JP2003283076A - High frequency board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a board exhibiting excellent dielectric characteristics in the high frequency region, especially an excellent dielectric loss tangent, and excellent heat resistance, a prepreg and a metal foil with resin. <P>SOLUTION: In the high frequency board produced by polymerizing and hardening a polymer composite, the polymer composite contains a fluorene compound, an indene compound or a mixture thereof having at least one polymer unsaturation group in one molecule. A prepreg produced by impregnating a glass cloth with the polymer composite, and a metal foil with resin produced by coating a copper foil with the polymer composite are also provided. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high frequency substrate suitable for electronic components and circuit boards used in a high frequency region.

[0002]

2. Description of the Related Art With the progress of the advanced information society in recent years,
In the fields of information processing and information communication, higher speed and higher functionality have been demanded. Along with this, higher performance has been required for materials of parts used for computers and mobile communication devices. To cope with the increase in the amount of information, the calculation speed must be improved, but for this purpose, the signal propagation speed must be increased, that is, the signal propagation delay time must be shortened. Here, the delay of signal propagation is closely related to the dielectric constant of the material, and the lower the dielectric constant, the more advantageous the reduction of the delay time. In the field of information communication, the frequency to be used is shifting to higher frequency with the increase in the number of channels of mobile communication devices. Since a high frequency has a property of being converted into heat and losing, a material having a small transmission loss is required to efficiently transfer an electric signal. The transmission loss is closely related to the dielectric constant and the dielectric loss tangent, and the lower these are, the smaller the transmission loss becomes. From such a background, in the fields of information processing and information communication, there is a strong demand for a high frequency substrate using a material having a low dielectric constant and a low dielectric loss tangent.

As a material used for such a high frequency substrate, for example, polybenzocyclobutene (RA Kirchhof)
f et al., Macromol. Symp. 54/55, 531 (1992)), fluorinated polybiphenylene ether (JP-A-10-74751), polyphenylene compound having a heterocyclic side chain (JP-A-9-278879). Gazette), polyfumaric acid ester (JP-A-9-208697), polynorbornene (JP-A-5-214079), polyquinoxaline (Patent No. 27057).
99 gazette), fluorinated polyquinoline (Table 6-500591)
Gazette), a side chain allyl group-substituted polyphenylene ether (JP-A-64-69628, JP-A-4-183707,
6-2007096), polyphenylene ether end-capped with an allyl group or a propargyl group (Japanese Patent Publication No. 7-51625).
Gazette) and the like. However, the materials proposed in these prior arts have a low crosslink density, a large linear expansion coefficient, a poor chemical resistance, a poor toughness, a complicated manufacturing process, and a multi-step process. Actually, there are various problems such as the need for a special solvent for shaping.

The present inventors have previously proposed a novel vinylbenzyl ether compound (Japanese Patent Laid-Open No. 9-31006). This compound is a compound showing a low dielectric constant, a low dielectric loss tangent, and a low water absorption in a wide temperature and frequency range,
It is one of the few materials that meets the current stringent requirements for substrate materials. However, the performance required for the substrate material is becoming higher and higher, and further excellent dielectric properties are required for the next-generation communication equipments in the future.

[0005]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a substrate, a prepreg, and a resin-coated metal foil which have excellent dielectric properties, particularly low dielectric loss tangent, and excellent heat resistance in the high frequency range. is there.

[0006]

According to a first aspect of the present invention, in a high frequency substrate obtained by polymerizing and curing a polymerizable composition, the polymerizable composition has at least one polymerizable unsaturated group in one molecule. A high frequency substrate comprising a fluorene compound having: (except when all the polymerizable unsaturated groups are vinylbenzyl groups). In the invention of claim 2, the fluorene compound has an allyl group and / or a propargyl group as the polymerizable unsaturated group, or has both one or more of the unsaturated groups and a vinylbenzyl group. It is a high frequency substrate. According to a third aspect of the present invention, in a high frequency substrate obtained by polymerizing and curing a polymerizable composition, the polymerizable composition comprises:
A high frequency substrate comprising an indene compound having at least one polymerizable unsaturated group in one molecule. The invention of claim 4 is the high frequency substrate according to claim 3, wherein the polymerizable unsaturated group is a vinylbenzyl group, an allyl group and / or a propargyl group. According to a fifth aspect of the present invention, in a high frequency substrate obtained by polymerizing and curing a polymerizable composition, the polymerizable composition comprises a fluorene compound having at least one polymerizable unsaturated group in one molecule, and
A high frequency substrate comprising: an indene compound having at least one polymerizable unsaturated group in the molecule. In the invention of claim 6, the fluorene compound is one kind or two or more kinds of compounds represented by the following general formula 1, and the polymerizable composition is the fluorene compound, vinylbenzyl halide, allyl halide and propargyl halide. The high frequency substrate according to claim 2, comprising a compound obtained by reacting a halogen compound having at least one polymerizable unsaturated group selected from the group with a dihalomethyl compound having 2 to 20 carbon atoms in the presence of an alkali. Is. (General formula 1)

[0007]

[Chemical 3]

(Wherein R is a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, which may be the same or different, an alkoxy group, a thioalkoxy group, a thioaryloxy group and an aryl group. In the invention of claim 7, the indene compound is one kind or two or more kinds of compounds represented by the following general formula 2, and the polymerizable composition is the indene compound and vinylbenzyl. A compound obtained by reacting a halogen compound having at least one polymerizable unsaturated group selected from halides, allyl halides and propargyl halides with a dihalomethyl compound having 2 to 20 carbon atoms in the presence of an alkali. 4 is a high frequency substrate. (General formula 2)

[0009]

[Chemical 4]

(In the formula, R is a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms which may be the same or different, an alkoxy group, a thioalkoxy group, a thioaryloxy group and an aryl group. In the invention of claim 8, the fluorene compound is represented by the general formula 1
The indene compound is one or more of the compounds represented by the general formula 2, and the polymerizable composition is the fluorene compound and the indene. Obtained by reacting a compound, a halogen compound having at least one polymerizable unsaturated group selected from vinylbenzyl halide, allyl halide and propargyl halide, and a dihalomethyl compound having 2 to 20 carbon atoms in the presence of alkali. The high frequency substrate according to claim 5, further comprising a compound. The invention of claim 9 is such that the equivalent ratio of the halomethyl group of the halogen compound having a polymerizable unsaturated group to the halomethyl group of the dihalomethyl compound having 2 to 20 carbon atoms is 0.9 / 0.1 to 0.1 / 0.9. The high frequency substrate according to any one of 1. The invention of claim 10 is a composition in which the polymerizable composition comprises a fluorene compound having at least one polymerizable unsaturated group in one molecule and a compound copolymerizable therewith. The high frequency substrate described in. The invention of claim 11 is a composition in which the polymerizable composition comprises an indene compound having at least one polymerizable unsaturated group in one molecule and a compound copolymerizable therewith. The high frequency substrate described in. The invention of claim 12 is a prepreg obtained by impregnating a fibrous material with the polymerizable composition according to claim 1, 3, 5, 6, 7, 8, 10 or 11. The invention of claim 13 is the prepreg according to claim 12, wherein the fiber material is glass cloth. A fourteenth aspect of the present invention is a high-frequency substrate obtained by heating or pressing the prepreg according to the twelfth or thirteenth aspect alone or in a laminated manner. A fifteenth aspect of the present invention is a metal-clad high-frequency substrate obtained by singly or laminating the prepreg according to the twelfth or thirteenth aspect, further stacking metal foils, and applying heat and pressure. According to a sixteenth aspect of the present invention, a resin is obtained by coating the metal foil with the polymerizable composition according to the first, third, fifth, sixth, seventh, eighth, tenth or eleventh aspect, and integrating the two. It is a metal foil. According to a seventeenth aspect of the invention, the polymerizable composition according to the first, third, fifth, sixth, seventh, eighth, tenth or eleventh aspect is applied onto the conductive layer, polymerized and cured, and further on the cured product. A multi-layer laminated substrate having a conductive layer.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The polymerizable composition used in the present invention has the following five modes. (1) Includes a fluorene compound having at least one polymerizable unsaturated group in one molecule; (2) Includes an indene compound having at least one polymerizable unsaturated group in one molecule; (3) At least one in one molecule A mixture of a fluorene compound having one polymerizable unsaturated group and an indene compound having at least one polymerizable unsaturated group in one molecule; (4) fluorene having at least one polymerizable unsaturated group in one molecule A composition comprising a compound and a compound copolymerizable therewith; (5) an indene compound having at least one polymerizable unsaturated group in one molecule, and a compound copolymerizable therewith Composition.

First, the mode (1) will be described. The fluorene compound having at least one polymerizable unsaturated group in one molecule is not particularly limited, but for example, has an allyl group and / or propargyl group as the polymerizable unsaturated group, or one of the unsaturated groups. A compound having both of the above and a vinylbenzyl group is preferable. More specifically, the polymerizable composition of (1) above
As the fluorene compound, one or more compounds represented by the general formula 1 are used, and a halogen compound having at least one polymerizable unsaturated group selected from vinylbenzyl halide, allyl halide and propargyl halide is used. It is preferable to include a compound obtained by reacting a dihalomethyl compound having 2 to 20 carbon atoms in the presence of an alkali. In such a compound, the halogen compound and the dihalomethyl compound are considered to be bonded to the 9-position of the fluorene skeleton.

Examples of the halide having a polymerizable unsaturated group include m-vinylbenzyl chloride, p-vinylbenzyl chloride, m-vinylbenzyl bromide and p-vinylbenzyl bromide.
Examples thereof include vinylbenzyl bromide, allyl chloride, allyl bromide, propargyl chloride and propargyl bromide, and these may be used alone or in combination of two or more.

The dihalomethyl compound having 2 to 20 carbon atoms (the dihalomethyl compound in the present invention is a compound having _two —CH ₂ X (wherein X represents a halogen atom) groups in the molecule. ), For example, 1,2-dichloroethane, 1,2-dibromoethane, 1,3-dichloropropane,
1,3-dibromopropane, 1,4-dichlorobutane, 1,4-
Alkylene dihalides such as dibromobutane, o-xylylene dichloride, o-xylylene dibromide, m-xylylene dichloride, m-xylylene dibromide, p
-Xylylene dichloride, p-xylylene dibromide, 4,4'-bis (chloromethyl) biphenyl, 4,4'-bis (chloromethyl) diphenyl ether, 4,4'-bis (chloromethyl) diphenyl sulfide, 2, Dihalomethyl compounds such as 6-bis (bromomethyl) naphthalene, 1,8-bis (bromomethyl) naphthalene, and 1,4-bis (chloromethyl) naphthalene are listed, and each of them is independent within a range where intramolecular cyclization does not occur. However, two or more kinds may be mixed and used.

The equivalent ratio of the halomethyl group of the halide having a polymerizable unsaturated group to the halomethyl group of the dihalomethyl compound having 2 to 20 carbon atoms can be selected within the range where gelation by the dihalomethyl compound does not occur, but is 0.9 / 0.1. ~ 0.1
/0.9 is preferable. When the amount of the halide having a polymerizable unsaturated group is less than that, the curability deteriorates, and the physical properties of the cured product such as heat resistance deteriorate.

As the reaction solvent, dimethylformamide,
Dimethylsulfoxide, dimethylacetamide, N-methylpyrrolidone, dioxane, acetonitrile, tetrahydrofuran, ethylene glycol dimethyl ether,
1,3-dimethoxypropane, 1,2-dimethoxypropane,
Tetramethylene sulfone, hexamethylphosphoamide,
Examples include methyl ethyl ketone, methyl isobutyl ketone, acetone, cyclohexane, methyl cyclohexane, toluene, xylene, etc., and mixtures thereof. From among these, a solvent species that makes the reaction system uniform depending on the raw material species and reaction conditions can be selected. Good.

Examples of the alkali include alkali metal or alkaline earth metal alkoxides, hydrides and hydroxides such as sodium methoxide, sodium ethoxide, sodium hydride, potassium hydride, sodium hydroxide and potassium hydroxide. The alkaline species may be selected depending on whether the reaction system is a non-aqueous system or a water-containing system. The proportion of alkali used is preferably 1.1 to 3.0 equivalents per equivalent of the starting halomethyl group. If the equivalent is less than 1.1, the reaction rate will be significantly slowed down, or the reaction will not proceed completely and the raw materials will remain, adversely affecting the cured physical properties, and even if used in excess of 3 equivalents, residual alkali It is not economical because a large amount of cleaning water is used for removal.

A phase transfer catalyst can be used for the reaction in the presence of alkali. For example, as a phase transfer catalyst, various onium salts, for example, quaternary ammonium compounds such as tetra-n-butylammonium bromide, tetra-n-butylammonium hydrogensulfate, benzyltrimethylammonium chloride, tricaprylmethylammonium chloride, tetra-n-
Examples thereof include quaternary phosphonium compounds such as butylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium chloride and tetraphenylphosphonium bromide, tertiary sulfonium compounds such as benzyltetramethylenesulfonium bromide and mixtures thereof. The amount of these phase transfer catalysts used cannot be unconditionally specified because the catalytic effect varies depending on the catalyst species or the reaction temperature, but generally 0.01 to 0.5 equivalent is sufficient with respect to 1 equivalent of the halomethyl group of the raw material. Is.

The reaction temperature and reaction time cannot be specified unconditionally because they vary depending on the kind of the starting material compound used and the reaction conditions, but may be 0.5 to 20 hours at 30 to 100 ° C., respectively. A reaction temperature of more than 100 ° C. is not preferable because unfavorable reactions such as thermal polymerization may occur at the same time. The reaction proceeds even at a temperature lower than 30 ° C, but it is not economical because it takes a long time.

If desired, a polymerization inhibitor may be added to the reaction system, for example, t-butylcatechol, 2,4-
Di-t-butylphenol, 2-t-butylphenol, 2
-T-butyl-4-nitrophenol, 2,4-dinitrophenol, hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, t-butylhydroquinone, resorcin, pyrogallol, phenothiazine,
Examples include copper salts. The amount of these polymerization inhibitors used is
Since the effect varies depending on the type, it cannot be specified unconditionally, but several ppm to 2000 ppm is sufficient for the polymerizable composition.

Next, the mode (2) will be described. The indene compound having at least one polymerizable unsaturated group in one molecule is not particularly limited, but for example, a compound having a vinylbenzyl group, an allyl group and / or a propargyl group as the polymerizable unsaturated group is preferable. More specifically, the polymerizable composition of (2) above
As the indene compound, one or more compounds represented by the general formula 2 are used, and a halogen compound having at least one polymerizable unsaturated group selected from vinylbenzyl halide, allyl halide and propargyl halide is used. The compound is preferably a compound obtained by reacting a dihalomethyl compound having 2 to 20 carbon atoms in the presence of an alkali. In such a compound, the halogen compound and the dihalomethyl compound are considered to be bonded to the 1,3 positions of the indene skeleton. The halide having a polymerizable unsaturated group, the dihalomethyl compound having 2 to 20 carbon atoms, the equivalent ratio of the two, the reaction solvent, the alkali species, the phase transfer catalyst species, the reaction conditions and the like are the same as those in the embodiment of (1). Is the same.

Next, the mode (3) will be described. In this aspect, the fluorene compound having at least one polymerizable unsaturated group in one molecule and the indene compound having at least one polymerizable unsaturated group in one molecule are the same as those in the above aspects (1) and (2). I can list things. In this case, the mixing ratio of the fluorene compound and the indene compound is 0.1 / 0.9 to 0.9 / 0.1 (weight ratio)
Is.

Next, the mode (4) will be described. In this aspect, as the fluorene compound having at least one polymerizable unsaturated group in one molecule, the same ones as in the above aspect (1) can be mentioned. As the compound copolymerizable with the fluorene compound, there are polymers, oligomers and / or monomers, and specific examples thereof include vinyl ester resins, unsaturated polyester resins, diallyl phthalate resins, maleimide resins, polyphenol polycyanate resins. Polymers such as epoxy resins, oligomers having a polymerizable unsaturated group such as vinylbenzyl ether resins, monomers and prepolymers such as triallyl isocyanurate and triallyl cyanurate, and vinylbenzyl compounds such as fluorene. . Furthermore, monomers such as styrene, vinyltoluene, divinylbenzene, vinylbenzyl ether compounds, and various known monofunctional or polyfunctional (meth) acrylic acid derivative compounds can be used. The amount of the copolymerizable compound used depends on the type of the copolymerizable compound, compatibility,
Although it cannot be specified unconditionally because it depends on the use of the cured product, etc., it is 0 to 100 parts by weight of the fluorene compound.
300 parts by weight, preferably 0 to 100 parts by weight. Three
If it is used in an amount of more than 00 parts by weight, the dielectric properties are deteriorated and separation / exudation from the composition is likely to occur, which is not preferable.

Next, the mode (5) will be described. In this aspect, examples of the indene compound having at least one polymerizable unsaturated group in one molecule are the same as those in the aspect (2). The compound copolymerizable with the indene compound and the amount of the compound used are the same as those in the aspect (4).

The dielectric composition and flame retardancy can be adjusted by adding a filler and a flame retardant to the polymerizable composition of the present invention with a kneader, blender, roll or the like, if necessary. Examples of the filler are silica, alumina, zirconia, titanium dioxide, magnesium hydroxide,
Examples thereof include aluminum hydroxide, calcium carbonate, various dielectric ceramics, and the like. As the flame retardant, a halogen-based, phosphorus-based, nitrogen-based, or other commercially available flame retardant can be used.

For the polymerization and curing of the polymerizable composition, known methods such as heat, light and electron beam can be adopted. It is also useful to use a curing agent to accelerate the curing reaction. The curing temperature varies depending on the type of the polymerizable unsaturated group, the type of the curing agent and the amount used, and therefore cannot be specified unconditionally, but is 20 to 250 ° C, preferably 50 to 250 ° C. If the curing temperature is lower than 20 ° C, curing may be insufficient, which is not preferable.

When a curing agent is used, for example, benzoyl peroxide, cumene hydroperoxide, 2,
5-Dimethyl-2,5-di (t-butylperoxy) hexyne-3, t-butylcumyl peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, t-
Butyl perbenzoate and the like can be used depending on the application. The amount used varies depending on the type and concentration of unsaturated groups in the polymerizable composition, the type of curing agent used, half-life temperature, required stability, etc., but is generally 0 to 10% by weight of the composition. .

In addition, known curing accelerators such as manganese naphthenate, lead naphthenate, zinc naphthenate, cobalt naphthenate, zinc octylate, dimethylaniline and phenylmorpholine can be used. Further, a known curing retarder such as hydroquinone, benzoquinone, and a copper salt may be blended in order to adjust the curing conditions.

The high frequency substrate of the present invention thus obtained is suitable for use in a high frequency region of 100 MHz or higher, particularly 1 GHz or higher. In such a high frequency region, the dielectric loss tangent can be maintained at about 0.002 to 0.01.

The present invention also provides a prepreg obtained by impregnating a fibrous material with the above-mentioned polymerizable composition. As the fiber material used for preparing the prepreg of the present invention, glass fiber, carbon fiber, aromatic polyamide fiber,
Known fiber materials such as silicon carbide fibers and alumina fibers can be used, but it is preferable to use glass cloth made of glass fibers having low dielectric properties (low dielectric constant, low dielectric loss tangent). The content of the fiber material is 30 to 70% by weight with respect to the prepreg from the viewpoint of strength and moldability.
Is preferred. In the present invention, as a method of impregnating the fiber material with the polymerizable composition, any known solvent method or solventless method can be used.
As the solvent used in the solvent method, the residual solvent in the prepreg is reduced as much as possible, and the heat resistance is reduced or cracked, and a solvent having a relatively low boiling point in order to avoid the occurrence of voids, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. The above-mentioned ketone solvents, aromatic hydrocarbon solvents such as benzene and toluene, and the like can be used. A prepreg can be obtained by subjecting the fibrous material impregnated with the polymerizable composition to drying and heat treatment at 80 to 130 ° C. for 10 to 180 minutes, if necessary.

The obtained prepreg can be used alone or in a laminated form to apply heat and pressure to obtain a high frequency substrate. That is, a high-frequency substrate can be obtained by using a prepreg alone having a predetermined thickness, or stacking prepregs so as to have a predetermined thickness, and performing heat-press molding by a known method such as hot pressing. The molding conditions are 80 to 250 ° C, preferably 100 to 200 ° C.
The pressure is 5 to 100 kg / cm ^{2 and} the time is 0.5 to 10 hours, for example, and it is also effective to raise the temperature stepwise as necessary.

The present invention also provides a metal-clad high-frequency substrate obtained by singly or laminating the above prepregs, further stacking metal foils, and applying heat and pressure. That is, a prepreg having a predetermined thickness alone, or prepregs are laminated so as to have a predetermined thickness, metal foils are laminated on both surfaces of the laminated body, and the metal-clad high-frequency substrate is obtained by performing the heating and pressurizing. be able to.
Examples of the metal foil used in the present invention include copper, gold, silver, aluminum and the like, but copper is preferable. If necessary, electrolytic foil or rolled foil can be used.

Further, the above-mentioned polymerizable composition or a solution thereof is applied onto a metal foil such as the above-mentioned copper foil by a doctor blade coating method or the like, and at 80 to 130 ° C. for 10 minutes to 18 minutes.
It is also possible to obtain a resin-coated metal foil in which the both are integrated by performing drying for 0 minutes and heat treatment, and this may be used as a high-frequency substrate. Alternatively, a resin laminated metal foil may be layered on a core material and subjected to heat and pressure molding to form a multilayer laminated substrate.

Further, according to the present invention, there is provided a multi-layer laminated substrate in which the above-mentioned polymerizable composition is applied onto a conductive layer, polymerized and cured, and a conductive layer is further provided on the cured product. . Such a multilayer laminated substrate uses, for example, a copper foil having a thickness of 18 μm as a conductive layer, a polymerizable composition is applied thereon as an insulating layer having a thickness of 20 to 200 μm, preferably 50 to 100 μm, and heat-cured, It can be manufactured by a so-called build-up method, in which a conductive layer is further formed on it.

[0035]

The present invention will be further described below with reference to examples and comparative examples, but the present invention is not limited to these examples. In addition, unless otherwise indicated, the part in an example means a weight part. The measuring methods used in the examples are shown below.

Dielectric property: Using a vector network analyzer HP8753E manufactured by HP, a dielectric constant and a dielectric loss tangent at 5 GHz were measured by a cavity resonator perturbation method using a 1.6 mm × 1.5 mm × 75 mm prismatic test piece. ¹ H-nuclear magnetic resonance spectrum ( ¹ H-NMR): Tetramethylsilane was used as an internal standard substance, and JNM-LA300 manufactured by JEOL Ltd.
Was measured using. Gel permeation chromatography (GPC): Shodex GPCSYSTEM 21 (column KF-802, KF- manufactured by Showa Denko KK)
803, KF-805) was used as the eluent and the elution rate was 1 ml / min. This GPC was used to confirm the molecular weight. Solder heat resistance test: conducted according to JIS C 0054, 260 ° C
It was immersed for 120 seconds in the solder bath of No. 1 and it was confirmed that there was no change in surface condition or shape.

(Synthesis Example 1) 249 g (1.5 mol) of fluorene and 250 g of toluene were placed in a flask equipped with a temperature controller, a stirrer, a cooling condenser, a dropping funnel, and an oxygen inlet.
22 g of tetra-n-butylammonium bromide (0.069
Mol), 76 g (1.0 mol) of allyl chloride, 335 g of vinylbenzyl chloride CMS-AM (m / p isomer: 50/50 wt% mixture) manufactured by Seimi Chemical Co., Ltd. (purity 91%, 2.0 mol)
Was charged, and the temperature was raised to 40 ° C. with stirring to form a uniform solution. To this, 240 g of 50 wt% NaOH aqueous solution (NaOH, 6 mol)
Was added and then reacted at 60 ° C. for 8 hours. Next, after neutralizing the contents of the flask with 2N hydrochloric acid, washed twice with distilled water,
After the toluene was distilled off under reduced pressure, the obtained orange viscous liquid was vacuum dried to obtain a semi-solid compound in which fluorene was substituted with vinylbenzyl group and allyl group. This is designated as Compound 1. Confirmation of Compound 1 is ¹ H
-By NMR.

(Synthesis Example 2) A flask equipped with a temperature controller, a stirrer, a cooling condenser, a dropping funnel, and a nitrogen inlet was replaced with nitrogen, and 46.5 g (0.4 mol) of indene, 200 g of toluene, and tetra-n were added thereto. -Butyl ammonium bromide 7.75 g (0.024 mol), phenothiazine 0.08 g
(0.0004 mol), 128.0 g of 50 wt% NaOH aqueous solution (NaOH, 1.
(6 mol) was charged and the temperature was raised to 50 ° C. with stirring to form a uniform solution. To the dark blue-green solution, Seimi Chemical Co. vinylbenzyl chloride CMS-AM (m / p isomer: 50/50)
13% (wt% mixture) (purity 91%, 0.8 mol) was added dropwise over 15 minutes, and then the mixture was reacted at 50 to 52 ° C for 10 hours. Then, after neutralizing the contents of the flask with 2N hydrochloric acid, washed twice with distilled water, after distilling off the toluene under reduced pressure, the orange viscous liquid obtained was washed with methanol and then vacuum dried, A liquid compound in which indene was substituted with a vinylbenzyl group was obtained. This is designated as Compound 2. The compound 2 was confirmed by ¹ H-NMR.

(Synthesis Example 3) An indene was placed in a flask equipped with a temperature controller, a stirrer, a cooling condenser and a dropping funnel.
55 g (0.48 mol), fluorene 237 g (1.43 mol), toluene 1000 g, tetra-n-butylammonium bromide
22 g (0.069 mol), p-xylylene dichloride 250 g (1.43
Mol), vinylbenzyl chloride manufactured by Seimi Chemical Co., Ltd.
240 g (purity 91%, 1.43 mol) of CMS-AM (m / p isomer: 50/50 wt% mixture) was charged, and the temperature was raised to 40 ° C with stirring to form a uniform solution. 50 wt% NaOH aqueous solution 34
4 g (NaOH, 8.6 mol) was added, and then the mixture was reacted at 70 ° C. for 8 hours. Next, after neutralizing the contents of the flask with 2N hydrochloric acid, washed twice with distilled water, after distilling off the toluene under reduced pressure, the resulting orange viscous liquid was washed with methanol, and by vacuum drying, A solid compound having a weight average molecular weight Mw of 3,000 was obtained in which a vinylbenzyl group was substituted in an oligomer compound in which fluorene and indene were linked by xylylene. This is designated as Compound 3. Confirmation of Compound 3 is ¹ H
-By NMR.

(Comparative Synthesis Example 1) Temperature controller, stirring device,
In a 1 liter four-necked flask equipped with a cooling condenser and a dropping funnel, dicyclopentadiene skeleton phenol resin DPP-3H (special petroleum resin manufactured by Nippon Petrochemical Co., Ltd.) 45 g (0.25 equivalent), vinylbenzyl chloride CMS-AM (M- / p-isomer: 50/50 wt%
Mixture)) 38.1 g (purity 91%, 0.25 mol), tetra-n-butylammonium bromide 2.4 g,
At a temperature of 75 ° C., 0.038 g of 2,4-dinitrophenol and 200 g of methyl ethyl ketone were charged and dissolved with stirring.
40 g of 50% by weight NaOH aqueous solution (NaOH purity 95
%, 0.475 mol) over 20 minutes and then 7
Stirring was continued for 4 hours at 5 ° C. 2N after cooling to room temperature
After neutralizing the reaction mixture with hydrochloric acid and adding 100 g of toluene, the organic layer was washed 3 times with 300 g of distilled water. After removing methyl ethyl ketone under reduced pressure, 300 ml of the reaction product
Of methanol, the solid content was collected by filtration, and dried in a vacuum oven at 50 ° C. to obtain a vinylbenzyl ether compound in a yield of 95%. This is designated as Compound 4.

(Example 1) A 60% toluene solution of Compound 1 was impregnated in glass cloth WEA18K105BZ2 (Nitto Boseki Co., Ltd.) and dried at 120 ° C for 60 minutes to obtain a prepreg. 10 plies of this prepreg are laminated and subjected to heat and pressure molding (40 kg / cm ² ) at 150 ° C. for 2 hours, 180 ° C. for 5 hours, and 200 ° C. for 5 hours to obtain a laminate having a plate thickness of 1.6 mm and a glass fiber content of 60% Got

Example 2 Compound 2 was used as glass cloth WEA1.
After impregnating it with 8K105BZ2 (Nitto Boseki Co., Ltd.), it was left at 120 ° C. for 30 minutes to obtain a prepreg. 10 plies of this prepreg were laminated and subjected to heat and pressure molding (40 kg / cm ² ) at 150 ° C. for 2 hours and 180 ° C. for 6 hours to obtain a laminated plate having a plate thickness of 1.6 mm and a glass fiber content of 62%.

Example 3 A glass cloth WEA18K105BZ2 (Nitto Boseki Co., Ltd.) was impregnated with a 60% toluene solution of the compound 3 and dried at 120 ° C. for 60 minutes to obtain a prepreg. 10 plies of this prepreg were laminated and subjected to heat and pressure molding (40 kg / cm ² ) at 150 ° C. for 2 hours and 180 ° C. for 6 hours to obtain a laminated plate having a plate thickness of 1.6 mm and a glass fiber content of 60%.

Example 4 A resin solution prepared by adding 10 parts of phenylmaleimide to 90 parts of the compound 1 to prepare a 60% toluene solution was impregnated into a glass cloth WEA18K105BZ2 (Nitobo Co., Ltd.) and then 120 ° C. And dried for 60 minutes to obtain a prepreg. Laminate 10 plies of this prepreg,
Heat press molding (40 kg / cm ² ) was performed at 150 ° C. for 2 hours, 180 ° C. for 5 hours, and 200 ° C. for 5 hours to obtain a laminate having a plate thickness of 1.6 mm and a glass fiber content of 61%.

Example 5 A resin solution prepared by dissolving 100 parts of compound 1 and 120 parts of compound 2 in 80 parts of toluene was applied to a 35 μm copper foil (3EC / Mitsui Metal Industry Co., Ltd.) to give a thickness of 10 parts.
Coat to 0 μm and dry at 100 ° C for 60 minutes,
Further, it was heated at 120 ° C. for 2 hours to be in a semi-cured state (two were prepared). The two copper foils with resin are placed on top of each other so that the resin is in contact with each other, and the temperature is 150 ° C for 2 hours and 180 ° C for 6 hours.
After heat and pressure molding for 40 hours (40 kg / cm ² ), the peel strength of the copper foil was measured by the method of JIS C 6481 using the obtained sample, and the result was 1.2 kgf / cm.

Comparative Example 1 Compound 4 was dissolved in 60% toluene to prepare a resin solution, and this resin solution was impregnated into glass cloth WEA18K105BZ2 (Nittobo Co., Ltd.), and then 12
It was dried at 0 ° C for 90 minutes to obtain a prepreg. This prepreg 10 ply is laminated and subjected to heat and pressure molding (40 kg / cm ² ) at 150 ° C. for 2 hours and 180 ° C. for 6 hours to obtain a plate thickness of 1.6 mm,
A laminated plate having a glass fiber content of 62% was obtained.

(Comparative Example 2) 90 parts of bisphenol A type epoxy resin Epicoat 1001 (manufactured by Japan Epoxy Resins Co., Ltd.) and novolac type epoxy resin DEN438.
A resin solution prepared by dissolving 10 parts (manufactured by Dow Chemical Japan Co., Ltd.), 5 parts of dicyandiamide as a curing agent, and 0.3 parts of benzyldimethylamine as a curing accelerator in 70 parts of acetone was prepared as a glass cloth WEA18K105BZ2 (Nittobo). Co., Ltd.) and then at 160C for 5 minutes, then 160
It was dried at ℃ for 5 minutes to obtain a prepreg. This prepreg 10
Plies are laminated and heated and pressed at 160 ° C for 1 hour (7
0 kg / cm ² ) to obtain a laminated plate having a plate thickness of 1.6 mm and a glass fiber content of 62%.

The characteristics of the laminates obtained in the above Examples and Comparative Examples are shown in Table 1.

[0049]

[Table 1]

[0050]

According to the present invention, there are provided a substrate, a prepreg, and a resin-coated metal foil which have excellent dielectric properties, particularly low dielectric loss tangent, and excellent heat resistance in a high frequency range.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) H05K 3/46 H05K 3/46 T // C08L 45:00 C08L 45:00 (72) Inventor Haruo Yoshida Tokyo 1-12-7 Narusedai, Miyakomachida (72) Inventor Joji Shibata 2-4-20 Hinode, Honjo City, Saitama Prefecture (reference) 4F072 AA07 AB06 AB08 AB09 AB10 AB29 AB30 AD03 AD05 AD09 AD55 AE02 AE07 AE08 AG03 AG17 AG19 AH02 AH21 AH25 AJ04 AK02 AK03 AK14 AL13 4F100 AB01A AG00B AK11B AK11K BA02 DG12B DH02B GB43 JG05 JG10 JJ03 4J100 AB07P AB15P BC48P CA01 CA04 JA44 5E346 AA12 CC04 CC14 DD12 HH06

Claims (17)

[Claims] 1. A high frequency substrate obtained by polymerizing and curing a polymerizable composition, wherein the polymerizable composition contains a fluorene compound having at least one polymerizable unsaturated group in one molecule. High frequency substrate (except when all the polymerizable unsaturated groups are vinylbenzyl groups). 2. The high frequency wave according to claim 1, wherein the fluorene compound has an allyl group and / or a propargyl group as a polymerizable unsaturated group, or has both one or more of the unsaturated groups and a vinylbenzyl group. Substrate. 3. A high frequency substrate obtained by polymerizing and curing a polymerizable composition, wherein the polymerizable composition contains an indene compound having at least one polymerizable unsaturated group in one molecule. High frequency board. 4. The high frequency substrate according to claim 3, wherein the polymerizable unsaturated group is a vinylbenzyl group, an allyl group and / or a propargyl group. 5. A high-frequency substrate obtained by polymerizing and curing a polymerizable composition, wherein the polymerizable composition has a fluorene compound having at least one polymerizable unsaturated group in one molecule and at least 1 in one molecule. A high frequency substrate comprising: an indene compound having two polymerizable unsaturated groups. 6. The fluorene compound is one or more compounds represented by the following general formula 1, and the polymerizable composition is selected from the fluorene compound, vinylbenzyl halide, allyl halide and propargyl halide. The high frequency substrate according to claim 2, comprising a compound obtained by reacting at least one kind of halogen compound having a polymerizable unsaturated group with a dihalomethyl compound having 2 to 20 carbon atoms in the presence of an alkali. (General formula 1) (In the formula, R represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms which may be the same or different, an alkoxy group,
Denotes one or more groups selected from a thioalkoxy group, a thioaryloxy group and an aryl group) 7. The indene compound is one or more compounds represented by the following general formula 2, and the polymerizable composition is selected from the indene compound, vinylbenzyl halide, allyl halide and propargyl halide. The high frequency substrate according to claim 4, comprising a compound obtained by reacting a halogen compound having at least one kind of polymerizable unsaturated group with a dihalomethyl compound having 2 to 20 carbon atoms in the presence of an alkali. (General formula 2) (In the formula, R represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms which may be the same or different, an alkoxy group,
Denotes one or more groups selected from a thioalkoxy group, a thioaryloxy group and an aryl group) 8. The fluorene compound is one or more of the compounds represented by the general formula 1, and the indene compound is one or two of the compounds represented by the general formula 2.
At least one and the polymerizable composition, the fluorene compound, the indene compound, a vinyl benzyl halide, a halogen compound having at least one or more polymerizable unsaturated group selected from allyl halide and propargyl halide, The high frequency substrate according to claim 5, comprising a compound obtained by reacting a dihalomethyl compound having 2 to 20 carbon atoms in the presence of an alkali. 9. The equivalent ratio between the halomethyl group of the halogen compound having a polymerizable unsaturated group and the halomethyl group of the dihalomethyl compound having 2 to 20 carbon atoms is 0.9 / 0.1 to 0.1 / 0.9. The high frequency substrate as described in 1 above. 10. The composition according to claim 1, wherein the polymerizable composition is a mixture of a fluorene compound having at least one polymerizable unsaturated group in one molecule and a compound copolymerizable therewith. High frequency board. 11. The composition according to claim 3, wherein the polymerizable composition is a mixture of an indene compound having at least one polymerizable unsaturated group in one molecule and a compound copolymerizable therewith. High frequency board. 12. The method according to claim 1, 3, 5, 6, 7, 8, and 10.
Alternatively, a prepreg obtained by impregnating a fibrous material with the polymerizable composition as described in 11 above. 13. The prepreg according to claim 12, wherein the fiber material is glass cloth. 14. A high frequency substrate obtained by subjecting the prepreg according to claim 12 or 13 alone or by laminating the prepregs to heating and pressing. 15. A metal-clad high-frequency substrate obtained by singly or laminating the prepreg according to claim 12 or 13, and further stacking metal foils and applying heat and pressure. 16. The method according to claim 1, 3, 5, 6, on a metal foil.
A resin-coated metal foil obtained by applying the polymerizable composition as described in 7, 8, 10 or 11 and integrating both. 17. The method according to claim 1, 3, 5, 6, on the conductive layer.
A multi-layer laminated substrate characterized in that the polymerizable composition according to 7, 8, 10 or 11 is applied, polymerized and cured, and a conductive layer is further provided on the cured product.