JP2003012710A - Resin composition having low dielectric loss tangent, cured product of the same, prepreg using the same composition, laminated plate and multilayered printed board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition having a low dielectric constant and a low dielectric loss tangent, which is nonvolatile, is excellent in solubility and compatibility with various resins and contains a crosslinking agent, expresses good heat resistance and flexibility after curing the same, and provide a cured product of the same, a prepreg, a laminated plate and a multilayered printed board using the same. SOLUTION: The resin composition comprises a crosslinking ingredient having several styrene groups expressed by the formula (wherein R expresses a hydrocarbon skeleton; R<1> s are the same or mutually different and express each H or a 1-20C hydrocarbon group; R<2> , R<3> and R<4> are the same or different and express each H or a 1-6C alkyl; (m) is 1-4 integer; (n) is >=2 integer) and having <=1000 weight average molecular weight and a polymer. The resin composition gives the cured product having >=170 deg.C glass transition temperature by curing the same at 180 deg.C for 100 minutes or having >=500 MPa elastic modulus at 170 deg.C. The cured product of the same, the prepreg, the laminated plate and the multilayered printed board using the resin composition are also provided.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a printed wiring board having a low dielectric loss for dealing with high frequency signals, a laminated board with a conductor, a prepreg, a low dielectric loss tangent resin composition used for producing them, and a cured product thereof. .

[0002]

2. Description of the Related Art In recent years, the signal band of information communication devices such as PHS and mobile phones and the CPU clock time of computers have reached the GHz band, and higher frequencies have been in progress. The dielectric loss of an electrical signal is proportional to the product of the square root of the dielectric constant of the insulator forming the circuit, the dissipation factor and the frequency of the signal used. Therefore, the higher the frequency of the signal used, the larger the dielectric loss. Since the dielectric loss attenuates the electric signal and impairs the reliability of the signal, it is necessary to select a material having a small dielectric constant and a small dielectric loss tangent for the insulator in order to suppress it. Removal of polar groups in the molecular structure is effective for lowering the dielectric constant and lowering the dielectric loss tangent of insulators. Fluororesin, curable polyolefin, cyanate ester resin, curable polyphenylene oxide, allyl-modified polyphenylene ether, divinyl. Polyetherimides modified with benzene or divinylnaphthalene have been proposed.

Polytetrafluoroethylene (PTFE)
The fluororesin typified by 1) has a low dielectric constant and a low dielectric loss tangent, and is used as a substrate material for handling high frequency signals.
However, since PTFE is a thermoplastic resin, it has a large expansion and contraction during molding and is a difficult material to handle. Further, various proposals have been made for imparting crosslinkability and solubility to fluororesins, but those materials are generally expensive and many of them are inferior to PTFE in terms of characteristics. On the contrary,
Various non-fluorine-based resins having a low dielectric constant and a low dielectric loss tangent, which are soluble in an organic solvent and are easy to handle, have been studied. For example, an example in which a glass cloth is impregnated with a diene-based polymer such as polybutadiene described in JP-A-8-208856 and cured with a peroxide; as described in JP-A-10-158337, an norbornene-based addition type polymer has an epoxy group. Examples of cyclic polyolefins having introduced thereinto and imparting curability; JP-A-11-12
As described in 4491, an example in which a cyanate ester, a diene-based polymer and an epoxy resin are heated to B-stage; an example of a modified resin composed of polyphenylene oxide, a diene-based polymer and triallyl isocyanate described in JP-A-9-118759; Examples of resin compositions comprising allylated polyphenylene ether and triallyl isocyanate described in JP-A-9-246429;
Examples of alloying polyetherimide described in JP-A-156159 with styrene, divinylbenzene or divinylnaphthalene; synthesized by Williamson reaction from dihydroxy compound described in JP-A-5-78552 and chloromethylstyrene, for example, hydroquinone bis (vinyl There are many examples such as a resin composition comprising a benzyl) ether and a novolac phenol resin. Many of the above examples have described that divinylbenzene may be included as a cross-linking agent or co-agent. This is because divinylbenzene does not have a polar group in its structure, and its cured product has a low dielectric constant and dielectric loss tangent, and a thermal decomposition temperature of 350.
This is due to the high temperature above ℃. However, since the divinylbenzene cured product is extremely brittle, it has a drawback that the cured product is likely to crack during curing. Therefore, the amount of divinylbenzene added is usually set lower than that of other resin components. In the example of JP-A-5-156159 in which divinylbenzene is used as the main crosslinking agent, the addition amount is about 9% of the total resin. The divinylnaphthalene described in the publication also has the same problem as divinylbenzene in terms of brittleness of a cured product. In addition, since divinylbenzene is volatile, it has a drawback that it is hard to control the properties of the cured product because it is volatilized during curing. On the other hand, JP-A-5-78552 discloses that a bisstyrene compound such as hydroquinone bis (vinylbenzyl) ether is non-volatile and gives a cured product having high flexibility. However, in general, the alkylene ether group is more disadvantageous than the alkylene group and the arylene group in terms of dielectric constant, dielectric loss tangent and heat resistance. A hydrocarbon-based skeleton such as an alkylene group and an arylene group is preferable for the structure that bonds the styrene groups. Examples of polyfunctional styrene compounds in which styrene groups are bonded with ethylene groups are described in JP-A-9-208625.
2-bis (vinylphenyl) ethane, Makromol.
Chem. vol. 187, page 23 (1986), there is a divinylbenzene oligomer having a vinyl group in the side chain. However, in these reports, mechanical strength, heat resistance,
No studies have been made on the permittivity or loss tangent.

[0004]

Divinylbenzene, which has hitherto been used as a cross-linking agent capable of lowering the dielectric constant and dielectric loss tangent after curing of a composition containing it, is volatile and its curing property. It had drawbacks such as being fragile. The object of the present invention is to have a low dielectric constant and dielectric loss tangent,
A resin composition, a cured product thereof, and a prepreg using the composition, which is non-volatile, has excellent solubility and compatibility with various resins, and further includes a crosslinking agent having good heat resistance and flexibility after curing. To provide a laminated board and a multilayer printed circuit board.

[0005]

The present invention includes the following inventions. (1) The following general formula:

[Chemical 3] (In the formula, R represents a hydrocarbon skeleton, R ¹ is the same or different and represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ² , R ³ and R ⁴ are the same or different. , A hydrogen atom or an alkyl group having 1 to 6 carbon atoms, m is an integer of 1 to 4, and n is an integer of 2 or more.), A crosslinking component having a plurality of styrene groups and having a weight average molecular weight of 1000 or less. And a high molecular weight polymer, wherein the cured product obtained by curing the resin composition at 180 ° C. for 100 minutes has a glass transition temperature of 170 ° C. or higher, or the cured product. Of the resin composition having an elastic modulus at 170 ° C. of 500 MPa or more. (2) The composition according to (1), further containing at least one of a curing catalyst capable of polymerizing a styrene group and a polymerization inhibitor capable of suppressing the polymerization of the styrene group. (3) The amount of the curing catalyst added is 0.0005 to 10 with respect to 100 parts by weight of the total of the crosslinking component and the high molecular weight material.
The amount of the polymerization inhibitor added is 0.0005 parts by weight.
The composition according to (2) above, which is 5 parts by weight. (4) The composition according to any one of (1) to (3), wherein the high molecular weight polymer has a glass transition temperature of 170 ° C. or higher. (5) The high molecular weight compound is butadiene, isoprene, styrene, methylstyrene, ethylstyrene, divinylbenzene, acrylic ester, acrylonitrile, N-
At least one resin selected from the group consisting of a polymer consisting of at least one of phenylmaleimide and N-vinylphenylmaleimide, a polyphenylene oxide which may have a substituent, and a polyolefin having an alicyclic structure ( The composition according to any one of 1) to (4). (6) The following general formula:

[Chemical 4] (In the formula, R represents a hydrocarbon skeleton, R ¹ is the same or different and represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ² , R ³ and R ⁴ are the same or different. , A hydrogen atom or an alkyl group having 1 to 6 carbon atoms, m is an integer of 1 to 4, and n is an integer of 2 or more.), A crosslinking component having a plurality of styrene groups and having a weight average molecular weight of 1000 or less. Which is a cured product obtained by curing a resin composition containing a polymer and a high molecular weight polymer, and has a glass transition temperature of 170 ° C. or higher, or an elastic modulus at 170 ° C. of 500 MPa.
The cured product that is the above. (7) A cured product of the composition according to any one of (1) to (5). (8) A prepreg obtained by impregnating an organic or inorganic cloth or nonwoven fabric with the composition according to any one of (1) to (5) and drying the composition. (9) A cured product of the prepreg according to (8) above. (10) A laminated board having conductor layers provided on both surfaces or one surface of the prepreg or the cured product thereof described in (8). (11) A multilayer printed circuit board obtained by wiring the conductor layers of the laminated board according to (10) above, and laminating and adhering the laminated boards through a prepreg.

(Function) It has already been described that the cured product of divinylbenzene has high heat resistance and low dielectric constant and dielectric loss tangent. According to the present invention, a resin composition containing a cross-linking component of a nonvolatile hydrocarbon skeleton having a plurality of styrene groups and a weight average molecular weight of 1,000 or less and a high molecular weight substance does not crack during curing, and has a dielectric constant and a dielectric loss tangent. Was found to give a low cured product. Since the styrene groups are bonded by a flexible hydrocarbon skeleton such as an alkylene group, cracks do not occur during curing. Further, a low dielectric loss tangent resin composition having a glass transition temperature after curing of 170 ° C. or higher, or an elastic modulus at 170 ° C. after curing of 500 MPa or higher is processed at high temperatures such as gold wire bonding and soldering. Since the deformation is small in the process,
It is suitable as an insulating material for electronic components such as multi-chip modules and multilayer printed circuit boards.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The resin composition of the present invention and its cured product will be described. The resin composition of the present invention has the following general formula:

[Chemical 5] (In the formula, R represents a hydrocarbon skeleton, R ¹ is the same or different and represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ² , R ³ and R ⁴ are the same or different. , A hydrogen atom or an alkyl group having 1 to 6 carbon atoms, m is an integer of 1 to 4, and n is an integer of 2 or more.), A crosslinking component having a plurality of styrene groups and having a weight average molecular weight of 1000 or less. And a high molecular weight polymer, wherein the cured product obtained by curing the resin composition at 180 ° C. for 100 minutes has a glass transition temperature of 170 ° C. or higher, or the cured product. Of the resin composition having an elastic modulus at 170 ° C. of 500 MPa or more, the glass transition temperature of the cured product is 170 to 300 ° C., or the elastic modulus of the cured product at 170 ° C. is 500 to 3000 MPa. Is preferred.

The cured product of the present invention is a cured product obtained by curing a resin composition containing the above-mentioned crosslinking component and a high molecular weight substance, and has a glass transition temperature of 170 ° C. or higher, or 170. It is a cured product having an elastic modulus at 500C of 500 MPa or more and a glass transition temperature of 170 to 300C.
Or the elastic modulus at 170 ° C. is 500 to 30
It is preferably 00 MPa.

In the present specification, the glass transition temperature is the ratio of the loss elastic modulus to the storage elastic modulus when observing the dynamic viscoelastic property under the condition of the temperature rising rate of 5 ° C./min.
The temperature at which δ reaches a peak is shown, and the elastic modulus is the elastic modulus at 170 ° C. measured under the same conditions. Dielectric loss of electric signals can be reduced by using a printed board having a low dielectric constant and a low dielectric loss tangent, a high glass transition temperature, and a cured product of the resin composition of the present invention having a high elastic modulus at a high temperature for an insulating layer. It is possible to suppress the deformation to a low level and suppress deformation in a high temperature working process such as gold wire bonding and soldering.

In the above formula, the hydrocarbon skeleton represented by R is not particularly limited as long as the weight average molecular weight of the crosslinking component is 1000 or less. That is, the hydrocarbon skeleton represented by R has a substituent in the styrene group, R ¹ , R ² ,
It can be appropriately selected depending on the presence or absence of R ³ and R ⁴ , their size, and the numbers of m and n, but generally, the number of carbon atoms is 1 to 6.
It is 0, and preferably has 2 to 30 carbon atoms. The hydrocarbon skeleton represented by R may be linear or branched, and may contain one or more ring structures such as an alicyclic structure and an aromatic ring structure. , Ethynylene, etc. may be included.

Examples of the hydrocarbon skeleton represented by R include ethylene, trimethylene, tetramethylene, methyltrimethylene, methyltetramethylene, pentamethylene, methylpentamethylene, cyclopentylene, cyclohexylene, phenylene, phenylenediethylene, Examples include xylylene and 1-phenylene-3-methylpropenylene.

In the above formula, the hydrocarbon group represented by R ¹ has 1 to 20 carbon atoms, preferably 1 to 1 carbon atoms.
0, linear or branched alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, pentyl, hexyl, decyl, eicosyl; 2 to 20 carbon atoms, preferably Is a linear or branched alkenyl group having 2 to 10 carbon atoms such as vinyl, 1-propenyl, 2-propenyl, 2-methylallyl; aryl group such as phenyl, naphthyl,
Examples include benzyl, phenethyl, styryl and cinnamyl.

In the above formula, n is an integer of 2 or more.
From that, R¹Is present, and m is an integer of 2 to 4,
Also, R¹There are multiple, but there are multiple such
R¹May be the same or different, and their bonding positions are also the same.
It may be one or different. In the above formula, R², R³
Or R^FourThe alkyl group represented by has 1 to 6 carbon atoms.
A linear or branched alkyl group of, for example, methyl,
Ethyl, n-propyl, isopropyl, n-butyl, a
Examples include sobutyl and hexyl. In the above formula,
Optionally substituted vinyl group [(R³) (R^Four) C = C
(R ²)-] Is preferably relative to R on the benzene ring.
Exists in the meta position or the para position.

The crosslinking component used in the present invention is preferably a polyfunctional monomer having a plurality of (optionally substituted) styrene groups and a weight average molecular weight of 1,000 or less. Styrene groups are highly reactive and have a very low dielectric constant and loss tangent. A hydrocarbon skeleton is preferably used as the skeleton of the crosslinking component from the viewpoint of dielectric constant and dielectric loss tangent. This makes it possible to impart nonvolatility and flexibility to the crosslinking component without impairing the low dielectric constant and low dielectric loss tangent of the styrene group. Further, by selecting a cross-linking component having a weight average molecular weight of 1,000 or less, it exhibits melt flowability at a relatively low temperature and has good solubility in an organic solvent, which facilitates molding and varnishing. If the weight average molecular weight of the cross-linking component is too large, the melt fluidity may be low, and cross-linking may occur during molding, resulting in poor molding. The weight average molecular weight of the crosslinking component is not limited as long as it is 1,000 or less, but preferably 200 to 500.

Preferred examples of the crosslinking component are 1,2-
Bis (p-vinylphenyl) ethane, 1,2-bis (m
-Vinylphenyl) ethane, 1- (p-vinylphenyl) -2- (m-vinylphenyl) ethane, 1,4-bis (p-vinylphenylethyl) benzene, 1,4-bis (m-vinylphenylethyl) ) Benzene, 1,3-bis (p-vinylphenylethyl) benzene, 1,3-bis (m-vinylphenylethyl) benzene, 1- (p-
Vinylphenylethyl) -4- (m-vinylphenylethyl) benzene, 1- (p-vinylphenylethyl)-
Examples thereof include 3- (m-vinylphenylethyl) benzene and a divinylbenzene polymer (oligomer) having a vinyl group in its side chain. These cross-linking components may be used in combination of two or more.

As a method for synthesizing the crosslinking component preferably used in the present invention, Makromol, which is a method of coupling halogenoalkylstyrene synthesized by the method described in JP-A No. 11-60519 with various halides by Grignard reaction, is described. ． Chem. vol. 18
7, 23 (1986), a method for synthesizing a divinylbenzene oligomer having a vinyl group in its side chain can be mentioned, but not limited thereto. The cross-linking component thus obtained cross-links at a relatively low temperature of 180 ° C. or lower without adding a curing catalyst, and gives a cured product having high heat resistance and a low dielectric constant and dielectric loss tangent. However, when the crosslinking component is used alone without being combined with a high molecular weight substance,
In some cases, the tack-free property of the prepreg cannot be obtained, or in some cases, sufficient mechanical strength cannot be obtained after curing.

The present invention is characterized by improving the tack-free property and the mechanical strength of the cured product by combining the above-mentioned cross-linking component and the high molecular weight substance. The polymer used in the present invention has a glass transition temperature of 1
70 ° C or higher, or an elastic modulus at 170 ° C of 5
It is preferably a soluble polymer having a pressure of at least 00 MPa and easily varnishing, and has a glass transition temperature of 170.
~ 300 ° C, or 170 ° C has an elastic modulus of 5
More preferably, it is from 00 to 3000 MPa. When the high molecular weight material has curability, the glass transition temperature after curing is preferably 170 ° C. or higher, or the elastic modulus at 170 ° C. is preferably 500 MPa or higher, and the glass transition temperature after curing is 170 to 300. ℃ or 170
It is more preferable that the elastic modulus at ° C is 500 to 3000 MPa. Specific examples of such high molecular weight compounds include butadiene, isoprene, styrene, methylstyrene, ethylstyrene, divinylbenzene, acrylic acid esters (eg, methyl acrylate, butyl acrylate, phenyl acrylate, etc.), acrylonitrile. And a monomer selected from N-phenylmaleimide and N-
Examples thereof include, but are not limited to, a copolymer with vinylphenyl maleimide, a polyphenylene oxide which may have a substituent, and a polyolefin having an alicyclic structure. Since the crosslinking component used in the present invention is soluble in most organic solvents, it can be mixed with various high molecular weight substances to obtain a uniform varnish. Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, aromatic hydrocarbons such as toluene and xylene, N, N-dimethylformamide, and the like.
Examples include amides such as N, N-dimethylacetamide, diethyl ether, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethers such as tetrahydrofuran and dioxane, alcohols such as methanol, ethanol, and isopropanol, and organic solvents of these. Can be used alone or in combination of two or more. The rubber-like component such as butadiene, isoprene and acrylic acid ester imparts flexibility and adhesiveness to the cured product of the resin composition containing it and imparts smoothness to the coating film. Styrene, ethylstyrene, and / or acrylonitrile have the function of improving the heat resistance of the cured product by copolymerizing with the rubber-like component. Using divinylbenzene and / or N-vinylphenylmaleimide, a high molecular weight compound having a functional group in the side chain can be synthesized by a known ionic polymerization method.
In particular, N-vinylphenylmaleimide is easy to copolymerize with various monomers because only maleimide group is polymerized by anionic polymerization and only styrene group is polymerized by cationic polymerization, and the glass transition temperature of the copolymer is high. . Further, since the high molecular weight compound having a functional group in the side chain reacts with the crosslinking component, the resin composition containing the high molecular weight compound and the crosslinking component is suppressed from phase separation after curing, and a strong cured product is obtained. give. Polyphenylene oxide and polyolefin having an alicyclic structure are heat-resistant polymers, and by being alloyed with the above-mentioned cross-linking component, it is possible to impart flexibility and adhesiveness to the cured product and improve its mechanical strength. These high molecular weight compounds may be used alone or in combination. For example, it is preferable to combine polyphenylene oxide and polybutadiene.

The composition of the present invention is used for the purpose of improving the mechanical strength of the cured product, reducing the coefficient of thermal expansion, adjusting the dielectric constant, and improving the adhesive strength with plated wiring due to weight reduction or surface roughening. Fillers can be added for this purpose. In order to improve mechanical strength, it is preferable to add a fibrous filler such as aluminum borate whiskers or carbon fibers.
In order to reduce the coefficient of thermal expansion, it is preferable to fill spherical fillers having different particle diameters such as silicon oxide at a high ratio. In adjusting the dielectric constant, it is preferable to add titanium oxide having a high dielectric constant to increase the dielectric constant or to add borosilicate glass balloon having a low dielectric constant to reduce the dielectric constant. For surface roughening, it is preferable to add a filler soluble in an alkaline aqueous solution, such as calcium carbonate or magnesium hydroxide. These fillers may be used alone or in combination.

A crosslinking component contained in the resin composition of the present invention,
There is no particular limitation on the amount of the high molecular weight material and the filler added, but the crosslinking component is 5 to 95 parts by weight, and the high molecular weight material is 95 to
It is preferable to add 5 parts by weight and the filler in the range of 70 to 5 parts by weight. Within the above composition range, a composition is selected according to the purpose such as imparting film-forming properties, improving strength, reducing thermal expansion coefficient, adjusting dielectric constant, improving adhesion to plated wiring by weight reduction and surface roughening. Can be adjusted. As a more preferable composition, the crosslinking component is 50 to 95 parts by weight and the high molecular weight component is
0 to 5 parts by weight, the filler is 70 to 5 parts by weight, and more preferable composition is 50 to 80 parts by weight of the crosslinking component, 50 to 20 parts by weight of the high molecular weight component, and 70 to 5 parts by weight of the filler. With this composition range, the solvent resistance of the cured product is maintained even when a high molecular weight polymer having no crosslinkable functional group is used.

The resin composition of the present invention can be cured only by heating without adding a curing catalyst, but a curing catalyst capable of polymerizing a styrene group can be added for the purpose of improving curing efficiency. The addition amount is not particularly limited, but since the residue of the curing catalyst may adversely affect the dielectric properties, the total amount of the crosslinking component and the high molecular weight compound is 1
0.0005 to 10 parts by weight is desirable with respect to 00 parts by weight. By adding the curing catalyst in the above range, the polymerization reaction of the styrene group is promoted, and a strong cured product can be obtained at low temperature. Examples of curing catalysts that generate cation or radical active species capable of initiating the polymerization of styrene groups by heat or light are shown below. Examples of the cationic polymerization initiator include diallyliodonium salts having BF ₄ , PF ₆ , AsF ₆ , and SbF ₆ as counter anions, triallyl sulfonium salts and aliphatic sulfonium salts, and Asahi Denka Kogyo SP-70, 172, CP-66, Nippon Soda C
I-2855, 2823, Sanshin Chemical Industry SI-100
Commercial products such as L and SI-150L can be used. Examples of the radical polymerization initiator include benzoin compounds such as benzoin and benzoinmethyl, acetophenone compounds such as acetophenone and 2,2-dimethoxy-2-phenylacetophenone, and thioxanthone compounds such as thioxanthone and 2,4-diethylthioxanthone. Compound, 4,4'-diazidochalcone, 2,6
-Bis (4'-azidobenzal) cyclohexanone and bisazide compounds such as 4,4'-diazidobenzophenone, azobisisobutylnitrile, 2,2-azobispropane, m, m'-azoxystyrene and hydrazone Azo compounds, and 2,5-dimethyl-
2,5-di (t-butylperoxy) hexane and 2,
Examples thereof include 5-dimethyl-2,5-di (t-butylperoxy) hexyne-3 and organic peroxides such as dicumyl peroxide. In particular, it is desirable to add an organic peroxide or a bisazide compound which can cause hydrogen abstraction of a compound having no functional group and can bring about crosslinking between the crosslinking component and the high molecular weight substance.

A polymerization inhibitor may be added to the resin composition of the present invention in order to increase storage stability. The addition amount is preferably in a range that does not significantly impair the dielectric properties and the reactivity during curing, and is 0.0005 to 5 with respect to 100 parts by weight of the total of the crosslinking component and the high molecular weight body.
It is desirable to use parts by weight. When the polymerization inhibitor is added within the above range, an excessive crosslinking reaction during storage can be suppressed, and no significant curing trouble is caused during curing. Examples of the polymerization inhibitor include hydroquinone and p-
Benzoquinone, chloranil, trimethylquinone, 4-t
And quinones such as butylpyrocatechol and aromatic diols.

The resin composition of the present invention can be used as a prepreg by impregnating an organic or inorganic cloth or nonwoven fabric and drying it. The base material of the prepreg is not particularly limited, and various glass cloths, glass non-woven fabrics, aramid non-woven fabrics, porous PTFE and the like can be used. The prepreg is produced by immersing a cloth or a non-woven fabric as a base material in a varnish produced by using a resin composition, and then drying this. Drying conditions after impregnation depend on the resin composition, but when toluene is used as a solvent, for example, it is preferable to dry at 80 to 130 ° C. for about 30 to 90 minutes.

By laminating a conductor foil such as an electrolytic copper foil on the prepreg of the present invention and subjecting it to hot pressing, a laminate having a conductor layer on its surface can be produced. The copper foil preferably has a thickness of about 12 to 36 μm. The condition of pressure pressing depends on the resin composition, but when cyclic polyolefin is used as the high molecular weight substance, for example, 12
It is preferable to perform molding at 0 to 180 ° C. and 1.0 to 5 MPa for 1 to 3 hours.

It is also possible to fabricate a multilayer printed circuit board by wiring the conductor layers of this laminated plate by an ordinary etching method, laminating a plurality of the conductor layers through the prepreg, and heating and pressing to laminate them. The multilayer printed circuit board thus obtained has a low dielectric loss tangent,
It becomes a multilayer printed circuit board with small dielectric loss. Further, the multilayer printed circuit board of the present invention has a high glass transition temperature and a high elastic modulus at a high temperature, and therefore can sufficiently cope with a high temperature processing process such as gold wire bonding and soldering.

[0025]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In the following description, “parts” means “parts by weight” unless otherwise specified. Tables 1 to 3 show the compositions of the examples and comparative examples of the present invention and their characteristics. The names of reagents used in Examples and Comparative Examples, synthesis methods, varnish preparation methods, and cured product evaluation methods will be described below.

(1) Synthesis of 1,2-bis (vinylphenyl) ethane (BVPE) 1,2-bis (vinylphenyl) ethane (BVPE)
Was synthesized by a known method as shown below. 500 m
5.36 g (220 mmol) of granular magnesium for Grignard reaction (manufactured by Kanto Kagaku Co., Ltd.) was placed in a 3-necked flask having a volume of 1, and a dropping funnel, a nitrogen introducing tube and a septum cap were attached. The whole system was heated and dehydrated with a dryer while stirring the magnesium particles with a stirrer under a nitrogen stream. 300 ml of dry tetrahydrofuran was taken in a syringe and injected through a septum cap. Solution at -5 ° C
After cooling to 30 ° C., 30.5 g (200 m) of vinylbenzyl chloride (VBC, manufactured by Tokyo Kasei) using a dropping funnel.
1) was added dropwise over about 4 hours. 0 ° C / 2 after dropping
Stirring was continued for 0 hours. After completion of the reaction, the reaction solution was filtered to remove residual magnesium, and concentrated with an evaporator. The concentrated solution was diluted with hexane, washed once with a 3.6% hydrochloric acid aqueous solution and three times with pure water, and then dehydrated with magnesium sulfate. The dewatered solution was passed through a short column of silica gel (Wako gel C300 manufactured by Wako Pure Chemical Industries) / hexane for purification, and vacuum dried to obtain BVPE. The obtained BVPE was a mixture of m-m form (liquid form), m-p form (liquid form) and p-p form (crystal), and the yield was 90%. ¹ H-N
When the structure was examined by MR, the value was in agreement with the literature value (6H-vinyl: α-2H, 6.7, β-4H,
5.7, 5.2; 8H-aromatic: 7.1 to 7.
35; 4H-methylene: 2.9). This BVPE was used as a crosslinking component.

(2) Polydivinylbenzene (polyD)
Synthesis of VB) Polydivinylbenzene (polyDVB) was synthesized by a known method as shown below. 520 ml of diisopropylamine THF solution (diisopropylamine content 101 g = 1 mol) was placed in a nitrogen-substituted 1000 ml three-necked flask. 11 ml of n-butyllithium hexane solution (n-butyllithium content 1.9 g = 2
0 mmol) was added. 140 mmol (18.2 g)
Of divinylbenzene was added. Stir for 60 minutes at room temperature. The reaction was stopped by adding methanol. The reaction solution was concentrated with an evaporator, reprecipitated with cold methanol and dried to obtain polydivinylbenzene. The yield is about 50%,
The molecular weight was about 20,000. Polydivinylbenzene was soluble and had a vinyl group in the side chain (4H-
Aromatic: 6.5-7.2; 3H-Vinyl: 5-
6.5; 3H-methylene, methine: 1-2). This polydivinylbenzene was used as the crosslinking component in Comparative Example 5.

(3) Other reagents As the other high molecular weight substances and the crosslinking component, the followings were used. High molecular weight product; Zeonor: manufactured by Zeon Corporation, cyclic polyolefin (Z
eonor1600R) PPE: made by Aldrich, poly-2,6-dimethyl-
1,4-Phenylene oxide Crosslinking component of Comparative Example 4; DVB: Wako Pure Chemical Industries, Ltd. divinylbenzene curing catalyst; 25B: NOF Corporation 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne- 3 (Perhexin 25B) Organic non-woven fabric; Kuraray Vectran K-9 DuPont Surmount E210 glass cloth; Nittobo # 2116

(4) Method for preparing varnish A resin composition varnish was prepared by dissolving a predetermined amount of a high molecular weight substance, a crosslinking component and a curing catalyst in chloroform or carbon disulfide.

(5) Preparation of resin plate After coating the varnish on a PET film and drying it,
This was peeled off and put in a predetermined amount in a Teflon (registered trademark) spacer, and heated and pressed under vacuum through a polyimide film and a mirror plate to obtain a resin plate as a cured product. Heating conditions are 120 ° C / 30 minutes, 150 ° C / 30
Min, 180 ° C./100 minutes, and multi-stage heating was performed at a pressing pressure of 1.5 MPa. The size of the resin plate is 70 × 70 × 1m
m.

(6) Preparation of prepregs In all the prepregs prepared in the examples, a predetermined organic non-woven fabric or glass cloth is impregnated with a varnish of the resin composition and dried at room temperature for about 1 hour and at 90 ° C. for 60 minutes. It was produced by Table 3 shows the names of the base materials used and the resin contents (contents of the high molecular weight product and the crosslinking component).

(7) Preparation of prepreg cured product In order to know the characteristics of the prepreg when it was made into a laminated board, the prepreg prepared by the above method was heated and pressed under vacuum to prepare a simulated substrate. Heating conditions are 120 ° C / 30 minutes, 1
50 ° C / 30 minutes, 180 ° C / 100 minutes, press pressure 1.
It was a multi-stage heating of 5 MPa. Simulated board is 70 × 70 ×
It was set to 0.14 to 0.3 mm.

(8) Measurement of dielectric constant and dielectric loss tangent The dielectric constant and dielectric loss tangent were observed at 10 GHz by a cavity resonance method (8722ES type network analyzer manufactured by Agilent Technologies, a cavity resonator manufactured by Kanto Electronics Co., Ltd.).

(9) Measurement of Tensile Strength and Elongation Tensile strength and elongation were measured using a Shimadzu AGS-100 type tensile tester using a columnar sample with a thickness of 1 mm, a width of 1 mm and a length of 70 mm, at room temperature and between fulcrums. Distance 20mm Tensile speed 1
The measurement was performed under the condition of 0 mm / min.

(10) Glass transition temperature (Tg), elastic modulus Tg, and elastic modulus are DVA-200 manufactured by IT Measurement Control Co., Ltd.
It was determined by observing the elastic modulus at 170 ° C. at the peak position of tan δ using a viscoelasticity measuring apparatus (DMA). The sample shape and the distance between fulcrums were the same as those of the tensile strength sample, and the temperature rising rate was 5 ° C / min.

(11) Peel Strength A sample for peel strength measurement was prepared by forming each resin composition on a rough surface of an electrolytic copper foil (18 μm) to form a resin layer under the same conditions as in the method for preparing a resin plate. The resin layer had a thickness of 2 mm and a size of 70 × 70 mm. The electrolytic copper foil on the resin layer was cut into a width of 10 mm, and its peel strength was measured.

Comparative Example 1 Comparative Example 1 is an example of a resin composition consisting only of cyclic polyolefin resin Zeonor as a high molecular weight material. A cured product of this composition was prepared as a resin plate by putting a predetermined amount of pellets into a metal spacer and heating and pressurizing under vacuum through a polyimide film and a mirror plate. Heating condition is 260 ℃ /
The pressing pressure was 1.5 MPa for 30 minutes. Resin plate is 70
It was set to × 70 × 1 mm. This resin plate has a dielectric constant of 2.2.
0, the dielectric loss tangent is 0.0007, which are both very low.
g is 185 ° C. and the elastic modulus is 1190 MPa, which are both high. However, since this resin does not have curability, it swells in an organic solvent. Further, the heating temperature at the time of molding was required to be about 260 ° C.

Comparative Example 2 Comparative Example 2 is an example of a resin composition consisting only of PPE as a high molecular weight material. A cured product of this composition was produced as a resin plate by placing a predetermined amount of resin powder in a metal spacer and heating and pressurizing it through a polyimide film and a mirror plate under vacuum. Heating conditions are 320 ° C / 30 minutes, press pressure 1.5M
It was Pa. The resin plate was 70 × 70 × 1 mm. This resin plate has a dielectric constant of 2.41 and a dielectric loss tangent of 0.0022.
Very low, Tg is 229 ℃, elastic modulus is 2000MP
Both are high. However, since this resin does not have curability, it swells in an organic solvent. The molding temperature is 32
About 0 ° C was necessary.

[Comparative Example 3] In Comparative Example 3, the crosslinking components 1 and 2 were used.
-Bis (vinylphenyl) ethane (BVPE) and BV
It is an example of a resin composition containing 1 wt% of the curing catalyst 25B with respect to the weight of PE. A cured product of this composition was prepared as a resin plate by injecting the resin composition in a solvent-free state between two glass plates to which a Teflon spacer was attached, sealing the mixture, and heating and curing. The heating condition is 1
20 ° C / 30 minutes, 150 ° C / 30 minutes, 180 ° C / 100
Minute multi-stage heating. The resin plate was 70 × 70 × 1 mm. The produced resin plate has a low dielectric constant of 2.56, a low dielectric loss tangent of 0.0017, a Tg of 400 ° C. or higher, and a high elastic modulus of 2590 MPa. Since it has curability, it has excellent solvent resistance. The curing temperature is relatively low at 180 ° C. However, it has a problem in that the tensile strength is as small as 31.2 MPa and the elongation is as small as 2%.

Examples 1 to 3 In Examples 1 to 3, Zeonor, which is a high molecular weight substance, and BVPE, which is a cross-linking component, are contained in different blending ratios, and further, 1% by weight of the resin component is cured. It is an example of a resin composition containing a catalyst 25B. Cured products of these compositions were prepared as a resin plate by preparing a varnish using sulfur disulfide as a solvent and using the method described above. As is clear from each example, the dielectric constant and dielectric loss tangent of each resin plate are very low, and the dielectric constant is 2.27.
Is about 2.35, and the dielectric loss tangent is 0.0013 to 0.00.
It was 17. The other properties reflect the properties of the added high molecular weight polymer, and the tensile strength is 68 to 79 MPa and the elongation is 2
1-28%, Tg 178-183 ° C, elastic modulus 100
0 ~ 1130MPa, peel strength 0.7 ~ 1.2N /
It showed an excellent value of m. Since the present resin composition has curability, it has excellent solvent resistance. The molding temperature is 180 ℃
Therefore, molding at a low temperature was possible.

[Examples 4 to 6] In Examples 4 to 6, PPE, which is a high molecular weight polymer, and BVPE, which is a cross-linking component, are contained in different blending ratios, and 1 to the weight of the resin component is added.
It is an example of a resin composition containing a wt% curing catalyst 25B. Cured products of these resin compositions were prepared as resin plates by preparing a varnish using chloroform as a solvent and using the method described above. As is clear from each example, the dielectric constant and dielectric loss tangent of this resin composition are very low, and the dielectric constant is 2.4.
3 to 2.45 and the dielectric loss tangent is 0.0017 to 0.0.
It was 019. The other properties reflect the properties of the added high molecular weight polymer, the tensile strength is 63 to 82 MPa, the elongation is 26 to 47%, the Tg is 210 to 225 ° C., and the elastic modulus is 24.
70-2530 MPa, peel strength 0.7-1.2N
/ M, which was an excellent value. Since the resin composition has curability, it has excellent solvent resistance. The molding temperature is 18
It was 0 ° C, and molding at a low temperature was possible. The results of Comparative Examples 1 to 3 and Examples 1 to 6 are shown in Table 1 below.

[0042]

[Table 1]

[Comparative Example 4] In Comparative Example 4, DVB and DV are used.
Including 1 wt% of the curing catalyst 25B based on the weight of B,
It is an example of a resin composition containing no high molecular weight material. A cured product of this composition was produced as a resin plate by the above method without using a solvent. This resin plate was very brittle and cracked during curing and cooling and could not be evaluated.

Comparative Example 5 Comparative Example 5 has a molecular weight of about 200.
No. 00 PolyDVB as a cross-linking component, PPE as a high molecular weight component in an amount of 50 parts by weight, and 1 wt% of the curing catalyst 25B based on the weight of the resin component. The hardened | cured material of this composition prepared the varnish using chloroform as a solvent, and produced it as a resin plate by the above-mentioned method. It was confirmed that this resin plate had insufficient melt fluidity because the molecular weight of the cross-linking agent was large, and a molded plate could not be produced.

[Comparative Example 6] In Comparative Example 6, PPE as a high molecular weight polymer and BVPE as a cross-linking component were each added to 5 parts.
It is an example of a resin composition containing 0 part by weight and further containing a curing catalyst in an excess of 20 wt% with respect to the total weight of the resin components. The hardened | cured material of this composition prepared the varnish using chloroform as a solvent, and produced it as a resin plate by the above-mentioned method. This resin plate had an increased dielectric constant of 2.6 and a dielectric loss tangent of 0.003 due to the excessive addition of the curing catalyst. Also,
Since the curing speed was high, the fluidity at the time of molding was lowered, and the shape and thickness of the resin plate became uneven.

Examples 7 and 8 In Examples 7 and 8, PPE as a high molecular weight substance and BVPE as a crosslinking component were used.
Is an example of a resin composition containing 50 parts by weight of each of the above and further containing 10 wt% or 5 wt% of the curing catalyst 25B with respect to the weight of the resin component. The hardened | cured material of this composition prepared the varnish using chloroform as a solvent, and produced it as a resin plate by the above-mentioned method. If the amount of the curing catalyst is 10 wt% or less, this resin plate does not cause defective molding. Also, the dielectric constant is 2.43 and the dielectric loss tangent is 0.0018.
It was ~ 0.0019, and no remarkable deterioration in properties was observed. The results of Comparative Examples 4 to 6 and Examples 7 to 8 are shown in Table 2 below;

[0047]

[Table 2]

[Examples 9 to 11] Table 3 shows the constitution and dielectric properties of prepregs prepared by impregnating the resin composition of the present invention with various base materials. All the prepared prepregs have tack-free properties. To prepare the prepreg, 50 parts by weight of each of the resin composition prepared in Example 5, that is, PPE as a high molecular weight substance and BVPE as a crosslinking component, and 1 wt% of the curing catalyst 25B with respect to the weight of the resin component were used. A resin composition comprising was used. The prepreg is a varnish prepared by using chloroform as an organic solvent, impregnating the varnish into a predetermined organic non-woven fabric or glass cloth, and then at room temperature for about 1 hour at 90 ° C. for 60 hours.
It was made by drying for a minute. Table 3 shows each substrate name and resin content. The prepreg prepared as described above was heated and pressed under vacuum to be cured to prepare a simulated substrate. Heating conditions are 120 ° C / 30 minutes, 150 ° C / 30
Min, 180 ° C./100 minutes, and multi-stage heating with a pressing pressure of 1.5 MPa. Simulated substrate is 70 × 70 × 0.14〜
It was 0.3 mm. The simulated substrate of Example 9 using glass cloth (# 2116) as a base material has a dielectric constant of 3.12, a dielectric loss tangent of 0.0038, and an organic non-woven fabric (K-9) as a base material of Example 10. The substrate had a dielectric constant of 2.51, a dielectric loss tangent of 0.0027, and the simulated substrate of Example 11 based on E210 had a dielectric constant of 2.61 and a dielectric loss tangent of 0.0024. Both have good dielectric properties. Examples 9 to 1
The results of 1 are shown in Table 3 below;

[0049]

[Table 3]

[Example 12] Rough surfaces of electrolytic copper foil were attached to both surfaces of the prepreg prepared in Example 9, and pressed and heated under vacuum to prepare a double-sided copper-clad laminate. The heating condition is 1
20 ° C / 30 minutes, 150 ° C / 30 minutes, 180 ° C / 100
Min, the press pressure was 1.5 MPa. The copper foil and the prepreg showed good adhesion. This made it possible to fabricate a multilayer printed circuit board.

[Embodiment 13] An example of producing the multilayer printed circuit board of the present invention will be described below. (A) Photoresist (HS42 manufactured by Hitachi Chemical Co., Ltd.) was formed on one surface of the double-sided copper-clad laminate obtained in Example 12.
5) was laminated and exposed on the entire surface. Then, a photoresist (HS425 manufactured by Hitachi Chemical Co., Ltd.) was laminated on the remaining copper surface to expose the test pattern, and the photoresist in the unexposed portion was developed with a 1% sodium carbonate solution. (B) The exposed copper foil was removed by etching with an etching solution containing 5% sulfuric acid and 5% hydrogen peroxide to form a conductor wiring on one surface of the double-sided copper-clad laminate. (C) The remaining photoresist was removed with a 3% sodium hydroxide solution to obtain a wiring board having wiring on one surface. Two wiring boards were produced in the same manner.
(D) The prepreg of Example 9 was sandwiched between the wiring-side surfaces of two wiring boards, and heated and pressed under vacuum to form a multilayer structure. The heating conditions are 120 ° C / 30 minutes, 150 ° C / 30 minutes, 180 ° C.
/ 100 minutes, multi-stage heating with a press pressure of 1.5 MPa. (E) A photoresist (HS425 manufactured by Hitachi Chemical Co., Ltd.) is laminated on the exterior copper on both sides of the produced multilayer board to expose the test pattern, and the photoresist in the unexposed portion is 1%.
It was developed with a sodium carbonate solution. (F) The exposed copper foil was removed by etching with an etching solution containing 5% sulfuric acid and 5% hydrogen peroxide, and the remaining photoresist was removed with a 3% sodium hydroxide solution to form exterior wiring. (G) A through hole for connecting the inner layer wiring and the outer wiring was formed by drilling. (H) The wiring board was dipped in a colloidal solution of a plating catalyst to apply the catalyst to the board surface in the through holes.
(I) After the activation treatment of the plating catalyst, a seed film of about 1 μm was provided by electroless plating (CUST2000 manufactured by Hitachi Chemical Co., Ltd.). (J) Photoresist (HN92 manufactured by Hitachi Chemical
0) was laminated on both sides of the wiring board. (K) After exposure by masking the through hole and the end of the wiring board, 3%
It was developed with sodium carbonate and an opening was provided. (L) Electrodes were set at the ends of the wiring board, and electrolytic copper plating was performed to form plated copper in a thickness of about 18 μm. (M) The electrode portion was cut off and the remaining photoresist was removed with a 5% aqueous sodium hydroxide solution. (N) A wiring board was immersed in an etching solution containing 5% sulfuric acid and 5% hydrogen peroxide, and was etched by about 1 μm to remove the seed film, thereby producing a multilayer wiring board. Place this multilayer wiring board in a solder reflow bath at 200 ° C for 10 minutes, 2
After being held in a 88 ° C. solder bath for 1 minute, no resin interface, peeling of wiring, etc. occurred.

[0052]

According to the present invention, a cured product having a low dielectric constant and a low dielectric loss tangent, a high glass transition temperature, and a large tensile strength and elongation can be obtained. The resin composition is suitable as an insulating material for high-frequency electrical components, and can be applied to a high-frequency signal wiring board and a prepreg used for the same.

[Brief description of drawings]

FIG. 1 is a schematic view showing a process for manufacturing a multilayer wiring board.

[Explanation of symbols]

1 ... Electrolytic copper foil, 2 ... Resin substrate, 3 ... Photoresist, 4
... prepreg, 5 ... inner layer wiring, 6 ... outer layer wiring, 7 ... through hole, 8 ... plating catalyst, 9 ... seed film, 10 ... open hole portion,
11 ... Electrode, 12 ... Plated copper

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) // C08L 57:00 C08L 57:00 (72) Inventor Keiro Ishikawa 7-1, Omika-cho, Hitachi-shi, Ibaraki No. 1 Hitachi Ltd. Hitachi Research Laboratory (72) Inventor Takao Miwa 7-1 Omika-cho, Hitachi City, Ibaraki Prefecture F-term inside Hitachi Research Laboratory Hitachi Ltd. (reference) 4F072 AB29 AD02 AD03 AD05 AD09 AG03 AL13 4J011 PA54 PA64 PA65 PA69 PA70 PC02 4J026 AA11 AA17 AA18 AA42 AA49 AA57 AA68 AA69 BA07 DB15 GA07 5E346 AA06 AA12 AA15 AA22 BB01 CC02 CC08 CC31 DD02 DD31 EE02 EE06 EE07 EE09 HGG28 H06 HGG18 H06

Claims (11)

[Claims] 1. The following general formula: (In the formula, R represents a hydrocarbon skeleton, R ¹ is the same or different and represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ² , R ³ and R ⁴ are the same or different. , A hydrogen atom or an alkyl group having 1 to 6 carbon atoms, m is an integer of 1 to 4, and n is an integer of 2 or more.), A crosslinking component having a plurality of styrene groups and having a weight average molecular weight of 1000 or less. And a high molecular weight polymer, wherein the cured product obtained by curing the resin composition at 180 ° C. for 100 minutes has a glass transition temperature of 170 ° C. or higher, or the cured product. Of the resin composition having an elastic modulus at 170 ° C. of 500 MPa or more. 2. The composition according to claim 1, further comprising at least one of a curing catalyst capable of polymerizing a styrene group and a polymerization inhibitor capable of suppressing the polymerization of the styrene group. 3. A total of 10 of the crosslinking component and the high molecular weight substance.
The addition amount of the curing catalyst is 0.000 with respect to 0 part by weight.
5 to 10 parts by weight, and the amount of the polymerization inhibitor added is 0.
The composition according to claim 2, which is from 0005 to 5 parts by weight. 4. The glass transition temperature of the polymer is 17
The composition according to any one of claims 1 to 3, which has a temperature of 0 ° C or higher. 5. The polymer, wherein the high molecular weight polymer is at least one of butadiene, isoprene, styrene, methylstyrene, ethylstyrene, divinylbenzene, acrylic acid ester, acrylonitrile, N-phenylmaleimide and N-vinylphenylmaleimide, The composition according to any one of claims 1 to 4, which is at least one resin selected from the group consisting of a polyphenylene oxide which may have a substituent and a polyolefin having an alicyclic structure. 6. The following general formula: (In the formula, R represents a hydrocarbon skeleton, R ¹ is the same or different and represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ² , R ³ and R ⁴ are the same or different. , A hydrogen atom or an alkyl group having 1 to 6 carbon atoms, m is an integer of 1 to 4, and n is an integer of 2 or more.), A crosslinking component having a plurality of styrene groups and having a weight average molecular weight of 1000 or less. Which is a cured product obtained by curing a resin composition containing a polymer and a high molecular weight polymer, and has a glass transition temperature of 170 ° C. or higher, or an elastic modulus at 170 ° C. of 500 MPa.
The cured product that is the above. 7. A cured product of the composition according to claim 1. 8. An organic or inorganic cloth or nonwoven fabric is impregnated with the composition according to any one of claims 1 to 5,
A dried prepreg. 9. A cured product of the prepreg according to claim 8. 10. A laminated board having conductor layers provided on both sides or one side of the prepreg according to claim 8 or a cured product thereof. 11. A multilayer printed circuit board, which is obtained by wiring a conductor layer of the laminated board according to claim 10 and then laminating and adhering the laminated board through a prepreg.