JPH04239018A - New curable polyphenylene ether/epoxy resin composition, and composite material and laminate prepared therefrom - Google Patents

Abstract

PURPOSE:To provide a new curable polyphenylene ether/epoxy resin composition which has the excellent dielectric properties of polyphenylene ether and the well-balanced properties and economical profitability of epoxy resin and can develop excellent heat resistance and flame retardancy when cured. CONSTITUTION:A reaction product (a) of a polyphenylene ether resin with an unsaturated carboxylic acid or anhydride is mixed with triallyl isocyanurate and/or triallyl cyanurate (b) and a resin composition (c) essentially consisting of brominated bisphenol polyglycidyl ether epoxy resin, a novolac epoxy resin and a phenolic resin and optionally an initiator and a cure accelerator. The obtained mixture is formed into a film or infiltrated into a base to obtain a composite material. The film or composite material is optionally laminated with a metallic foil or sheet, and then heated and cured. The mixing ratio between components (a) and (b) is such that 98-40 pts.wt. component (a) is used per 2-60 pts.wt component (b) and component (c) is used in an amount of 10-90 pts.wt. per 90-10 pts.wt. total of components (a) and (b).

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention relates to a curable polyphenylene ether epoxy resin composition using a reaction product of a polyphenylene ether resin and an unsaturated carboxylic acid or an acid anhydride, and a hardened polyphenylene ether epoxy resin composition obtained by curing the same. Regarding the body. Furthermore, the present invention relates to a composite material made of the resin composition and a base material, a cured product thereof, a laminate made of the cured product and metal foil, and a laminate made of the cured product and a metal plate.

The resin composition of the present invention exhibits excellent chemical resistance, dielectric properties, heat resistance, and flame retardancy after curing, and is used as a dielectric material and insulation material in fields such as the electrical industry, electronic industry, and space/aircraft industry. It can be used for materials, heat-resistant materials, structural materials, etc. In particular, it can be used as single-sided, double-sided, multilayer printed circuit boards, flexible printed circuit boards, semi-rigid boards, and boards with excellent heat dissipation properties.

0003

[Prior Art] In recent years, there has been a remarkable trend toward smaller packaging methods and higher density mounting methods in the field of electronic equipment for communications, consumer use, industrial use, etc. Heat resistance, 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 traditionally been used. Although these have a good balance of various performances, they have the disadvantage of poor electrical properties, particularly poor dielectric properties in the high frequency range. Polyphenylene ether has recently attracted attention as a new material that can solve this problem, and attempts are being made to apply it to copper-clad laminates.

[0004] Japanese Patent Publication No. 64-3223 discloses combinations of polyphenylene ether and various epoxy resins. Commonly used epoxy resins include polyglycidyl ethers of bisphenol A, 3,3',5,5'-tetrabromobisphenol A, and epoxyphenol novolac resins, and various resins including amines are used. Curing is performed using known curing agents. However, the polyphenylene ether used here has not undergone any chemical modification and exhibits no chemical resistance, so the cured product is significantly inferior to the boiling trichlorethylene properties required for printed circuit board materials. .

As a material with improved chemical resistance, US Pat. No. 4,912,172 discloses a resin composition comprising (i) polyphenylene ether, (ii) bisphenol polyglycidyl ether, and (iii) aluminum or zinc salt. ing. Further, as materials imparted with flame retardancy, JP-A Nos. 2-55721, 2-55722, and 2-222412 disclose (i) polyphenylene ether, (ii) bromine-containing epoxy resin compositions, (iii) novolak resin, (iv) imidazole and polyamines, (v) zinc salt, (vi) Sb2
A resin composition comprising O5 is disclosed.

JP-A-2-269732 discloses (i) as a composition for improving the flowability of resin during molding.
) a low molecular weight polyphenylene ether, (ii) an epoxy resin composition containing bromine, (iii) an imidazole and polyamines, and (iv) a resin composition comprising an aluminum or zinc salt.

[0007] Furthermore, as a material obtained by treating polyphenylene ether itself, JP-A-2-135216 discloses (i) a reaction product of polyphenylene ether and an unsaturated carboxylic acid or an acid anhydride, (ii) polyepoxy JP-A-2-166115 discloses a resin composition consisting of a compound, (iii) an epoxy curing catalyst, (i) a melt-processed polyphenylene ether, (ii) a polyepoxy compound, and (iii) an epoxy curing catalyst. A resin composition consisting of the following is disclosed.

However, it has been found that even in the above series of resin compositions, the improvement in trichlorethylene resistance after curing is still insufficient, and significant changes in appearance such as roughness are observed after boiling trichlorethylene. Furthermore, as shown in Example 6 in JP-A-2-55721, the dielectric constant is 4.19 even though polyphenylene ether is used at about 1/2 of the total resin composition.
and sufficient improvements have not been made. This is commercially available glass/
Dielectric constant of epoxy resin copper-clad laminate: 4.5 (resin amount approx. 4
0%).

[0009] European Patent No. 315,829 discloses a resin composition comprising polyphenylene ether, bisphenol A type epoxy resin, and an amine curing agent. However, there is no explanation in the specification regarding the chemical resistance of this cured product, and since the required properties have recently become more and more severe,
Similar to No. 3223, further improvement in chemical resistance is awaited.

0010

[Problems to be Solved by the Invention] The present invention has been made in view of the above circumstances, and combines the excellent dielectric properties of polyphenylene ether with the well-balanced performance and economic efficiency of epoxy resin. The present invention also aims to provide a novel curable polyphenylene ether epoxy resin composition that exhibits excellent chemical resistance, heat resistance, and flame retardancy after curing.

[0011]

[Means for Solving the Problems] As a result of extensive studies in order to solve the above-mentioned problems, the present inventors have discovered a novel resin composition that meets the purpose of the present invention, and have completed the present invention. It has arrived. The present invention uses a polyphenylene ether resin modified with an unsaturated carboxylic acid or an acid anhydride, triallyl isocyanurate and/or triallyl cyanurate, a specific epoxy resin, and a phenol resin as a curing agent for the epoxy resin. This was made based on the discovery that by doing so, not only the above-mentioned problems could be solved, but also a resin composition with excellent solvent film-forming properties and storage stability could be obtained. To describe the present invention in more detail, the present invention is comprised of the following seven inventions.

That is, the first aspect of the present invention is (a) a reaction product of a polyphenylene ether resin and an unsaturated carboxylic acid or acid anhydride, (b) triallyl isocyanurate and/or triallyl cyanurate, and ( c) (i) Brominated bisphenol polyglycidyl ether epoxy resin, (ii) novolac epoxy resin,
(iii) A curable polyphenylene ether epoxy resin composition comprising a resin composition containing a phenolic resin as an essential component, wherein the sum of components (a) and (b) is 100%.
Component (a) is 98 to 40 parts by weight based on parts by weight, (
b) component is 2 to 60 parts by weight, and (a) to (c)
Curable polyphenylene ether, characterized in that (a) + (b) components are 90 to 10 parts by weight, and (c) component is 10 to 90 parts by weight, based on 100 parts by weight of the sum of the components.
An epoxy resin composition is provided.

A second aspect of the present invention provides a cured polyphenylene ether/epoxy resin composition obtained by curing the curable polyphenylene ether/epoxy resin composition of the first invention. A third aspect of the present invention provides a curable composite material comprising the curable polyphenylene ether epoxy resin composition of the first aspect and a base material. The fourth aspect of the present invention is
A cured composite material obtained by curing the curable composite material of the third invention is provided. A fifth aspect of the present invention provides a laminate comprising the cured composite material of the fourth aspect and metal foil. A sixth aspect of the present invention provides a laminate in which an insulating layer made of the cured composite material of the fourth aspect is laminated on a metal base. Finally, the seventh aspect of the present invention is a metal base having an insulating layer made of the cured composite material of the fourth aspect laminated on at least one side of the metal base, and a metal foil laminated on at least the outermost layer of the insulating layer. Provides stretched laminates.

The above seven inventions will be explained in detail below. First, the curable polyphenylene ether epoxy resin composition and its cured product, which are the first and second aspects of the present invention, will be explained. The polyphenylene ether resin used in the production of component (a) of the first curable polyphenylene ether/epoxy resin composition of the present invention is represented by the following general formula (I).

[0015]

[Formula, m is an integer of 1 to 6, J is a polyphenylene ether chain substantially composed of units represented by the following formula (II),

[0016]

[Formula 2] (Here, R1 to R4 each independently represent a lower alkyl group, an aryl group, a haloalkyl group, a halogen atom, or a hydrogen atom.) When m is 1, Q represents a hydrogen atom, and m
When is 2 or more, it represents a residue of a polyfunctional phenol compound having 2 to 6 phenolic hydroxyl groups in one molecule and polymerization-inactive substituents at the ortho and para positions of the phenolic hydroxyl group. ] R1 in general formula (II)
Examples of the lower alkyl group represented by ~R4 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and sec-butyl. Examples of aryl groups include phenyl groups. Examples of haloalkyl groups include bromomethyl group, chloromethyl group, and the like. An example of a halogen atom is
Examples include bromine and chlorine. Representative examples of Q in general formula (I) include compounds represented by the following four general formulas.

[0017]

[Formula 3] [In the formula, A1 and A2 are the same or different carbon numbers 1 to 1]
4 represents a linear alkyl group, X represents an aliphatic hydrocarbon residue and a substituted derivative thereof, an aralkyl group and a substituted derivative thereof, oxygen, sulfur, a sulfonyl group, a carbonyl group, and Y represents an aliphatic hydrocarbon Represents residues and substituted derivatives thereof, aromatic hydrocarbon residues and substituted derivatives thereof, aralkyl groups and substituted derivatives thereof, Z represents oxygen, sulfur, sulfonyl group, carbonyl group, and 2 directly bonded to A2. The bonding positions of the two phenyl groups, A2 and
Represents an integer of 6. ] As a specific example,

[0018]

[C4]

[C5] etc.

In addition to the unit represented by general formula (II), the polyphenylene ether chain represented by J in general formula (I) may contain a unit represented by the following general formula (III). good.

[0020]

[In the formula, R5 to R9 each independently represent a hydrogen atom, a halogen atom, a lower alkyl group, an aryl group, or a haloalkyl group, and R10 and R11 each independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, It represents an aryl group or a substituted aryl group, and R10 and R11 are never hydrogen at the same time]. Examples of units of general formula (III) are:

[0021]

[Chemical formula 7] etc. In addition, the above formulas (II) and (III)
The unit may contain units obtained by graft polymerizing a polymerizable monomer having an unsaturated bond such as styrene or methyl methacrylate to the unit.

Preferred examples of the polyphenylene ether resin of general formula (I) used in the present invention include 2,6-
Poly(2,6) obtained by homopolymerization of dimethylphenol
-dimethyl-1,4-phenylene ether), poly(2
, 6-dimethyl-1,4-phenylene ether) styrene graft copolymer, 2,6-dimethylphenol and 2,3,6-trimethylphenol copolymer, 2,6-dimethylphenol and 2,3,6-trimethylphenol copolymer
- Copolymer of dimethylphenol and 2,6-dimethyl-3-phenylphenol, 2,6-dimethylphenol is converted into a polyfunctional phenol compound Q-(H)m (m is 2 to
Polyfunctional polyphenylene ether resin obtained by polymerization in the presence of (an integer of 6), for example, JP-A-63-30122
Copolymers containing units of general formulas (II) and (III) as disclosed in No. 2 and JP-A-1-297428 can be mentioned.

Regarding the molecular weight of the polyphenylene ether resin described above, the viscosity number η sp/c measured in a 0.5 g/dl chloroform solution at 30° C. is 0.1 to 1.0.
Those within this range can be used satisfactorily. For compositions in which molten resin flow is important, for example prepregs for multilayer wiring boards, resins with a low viscosity number are preferred.

Component (a) used in the present invention is produced by reacting the above polyphenylene ether resin with an unsaturated carboxylic acid or 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, etc., of which maleic anhydride, Fumaric acid is best used. The reaction is carried out by heating the polyphenylene ether resin and the unsaturated carboxylic acid or acid anhydride in a temperature range of 100°C to 390°C. At this time, a radical initiator may be present. Although both the solution method and the melt mixing method can be used, the melt mixing method using an extruder or the like can be carried out more easily and is suitable for the purpose of the present invention. The proportion of unsaturated carboxylic acid or acid anhydride is 0.01 to 5 parts by weight per 100 parts by weight of polyphenylene ether resin.
．． 0 parts by weight, preferably 0.1 to 3.0 parts by weight.

In the present invention, the role played by the unsaturated galboxic acid or acid anhydride in the polyphenylene ether resin is not known in detail so far. However, it is presumed that it plays an important role in increasing the compatibility between the polyphenylene ether resin and the epoxy resin, improving chemical resistance and heat resistance, and at the same time imparting film-forming properties to the resin composition.

The triallyl isocyanurate and/or triallyl cyanurate used as the component (b) of the first curable polyphenylene ether/epoxy resin composition of the present invention are trifunctional compounds represented by the following structural formulas, respectively. It is a sexual monomer.

[0027]

embedded image In carrying out the present invention, triallyl isocyanurate and triallyl cyanurate can be used not only individually, but also by mixing them in any ratio. In the present invention, triallyl isocyanurate and triallyl cyanurate exhibit their effects as a plasticizer and a crosslinking agent. That is, the resin flow during molding is improved and the crosslinking density is improved.

Curable polyphenylene ether of the present invention
The brominated bisphenol polyglycidyl ether epoxy resin used as one of the components (c) of the epoxy resin composition is represented by the following general formula (IV).

[0029]

[Formula 9] [wherein p is an integer of 0 to 4, and q has an average value of 0 to 1
, and A3 represents a lower alkyl group having 1 to 3 carbon atoms. Among these, those in which all p's are 2, q is substantially 0, and A3 is an isopropylidene group can best be used in the present invention.

The novolac epoxy resin also used as one of the components (c) is represented by the following general formula (V).

[0031]

[In the formula, n is a number with an average value of 0 to 10, and A4 represents a hydrogen atom, a methyl group, or a bromine atom. ] Among these, those in which the average value of n is 0 to 5 and A4 is a hydrogen atom or a methyl group can be most favorably used in the present invention.
One type or a combination of two or more types may be used.

The last component (c), phenolic resin, has two or more phenolic hydroxyl groups in one molecule, and includes phenol, cresol, xylenol, propylphenol, amylphenol, butylphenol, Novolac resins synthesized from octylphenol, phenylphenol, allylphenol, bisphenol A, etc. alone or in combination,
Refers to resol resin. Among these, novolak resins and resol resins synthesized from butylphenol or phenylphenol are (a), (b), (c) (i), (
Since it has excellent compatibility with each component c)(ii), it can best be used in the present invention, and one type or two or more types can be used in combination.

Of the above components (c), the brominated bisphenol polyglycidyl ether epoxy resin is essential for imparting flame retardancy, and the novolac epoxy resin is essential for improving chemical resistance and heat resistance by increasing crosslink density. . Furthermore, phenol resin acts as a curing agent for these epoxy resins, and is characterized by superior storage stability after resin compounding compared to other epoxy resin curing agents. In addition to the above, component (c) may contain other epoxy resins as long as they do not reduce properties such as flame retardancy, chemical resistance, and heat resistance.

Of the three components (a) to (c) explained above, the blending ratio of component (a) and component (b) is 98 to 40 parts by weight based on the total of 100 parts by weight of both components. parts by weight, component (b) is 2 to 60 parts by weight, more preferably 90 to 60 parts by weight of component (a), and 10 to 40 parts by weight of component (b).
If the amount of component (b) is less than 2 parts by weight, the improvement in chemical resistance will be insufficient, which is not preferable. On the other hand, if it exceeds 60 parts by weight, the dielectric properties, flame retardance, and moisture absorption properties will deteriorate, and the material will become extremely brittle after curing, which is not preferable.

The blending ratio of component (c) is (a) to (
c) (a) + (b) based on the sum of 100 parts by weight of the components
is 90 to 10 parts by weight, component (c) is 10 to 90 parts by weight, more preferably 70 to 10 parts by weight of components (a) + (b), and 30 to 90 parts by weight of component (c), even more preferably (a) + (b) component 60-20 parts by weight, (c) component 40
~80 parts by weight.

If the amount of component (c) is less than 10 parts by weight, chemical resistance and flame retardance may be insufficient, or adhesive strength may not be obtained when bonded to metal foil or the like as described later, which is not preferable. On the other hand, if component (c) exceeds 90 parts by weight, the dielectric properties deteriorate, which is not preferable.

The blending ratio of the brominated bisphenol polyglycidyl ether epoxy resin and the novolak epoxy resin in component (c) is determined by the balance between chemical resistance and flame retardance of the resin composition of the present invention as a whole. Although chemical resistance is improved by increasing the blending ratio of novolac epoxy resin, the bromine content based on the sum of components (a) to (c) is 5% by weight or more and 20% by weight or less. It is preferable to use a brominated bisphenol polyglycidyl ether epoxy resin. If the bromine content exceeds 20% by weight, the thermal stability of the resin composition will decrease, which is not preferred.

The proportion of the phenolic resin in component (c) is such that the amount of phenolic hydroxyl groups in the resin is from 0.5 to the total amount of epoxy groups in the epoxy resin.
The amount is preferably adjusted to 1.5 equivalents, more preferably 0.6 to 1.2 equivalents.

Methods for mixing the above components (a) to (c) include a solution mixing method in which they are uniformly dissolved or dispersed in a solvent, a melt blending method in which they are heated using an extruder, etc. is available. Solvents used for solution mixing include dichloromethane, chloroform,
Halogenated solvents such as trichlorethylene; benzene,
Aromatic solvents such as toluene and xylene; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone are used alone or in combination of two or more.

The resin composition of the present invention can be conveniently used in the form of a film. The manufacturing method is
For example, a normal solvent film forming method (casting method) can be used, and a film having an arbitrary thickness can be manufactured. Compositions suitable for the production of films are not particularly limited.

[0041] Although it is not intended to be a
0 parts by weight, component (b) is in the range of 2 to 50 parts by weight,
Based on the sum of 100 parts by weight of components (a) to (c), components (a)+(b) are in a range of 70 to 20 parts by weight, and component (c) is in a range of 30 to 80 parts by weight. (b) component and (c
) If the content of the component is less than the above range, the chemical resistance, flame retardance, and adhesion to metal foil will be insufficient as described above, which is not preferable. On the other hand, if it exceeds the above range, the film becomes brittle or sticky, resulting in poor handling properties, which is not preferable.

The resin composition of the present invention is cured by causing a crosslinking reaction by means such as heating, as described below, but in order to lower the temperature at that time or to accelerate the crosslinking reaction, a radical initiator or a curing accelerator is added. It may be used by containing an agent. As the radical initiator, common peroxides can be used.

Examples of the curing accelerator include amines, imidazole compounds, nitrogen-containing heterocyclic compounds such as diazabicycloundecene, organic phosphine compounds,
Known compounds such as organic phosphine/organic boron complexes, amine/organic boron complexes, quaternary ammonium compounds, and quaternary phosphonium compounds can be used. For details on the technology related to curing accelerators, see, for example, Hiroshi Kakiuchi (ed.),
"Recent Advances in Epoxy Resins" (Shokodo, 1990)
, Chapter 4 and its references. The radical initiator and the curing accelerator may be used alone or in combination of two or more.

In addition to the above-mentioned radical initiator and curing accelerator, the resin composition of the present invention may contain fillers and fillers in an amount within a range that does not impair the original properties, in order to impart desired performance depending on the intended use. Additives can be mixed and used. Examples of fillers include carbon black, silica, alumina, barium titanate, talc, mica, glass beads, glass hollow spheres, and the like. Additives include antioxidants,
Examples include heat stabilizers, antistatic agents, plasticizers, pigments, dyes, and colorants. In addition, for the purpose of further improving flame retardancy, chlorine-based, bromine-based, and phosphorus-based flame retardants, Sb2 O3, S
Flame retardant aids such as b2O5 and NaSbO3.1/4H2O can also be used together. Furthermore, it is also possible to blend one or more crosslinkable monomers such as allyl glycidyl ether, glycidyl methacrylate, and glycidyl acrylate, thermoplastic resins such as polyphenylene ether, or other thermosetting resins. .

The second cured polyphenylene ether/epoxy resin composition of the present invention is obtained by curing the above-mentioned curable polyphenylene ether/epoxy resin composition. The method of curing is arbitrary;
Methods using heat, light, electron beams, etc. can be employed.

When curing is carried out by heating, the temperature is 80 to 300°C, more preferably 150 to 250°C, although it varies depending on the presence or absence of a radical initiator and curing agent and the type thereof.
Selected in the range of °C. Also, the time is about 1 minute to 10 hours.
More preferably, it is 1 minute to 5 hours.

The resin composition of the obtained cured polyphenylene ether/epoxy resin composition can be analyzed using methods such as infrared absorption spectroscopy, high-resolution solid-state nuclear magnetic resonance spectroscopy, and pyrolysis gas chromatography. .

The cured polyphenylene ether epoxy resin composition of the present invention can be used satisfactorily in the form of a film. In addition, this cured polyphenylene ether
The epoxy resin composition can be used by being attached to a metal foil and/or a metal plate, similar to the cured composite material described below as the fourth invention.

Next, the third and fourth aspects of the present invention, the curable composite material and its cured product, will be explained. The curable composite material of the present invention is composed of the curable polyphenylene ether epoxy resin composition described above as the first aspect of the present invention and a base material. Substrates used in the present invention include various glass cloths or nonwoven glass cloths such as roving cloths, cloths, chopped mats, and surfacing mats; ceramic fiber cloths, asbestos cloths, metal fiber cloths, and other synthetic or natural inorganic fiber cloths; Woven or nonwoven fabrics obtained from synthetic fibers such as polyvinyl alcohol fibers, polyester fibers, acrylic fibers, and fully aromatic polyamide fibers; Natural fiber fabrics such as cotton fabrics, linen fabrics, and felt; Carbon fiber fabrics; Kraft paper, cotton paper, and paper. Natural cellulose fabrics such as glass mixed woven paper can 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, even more preferably 20 to 70 parts by weight, based on 100 parts by weight of the curable composite material. This is within the scope of the department. 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% by weight, the dielectric properties and flame retardance of the composite material will be poor.

[0051] A coupling agent may be used in the composite material of the present invention, if necessary, for the purpose of improving adhesion at the interface between the resin and the base material. As the coupling agent, common ones such as a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, a zircoaluminate coupling agent, etc. can be used.

[0052] As a method for producing the composite material of the present invention, for example, the components (a) to (c) described in the first section of the present invention, and other components as necessary, may be combined with the above-mentioned halogen-based and aromatic components. Examples include a method in which the material is uniformly dissolved or dispersed in a family-based or ketone-based solvent or a mixed solvent thereof, impregnated into a base material, and then dried.

[0053] Impregnation is carried out by dipping, coating, or the like. Impregnation can be repeated multiple times if necessary, and it is also possible to repeat impregnation using multiple solutions with different compositions and concentrations to finally adjust the desired resin composition and resin amount. It is.

[0054] The fourth cured 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 thereof is not particularly limited, and for example, a plurality of sheets of the curable composite material may be stacked, each layer may be bonded under heat and pressure, and at the same time, heat curing may be performed to obtain a cured composite material with a desired thickness. I can do it. It is also possible to obtain a cured composite material with a new layer configuration by combining a cured composite material that has been once adhesively cured and a curable composite material.

[0055] Laminate molding and curing are usually carried out simultaneously using a hot press or the like, but both may be carried out independently. That is, an uncured or semi-cured composite material obtained by lamination molding in advance can be cured by heat treatment or another method.

[0056] 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 500 kg/cm2 and a time of 1 minute to 10 hours, more preferably a temperature of 150 to 250 DEG C., a pressure of 1 to 100 kg/cm2, and a time of 1 minute to 5 hours.

Finally, the fifth, sixth, and seventh aspects of the present invention, which are laminates, laminates, and metal-clad laminates, will be explained. The laminate of the present invention is composed of the cured composite material and metal foil described above as the fourth aspect of the present invention. A laminate is also composed of a cured composite material and a metal plate, and a metal-clad laminate is composed of a cured composite material, metal foil, and a metal plate.

Examples of the metal foil used here include copper foil and aluminum foil. The thickness is not particularly limited, but is 5 to 200 μm, more preferably 5 to 200 μm.
The range is 100 μm.

Examples of the metal plate include iron plates, aluminum plates, silicon steel plates, and stainless steel plates. The thickness is not particularly limited, but is 0.2 mm to 10 mm.
, more preferably in the range of 0.2 mm to 5 mm. Before use, metal plates are mechanically polished by sanding with abrasive paper or abrasive cloth, wet blasting, dry blasting, etc. to improve their adhesion, and are also subjected to degreasing, etching, alumite treatment, chemical conversion coating treatment, etc. Can be used. For aluminum plates, it is preferable to degrease with sodium carbonate and etch with sodium hydroxide after polishing, but the method is not particularly limited.

Methods for producing the laminate, laminate, and metal-clad laminate of the present invention include, for example, the third method of the present invention.
The curable composite material described above as
Alternatively, a method can be mentioned in which metal plates are laminated in a layered structure according to the purpose, and the layers are bonded together under heat and pressure, and at the same time, the layers are thermally cured.

For example, in a laminate, a curable composite material and metal foil are laminated in an arbitrary layer configuration. Metal foil can be used both as a surface layer and as an intermediate layer. In a laminate, a curable composite material is laminated on one or both sides of a metal plate as a base. In metal-clad laminates,
It is based on a metal plate, and metal foil is laminated on one or both sides of the metal plate via a curable composite material. In this case, the metal foil is used as the outermost layer, but it may be used as an intermediate layer in addition to the outermost layer. In addition to the above, it is also possible to repeat lamination and curing multiple times to form a multilayer structure.

[0062] An adhesive can also be used to bond the metal foil and metal plate. Examples of adhesives include epoxy, acrylic, phenol, and cyanoacrylate adhesives, but are not particularly limited thereto. The above lamination molding and curing can be performed under the same conditions as in the fourth aspect of the present invention.

[0063]

[Examples] The present invention will be explained below with reference to examples in order to make it more clear, but the scope of the present invention is not limited to these examples.

Reference Example 1 100 parts by weight of poly(2,6-dimethyl-1,4-phenylene ether) having a viscosity number ηsp/c of 0.54 measured in a chloroform solution of 0.5 g/dl at 30°C, anhydrous 1.5 parts by weight of maleic acid, and 2,5-dimethyl-2,
5-di(t-butylperoxy)hexane (NOF)
After dry-blending 1.0 part by weight of Perhexa 25B) manufactured by Co., Ltd. at room temperature, it was extruded using a twin-screw extruder at a cylinder temperature of 300° C. and a screw rotation speed of 230 rpm. This polymer is designated as A.

Reference Example 2 Bifunctional polyphenylene ether (
After dry-blending 100 parts by weight of a product with a viscosity number ηsp/c of 0.40 measured with a chloroform solution of 0.5 g/dl at 30°C and 2 parts by weight of maleic anhydride, it was extruded under the same conditions as in Reference Example 1. I did it. The polymer obtained here is designated as B.

Reference Example 3 100 parts by weight of poly(2,6-dimethyl-1,4-phenylene ether) having a viscosity number ηsp/c of 0.31 measured in a chloroform solution of 0.5 g/dl at 30°C, anhydrous 1.5 parts by weight of maleic acid, and 2,5-dimethyl-2,
5-di(t-butylperoxy)hexane (NOF)
After dry blending 1.0 parts by weight of Peroxa 25B) manufactured by Co., Ltd. at room temperature, extrusion was performed under the same conditions as in Reference Example 1. The polymer obtained here is designated as C.

In the examples described below, the following components were used.

Brominated bisphenol A diglycidyl ether epoxy resin: Asahi Kasei AER735 Epoxy equivalent 350
Bromine content: 48% by weight Cresol novolac epoxy resin: Asahi Kasei ECN273 Epoxy equivalent: 217 Phenol novolac epoxy resin: Ciba Geigy EPN1138 Epoxy equivalent: 180 t-Butylphenol resole resin: Gun-Ei Chemical PS2657, PS2768 Phenylphenol novolac resin: Gun-Ei Chemical PS2880.

Initiator: 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3 (NOF Perhexine 25B) Curing accelerator: 2-methyl-4-methylimidazole (2E4MZ) Flame retardant Auxiliary agent: Sb2 O5 (Nissan Chemical NA-4800) Glass cloth: Made of E glass, area weight 48g/m2 and 105g/m2
Made of D glass, area weight 87g/m2.

As a comparative example, the following components were also used: Bisphenol A diglycidyl ether epoxy resin: Asahi Kasei AER331 Epoxy equivalent: 189 Low brominated bisphenol A polyglycidyl ether epoxy resin: Asahi Kasei AER771 Epoxy equivalent: 475
Bromine content: 20% by weight Curing agent: 4,4'-diaminodiphenylmethane (DDM) Curing accelerator or catalytic curing agent: 2-ethyl-4-methylimidazole (2E4MZ) Examples 1 to 3 Obtained in Reference Examples 1 and 2 Polymers A and B and the above-mentioned components were dissolved in chloroform with the composition shown in Table 1, and the solution was poured onto a Teflon plate to form a film. The resulting film has a thickness of approximately 10
It was 0 μm. Film formability was good in all cases, and no stickiness or the like on the surface was observed. After drying this film in an air oven, it was molded and cured in a vacuum press to obtain a cured product with a thickness of about 1 mm. All curing conditions were 220°C for 30 minutes. No change in appearance was observed in these cured products even after boiling them in trichlorethylene for 5 minutes.

Comparative Example 1 As shown in Table 1, Example 1 was prepared using AER331 and a catalytic amount of 2E4MZ as an epoxy resin and its curing agent, and without using triallyl isocyanurate, triallyl cyanurate, or an initiator. The same operations as in steps 3 to 3 were performed. When the obtained cured product was boiled in trichlorethylene for 5 minutes, swelling and warping were observed.

Examples 4 to 7 Each component was dissolved or dispersed in trichlorethylene according to the composition shown in Table 2. A glass cloth was dipped in this solution for impregnation and dried in an air oven. In Example 7, E glass cloth with a basis weight of 48 g/m2 was used, in Example 5, D glass cloth with a basis weight of 87 g/m2 was used, and in all other examples, a basis weight of 105 g/m2 was used.
E glass cloth was used. All of the obtained curable composite materials had no stickiness on the surface and were excellent in handleability.

[0073] Next, multiple sheets of the above curable composite material were stacked together so that the thickness after curing was about 0.8 mm, and copper foil with a thickness of 35 μm was placed on both sides of the composite material, which was then molded and hardened using a press molding machine. A laminate was obtained. Table 3 shows the curing conditions for each example. The pressure was 40 kg/cm2 in all cases. In all Examples, the resin flowed well during pressing.

Various physical properties of the thus obtained laminate were measured by the following methods, and good results as shown in Table 3 were obtained. 1. The laminate from which the trichlorethylene-resistant copper foil had been removed was cut into 25 mm square pieces, boiled in trichlorethylene for 5 minutes, and changes in appearance were visually observed. 2. The dielectric constant and dielectric loss tangent were measured at 1 MHz. 3. The laminate from which the solder heat-resistant copper foil has been removed is cut into 25 mm square pieces.
It was floated for 120 seconds in a solder bath at 0.degree. C., and changes in appearance were visually observed.

4. Copper foil peel strength A test piece with a width of 20 mm and a length of 100 mm was cut from the laminate, and a parallel cut of 10 mm in width was made on the copper foil surface, and then the peel strength was peeled off at a speed of 50 mm/min in a direction perpendicular to the surface. The copper foil was continuously peeled off, and the stress at that time was measured using a tensile tester, and the lowest stress value was shown. 5. Length 127mm, width 12.7mm from the laminate with flame retardant copper foil removed
A test piece of mm was cut out and tested according to the UL-94 test method.

[0076] The curable composite material obtained here was also
Although they were stored at ℃ for 3 months, they all maintained good resin flow, and no deterioration of the material was observed when they were made into a laminate. Furthermore, when the dynamic viscoelastic spectrum of the laminate obtained in Example 4 was measured, only one glass transition point, 220° C., was observed. This indicates that the above-mentioned components are extremely well compatible with each other, and it is presumed that as a result, a high glass transition point and good chemical resistance were achieved.

Comparative Examples 2 and 3 Curable composite materials and laminates were prepared using the compositions shown in Table 2 in the same manner as in Examples 4 to 7. When the trichlorethylene resistance of this laminate was measured, whitening of the surface and exposure of the glass cloth were observed. Furthermore, when the curable composite material was stored at 23° C., a decrease in resin flow during pressing was observed in Comparative Example 2 after about one week and in Comparative Example 3 after about one month.

Example 8 Three sheets of the curable composite material obtained in Example 4 were laminated on a 1.0 mm thick aluminum plate that had been subjected to polishing, degreasing, and etching treatment, and was heated at 40 kg/cm2 for 2 hours. A laminate was produced by press molding. The thermal resistance of this laminate is 2
4℃/w, and when no aluminum plate is used (6
It had excellent heat dissipation properties compared to 0°C/w). Thermal resistance was determined by forming a circuit on a 35 mm x 50 mm sample, soldering a 100 Ω chip resistor, and measuring the temperature rise after voltage application.

Example 9 Three sheets of the curable composite material obtained in Example 5 and a 35 μm thick copper foil were laminated on a 1.0 mm thick aluminum plate that had been subjected to polishing, degreasing, and etching. A metal-clad laminate was produced by press forming at 40 kg/cm2 for 30 minutes at ℃. The thermal resistance of this metal plate-clad laminate was measured in the same manner as in Example 8, and was found to be 24° C./w, indicating excellent heat dissipation.

[0080]

[Table 1]

[0081]

[Table 2]

[0082]

[Table 3]

[0083]

Effects of the Invention The curable polyphenylene ether epoxy resin composition of the present invention has the following characteristics. 1. Since the reaction product of the polyphenylene ether resin and the unsaturated carboxylic acid or acid anhydride used in the resin composition can be produced at low cost using an extruder or the like, it is possible to provide a resin composition with excellent economic efficiency. 2. The above-mentioned reaction product has excellent solvent film-forming properties, and therefore, films and curable composite materials with excellent handling properties and no stickiness on the surface can be obtained.

3. Since epoxy resin and phenol resin are used in combination, and triallyl isocyanurate and triallyl cyanurate have the effect of plasticizers, the resin flows well during pressing. 4. It has excellent storage stability, retains good resin flow even after being stored at 23°C for 3 months, and shows no deterioration in physical properties after curing. 5. The components used in the resin composition have excellent compatibility with each other, and can achieve excellent heat resistance and chemical resistance after curing.

[0085] Furthermore, the curable polyphenylene ether
A laminate, a laminate obtained using an epoxy resin composition,
Metal-clad laminates have the following characteristics. 1. This material has both flame retardancy and chemical resistance due to the use of brominated bisphenol polyglycidyl ether epoxy resin and novolak epoxy resin. The chemical resistance is particularly excellent due to the combined use of triallyl isocyanurate and triallyl cyanurate. 2. Even when epoxy resin or phenol resin is used as the main component, it exhibits a dielectric constant of approximately 4.0 or less, and is a material with excellent dielectric properties. 3. Heat resistance, adhesion with metal foil, dimensional stability, moisture absorption,
It also exhibits well-balanced physical properties such as heat dissipation.

Due to the above characteristics, the material of the present invention can be used as a dielectric material, an insulating material, a heat-resistant material, a structural material, etc. in fields such as the electrical industry, the electronic industry, and the space/aircraft industry. In particular, it is suitably used as single-sided, double-sided, multilayer printed circuit boards, flexible printed circuit boards, semi-rigid circuit boards, metal base boards, prepregs for multilayer printed circuit boards, and the like. Furthermore, because of its heat-resistant, moisture-absorbing, and insulating properties, the material of the present invention can be successfully used as a high-density circuit board with a line spacing of 100 μm or less, a multilayer circuit board with an interlayer insulation layer thickness of 200 μm or less, and an adhesive for mounting circuit boards. can.

Claims (10)

[Claims] Claim 1: (a) a reaction product of a polyphenylene ether resin and an unsaturated carboxylic acid or an acid anhydride; (b)
) triallyl isocyanurate and/or triallyl cyanurate, and (c) (i) brominated bisphenol polyglycidyl ether epoxy resin, (ii) novolak epoxy resin,
(iii) A curable polyphenylene ether epoxy resin composition comprising a resin composition containing a phenolic resin as an essential component, wherein the sum of components (a) and (b) is 100%.
Component (a) is 98 to 40 parts by weight based on parts by weight, (
b) component is 2 to 60 parts by weight, and (a) to (c)
Curable polyphenylene ether, characterized in that (a) + (b) components are 90 to 10 parts by weight, and (c) component is 10 to 90 parts by weight, based on 100 parts by weight of the sum of the components.
Epoxy resin composition. 2. A film comprising the curable polyphenylene ether epoxy resin composition according to claim 1. 3. A cured polyphenylene ether/epoxy resin composition obtained by curing the curable polyphenylene ether/epoxy resin composition according to claim 1. 4. A film comprising the cured polyphenylene ether epoxy resin composition according to claim 3. 5. (a) a reaction product of a polyphenylene ether resin and an unsaturated carboxylic acid or acid anhydride; (b)
) triallyl isocyanurate and/or triallyl cyanurate, (c) (i) brominated bisphenol polyglycidyl ether epoxy resin, (ii) novolak epoxy resin,
(iii) A curable composite material consisting of a resin composition containing a phenolic resin as an essential component, and (d) a base material, the composition comprising (a) component and (b)
Component (a) is 98 to 98 parts by weight based on 100 parts by weight of the total of the components.
40 parts by weight, component (b) is 2 to 60 parts by weight, and (a
) to (c) based on the sum of 100 parts by weight of components (a) +
Component (b) is 70 to 10 parts by weight, component (c) is 30 to 9 parts by weight.
0 parts by weight, and based on the sum of 100 parts by weight of components (a) to (d), components (a) to (c) are 95 to 10 parts by weight, and component (d) is 5 to 90 parts by weight. A curable composite material characterized by: 6. The curable composite material according to claim 5, wherein the bromine content is from 5% by weight to 20% by weight based on the sum of components (a) to (c). 7. A cured composite material obtained by curing the curable composite material according to claim 5 or 6. 8. A laminate comprising the cured composite material according to claim 7 and metal foil. 9. A laminate comprising an insulating layer made of the cured composite material according to claim 7 laminated on a metal base. 10. An insulating layer made of the cured composite material according to claim 7 is laminated on at least one side of the metal base, and a metal foil is laminated on at least the outermost layer of the insulating layer. metal-clad laminate.