JPH0218324B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a novel curable resin composition containing a polyphenylene ether resin as a component. A grafted polyphenylene ether resin grafted with a thermoplastic polymer or copolymer (b) of a compound containing one or more of () a polyfunctional maleimide (c) and a polyfunctional cyanate ester ( d), or a method for producing a curable graft copolymer-based resin composition by mixing or preliminarily reacting the above (c) and (d). 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 exhibits excellent thermal, mechanical, and electrical properties, and can be used in a wide range of applications 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, it can be cured using grafted polyphenylene ether resin, which is obtained by grafting a thermoplastic polymer or copolymer of a compound containing one or more olefinic unsaturated double bonds in the molecule to polyphenylene ether resin. A resin composition is not disclosed. The present inventors have conducted extensive studies with the aim of providing high-performance electronic materials using the above-mentioned grafted polyphenylene ether resin, and have found that resins obtained by modifying the graft copolymer using conventional methods are The present invention has been completed by discovering a curable graft copolymer-based resin composition that exhibits excellent performance that has not yet been satisfied. The molded article obtained from the curable graft copolymer-based resin composition of the present invention retains as much as possible the various properties inherent to the graft copolymer, while exhibiting particularly excellent solvent resistance and heat resistance. Its advantage is that it improves the defects of the graft copolymer by exhibiting good electrical properties and moldability. The configuration of the present invention will be explained below. First, the polyphenylene ether resin which is the 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. Even if the homopolymer consists of only one type of structural unit, the two formulas (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. ) or more, for example, poly(2,6-dimethyl-1,4-
phenylene)ether, poly(2-methyl-6-
Homopolymers represented by ethyl-1,4-phenylene) ether and poly(2,5-dimethyl-1,4-phenylene) ether; made from 2,6-dimethylphenol and 2,3,6-trimethylphenol The derived copolymers and 2-methyl-6-ethyl-1,4-phenylene ether and 2,3,6
Examples include copolymers typified by copolymers derived from -trimethylphenol.
Among them, poly(2,6-dimethyl-1,4-phenylene) ether and copolymers derived from 2,6-dimethylphenol and 2,3,6-trimethylphenol are practical polyphenylene Useful as an ether resin. These polyphenylene ether resins have a number average of 1000~
It is desired to have a molecular weight of 30,000. The use of a low molecular weight resin provides good solubility and good workability, while the use of a high molecular weight resin improves mechanical properties, so it may be selected as appropriate depending on the purpose of use. The thermoplastic polymer or copolymer of a compound containing one or more olefinically unsaturated double bonds in the molecule of component ()-b of the present invention is an unsaturated polymer having 2 to 18 carbon atoms. Any known thermoplastic resin may be used, which is produced by a polymerization method such as radical polymerization, cationic polymerization, or anionic polymerization using one or more saturated compounds, and the compounds include styrene, vinyltoluene, dimethylstyrene, chlorostyrene, α-methylstyrene, tert
- Aromatic vinyl compounds such as butylstyrene, vinylphenol, and vinylpyridine; Unsaturated nitrile compounds such as acrylonitrile, methacrylonitrile, and ethacrylonitrile; Unsaturated esters such as methyl acrylate, butyl acrylate, methyl methacrylate, and vinyl acetate Compounds; Conjugated diene compounds such as butadiene, isoprene, and 1,3-pentadiene; Vinyl halides such as vinyl chloride and vinylidene chloride; Olefins such as ethylene and propylene; Examples of thermoplastic resins include polystyrene resins. , impact-resistant polystyrene resin, ipsan resin, AAS resin, AS resin, ABS resin, MBS resin, and other styrenic resins; polyethylene resin, polypropylene resin, methylpentene polymer, vinyl chloride resin, ethylene-vinyl chloride copolymer resin, ethylene- Examples include substituted or unsubstituted olefin resins such as vinyl acetate copolymer, ethylene, vinyl acetate-vinyl chloride graft polymer resin, and vinylidene chloride resin; methacrylic resin. Among these thermoplastic resins, styrene resins and methacrylic resins are particularly preferred in the present invention from the viewpoint of compatibility with component a or component c. By grafting component ()-b to component ()-a described above, a grafted polyphenylene ether resin, which is component () of the present invention, is obtained.
The grafting reaction is carried out using a radical polymerization initiator such as di-tert-butyl peroxide, benzoyl, and 1 to 98 wt% polyphenylene ether resin as component a and 1 to 50 wt% as thermoplastic polymer or copolymer as component b. Peroxides such as peroxide, lauroyl peroxide, dicumyl peroxide, potassium persulfate, ammonium persulfate, sodium perborate, etc. are present in an amount of 0.1 to 15 parts by weight per 100 parts by weight of polyphenylene ether resin. By pre-reacting. The preliminary reaction is carried out at a temperature in the range of 70 to 300°C using an appropriate amount of an organic solvent or in bulk. 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 it is is particularly effective in the manufacturing process. This is preferable in terms of rationalization. Of course, it is not denied that other methods can also be used. When reacting in bulk, a predetermined amount of each component is added to a mixer such as a Henschel mixer, and the mixture is heated and stirred. Next, the polyfunctional maleimide which is the ()-c component 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 maleimide represented by the above formula has maleic anhydride and an amino group of 2 to 2.
It can be produced by a method known per se, in which maleamic acid is prepared by reacting with a polyamine having five polyamines, 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 paraphenylenediamine, meta or paraxylylenediamine, 1,4- or 1,3-cyclohexanediamine, hexahydroxylylenediamine,
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, These include 1-bis(4-aminophenyl)-1-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, instead of using the above-mentioned polyfunctional maleimide in the form of a so-called monomer, it can also be used, for example, in the form of a prepolymer with the amine exemplified above. The polyfunctional cyanate ester which is the component ()-d of the present invention is an organic compound having two or more cyanate ester groups and a prepolymer thereof,
A suitable cyanate ester has the following general 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. Further, 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. Moreover, the above ()-c, d components are, of course, c,
It can also be used as a pre-reactant obtained by subjecting d to a pre-heat reaction. Ingredients (), () of the present invention explained in detail above
The curable graft copolymer-based resin composition of the present invention is prepared by mixing as is or by pre-reacting after mixing. The blending ratio of components () and () can be varied over a wide range, and () is 2 to 99 wt% based on the total amount of components () and (), and component a,
1-98wt%, b component 1-50wt%, () 98-98wt%
1wt%, and c component 0-80wt%, d component 0-80wt%
Select from a range of 98wt%, taking into consideration the intended use. In addition, the mixing or pre-reaction method includes a method of obtaining the above-mentioned component () in the form of a solution and mixing the component () thereto, by heating as necessary in the presence of an organic solvent; A method may be used in which the respective components are mixed in powder form in the absence of a solvent, for example by heating in a Henshall mixer or the like, if necessary. Although the method for curing the curable resin composition of the present invention as described above is arbitrary, a heating method is usually used, and a temperature in the range of 50 to 400°C is generally selected, particularly 100 to 330°C. Temperatures in the range of .degree. 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. Molded products using the resin composition of the present invention,
When used for laminated products or adhesive structures,
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 compounding agents 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 _{2 ,} etc.; 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, staples, tows, webs, woven fabrics, non-woven fabrics, 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. 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, sulfur oxide, 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 described 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. The present invention will be specifically explained below using Examples and Comparative Examples. Parts and percentages are by weight unless otherwise specified. Examples 1 to 14 and Comparative Example 1 Intrinsic viscosity measured in chloroform at 25°C is 0.34
100 parts of phenylene ether copolymer (random copolymer derived from 95 mol % of 2,6-dimethylphenol and 5 mol % of 2,3,6-trimethylphenol, based on the monomers) of dl/gr in Table 1. 25 parts of the indicated thermoplastic polymer or copolymer,
After charging 100 parts of ethylbenzene and 4 parts of di-tert-butyl peroxide and purging the reaction system with nitrogen gas while stirring, the temperature inside the reactor was controlled to be maintained at around 150°C. The reaction was continued for 2 hours. The contents were taken out and dried at 180°C for 21 hours using a vacuum dryer to remove ethylbenzene and obtain a grafted polyphenylene ether resin. Prepolymer 20 obtained by pre-reacting 60 parts of the thus obtained grafted polyphenylene ether resin, 20 parts of bis(4-maleimidophenyl)methane and 2,2-bis(4-cyanatophenyl)propane at 150°C for 3 hours. The mixture was thoroughly mixed using a Henschel mixer. The resulting mixture was compression molded at 180°C for 3 hours to obtain a compression molded product. The results are shown in Table 1. Examples 15 to 28 and Comparative Examples 2 to 15 Graft polyphenylene ether resin of the polyphenylene ether copolymer used in Example 1 and a polymer obtained by polymerizing at least one vinyl compound, bis(4-maleimidophenyl) ) Methane and 2,2-bis(4-cyanatophenyl)propane were weighed at 60 parts, 20 parts, and 20 parts, respectively, and thoroughly mixed in a Henschel mixer. The obtained mixed composition was compression molded at a temperature of 260° C. for 2 hours to obtain a molded article. The resulting molded product was cut into 3 mm squares and subjected to continuous Soxhlet extraction with chloroform for 20 hours. The results are shown in Table 2. As a comparative example, screws (4
Soxhlet extraction was performed in the same manner on compression molded products made only of the grafted polyphenylene ether resin without using -maleimidophenyl)methane and 2,2-bis(4-cyanatophenyl)propane, and the results are shown in Table 2. Ta. Example 29 150 parts of poly(2,6-dimethyl-1,4-phenylene ether) having an intrinsic viscosity of 0.30 dl/gr as measured in chloroform at 25°C were placed in the glass autoclave of 1, 120 parts of toluene, and polystyrene (at 25°C).
The intrinsic viscosity of the polystyrene matrix measured by chloroform was 0.99 dl/gr) 16 parts and di-tert.
- Charge 20 parts of butyl peroxide and purge the reaction system of oxygen gas by blowing in nitrogen gas while stirring. Polymerization was carried out for 2.5 hours while controlling the reactor internal temperature to be maintained at around 150°C. Remove the contents and dry at 180℃ using a vacuum dryer.
was dried for 21 hours to remove toluene and obtain a grafted polyphenylene ether resin. 10 parts of bis(4-maleimidophenyl)methane and 2,2-bis(4-cyanatophenyl)propane
90 parts of the prepolymer was pre-reacted at 150°C for 4 hours to obtain a prepolymer, and 60 parts of this prepolymer and 40 parts of the above-mentioned grafted polyphenylene ether resin were dissolved in toluene to form a solution with a resin solid content of 25 wt% and impregnated into glass cloth. After drying at 110°C for 5 minutes, the temperature was raised to 140°C and dried for 15 minutes to obtain a prepreg. Four sheets of prepreg thus obtained were stacked, and copper foil was then placed on both sides, laminated and molded at 180℃ for 2 hours at a pressure of 100Kg/ ^cm2 , and then cured at 240℃ for 4 hours to a thickness of 0.4mm.
A copper-clad laminate was obtained. The test results for this laminate are shown in Table 3.

【table】

【table】

【table】

[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 approximately 3 mm square and subjected to continuous Soxhlet extraction for 18 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 "kink free damping viscoelasticity measuring device (RHES(A)"). (3) Copper foil peel strength: After making parallel cuts with a width of 10 mm, 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: The copper foil was peeled off. After that, it was cut into 50mm square pieces and measured using a dielectric loss measuring device.
Measured at IMHZ. (5) Rigidity modulus: When measuring the glass transition temperature, we drew a dynamic viscoelastic curve and derived the rigidity modulus at 250℃ from that diagram.

Claims (1)

[Claims] 1 () A thermoplastic resin polymer or copolymer (b) of a polyphenylene ether resin (a) containing one or more olefinic unsaturated double bonds in the molecule. A grafted polyphenylene ether resin grafted with () a polyfunctional maleimide (c) and a polyfunctional cyanate ester (d), or a preliminary reaction product of the above (c) and (d) is mixed or A method for producing a curable graft copolymer resin composition by preliminary reaction.