JPS5837043A - Curable resin composition - Google Patents

Abstract

PURPOSE:To provide a curable resin compsn. having improved solvent resistance, heat resistance, electrical properties and moldability, by mixing graft polyphenylene ether with a polyfunctional maleimide (and/or a polyfunctional cyanate ester.) CONSTITUTION:A curable resin compsn. is prepd. by mixing (or prereacting) (1) graft polyphenylene ether resin prepd. by grafting a compound having an alefinically unsaturated double bond (e.g., styrene) to polyphenylene ether resin (e.g., poly (2,6-dimethyl-1,4-phenylene) ether of number-average molecular weight of 1,000-30,000 and (2) at least one component selected from polyfunctional maleimides[e.g., bis (4-maleimidophenyl)methane], polyfunctional cyanate esters [e.g., 2,2-bis (4-cyanatophenyl)propane]and their prereactant.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a curable modified polyphenylene ether resin based resin composition KML, specifically (Summer 1 Polyphenylene Ether Resin) having one or more olefinic unsaturated double bonds in the molecule. A compound containing two or more (graft polyphenylene ether resin obtained by graft polymerization of bl), (If polyfunctional maleimides (C), polyfunctional cyanate esters (d), and the above (cl and ( A curable resin composition obtained by mixing or preliminarily reacting dl with at least one selected from the group force 1 consisting of a preliminary reaction product cam.・With the development of electrical equipment, there is a strong demand for smaller and simpler mounting methods, and in response, there is a desire to develop lightweight and high-performance electronic materials. A variety of research is underway to meet these demands. Especially for printed wiring boards, materials with better heat resistance, dimensional stability, and electrical properties are required to increase the degree of Vli of circuits. This printed wiring board usually uses a copper-clad laminate made of a hardening resin such as phenol resin or epoxy resin. Curable resins generally have a drawback of poor electrical properties, particularly poor electrical properties in a 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, and dimensional stability, and their mechanical properties are highly temperature dependent. Application fields and uses are extremely limited.

It is well known that polyphenylene ether resin exhibits excellent thermal, mechanical, and electrical properties, and is a resin that can be widely used as an industrial material and as a general molding material. The preparation method is also US Patent No. 3506874.
No., Special Publication No. 17880, Special Publication No. 52-50
As shown in extremely well-known documents such as Publication No. 991, these polyphenylene ether resins are essentially thermoplastic resins, and are inferior in heat resistance and solvent resistance compared to thermosetting resins. There is. Therefore, a number of methods have been proposed to increase resistance to organic solvents.
For example, a method of curing polyphenylene ether resin using metal flucorate as a catalyst (Japanese Patent Publication No. 44-297
52Jt publication), a method in which a crosslinking agent is added to a polyphenylene ether resin to form a three-dimensional network structure (US Patent No. 596,146), or a method in which a polyphenylene ether resin NFC thermosetting resin is blended. There are methods of curing it (Kihan 1s50-15519), etc. These methods require high temperatures close to the melting point of the polyphenylene ether resin (temperature t required during molding).
In the case of X, >, the catalyst, crosslinking agent, or thermosetting resin decomposes, causing discoloration and deterioration, as well as the generation of bubbles in the molded product, and various other disadvantages occur, so that it has not been put into practical use.

A curable resin composition of a grafted polyphenylene ether resin, which is obtained by graft polymerizing a compound containing one or more olefinically unsaturated double bonds in the molecule to a polyphenylene ether resin, has not been disclosed to date. 1 No 0 The present inventors have developed a high-performance electronic material using a copolymer obtained by graft-polymerizing a compound containing one or more olefinically unsaturated double bonds in the molecule to a polyphenylene ether resin. With the goal of providing this invention, we conducted extensive research and discovered a curable graft copolymer resin composition that exhibits excellent performance that did not exceed fII48 with resins obtained by modifying the graft copolymer using conventional methods. ,
The molded product obtained from this composition retains as much of the various properties inherent to the graft copolymer as possible, while exhibiting particularly excellent solvent resistance, heat resistance, electrical properties, and moldability. This invention improves the drawbacks of the graft copolymer.Hereinafter, the structure of the present invention will be explained.

First, the poly-7-enylene ether resin, which is the thermal component 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. A homopolymer consisting of only one set of units (in the formula, cap and R2 are lower alkyl groups having 1 to 3 carbon atoms, and B5 represents a hydrogen atom or a lower alkyl group having 1 to 5 vertical primes) species b) It may also be a copolymer in which two or more types are combined,
For example, poly(2,6-dimethyl-1,4-phenylene)ether, poly(2-methyl-6-ethyl-1,4
-phenylene)ether, poly(25-dimethyl-1
, 4-phenylene) ether;
2.6-cyphthylphenol and 2. Copolymers derived from S, 6-dimethylphenol and 2-methyl-
6-Nityru-14-phenylenenitert25,6-)
Poly(2,6-dimethyl-1,4-phenylene)ether and poly(2,6-dimethyl-1,4-phenylene)ether and -dimethylphenol and 2.5.6-drimethylphenol and 2! Copolymers derived from I) are useful as practical polyphenylene ether resins. These polyphenylene ether-based resins are expected to have a number average molecular weight of 1000 to 5000. If a low molecular weight resin is used, the solubility is good and the workability is good. On the other hand, a high molecular weight resin Component b of the present invention contains one or more olefinically unsaturated double bonds in the molecule. Number of carbon atoms is 2-18
It is 18f or a mixture of two or more unsaturated compounds, and the compounds include styrene, vinyltoluene, dimethylstyrene, chlorostyrene, α-methylstyrene,
Aromatic vinyl compounds such as tart-butylstyrene, vinylphenol, and vinylpyridine; Unsaturated nitrile compounds such as acrylonitrile, methacrylonitrile, and ethacrylonitrile; Unsaturated compounds such as methyl acrylate, butyl acrylate, methyl methacrylate, and vinyl acetate Ester compounds; butadiene, isoprene, 1. Conjugated diene compounds such as s-pentadiene; halogenated vinyl compounds such as vinyl chloride and vinylidene chloride; olefins such as ethylene and propylene; among these compounds, aromatic vinyl compounds, unsaturated nitrile compounds,
Particularly preferred are unsaturated ester compounds.

The above Kb component is used as a radical polymerization initiator, such as di-tcrt-butyl peroxide, benzoyl peroxide, lauroyl peroxide, dicumyl peroxide, potassium persulfate, ammonium persulfate, sodium perborate, etc. One or two of the peroxides
Polyphenylene ether tree 31910 with one or more seeds as one component
0 parts by weight. Used in the range of s to 15 parts by weight,
The component (11) of the present invention is produced by graft polymerization.The reaction conditions are in the range of 70 to 500°C,
Usually, a reaction is carried out using a moderate 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 one component polyphenylene ether resin from which the polymerization catalyst has been removed, and the reaction is carried out directly is especially recommended. This is preferable in terms of streamlining the process. Of course, the use of other methods is not ruled out.

In addition, the amount of component a and component b used is (a) component 1 to 98 wt.
H. Even the range of 1 to 40 wt of each component per can is selected in consideration of the intended use.

Polyfunctional maleimide II, which is one of the components of the present invention (
cl is a polymaleimide compound represented by the following general formula (21) having two or more maleimide groups in the molecule; , Xl and X2 are water atoms, halogen atoms, or lower alkyl groups, k represents an integer of 2 or more, usually 10 or less (0), and this polymaleimide compound also includes prepolymers derived from it. The maleimide represented by the above formula can be prepared by a method known per se in which maleic anhydride is reacted with a polyamine having 2 to 5 7-mino groups to form maleamic acid, and then maleamic acid is cyclized by dehydration. It is preferable that the polyamine used be an aromatic amine in terms of the heat resistance of the final resin, but if flexibility and flexibility of the resin are desired, an alicyclic amine may be used alone. Alternatively, they may be used in combination.Although primary amines are particularly desirable as polyvalent amines in terms of reactivity, iris 2a amines can also be used.Suitable amines include meta- or para-phenylene. Diamine, meta- or para-xylylenediamine-1,4- or 13-
Cyclohexanediamine, hexahydroxylylenediamine% 4.4'-diaminobiphenyl, bis(4-7
minophenyl)methane, bis(4-7minophenyl)ether, bis(4-7i nophenyl)sulfone, bis(
4-7 minnow 3-methylphenyl)methane, bis(4-
Amino-5,5-dimethylphenyl)methane, bis(4
-7minophenyl)cyclohexa/,2,2-bis(4
-7minophenyl)propane, 2,2-bis(4-amino-3-methylphenyl)propane, bis(4-amino-3-chlorophenyl)methane, 2.2-bis(3゜5
-') -j lomo4-7minophenyl)propane, bis(4-7minothenyl)phenylmethane 13.4-diaminophenyl-4? -7 Mino 7 Enil Mekun 1.1
-bis(4-yminophenyl)-1-phenylethane
Melamines with S-triacyphm, polyamines made by reacting aniline with phorine and linking benzene rings with methylene bonds. In the present invention, the above-mentioned polyfunctional maleimide is Instead of using K in the form of a polymer, it can also be used in the form of a prepolymer, for example with the amines exemplified above.

The polyfunctional cyanate ester (d), which is another summer component of the present invention, is an organic compound having two or more cyanate ester groups and a prepolymer thereof, and suitable cyanate esters are as follows. Formula % Formula % (3) (m in the formula is an integer of 2 or more and usually 5 or less, Rs is an aromatic organic group, and the cyanate ester group is attached to the aromatic ring of the organic group R. 0, which is a compound represented by 1. !
I-7 or 1,4-dicyanatobenzene, 1,5.5
- tridineptanatobenzene, 1°3-51.4-11.
6-11.8-12.6- or 2.7-dicyanatonaphthalene, 1°36-dolicyanatonaphthalene, 4
．． 4-diaminobiphenyl, bis(4-cyanatophenyl)methane, 2.2-bis(4-cyanatophenyl)propane%2.2-bis(3°5-dichloro-4-cyanatophenyl)propane, 2 .2-bis(5,5-
dibromo-4-cyanatophenyl)propane, bis(
4-cyanatophenyl) ether, bis(4-cyanatophenyl) thioether, bis(4-cyanatophenyl) sulfone, tris(4-cyantophenyl) phosphite, tris(4-cyantophenyl)
phosphates, and cyanate esters obtained by the reaction of novolacs with cyanogen halides. In addition to these, Tokuko Sho 41-1928, Tokko Sho 45-184
68, Special Publication No. 4J-4791, Special Publication No. 45-11712
, Japanese Patent Publication No. 46-41112, Japanese Patent Publication No. 47-26855, and Japanese Patent Application Laid-open No. 51-43149. Also, the above-mentioned polyfunctional cyanate esters can be used with monomineral acids, Lewis acids, These prepolymers can be used as prepolymers obtained by polymerization in the presence or absence of catalysts such as salts such as sodium carbonate or lithium chloride, phosphate esters such as tributylphosphine, or epoxy compounds. is formed by trimerization of the cyanide group in the cyanate ester.
ym-triazine in the molecule.

In the present invention, it is preferable to use the prepolymer having an average molecular weight of 400 to 6,000.

Furthermore, the above-mentioned polyfunctional cyanate ester can also be used in the form of a prepolymer with an amine.
Examples of No. 7 include those used for the synthesis and modification of the polyfunctional maleimide described above. Of course, the above-mentioned polyfunctional cyanate ester, its prepolymer, and prepolymer with amine can be used in the form of a mixture. Preliminary reaction mixtures obtained by pre-reacting in the presence of such compounds can also be suitably used.

The composition ratio of the above components (It and (11) can be appropriately selected from a wide range, but the grafted polyphenylene ether 11 fat of the component (summer) is 2 to 99 wt, and the component (summer) is 98 to 1 wt. As %, C component 0-80wt1
The range force λ of s%d component 0-98vt* is selected in consideration of the application and the like.

In addition, the composition can be prepared by mixing component (1) into a solution of component (1), or by separating component (1) into a powder and mixing it with component (II) using a Henschel mixer or the like. It is produced by adding it to a mixer and heating and stirring it.

Although the method of curing the resin composition of the present invention is arbitrary,
A heating method is usually used, and generally 50 to 400
i in the range of °C! The time required for curing is selected, particularly at a temperature in the range of 100 to 530°C, depending on the mode of use of the resin composition of the present invention, i.e., the thin m film b1
Alternatively, it depends on the force 1 of the relatively thick molded product or laminate, but it is usually 30 seconds to 10 hours, as long as the time sufficient for the inner fluff resin composition to harden is selected.

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 isotopic forces such as cobalt-40, sunlight, and light sources such as tungsten lamps, low-pressure or high-pressure mercury lamps, etc. It is also possible to adopt a method that uses active energy sources such as emitted light. Particularly in the case of photocuring, photosensitizers known per se, 9
Organic carbonyl compounds such as 4-henzoin, benzoin methyl ether, penzathrone, r-thraquinone, and benzophenone, and combinations of sensitizing dyes such as eosin, erythrosin, and acridine with various amines are added to the resin composition of the present invention per resin solid content. It can be added in an amount ranging up to 5.5% by weight, and this photocurable resin composition is useful for applications in the field of coatings.

Various additives may be added to the resin composition of the present invention in order to adjust the curing properties of the resin, modify the properties of the resin itself, or impart desired properties to the final resin product. be able to. 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, but the purpose is to promote the network structure! , a catalyst can be included in the composition. Examples of such catalysts include organic acids such as lead naphthenate/lead stearate, zinc octylate, zinc naphthenate, tin oleate, dibutyltin maleate, manganese naphthenate, cobalt naphthenate, resin IIR lead, etc. Metal salt; Company S J4
, metal chlorides such as ZnCJ2, υCJs, nitriethylenedi, organic bases such as amines, etc. are suitable.0 The amount of these catalysts used varies depending on the ms+ of the catalyst, the application and curing conditions, and - Although not generally prescribed, it is preferable to use a catalyst in a general sense, ie, in an amount of 5 parts by weight or less based on the total resin solids content.

The uninvented resin composition # can be blended with a natural, semi-synthetic or synthetic resin in an amount that does not impair the inherent properties of the composition, in order to impart desired performance depending on its use. 0 Such resins include drying oils, non-drying oils, oleosin, rosin, shrug, copal, oil-modified rosin, phenol resin, alkyd resin 1 epoxy resin, R resin - melamine resin 1 polyester resin, vinyl butyral resin , vinyl acetate resin, vinyl chloride resin, acrylic resin to silicone resin, rubber, etc., and these may be used in -11 years old or in combination of two or more types.

Furthermore, if desired, reinforcing materials or fillers in the form of MS or powder may be included. Examples of powdered reinforcing materials or fillers include carbon black, finely powdered silica, fired clay, Basic magnesium silicate, cane earth powder, aj remina, calcium envyate, magnesinum legate, magnesium oxide, kaolin, sericite, and boron nitride may be mentioned. "Wear.

Fibrous reinforcement materials include ceramic fiber, asbestos,
Examples of the fibers include inorganic fibers such as carbon fiber, glass fiber, slag-wool, and carbon 7-iper, and natural fibers and synthetic fibers such as paper, pulp, wood flour, cotton, linters, and polyimide fibers. The above-mentioned ridge fiber reinforcement material includes small fibers,
It can be used in the form of stable, tow, web, woven fabric, non-woven fabric, or paper product. These reinforcing materials or fillers vary depending on the application, but for use in laminated materials and molding materials, 1 fltll of wood 10011t is used.
It can be used in an amount of r 4001tilst for WK. In addition, for the purpose of making the resin composition of the present invention flame retardant, the polyphenylene ether resin has the well-known Ji111
IA agents such as phosphoric acid esters, halogenated organic compounds, or a combination of halides and antimony compounds can also be blended.Furthermore, for the purpose of coloring the resin composition, titanium oxide, etc. Coloring pigments such as white pigments, yellow lead, carbon black, iron black, molybdenum red, cadmium yellow, and cadmium red, or various organic dyes and pigments can also be contained. When used for purposes,
In addition to the above coloring pigments, there are also rust preventive raw materials such as zinc chromate), aRs base/gala, zinc, and strontium chromate; anti-sagging agents such as aluminum steering acid; dispersants; thickeners; Pigment: All you have to do is mix in paint compounding agents that are well known to each other, such as ill fuel.◎
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 powder base material, and lamination molding using a molding material impregnated into a fiber reinforcing material. Here, unless otherwise specified, parts and numbers are based on weight.

Examples 1-2 and Comparative Example 1 Intrinsic viscosity determined with chloroform at 25°C.

45 dll/f of poly(2,6-cymethyl-1.4-
Phenylene ether) 60 parts of 100IS% styrene, 110 parts of ethylbenzene and 6 parts of di-tart-butyl peroxide were uniformly mixed at 100°C with stirring.
After decomposition, nitrogen gas was blown into the reaction system to purge the oxygen gas in the reaction system. After polymerization for 2.5 hours under control L so that the reactor internal temperature was maintained between 145 and 150°C, the contents Take out the items and dry them at 180℃ using a vacuum dryer.
The mixture was dried for 14 hours to remove ethylbenzene and unreacted styrene to obtain a grafted polyphenylene ether resin.

The polystyrene content of this grafted polyphenylene ether resin was determined to be 9 wt% by infrared collection spectrum analysis.
Met.

This graphite polyphenylene ether resin and bis(4-
(maleimidophenyl)methane in the proportions shown in Table 1 using a Henschel mixer, and the resulting mixed compositions were compression-molded at 250 DEG C. and 150 DEG C. for 2 hours. Cut the obtained molded product into 3 squares and use Croixform.
Continuous Sotsuta sled extraction was carried out for 0 hours, and the residue that did not elute in 10 hours was expressed in %.The results are shown in Table 1. Table 1 also shows a graph excluding bis(4-maleimidophenyl)methane (results for compressed crystals containing only toborifuenisin ether resin) for comparison.

Example 3 Grafted polyphenylene ether resin obtained in Example 1
! Part IO and 70 parts of 2,2-bis(4-cyanatophenyl)propane were thoroughly mixed in a Henschel mixer.

The obtained mixed composition was heated at a temperature of 250 t for 2 hours, 15
Compression molding was performed at a pressure of 01f/C1f. The obtained molded product was cut into 5 m square pieces, subjected to continuous Soxhlet extraction with chloroform for 20 hours, and the residue that did not dissolve in wa form was expressed in %. The results are shown in Table 111.

Shimajo Examples 4 to 5 and Comparative Example 2 Intrinsic viscosity determined in chloroform at 25°C and 5°C was 0°34 d
lAlt phenylene ether copolymer (0.5 mol% of 2.6-cyphthylphenol and 2.S
, 6-) Random copolymer derived from 5 mol% of trimethylphenol) 150 parts, 64 parts of methyl methacrylate, 180 parts of ethylbenzene and
Add 6 parts of art-butyl peroxide and heat to 100°C.
After uniformly dissolving with stirring, nitrogen gas was blown into the reaction system to purge the oxygen gas in the reaction system until the internal temperature of the reactor reached 150℃.
Polymerization was carried out for 2.5 hours while keeping the temperature around 0.degree.

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 Gra7 tobolyphenylene ether resin. According to infrared absorption spectrum analysis, the polymethyl methacrylate content was 5 wt%.

This grafted polyphenylene ether resin and bis(4-
Maleimidophenyl Jmethane and maleimidophenyl Jmethane were mixed in a Hennoel mixer in the proportions shown in Table 2, and the resulting mixed compositions were compression molded at 250° C. and 15 billion ml for 2 hours. The obtained molded product was cut into 3 pieces and subjected to continuous Soxhlet extraction with chloroform for 20 hours. The residue not eluted in chloroform was expressed as %. 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 Gelatin polyphenylene ether resin obtained in Example 4
401m and 60 parts of a prepolymer obtained by preliminarily reacting 2.2-bis(4-cyanaFphenyl)propane at 150°C for 3 hours were thoroughly mixed in a Henschel mixer. The obtained mixed composition was heated at 1501W for 2 hours at a temperature of 250°C.
Compression molding was performed at a pressure of 11. The obtained molded product was cut into three simple square pieces and subjected to continuous Soxhlet extraction with chloroform for 20 hours. The results are shown in Table 2.

The glass transition temperature was also measured at the same time.

Example 7 and Comparative Example 3 Intrinsic viscosity measured in chloroform at 25°C is 0°54 d
lA/r phenylene ether copolymer (95 mol % of 2.6-dimethylphenol and 2.3.
6-) Random copolymer derived from 5 mol% of trimethylphenol) 100 parts, styrene 200 parts,
100 parts of ethylbenzene and 2 parts of di-1-butyl peroxide were charged, and after uniformly dissolving them 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°C, and the contents were taken out and dried at 180°C for 14 hours using a vacuum dryer to remove ethylbenzene and unreacted styrene. was removed to obtain a grafted polyphenylene ether resin. According to infrared absorption spectrum analysis, the polystyrene content is 3.
It was 4%.

Poly()z-nylmethylene) polymaleimide produced by reacting poly(phenylmethylene) polyamines obtained by the reaction of aniline and formaldehyde with maleic anhydride (having an average of 3 N-phenylmaleimide residues in the molecule) 30 parts of 2.2-bis(4-cyanatophenyl)propane and 70 parts of 2.2-bis(4-cyanatophenyl)propane were pre-reacted at 110°C for 2 hours to obtain 5 parts of maleimide-cyanate ester prepolymer and 95 parts of nylene ether resin were thoroughly mixed with a Henschel mixer. The obtained mixed composition was placed between steel foils to a predetermined thickness of 1.5 mm.
s + m ~ t, 611s) VC, 250℃
A double-sided steel-clad specimen was prepared by compression molding at a temperature of 150 b/d for 2 hours and a pressure of 150 b/d.

The copper foil of this test piece was peeled off and cut into approximately 5mm square dice, and Soxhlet extraction was performed continuously in chloroform for 20 hours.
%Met. Comparative example.

As a result, 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 extracted into chloroform was less than 1%.

Various tests were conducted using the test pieces, and the results are shown in Table 5.

Example 8 and Comparative Example 4 Intrinsic viscosity measured in chloroform at 25°C is 0°50 d
finidine ether copolymer of lAlt (95 mol% of 2.6-dimethylphenol and 2.S
, 6-) Random copolymer derived from 5 mol% of trimethylphenol) 200 parts, styrene 150 parts, acrylic R2) 1 full 70 parts, ethylbenzene 2
00 parts and 5 parts of dicumyl peroxide at 100℃
After uniformly dissolving <@ while stirring, nitrogen gas was introduced into the reactor to purge the oxygen gas in the reaction system.9 The internal temperature of the reactor was 14
Polymerization was carried out for 2 hours while controlling the temperature between 5 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. Infrared absorption spectroscopy showed that the content of styrene-7curanido'9yl copolymer was 28vt%, and the content of acr+7px)lyl in the styrene-acrylonitrile copolymer was 25vt%.

Bis(4-maleimidophenyl)methane 9°8 parts,
2, 2-bis(4-cyanatophenyl)boupan 8
7.8 parts, and epoxy resin (product name: Ebitsu)
152. Shell Chemical Exhibition) 2.4% was reacted with stirring at 130°C for 4 hours to produce a prepolymer consisting of maleimides, cyanate esters and epoxy compounds, and 40 parts of the prepolymer and the grafted polyphenylene ether 114 obtained above. 60 parts of fat were thoroughly mixed with a Henschel mixer.

The obtained assembly composition is placed between steel foils to a predetermined thickness of 1.5
The specimens were placed in such a manner that the parts were m ~ 1, 6 m) k, and compression molded at a temperature of 250° C. for 2 hours and a pressure of 100 rad to create a double-sided steel-clad specimen. The steel foil of this test piece was peeled off and cut into approximately 3IllI square pieces, and Soxhlet extraction was carried out continuously for 20 hours with anform. As a result, the amount of residue that could not be eluted into chloroform was 97%. As a comparative example, a similar Soxhlet extraction was performed on a test piece made only of the Gra7 polyphenylene ether resin.

The amount of residue not eluted in chloroform was 1% or less.

Various tests were conducted using the test pieces, and the results are shown in Table 3.

Example 9 Grafted polyphenylene ether resin obtained in Example 1
20 parts and Il! Prepolymer consisting of maleimide, cyanate ester and epoxy compound obtained in Example 8
80 parts and dissolved in toluene to obtain a resin solid content of 25 wt.
% solution and impregnated it into a glass woven fabric, heated to 110°C for 5 minutes, then raised the temperature to 140°C and dried for 15 minutes to obtain a prepreg. 11m long, 2 hours at 200℃, 100℃ pressure.
After lamination molding at Kp/d, the pressure was 10 at 240°C for 4 hours.
It was cured under the conditions of 0 to ν- to obtain a copper-clad laminate with a thickness of 0.4 m.

The test results for this laminate are shown in Table 5.

Example 10 and Comparative Example 5 Intrinsic viscosity measured in chloroform at 25°C is 0°45 d
l'slr pou (2,6-cymethyl-1,4-7 dinilene ether) 150 [-) toluene 250 parts VC1
The mixture was heated to 00°C and stirred to dissolve.

Next, 120 parts of Megyol methacrylate and 5 parts of dicumyl peroxide were added, nitrogen gas was blown in to purge the oxygen gas in the reaction system, and the temperature inside the reactor was controlled to be maintained at around 150°C. Polymerization was continued for 2.5 hours. The contents were taken out and dried at 180° C. for 21 hours using a vacuum dryer to remove toluene and unreacted methyl methacrylate to obtain a grafted polyphenylene ether resin. The content of polymethyl methacrylate was 50% from infrared 1s absorption spectrum analysis.

Poly(phenylmethylene)polymaleimide produced by reacting poly(phenylmethylene)polyamines obtained by the reaction of aniline and formaldehyde with maleic anhydride (having an average of 3 KN-phenylmaleimide residues in the molecule)! The IO part and 70 parts of 2,2-bis(4-cyanatophenyl)propane were reacted at 110°C with stirring for 2 hours to obtain a prepolymer of maleimides and cyanate esters, which was then reacted with 20 parts of the above mixture. 80 parts of the obtained Gra7 polyphenylene ether resin were thoroughly mixed in a Henschel ζ mixer. .

The obtained mixed composition is placed on a copper foil to a predetermined thickness of 1.5~
1. dm) / at a temperature of 250℃ for 2 hours.
A double-sided steel-clad test piece was prepared by compression molding at a pressure of 100 Kv'a11. The steel foil of the test piece was peeled off and cut into approximately 3 square pieces, and the sample was subjected to continuous Soxhlet extraction with chloroform for 20 hours. As a result, the amount of residue that did not release chloroform was 75%.

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 1% or less.

Various tests were conducted using the test pieces, and the results are shown in Table 3.

Example 11 and Comparative Example 6 O, S Od4's measured in chloroform at 25°C
lr phenylene ether polymer (95 mol% of 2.6-cyphthylphenol and 2.5.4% on monomer basis)
-) Random copolymer derived from 5 mol% of trimethylphenol) 10011, butyl acrylate 5
0 parts, 120 parts of ethylbenzene and g-tert-
After charging 2 parts of butyl peroxide and homogenizing the mixture at 100°C with stirring, nitrogen gas was blown in to purge the oxygen gas in the reaction system, and the internal source of the 8 reactor was 145.
Polymerization was carried out for 2 hours while controlling the temperature to be maintained at ℃ms. Take out the contents and use a vacuum dryer to dry
The mixture was dried at ℃ for 21 hours to remove ethylbenzene and unreacted butyl acrylate to obtain a graft copolymer. The content of polybutyl acrylate was 20 wt%.

, bis(4-maleimidophenyl)methane 10
and 2,2-bis(4-cyanatophenyl)propane
A prepolymer was prepared by preliminary reaction 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 sufficiently mixed in a Henschel ζ mixer.

The resulting mixed composition was heated to a cylinder temperature of 25°C.
The mixed composition was extruded and pelletized using a λB-30 twin-screw extruder (manufactured by Nakagama Kikai Seisakusho) K set at 0°C, and the pelletized mixed composition was placed between copper foils to a predetermined thickness (1.5 to 1.6 mm). ■)k
The specimen was placed at 250° C. for 2 hours at 1 g of KLvIbl to prepare a double-sided steel-clad test piece.

The copper foil of this test piece was peeled off, cut into approximately 3 fl 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 in chloroform 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.

The amount of residue that could not be eluted in the fluoroform was 1% or less.

Various tests were conducted using the test pieces, and the results are shown in Table 3.

Example 12 Bis(4-maleimidophenyl)methane 9°8 parts, 2
．． 2-bis(4-cyanatophenyl)propane 87.
8 parts and epoxy resin (trade name: Epicor) 15
2. A prepolymer consisting of maleimide, cyanate ester and epoxy compound was prepared by pre-reacting 2.4 parts of Shell Chemical Co., Ltd.) at 130°C for 4 hours, and 85 parts of the prepolymer and the same graft as obtained in Example 4 were prepared. 15 parts of polyphenylene ether resin were dissolved in toluene,
A glass fiber was impregnated with a solution hL having a resin solid content of 25 wt%, and then heated to 110° C. for 5 minutes, and then heated to 140° C. and dried for 15 minutes to obtain a prepreg. The prepregs obtained in this way were laminated with four sheets, and copper foil was layered on both sides at 140°C for 0, s hours, at 150°C for 0.5 hours, and then at 180°C for 1 hour at a pressure of 100°C. ,
Further, it was post-cured at 240° C. for 4 hours to obtain a copper-clad laminate having a thickness of 0.4 m.

The test results for this laminate are shown in Table 3.

The testing method for betting performance in the table is as follows.

(1) Chloroform extraction residue: Peel off the copper foil.

It was cut into dice about 311+Im square and subjected to continuous Soxhlet extraction for 20 hours.

Before extraction test for unextractable residues Expressed as a percentage of the weight.

(2) Glass transition temperature: Peel off copper foil, width 0°7
A slender rod-shaped test piece with a length of about 1.2 mm and a length of about 70 m was cut out, and measured using a kink-free damping lid viscoelasticity measuring device (manufactured by HBBC Jinsha Co., Ltd.) Jk.

(3) Steel foil peeling strength: After making parallel cuts 10 m wide on the steel foil surface, the steel foil was pulled and peeled in a direction perpendicular to one surface, and the stress at that time was measured using a Tensilon. (4) Dielectric constant and dielectric voltage #! : After peeling off the copper foil, it was cut into 50 square pieces and measured at IMHz using a #electrical loss measuring device.

(-Solder heat resistance: Cut the test piece into 25A1 square pieces.

If both sides are steel-clad, tear off one box.

Create a measurement sample. Han at 260℃ Float the sample in the bath with the copper foil side facing down.

Time until peeling occurs is characterized by To patent application Sanyu Gas Chemical Co., Ltd. Representative Kazuyoshi Nagano

Claims (1)

[Claims] (1) Polyphenylene ether resin (aIVc compound containing one or more olefinically unsaturated double bonds in the molecule (grafted polyphenylene resin obtained by graft polymerization of BL), and (厘) polyfunctional maleimide ,!9(cl, polyfunctional cyanate ester tA(a),': Preliminary reaction of Js and the above (c) with (dl) - mixing or preliminary reaction of at least one selected from the group Toi consisting of 1) Curable resin composition made by reacting