R1-R
4 may be the same or different. ] In the present invention (the 10% lume-extractable polypolyphelene ether resin is the first aspect of the present invention), among the small curable polyfunctional polyphenylene needle resin compositions, there is a polyphenylene needle resin composition that undergoes a curing reaction during the curing process. The components that could not contribute sufficiently were extracted. However, the composition of the small lume-extractable borea nylene ether resin composition does not necessarily match the composition of the original curable polyfunctional polyphenylene needle resin composition. The ratio of the polyphenylene ether represented by the formula (If) to the triallyl isocyanurate and/or l-lylyl cyanurate is not limited.The average substitution rate of the polyphenylene ether represented by the general formula (If) is also as shown in the first aspect of the present invention. It does not necessarily match the average substitution rate of the curable polyfunctional boria-1-nylene ether resin of component (a).
The residue of hydrogen or a difunctional phenol compound represented by Q' in the a) component may or may not be confirmed in the extract. As a means for confirming the structure of these taro-form-extractable borif-1-nylene T-pull resin compositions, the NMR spectroscopy method is effective as described above, and NMR is particularly effective. Further, the IR spectrum method can also be used.

To summarize the characteristics of the cured polyphenylene ether resin composition, which is the second aspect of the present invention, the first is its excellent fIJ chemical properties. A cured product of only polyphenylene needle containing triallyl isocyanurate-1 to J and/or triallyl cyanurate swells significantly by boiling in tric[10]-dylene,
In contrast, the cured polyphenylene ether resin composition of the present invention showed little swelling and no change in appearance was observed even when subjected to the same treatment. The second feature is that the excellent dielectric properties (low dielectric constant, low dielectric loss tangent) of borif-1-nylene-1-del are not impaired, making it useful as a material for pudding substrates and the like.

In general, the curing reaction according to the present invention is a curable polyfunctional borinoenylene.
Because it occurs through the addition reaction of the aryl 4-fluor group in film without, sea 1
-The characteristic that molded products can be obtained is also right.

Next, the third aspect of the present invention, the curable multifunctional composite '+A', will be explained. This curable composite material is a composite material consisting of the curable polyfunctional polyphenylene needle resin composition described as the first aspect of the present invention and a base material. The sealing materials used in the present invention include various cloths such as loading cloth, cloth, chopped pine 1-1ν-facing pine; ceramic w4M iro, asbeth 1~ cloth, metal fiber cloth, and other synthetic or natural inorganic fibers. Fabric; woven 'f' [i or non-woven fabric; cotton cloth, linen cloth, fel 1~ etc. Natural fiber cloth: carbon fiber fiber;
-S based fabrics can be used alone or in combination of two or more types/1B.

As a method of compounding the curable polyfunctional polyphenylene ether resin composition shown in the first aspect of the present invention and the above-mentioned base material, the resin composition may be mixed with a small halogen-substituted hydrocarbon or aromatic
A method is used in which the solvent is dissolved in a single or mixed solvent selected from group hydrocarbons, impregnated into a base material, and then dried and covered. Impregnation is usually done by dipping or coating.
: It is done in.

Impregnation can be repeated multiple times if necessary,
Further, at this time, it is also possible to repeat the -C impregnation using a plurality of solutions having different compositions and concentrations, and finally adjust the desired resin composition and resin amount.

The resin composition suitable for the curable composite material of the present invention is similar to the first curable polyfunctional polyfunctional polyphenylene ether resin composition of the present invention, in which the curable polyfunctional polyphenylene ether resin as the component (a) is 98 to 40% by weight. %, component (b) triallyl isocyanurate and/or 1-realyl cyanurate-1 is in a proportion of 2 to 60% by weight, and the above-mentioned initiator may be further blended as a third component. The preferred amount of the initiator is the same as the first aspect of the present invention, and is 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on the sum of components (a) and (b). . In addition to the initiator, the above-mentioned fillers and additives can also be blended depending on the purpose.

The blending 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 even more preferably 20 to 70% by weight. %, the resin component is preferably 95-10% by weight, more preferably 90-20% by weight, even more preferably 80-30% by weight.

If 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 W material is less than 90% by weight.
If the amount is too large, the electrical properties of the composite material will deteriorate, which is not preferable.

As for the characteristics of the curable composite material according to the third aspect of the present invention described above, the characteristics of the curable polyfunctional polyphenylene 1-thyl resin composition described in the first aspect of the present invention apply as they are. In other words, its first characteristics are excellent film forming properties, surface smoothness, and ease of handling without stickiness, second is storage stability, and third is excellent thermoformability. .

Next, the cured composite material according to the fourth aspect of the present invention will be explained. This cured composite material is a composite material consisting of the cured polyphenylene ether resin composition described as the second aspect of the present invention and a base material, and is not particularly limited to the third curable composite material of the present invention. It can be obtained by curing by a method such as heating. For example, a cured composite material having a desired thickness can be obtained by stacking a plurality of sheets of the curable composite material, compressing the spaces between each layer with a handler under heat and pressure, and simultaneously performing heat curing. During lamination, (as the first aspect of the present invention) a small solid curable multifunctional polyphenylene ether resin composition shaped into a film may be used in combination with the above-mentioned curable composite material. It is also possible to obtain a cured composite material with a new layer structure by combining a cured composite material that has been adhesively cured with a curable composite material and/or a curable multifunctional polyphenylene needle resin composition.

Laminate molding and curing are usually performed simultaneously using a hot press or the like, but both may be performed independently. That is, uncured or semi-cured composite material obtained by lamination molding in advance,
Hardening can be achieved by heat treatment or other processing. Molding J3J, hardening 1 unit, temperature 100
~350'C, work) 0.1 to 1000 to 9/cri
, a time range of 1 minute to 5 hours, more preferably a temperature of 191
50□”3 (10°C1 pressure 1~500 Kg/ctr
i.

It may be carried out within the range of 1 minute to 3 hours during lh.

The blending ratio of the base material and resin component to be applied to the cured composite material of the present invention is not particularly limited.
% by weight, more preferably 10-80% by weight, even more preferably 20-70% by weight, the resin component is 95-10% by weight.
It is preferably 90 to 20% by weight, still more preferably 80 to 30% by weight. Base material is 5%
If the amount is less, the dimensional stability and strength of the cured composite material will be insufficient, and if the amount of the base material is more than 90%, the electrical properties of the cured composite material will be poor.

Since the cured composite material of the present invention is a composite material of the cured polyphenylene ether resin composition described as the second aspect of the present invention and a base material, the characteristics of the cured polyphenylene ether resin composition described in detail of the present invention are as follows. You can apply it as is. That is, the resin component of the cured composite material of the present invention is a cured polyphenylene ether resin composition consisting of a chloroform-nonextractable polyphenylene ether resin and a chloroborm extractable polyphenylene ether resin composition, and the cured polyphenylene ether resin The composition was analyzed by pyrolysis gas chroma 1-graphie, and it was found that: ■2-
Methylphenol, ■2,6-dimethylphenol, ■
2,4-dimethylphenol, ■2.4.6-drimethylphenol, and ■triallylisocyanurate and/or 1~lylyl cyanurate-1~ are produced as thermal decomposition products, and the peak areas of these ■~■ The ratio satisfies the following inequality, [5] 0.05≦
× (1) ten (2) + (3) + (4) 100 ≦ 40 [where (1), (2), (3), (4) and [5]
represent the peak areas of the pyrolysis gas chromatogram caused by the pyrolysis components (1), (2), (2), (2) and (2), respectively. ] and the amount of the cured polyphenylene needle resin composition obtained by treating the cured composite material in chloroform at 23° C. for 12 hours. 0.01% or more and 5% by weight or less based on D
The O-form extractable polyphenylene needle resin composition is characterized in that it contains a unit represented by the following general formula (II>) and 1 to arylyl isocyanurate and/or 1 to lylyl cyanurate.

(Here, R1, R2, R3 and R4 are each independently a hydrogen atom, an allyl group or a propargyl group, and R1-
at least one of R4 is other than hydrogen, and R1-R
4 may be the same or different. ] Pyrolysis Gas Chroma 1 - Method of Analysis by Graphie] [] The analysis method of the form-extractable polyphenylene ether resin composition is as described in the second section of the present invention.

As for the characteristics of the cured composite material according to the fourth aspect of the present invention described above, the characteristics of the cured polyphenylene sub-chill resin composition described in the second aspect of the present invention apply as they are. The first feature is excellent chemical resistance, the second feature is excellent dielectric properties, and the third feature is that uniform molded products without voids can be obtained. In addition, the cured composite material of the present invention has excellent solder heat resistance, and
Even when heating was continued for 120 seconds on a solder bath at 0° C., no change in appearance was observed. It also had excellent mechanical strength and dimensional stability (X-Y and Zh directions). All these characteristics indicate that this cured composite material can be advantageously used as a printed circuit board material, in particular as a material for multilayer boards.

Finally, the fifth aspect of the present invention, the laminate, will be explained. This laminate is a laminate consisting of the cured composite described above as the fourth aspect of the present invention and metal foil. Examples of the metal heat used in the present invention include steel parts, aluminum foil, and the like. The thickness is not particularly limited, or is 5 to 200 μm1
More preferably, it is in the range of 5 to ioo μm.

The method for obtaining the laminate of the present invention is not particularly limited, but for example, a plurality of layers of the third curable composite 'vJ material of the present invention and metal foil are stacked in a layer configuration depending on the purpose, and heated. H
- It can be obtained by adhering and tightening the layers underneath and simultaneously performing heat curing.

At this time, the metal foil can be attached to the surface layer or can be used as an intermediate layer. Further, the curable polyphenylene ether resin composition described as the first aspect of the present invention formed into a film may be used in combination with the above-mentioned curable composite material.

Furthermore, -i adhesively cured laminates or a laminate and metal foil can be laminated via the above-mentioned curable polyphelene ether resin composition or curable composite material to obtain a laminate with a new layer structure. is also possible. An adhesive can also be used to bond the metal foil. Examples of adhesives include epoxy, acrylic, phenol, and cyanoacrylate adhesives, but are not particularly limited thereto.

Laminate molding and curing are usually performed simultaneously using a hot press or the like, but both may be performed independently. That is, an uncured or semi-cured laminate that has been previously formed into a laminate can be cured by heat treatment or another method. Molding, curing, and curing are performed at a temperature of 100~
350°C1 pressure 0.1・1100ON/cffl,
The time range is from 1 minute to 5 hours, more preferably the temperature is 150
~300°C, pressure 1~500 K'J/cri.

It may be carried out for a time ranging from 1 minute to 3 hours.

The blending 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, and even more preferably 20 to 90% by weight.
70% by weight, the resin component is 95 to 10% by weight, more preferably 90 to 20% by weight, even more preferably 80 to 10% by weight.
300 to 30 weight is good. If the amount of the base material is less than 5% J, the laminate will have insufficient J-temperature properties and strength, and if the amount of the base material is more than 90% by weight, the electrical properties of the laminate will be undesirable.

Since the laminate of the present invention is a laminate consisting of a small solid hardened composite material and metal foil (as the fourth aspect of the present invention), its characteristics and analysis method are as described in the fourth aspect of the present invention. be.

Above) The characteristics of the laminate which is the fifth aspect of the present invention which has been reduced are the characteristics of the cured polyphelene ether resin composition described in the second aspect of the present invention and the characteristics of the cured composite of the fourth aspect of the present invention. The same applies.

However, the first characteristic is excellent chemical resistance, the second is excellent dielectric properties, the third is that uniform and void-free molded products can be obtained, and the fourth is that it is easy to solder. Examples include heat resistance, mechanical strength, and dimensional stability. In addition to these, the laminate of the present invention also had excellent adhesion to metal foil.

All of the following features indicate that this laminate can be used as a printed circuit board material, especially as a +A material for multilayer boards.

〔Example〕

EXAMPLES Hereinafter, in order to further clarify the present invention, the present invention will be explained using Examples, but the scope of the present invention is not limited to these Examples.

Example 1-7 Synthesis of curable polyphenyleneconidel resin - following formula (i
As a representative example of the curable polyphenylene 1-pull resin shown in Table 1, an allyl group-substituted polyphenylene 1-pull resin shown in Table 1 was synthesized. Although the synthesis method is the same in all cases, Example 3 will be explained as a representative example.

Viscosity number η8. measured in chloroform solution at 30'C, 0.5 g/dl. /C is 0.57 trifunctional polyph ■
Ren ether [1 to polymerized from lis(3,5-dimethyl-4-hydroxyphenyl)ethane and 2,6-dimethylphenol. Hereinafter 1) P [abbreviated as E-1] 3
507 as Tei~rahydrofuran (hereinafter abbreviated as THF)
Ru. ) and n-butyllithium (1,
5 mol/l! , Hekilin solution) was added thereto, and the mixture was reacted at 40° C. for 1 hour under a nitrogen atmosphere. Subsequently, allylbu[]mite 3 (7) was added and stirred for another 30 minutes at 40'C.Finally, a mixed solution of water 2.8.111, methanol 2.8, and Q was added to precipitate the polymer. .

After repeating filtration and washing with methanol five times, it was vacuum dried at 80'C for 14 hours to obtain a white powdery allyl group-substituted one P[-1. The average substitution rate of allyl groups determined by 'H-NMR was 10%. 30'C again.

The viscosity number ηsp/C measured in a form solution of 0.5c,y/old glue [''1'' was 0.61.

In Examples 1, 2, and 4 to 7, polyphenylene Tj-ru having different average substitution ratios of allyl groups was synthesized by changing the amounts of )-butyllithium and allyl bromide.

Curable polyphenylene ether resin composition A resin composition was prepared with the composition shown in Table 1.

The method will be explained using Example 3 as an example.

Allyl group substitution with an average substitution rate of 10% [1) L-15,4
9, (-Reallylisocyanuride-1- (abbreviated as AIC) 0.69, as an initiator? , 5-dimebru 2
．． 0-di(1-bubble bar A-xi) to-1-syn-3(
Verhexin 25B made by NOF ■ > 0.18y in 1
~Riku] [Dissolved in 120ml of 1 liter and heated to 23°C.
The film was formed using the 4-(7-staining method). The thickness of this film was approximately 1 () μUL, and the surface was excellent in smoothness.
It was non-sticky.

Similarly, for the example of Sen, a refilm-like resin composition was obtained using the chelesting method using Pahexin 253 manufactured by Nippon Oil & Fats IQ as an initiator. All had excellent film-forming properties, and a smooth, non-sticky film was obtained.

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

Cured Polyphenylene Needle Resin Composition Twelve films of the resin composition obtained by the above method were stacked together and heated from room temperature to 280°C using a vacuum press to shrink the composition to 280°C.
After being held at .degree. C. for 30 minutes, the mixture was cooled to obtain a cured polyphenylene ether resin composition having a thickness of about 1 tmn.

In all Examples, the films had low glass transition temperatures and excellent fluidity, so press molding was easy. Table 2 summarizes the physical properties of the obtained sheet-like cured product.

Measurement of each physical property was performed by the method described below.

1. Amount of extractable polyphenylene ether resin silk composition 1. Grind a part of 1~ with a file to make a fine powder, 10
It was immersed in a small lum at 23° C. for 12 hours, and the weight before and after was determined according to the following formula.

Chloro 7J＼lum exportable polyphenylene 1--Dell resin composition amount--Weight before immersion in chloroform 2) Pyrolysis production ratio of J-nols and TAIC Pyrolysis gas chromatography of the fine powder of the sheet-like cured product It was obtained by covering the analysis with . The measurement conditions for pyrolysis gas chromatography are as follows.

(Pyrolysis equipment) [1 Water analysis]-Industry Curie point pyrolyzer
JHP-33 Δ-Bun Warm Polishing 300°C Heat Mining 1590°C, 4 seconds (Gas Chromatograph) Huuret Paracard 5890A Column J & Misha DB-10
, 25 excitation + 1. D, ”
This was done by comparing the -IR spec.

The thermal decomposition product ratio of phenols and IAIC was calculated according to the following formula.

Thermal decomposition ratio of phenols and TAIC - (1) 10 (
2) -1-[:3) 10C4) (in the formula, [1] is 2-
Methylphenol, [2] is 2,6-dimedylphenol, [3] is 2,4-dimedylphenol, [
4] is 2,4.6-1 Herimebrug 1 Nord, [5]
represents each peak area of TAIC. ) 3. Glass transition temperature was determined by differential scanning calorimetry 1f (DSC).

4. Trichlorethylene Resistance Sea The cured product in the shape of 1-1 was cut into approximately 15 cocoon angles, boiled in trichlorethylene for 5 minutes, and the weight increase 5 minutes after removal was determined from the following formula. In addition, changes in appearance were visually observed.

Weight increase- 5. Permittivity, dielectric loss tangent The measurement was performed at 1t4Hz.

All of the examples had good trichlorethylene resistance and excellent dielectric properties.

On the other hand, the following analysis was conducted to confirm the structure of the cured polyphenylene ether resin composition.

First, the FT-IR (diffuse reflection method) of the finely powdered cured product was measured, and the presence of a polyphenylene ether skeleton was confirmed in all Examples. The assignment of the main peaks was as follows.

νS CC (1603 cm-1> νaso -C (119 km-') At the same time, absorption of carbonyl group due to -rAIC was confirmed at 1700 cm-1.

Next, the fine powder of the cured product was immersed in deuterated chloroform (CD (J3)) at 23°C for 12 hours to extract the chloroform-extractable polyphenylene ether resin composition. When NMR was measured, polyphenylene ether chains and two types of allyl groups were confirmed in all Examples. One of the allyl groups had the same chemical shift 1 as the allyl group of the curable borine 1-nyleether resin used as a raw material for the resin composition. The other allyl group was the allyl group of 1'' A I C. The assignment of the main peaks is as follows.

1.9-2.21) Dm (Mebble group of PPE) * 4.5 ppm (--C of IAIC)-
120+-1=C+2)*4.8 ~5. OpDm (PPE--CH2
Cl-1=cH2)*5.2 ~5.41)l)m (-CH of TAIC
2CH=C)-12)5.6 6.0ppm (IA
IC and PPF *CH2Cl~l=Cl-12) 6.3~6.6 ppm (Phenyl group of I'PE) Comparative Examples 1-3 As shown in Table 1, in Comparative Example 1, PI)E-1 A resin composition was prepared using the compound as it was. In Comparative Examples 2 and 3, 0.0.0 of an allyl group was added to PPEI in the same manner as in Example 3.
The one containing 5% was used.

An attempt was made to form a resin composition into a film using the same method as in Examples 1 to 7, but in all cases a large number of fine cracks were formed and the film did not form. Film formation became possible by changing the drying temperature from 23°C to 50°C, but a film with a smooth surface could not be obtained.

Using this film, thermosetting and physical properties of the cured product were measured 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 absent or insufficient, and the 1-lichloro-1'' ethylene resistance was poor compared to the examples.

(Left below) Examples 8 to 11 Synthesis of curable polyphenylene-[-del resin As a representative example of a curable borinoenylene ether resin, propargyl group-substituted polyphenylene ethers as shown in Table 3 were synthesized.Synthesis method Examples 8 and 9 will be described as representative examples.

4 in Example 8. , t, 30℃, 0.5g/old Kroto 1
The same polyfunctional poly(2,6-dimethyl-1
, 4] 350 g of τNylene Ter)] Do1F7.
Dissolved in O and Q, added 580 d of n-butylridium (1.5 mol of Q1 hexane solution), and under nitrogen atmosphere.
The reaction was carried out at 40'C for 1 hour. Next, Pu [1 Pargil 7
Add Diromide 1039 and keep at 40°C for another 20 minutes.
Stir for 1 minute.

Finally, a mixed solution of 2.8 g of water and 2.8 ρ of methanol was added to precipitate the polymer. 4 filtration and methanol washing
After repeating this process several times, it was vacuum dried at 80°C for 14 hours to obtain a white powdery polyfunctional poly(nylene ether) substituted with zoI'pal=V group. 'H-NMR was determined by J.
The average substitution rate of pargyl groups was 7%. Also 30℃,
The viscosity number η and p/C measured with a small lum solution of 0.5 g/dl glue were 0.39.

In Example 9, Example 3 was added to polyfunctional polyphenylene ether.
11% allyl group was introduced using the same method as above.

This allyl group-substituted polyfunctional polyphenylene needle 220
Dissolve 9 in 1" Roborum 5.0 ρ, bromine 12 d
was added and stirred at room temperature for 30 minutes. The reaction mixture was diluted with methanol 10. The polymer was poured into Q and the polymer was precipitated, followed by filtration and washing with methanol three times, followed by vacuum drying at 80°C for 14 hours. The entire amount of the obtained white powder product was diluted with HF.
8.0.9 and cooled to -15°C. Add lithium diisopropylamide under nitrogen atmosphere here.
+ 1 solution (1,2 mol Otsu Q) 40 (add 7, 20
Stir for a minute. Finally, mix this reaction mixture with methanol 10
The polymer was precipitated by filtration and washing with methanol four times, followed by vacuum drying at 80°C for 14 hours.

When 1H-NMR of the obtained polymer was measured, all the original allyl groups were converted to propargyl groups, and the substitution rate was 13%. 30°C, 0.5g/
The viscosity number measured with a chloroform solution was 0. It was old.

In Examples 10 and 11, polymer 1-nylene ether was synthesized in the same manner as in Example 8.

Curable Polyphenylene Edel Resin Composition As shown in Table 3, polyphenylene ether substituted with a pargyl group, TAIC, and Perhexine 2513 manufactured by Nihon Yushiki Co., Ltd. as an initiator were used, and the composition was exactly the same as in Examples 1 to 7. The film was formed using the following method. In each case, a smooth film with a non-sticky surface was obtained. These films also have a temperature of 3 at room temperature.
No gluing occurred even after being left for several months, and the product had excellent long-term storage stability.

Films prepared on cured polyphenylene needle resin compositions were pressed in the same manner as Examples 1-7.

The curing conditions were 200°C x 1 hour. The physical properties of the cured products were measured according to the same method as in Examples 1 to 7. The results are summarized in Table 4. Both have extremely good press formability.
Excellent trichlorethylene resistance and dielectric properties after curing
He showed Haku.

In addition, in order to confirm the structure of the cured product, F=-r-IR (diffuse reflection method) and 'H-NMR of the weight 1'' L1 form extract were measured in the same manner as in Examples 1 to 7.

[The skeleton of polyphenylene ether was confirmed from the IR measurement. On the other hand, 'H-NMR measurements revealed that the same structure and T
AIG was confirmed.

Comparative Examples 4 and 5 As shown in Table 3, Examples 8 to 11 were prepared using polyphenylene ether (synthesized by the same method as Example 8) with an average substitution rate of 10 pargyl groups of 0.05% as Comparative Example 4. performed the same operation. However, both the film formability and the resistance to dichloroethylene after curing were not good.

In addition, as Comparative Example 5, in Example 10, press strip 1
Heat curing was performed at 320°C for 12 hours.

Although the obtained cured product contained 0% of the chloroborum-extractable polyphelene ether resin composition, it was extremely brittle and could not be used in practical use.

Examples 12 to 18 Curable Composite Materials As shown in Table 5, allyl group-substituted polyphenylene needles and base materials were composited. In Examples 12 to 16, the same cured ↑4 Polyph J Nylene Edel resin as in Examples 2 to 6 was used and the same resin composition was used. Examples 17-1
9, the same curable polyno T as in Examples 8 to 10, respectively.
The test was carried out using Niren King Blue resin with the same resin composition. Using Example 13 as a representative example, the method of compounding will be explained.

The average substitution rate of allyl groups is 10%, and the viscosity number η3. /C is 0
．． Allyl group-substituted PPE-2009, l A
I C22,29, 2,5-dimethyl as initiator2.
6.7 g of 5-di(t-bubbleperoxy)hexine~3 (Perhexine 25B manufactured by NOF ■) was mixed with 1. Dissolved in ON. This solution has a basis weight of 105g.
Impregnation was carried out by immersing a glass cloth at 23°C, air-dried at 23°C for 12 hours, and further vacuum-dried at 80°C for 8 hours. The weight fraction of the glass film in the resulting curable composite material was 50%. This curable composite material had excellent surface smoothness and no stickiness. Also at room temperature 3
It did not gel even after being left for several months, and had excellent long-term storage stability.

Examples 12.14 to 16 were carried out in exactly the same manner. In Examples 17 and 18, a curable composite material with a weight fraction of the base material of 30% was obtained using a glass cloth with a diameter of J'489/m.In Example 19, a J'489/m glass cloth was used instead of the glass cloth. 'Iri' quartz cloth was used. Both had excellent film formability and storage stability.

Curable composite material and laminate 12 sheets of the curable composite material obtained by the above method are stacked,
A 35 μm copper foil was placed on both sides, heated and compressed using a press molding machine from room temperature to 200°C at a pressure of 100 kg/ci, held at 200°C for 30 minutes, and then cooled to a thickness of approximately 1.
．． A 6# laminate was obtained. However, in Example 12, the curing conditions were 220'CX for 30 minutes. Also, Example 15゜16
In this case, curing was performed without using copper foil. Table 6 summarizes the physical properties of the obtained laminate and cured composite material.

Measurement of each physical property was carried out using the method described below.

1. Laminate from which trichloroethylene-resistant copper foil has been removed or cured composite vJ'F4 2.
It was cut into 5 mrn square pieces, boiled for 5 minutes in a Triquetre Loeblen, and the increase in weight after 55 minutes after being taken out was determined from the following formula. Changes in appearance were also observed using a microscope.

Heavy f72 increase Weight after boiling - Weight before boiling X100 (%) Weight before boiling 2. Permittivity, dielectric loss tangent Measurements were made with 1HIIZ.

3. Laminate with solder heat-resistant copper foil removed or cured composite material 25##
A corner was cut out, floated in a solder bath at 260'C for 120 seconds, and changes in appearance were visually observed.

4. Copper foil peel strength from laminate: width 25Irun1 length 100. After cutting out the test piece and making parallel cuts with a width of 10 # on the copper foil surface, the copper foil was continuously peeled off at a speed of 50 m/min in the direction of force perpendicular to the surface. The stress was measured using a tensile tester, and the lowest stress value was shown.

All of the examples exhibited good trichlorethylene resistance, dielectric properties, solder heat resistance of 1K, and copper liquor contact strength of 1.

(Left below) [Operations and Effects of the Invention] To summarize the features of the curable polyfunctional borinoenylene ether resin composition, which is the first aspect of the present invention, the first feature is that it has excellent film formability by the casting method. It is. For example, commonly used polyphenylene ethers such as poly(2,6-lame blue 14 phenylene ether) have almost no solvent film-forming properties, so or triallyl cyanuride
Even if mixed with 1 to 1, it is not possible to obtain a strong and smooth film. On the other hand, the allyl group- and/or propargyl group-substituted boline-1-nylene ether used in the present invention has extremely excellent film-forming properties, so even when used in the resin composition of the present invention, the strength and It was possible to obtain a film with excellent surface properties. Furthermore, the surface was not sticky and was easy to handle. The second feature is that it has excellent storage stability, and can be stored in solution or film form at room temperature for three months without gelation. The third feature is that it has a low glass transition temperature and excellent fluidity, making it easy to thermoform.

This is because triallyl isocyanure-I to J and/or 1 to triallyl cyanurate-1 exhibits the effect as a plasticizer ('), and depending on the composition selected for one serving, the temperature is 80 to 160℃. This low glass transition temperature was achieved.

The second feature of the cured borinoenylene ether resin composition of the present invention is that it has excellent chemical resistance. This is due to the effect of triallyl isocyanurate J3 and/or 1 ~ realyl cyanurate 1 ~ and polyphenylene cony.
This is due to both the effects of the allyl group and/or the ``pargyl group'' introduced into the molecule, and if one of the two effects is lacking, significant swelling loss occurs due to boiling in tric[]roethylene. Changes in appearance were observed.

The second feature is that the excellent dielectric properties (low dielectric constant, low dielectric loss tangent) of polyphenylene ether are not impaired. Further, the curing reaction applicable to the present invention is curable polyph J
Nylene]--Allyl group or propargyl group a in chill resin
3J, bi, 1 ~ Realyl isocyanurate 1 ~ OJ, bi/
Or, because it occurs due to the addition reaction of the allyl group in triallyl cyanurate, by-products such as water and gas caused by the synthesis reaction are not produced, such as in epoxy resins and polyimide resins, resulting in uniform and void-free films and sheets. 1. Another feature is that molded products can be obtained.

As for the features of the curable composite material which is the third aspect of the present invention, the features of the curable boria-denylene ether resin composition described in the first aspect of the present invention apply as they are. In other words, its first feature is excellent film forming properties, smooth surface, and good handling without stickiness, and second is its storage stability.
Thirdly, it has excellent thermoformability.

As the features of the cured composite material according to the fourth aspect of the present invention, the features of the cured polyphenylene]--ter resin composition described in the second aspect of the present invention apply as they are.

The first feature is excellent chemical resistance, the second feature is excellent dielectric properties, and the third feature is that uniform molded products without voids can be obtained. In addition, the cured composite vJ rice of the present invention has excellent solder heat resistance, and no change in appearance was observed even when heated for 120 seconds in a 260°C solder bath. It was also excellent in mechanical strength and dimensional stability <X-Y and 7 directions).

Finally, as the features of the laminate which is the fifth aspect of the present invention, the features of the cured polyphenylene ether resin composition described in the second aspect of the present invention and the features of the cured composite body of the fourth aspect of the present invention are directly applicable. In other words, the first feature is excellent chemical resistance, the second is excellent dielectric properties, and the third is that uniform molded products without voids can be obtained.
Fourthly, solder heat resistance, mechanical strength, and dimensional stability are mentioned. In addition to these, the laminate of the present invention also had excellent adhesion to 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, Z7J has excellent formability during film formation and dimensional stability, making it advantageous as a material for flexible substrates, three-dimensional printed circuit boards by injection molding, single-sided or double-sided steel-clad laminates, prepregs for multilayer circuit boards, etc. Can be used. Other uses include semiconductor encapsulation materials, satellite broadcasting antenna base materials, VL
Examples include insulating films for SI, materials for microwave ovens, and heat-resistant adhesives.

Claims (1)

[Scope of Claims] 1) (a) A curable multifunctional polyphenylene ether resin consisting essentially of the following general formula (I), which has an average of allyl groups and/or propargyl groups defined by the following formula: Curable polyfunctional polyphenylene ether resin with a substitution rate of 0.1 mol% or more and 100 mol% or less and average substitution rate = (total number of moles of allyl groups and/or propargyl groups) / (total number of moles of phenyl groups) × 100(%)(b)
A resin composition containing triallyl isocyanurate and/or triallyl cyanurate, in which component (a) is 98 to 40% by weight and component (b) is 98 to 40% by weight based on the sum of (a) and (b). A curable polyfunctional polyphenylene ether resin composition having a content of 2 to 60% by weight. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, m is an integer from 3 to 6, and J' is a general formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (Here, R_1 , R_2, R_3 and R_4 are each independently a hydrogen atom, an allyl group or a propargyl group, and 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 a unit represented by - Represents a residue Q of a hexafunctional phenol compound and/or Q substituted with an allyl group and/or a propargyl group, and the 3 to 6 polyphenylene ether chains bonded to Q' may be the same or different. ] 2) The average substitution rate of allyl groups and/or propargyl groups in the curable polyfunctional polyphenylene ether resin is 0.5.
The curable polyfunctional polyphenylene ether resin composition according to claim 1, which has a content of mol % or more and 50 mol % or less. 3) A cured polyphenylene ether resin composition consisting of a chloroform-nonextractable polyphenylene ether resin and a chloroform-extractable polyphenylene ether resin composition, and the cured polyphenylene ether resin composition was analyzed by pyrolysis gas chromatography to show [1] 2-methylphenol, [2]2,6-dimethylphenol,
[3] 2,4-dimethylphenol, [4] 2,4,6
- trimethylphenol and [5] triallylisocyanurate and/or triallyl cyanurate are produced as thermally decomposable products, and these [1] to [5]
] satisfies the following inequality, 0.05≦{[5]/[1]+[2]+[3]+[4]
}×100≦40 [here [1], [2], [3], [4] and [5]
are the thermal decomposition components [1], [2], [3], [4] respectively.
and represents the peak area of the pyrolysis gas chromatogram resulting from [5]. ] and 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 based on the cured polyphenylene ether resin composition. .01% by weight or more5
% by weight or less, and the chloroform-extractable polyphenylene ether resin composition contains a unit represented by the following general formula (II), triallyl isocyanurate and/or
Or a cured polyphenylene ether resin composition characterized by containing triallyl anurate. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) [Here, R_1, R_2, R_3, and R_4 are each independently a hydrogen atom, an allyl group, or a propargyl group, and at least one of R_1 to R_4 is a group other than hydrogen. can be,
And R_1 to R_4 may be the same or different. ] 4) A curable composite material comprising a curable polyfunctional polyphenylene ether resin composition and a base material, wherein the curable polyfunctional polyphenylene ether resin composition is (a) substantially composed of the following general formula (I). A curable multifunctional polyphenylene ether resin composed of
．． Curable polyfunctional polyphenylene ether resin that is 1 mol% or more and 100 mol% or less and average substitution rate = (total number of moles of allyl group and/or propargyl group) / total number of moles of phenyl group x 100 (%) (b) Contains triallyl isocyanurate and/or triallyl cyanurate, with component (a) being 98 to 40% by weight and component (b) being 2 to 60% by weight based on the sum of (a) and (b). A curable composite material characterized in that by weight %. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, m is an integer from 3 to 6, and J' is a general formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (Here, R_1 , R_2, R_3 and R_4 are each independently a hydrogen atom, an allyl group or a propargyl group, and 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' has 3 to 6 phenolic hydroxyl groups in one molecule, and the ortho and Represents a residue Q of a 3- to 6-functional phenol compound having a polymerization-inactive substituent at the para position and/or a Q substituted with an allyl group and/or a propargyl group, The polyphenylene ether chains may be the same or different. ] 5) The average substitution rate of allyl groups and/or propargyl groups in the curable polyfunctional polyphenylene ether resin is 0.5.
The curable composite material according to claim 4, which has a content of mol % or more and 50 mol % or less. 6) A cured composite material comprising a curable polyfunctional polyphenylene ether resin composition and a base material, the cured polyphenylene ether resin composition comprising a chloroform non-extractable polyphenylene ether resin and a chloroform extractable polyphenylene ether resin composition. and by analysis by pyrolysis gas chromatography, [1] 2-methylphenol, [2] 2,6-dimethylphenol,
[3] 2,4-dimethylphenol, [4] 2,4,6
- trimethylphenol and [5] triallyl isocyanurate and/or triallyl cyanurate are produced as thermal decomposition products, and these [1] to [5]
The peak area ratio of satisfies the following inequality, 0.05≦{[5]/[1]+[2]+[3]+[4]
}×100≦40 [here [1], [2], [3], [4] and [5]
are the thermal decomposition components [1], [2], [3], [4] respectively.
and represents the peak area of the pyrolysis gas chromatogram resulting from [5]. ] And the cured composite material was heated with chloroform at 23°C for 12 hours.
The amount of the chloroform-extractable polyphenylene ether resin composition obtained by the time treatment is 0.01% by weight or more and 5% by weight or less based on the cured polyphenylene ether resin composition, and the chloroform-extractable polyphenylene ether resin composition The object has the following general formula (II)
A cured composite material comprising a unit represented by: and triallyl isocyanurate and/or triallyl cyanurate. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) [Here, R_1, R_2, R_3, and R_4 are each independently a hydrogen atom, an allyl group, or a propargyl group, and at least one of R_1 to R_4 is a group other than hydrogen. can be,
And R_1 to R_4 may be the same or different. ] 7) A laminate comprising a cured composite material in which a cured polyphenylene ether resin composition and a base material are combined and a metal foil, wherein the cured polyphenylene ether resin composition is a chloroform-nonextractable polyphenylene ether resin and a chloroform-extractable polyphenylene ether resin. It consists of a polyphenylene ether resin composition, and analysis by pyrolysis gas chromatography shows that [1] 2-methylphenol, [2] 2,6-
Dimethylphenol, [3] 2,4-dimethylphenol, [4] 2,4,6-trimethylphenol, and [5] triallyl isocyanurate and/or triallyl cyanurate are produced as thermal decomposition products, and The peak area ratio of these [1] to [5] satisfies the following inequality, 0.05≦{[5]/[1]+[2]+[3]+[4]
}×100≦40 [here [1], [2], [3], [4] and [5]
are the thermal decomposition components [1], [2], [3], [4] respectively.
and represents the peak area of the pyrolysis gas chromatogram resulting from [5]. ] and 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% by weight or more and 5% by weight or less based on the cured polyphenylene ether resin composition. A laminate characterized in that the chloroform-extractable polyphenylene ether resin composition contains a unit represented by the following general formula (II) and triallyl isocyanurate and/or triallyl cyanurate. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) [Here, R_1, R_2, R_3, and R_4 are each independently a hydrogen atom, an allyl group, or a propargyl group, and at least one of R_1 to R_4 is a group other than hydrogen. can be,
And R_1 to R_4 may be the same or different. ]