HK1086851B - Curable resin composition, curable film and cured film - Google Patents

Description

Curable resin composition, curable film, and cured film

Technical Field

The present invention relates to a curable resin composition which is excellent in low dielectric properties and heat resistance and from which a curable film having no tackiness and good processability can be obtained, a curable film obtained from the above curable resin and a film obtained by curing the above curable film. The curable film or the film in the present invention is suitable as an electrical insulating material for high frequency use and the like.

Background

In recent years, signal bands of CPU clock time (clock time) of information transmission devices such as PHS or portable phones and computers reach GHz band, and higher frequencies have come to be used. The dielectric loss of an electrical signal is proportional to the product of the square root of the dielectric constant of the insulator that makes up the circuit, its dielectric loss tangent, and the frequency of the signal used. Thus, as the frequency of the signal used increases, the dielectric loss increases. The dielectric loss suppresses the electric signal, and deteriorates reliability of the electric signal. In order to prevent such destruction, it is necessary to select a material having a small dielectric constant and a small dielectric loss tangent as the insulator. Fluorine-containing resins, polyolefin resins, polystyrene resins, polyphenylene ether resins, and the like are recommended as such materials. However, although these resins are excellent in low dielectric properties, most compounds have problems in chemical resistance or moldability. Films made of the above resins as electrical insulating materials, such as films made of polyphenylene ether resins, have ｃA problem in terms of elasticity (e.g., JP- ｃA-7-18836 2); films made from low molecular weight styrene compounds such as divinylbenzene tend to be tacky and the products resulting from curing thereof are brittle (e.g. JP-A-200 2-249531). Further, in order to meet the demand for low dielectric properties, the present inventors have developed ｃA vinyl compound derivative of ｃA bifunctional polyphenylene ether oligomer (e.g., JP-A-2004-059644). These derivatives are excellent in low dielectric properties. However, films obtained from these derivatives are susceptible to chipping. Thus, improvements are still needed.

Disclosure of Invention

An object of the present invention is to provide a curable resin composition from which a tack-free curable film can be obtained, which has a low dielectric constant and a low dielectric loss tangent while still obtaining a cured product having excellent heat resistance from the composition, a curable film obtained from the above curable resin, and a film obtained by curing the above curable film.

The present invention provides a curable resin composition containing the essential components of a vinyl compound of the general formula (1) and a high molecular weight compound having a weight average molecular weight of at least 10,000.

The present invention further provides a curable film made by processing the above curable resin into film form.

The present invention still further provides a film obtained by curing the above curable film.

Wherein R is₁、R₂、R₃、R₄、R₅、R₆And R₇Identical or different, represent a hydrogen atom, a halogen atom, an alkyl group or a halogen-substituted alkyl group.

- (O-X-O) -represents a moiety of formula (2) or formula (3) or represents at least two moieties of formula (2) and/or formula (3),

wherein R is₈、R₉、R₁₀、R₁₄And R₁₅Identical or different, represents a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group; r₁₁、R₁₂And R₁₃The same or different, represents a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group,

wherein R is₁₆、R₁₇、R₂₂And R₂₃Identical or different, represents a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group; r₁₈、R₁₉、R₂₀And R₂₁The same or different, represents a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group, and A is a linear, branched or cyclic hydrocarbon having 20 or less carbon atoms.

- (Y-O) -represents a moiety of formula (4) or a random arrangement of at least two moieties of formula (4).

Wherein R is₂₄And R₂₅Identical or different, represents a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group; r₂₆And R₂₇The same or different, represents a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group,

z represents an organic group having at least one carbon atom, which group may contain an oxygen atom, a nitrogen atom, a sulfur atom and/or a halogen atom.

If at least one of a and b is not 0, then a and b are integers from 0 to 30, respectively, and

c and d are integers of 0 or 1, respectively.

Effects of the invention

A tack-free curable film or coating film can be obtained by using the curable resin composition of the present invention. The film obtained by curing the curable film or the coating film has low dielectric properties and high heat resistance, so that the film can be used for an insulating material for high-frequency electric parts, an insulating material for semiconductors, a material for multilayer printed circuit boards, a coating material, a coating, a film for adhesives or condensers, and the like. Therefore, the industrial significance of the present invention is considerable.

Detailed Description

The present inventors have made diligent studies in order to attain the aforementioned object and, as a result, have found that a tack-free curable film obtained by curing a resin composition obtained by combining a high molecular weight compound having a weight average molecular weight of at least 10,000 with a terminal vinyl compound of a bifunctional polyphenylene ether oligomer retaining excellent dielectric properties and high heat resistance of a polyphenylene ether structure while having a specific structure can be obtained, which is capable of producing a cured film having a low dielectric constant and a low dielectric loss tangent. On the basis of the above findings, the present inventors have completed the present invention.

The vinyl compound of the general formula (1) used in the curable resin composition of the present invention is not particularly limited as long as it is selected from the vinyl compounds of the general formula (1) wherein R is₁、R₂、R₃、R₄、R₅、R₆And R₇The same or different, represent a hydrogen atom, a halogen atom, an alkyl group or a halogen-substituted alkyl group; - (O-X-O) -represents a moiety of formula (2) or formula (3) or represents at least two moieties of formula (2) and/or formula (3), wherein R₈、R₉、R₁₀、R₁₄、R₁₅、R₁₆、R₁₇、R₂₂And R₂₃Identical or different, represents a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group, R₁₁、R₁₂、R₁₃、R₁₈、R₁₉、R₂₀And R₂₁Identical or different, represents a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group, A is a linear, branched or cyclic hydrocarbon having 20 or less carbon atoms; - (Y-O) -represents a moiety of formula (4) or a random arrangement of at least two moieties of formula (4), wherein R₂₄And R₂₅Identical or different, represents a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group; r₂₆And R₂₇The same or different, represents a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group; z represents an organic group having at least one carbon atom, which group may comprise an oxygen atom, a nitrogen atom, a sulfur atom and/or a halogen atom; if at least one of a and b is not 0, a and b are integers of 0 to 30, respectively; c and d are integers of 0 or 1, respectively. In these ethylene of the general formula (1)Of the above compounds, the preferred vinyl compound is that wherein R is₁、R₂、R₃、R₄、R₅、R₆And R₇Is a hydrogen atom, R₈、R₉、R₁₀、R₁₄、R₁₅、R₁₆、R₁₇、R₂₂And R₂₃Is an alkyl group having 3 or less carbon atoms, R₁₁、R₁₂、R₁₃、R₁₈、R₁₉、R₂₀And R₂₁Is a hydrogen atom or an alkyl group having 3 or less carbon atoms, Z is a methylene group, and c and d are each 1. Particularly preferred vinyl compounds are those wherein- (O-X-O) -represented by the general formula (2) or the general formula (3) is a moiety of the general formula (5) or the general formula (6), - (Y-O) -represented by the general formula (4) is a moiety of the general formula (7) or the general formula (8), or a random combination of the moieties of the general formula (7) and the general formula (8).

Wherein R is₁₈、R₂₁Represents a hydrogen atom or a methyl group, and A is a linear, branched or cyclic hydrocarbon having 20 or less carbon atoms.

The vinyl compound of the formula (1) preferably has a number average molecular weight of 500 to 3,000. When the number average molecular weight is less than 500, a curable film having tackiness is easily formed. When it is more than 3,000, the solubility of the vinyl compound in the solvent is reduced. The method for producing the vinyl compound is not particularly limited. The vinyl compound can be produced, for example, by the methods disclosed in JP-A-2004-59644 and JP-A-2004-67727.

The amount of the vinyl compound of the general formula (1) in the curable resin composition of the present invention is not particularly limited. However, if the amount of the vinyl compound is too small, it is impossible to obtain desired low dielectric properties, heat resistance, adhesiveness and curing properties. Therefore, the amount of the vinyl compound of the formula (1) in the curable resin composition is preferably 5 to 95% by weight, more preferably 20 to 85% by weight.

The high molecular weight compound having a weight average molecular weight of at least 10,000 used in the curable resin composition of the present invention preferably has film-forming (film-forming) ability while not deteriorating the low dielectric properties and heat resistance of the vinyl compound of the general formula (1). Specific examples of such high molecular weight compounds include butadiene elastomers such as styrene butadiene copolymer (SBR) and acrylonitrile butadiene copolymer; styrene thermoplastic elastomers such as styrene butadiene styrene copolymer, hydrogenated styrene butadiene styrene copolymer, styrene isoprene styrene copolymer (SIS), hydrogenated styrene isoprene styrene copolymer and hydrogenated styrene (butadiene/isoprene) styrene copolymer; and thermoplastic resins such as polystyrene, polyester and polycarbonate. These high molecular weight compounds may be used alone or in combination. Among these high molecular weight compounds, styrene thermoplastic elastomers such as styrene butadiene styrene copolymer, hydrogenated styrene butadiene styrene copolymer, styrene isoprene styrene copolymer, hydrogenated styrene isoprene styrene copolymer and hydrogenated styrene (butadiene/isoprene) styrene copolymer are preferable. In particular, styrene isoprene styrene copolymers, hydrogenated styrene butadiene styrene copolymers, hydrogenated styrene isoprene styrene copolymers, and hydrogenated styrene (butadiene/isoprene) styrene copolymers are more preferable because these copolymers have higher heat resistance.

When a styrene thermoplastic elastomer is used, the styrene content in the elastomer is not particularly limited. When higher heat resistance is required, the styrene content in the elastomer is preferably from 10 to 70 wt%, more preferably from 20 to 50 wt%. Further, the weight average molecular weight of the styrene thermoplastic elastomer is not particularly limited as long as it is at least 10,000. When it is too large, it is difficult to mix the styrenic thermoplastic elastomer with the vinyl compound. Therefore, it is preferably 10,000 to 300,000.

In the curable resin composition of the present invention, the mixing ratio of the vinyl compound of the general formula (1) and the high molecular weight compound is not particularly limited. However, when the amount of the high molecular weight compound is too large, the intended heat resistance and curability cannot be obtained. When the amount of the high molecular weight compound is too small, the film forming ability is lowered. Therefore, the weight ratio of the vinyl compound of the formula (1) to the high molecular weight compound is preferably from 20: 80 to 95: 5, more preferably from 30: 70 to 85: 15.

The curable resin composition of the present invention cures itself under heat. In order to increase the curing speed, and further, to improve processability, economic efficiency, etc., a heat curing catalyst may be added to the curable composition. The thermal curing catalyst is selected from the group of thermal curing catalysts capable of generating a cationic or radical active species capable of initiating polymerization of vinyl groups under conditions of heat or light. For example, the cationic polymerization initiator includes diallyl iodonium salt, triallyl sulfonium salt and aliphatic sulfonium salt, which use BF₄、PF₆、AsF₆Or SbF₆As a counter anion. These cationic polymerization initiators are readily available as commercial products, such as SP70, SP172 and CP66, supplied by Asahi Denka Kogyo K.K., CI2855 and CI2823 supplied by Nippon Soda Co., Ltd., and SI100L and SI150L supplied by Sanshin Chemical Industry Co., Ltd. The radical polymerization initiator includes benzoin compounds such as benzoin and methylbenzoin, acetophenone compounds such as acetophenone and 2, 2-dimethoxy-2-phenylacetophenone, thioxanthone compounds such as thioxanthone and 2, 4-diethylthioxanthone, diazide compounds such as 4, 4 ' -diazidochalcone, 2, 6-bis (4 ' -azidobenzylidene) cyclohexanone and 4, 4 ' -diazidobenzophenone, azo compounds such as azobisisobutyronitrile and 2, 2-azobispropane and hydrazone, organic peroxides such as 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane and 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexyne-3 and dicumyl peroxide. These curing catalysts may be used alone or in combination.

A polymerization inhibitor may be added to the curable resin composition of the present invention to improve the storage stability. The polymerization inhibitor is selected from those commonly known. Examples thereof include quinones such as hydroquinone, methylhydroquinone, p-benzoquinone, chloranil and trimethylquinone, and aromatic glycols. These polymerization inhibitors may be used alone or in combination.

The curable resin composition of the present invention may further contain known flame retardants, fillers, coupling agents, thermosetting resins, dyes, pigments, thickeners, lubricants, antifoaming agents, ultraviolet absorbers, or the like, as necessary, to modify the physical properties thereof.

The flame retardant is selected from those generally known. Examples thereof include halogen flame retardants such as brominated epoxy resins, brominated polycarbonates, brominated polystyrenes, brominated styrenes, brominated phthalimides, tetrabromobisphenol a, pentabromobenzyl (meth) acrylate, pentabromotoluene, tribromophenol, hexabromobenzene, decabromodiphenyl ether, chlorinated polystyrenes, chlorinated paraffins; phosphorus flame retardants such as red phosphorus, tricresyl phosphate, triphenyl phosphate, cresyl diphenyl phosphate, trixylyl phosphate, trialkyl phosphate, dialkyl phosphate, tris (chloroethyl) phosphate, and phosphazene; inorganic flame retardants such as aluminum hydroxide, magnesium hydroxide, zinc borate and antimony trioxide. These flame retardants may be used alone or in combination.

Examples of the fillers include fibrous fillers such as glass fibers, carbon fibers, aramid fibers, silicon carbide fibers, alumina fibers and boron fibers; inorganic whiskers such as silicon carbide, silicon nitride, magnesium oxide, potassium titanate, and aluminum titanate; inorganic needle-shaped fillers such as silica lime, baddeleyite, phosphate fibers and sepiolite; inorganic spherical fillers such as powdery silica, fused silica, talc, alumina, barium titanate, mica and glass spheres; organic fillers such as fine particle polymers obtained by crosslinking (meth) acrylates, styrene, and the like. These fillers may be used alone or in combination.

Examples of the coupling agent include silane type coupling agents such as vinyltrichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, gamma-glycidoxypropylmethyldiethoxysilane, N-beta (aminoethyl) gamma-aminopropylmethylmethoxysilane, gamma-aminopropyltriethoxysilane, N-phenyl-gamma-aminopropyltrimethoxysilane, gamma-mercaptopropyltrimethoxysilane and gamma-chloropropyltrimethoxysilane; a titanate type coupling agent; an aluminum type coupling agent, a zirconium aluminate type coupling agent, a siloxane type coupling agent, and a fluorine type coupling agent. These coupling agents may be used alone or in combination.

Examples of the thermosetting resin include epoxy resins such as bisphenol a type epoxy, bisphenol F type epoxy, phenol novolac type epoxy, cresol novolac type epoxy and dicyclopentadiene novolac type epoxy; (meth) acrylates such as bisphenol A type epoxy (meth) acrylate, phenol novolac type epoxy (meth) acrylate, trimethylolpropane tri (meth) acrylate, and dipentaerythritol hexa (meth) acrylate; vinyl compounds such as styrene, divinylbenzene and divinylnaphthalene; cyanate ester resins such as bisphenol a dicyanate, tetramethyl bisphenol F cyanate, bisphenol M cyanate and phenol novolac type cyanate; an oxetane resin; benzocyclobutene resins and benzoxazine resins. These thermosetting resins may be used alone or in combination.

The curable film of the present invention is explained below. The curable film of the present invention is obtained by processing the curable resin composition of the present invention into a film form. The curable resin composition is processed into a film form by, for example, dissolving the curable resin composition in a solvent, adding the resulting resin composition solution to a release film or a conductor foil such as a copper foil, and then drying the solution.

Examples of the solvent used include acetone, methyl ethyl ketone, ethylene glycol monoethyl ether acetate, propylene glycol dimethyl ether, toluene, xylene, tetrahydrofuran, and N, N-dimethylformamide (dimethylfomamide). The solvent is not limited to the above examples. These solvents may be used alone or in combination.

The drying conditions for drying the solvent are not particularly limited. However, when the drying temperature is too low, the solvent may easily remain in the curable film, and when the temperature is too high, the vinyl compound may be cured. Therefore, it is preferable to dry at a temperature of 40 to 150 ℃ for 1 to 90 minutes. The thickness of the curable film can be adjusted by the concentration of the resin composition and the applied thickness. If the application thickness is too thick, the solvent tends to remain inside during the drying time. Therefore, the thickness of the curable film is preferably 0.1 to 500 μm.

The film of the present invention can be obtained by curing the curable film of the present invention under heating. The curing conditions vary depending on whether a polymerization initiator is present and whether other thermosetting resins are used in combination. Curing is preferably carried out at 150 to 250 ℃ for 0.5 to 5 hours. In addition, pressure may be used as needed.

Examples

The present invention is specifically explained below by referring to examples and comparative examples, and the present invention is not limited to these examples. The detection method is as follows.

1) The number average molecular weight and the weight average molecular weight were obtained by Gel Permeation Chromatography (GPC). Data processing was performed according to the GPC curve and the molecular weight calibration curve of the sample. The molecular weight calibration curve is obtained by calculating an approximation of the relationship between the molecular weight of the standard polystyrene and its dissolution time according to the following formula,

LogM＝A₀X³+A₁X²+A₂X+A₃+A₄/X²

wherein M: molecular weight, X: elution time-19 (min), and a: coefficient of performance

2) With 2, 6-dimethylbenzenePhenol as a standard reference and dry dichloromethane as a solvent, which was determined to be 3600cm in IR analysis (method of solution cell; cell thickness 1mm)^-1The hydroxyl group equivalent is determined from the absorption strength of (c).

3) With respect to appearance, the appearance of the curable film can be visually observed for the presence of cracks.

O: no crack X: occurrence of cracks

4) As for the tackiness, the presence or absence of tackiness of the curable film at 25 ℃ can be judged by touching the film with a finger.

O: no viscosity X: viscosity of

5) According to TMA tension method, the glass transition temperature was measured under conditions of a load of 5g, a span of 10mm and a temperature increase rate of 10 ℃ per minute.

6) As for the dielectric constant and the dielectric loss tangent, the value at 10GHz can be measured by the cavity resonance interference method.

7) With respect to chemical resistance, the film was immersed in toluene at 25 ℃ for 24 hours, and the change in appearance was observed.

O: no change X: dissolution

8) As for flexibility, a film was cut into a strip 15mm wide and 100mm long, which was bent 180 degrees in the major axis direction, and then a cylinder weighing 2kg and having a flat bottom surface and a diameter of 70mm was placed on the wrinkle for 30 seconds to observe whether there was a crack.

O: no crack X: finding cracks

Synthesis example 1

Synthesis of bifunctional phenylene Ether oligomer

A12 liter long reactor equipped with a stirrer, a thermometer, an air-introducing tube and a baffle was charged with 3.88g (17.4mmol) of CuBr₂0.75g (4.4mmol) of N, N' -di-t-butylvinyldiamine, 28.04g (277.6 mmol)) And 2600g of toluene. These components were stirred at a reaction temperature of 40 ℃. 129.32g (0.48mol) of 2,2 ', 3, 3', 5, 5 '-hexamethyl- (1, 1' -bisphenyl) -4, 4 '-diol, 292.19g (2.40mol) of 2, 6-dimethylphenol, 0.51g (2.9mmol) of N, N' -di-t-butylvinyldiamine and 10.90g (108.0mmol) of N-butyldimethylamine were dissolved in 2300g of methanol in advance to prepare a mixed solution. The mixed solution was added dropwise to the mixture in the reactor over 230 minutes while bubbling a nitrogen-air mixed gas having an oxygen concentration of 8% at a rate of 5.2L/min with stirring. After the completion of the addition, 1500g of water in which 19.89g (52.3mmol) of tetrasodium ethylenediaminetetraacetate was dissolved was added to the stirred mixture to terminate the reaction. The aqueous and organic layers were separated. The organic layer was then washed with 1N aqueous hydrochloric acid and then with pure water. The resulting solution was concentrated to 50% by weight with an evaporator to obtain 833.40g of a toluene solution of a bifunctional phenylene ether oligomer (resin "A"). The resin "A" had a number average molecular weight of 930, a weight average molecular weight of 1460, and an equivalent of hydroxyl group of 465.

Synthesis of vinyl Compounds

A reactor equipped with a stirrer, a thermometer and a reflux tube was charged with 833.40g of a toluene solution of resin "A", 160.80g of vinylbenzylchloride (CMS-P; supplied by Seimi chemical Co., Ltd.), 1600g of methylene chloride, 12.95g of benzyldimethylamine, 420g of pure water and 175.9g of a 30.5% by weight aqueous sodium hydroxide solution, and the mixture was stirred at a reaction temperature of 40 ℃ for 24 hours. The organic layer was washed with 1N aqueous hydrochloric acid and then with pure water. The thus-obtained solution was concentrated by an evaporator, and the concentrated solution was added dropwise to methanol to obtain a solid, which was recovered by filtration. The solid was dried under vacuum to give 501.43g of vinyl compound "B". The vinyl compound "B" had a number average molecular weight of 1,165 and a weight average molecular weight of 1,630.

Synthesis example 2

Synthesis of bifunctional phenylene Ether oligomer

To a tube equipped with a stirrer, a thermometer and an air inletAnd a baffled Long reactor having a volume of 12 liters was charged with 9.36g (42.1mmol) of CuBr₂1.81g (10.5mmol) of N, N' -di-t-butylvinyldiamine, 67.77g (671.0mmol) of N-butyldimethylamine and 2600g of toluene. These components were stirred at a reaction temperature of 40 ℃. 129.32g (0.48mol) of 2,2 ', 3, 3', 5, 5 '-hexamethyl- (1, 1' -bisphenyl) -4, 4 '-diol, 878.4g (7.2mol) of 2, 6-dimethylphenol, 1.22g (7.2mmol) of N, N' -di-t-butylvinyldiamine and 26.35g (206.9mmol) of N-butyldimethylamine were dissolved in 2300g of methanol in advance to prepare a mixed solution. The mixed solution was added dropwise to the mixture in the reactor over 230 minutes while bubbling a nitrogen-air mixed gas having an oxygen concentration of 8% at a rate of 5.2L/min with stirring. After the end of the addition, 1500g of water in which 48.06g (126.4mmol) of tetrasodium ethylenediaminetetraacetate was dissolved was added to the stirred mixture to terminate the reaction. The aqueous and organic layers were separated. The organic layer was then washed with 1N aqueous hydrochloric acid and then with pure water. The resulting solution was concentrated to 50% by weight with an evaporator to obtain 1,981g of a toluene solution of a bifunctional phenylene ether oligomer (resin "C"). The resin "C" had a number average molecular weight of 1,975, a weight average molecular weight of 3,514, and an equivalent of hydroxyl group of 990.

Synthesis of vinyl Compounds

A reactor equipped with a stirrer, a thermometer and a reflux tube was charged with 833.40g of a toluene solution of resin "C", 76.7g of vinylbenzylchloride (CMS-P), 1,600g of dichloromethane, 6.2g of benzyldimethylamine, 199.5g of pure water and 83.6g of a 30.5% by weight aqueous sodium hydroxide solution. The mixture was stirred at a reaction temperature of 40 ℃ for 24 hours. The organic layer was washed with 1N aqueous hydrochloric acid and then with pure water. The thus-obtained solution was concentrated with an evaporator. The concentrated solution was added dropwise to methanol to obtain a solid, which was recovered by filtration. The recovered solid was dried under vacuum to obtain 450.1g of vinyl compound "D". The vinyl compound "D" had a number average molecular weight of 2,250 and a weight average molecular weight of 3,920.

Synthesis example 3

Synthesis of bifunctional phenylene Ether oligomer

A12 liter long reactor equipped with a stirrer, a thermometer, an air introduction tube and a baffle was charged with 13.1g (0.12mol) of CuCl, 707.0g (5.5mol) of di-n-butylamine and 4000g of methyl ethyl ketone. These components were stirred at a reaction temperature of 40 ℃. 410.2g (1.6mol) of 4, 4' -methylenebis (2, 6-dimethylphenol) and 586.5g (4.8mol) of 2, 6-dimethylphenol were dissolved in 8,000g of methyl ethyl ketone in advance to prepare a mixed solution. The mixed solution was added dropwise to the mixture in the reactor while bubbling with 2L/min of air, and stirred. An aqueous solution of disodium dihydrogen ethylenediamine tetraacetate was added to the stirred mixture to terminate the reaction. Then washed with 1N aqueous hydrochloric acid and then with pure water. The resulting solution was concentrated by an evaporator and dried under reduced pressure to obtain 946.6g of a bifunctional phenylene ether oligomer (resin "E"). The resin "E" had a number average molecular weight of 801, a weight average molecular weight of 1,081, and an equivalent weight of hydroxyl group of 455.

Synthesis of vinyl Compounds

To a reactor equipped with a stirrer, a thermometer and a reflux tube were charged 480.0g of resin "E", 260.2g of vinylbenzylchloride (CMS-P), 2,000g of tetrahydrofuran, 240.1g of potassium carbonate and 60.0g of 18-crown-6 ether. The mixture was stirred at a reaction temperature of 30 ℃ for 6 hours. The resulting solution was concentrated by an evaporator, diluted with 2,000g of toluene and then washed with water. The organic layer was concentrated and added dropwise to methanol to obtain a solid, which was recovered by filtration. The recovered solid was dried under vacuum to give 392.2g of vinyl compound "F". The vinyl compound "F" had a number average molecular weight of 988 and a weight average molecular weight of 1,420.

Synthesis example 4

Synthesis of bifunctional phenylene Ether oligomer

A12 liter long reactor equipped with a stirrer, a thermometer, an air introduction tube and a baffle was charged with 13.1g (0.12mol) of CuCl, 707.0g (5.5mol) of di-n-butylamine and 4,000g of methyl ethyl ketone. These components were stirred at a reaction temperature of 40 ℃. 82.1g (0.32mol) of 4, 4' -methylenebis (2, 6-dimethylphenol) and 586.5g (4.8mol) of 2, 6-dimethylphenol were dissolved in 8,000g of methyl ethyl ketone in advance to prepare a mixed solution. The mixed solution was added dropwise to the mixture in the reactor while bubbling with 2L/min of air, and stirred. An aqueous solution of disodium dihydrogen ethylenediamine tetraacetate was added to the stirred mixture to terminate the reaction. Then washed with 1N aqueous hydrochloric acid and then with pure water. The resulting solution was concentrated by an evaporator and dried under reduced pressure to obtain 632.5G of a bifunctional phenylene ether oligomer (resin "G"). The resin "G" had a number average molecular weight of 1,884, a weight average molecular weight of 3,763, and an equivalent weight of hydroxyl groups of 840.

Synthesis of vinyl Compounds

To a reactor equipped with a stirrer, a thermometer and a reflux tube were charged 480.0G of resin "G", 140.5G of vinylbenzylchloride (CMS-P), 2,000G of tetrahydrofuran, 129.6G of potassium carbonate and 32.4G of 18-crown-6 ether. The mixture was stirred at a reaction temperature of 30 ℃ for 6 hours. The resulting solution was concentrated by an evaporator, diluted with 2,000g of toluene and then washed with water. The organic layer was concentrated and added dropwise to methanol to obtain a solid, which was recovered by filtration. The solid was dried under vacuum to give 415.3g of vinyl compound "H". The vinyl compound "H" had a number average molecular weight of 2,128 and a weight average molecular weight of 4,021.

Examples 1 to 7 and comparative examples 1 to 5

One of vinyl compound "B" obtained in Synthesis example 1, vinyl compound "D" obtained in Synthesis example 2, vinyl compound "F" obtained in Synthesis example 3 and divinylbenzene (DVB-960: supplied by Nippon Steel Chemical Group) and/or one of various high molecular weight compounds in the amounts shown in Table one were dissolved in toluene to obtain varnishes having a resin solid content of 30% by weight (15% by weight in examples 3, 4 and 5). The varnish was applied to a 1 μm electrolytic copper foil (3 EC-III: supplied by MITSUI MINING & SMELTING CO., LTD) with a small squeegee, and the applied varnish was dried at 50 ℃ for 5 minutes to obtain a copper-foil-attached (copper-foil-attached) curable film having a resin layer thickness of about 15 μm. The appearance and tackiness of the thus obtained curable film attached to the copper foil were determined. The results are shown in table one. The curable film attached to the copper foil was then heated at 200 ℃ for 90 minutes at a temperature ramp rate of 4 ℃/minute in an inert oven under nitrogen. The copper foil was removed by etching to obtain a film. The thickness of the film was about 15 μm. The glass transition temperature, dielectric constant, dielectric loss tangent, chemical resistance and flexibility of the resulting film were determined. The results are shown in Table II.

Watch 1

		Ex.1	Ex.2	Ex.3	Ex.4	Ex.5	Ex.6
								Curing component	Resin B	70	70	85	85	85	-
Resin D	-	-	-	-	-	70
								Resin E	-	-	-	-	-	-
Divinylbenzene	-	-	-	-	-	-
								High molecular weight chemical combination	TR2003	-	-	-	-	-	30
TR2827	30	-	-	-	-	-
								SIS5229	-	30	-	-	-	-

Ex. ═ example

Ex. ═ example, cex. ═ comparative example

TR2003, TR 2827: styrene butadiene styrene copolymer (weight average molecular weight of about 100,000, supplied by JSR)

SIS 5229: styrene isoprene styrene copolymer (weight average molecular weight of about 200,000, supplied by JSR)

SEPTON 2006: hydrogenated styrene isoprene styrene copolymer (weight average molecular weight of about 200,000, supplied by KURARAY co., ltd.)

SEPTON 4055: hydrogenated styrene (butadiene/isoprene) styrene copolymer (weight average molecular weight of about 200,000, supplied by KURARAY co., ltd.)

SEPTON 8007: hydrogenated styrene butadiene styrene copolymer (weight average molecular weight of about 100,000, supplied by KURARAY co., ltd.)

Watch two

	Ex.1	Ex.2	Ex.3	Ex.4
					Glass transition temperature (. degree. C.)	179	183	185	184
Dielectric constant (10GHz)	2.44	2.43	2.43	2.45
					Dielectric loss tangent (10GHz)	0.0023	0.0024	0.0025	0.0025
Chemical resistance	O	O	O	O
					Flexibility	O	O	O	O

Ex. -, for the examples,

	Ex.5	Ex.6	Ex.7	CEx.5
					glass transition temperature (. degree. C.)	187	175	169	72
Dielectric constant (10GHz)	2.44	2.44	2.42	2.30
					Dielectric loss tangent (10GHz)	0.0026	0.0024	0.0022	0.0022
Chemical resistance	O	O	O	X
					Flexibility	O	O	O	O

Ex. ═ example, cex. ═ comparative example

Examples 8 to 19

One of the vinyl compound "D" obtained in synthesis example 2, the vinyl compound "F" obtained in synthesis example 3, and the vinyl compound "H" obtained in synthesis example 4 and one of various high molecular weight compounds were mixed as a vinyl compound: the high molecular weight compounds were mixed in a weight ratio of 70: 30, and the mixture was dissolved in toluene to obtain a varnish having a resin solid content of 20% by weight. The varnish was applied to a 100 μm thick PET film (Lumirror-T: supplied by Toray Industries, Inc.) with small squeegees (300 μm spacing), and the applied varnish was dried at 80 ℃ for 5 minutes to give a curable film having a resin layer thickness of about 30 μm. The appearance and tackiness of the thus obtained curable film were determined. The curable film was then heated at 200 ℃ for 30 minutes at a temperature ramp of 4 ℃/minute in an inert oven under nitrogen, and the PET film was then manually removed to give a film. The thickness of the film was about 30 μm. The glass transition temperature, dielectric constant, dielectric loss tangent, chemical resistance and flexibility of the resulting film were determined. The results are shown in Table three.

TABLE 3

Ex.8

Ex.9

Ex.10

Ex.11

Ex.12

Ex.13

Vinyl compound

Resin D

Resin D

Resin D

Resin D

Resin D

Resin D

High molecular weight compound

TR2250

TR2827

HYBRAR5127

SEPTON2104

SEPTON2007

SEPTON4033

Class of high molecular weight compounds

SBS

SBS

SIS

Hydro-SIS

Hydro-SIS

SEEPS

Styrene content in the high molecular weight Compound (wt%)

52

24

20

65

30

30

Appearance of curable films

O

O

O

O

O

O

Tackiness of the curable film

O

O

O

O

O

O

Glass transition temperature (. degree. C.)

171

174

185

181

205

192

Dielectric constant (10GHz)

2.54

2.41

2.48

2.53

2.46

2.48

Dielectric loss tangent (10GHz)

0.0024

0.0023

0.0021

0.0023

0.0019

0.0018

Chemical resistance

O

O

O

O

O

O

Flexibility

O

O

O

O

O

O

Ex. ═ example, Hydro-SIS ═ hydrogenated SIS

Ex.14

Ex.15

Ex.16

Ex.17

Ex.18

Ex.19

Vinyl compound

Resin D

Resin D

Resin D

Resin D

Resin F

Resin H

High molecular weight compound

HYBRAR7125

SEPTON8104

TuftecH1051

TuftecH1053

TuftecH1053

Tuftec H1053

Class of high molecular weight compounds

Hydro-SIS

Hydro-SBS

Hydro-SBS

Hydro-SBS

Hydro-SBS

Hydro- SBS

Styrene content in the high molecular weight Compound (wt%)

20

60

42

29

29

29

Appearance of curable films

O

O

O

O

O

O

Tackiness of the curable film

O

O

O

O

O

O

Glass transition temperature (. degree. C.)

200

181

199

206

191

205

Dielectric constant (10GHz)

2.45

2.51

2.49

2.45

2.42

2.44

Dielectric loss tangent (10GHz)

0.0021

0.0022

0.0017

0.0018

0.0023

0.0021

Chemical resistance

O

O

O

O

O

O

Flexibility

O

O

O

O

O

O

Ex. ═ example, Hydro-SIS ═ hydrogenated SIS, Hydro-SBS ═ hydrogenated SBS

TR 2250: styrene butadiene styrene copolymer (SBS) (weight average molecular weight approximately 100,000, supplied by JSR)

HYBRAR 5127: styrene isoprene styrene copolymer (SIS) (weight average molecular weight of about 120,000, supplied by KURARAY CO., LTD.)

HYBRAR 7125: hydrogenated styrene isoprene styrene copolymer (hydrogenated SIS) (weight average molecular weight approximately 100,000, supplied by KURARAAY CO., LTD.)

SEPTON 2104: hydrogenated styrene isoprene styrene copolymer (hydrogenated SIS) (weight average molecular weight approximately 90,000, supplied by KURARAAY CO., LTD.)

SEPTON 2007: hydrogenated styrene isoprene styrene copolymer (hydrogenated SIS) (weight average molecular weight approximately 80,000, supplied by KURARAAY CO., LTD.)

SEPTON 4033: hydrogenated styrene (butadiene/isoprene) styrene copolymer (SEEPS) (weight average molecular weight of about 100,000, supplied by KURARAAY CO., LTD.)

SEPTON 8104: hydrogenated styrene butadiene styrene copolymer (hydrogenated SBS) (weight average molecular weight approximately 120,000, supplied by KURAAY CO., LTD.)

Tuftec H1051: hydrogenated styrene butadiene styrene copolymer (hydrogenated SBS) (weight average molecular weight approximately 70,000, supplied by Asahi Kasei Corporation)

Tuftec H1053: hydrogenated styrene butadiene styrene copolymer (hydrogenated SBS) (weight average molecular weight approximately 70,000, supplied by Asahi Kasei Corporation)

Examples 20 to 22

The vinyl compound "D" obtained in Synthesis example 2 and one of various high molecular weight compounds were mixed in a weight ratio of the vinyl compound to the high molecular weight compound of 50: 50, and the mixture was dissolved in toluene to obtain a varnish having a resin solid content of 20% by weight. The varnish was applied to a 100 μm thick PET film (Lumirror-T) with small squeegees (300 μm spacing) and the applied varnish was dried at 80 ℃ for 5 minutes to give a curable film having a resin layer thickness of about 30 μm. The appearance and tackiness of the thus obtained curable film were determined. The curable film was then heated at 200 ℃ for 30 minutes at a temperature ramp of 4 ℃/minute in an inert oven under nitrogen, and the PET film was then manually removed to give a film. The thickness of the resulting film was about 30 μm. The glass transition temperature, dielectric constant, dielectric loss tangent, chemical resistance and flexibility of the resulting film were determined. The results are shown in Table four.

Watch four

	Ex.20	Ex.21	Ex.22
				Vinyl compound	Resin D	Resin D	Resin D
High molecular weight compound	TR2003	Tuftec H1051	Tuftec H1053
				Class of high molecular weight compounds	SBS	Hydrogenated SBS	Hydrogenated SBS
Styrene content in the high molecular weight Compound (wt%)	43	42	29
				Appearance of curable films	O	O	O
Tackiness of the curable film	O	O	O
				Glass transition temperature (. degree. C.)	162	185	199
Dielectric constant (10GHz)	2.38	2.39	2.41
				Dielectric loss tangent (10GHz)	0.0022	0.0017	0.0016
Chemical resistance	O	O	O
				Flexibility	O	O	O

Examples 23 to 25

The vinyl compound "D" obtained in synthesis example 2 and one of various high molecular weight compounds were synthesized as a vinyl compound "D": the high molecular weight compounds were mixed in a weight ratio of 30: 70, and the mixture was dissolved in toluene to obtain a varnish having a resin solid content of 20% by weight. The varnish was applied to a 100 μm thick PET film (Lumirror-T) with small squeegees (300 μm spacing) and the applied varnish was dried at 80 ℃ for 5 minutes to give a curable film having a resin layer thickness of about 30 μm. The appearance and tackiness of the thus obtained curable film were determined. The curable film was then heated at 200 ℃ for 30 minutes at a temperature ramp of 4 ℃/minute in an inert oven under nitrogen, and the PET film was then manually removed to give a film. The thickness of the resulting film was about 30 μm. The glass transition temperature, dielectric constant, dielectric loss tangent, chemical resistance and flexibility of the resulting film were determined. The results are shown in Table five.

Watch five

	Ex.23	Ex.24	Ex.25
				Vinyl compound	Resin D	Resin D	Resin D
High molecular weight compound	TR2003	Tuftec H1051	Tuftec H1053
				Class of high molecular weight compounds	SBS	Hydrogenated SBS	Hydrogenated SBS
Styrene content in the high molecular weight Compound (wt%)	43	42	29
				Appearance of curable films	O	O	O
Tackiness of the curable film	O	O	O
				Glass transition temperature (. degree. C.)	138	172	177
Dielectric constant (10GHz)	2.42	2.41	2.39
				Dielectric loss tangent (10GHz)	0.0029	0.0019	0.0020
Chemical resistance	O	O	O
				Flexibility	O	O	O

Example 26

A toluene solution having a resin solid content of 20% by weight and having the curable resin composition constituted in example 19 was applied to 18 μm electrolytic copper foil (3EC-III) with a small squeegee (400 μm interval), and the applied solution was dried with an air drying agent at 80 ℃ for 5 minutes, to thereby obtain a curable film attached to the copper foil with a thickness of about 40 μm per one resin layer. The curable film attached to the copper foil was placed on both sides of a core material (EL190, copper foil 18 μm thick, supplied by Mitsubishi Gas Chemical co., inc.) each of which was flattened, one film was placed on one side and the other film was placed on the other side, and the resulting device was cured at 200 ℃ and 2MPa for 2 hours to obtain four-layered plates. The copper foil peel strength of the outermost copper foil was 0.8 kN/m. Further, the outermost copper foil was removed by etching, and as a result, it was found that the inner layer pattern was buried without any voids.

Claims (8)

1. A curable resin composition containing an essential component of a high molecular weight compound having a weight average molecular weight of 10,000 to 300,000 and a vinyl compound of the general formula (1),

wherein the vinyl compound of the general formula (1): the weight ratio of the high molecular weight compound is 20: 80 to 95: 5,

the high molecular weight compound is at least one compound selected from the group consisting of: styrene isoprene styrene copolymer, styrene butadiene styrene copolymer, hydrogenated styrene isoprene styrene copolymer or hydrogenated styrene (butadiene/isoprene) styrene copolymer,

R₁、R₂、R₃、R₄、R₅、R₆and R₇Represents a hydrogen atom, and is represented by,

- (O-X-O) -represents a moiety of the general formula (2) or the general formula (3),

wherein R is₈、R₉、R₁₀、R₁₄And R₁₅Identical or different, represents a halogen atom, an alkyl group having 6 or less carbon atoms; r₁₁、R₁₂And R₁₃The same or different, represents a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms,

wherein R is₁₆、R₁₇、R₂₂And R₂₃Identical or different, represents a halogen atom, an alkyl group having 6 or less carbon atoms; r₁₈、R₁₉、R₂₀And R₂₁Identical or different, represents a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, A is a linear, branched or cyclic hydrocarbon having 20 or less carbon atoms,

- (Y-O) -represents a moiety of formula (4) or a random combination of at least two moieties of formula (4),

wherein R is₂₄And R₂₅Identical or different, represents a halogen atom, an alkyl group having 6 or less carbon atoms; r₂₆And R₂₇The same or different, represents a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms,

z represents an organic group having at least one carbon atom,

if at least one of a and b is not 0, then a and b are integers from 0 to 30, respectively, and

c and d are integers of 0 or 1, respectively.

2. The curable resin composition according to claim 1, wherein Z represents an organic group having at least one carbon atom and at least one atom selected from an oxygen atom, a nitrogen atom, a sulfur atom or a halogen atom.

3. The curable resin composition according to claim 1, wherein- (O-X-O) -is a moiety of formula (5) or formula (6), - (Y-O) -is a moiety of formula (7) or formula (8), or a random combination of moieties of formula (7) and formula (8),

wherein R is₁₈、R₂₁Represents a hydrogen atom or a methyl group, A is a linear, branched or cyclic hydrocarbon having 20 or less carbon atoms,

4. the curable resin composition according to claim 1, wherein the vinyl compound of the general formula (1) has a number average molecular weight of 500 to 3,000.

5. A curable film made by processing the curable resin composition of claim 1 into film form.

6. A curable film according to claim 5 having a conductor layer on at least one surface.

7. A film obtained by curing the curable film according to claim 5.

8. A film obtained by curing the curable film according to claim 6.