JP2003138127A - Filler for thermosetting polyphenylene ether resin and resin composition using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyphenylene ether resin composition having excellent moldability and excellent mechanical strength, flame retardance and heat resistance after curing without deteriorating dielectric characteristics. SOLUTION: This curable polyphenylene ether resin composition comprises (a) the thermosetting polyphenylene ether resin and (b) a filler subjected to surface treatment with at least one kind of silane coupling agent selected from silane compounds having structures represented by formula (1), formula (2), formula (3) and formula (4) in an amount of 1-800 pts.wt. based on 100 pts.wt. of the component (a).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a surface-treated filler and a thermosetting polyphenylene ether resin composition containing them. Furthermore, the present invention relates to a composite material composed of the resin composition and a substrate, a film composed of the resin composition, a resin-coated metal foil composed of the resin composition film and a metal foil, and a cured product thereof.

[0002]

2. Description of the Related Art In recent years, there has been a remarkable trend toward miniaturization and high density of mounting methods in the field of electronic devices for communication, consumer use, industrial use, etc., and also in terms of materials, heat resistance and dimensional stability Properties, high strength, electrical characteristics, and excellent moldability are being demanded. For example, as a printed wiring board, a copper clad laminate made of a phenol resin, an epoxy resin, a polyphenylene ether resin or the like has been conventionally used. Although these have various performances in a well-balanced manner, they may not be sufficient for use as laminated plates or sealing materials in terms of dimensional stability and flame retardancy due to the coefficient of thermal expansion with other constituent materials. . Therefore, in order to cope with such a situation, a filler such as silica is used to reduce the coefficient of thermal expansion of the resin composition, and a filler such as aluminum hydroxide, high melting point glass, and melamine polyphosphate is used for flame retardancy. Attempts have been made to improve sex.

However, since the filler and the resin have a low affinity, the molding processability is lowered due to the increase of the melt viscosity due to the addition of the filler and the dispersibility is reduced due to the aggregation of the filler. There was a problem that the mechanical strength of the obtained molded product was lowered.

[0004]

The object of the present invention is to provide an excellent polyphenylene ether resin by a thermosetting polyphenylene ether resin composition containing a filler surface-treated with a specific silane coupling agent. An object of the present invention is to provide a curable polyphenylene ether-based resin composition which is excellent in molding processability without impairing dielectric properties, has heat resistance after curing, and has excellent mechanical strength and flame retardancy.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a thermosetting polyphenylene ether resin, formula (1), formula (2), and formula (3) A composition comprising a filler surface-treated with at least one silane coupling agent selected from the silane compounds having a structure represented by the formula (4), thereby improving the affinity and fluidity of both. The inventors have found that the mechanical strength of the obtained cured product can be improved, and completed the present invention.

[0006]

[Chemical 3]

(Where R1 is an alkyl group having 1 to 4 carbon atoms, R2 is an alkyl group having 1 to 4 carbon atoms or a phenyl group, and R3 is an alkenyl group having 2 to 4 carbon atoms). , 1. Surface treatment of the filler with at least one silane coupling agent selected from silane compounds having a structure represented by formula (1), formula (2), formula (3), or formula (4) Characteristic surface treatment filler.

[0008]

[Chemical 4]

(Wherein R1 is an alkyl group having 1 to 4 carbon atoms, R2 is an alkyl group having 1 to 4 carbon atoms or a phenyl group, and R3 is an alkenyl group having 2 to 4 carbon atoms). (A) a thermosetting polyphenylene ether-based resin, and (b) at least one kind selected from silane compounds having a structure represented by formula (1), formula (2), formula (3), or formula (4) The filler surface-treated with the silane coupling agent is 1 to 800 based on 100 parts by weight of the component (a).
A thermosetting polyphenylene ether-based resin composition, characterized by containing (b) part by weight.

[0010]

[Chemical 5]

(Where R1 is an alkyl group having 1 to 4 carbon atoms, R2 is an alkyl group having 1 to 4 carbon atoms or a phenyl group, and R3 is an alkenyl group having 2 to 4 carbon atoms). A thermosetting composite material comprising the second thermosetting polyphenylene ether resin composition of the present invention and a substrate. 4. A cured composite material obtained by curing the third thermosetting composite material of the present invention. 5. A thermosetting film comprising the second thermosetting polyphenylene ether resin composition of the present invention.

6. A cured film obtained by curing the fifth thermosetting film of the present invention. 7. A metal foil with a thermosetting resin, which comprises the sixth thermosetting film of the present invention and a metal foil. 8. A metal foil with a thermosetting resin obtained by curing the metal foil with a thermosetting resin according to the seventh aspect of the present invention. 9. A laminated board having at least one insulating layer selected from the third thermosetting composite material of the present invention, the fifth thermosetting film, and the metal foil with a thermosetting resin according to the seventh aspect. Is.

The present invention will be described in detail below.
The filler before the surface treatment used in the present invention is not particularly limited, barium sulfate, calcium carbonate,
Inorganic fillers such as barium titanate, silicon oxide powder, amorphous silica, talc, clay, mica powder, melamine phosphate, melamine polyphosphate and polyphosphoric acid amide, organic fillers such as silicon powder, nylon powder and fluorine powder Can be given. The shape of these fillers is preferably 50 μm or less in average particle diameter, more preferably 10 μm.
The following powders can be used in any of spherical, fibrous, and amorphous shapes. If the average particle size is larger than 50 μm, the coarse particles hinder the molding of a fine electronic circuit.

The silane compound used as the surface treating agent of the present invention is represented by the formula (1), the formula (2), the formula (3) and the formula (4).
It is at least one silane coupling agent selected from silane compounds having a structure represented by:

[0015]

[Chemical 6]

(Wherein R1 is an alkyl group having 1 to 4 carbon atoms, R2 is an alkyl group having 1 to 4 carbon atoms or a phenyl group, and R3 is an alkenyl group having 2 to 4 carbon atoms). The substituent R1 having 1 to 4 carbon atoms
Is an alkyl group having 1 to 4 carbon atoms or a phenyl group, and the substituent R3 is an alkylene group having 2 to 4 carbon atoms. Considering the reactivity with the filler, the substituent R1 preferably has 1 and 2 carbon atoms, and specific examples thereof include a methyl group and an ethyl group. Substituent R2
Is preferably an alkyl group having 2 to 4 carbon atoms in view of the production cost of the silane compound, and specific examples thereof include a propyl group. Further, the substituent R3 is preferably an alkenyl group having 2 to 3 carbon atoms, and specific examples thereof include a vinyl group and an allyl group.

The filler (b) obtained by the surface treatment reacts with the alkoxy group in the silane compound structure to form a chemical bond, and reacts with the polar group contained in the filler to improve the affinity between the filler and the resin. improves. Further, by crosslinking reaction with a compound having radical reactivity such as triallyl isocyanurate and / or triallyl cyanurate in the resin composition, the affinity between the filler and the resin is further improved and the mechanical strength is improved. Improve. The amount of surface treatment of the filler is not particularly limited, and depends on the specific surface area of the filler, but is preferably 0.1 to 10 wt% with respect to the untreated filler.

If this treatment amount is less than 0.1 wt%,
Sufficient fluidity of the resin composition using these fillers and mechanical strength of the molded product cannot be obtained, and if it is more than 10 wt%, the fillers will rather agglomerate or the flame retardant performance will decrease, which is preferable. Absent. A more preferable range of throughput is
It is 0.3 to 5 wt%. The method of surface treatment is not particularly limited, but while stirring the filler with a kneading machine such as a Henschel mixer, it is possible to use the formula (1), the formula (2), the formula (3), and the formula (4). A dry method in which a surface treatment is performed by adding a solution in which a silane compound having a structure represented by alcohol is added, and a wet method in which a filler is mixed in the solution and then the solvent is distilled off are exemplified. To be

The thermosetting polyphenylene ether resin used as the component (a) of the present invention contains a polyphenylene ether resin (including modified products) as a component. The content of the polyphenylene ether-based resin (including modified products) is the thermosetting polyphenylene ether-based resin 10
It is 40 to 98 parts by weight, preferably 43 to 90 parts by weight, based on 0 parts by weight.

Preferred examples of the above polyphenylene ether resin include poly (2,6-dimethyl-1,4-phenylene ether) obtained by homopolymerization of 2,6-dimethylphenol, and poly (2,6-dimethyl). -1,4-
Phenylene ether) styrene graft polymer, 2,
Copolymer of 6-dimethylphenol and 2,3,6-trimethylphenol, 2,6-dimethylphenol and 2-
Copolymer of methyl-6-phenylphenol, 2,6-
A polyfunctional polyphenylene ether resin obtained by polymerizing dimethylphenol in the presence of a polyfunctional phenol compound, for example, JP-A-63-301222 and JP-A-1.
Examples thereof include copolymers containing the units of the general formulas (A) and (B) as disclosed in JP-A-297428.

Further, the polyphenylene ether-based resin referred to in the present invention includes a modified product, and a preferable example of such a modified product is a polyphenylene ether resin containing an unsaturated group (JP-A-64-96628). , JP 1-
No. 113425, JP-A-11-113426), and a reaction product of a polyphenylene ether resin with an unsaturated carboxylic acid and / or an acid anhydride. The molecular weight of the polyphenylene ether resin used in the present invention is 30 ° C., 0.5 gr.
Viscosity number ηsp / c measured with a chloroform solution of 1 / dl
Can be favorably used. It is preferably in the range of 0.2 to 0.9.

Next, as the resin compounded in addition to the above polyphenylene ether resin, any resin may be used as long as it does not impair the object of the present invention. As such a resin, specifically, a phenol resin, an epoxy resin, a diallyl phthalate, divinylbenzene, a polyfunctional acryloyl compound, a polyfunctional methacryloyl compound, a polyfunctional maleimide, a polyfunctional cyanate ester,
Polyfunctional isocyanates, unsaturated polyesters, triallyl isocyanurates, triallyl cyanurates, polybutadienes, crosslinkable polymers such as styrene-butadiene / styrene-butadiene-styrene, hydrogenated block copolymers, various thermoplastic resins, various The thermosetting resin and the like are listed. These are generally compounded for the purpose of improving the physical properties of a substrate produced by laminating and molding a composite material, a resin-coated metal foil and / or a film.

Preferred examples of the thermosetting polyphenylene ether resin used in the present invention include polyphenylene ether and triallyl isocyanurate and / or triallyl cyanurate, polyphenylene ether containing an unsaturated group and triallyl isocyanurate and / or
Or triallyl cyanurate, unsaturated carboxylic acid and / or
Alternatively, a reaction product of an acid anhydride and a polyphenylene ether resin, triallyl isocyanurate and / or triallyl cyanurate, etc. may be mentioned. The blending amount of each component in these systems is selected according to the purpose.

The blending ratio of the component (b) is 10 parts of the component (a).
1 to 800 parts by weight, preferably 3 parts by weight, based on 0 parts by weight
~ 500 parts by weight. When the amount of the component (b) is less than 1 part by weight, the performance expected of the filler such as flame retardancy of the thermosetting polyphenylene ether resin composition of the present invention is insufficient, which is not preferable. Further, when the amount exceeds 800 parts by weight, the effect of the filler addition such as the improvement of the thermal expansion coefficient is further improved, but the fluidity of the resin composition is lost, and the effect of forming a laminate with the metal foil is improved. It is not preferable because the adhesiveness decreases.

As a method for mixing the above components (a) and (b), a solution mixing method in which the two components are uniformly dissolved / dispersed in a solvent is adopted, but the dispersibility of the component (b) is further improved. Therefore, it is preferable to use a disperser such as a planetary system, a ball mill or a bead mill system, or a three-roll mill system. As the solvent used in the solution mixing method,
Aromatic hydrocarbons such as benzene, toluene, xylene,
Examples of the solvent include halogen solvents such as dichloromethane, chloroform and trichloroethylene, and THF. These can be used alone or in combination.

The thermosetting polyphenylene ether-based resin composition of the present invention undergoes a crosslinking reaction by heating to be cured, but radical initiation is carried out for the purpose of lowering the reaction temperature at that time or accelerating the crosslinking reaction of unsaturated groups. You may use it, including an agent. The amount of the radical initiator used in the curable polyphenylene ether resin composition of the present invention is 0.1 to 10 parts by weight, preferably 0.1 to 8 parts by weight, based on 100 parts by weight of the component (a). .

Typical examples of the radical initiator will be given below.
Benzoyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di (t-
Butyl peroxy) hexyne-3, di-t-butyl peroxide, t-butyl cumyl peroxide, α, α
-Bis (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, dicumyl peroxide, di-t
-Butylperoxyisophthalate, t-butylperoxybenzoate, 2,2-bis (t-butylperoxy) butane, 2,2-bis (t-butylperoxy) octane, 2,5-dimethyl-2, Examples thereof include peroxides such as 5-di (benzoylperoxy) hexane, di (trimethylsilyl) peroxide and trimethylsilyltriphenylsilylperoxide.

A cured product of a thermosetting composite material comprising the thermosetting polyphenylene ether resin composition of the present invention and a substrate, a cured product of a thermosetting film comprising the resin composition,
The cured product of the thermosetting laminate composed of the thermosetting film composed of the resin composition and the metal foil is obtained by thermosetting the composition described above. The heating conditions vary depending on the type of radical initiator,
It is selected in the range of 80 to 300 ° C, more preferably 120 to 250 ° C. The curing time is 1 minute to 10 hours, more preferably 1 minute to 5 hours.

The thermosetting polyphenylene ether resin composition of the present invention contains additives and fillers in the composition in an amount within a range that does not impair the original performance for the purpose of imparting desired performance depending on the application. It is also possible to use it by including it. For example, additives such as imidazole-based, thiazole-based, triazole-based, silane coupling agents, and other copper adhesion promoters can be used. Further, if necessary, known and commonly used colorants such as phthalocyanine blue, phthalocyanine green, iodin green, disazo yellow, titanium oxide, and carbon black can be used. It is also possible to use a chlorine-based, bromine-based, or phosphorus-based flame retardant or flame retardant auxiliary together for the purpose of further improving the flame retardancy.

Next, the curable composite material of the present invention and its cured product will be described. The thermosetting composite material of the present invention,
(A) Thermosetting polyphenylene ether resin, (b)
Filler surface-treated with at least one silane coupling agent selected from the group consisting of silane compounds having structures represented by formula (1), formula (2), formula (3), and formula (4) , (C) base material.

[0031]

[Chemical 7]

(Wherein R1 is an alkyl group having 1 to 4 carbon atoms, R2 is an alkyl group having 1 to 4 carbon atoms or a phenyl group, and R3 is an alkenyl group having 2 to 4 carbon atoms). As the base material, various kinds of glass cloth such as roving cloth, cloth, chopped mat, surfing mat, asbestos cloth, metal fiber cloth and other synthetic or natural inorganic fiber cloth; polyvinyl alcohol fiber, polyester fiber, acrylic fiber, wholly aromatic Woven or non-woven fabrics obtained from liquid crystal fibers such as group polyamide fibers, aromatic polyester fibers, polybenzazole fibers, and synthetic fibers such as polytetrafluoroethylene fibers; cotton cloth,
Natural fibers such as linen and felt; carbon fiber cloth; cellulosic natural cellulosic cloth such as kraft paper, cotton paper, paper-glass mixed fiber paper, etc. may be used alone or in combination of two or more kinds.

(C) in the thermosetting composite material of the present invention
The ratio of the components is 5 to 90 parts by weight, preferably 10 to the total amount of the components (a), (b) and (c).
80 parts by weight, more preferably 20 to 70 parts by weight.
When the amount of component (c) is less than 5 parts by weight, the amount is less, the dimensional stability and strength after curing of the curable composite material are insufficient, and when the amount of the base material is more than 90 parts by weight, a cured product of the curable composite material is obtained. Is inferior in dielectric properties and is not preferable.

In the curable composite material of the present invention, if necessary, other than the silane coupling agent of the present invention, the performance is not impaired for the purpose of improving the adhesiveness at the interface between the resin composition layer and the substrate. A known coupling agent can be used. As this coupling agent, a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, a zircoaluminate coupling agent, or the like can be used.

Examples of the method for producing the curable composite material of the present invention include a method of uniformly dissolving / dispersing the curable polyphenylene ether resin composition of the present invention in a solvent, impregnating a base material, and then drying. To be Examples of the solvent used here include, in addition to the aromatic hydrocarbon solvent and the halogen solvent used in the production of the resin composition of the present invention, a ketone solvent, dimethylformamide, dimethylsulfoxide, and the like. Used alone or as a mixture.

Impregnation is carried out by dipping, coating or the like. The impregnation can be repeated a plurality of times as necessary, and at this time, the impregnation can be repeated using a plurality of solutions having different compositions and concentrations, and a plurality of solutions having different compositions and concentrations can be used. It is possible to repeat the impregnation and finally adjust the resin composition and the resin amount to be desired. The cured product of the curable composite material of the present invention is obtained by curing the curable composite material thus obtained by a method such as heating. The manufacturing method is not particularly limited, and for example, a plurality of curable composite materials may be overlapped and each layer may be bonded under heat and pressure, and at the same time, heat curing may be performed to obtain a cured body having a desired thickness. . It is also possible to obtain a cured product having a new layer structure by combining a cured product that has been adhesively cured once and a cured product.

Lamination and curing are usually carried out using a hot press or the like.
It will be done at the same time, but both can be done independently
Yes. That is, the uncured product obtained by laminating in advance
Or heat-treating a semi-curable curable composite material or another
It can also be cured by treating with a method.
Laminating and curing are performed at a temperature of 80 to 300 ° C. and a pressure of 0.
1 to 500 kg / cm ², Time range from 1 minute to 10 hours,
More preferably, the temperature is 150 to 250 ° C. and the pressure is 1 to 10.
0 kg / cm², The time can be 1 minute to 5 hours.
it can.

Next, the thermosetting film will be described. The thermosetting film is a film made of a thermosetting polyphenylene ether resin composition, and the thickness of the film is 1 μm to 5 mm, preferably 5 μm.
~ 1 mm. As a method for producing the thermosetting film of the present invention, the thermosetting polyphenylene ether-based resin composition of the present invention is uniformly dissolved / dispersed in a solvent and formed on a self-supporting film or the like, and then peeled off. It is obtained by doing. Examples of the method for forming a film include a method of forming a film by a doctor blade method or the like, and an extrusion molding using an extruder equipped with a T-die. Examples of the solvent used here include, in addition to the aromatic hydrocarbon solvent and the halogen solvent used in the production of the resin composition of the present invention, a ketone solvent, dimethylformamide, dimethylsulfoxide, and the like. Used alone or as a mixture.

The self-supporting film mentioned here is used as a reinforcing material for maintaining the shape of the thermosetting resin film, and is a stack of arbitrary films. Specific examples include polyethylene terephthalate film, polyimide film, aramid film and the like. The thermosetting film of the present invention is obtained by curing the thermosetting film by a method such as heating under the same conditions as the cured composite material of the present invention.

Next, the metal foil with thermosetting resin will be described. The term "metal foil with thermosetting resin" used herein means a thermosetting film made of a thermosetting polyphenylene ether resin composition and a metal foil. The thickness of the film is not particularly limited, but is usually 0.5 μm to 5 mm. The metal foil used here is preferably a conductive metal foil, such a metal foil is easily available, and since it can be easily etched, for example, a copper foil, an aluminum foil, Examples include tin foil and gold foil. The thickness is not particularly limited, but preferably 200 μm or less,
More preferably, it is 100 μm or less.

A method for producing the metal foil with a thermosetting resin of the present invention will be described. As a method of forming a film of a thermosetting polyphenylene ether resin composition, for example, a method of applying the components (a) and (b) to a metal foil, or a thermosetting resin composition prepared in advance Examples of the method include a method of heating and pressure-bonding a metal foil on the film made of, a method of laminating a metal of copper or aluminum on the film made of a thermosetting resin composition by means such as sputtering, vapor deposition, and plating. Further, the metal foil and the thermosetting resin film may be adhered by an adhesive. Examples of the adhesive include epoxy-based, acrylic-based, phenol-based, and cyanoacrylate-based adhesives, but are not particularly limited thereto. Further, the surface of the metal foil which is in contact with the thermosetting resin film may be roughened and / or surface-treated with a coupling agent, imidazole, triazole, thiazole or the like. As the coupling agent, a general one such as a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, a zircoaluminate coupling agent can be used.

The thermosetting resin-coated metal foil of the present invention is obtained by curing it by a method such as heating under the same conditions as the cured composite material of the present invention. Finally, the laminated plate of the present invention will be described. On the substrate, the thermosetting composite material of the third invention, the curing composite material of the fourth invention, the metal foil with the thermosetting resin of the fifth invention, the metal foil with the curing resin of the sixth invention are layered according to the purpose. It is constructed by stacking.
The manufacturing method is not particularly limited, for example, a plurality of the thermosetting composite material and a metal foil with a curable resin are laminated on a substrate, and each layer is adhered under heat and pressure while performing thermal crosslinking. , Obtain a laminated board of desired thickness,
Stack multiple copper foils with thermosetting resin on the board,
It is possible to obtain a laminate having a desired thickness by bonding the layers under heat and pressure and at the same time thermosetting. The metal foil can be used as both the surface layer and the intermediate layer. It is also possible to repeat lamination and curing a plurality of times to successively form a multilayer.

The substrate used in the present invention is not particularly limited, but examples thereof include a double-sided copper-clad laminate and a single-sided copper-clad laminate. When the double-sided copper-clad laminate or the single-sided copper-clad laminate is used, the circuit pattern may be formed on the substrate in advance. As described above, the thermosetting composite material using the thermosetting polyphenylene ether resin composition of the present invention and the cured composite material thereof, the metal foil with the thermosetting resin, the metal foil with the curable resin, and the laminate are made of polyphenylene. In addition to the excellent fluidity during melt molding while maintaining the excellent dielectric properties of ether resins, it also has a low coefficient of thermal expansion after curing and excellent heat resistance, so it can be used as an insulating material in the field of the electrical industry. You can In particular, it is suitable for single-sided printed wiring boards, double-sided printed wiring boards, multilayer printed wiring boards, flexible printed wiring boards, etc. in the electric industry.

[0044]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail below with reference to Examples and Comparative Examples. The present invention is not limited to these. Molding of the obtained curable composition and evaluation of physical properties of the cured product were carried out according to the following methods. The physical properties of the cured product obtained as described above were measured by the following methods. [Evaluation of Physical Properties of Thermosetting Composite Material] 1. Three resin flowable thermosetting composite materials were layered and pressed at 180 ° C. for 10 minutes with a press molding machine at a surface thickness of 30 kg / cm ² , and the protruding resin composition was weighed to determine the volume of the resin composition. . A value obtained by dividing this by the volume of only the resin composition in the curable composite material before pressing was shown. [Evaluation of physical properties of cured composite material] 1. The measurement was performed at a dielectric constant and a dielectric loss tangent of 1 MHz. 2. Cut the cured product from which the solder heat resistant copper foil has been removed into 25 mm squares, 260
It was floated in a solder bath at ℃ for 120 seconds, and the change in appearance was visually observed. 3. Thermal expansion characteristics and glass transition temperature The cured product from which the copper foil has been removed is cut into a 7 mm square, and the thermal expansion coefficient (compression) and the glass transition temperature in the thickness direction are increased at a rate of 20.
It was measured by a thermomechanical analyzer at a rate of ° C / min. (The coefficient of thermal expansion here is a numerical value obtained by dividing the rate of change of the sample thickness when the temperature of the sample is raised from 30 ° C. to 150 ° C. by 120 ° C. (150 ° C.-30 ° C.) which is the change in temperature. .) 4. A test piece with a width of 20 mm and a length of 100 mm was cut out from the cured copper foil peel strength, and after making parallel cuts with a width of 10 mm on the copper foil surface, the speed was 50 mm / min in the direction perpendicular to the surface. Then, the copper foil was continuously peeled off, and the stress at that time was measured by a tensile tester, and the minimum value of the stress was shown. 5. Length 127 mm, width 12.7 from the cured product from which flame-retardant copper foil has been removed
mm test pieces were cut out, and the test was performed according to the UL-94V test method.

[Evaluation of Physical Properties of Metal Foil with Cured Resin] 1. The measurement was performed at a dielectric constant and a dielectric loss tangent of 1 MHz. 2. Cut the cured product from which the solder heat resistant copper foil has been removed into 25 mm squares, 260
It was floated in a solder bath at ℃ for 120 seconds, and the change in appearance was visually observed. 3. Thermal expansion characteristics and glass transition temperature A strip-shaped test piece with a width of 4 mm and a length of 20 mm was cut out from the cured product from which the copper foil was removed, and the thermal expansion coefficient (tensile) in the surface direction.
The glass transition temperature was measured by a thermomechanical analyzer at a temperature rising rate of 20 ° C./min. (The coefficient of thermal expansion here means the rate of increase in the sample thickness when the temperature of the sample is increased from 30 ° C to 150 ° C, which is the change in temperature of 120 ° C (150
(° C-30 ° C). ) 4. Copper foil peeling strength From the cured product obtained by sandwiching the cured composite from which the copper foil has been removed with the resin side of the two copper foils with thermosetting resin and curing, a width of 20 m
Cut out a test piece of m and 100 mm in length, and width 1 on the copper foil surface.
After making a parallel cut of 0 mm, the copper foil is continuously peeled off at a speed of 50 mm / min in the direction perpendicular to the surface, and the stress at that time is measured by a tensile tester, and the stress The lowest value was shown. 5. From the cured body from which the flame-retardant copper foil has been removed, length 127 mm, width 12.
A 7 mm test piece was cut out, and the test was performed according to the UL-94V test method. 6. Tensile strength, tensile elastic modulus Two pieces of copper foil with thermosetting resin are laminated so that the copper is on the outside, and the copper foil is removed from the heat-cured cured product, and a test piece with a length of 200 mm and a width of 15 mm is prepared. The tensile strength and the tensile elastic modulus were measured by cutting out and obtaining the stress-strain diagram of the stress obtained at a test speed of 5 mm / min with a tensile tester using a continuous non-contact type video extensometer. .

[Evaluation of Physical Properties of Cured Film] 1. Thermal expansion characteristics and glass transition temperature From the cured product from which the copper foil has been removed, a 7 mm square test piece is cut out, and the thermal expansion coefficient (compression) and the glass transition temperature in the thickness direction are increased at a heating rate of 20 ° C./min. It was measured by a thermomechanical analyzer. (The coefficient of thermal expansion here is a numerical value obtained by dividing the rate of change of the sample thickness when the temperature of the sample is raised from 30 ° C. to 150 ° C. by 120 ° C. (150 ° C.-30 ° C.) which is the change in temperature. .) 2. Bending strength From the cured product with copper foil removed, length 20 mm, width 25 m
Bending strength was measured from a stress-deflection curve obtained at a test speed of 1 mm / min using a 3-point bending tester.

In the examples below, the following components were used. <Silane compound for surface treatment> In a 1000 cc three-necked flask, triallyl isocyanurate (Nippon Kasei Co., Ltd.)
100 parts by weight of Co., Ltd.) and 400 ml of dehydrated toluene (made by Wako Pure Chemical Industries, Ltd.) are put and stirred, 60 parts by weight of triethoxysilane (made by Tokyo Kasei Co., Ltd.) is dropped with a dropping funnel, and then platinum is added. -Adding 0.6 parts of divinyltetramethylsiloxane complex (manufactured by Chisso Corporation), 12
A heating reaction was carried out at 0 ° C. for 4 hours. All the reactions were performed under a nitrogen atmosphere. Then, the toluene solution was distilled off, and the silane compound of the formula (5) and the formula (6) was obtained by refining under reduced pressure.

[0048]

[Chemical 8]

<Modified polyphenylene ether resin> 30
Poly (2,6-dimethyl-) having a viscosity number ηsp / c of 0.40 measured at 0.5 ° C. in a chloroform solution of 0.5 gr / dl.
100 parts by weight of 1,4-diphenylene ether) and 1.5 parts by weight of maleic anhydride were dry blended at room temperature, then the cylinder temperature was 300 ° C. and the screw rotation speed was 230.
It was extruded by a twin-screw extruder under the condition of rpm. 30 ℃,
The viscosity number ηsp / c of the reaction product measured with a 0.5 gr / dl chloroform solution was 0.43. <Polymerization Initiator> 2,5-Dimethyl-2,5-di (t-butylperoxy) hexyne-3 (Perhexin 2 manufactured by NOF Corporation)
5B) <Silica> Spherical silica (average particle size: 0.8 to 1.2 μ)
m; manufactured by Admatechs Co., Ltd. Admafine SO-C
3) was used as a raw material and treated with the above-mentioned silane coupling agent for surface treatment (treatment amount 1.0 wt.%). <Triallyl isocyanurate> TAIC (trade name, manufactured by Nippon Kasei Co., Ltd.) <Rubber> • HIPS 8117 (trade name, manufactured by Asahi Kasei Corporation) • Tuftec H1285 (trade name, manufactured by Asahi Kasei Corporation) <Flame retardant> Melamine polyphosphate (average particle size: 1 μm;
DSM) was used as a raw material and treated with the above-mentioned silane coupling agent for surface treatment (treatment amount 1.0 wt.%). <Glass cloth> Made of E glass with a unit weight of 48 g / m ²

[0050]

[Example 1] [Thermosetting composite material] Modified polyphenylene ether resin, triallyl isocyanurate, silica treated with a silane compound (5) for surface treatment and having a surface treatment amount of 1 wt%, a flame retardant, a radical initiator and auxiliary materials Rubber (HIPS8117) with the composition shown in Table 1 at 80 ° C
A toluene solution having a solid content of 45 wt% was prepared. Glass cloth (E glass cloth) was immersed in this solution for impregnation, and dried in an air oven to obtain a thermosetting composite material. Next, a plurality of the above-mentioned thermosetting composite materials are superposed so that the thickness after curing becomes about 0.8 mm, and 35 μm copper foil is placed on both surfaces thereof and 180 ° C. in a vacuum press,
A cured composite material was obtained at a surface pressure of 30 kg / cm ² for 1 hour.

[0051]

Example 2 [Metallic Foil with Thermosetting Resin] The toluene solution shown in Table 1 prepared in the same manner as in Example 1 was cast and coated on a copper foil of 18 μm to form a film having a thickness of 60 μm. A metal foil with a curable resin was prepared. Then, 18 on the surface of the film with the thermosetting resin.
Place copper foil of μm on the vacuum press at 180 ℃, surface pressure of 30
A metal foil with a cured resin was obtained in kg / cm ² for 1 hour.

[0052]

Examples 3 and 4 Examples 1 and 2 except that silica and the flame retardant are treated with the silane compound (6) for surface treatment.
A thermosetting composite material, a thermosetting resin-attached metal foil, and a cured composite material or a cured resin-attached metal foil, which are cured products of the thermosetting composite material and the thermosetting resin, were prepared in the same manner as above.

[0053]

[Example 5] [Thermosetting resin film] Modified polyphenylene ether resin, triallyl isocyanurate, surface treatment amount of 1 wt% treated with silane compound (5) for surface treatment
% Silica, flame retardant, radical initiator and rubber (Tuftec H1285) having the composition shown in Table 1 to prepare a toluene solution having a solid content of 45 wt% at 80 ° C. The solution was used as a support and coated on a PET film of 50 μm and dried at 60 ° C. for 20 minutes to prepare a thermosetting polyphenylene ether resin composition film having a thickness of 60 μm. After that, the thermosetting resin film was peeled off from the PET film, and a plurality of thermosetting resin films were laminated so that the film thickness after molding was about 1 mm, and 35 μm on both sides thereof.
Place the copper foil in a vacuum press at 200 ℃, surface pressure 30kg
/ Cm ² , cured for 1 hour to obtain a cured film.

[0054]

[Example 6] [Laminate] A copper foil surface of a double-sided copper-clad laminate having a thickness of 0.3 mm was blackened (formed with copper oxide) and then reduced to form an adhesive base, and the heat generated in Example 4 was used. A curable resin-coated metal foil having a resin film thickness of 60 μm was laminated on both sides and heat-cured to prepare a sequentially laminated plate. Observation of a cross section of this successive laminated plate with an optical microscope showed no occurrence of resin cracks.

[0055]

[Comparative Examples 1 and 2] Treatment of silica and melamine polyphosphate which is a flame retardant with N-phenyl-γ-aminopropyltrimethoxysilane (KBM573 manufactured by Shin-Etsu Chemical Co., Ltd.) (treatment amount 1.0 wt%). Example 1 except
A curable composite material, a curable resin-attached metal foil and a cured composite material or a cured resin-attached metal foil, which are cured products thereof, were prepared in the same manner as in No. 2 by the same method. The fluidity and mechanical strength were lower than those of the examples.

[0056]

Comparative Example 3 A thermosetting resin film was prepared with the same composition as in Example 5 except that the silica surface was treated with KBM573 (treatment amount 1.0 wt%). The obtained cured resin film was inferior in flexural strength to Example 5.

[0057]

[Comparative Example 4] [Laminate] A curable resin prepared in Comparative Example 2 was prepared by blackening the surface of the copper foil of a double-sided copper-clad laminate having a thickness of 3 mm (forming copper oxide) and then reducing it to form an adhesive base. Metal foils having a resin film thickness of 60 μm were laminated on both sides and heat-cured to prepare a laminated sheet. When a cross section of this successive laminated plate was observed with an optical microscope, the occurrence of resin cracks was observed.

[0058]

[Table 1]

[0059]

The curable polyphenylene ether-based resin composition of the present invention comprises a polyphenylene ether-based resin composition containing a filler surface-treated with a specific silane coupling agent. It has excellent moldability without impairing its excellent dielectric properties, and has excellent mechanical strength and flame retardancy in addition to heat resistance after curing.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08J 5/24 C08J 5/24 C08K 9/06 C08K 9/06 C09K 3/00 C09K 3/00 R F term (reference) 4F071 AA51 AB26 AE17 AF14 AF40 AF45 AF47 AH13 BA02 BB02 BC02 4F072 AA02 AA04 AA05 AA07 AB03 AB05 AB11 AB28 AB29 AD42 AE01 AF21 AG03 AH04 AK05 AL11 4F100 AA20H AB01B AB17 AB17B AB33B AG00 AH06A AH07A AK54A AS00A AT00A BA01 BA02 BA03 BA04 BA05 BA06 BA13 CA08 CA23A DG01 DG11 DH01A EJ08A EJ64A EJ82 GB43 JB13A JG05 JJ07 JK01 JL01 4H049 VN01 VP01 VQ59 VR21 VR43 VU21 VU22 VW02 4J002 CH071 DJ016 FB146 FD016 GF00 GQ00

Claims (9)

[Claims] 1. The filler is at least one silane coupling agent selected from silane compounds having structures represented by formula (1), formula (2), formula (3) and formula (4). A surface-treated filler for thermosetting polyphenylene ether resin, which is characterized by being surface-treated. [Chemical 1] (Here, R1 is an alkyl group having 1 to 4 carbon atoms, and R2 is
An alkyl group having 1 to 4 carbon atoms or a phenyl group, R3 is
An alkenyl group having 2 to 4 carbon atoms) 2. A thermosetting polyphenylene ether resin, and (b) a silane compound having a structure represented by formula (1), formula (2), formula (3) or formula (4). Based on 100 parts by weight of the component (a), the filler surface-treated with at least one silane coupling agent
A thermosetting polyphenylene ether-based resin composition comprising 1 to 800 parts by weight of component (b). [Chemical 2] (Here, R1 is an alkyl group having 1 to 4 carbon atoms, and R2 is
An alkyl group having 1 to 4 carbon atoms or a phenyl group, R3 is
An alkenyl group having 2 to 4 carbon atoms) 3. A thermosetting composite material comprising the thermosetting polyphenylene ether resin composition according to claim 2 and a substrate. 4. A cured composite material obtained by curing the thermosetting composite material according to claim 3. 5. A thermosetting film comprising the thermosetting polyphenylene ether resin composition according to claim 2. 6. A cured film obtained by curing the thermosetting film according to claim 5. 7. A metal foil with a thermosetting resin, comprising the thermosetting film according to claim 6 and a metal foil. 8. A metal foil with a cured resin obtained by curing the metal foil with a thermosetting resin according to claim 7. 9. A thermosetting composite material according to claim 3, a thermosetting film according to claim 5, and at least one insulating layer selected from the metal foil with a thermosetting resin according to claim 7. Laminated board characterized by.