JPH0218325B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a resin composition based on a curable modified polyphenylene ether resin, and more specifically, () the polyphenylene ether resin (a) has one or more olefinic unsaturated double bonds in the molecule. A grafted polyphenylene ether resin obtained by graft polymerizing two or more compounds (b), () a polyfunctional maleimide (c), a polyfunctional cyanate ester (d), and the above (c) and ( This is a method for producing a curable resin composition by mixing or pre-reacting d) with at least one selected from the group consisting of pre-reactants. In recent years, with the development of electronic and electrical equipment for communications, consumer use, industrial use, etc., there has been a strong demand for miniaturization and simplification of mounting methods, and in response to this demand, the development of lightweight and high-performance electronic materials is desired. In the field of polymer materials, various research efforts are underway to meet this demand. In particular, for printed wiring boards, materials with better heat resistance, dimensional stability, or electrical properties are required to increase the density of circuits. This printed wiring board usually uses a copper-clad laminate made of thermosetting resin such as phenolic resin or epoxy resin as a base material. However, conventionally used thermosetting resins have a drawback in that they generally have poor electrical properties, particularly in the high frequency range. On the other hand, many thermoplastic resins have excellent electrical properties, and attempts have been made to apply particularly heat-resistant thermoplastic resins to materials for electronic devices. However, compared to thermosetting resins, thermoplastic resins are inferior in heat resistance, solvent resistance, dimensional stability, etc., and their mechanical properties are highly temperature dependent, making them difficult to apply in various fields of application. Its uses are extremely limited. It is well known that polyphenylene ether resin is a resin that exhibits excellent thermal, mechanical, and electrical properties and can be widely used as an industrial material and as a general molding material. The manufacturing method is also disclosed in various known documents such as US Pat. However, these polyphenylene ether resins are essentially thermoplastic resins, and are inferior in heat resistance, solvent resistance, etc. when compared with thermosetting resins.
Therefore, several methods have been proposed to increase the resistance to organic solvents. A method of adding a crosslinking agent to a resin to form a three-dimensional network structure (U.S. Patent No.
3396146) or a method of blending a thermosetting resin with a polyphenylene ether resin and curing it (Japanese Patent Publication No. 15519/1983). In these methods, at high temperatures close to the melting point of the polyphenylene ether resin (the temperature required during molding), the catalyst, crosslinking agent, or thermosetting resin decomposes, causing discoloration and deterioration, and the molded product deteriorates. It has not been put into practical use due to various problems such as the generation of air bubbles. In addition, curable resin compositions of grafted polyphenylene ether resins in which a compound containing one or more olefinic unsaturated double bonds in the molecule is graft-polymerized to polyphenylene ether resins have not been disclosed to date. It has not been. The present inventors provide a high-performance electronic material using a copolymer obtained by graft-polymerizing a compound containing one or more olefinic unsaturated double bonds in the molecule to a polyphenylene ether resin. With the goal of achieving this goal, we conducted extensive research and discovered a curable graft copolymer resin composition that exhibits excellent performance that cannot be met by resins obtained by modifying the graft copolymer using conventional methods. The molded article obtained from this composition exhibits particularly excellent solvent resistance, heat resistance, electrical properties, and moldability while retaining as much of the various properties inherent to the graft copolymer as possible. This method improves the drawbacks of the graft copolymer. The configuration of the present invention will be explained below. First, polyphenylene ether resin, which is component a of the present invention, is known per se, and is a general term for polymers having a repeating structural unit represented by the following general formula (1) as a skeleton. One set (In the formula, R ₁ and R ₂ are lower alkyl groups having 1 to 3 carbon atoms, and R ₃ is a hydrogen atom or a lower alkyl group having 1 to 3 carbon atoms.
represents a lower alkyl group. ) It may be a homopolymer consisting only of the species or a copolymer consisting of two or more species; for example, poly(2,6-dimethyl-1,4-phenylene) ether, poly(2,6-dimethyl-1,4-phenylene) ether, poly(2,6-dimethyl-1,4-phenylene) ether, -Methyl-6-ethyl-
1,4-phenylene)ether, poly(2,5-
Homopolymers represented by dimethyl-1,4-phenylene) ether; copolymers derived from 2,6-dimethylphenol and 2,3,6-trimethylphenol, and 2-methyl-6-ethyl-1 ，
Examples include copolymers typified by copolymers derived from 4-phenylene ether and 2,3,6-trimethylphenol. Among them,
Poly(2,6-dimethyl-1,4-phenylene)
Ethers and copolymers derived from 2,6-dimethylphenol and 2,3,6-trimethylphenol are useful as practical polyphenylene ether resins. These polyphenylene ether resins are desired to have a number average molecular weight of 1,000 to 30,000. Using a low molecular weight resin has good solubility and workability.
On the other hand, since the use of a high molecular weight resin improves mechanical properties, it may be selected as appropriate depending on the purpose of use. One or two unsaturated compounds having 2 to 18 carbon atoms containing one or more olefinic unsaturated double bonds in the molecule of component b of the present invention.
It is a mixture of more than one species, and the compounds include aromatic vinyl compounds such as styrene, vinyltoluene, dimethylstyrene, chlorostyrene, α-methylstyrene, tert-butylstyrene, vinylphenol, and vinylpyridine; acrylonitrile, methacrylonitrile, and ethane. Unsaturated nitrile compounds such as crylonitrile; unsaturated ester compounds such as methyl acrylate, butyl acrylate, methyl methacrylate, and vinyl acetate; conjugated diene compounds such as butadiene, isoprene, and 1,3-pentadiene; vinyl chloride, vinylidene chloride Examples include halogenated vinyl compounds such as olefins such as ethylene and propylene, and among these compounds, aromatic vinyl compounds, unsaturated nitrile compounds, and unsaturated ester compounds are particularly preferred. Adding component b to the above component a as a radical polymerization initiator,
For example, di-tert-butyl peroxide, benzoyl peroxide, lauroyl peroxide, dicumyl peroxide, potassium persulfate,
Grafting is carried out by using one or more peroxides such as ammonium persulfate and sodium perborate in an amount of 0.3 to 15 parts by weight based on 100 parts by weight of the polyphenylene ether resin as component a. The component () of the present invention is produced by polymerization. The reaction conditions are in the range of 70 to 300°C, and the reaction is usually carried out using an appropriate amount of an organic solvent. When using an organic solvent, a method in which component b and a radical polymerization initiator are added to the reaction solution of polyphenylene ether resin (component a) from which the polymerization catalyst has been removed and the reaction is carried out as is is particularly effective in the production process. This is preferable in terms of rationalization. Of course, it is not denied that other methods can also be used. In addition, the usage amounts of component a and component b are (a) component 1 to
98wt%, component (b) is selected from the range of 1 to 40wt% in consideration of the intended use. The polyfunctional maleimide (c), which is one of the components of the present invention, is a polymaleimide compound represented by the following general formula (2) having two or more maleimide groups in the molecule. (In the formula, R ₄ is an aromatic or aliphatic polyvalent organic group described below, X ₁ and X ₂ are hydrogen atoms,
It is a halogen atom or a lower alkyl group, and k represents an integer of 2 or more, usually 10 or less. ) and prepolymers derived from this polymaleimide compound. The maleimides represented by the above formula contain maleic anhydride and 2 to 5 amino groups.
It can be produced by a method known per se, in which maleamic acid is prepared by reacting it with a polyamine contained therein, and then the maleamic acid is cyclized by dehydration.
It is preferable that the polyamines used are aromatic amines in terms of the heat resistance of the final resin, but if flexibility and flexibility of the resin are desired, alicyclic amines may be used alone or in combination. good. Furthermore, it is particularly desirable that the polyvalent amines be primary amines in terms of reactivity, but secondary amines can also be used. Suitable amines include meta or paraphenylene diamine, meta or para xylylene diamine, 1,4- or 1,3-cyclohexane diamine, hexahydroxylylene diamine, 4,
4'-diaminobiphenyl, bis(4-aminophenyl)methane, bis(4-aminophenyl)ether, bis(4-aminophenyl)sulfone, bis(4-amino-3-methylphenyl)methane,
Bis(4-amino-3,5-dimethylphenyl)
Methane, bis(4-aminophenyl)cyclohexane, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-amino-3-methylphenyl)propane, bis(4-amino-3-chlorophenyl)methane, 2,2-bis(3,5-dibromo-4-aminophenyl)propane, bis(4-aminophenyl)phenylmethane, 3,4
-diaminophenyl-4'-aminophenylmethane, 1,1-bis(4-aminophenyl)-1-
These include phenylethane, melamines having an s-triazine ring, and polyamines made by reacting aniline with formalin and linking benzene rings with methylene bonds. In the present invention, the above-mentioned polyfunctional maleimide can also be used in the form of a prepolymer with the amine exemplified above, for example, instead of being used in the form of a so-called monomer. The polyfunctional cyanate ester (d), which is another component of the present invention, is an organic compound having two or more cyanate ester groups and its prepolymer. Formula R ₅ -(O-C≡N)m...(3) (m in the formula is an integer of 2 or more and usually 5 or less,
R ₅ is an aromatic organic group, and the cyanate ester group is bonded to the aromatic ring of the organic group R. Specific examples include 1,3- or 1,4-dicyanatobenzene,
1,3,5-tricyanatobenzene, 1,3
-, 1,4-, 1,6-, 1,8-, 2,6- or 2,7-dicyanatonaphthalene, 1,3,
6-tricyanatonaphthalene, 4,4-dicyanatobiphenyl, bis(4-cyanatophenyl)methane, 2,2-bis(4-cyanatophenyl)propane, 2,2-bis(3, 5-dichloro-4-cyanatophenyl)propane, 2,2
-Bis(3,5-dibromo-4-cyanatophenyl)propane, bis(4-cyanatophenyl)ether, bis(4-cyanatophenyl)
Thioether, bis(4-cyanatophenyl)
Sulfone, tris(4-cyanatophenyl) phosphite, tris(4-cyanatophenyl)
These include phosphates and cyanate esters obtained by the reaction of novolacs with cyanogen halides. These other Tokko Sho 41-1928, Tokko Sho
43-18468, Special Publication 44-4791, Special Publication 45-11712,
Special Publication No. 46-41112, Special Publication No. 47-26853, and Special Publication No. 1989
Cyanic acid esters described in 51-63149 and the like can also be used. Alternatively, the above-mentioned polyfunctional cyanate ester may be treated in the presence or absence of a mineral acid, a Lewis acid, a salt such as sodium carbonate or lithium chloride, a phosphate ester such as tributylphosphine, or a catalyst such as an epoxy compound. It can be used as a prepolymer obtained by polymerizing. These prepolymers generally have a sym-triazine ring in the molecule, which is formed by trimerization of the cyanide group in the cyanate ester. In the present invention, it is preferable to use the prepolymer having an average molecular weight of 400 to 6,000. Furthermore, the polyfunctional cyanate esters described above can also be used in the form of prepolymers with amines. Examples of amines that can be suitably used include those used in the synthesis and modification of the polyfunctional maleimide described above. Of course, the polyfunctional cyanate esters mentioned above, their prepolymers and prepolymers with amines can be used in the form of mixtures. Further, as component (), a pre-reacted product obtained by pre-reacting the above-mentioned components (c) and (d) without a catalyst or in the presence of a catalyst can also be suitably used. The composition ratio of the above components () and () can be appropriately selected from a wide range, but the grafted polyphenylene ether resin of component () is 2 to 99 wt%, and the component () is 98 to 1 wt%. ,c
From the range of component 0 to 80 wt%, d component 0 to 98 wt%,
Select by considering usage etc. In addition, the composition can be prepared by mixing the component () into a solution of the component (), or by separating the component () to obtain a powder and mixing this and the component () in a mixer such as a Henschel mixer. It is manufactured by adding and heating and stirring. Although the method for curing the resin composition of the present invention is arbitrary, a heating method is usually used, and generally
Temperatures in the range 50 to 400°C are chosen, especially 100 to 400°C.
Temperatures in the range of 330°C are preferred. The time required for curing varies depending on how the resin composition of the present invention is used, that is, whether it is a thin coating film or a relatively thick molded product or laminate, but is usually 30 seconds. A time sufficient for the resin composition to harden may be selected from a range of 10 to 10 hours. When the resin composition of the present invention is used for molded products, laminate products, adhesive structures, etc., it is desirable to apply pressure during the heat curing described above. Other curing methods include electron beams from various accelerators, ionizing radiation such as gamma rays from isotopes such as cobalt-60; sunlight; light emitted from light sources such as tungsten lamps, low-pressure or high-pressure mercury lamps, etc. A method using active energy rays can also be adopted. Particularly in the case of photocuring, photosensitizers known per se, such as benzoin, benzoin methyl ether, benzathurone,
Organic carbonyl compounds such as anthraquinone and benzophenone, combinations of sensitizing dyes such as eosin, erythrosine, and acridine, and various amines are added to the resin composition of the present invention in amounts ranging up to 5% by weight based on the resin solid content. This photocurable resin composition is effective when applied to the field of painting. In the resin composition of the present invention, for the purpose of adjusting the thermosetting properties of the resin, changing the properties of the resin itself, or imparting desired properties to the final resin product,
Various formulation examples can be blended. for example,
The resin composition of the present invention reacts under heating or pressure to form a network structure and becomes a heat-resistant resin, and a catalyst may be included in the composition for the purpose of promoting the network structure. Examples of such catalysts include organic acid metals such as lead naphthenate, lead stearate, zinc octylate, zinc naphthenate, tin oleate, dibutyltin maleate, manganese naphthenate, cobalt naphthenate, lead resinate, etc. Salts; metal chlorides such as SnCl ₄ , ZnCl ₂ , AlCl ₃ and the like; organic bases such as triethylenediamine, etc. are suitable. The amount of these catalysts used depends on the type of catalyst and
Although the amount of the catalyst varies considerably depending on the application and the curing conditions and cannot be specified unconditionally, it is preferable to use the amount of the catalyst in a general sense, that is, an amount of 5% by weight or less based on the total resin solid content. The resin composition of the present invention may contain natural, semi-synthetic or synthetic resins in an amount within a range that does not impair the original properties of the composition, in order to impart desired performance depending on the intended use. . Such resins include oleosin such as drying oil and non-drying oil;
Rosin, Sierra Tsuk, Copal, Oil Modified Rosin,
Phenol resin, alkyd resin, epoxy resin,
Examples include urea resin, melamine resin, polyester resin, vinyl butyral resin, vinyl acetate resin, vinyl chloride resin, acrylic resin, silicone resin, rubber, etc., and these may be used alone or in combination of two or more. Furthermore, if desired, reinforcing materials or fillers in the form of fibers or powder can also be included. Powdered reinforcements or fillers include carbon black, finely powdered silica, calcined clay, basic magnesium silicate, diatomaceous earth powder, alumina, calcium carbonate, magnesium carbonate, magnesium oxide, kaolin, sericite, and boron nitride. can be mentioned. Examples of fibrous reinforcing materials include inorganic fibers such as ceramic fiber, asbestos, rock wool, glass fiber, slag/wool, and carbon fiber, as well as paper,
Examples include natural fibers or synthetic fibers such as pulp, wood flour, cotton, linters, and polyimide fibers.
The above-mentioned fibrous reinforcing material can be used in the form of fibrils, stable, tow, web, woven fabric, non-woven fabric, or paper products. These reinforcing materials or fillers may be used in amounts of up to 400 parts by weight per 100 parts by weight of resin solid content for laminated materials and molding materials, although this will vary depending on the application. In addition, for the purpose of making the resin composition of the present invention flame retardant, known flame retardants such as phosphoric acid esters, halogenated organic compounds, or a combination of halides and antimony compounds may be added to the polyphenylene ether resin. It can also be blended. Furthermore, for the purpose of coloring the resin composition, white pigments such as titanium oxide, coloring pigments such as yellow lead, carbon black, iron black, molybdenum red, smelt, cadmium yellow, cadmium red, or various organic dyes may be used. Pigments can also be included. When the resin composition of the present invention is used as a paint, zinc chromate,
Anticorrosive pigments such as red lead, red iron, zinc, and strontium chromate; Anti-sagging agents such as aluminum stearate; Dispersants; Thickeners; Paint film modifiers, extender pigments; Flame retardants, etc. A paint compounding agent may be appropriately blended. The resin composition of the present invention can be applied to various uses as mentioned above, and various processing methods can be applied depending on the use. Various methods can be applied, such as shell molding using a molding material impregnated into a base material or lamination molding using a molding material impregnated into a fiber reinforcing material. Hereinafter, the present invention will be specifically explained using Examples and Comparative Examples. Parts and percentages are by weight unless otherwise specified. Examples 1-2 and Comparative Example 1 Intrinsic viscosity measured in chloroform at 25°C 0.45
dl/g of poly(2,6-dimethyl-1,4-phenylene ether), 60 parts of styrene, 110 parts of ethylbenzene, and 6 parts of di-tert-butyl peroxide were uniformly dissolved with stirring at 100°C. After that, nitrogen gas was blown into the reaction system to purge the oxygen gas in the reaction system. After polymerizing for 2.5 hours while controlling the reactor internal temperature to be maintained between 145 and 150℃, the contents were taken out and dried using a vacuum dryer.
Ethylbenzene and unreacted styrene were removed by drying at 180°C for 14 hours to obtain a grafted polyphenylene ether resin. The polystyrene content of this grafted polyphenylene ether resin was found to be 9 wt% by infrared absorption spectrum analysis. This grafted polyphenylene ether resin and bis(4-maleimidophenyl)methane were mixed in a Henschel mixer in the proportions shown in Table 1, and the resulting mixed composition was mixed at 250°C and 150 kg/cm ² . It was compression molded for 2 hours. The obtained molded product is 3mm
It was cut into corners and subjected to continuous Soxhlet extraction with chloroform for 20 hours, and the residue that did not dissolve in chloroform was expressed as %. The results are shown in Table 1.
Also, in Table 1, bis(4-maleimidophenyl)
The results for compression molded products made only of grafted polyphenylene ether resin without methane are shown for comparison. Example 3 30 parts of the grafted polyphenylene ether resin obtained in Example 1 and 70 parts of 2,2-bis(4-cyanatophenyl)propane were thoroughly mixed in a Henschel mixer. The obtained mixed composition was compression molded at a temperature of 250° C. for 2 hours and a pressure of 150 kg/cm ² . The obtained molded product was cut into 3 mm squares and diluted with chloroform.
Time-continuous Soxhlet extraction was performed, and the residue that could not be eluted in chloroform was expressed in %. Results first
Shown in the table.

[Table] Examples 4 to 5 and Comparative Example 2 Intrinsic viscosity measured in chloroform at 25°C is 0.34
dl/gr phenylene ether copolymer (2,6-dimethylphenol 0.5 mol% based on monomers)
and 5 mol% of 2,3,6-trimethylphenol), 64 parts of methyl methacrylate, 180 parts of ethylbenzene, and 6 parts of di-tert-butyl peroxide were charged and stirred at 100°C. After uniformly dissolving the mixture, nitrogen gas was blown in to purge the reaction system of oxygen gas, and polymerization was carried out for 2.5 hours while controlling the reactor internal temperature to be maintained at around 150°C. The contents were taken out and dried at 180° C. for 21 hours using a vacuum dryer to remove ethylbenzene and unreacted methyl methacrylate to obtain a grafted polyphenylene ether resin. According to infrared absorption spectrum analysis, the polymethyl methacrylate content was 5 wt%. This grafted polyphenylene ether resin and bis(4-maleimidophenyl)methane were mixed in a Henschel mixer in the proportions shown in Table 2, and the resulting mixed composition was mixed at 250°C and 150 kg/ ^cm2. Compression molding was performed for 2 hours. The obtained molded product is
It was cut into mm squares and subjected to continuous Soxhlet extraction with chloroform for 20 hours, and the residue that did not dissolve in chloroform was expressed as a percentage. The results are shown in Table 2. For comparison, Table 2 shows the results for compression molded products made only of grafted polyphenylene ether resin without bis(4-maleimidophenyl)methane. Example 6 40 parts of the grafted polyphenylene ether resin obtained in Example 4 and 60 parts of a prepolymer obtained by pre-reacting 2,2-bis(4-cyanatophenyl)propane at 150°C for 3 hours were mixed in a Henschel mixer. Mix thoroughly. The obtained mixed composition was compression molded at a temperature of 250° C. for 2 hours and a pressure of 150 kg/cm ² . The obtained molded product was cut into 3 mm squares and soaked in chloroform.
Table 2 shows the results of continuous Soxhlet extraction for 20 hours. The glass transition temperature was also measured at the same time.

[Table] Example 7 and Comparative Example 3 Intrinsic viscosity measured in chloroform at 25°C is 0.34
100 parts of dl/gr phenylene ether copolymer (a random copolymer derived from 95 mol% of 2,6-dimethylphenol and 5 mol% of 2,3,6-trimethylphenol on a monomer basis), 200 parts of styrene, After 100 parts of ethylbenzene and 2 parts of di-t-butyl peroxide were charged and uniformly dissolved while stirring at 100°C, nitrogen gas was blown in to purge the reaction system of oxygen gas. Polymerization was carried out for 2 hours while controlling the internal temperature of the reactor to be maintained between 145 and 150℃, and the contents were taken out and dried at 180℃ for 14 hours using a vacuum dryer to remove ethylbenzene and unreacted styrene. This was removed to obtain a grafted polyphenylene ether resin. Infrared absorption spectrum analysis revealed that the polystyrene content was 34%. Poly(phenylmethylene) polymaleimide produced by reacting poly(phenylmethylene) polyamines obtained by the reaction of aniline and formaldehyde with maleic anhydride (average of 3 N-phenylmaleimide residues in the molecule) ) and 30 parts of 2,2-bis(4-cyanatophenyl)propane
5 parts of maleimide-cyanate ester prepolymer obtained by pre-reacting 70 parts of maleimide-cyanate ester prepolymer at 110°C for 2 hours,
Grafted polyphenylene ether resin obtained above
95 parts were thoroughly mixed with a Henschel mixer. The resulting mixed composition is placed between copper foils to a predetermined thickness (1.5
mm to 1.6 mm), and heated to 250℃ for 2 hours.
A double-sided copper-clad test piece was prepared by compression molding at a pressure of 150 kg/cm ² for an hour. The copper foil of this test piece was peeled off and cut into dice of about 3 mm square and subjected to continuous Soxhlet extraction with chloroform for 20 hours. As a result, the amount of residue that could not be eluted into chloroform was 45%. As a comparative example, a similar Soxhlet extraction was performed on a test piece made only of the grafted polyphenylene ether resin, and as a result, the amount of residue that could not be eluted in chloroform was less than 1%. Various tests were conducted using the test pieces, and the results are shown in Table 3. Example 8 and Comparative Example 4 Intrinsic viscosity measured in chloroform at 25°C is 0.50
200 parts of dl/gr phenylene ether copolymer (a random copolymer derived from 95 mol% of 2,6-dimethylphenol and 5 mol% of 2,3,6-trimethylphenol on a monomer basis), 150 parts of styrene, 100 parts of acrylonitrile, 200 parts of ethylbenzene and 5 parts of dicumyl peroxide
After uniformly dissolving the mixture while stirring at °C, nitrogen gas was blown in to purge the reaction system of oxygen gas. Polymerization was carried out for 2 hours while controlling the reactor internal temperature to be maintained between 145 and 150°C. The contents were taken out and dried at 180° C. for 14 hours using a vacuum dryer to remove ethylbenzene and unreacted styrene and acrylonitrile to obtain a grafted polyphenylene ether resin. According to infrared absorption spectrum analysis, the content of styrene-acrylonitrile copolymer is 28wt%, and the content of acrylonitrile in styrene-acrylonitrile copolymer is
It was 25wt%. 9.8 parts of bis(4-maleimidophenyl)methane,
2,2-bis(4-cyanatophenyl)propane
87.8 parts and 2.4 parts of an epoxy resin (trade name: Epicote 152, manufactured by Ciel Chemical) were reacted at 130°C with stirring for 4 hours to produce a prepolymer consisting of maleimide, cyanate ester and epoxy compound. 40 parts and 60 parts of the grafted polyphenylene ether resin obtained above were thoroughly mixed in a Henschel mixer. The obtained mixed composition was placed between copper foils to a predetermined thickness (1.5 mm to 1.6 mm), and compression molded at a temperature of 250°C for 2 hours at a pressure of 100 kg/cm ² and coated with copper on both sides. A test piece was prepared. The copper foil of this test piece was peeled off, cut into approximately 3 mm squares, and subjected to continuous Soxhlet extraction with chloroform for 20 hours. As a result, the amount of residue that could not be eluted in chloroform was 97%. As a comparative example, a similar Soxhlet extraction was performed on a test piece made only of the grafted polyphenylene ether resin, and as a result, the amount of residue that could not be eluted in chloroform was less than 1%. Various tests were conducted using the test pieces, and the results are shown in Table 3. Example 9 20 parts of the grafted polyphenylene ether resin obtained in Example 1 and 80 parts of the prepolymer consisting of maleimides, cyanate esters and epoxy compounds obtained in Example 8 were dissolved in toluene to reduce the resin solid content. After impregnating a glass woven fabric with a 25wt% solution,
The prepreg was dried at 110°C for 5 minutes, then raised to 140°C for 15 minutes. Four sheets of the thus obtained prepreg were stacked, copper foil was further placed on both sides, and the layers were laminated at a temperature of 200℃ for 2 hours and a pressure of 100Kg/ ^cm2 , and then cured at a pressure of 100Kg/ ^cm2 at 240℃ for 4 hours. A copper-clad laminate with a thickness of 0.4 mm was obtained. The test results for this laminate are shown in Table 3. Example 10 and Comparative Example 5 Intrinsic viscosity measured in chloroform at 25°C is 0.45
150 parts of dl/gr poly(2,6-dimethyl-1,4-phenylene ether) was added to 250 parts of toluene at 100°C.
The mixture was heated and stirred to dissolve. Next, 120 parts of methyl methacrylate and 5 parts of dicumyl peroxide were added, nitrogen gas was blown in to purge the reaction system of oxygen gas, and the temperature inside the reactor was controlled to be maintained at around 150°C. Time overlapped. Remove the contents and dry at 180℃ using a vacuum dryer.
The mixture was dried for 21 hours to remove toluene and unreacted methyl methacrylate to obtain a grafted polyphenylene ether resin. Based on infrared absorption spectrum analysis, the content of polymethyl methacrylate is 30%.
It was hot. Poly(phenylmethylene) polymaleimide produced by reacting poly(phenylmethylene) polyamines obtained by the reaction of aniline and formaldehyde with maleic anhydride (average of 3 N-phenylmaleimide residues in the molecule) ) and 30 parts of 2,2-bis(4-cyanatophenyl)propane
70 parts at 110℃ for 2 hours with stirring,
A prepolymer of maleimides and cyanate esters was prepared, and 20 parts of this prepolymer and 80 parts of the grafted polyphenylene ether resin obtained above were thoroughly mixed using a Henschel mixer. The obtained mixed composition was placed between copper foils to a predetermined thickness (1.5 mm to 1.6 mm) and compression molded at a temperature of 250°C for 2 hours at a pressure of 100 kg/cm ² and then subjected to a double-sided copper cladding test. I created a piece. The copper foil of this test piece was peeled off, cut into approximately 3 mm square pieces, and subjected to continuous Soxhlet extraction with chloroform for 20 hours. As a result, the amount of residue that could not be eluted into chloroform was 73%. For comparison, a similar Soxhlet extraction was performed on a test piece made only of the grafted polyphenylene ether resin, and as a result, the amount of residue that could not be eluted in chloroform was less than 1%. Various tests were conducted using the test pieces, and the results are shown in Table 3. Example 11 and Comparative Example 6 Phenylene ether copolymer (95 mol% of 2,6-dimethylphenol and 2,3,
100 parts of a random copolymer derived from 5 mol% of 6-trimethylphenol, 50 parts of butyl acrylate, 120 parts of ethylbenzene, and di-tert.
- After charging 2 parts of butyl peroxide and dissolving it uniformly while stirring at 100°C, blow nitrogen gas to purge the oxygen gas in the reaction system, and then maintain the internal temperature of the reactor at around 145°C. Polymerization was allowed to proceed for 2 hours under controlled conditions. The contents were taken out and dried at 180° C. for 21 hours using a vacuum dryer to remove ethylbenzene and unreacted tylacrylate to obtain a graft copolymer. The content of polybutyl acrylate was 20 wt%. 10 parts of bis(4-maleimidophenyl)methane and 2,2-bis(4-cyanatophenyl)propane
A prepolymer was obtained by preliminarily reacting with 90 parts at 150° C. for 4 hours, and 50 parts of this prepolymer and 50 parts of the grafted polyphenylene ether resin obtained above were thoroughly mixed in a Henschel mixer. The obtained mixed composition was extruded into pellets using an AS-30 twin-screw extruder (manufactured by Nakatani Kikai Seisakusho) with a maximum cylinder temperature of 250°C, and the pelletized mixed composition was passed between copper foils. 250℃, 100Kg/
A test piece with copper cladding on both sides was prepared by compressing it for 2 hours under the condition of cm ² . The copper foil of this test piece was peeled off, cut into approximately 3 mm squares, and subjected to continuous Soxhlet extraction with chloroform for 20 hours.
It was 97%. As a comparative example, a similar Soxhlet extraction was performed on a test piece containing only the graft copolymer, excluding the prepolymer of maleimide and cyanate ester, and as a result, the amount of residue that could not be eluted in chloroform was less than 1%. Various tests were conducted using the test pieces, and the results are shown in Table 3. Example 12 9.8 parts of bis(4-maleimidophenyl)methane,
2,2-bis(4-cyanatophenyl)propane
87.8 parts and epoxy resin (product name: Epicote
152 (manufactured by Ciel Chemical) were pre-reacted at 130°C for 4 hours to produce a prepolymer consisting of maleimides, cyanate esters and epoxy compounds, and 85 parts of the prepolymer and the same graft as obtained in Example 4 were prepared. Dissolve 15 parts of polyphenylene ether resin in toluene to make a solution with a resin solid content of 25 wt%,
A glass woven fabric was impregnated with this, and then heated to 110°C for 5 minutes, then raised to 140°C and dried for 15 minutes to obtain a prepreg. The prepreg thus obtained was
Stack the sheets, then cover both sides with copper foil. 140℃ for 0.5 hours, 150℃ for 0.5 hours, and 180℃ for 1 hour.
Laminate molding was carried out under a pressure of Kg/cm ² and the product was further cured at 240° C. for 4 hours to obtain a copper-clad laminate having a thickness of 0.4 mm. The test results for this laminate are shown in Table 3.

[Table] The test methods for various performances in the table are as follows. (1) Chloroform extraction residue: Peel off the copper foil,
The pieces were cut into dice of about 3 mm square, subjected to continuous Soxhlet extraction for 20 hours, and the unextracted residue was expressed as a percentage of the weight before the extraction test. (2) Glass transition temperature: peel off copper foil, width 0.7~
A slender rod-shaped test piece of 1.2 mm and approximately 70 mm in length was cut out and measured using a "twist free damping type viscoelasticity measuring device (manufactured by RHESCA)". (3) Copper foil peeling strength: After making parallel cuts with a width of 10 mm on the copper foil surface, the copper foil was peeled off in a direction perpendicular to the surface, and the stress at that time was measured using a Tensilon. (4) Dielectric constant and dielectric loss tangent: After peeling off the copper foil, cut it into 50 mm squares and measure with a dielectric loss measuring device.
Measured at IMHZ. (5) Solder heat resistance: Cut the test piece into 25 mm squares, and if both sides are copper-plated, peel off one side to create a measurement sample. Float the sample with the copper foil side down in a solder bath at 260℃ and measure the time until blistering or peeling occurs.

Claims (1)

[Scope of Claims] 1 () A grafted polyphenylene ether resin (a) grafted with a compound (b) containing one or more olefinically unsaturated double bonds in the molecule. Nylene ether resin and () at least one member selected from the group consisting of a polyfunctional maleimide (c), a polyfunctional cyanate ester (d), and a preliminary reaction product of the above (c) and (d). A method for producing a curable resin composition by mixing or pre-reacting.