JP2005089636A - Prepreg for laminated sheet and laminated sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a prepreg for a laminated sheet, having an excellent dielectric constant and dielectric loss tangent, and also having excellent moldability, heat resistance and the like; and to provide a metal-clad laminated sheet using the prepreg. <P>SOLUTION: The prepreg for the laminated sheet comprises a resin composition containing a vinyl compound having a specific structure as an essential component, and a base material. The metal-clad laminated sheet is obtained by using the prepreg. As a result, the prepreg for the laminated sheet and the metal-clad laminated sheet, having the low dielectric constant and the low dielectric loss tangent, and also having the good moldability, heat resistance and the like are obtained. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a prepreg for a laminate using a resin composition using a vinyl compound having a specific structure, and the prepreg, a metal foil laminate, and a metal-clad laminate. The metal-clad laminate obtained from the present invention has a low dielectric constant and a low dielectric loss tangent, and is a material useful as a printed wiring board used for high frequency applications.

In recent years, with the advancement of communication and computers, the frequency has been increased, and the printed wiring board is required to have low dielectric properties for the purpose of improving the signal transmission speed and reducing the transmission loss. To meet this demand, thermoplastic resins such as fluororesins and polyphenylene ethers with excellent dielectric properties, epoxy resins on polyphenylene ether, vinyl compounds mainly composed of styrene, cyanate ester resins and bismaleimide triazine resins However, a composition with good dielectric properties has a high melting point and softening point, so that high temperature and high pressure are required for molding, moldability is insufficient, and a cured product is hard. It is brittle and has problems in adhesion and solder resistance, and further improvement has been desired. As an example of using a vinyl compound, a technique for improving dielectric properties using a polyetherimide and a vinyl-divinyl copolymer (see, for example, Patent Document 1) is a method for producing a vinyl-divinyl copolymer. The styrene divinylbenzene that is the monomer tends to volatilize and the composition changes, and the resulting product is brittle. Further, a composition in which a novolac type aromatic hydrocarbon and a formaldehyde resin are both made flexible by using a divinyl compound having an alkylene ether structure at the center has been proposed (see, for example, Patent Document 2). However, the dielectric properties are unknown.
JP-A-5-156159 Japanese Patent Laid-Open No. 5-78552

  An object of the present invention is a laminated board that has excellent dielectric constant and dielectric loss tangent among required characteristics, as well as excellent moldability, heat resistance, etc., in order to respond to usage patterns that have been significantly increased in frequency in printed wiring board materials in recent years. Prepreg, and a metal-clad laminate using the same.

The present invention uses a vinyl compound having a specific structure as an essential component, and if necessary, by using a resin composition containing a thermosetting resin or a thermoplastic resin, the dielectric properties, moldability, and heat resistance are improved. The present inventors have found that excellent prepregs for laminates and metal-clad laminates have been completed. That is, the present invention relates to a prepreg for a laminate comprising a resin composition having a vinyl compound having a specific structure represented by the general formula (1) and a base material, and a metal-clad laminate comprising the prepreg and a metal foil. It is.



(Wherein R1, R2, R3, R4, R5, R6, R7 may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group, a halogenated alkyl group or a phenyl group.-(OXO)- Consists of one structure or two or more structures defined by structural formula (2) and structural formula (3), R8, R9, R10, R14, R15 may be the same or different and may be a halogen atom or R 11, R 12 and R 13 may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. R22 and R23 may be the same or different and are a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and R18, R19, R20, and R21 may be the same or different, and may be a hydrogen atom, a halogen atom, or An alkyl group having 6 or less carbon atoms or a phenyl group, and A is 20 carbon atoms. The following linear, branched or cyclic hydrocarbons:-(YO)-is one type of structure defined by structural formula (4), or two or more types defined by structural formula (4) R24 and R25 may be the same or different, and may be a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and R26 and R27 may be the same or different. , A hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, Z is an organic group having 1 or more carbon atoms, and may contain an oxygen atom, a nitrogen atom, a sulfur atom, or a halogen atom. a and b each represents an integer of 0 to 30 in which at least one of them is not 0. c and d represent an integer of 0 or 1.)

  The prepreg for a laminate and the metal-clad laminate of the present invention have a low dielectric constant and a low dielectric loss tangent, and have good moldability and heat resistance. Therefore, it is suitable as an insulating material for high-frequency electrical components, and is suitable as a material for high-frequency signal wiring boards.

  The vinyl compound which is an essential component of the present invention is not particularly limited as long as it is a vinyl compound represented by the general formula (1). In the general formula (1), R1, R2, R3, R4, R5, R6, and R7 may be the same or different, and are a hydrogen atom, a halogen atom, an alkyl group, a halogenated alkyl group, or a phenyl group. -(O-X-O)-consists of one type of structure or two or more types of structures defined by structural formula (2) and structural formula (3). R8, R9, R10, R14, and R15 may be the same or different and are a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. R11, R12, and R13 may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. R16, R17, R22, and R23 may be the same or different and are a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. R18, R19, R20, and R21 may be the same or different and are 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)-is one type of structure defined by structural formula (4) or two or more types of structures defined by structural formula (4) arranged at random. R24 and R25 may be the same or different and are a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. R26 and R27 may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. Z is an organic group having 1 or more carbon atoms, and may contain an oxygen atom, a nitrogen atom, a sulfur atom, or a halogen atom. a and b each represents an integer of 0 to 30, at least one of which is not 0. c and d are integers of 0 or 1, in particular, R1, R2, R3, R4, R5, R6, R7 are hydrogen atoms, R8, R9, R10, R14, R15, R16, R17, R22, R23 are Preferred is an alkyl group having 3 or less carbon atoms, R11, R12, R13, R18, R19, R20, or R21 is a hydrogen atom or an alkyl group having 3 or less carbon atoms, Z is a methylene group, and c and d are 1 vinyl compounds. is there.

  The method for producing the vinyl compound represented by the general formula (1) is not particularly limited. For example, it is produced by the method described in Japanese Patent Application Nos. 2002-216724, 2002-224937, 2003-110687, and the like. can do. The number average molecular weight of the vinyl compound represented by the general formula (1) is preferably in the range of 500 to 3,000. When the number average molecular weight exceeds 3,000, as the melting point increases, solubility in solvents and reactivity decrease, and when the number average molecular weight is less than 500, low dielectric properties tend to be hardly exhibited.

  The thermosetting resin used in the resin composition used in the present invention is not particularly limited as long as it is a thermosetting resin used in printed wiring materials. Representative examples of thermosetting resins include epoxy resins, cyanate ester resins, bismaleimide-cyanate ester resins, maleimide resins, polyimide resins, unsaturated group-containing polyphenylene ether resins, and the like. It is also possible to use a combination of more than one species as appropriate. As a suitable thing, an epoxy resin or a cyanate ester resin is mentioned. The thermosetting resin used in the present invention can be used in combination with a thermosetting resin curing agent and a curing accelerator, if necessary. These are well known and are not particularly limited as long as they are generally used as a curing agent and a curing accelerator for thermosetting resins.

  The epoxy resin suitably used in the present invention is not particularly limited as long as it is a compound having two or more epoxy groups in one molecule. Specifically, bisphenol A type epoxy, bisphenol F type epoxy, bisphenol Z type epoxy, biphenol epoxy, tetramethyl biphenol epoxy, hexamethylbiphenol epoxy, xylene novolac epoxy, biphenyl novolac epoxy, dicyclopentadiene novolak -Epoxy, phenol novolac-epoxy, cresol novolac-epoxy, or brominated flame-retardant epoxy resins thereof are exemplified and can be used alone or in combination of two or more kinds.

  The cyanate ester resin suitably used in the present invention is not particularly limited as long as it is a compound having two or more cyanate groups in one molecule. Specifically, 1,3- or 1,4-dicyanate benzene, 1,3,5-tricyanate benzene, 1,3-, 1,4-, 1,6-, 1,8-, 2, 6- or 2,7-dicyanate naphthalene, 1,3,6-tricyanate naphthalene, 4,4'-dicyanate biphenyl, bis (4-cyanatephenyl) methane, 2,2-bis (4-cyanatephenyl) Examples include propane, 2,2-bis (3,5-dibromo-4-cyanatephenyl) propane, bis (4-cyanatephenyl) ether, and cyanates obtained by the reaction of novolac and cyanogen halide. It is also possible to use seeds or a combination of two or more kinds as appropriate.

  Examples of the thermoplastic resin used in the resin composition used in the present invention include polycarbonate, polyphenylene ether, acrylic resin, methacrylic resin, ABS resin, polysulfone, polystyrene, and polyolefin. However, it is not limited to these.

  In the resin composition containing the vinyl compound represented by the general formula (1) used in the present invention as an essential component, a thermosetting catalyst is added for the purpose of improving the workability and economy by increasing the curing rate. Can do. As the thermosetting catalyst, one that generates a cation or radical active species capable of initiating polymerization of a vinyl group by heat or light can be used. For example, the cationic polymerization initiator includes diallyl iodonium salt, triallyl sulfonium salt and aliphatic sulfonium salt having BF4, PF6, AsF6, SbF6 as a counter anion, and the radical polymerization initiator includes benzoin, benzoin methyl, etc. Benzoin compounds, acetophenone, acetophenone compounds such as 2,2-dimethoxy-2-phenylacetophenone, thioxanthone compounds such as thioxanthone and 2,4-diethylthioxanthone, 4,4′-diazidochalcone, 2,6- Bis (4'-azidobenzal) cyclohexanone, bisazide compounds such as 4,4'-diazidobenzophenone, azo compounds such as azobisisobutyronitrile, 2,2-azobispropane, hydrazone, 2,5-dimethyl-2.5 -Di (t-butylperoxy) hexane, 2,5-dimethyl-2.5-di (t-butylperoxy) hexane Down -3, organic peroxides such as dicumyl peroxide. These can be used alone or in admixture of two or more.

  The resin composition used in the present invention includes known inorganic or organic fillers, dyes, pigments, thickeners, lubricants, antifoaming agents, coupling agents, photosensitizers, ultraviolet absorbers, flame retardants. Various additives such as can be added as desired.

  The organic solvent used as necessary in the present invention is not particularly limited as long as it is compatible with the resin composition. Specific examples include acetone, methyl ethyl ketone, ethylene glycol monomethyl ether acetate, propylene glycol dimethyl ether, toluene, xylene, tetrahydrofuran, N, N-dimethylformamide, and the like, or a mixture of two or more solvents is used as appropriate. It is possible.

  As the base material used in the present invention, well-known materials used for various printed wiring board materials can be used. Specific examples include woven and non-woven fabrics made of glass fibers such as E glass, D glass, S glass, NE glass, and quartz, woven and non-woven fabrics made of inorganic materials typified by ceramics, porous materials, and sheets. It is selected as appropriate according to the intended use and performance, and can be used alone or in combination of two or more if necessary. The thickness of the substrate is not particularly limited, but usually about 20 to 200 μm is used. In addition, those surface-treated with a silane coupling agent or the like and those subjected to physical opening treatment can be suitably used from the viewpoint of moisture absorption heat resistance.

  The manufacturing method of the prepreg for laminated boards of this invention will be specifically limited if the prepreg is obtained by combining the resin composition which has the vinyl compound shown by General formula (1) as an essential component, and a base material. is not. Specifically, after impregnating or applying the above resin composition to a substrate, it is B-staged by a method of heating in a dryer at 100 to 200 ° C. for 1 to 30 minutes to produce a prepreg. Examples are methods. The adhesion amount of the resin composition to the substrate is in the range of 30 to 90% by weight in terms of the resin amount of the prepreg.

  The metal-clad laminate which is a preferred embodiment of the present invention is a laminate formed by using the above-described laminate prepreg. Specifically, the above-described prepreg is suitably produced by laminating one or more of the prepregs and laminating with a structure in which a metal foil such as copper or aluminum is disposed on one or both sides as desired. The metal foil to be used is not particularly limited as long as it is used for a printed wiring board material.

  As a molding condition of the metal-clad laminate, a general method for laminates for printed wiring boards and multilayer boards can be applied. For example, a multi-stage press, a multi-stage vacuum press, continuous molding, an autoclave molding machine, etc. are used, and temperature: 100 to 300 ° C., pressure: 0.2 to 10 MPa, heating time: 0.1 to 5 hours are common. is there. Moreover, it is also possible to make a multilayer board by combining the prepreg of the present invention and a separately prepared wiring board for an inner layer, and laminate molding.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. “Parts” and “%” represent parts by weight and% by weight.

Synthesis example 1
(Synthesis of bifunctional phenylene ether oligomer)
CuBr ₂ 3.88g (17.4mmol), N, N'-di-t-butylethylenediamine 0.75g (4.4mmol), n-, in a 12L vertical reactor with stirrer, thermometer, air inlet tube and baffle plate Butyldimethylamine 28.04 g (277.6 mmol) and toluene 2,600 g were charged, stirred at a reaction temperature of 40 ° C., and dissolved in 2,300 g of methanol in advance, 2,2 ′-, 3,3 ′-, 5,5 '-Hexamethyl- (1,1'-biphenol) -4,4'-diol 129.32g (0.48mol), 2,6-dimethylphenol 292.19g (2.40mol), N, N'-di-t-butylethylenediamine A mixed solution of 0.51 g (2.9 mmol) and 10.90 g (108.0 mmol) of n-butyldimethylamine (a divalent phenol compound represented by Structural Formula (2) and a monovalent phenol represented by Structural Formula (3) A mixture gas prepared by mixing nitrogen and air to adjust the oxygen concentration to 8% was added dropwise over 230 minutes while bubbling at a flow rate of 5.2 L / min. . After completion of the dropwise addition, 1,500 g of water in which 19.89 g (52.3 mmol) of ethylenediaminetetraacetic acid tetrasodium was dissolved was added to stop the reaction. The aqueous layer and the organic layer were separated, and the organic layer was washed with a 1N hydrochloric acid aqueous solution and then with pure water. The obtained solution was concentrated to 50 wt% with an evaporator to obtain 833.40 g of a toluene solution of a bifunctional phenylene ether oligomer (resin “A”). Resin “A” had a number average molecular weight of 930, a weight average molecular weight of 1,460, and a hydroxyl group equivalent of 465.

(Synthesis of vinyl compounds)
In a reactor equipped with a stirrer, thermometer, reflux tube, 833.40 g of toluene solution of resin “A”, vinylbenzyl chloride (trade name CMS-P; manufactured by Seimi Chemical Co., Ltd.) 160.80 g, methylene chloride 1600 g, benzyldimethyl 12.95 g of amine, 420 g of pure water and 175.9 g of 30.5 wt% NaOH solution were charged, and the mixture was stirred at a reaction temperature of 40 ° C. After stirring for 24 hours, the organic layer was washed with a 1N aqueous hydrochloric acid solution and then with pure water. The obtained solution was concentrated with an evaporator, dropped into methanol for solidification, and the solid was collected by filtration and vacuum dried to obtain 501.43 g of Resin “B”. The number average molecular weight of Resin “B” was 1165, and the weight average molecular weight was 1630.

Synthesis example 2
(Synthesis of bifunctional phenylene ether oligomer)
CuL 13.1g (0.12mol), Di-n-butylamine 707.0g (5.5mol), and methyl ethyl ketone 4000g were charged into a 12L vertical reactor equipped with a stirrer, thermometer, air inlet tube and baffle, and the reaction temperature was 40 ℃. 2L of 4,4'-methylenebis (2,6-dimethylphenol) 410.2g (1.6mol) and 2,6-dimethylphenol 586.5g (4.8mol) dissolved in 8000g of methyl ethyl ketone in advance Stirring was continued while bubbling air at / min. Ethylenediaminetetraacetic acid dihydrogen disodium aqueous solution was added to this, and reaction was stopped. Then, after washing | cleaning 3 times with 1N hydrochloric acid aqueous solution, it wash | cleaned with ion-exchange water. The obtained solution was concentrated with an evaporator and further dried under reduced pressure to obtain 946.6 g of a bifunctional phenylene ether oligomer (resin “C”). Resin “C” had a number average molecular weight of 801, a weight average molecular weight of 1081, and a hydroxyl group equivalent of 455.

(Synthesis of vinyl compounds)
In a reactor equipped with a stirrer, a thermometer and a reflux tube, 480.0 g of resin “C”, vinylbenzyl chloride (trade name CMS-P; manufactured by Seimi Chemical Co., Ltd.) 260.2 g, tetrahydrofuran 2000 g, potassium carbonate 240.1 g, 18 -60.0 g of crown-6-ether was charged and stirred at a reaction temperature of 30 ° C. After stirring for 6 hours, the mixture was concentrated with an evaporator, diluted with 2000 g of toluene, and washed with water. The organic layer was concentrated and dropped into methanol for solidification, and the solid was collected by filtration and vacuum dried to obtain 392.2 g of Resin “D”. The number average molecular weight of Resin “D” was 988, and the weight average molecular weight was 1420.

Examples 1 and 2
Resins “B” and “D” obtained in Synthesis Example 1 were each dissolved in methyl ethyl ketone and adjusted so that the resin content was 60%. Glass for laminates (E glass, basis weight: 110 g / m ² , manufactured by Nittobo) is immersed in individual varnishes, impregnated with resin, dried at 160 ° C. for 3 minutes, and has no tack property, 170 ° C. Gel time: 120 to 150 seconds of “prepreg B” and “prepreg D” were obtained. Next, 4 pieces of “prepreg B” and “prepreg D” are stacked, 12μm electrolytic copper foil is placed on the upper and lower surfaces, and pressed for 2 hours under the conditions of temperature 200 ° C and pressure 2MPa. Each double-sided copper-clad laminate was prepared. In addition, “prepreg B” and “prepreg D” are arranged on both sides of the core material (copper foil thickness 35 μm) patterned on both sides, and 12 μm electrolytic copper foil is further arranged on both sides. Pressing was performed for 2 hours under the conditions of ° C. and a pressure of 2 MPa to prepare four-layer plates. The characteristics of this double-sided copper clad laminate and the evaluation results of the formability of the four-layer board are shown in Table 2.

Examples 3-6
The blending ratio shown in Table-1 is adjusted so that the resin content is 60% to make a varnish, immersed in the varnish in the base material shown in Table-1, impregnated with the resin, and then dried at 160 ° C. for 3 minutes to prepare the prepreg. Obtained. Four prepregs were stacked, 12 μm electrolytic copper foils were placed on the upper and lower surfaces, and pressed for 2 hours under the conditions of a temperature of 200 ° C. and a pressure of 2 MPa to produce a 0.4 mm thick double-sided copper-clad laminate. Also, one prepreg is placed on each side of the core material (copper foil thickness 35μm) patterned on both sides, and further 18μm electrolytic copper foil is placed on both sides, and the temperature is 200 ℃ and the pressure is 2MPa for 2 hours. A four-layer board was produced by pressing. The characteristics of this double-sided copper clad laminate and the evaluation results of the formability of the four-layer board are shown in Table 2.

Comparative Examples 1 and 2
The blending ratio shown in Table 1 was adjusted so that the resin content would be 60% to obtain a varnish. The substrate was immersed in a varnish, impregnated with resin, and then dried at 160 ° C. for 3 minutes to obtain a prepreg. Four prepregs were stacked, 12 μm electrolytic copper foil was placed on both sides, and pressed for 2 hours under the conditions of a temperature of 200 ° C. and a pressure of 2 MPa to prepare a 0.4 mm thick double-sided copper-clad laminate. Also, one prepreg is placed on each side of the core material (copper foil thickness 35μm) patterned on both sides, and 18μm electrolytic copper foil is placed on both sides, and the temperature is 200 ℃ and the pressure is 2MPa for 2 hours. A four-layer board was produced by pressing. The characteristics of this double-sided copper-clad laminate and the evaluation results of the formability of the four-layer board are shown in Table 2.
(Raw material)
BT2110: Bismaleimide triazine prepolymer (Mitsubishi Gas Chemical)
FR53: Brominated polycarbonate (manufactured by Mitsubishi Gas Chemical)
Epicron 153: Bisphenol A type brominated epoxy resin (Dainippon Ink)
PPE: Polyphenylene ether (Mitsubishi Gas Chemical)
E: E glass cloth (basis weight: 110 g / m ² , manufactured by Nittobo)
NE: NE glass cloth (basis weight: 110 g / m ² , manufactured by Nittobo)
D: D glass cloth (basis weight: 110 g / m ² , manufactured by Arisawa Seisakusho)
Copper foil: 3EC-III (Mitsui Metal Mining)
(Measurement condition)
Dielectric constant / dielectric loss tangent: Measured by cavity resonance perturbation method. (Measurement frequency 1GHz)
Heat resistance: The test piece is immersed in boiling water for 1 hour, then immersed in a solder bath at 260 ° C for 30 seconds, and the appearance is visually determined. (○: No bulging △: Small bulge ×: Large bulge)
Formability: The embedding property of the inner layer pattern of the four-layer board is visually determined. (○: No void △: Small void ×: Large void)

Claims (3)

A prepreg for a laminate comprising a resin composition containing a vinyl compound represented by the general formula (1) as an essential component and a substrate.



(Wherein R1, R2, R3, R4, R5, R6, R7 may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group, a halogenated alkyl group or a phenyl group.-(OXO)- Consists of one structure or two or more structures defined by structural formula (2) and structural formula (3), R8, R9, R10, R14, R15 may be the same or different and may be a halogen atom or R 11, R 12 and R 13 may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. R22 and R23 may be the same or different and are a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and R18, R19, R20, and R21 may be the same or different, and may be a hydrogen atom, a halogen atom, or An alkyl group having 6 or less carbon atoms or a phenyl group, and A is 20 carbon atoms. The following linear, branched or cyclic hydrocarbons:-(YO)-is one type of structure defined by structural formula (4), or two or more types defined by structural formula (4) R24 and R25 may be the same or different, and may be a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and R26 and R27 may be the same or different. , A hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, Z is an organic group having 1 or more carbon atoms, and may contain an oxygen atom, a nitrogen atom, a sulfur atom, or a halogen atom. a and b each represents an integer of 0 to 30 in which at least one of them is not 0. c and d represent an integer of 0 or 1.) The prepreg for a laminated board according to claim 1, wherein the resin composition is a thermosetting resin and / or a thermoplastic resin. A metal-clad laminate comprising the laminate prepreg according to claim 1 or 2 and a metal foil.