JPH06116349A - Polyphenylene ether resin composition and composite material therefrom - Google Patents

Abstract

PURPOSE:To provide the subject composition excellent in the resin fluidity in its molding and the adhesiveness to metal after cured. CONSTITUTION:The objective composition essentially comprise an unsaturated group-bearing polyphenylene ether, a reactional product from polyphenylene ether and an unsaturated carboxylic acid (or its anhydride), and (C) triallyl (iso)cyanurate, with its composition within a specified range.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a curable polyphenylene ether resin composition and a cured product obtained by curing the same. Furthermore, the present invention relates to a curable composite material composed of the resin composition and a substrate, a cured product thereof, and a laminate composed of the cured product and a metal foil. Since the resin composition of the present invention has excellent chemical resistance, dielectric properties, heat resistance, flame retardancy, and adhesiveness with metals after curing, it can be used in the electronic industry, space,
It can be used as a dielectric material, an insulating material, and a heat-resistant material in the fields such as the aircraft industry.

[0002]

2. Description of the Related Art 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. Heat resistance, dimensional stability, electrical properties, flame retardancy, and moldability 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 used. Although these have various performances in good balance,
It has the drawback of poor electrical properties, especially dielectric properties in the high frequency range. 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 excellent in mechanical properties 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, the polyphenylene ether is deformed when exposed to a high temperature of 200 ° C. or higher, causing a significant decrease in mechanical strength and peeling of the copper foil formed on the resin surface for a circuit. 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 method for improving the heat resistance and chemical resistance of polyphenylene ether, there has been proposed a method of introducing a crosslinkable functional group into the chain of polyphenylene ether and further curing it to use it as a cured polyphenylene ether. . As a specific example, a polymer of 2-allyl-6-methylphenol or 2,6-diallylphenol is a Journal of Polymer Science.
Ce magazine, Vol. 49, p. 267 (1961). U.S. Pat. Nos. 3,281,393 and 34220
No. 62 discloses a copolymer of 2,6-dimethylphenol and 2-allyl-6-methylphenol or 2,6-diallylphenol. US Patent No. 4
No. 634,742 discloses vinyl group-substituted polyphenylene ethers.

Further, the present inventor has 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, and obtained. It has been found that the cured product obtained is insoluble in aromatic hydrocarbon solvents and halogen-substituted hydrocarbon solvents and has excellent dielectric properties (Japanese Patent Laid-Open No. 1-69628 and 1-96).
69629, 1-113425, 1-1134
No. 26). However, any of the curable polyphenylene ethers described above had a high melt viscosity in terms of a material for a laminated plate, and thus the flowability during molding was sometimes insufficient.

The present inventors have also proposed to add triallyl isocyanurate and / or triallyl cyanurate for the purpose of improving the resin flowability (Japanese Patent Laid-Open No. 2-208355). However, since the industrially available polyphenylene ether resin is a relatively high molecular weight polymer, the resin flowability may be insufficient even if triallyl isocyanurate and / or triallyl cyanurate is added. Alternatively, when a relatively large amount of triallyl isocyanurate and / or triallyl cyanurate is added, the cured product may become brittle or the adhesive to the copper foil may become low.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and it does not impair the excellent dielectric properties and mechanical properties of curable polyphenylene ether, and has excellent resistance after curing. It is intended to provide a novel curable polyphenylene ether resin composition which has chemical resistance, heat resistance, and adhesiveness to a metal and exhibits a good resin flow during molding.

The melt flowability of the thermosetting resin of the prepreg used in the production of a printed wiring board, particularly a multilayer printed wiring board, causes the conductor circuit surface having the unevenness of the wiring to adhere to the other conductor circuit surface or the metal foil. In this case, it affects whether or not the resin is sufficiently filled in the unevenness of the wiring, and is important from the viewpoint of product reliability. However, polyphenylene ether resin is an important resin in the low dielectric constant thermosetting resin that is being developed, because it has the characteristics of low dielectric constant and low cost, but the melt flowability of the resin is not sufficient, and printed wiring board manufacturing In some cases, it was not possible to ensure the reliability of the product as a resin for automobiles.

The present invention provides a low dielectric constant thermosetting resin composition using a polyphenylene ether resin and having an improved melt flowability. The above part was described by taking the production of a multilayer printed wiring board as an example. However, since the resin composition of the present invention has good resin flowability, this resin composition is also suitably used for the production of other molded articles. obtain.

[0010]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to solve the above-mentioned problems, and as a result, have found a novel resin composition in accordance with the object of the present invention and completed the present invention. Arrived The present invention comprises the following five inventions.

That is, the first aspect of the present invention is that (a) a polyphenylene ether resin containing an unsaturated group, (b) a reaction product of a polyphenylene ether and an unsaturated carboxylic acid or an acid anhydride, and (c) triallyl isocyanate. A composition containing nurate and / or triallyl cyanurate as an essential component, wherein the weight ratio of component (a) to component (b) is 9
9/1 to 1/99, and the weight ratio of the sum of the weights of the component (a) and the component (b) and the weight ratio of the component (c) is 98/2 to 2/98, a curable polyphenylene ether. A resin composition is provided.

A second aspect of the present invention provides a cured polyphenylene ether resin composition obtained by curing the resin composition of the first aspect. A third aspect of the present invention is (a) a polyphenylene ether resin containing an unsaturated group, (b) a reaction product of a polyphenylene ether and an unsaturated carboxylic acid or an acid anhydride, and (c) a triallyl isocyanurate and / or A composition containing triallyl cyanurate as an essential component, wherein the weight ratio of the component (a) and the component (b) is 99.
/ 1 to 1/99, and the weight ratio of the sum of the weights of the component (a) and the component (b) and the weight ratio of the component (c) is 98/2 to 2/98, which is a curable polyphenylene ether resin. A composite material comprising a composition and a substrate is provided.

A fourth aspect of the present invention provides a cured composite material obtained by curing the curable composite material of the third aspect. A fifth aspect of the present invention provides a laminate comprising the cured composite material of the fourth aspect and a metal foil.

First, the first and second curable resin compositions of the present invention and their cured products will be described. The unsaturated group-containing polyphenylene ether resin used as the component (a) of the curable polyphenylene ether-based resin composition means a carbon-carbon double bond and / or a carbon-carbon triple bond as a side chain with respect to the polyphenylene ethers. It refers to the one in which a functional group containing is introduced. An example thereof is a resin comprising a reaction product of a polyphenylene ether resin represented by the following general formula (I) and an alkenyl halide of the general formula (III) and / or an alkynyl halide of the general formula (IV),

[0015]

[Chemical 1] [Wherein, m is an integer of 1 to 6, and J is a polyphenylene ether chain that is substantially composed of a unit represented by the following formula (II).

[0016]

[Chemical 2] Q represents a hydrogen atom when m is 1, and when m is 2 or more, it has 2 to 6 phenolic hydroxyl groups in one molecule and has a polymerization-inert substituent at the ortho and para positions of the phenol hydroxyl group. It represents the residue of the polyfunctional phenol compound having. ]

[0017]

[Chemical 3] [In the formula, L and k are each independently an integer of 1 to 4, and X and
Y is each independently chlorine, bromine or iodine, and R ₁ to
R ₄ is independently hydrogen, methyl group or ethyl group. ] X and / or Y, the following alkenyl group and /
Another example is a resin in which an alkynyl group is covalently bonded to a polyphenylene ether resin.

[0018]

[Chemical 4]

Explaining the polyphenylene ether resin of the general formula (I), typical examples of Q include compounds represented by the following four general formulas.

[0020]

[Chemical 5] [Wherein A ₁ and A ₂ represent the same or different linear alkyl groups having 1 to 4 carbon atoms, X ₁ represents an aliphatic hydrocarbon residue and a substituted derivative thereof, an aralkyl group and a substituted derivative thereof, Represents an oxygen, sulfur, sulfonyl group, carbonyl group, Y ₁ represents an aliphatic carbon-hydrogen residue and a substituted derivative thereof, an aromatic carbon-hydrogen residue and a substituted derivative thereof, an aralkyl group and a substituted derivative thereof, Z 1
₁ represents oxygen, sulfur, sulfonyl group or carbonyl group, and A
_Two phenyl groups directly bonded to 2, A ₂ and X ₁ , A ₂
And Y ₁ and A ₂ and Z ₁ are all at the ortho position of the phenolic hydroxyl group and para, r is 0 to 4 and S is 2
Represents an integer of 6; ] As a specific example,

[0021]

[Chemical 6]

[0022]

[Chemical 7] Etc. In the polyphenylene ether chain represented by J in the general formula (I), one or two or more of the units or terminal groups described below are contained unless the heat resistance and heat stability of the polyphenylene ether resin are reduced. May be included. i) a unit represented by the following general formula other than (II),

[0023]

[Chemical 8] [In the formula, R _{5 to} R ₈ each independently represent hydrogen, an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group. Ii) a unit represented by the following general formula,

[0024]

[Chemical 9] [Wherein R _{9 to} R ₁₅ each independently represent hydrogen, an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group, and R 9
₁₄ and R ₁₅ are not hydrogen at the same time. Iii) an end group represented by the following general formula,

[0025]

[Chemical 10] [In the formula, R _{16 to} R ₂₀ each independently represent hydrogen, an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group, and R _{16
21 to} R ₂₃ each independently represent hydrogen, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group or a substituted aryl group, and Ar represents an aryl group or a substituted aryl group. Iv) The above formula (II) and general formulas (V) to (VII)
A unit or terminal group obtained by graft-polymerizing a polymerizable monomer having an unsaturated bond such as styrene or methyl methacrylate with respect to the unit or terminal group. As an example of the unit of the general formula (V),

[0026]

[Chemical 11] [Here, Ph represents a phenyl group. ] Etc. are mentioned.
Examples of the unit of general formula (VI) include:

[0027]

[Chemical 12] Etc. Examples of the terminal group of the general formula (VII) include:

[0028]

[Chemical 13] Etc.

Specific examples of the alkenyl halide of the general formula (III) are shown below: allyl chloride, allyl bromide, allyl iodide, 4-bromo-1-butene, trans- and / or cis-1-bromo. -2
-Butene, trans- and / or cis-1-chloro-2-butene, 1-chloro-2-methyl-2-propene, 5-bromo-1-pentene, 4-bromo-2-methyl-2-butene, 6-bromo-1-hexene, 5-bromo-2-methyl-2-pentene and the like.

Specific examples of the alkynyl halide of the general formula (IV) include propargyl chloride, propargyl bromide, propargyl iodide, 4-bromo-1-butyne, 4-bromo-2-butyne, 5-bromo-1. -Pentyne, 5-bromo-2-pentyne, 1-iodo-2-pentyne, 1-iodo-3-hexyne, 6-bromo-1-hexane and the like. These alkenyl halides and alkynyl halides can be used alone or in combination of two or more.

The unsaturated group-introduced polyphenylene ether resin used in the component (a) of the present invention is, for example, JP-A-1-69628, 1-69629 and 1-1.
No. 13425, No. 1-113426, No. 2-2322
No. 60, No. 2-233759, the polyphenylene ether resin of the general formula (I) is metallized with an organic metal, followed by alkenyl halide (II).
It can be produced by a substitution reaction with I) and / or an alkenyl halide (IV). The polyphenylene ether resin produced according to the present method is composed of at least units represented by the following two or three structural formulas.

[0032]

[Chemical 14] [In the formula, R represents the alkenyl group (III ′) and / or alkynyl group (IV ′). Furthermore, in addition to the above, the following units may be included.

[0033]

[Chemical 15] [In the formula, M represents halogen. ]

The content of halogen derived from the above general formula (VIII) is in the range of 0 to 30% by weight, preferably the range of 0 to 20% by weight, based on the polyphenylene ether resin. The unsaturated group-introduced polyphenylene ether resin used in the present invention does not necessarily need to contain halogen. However, when the halogen is chlorine or bromine, there is an effect that flame retardancy can be imparted to the curable polyphenylene ether resin composition of the present invention. A preferable halogen content for imparting flame retardancy is 1% by weight or more. However, if it exceeds 30% by weight, the thermal stability of the polyphenylene ether resin itself is deteriorated, which is not preferable.

Preferred examples of the unsaturated group-introduced polyphenylene ether resin obtained by the above method include:
The resin which consists of the reaction product of polyphenylene ether-type resin and allyl bromide, allyl chloride, propargyl bromide, and propargyl chloride described below can be mentioned.

As the polyphenylene ether resin,
Poly (2,6-dimethyl-1,4-phenylene ether) obtained by homopolymerization of 2,6-dimethylphenol,
Polystyrene graft copolymer of poly (2,6-dimethyl-1,4-phenylene ether), copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, 2,6-dimethylphenol and 2 , 6-Dimethyl-3-phenylphenol copolymer, 2,6-dimethylphenol polyfunctional phenol compound

[0037]

[Chemical 16] A polyfunctional polyphenylene ether resin obtained by polymerization in the presence of a unit of the general formulas (V) and (VI) as disclosed in JP-A-63-301222 and JP-A-1-29748. And a resin containing a unit of the general formula (V) and an end group of the general formula (VII) as disclosed in Japanese Patent Application No. 1-135763.

Other examples of the polyphenylene ether resin containing an unsaturated group used in the curable polyphenylene ether resin composition of the present invention include resins containing the following repeating units.

[0039]

[Chemical 17] [In the formula, R ₂₄ and R ₂₅ each independently represent hydrogen, an alkyl group, or a phenyl group. ]

A specific example is US Pat. No. 3,422.
Copolymers of 2-allyl-6-methylphenol with 2,6-dimethylphenol as disclosed in 062, 2,6-Diallyl-4- as disclosed in U.S. Pat. No. 3,281,393. Bromophenol and 2,6-
Copolymer of dimethyl-4-bromophenol, Japanese Patent Publication No. 6
A copolymer of 2,6-diprenylphenol and 2,6-dimethylphenol as disclosed in 3-47733, also of 2,6-bis (2-butenyl) phenol and 2,6-dimethylphenol. Copolymer, also 2,
A copolymer of 6-dicinnamylphenol and 2,6-dimethylphenol, a homopolymer of 2-prenyl-6-methylphenol as disclosed in JP-A-58-27719, and also 2-prenyl-6. -A copolymer of methylphenol and 2,6-dimethylphenol, also 2-
A homopolymer of (2-butenyl) -6-methylphenol, a copolymer of 2- (2-butenyl) -6-methylphenol and 2,6-dimethylphenol, and a homopolymer of 2
-Cinnamyl-6-methylphenol homopolymer, also 2-cinnamyl-6-methylphenol and 2,6-
Examples thereof include a dimethylphenol copolymer.

A resin obtained by converting the methyl group at the 2,6-position of poly (2,6-dimethyl-1,4-phenylene ether) disclosed in US Pat. No. 4,634,742 into a vinyl group, also poly ( A resin obtained by introducing a vinyl group into the 3,5-position of the phenyl group of (2,6-dimethyl-1,4-phenylene ether) is also a preferable example of the polyphenylene ether resin containing an unsaturated group used in the present invention. Is one.

The range of the unsaturated group content of the polyphenylene ether resin containing an unsaturated group used in the present invention is 0.1 mol% or more and 100 mol% or less, more preferably 0. It is preferably 5 mol% or more and 50% or less.

[0043]

[Equation 1]

If the unsaturated group content is less than 0.1 mol%, the chemical resistance after curing is insufficiently improved, which is not preferable. On the contrary, if it exceeds 100 mol%, it becomes very brittle after curing, which is not preferable. Regarding the molecular weight of the unsaturated group-introduced polyphenylene ether resin used in the present invention, the viscosity number η _sp / c measured with a chloroform solution at 30 ° C. and 0.5 g / dl is 0.35 to 0.
Those in the range of 80 can be used favorably. When the viscosity number is 0.35 or less, the resin becomes mechanically brittle, which is not preferable. On the other hand, when it is 0.80 or more, the resin flowability at the time of molding the composition is lowered, and the effect of the present invention cannot be obtained.

The reaction product of the polyphenylene ether used as the component (b) of the curable resin composition of the present invention with the unsaturated carboxylic acid or acid anhydride is obtained by converting the polyphenylene ether resin of the general formula 1 into the unsaturated carboxylic acid or It is produced by reacting with an acid anhydride. Examples of suitable acids and acid anhydrides include acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, glutaconic anhydride, citraconic anhydride and the like. Maleic anhydride is particularly preferred in terms of availability and handling.

The reaction is carried out by heating the polyphenylene ether resin and the unsaturated carboxylic acid or acid anhydride in the temperature range of 100 ° C to 390 ° C. At this time, a radical initiator may coexist. Both the solution method and the melt-mixing method can be used, but the melt-mixing method using an extruder or the like is simpler and more suitable for the purpose of the present invention.
The ratio of the unsaturated carboxylic acid or the acid anhydride is 0.01 to 5. With respect to 100 parts by weight of the polyphenylene ether resin.
It is 0 parts by weight, preferably 0.1 to 3.0 parts by weight.

The molecular weight of the obtained reaction product was lowered during this reaction, and was 0.2 in terms of viscosity number measured under the same conditions as above.
The range is from ~ 0.75. The triallyl isocyanurate and / or triallyl cyanurate used as the component (c) of the curable resin composition of the present invention is a trifunctional monomer represented by the following structural formula.

[0048]

[Chemical 18]

In carrying out the present invention, triallyl isocyanurate and triallyl cyanurate may be used alone, or both may be mixed and used at an arbitrary ratio. In the present invention,
Triallyl isocyanurate and triallyl cyanurate act as a plasticizer and a crosslinking agent. That is, it improves the flow of resin during pressing and the crosslink density.

The compounding ratio of the resin composition of the present invention can be varied over a wide range. The weight ratio of the component (a) and the component (b) is 99/1 to 1/99.
Within the range, the effect of the present invention is obtained. If this weight ratio is larger than 99/1 (that is, the amount of the component (b) added is small), the effect of improving the resin flowability at the time of molding the composition becomes small and the effect of addition is insufficient. If the weight ratio is less than 1/99 (that is, the amount of the component (b) added is large), the chemical resistance and dielectric properties of the cured product will be lower than those expected by the present invention. A more preferable weight ratio range is 90/10 to 10/90.

When selecting the combination of the components (a) and (b), the molecular weight of each can be selected without considering the molecular weight of the other component, but the viscosity number of the component (b) is (a). It is preferable that the viscosity number is smaller than the viscosity number of the components from the viewpoint of the effect of improving the resin flowability. The effect of the present invention is obtained when the ratio of the sum of the weights of the components (a) and (b) and the weight of the component (c) is 98/2 to 2/98. If this weight ratio exceeds 98/2 (that is, the addition amount of the component (c) is small), the chemical resistance of the cured product is insufficient. On the other hand, if it is less than 2/98 (that is, the amount of the component (c) added is large), the dielectric properties and mechanical properties of the cured product deteriorate, which is not preferable. A more preferable weight ratio range is 90/10 to 10/90.

As a method for mixing the three components (a) to (c) described above, a solution mixing method in which the three components are uniformly dissolved or dispersed in a solvent, or melting by heating with an extruder or the like. A blending method or the like can be used. As the solvent used for the solution mixing, halogen-based solvents such as dichloromethane, chloroform and trichloroethylene; aromatic-based solvents such as benzene, toluene and xylene; and tetrahydrofuran are used alone or in combination of two or more.

As will be described later, the resin composition of the present invention undergoes a crosslinking reaction by means of heating or the like to be cured, but it contains a radical initiator for the purpose of lowering the curing temperature or promoting the crosslinking reaction. You may use it. A usual peroxide can be used as the radical initiator. As the radical initiator, only one kind may be used alone, or two or more kinds may be used in combination.

The resin composition of the present invention may be used by blending an amount of a filler or an additive within 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,
Carbon black, silica, alumina, talc, mica,
Examples thereof include glass beads and glass hollow spheres.
As additives, antioxidants, heat stabilizers, antistatic agents,
Examples include plasticizers, pigments, dyes, colorants and the like. The chlorine in order to further improve the flame retardancy, bromine, and flame retardant _{phosphorus-based, Sb 2 O 3, Sb 2} O 5, NbSbO 3 · 1
A flame retardant aid such as / 4H ₂ O can also be used in combination. Furthermore, it is also possible to mix one or more kinds of other thermoplastic resins or thermosetting resins.

The second cured polyphenylene ether resin composition of the present invention is obtained by curing the curable polyphenylene ether resin cured product described above. The curing method is arbitrary, and a method using heat, light, an electron beam or the like can be adopted. When curing is performed by heating, the temperature is selected in the range of 80 to 300 ° C., and more preferably 150 to 250 ° C., although it varies depending on the presence or absence of the radical initiator and the curing agent and the type thereof. Also time is
It is about 1 minute to 10 hours, more preferably 1 minute to 5 hours.

The resin composition of the obtained cured polyphenylene ether resin composition can be analyzed by methods such as infrared absorption spectroscopy, high resolution solid state nuclear magnetic resonance spectroscopy and pyrolysis gas chromatography. Also, this curable polyphenylene ether resin composition can be used by laminating it with a metal foil and / or a metal plate, as in the case of the cured composite material described below as the fourth invention.

Next, the third and fourth curable composite materials of the present invention and their cured products will be described. The curable composite material of the present invention comprises the curable polyphenylene ether resin composition described above 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, asbestos cloth, metal fiber cloth and other synthetic or natural inorganic fiber cloth; polyvinyl alcohol fiber, polyester fiber, Woven or non-woven fabric obtained from synthetic resin such as acrylic fiber, wholly aromatic polyamide fiber, polytetrafluoroethylene fiber; natural fiber cloth such as cotton cloth, linen cloth, felt; carbon fiber cloth; kraft paper, cotton paper, paper-glass Natural cellulosic cloths such as mixed fibers may be used alone or in combination of two or more.

The proportion of the base material in the curable composite material of the present invention is 5 to 90 parts by weight, more preferably 10 to 80 parts by weight, further preferably 20 to 70 parts by weight, based on 100 parts by weight of the curable composite material. Is. If the amount of the base material is less than 5 parts 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 parts by weight, the dielectric properties and flame retardancy of the composite material will be poor, such being undesirable.

In the composite material of the present invention, a coupling agent can be used if necessary for the purpose of improving the adhesiveness at the interface between the resin and the substrate. As the coupling agent, silane coupling agents, titanate coupling agents, aluminum-based coupling agents, zircoaluminate coupling agents and the like can be used.

As the method for producing the composite material of the present invention, for example, (a) to (c) described in the first section of the present invention.
Examples include a method of uniformly dissolving or dispersing the components and, if necessary, other components in the above-mentioned halogen-based, aromatic-based, ketone-based solvent or a mixed solvent thereof, impregnating the base material, and then drying. .

Impregnation is carried out by dipping, coating or the like. 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.

The fourth curable composite material of the present invention is obtained by curing the curable composite material thus obtained by a method such as heating. The manufacturing method is not particularly limited, and for example, a plurality of the curable composite materials are stacked, and each layer is adhered under heat and pressure, and at the same time heat cured to obtain a cured composite material having a desired thickness. You can 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 and the curable composite material. 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, an uncured or semi-cured composite material obtained by laminating in advance can be cured by heat treatment or another method.

Molding and curing are carried out at a temperature of 80 to 300 ° C.
It can be carried out at a pressure of 0.1 to 1000 Kg / cm ² , a time of 1 minute to 10 hours, more preferably a temperature of 150 to 250 ° C., a pressure of 1 to 500 Kg / cm ² , and a time of 1 minute to 5 hours. .

Finally, the fifth embodiment of the present invention will be described. The laminate of the present invention is composed of the cured composite material and the metal foil described above as the fourth of the present invention. Examples of the metal foil used here include copper foil,
Aluminum foil etc. are mentioned. The thickness is not particularly limited, but 5-200 μm, more preferably 5-105.
It is in the range of μm.

The method for producing the laminate, the laminate and the metal-clad laminate of the present invention is, for example, the curable composite material described above as the third embodiment of the present invention and the metal foil and / or the metal plate. There may be mentioned a method in which the layers are laminated according to the above, and each layer is adhered under heat and pressure and at the same time heat-cured. In the laminate, the curable composite material and the metal foil are laminated in any layer structure. The metal foil can be used as both the surface layer and the intermediate layer. It is also possible to repeat lamination and curing a plurality of times to form a multilayer.

An adhesive may be used to bond the metal foil. Examples of the adhesive include epoxy type, acrylic type, phenol type and cyanoacrylate type, but are not particularly limited thereto. The lamination molding and curing described above can be performed under the same conditions as in the fourth aspect of the present invention.

[0067]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited thereto. In the examples below, the following components were used. -Initiator: 2,5-dimethyl-2,5-di (t-butylperoxin) hexyne-3 (NOF Perhexin 25B; abbreviated as PH25B) -Glass cloth: E-glass, basis weight 48 g / m ² or 105 g / M ² · Flame retardant: Decabromodiphenyl ether (Asahi Glass
AFR-1021) ・ Flame retardant: Sb ₂ O ₃ (Nippon Seiko PATOX-M)

[0068]

[Reference Example 1] Polyphenylene ether resin containing an unsaturated group Average substitution ratio 14%, ηsp / C = 0.62 (30 ° C.,
An allyl group-substituted polyphenylene ether (abbreviated as A-PPE) (0.5 g / dl, chloroform solution) was used.
According to known methods disclosed in US Pat.
It was synthesized from poly (2,6-dimethyl-1,4-phenylene ether) with /C=0.56.

[0069]

[Reference Example 2] Polyphenylene ether resin containing unsaturated group Average substitution rate 5%, ηsp / C = 0.40 (30 ° C, 0.
Propargyl group-substituted polyphenylene ether (abbreviated as P-PPE) (5 g / dl, chloroform solution) was prepared according to the known method disclosed in JP-A-1-69629.
Poly (2,6-dimethyl-1,4-p / C = 0.38)
Phenylene ether).

[0070]

[Reference Example 3] Reaction product of polyphenylene ether and unsaturated carboxylic acid or acid anhydride Poly (2, which has a number of years ηsp / C of 0.54 measured with a chloroform solution of 30 g at 0.5 g / dl) 6-dimethyl-1,4-phenylene ether) 100 parts by weight, maleic anhydride 1.5 parts by weight, and 2,5-dimethyl-
After dry-blending 1.0 part by weight of 2,5-di (t-butylperoxy) hexane (Perhexa 25B manufactured by NOF CORPORATION) at room temperature, biaxially at a cylinder temperature of 300 ° C. and a screw rotation speed of 230 rpm. A reaction product was obtained by extrusion with an extruder. Ηsp of this reaction product
/ C was 0.48. This reaction product is referred to below as MP
Abbreviated as PE.

[0071]

Examples 1 to 6 Curable polyphenylene ether resin composition and cured polyphenylene ether resin composition A-PPE or P-PPE, M-PPE, triallyl isocyanurate, curing agent, and initiator are shown in Table 1. The composition is mixed using a Henschel mixer, and is molded and cured by a press molding machine at 200 ° C. for 30 minutes,
A cured product having a thickness of about 1 mm was produced. The resin flowability during molding was good, and the cured product was uniform. This cured product did not show any change in appearance even after boiling in trichlorethylene for 5 minutes.

[0072]

Comparative Example 1 The same operation as in Example 1 was repeated without using triallyl isocyanurate and the initiator. When the obtained cured product was boiled in trichlorethylene for 5 minutes, expansion and warpage were observed.

[0073]

[Comparative Example 2] 70 parts of P-PPE, 30 parts of triallyl cyanurate and 6 parts of PH25B were mixed in a Henschel mixer, and molded and cured by a press molding machine at 200 ° C for 30 minutes to give a cured product having a thickness of about 1 mm. It was made. The cured product was slightly uneven in thickness and non-uniform.

[0074]

Comparative Example 3 40 parts of A-PPE, 60 parts of triallyl isocyanurate and 6 parts of PH25B were mixed in a Henschel mixer and molded and cured by a press molding machine at 200 ° C. for 30 minutes to give a cured product having a thickness of about 1 mm. It was made. The resin flowability during molding was good and the cured product was uniform. However, the obtained cured product was brittle.

[0075]

[Table 1]

[0076]

Examples 7 to 12 Curable composite material and laminate A-PPE or P-PPE, M-PPE, triallyl isocyanurate, curing agent, initiator, flame retardant and flame retardant auxiliary are shown in Table 2. Different compositions were dissolved or dispersed in trichlorethylene. A glass cloth was immersed in this solution for impregnation and dried in an air oven. A plurality of the above-mentioned curable composite materials were superposed so that the thickness after molding would be about 0.8 mm, and copper foil having a thickness of 35 μm was placed on both surfaces thereof and molded and cured by a press molding machine to obtain a laminate. . The curing conditions of each example are shown in Table 3. The pressure was 20 Kg / cm ^{2 in} all cases. In all of the examples, the resin flow during pressing was good. The physical properties of the laminate thus obtained were measured by the following methods, and good results as shown in Table 3 were obtained.

1. Trichloroethylene resistance The laminate from which the copper foil was removed was cut into 25 mm square pieces, boiled in trichlorethylene for 5 minutes, and the change in appearance was visually observed. 2. The dielectric constant and the dielectric loss tangent were measured at 1 MHz.

3. Solder heat resistance The laminated body from which the copper foil has been removed is cut into 25 mm squares, and 280
Floating in a solder bath at ℃ for 120 seconds, the change in appearance was visually observed. 4. Copper foil peeling strength A test piece having a width of 20 mm and a length of 100 mm was cut out from the laminate, and a parallel cut having a width of 10 mm was made on the copper foil surface, and then a speed of 50 mm / min in a direction perpendicular to the surface. Then, the copper foil was continuously peeled off, and the stress at that time was measured by a tensile tester, and the minimum value of the stress was shown.

5. Thermal expansion characteristics The laminate from which the copper foil was removed was cut into a 7 mm square, and the thermal expansion amount in the thickness direction was measured by a thermomechanical analyzer at a rate of temperature increase of 20 ° C / min. 6. Resin flow Curable composite materials are stacked on top of each other at 170 ° C. for 10 minutes at a surface pressure of 20 kg / cm ² by a press molding machine, and the resin that has squeezed out is weighed and the weight of the curable composite material before pressing is measured. The divided value is shown.

[0080]

[Comparative Example 4] A curable composite material was prepared in the same manner as in Example 7, except that the maleated polyphenylene ether was not used. When the resin flow of this curable composite material was measured, the resin flowability and the copper foil peeling strength were lower than those of Example 7.

[0081]

[Comparative Example 5] A curable composite material was produced in the same manner as in Example 8, except that the maleated polyphenylene ether was not used. When the resin flow of this curable composite material was measured, the resin flowability and the copper foil peeling strength were lower than those of Example 8.

[0082]

[Table 2]

[0083]

[Table 3]

[0084]

INDUSTRIAL APPLICABILITY The composition and composite material of the polyphenylene ether resin of the present invention exhibit good resin flowability during thermosetting molding, and are suitable for production of molded articles having complicated shapes.
A cured product, a laminate, or a metal-clad laminate obtained by using the composition of the polyphenylene ether resin of the present invention is a material having good chemical resistance, excellent thermal expansion characteristics, and excellent dielectric characteristics. That is, it has sufficient resistance to boiling trichlorethylene, has low thermal expansion characteristics, and exhibits a dielectric constant of approximately 3.5 or less. The laminate, laminate, and metal-clad laminate of the present invention have other well-balanced good properties in various physical properties such as heat resistance, flame retardancy, adhesiveness with metal, dimensional stability, and heat radiation. Indicates. Therefore, the material of the present invention can be used as a dielectric material, an insulating material, a heat-resistant material, etc. in the fields of electric industry, electronic industry, space / aircraft industry and the like. Particularly, it is suitably used as a single-sided, double-sided, multi-layer printed circuit board, semi-rigid substrate, metal base substrate, and prepreg for multi-layer printed circuit board.

Claims (5)

[Claims] 1. A polyphenylene ether resin containing (a) an unsaturated group, (b) a reaction product of a polyphenylene ether and an unsaturated carboxylic acid or an acid anhydride, and (c).
A composition containing triallyl isocyanurate and / or triallyl cyanurate as an essential component, which comprises (a)
The weight ratio of the component to the component (b) is 99/1 to 1/99, and the ratio of the sum of the weights of the component (a) and the component (b) and the weight of the component (c) is 98/2 to 2/98. And a curable polyphenylene ether resin composition. 2. A cured polyphenylene ether resin composition obtained by curing the resin composition according to claim 1. 3. A polyphenylene ether resin containing an unsaturated group, (b) a reaction product of a polyphenylene ether and an unsaturated carboxylic acid or an acid anhydride, and (c).
A composition containing triallyl isocyanurate and / or triallyl cyanurate as an essential component, which comprises (a)
The weight ratio of the component to the component (b) is 99/1 to 1/99, and the ratio of the sum of the weights of the component (a) and the component (b) and the weight of the component (c) is 98/2 to 2/98. And a curable polyphenylene ether resin composition, and a curable composite material comprising a substrate. 4. A cured composite material obtained by curing the curable composite material according to claim 3. 5. A laminate comprising the cured composite material according to claim 4 and a metal foil.