JP2003212941A - Dielectric tangent-lowering method and low dielectric tangent resin composition and electric part using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dielectric tangent-lowering method which can reproduce a stable dielectric constant and a dielectric tangent even when curing in an open system or a vacuum system, a resin composition, a low dielectric tangent resin composition and electric parts using the same. <P>SOLUTION: To a curable resin (A) wherein a dielectric tangent at 10 GHz of a cured material obtained by being cured at 180°C for 100 min is not less than 0.002, a curing component (B) wherein vapor pressure at 52°C is not more than 1 hPa and a dielectric tangent at 10 GHz of a cured material obtained by being cured at 180°C for 100 min is less than 0.002 is added. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electric component having a small dielectric loss for dealing with a high frequency signal, a resin composition used for manufacturing them, and a method for reducing a dielectric loss tangent of the resin composition.

[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 relative permittivity of the insulator forming the circuit, the dielectric loss tangent, and the frequency of the signal used. Therefore, the higher the frequency of the signal, the larger the dielectric loss.
Since the dielectric loss attenuates the electrical 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 to suppress it. Removal of polar groups in the molecular structure is effective for achieving a low dielectric constant and a low dielectric loss tangent of an insulator, and conventionally, a fluorine resin has been mainly used as a low dielectric loss tangent resin. On the other hand, as thermosetting low dielectric loss tangent resins soluble in organic solvents, curable polyolefins, cyanate ester resins, curable polyphenylene oxides, allyl-modified polyphenylene ethers, divinylbenzene or divinylnaphthalene-modified polyetherimides, etc. Has been made.

For example, an example in which a diene polymer such as polybutadiene described in JP-A-8-208856 is soaked in glass cloth and cured with peroxide; JP-A-10-15
Examples of cyclic polyolefins in which an epoxy group is introduced into a norbornene-based addition type polymer to impart curability as described in JP-A-8337; cyanate ester, diene-based polymer, epoxy as described in JP-A No. 11-124491. Example of heating resin to B stage; JP-A-9-1
Polyphenylene oxide described in 18759.
Examples of modified resins composed of diene polymer and triallyl isocyanate; examples of resin compositions composed of allylated polyphenylene ether, triallyl isocyanate described in JP-A-9-246429; JP-A-5-1561
Polyetherimide described in JP-A-59, styrene,
Example of alloying divinylbenzene or divinylnaphthalene; resin composed of, for example, hydroquinone bis (vinylbenzyl) ether and novolac phenol resin synthesized by Williamson reaction from dihydroxy compound and chloromethylstyrene described in JP-A-5-78552 There are many examples such as compositions. Many of the above examples describe 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 low dielectric loss tangent, and a thermal decomposition temperature of 350.
This is due to the high temperature above ℃.

In JP-A-5-78552, hydroquinone bis (vinylbenzyl) is used instead of divinylbenzene.
A polyfunctional vinyl benzyl ether compound such as ether is used. It has been shown that hydroquinone bis (vinylbenzyl) ether is non-volatile, and when cured together with a novolac phenolic resin, it gives a cured product with high flexibility.

In addition, as a compound similar to divinylbenzene, 1,2 in which styrene groups are bonded with an ethylene group is used.
-Bisvinylphenylethane (Japanese Patent Laid-Open No. 9-208625)
Gazette), Makromol. Chem. vol. 18
Although divinylbenzene oligomers having a vinyl group on the side chain described on pages 7 and 23 are known, no studies have been made on the dielectric constant, dielectric loss tangent, and curability of cured products of these polyfunctional styrene compounds. Further, little consideration has been given to lowering the dielectric loss tangent of a resin composition by blending the polyfunctional styrene compound with another curable resin.

Incidentally, Japanese Patent Laid-Open No. 2000-187831 entitled "Flame Retardant Substrate and Prepreg", and Japanese Patent Laid-Open No. 2001-267466 entitled "Power Amplifier Module".
The publication discloses a technique of using a polyvinyl benzyl ether compound as an organic resin material, but the dielectric property of a material containing an ether bond is deteriorated by the influence of an ether group.

[0007]

Various thermosetting low dielectric loss tangent resins which are soluble in an organic solvent and are easy to handle have been proposed in place of the fluororesin which has been used as a low dielectric loss tangent resin. In the examples of these thermosetting low dielectric loss tangent resins, it has been proposed to add divinylbenzene, which has a low dielectric constant and a low dielectric loss tangent and has a high heat resistance of the cured product, as a crosslinking component or a crosslinking aid. However, due to the brittleness of the cured product of divinylbenzene, the amount added was kept low. Therefore, the reduction of the dielectric constant and the reduction of the dielectric loss tangent due to the addition of divinylbenzene have not been sufficiently effective. Further, since divinylbenzene is volatile, there is a problem that when it is hardened and cured in a vacuum system or an open system, the divinylbenzene is volatilized and the dielectric properties of the cured product are not stable.

There is a proposal to add a non-volatile polyfunctional vinyl benzyl ether compound to the resin composition as a cross-linking component in place of divinyl benzene, but since the poly functional vinyl benzyl ether compound has an ether bond, it has a dielectric constant as low as that of divinyl benzene. Therefore, the resin composition does not have the ability to reduce the dielectric loss tangent of divinylbenzene. As a preferable cross-linking component instead of divinylbenzene, polyfunctional styrene of all hydrocarbons in which styrene groups are bonded by alkylene groups or arylene groups is considered, but regarding dielectric properties, curability, and volatility when blended with a curable resin. Has not been fully evaluated.

An object of the present invention is to provide a method for reducing the dielectric loss tangent of a resin composition capable of reproducing stable dielectric properties, a resin composition having a low dielectric loss tangent using the same, and an electric component using the same as an insulating layer. It is in.

[0010]

Means for Solving the Problems The gist of the present invention is that a cured product obtained by curing a general-purpose curable resin (A) at 180 ° C. for 100 minutes has a dielectric loss tangent of 0.002 at 10 GHz.
Low dielectric loss tangent of less than 1 and vapor pressure at 52 ° C for 1h
It is to blend the curable component (B) having a non-volatile property of Pa or less.

According to the present invention, a general-purpose curable resin (A) is used.
In addition, a cured component having a low dielectric loss tangent having a dielectric loss tangent of less than 0.002 at 10 GHz at 180 ° C. for 100 minutes and a nonvolatile property having a vapor pressure at 52 ° C. of 1 hPa or less. By blending (B), as is clear from the description of the examples described later, it is possible to suppress the variation in the dielectric properties due to the volatilization of the curing component (B) during curing and to reduce the amount of the curable resin composition. A dielectric loss tangent can be achieved.

As the above-mentioned curing component (B), a polyfunctional styrene compound having a hydrocarbon skeleton such as alkylene and arylene is preferable, and a cured product having a low dielectric constant and a low dielectric loss tangent that does not crack during curing is stabilized. You can get it.

Further, by using the low dielectric loss tangent resin composition as an insulator of an electric part, an electric part having a small dielectric loss can be manufactured.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The method for reducing the dielectric loss tangent, the composition and the cured product of the present invention will be described.

The method of reducing the dielectric loss tangent of the present invention is performed at 180 ° C.
General-purpose curable resin (A) having a dielectric loss tangent of 0.002 or more at 10 GHz obtained by curing for 100 minutes
Is a method of stably lowering the dielectric loss tangent. Non-volatile with vapor pressure of 1 hPa or less at 52 ° C and 180 ° C, 100
The low dielectric loss tangent is obtained by blending the general-purpose curable resin (A) with the curable component (B) having a low dielectric loss tangent of less than 0.002 at 10 GHz. Is made. 5 for curing component (B)
By using a non-volatile compound having a vapor pressure at 2 ° C. of 1 hPa or less, it is possible to prevent the curing component (B) having a low dielectric loss tangent from volatilizing from the resin composition.
The low dielectric loss tangent of the resin composition can be stably reproduced.

The curable resin (A) is not particularly limited as long as it is a curable resin, and may be one type of curable resin, or a resin composition which is a mixture of a plurality of curable resins. Is also good. Examples of the curable resin (A) include epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, aliphatic type epoxy resin, alicyclic epoxy resin, phenol novolac type epoxy resin, orthocresol novolak type epoxy resin. Resin: Resin having a phenolic hydroxyl group as a curing agent for epoxy resin, for example, novolac resin, resole resin, polyhydroxystyrene, polyhydroxyphenylmaleimide; cyanate ester resin, for example, bis (4-cyanatephenyl) methane, 1, 1 -Bis (4-cyanatephenyl) ethane, 2,2'-bis (4-cyanatephenyl) propane; maleimide resins, such as bis (4-maleimidophenyl) methane, 2,2'-bis (4-maleimidophenyl) Propane, side chain Having a maleimide group (4-vinylphenyl) maleimide polymer, having a styrene group in the side chain (4-vinylphenyl) maleimide polymer; (meth) acrylate resins, for example, 2-methyl -
2-propenic acid oxybisethylene ester, 2-methyl-2-propenic acid [1, 1'-
Bicyclohexyl] -4,4′-diyl ester, epoxy acrylate in which a photosensitive group such as an acrylic group or a methacrylic group is introduced into an epoxy resin, and the like.

Preferred examples of the curing component (B) include polyfunctional styrene compounds having a hydrocarbon skeleton such as divinylbenzene homopolymers and copolymers having a vinyl group in the side chain. A particularly preferred example is a polyfunctional styrene compound represented by the following general formula [1] and having a weight average molecular weight of 1,000 or less.

[0018]

[Chemical 4] (In the formula, R represents a hydrocarbon skeleton which may have a substituent, and R ² , R ³ and R ⁴ may be the same or different,
Represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, R ⁵ ,
R ⁶ , R ⁷ , and R ⁸ may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and n represents an integer of 2 or more. ) In the above formula, the hydrocarbon skeleton represented by R is not particularly limited as long as the weight average molecular weight of the curing component (B) is 1000 or less. That is, the hydrocarbon skeleton represented by R can be appropriately selected depending on the substituent in the styrene group, the presence or absence of R ^{2 to} R ⁸ and its size, and the number of n, but generally has 1 to 60 carbon atoms. 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, and further vinylene and ethynylene. It may have a functional group such as.

Examples of the hydrocarbon skeleton represented by R include ethylene, propylene, butylene, methylpropylene, methylbutylene, pentamethylene, methylpentamethylene, cyclopentylene, cyclohexylene, phenylenediethylene, xylylene and 1-phenylene-. 3-methylpropenylene etc. are mentioned.

In the above formula, the hydrocarbon group represented by R ^{5 to} R ⁸ has 1 to 20 carbon atoms, preferably 1 carbon atoms.
A linear or branched alkyl group of 10 such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, pentyl, hexyl,
Decyl, eicosyl; linear or branched alkenyl groups such as vinyl, 1-propenyl, 2-propenyl, 2-methylallyl; aryl groups such as phenyl, naphthyl, benzyl, phenylethyl, styryl,
Examples include cinnamil.

In the above formula, a plurality of such R ^{5 to} R ⁸ may be the same or different, and the bonding positions may be the same or different.

In the above formula, the alkyl group represented by R ² , R ³ or R ⁴ is a linear or branched alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl or n-.
Examples include propyl, isopropyl, n-butyl, isobutyl, hexyl and the like.

In the above formula, the vinyl group [(R ³ ) (R ⁴ ) C = C (R ² )-] which may have a substituent is preferably in the meta position relative to R on the benzene ring. Or it exists in the para position.

As the curing component (B) used in the present invention,
A polyfunctional styrene having a weight average molecular weight of 1,000 or less and having a plurality of styrene groups which may have a substituent is preferable. The skeleton of the curing component (B) is preferably a hydrocarbon skeleton from the viewpoint of dielectric constant and dielectric loss tangent. This makes it possible to impart non-volatility and flexibility to the curable component (B) without impairing the low dielectric constant and low dielectric loss tangent of the styrene group. Since the polyfunctional styrene compound having a hydrocarbon skeleton has no polar group in the structure, its dielectric loss tangent value is very small, and the dielectric loss tangent value at 10 GHz is less than 0.002. Therefore, when blended with a general-purpose curable resin (A) having a dielectric loss tangent value of 0.002 or more, the dielectric loss tangent of the entire resin composition can be reduced. Further, as the curing component (B), a weight average molecular weight of 100
By selecting a compound of 0 or less, the compatibility with various curable resins and polymers can be increased, and the melt fluidity at the time of molding can be increased, and the workability can be improved.
The weight average molecular weight of the curable component (B) is not particularly limited, but is preferably 1,000 or less, more preferably 200 to 500 for the reasons mentioned above.

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 the residue of the curing catalyst may adversely affect the dielectric properties, so the total amount of the resin component is 100 parts by weight,
It is desirable that the amount be 0.0005 to 10 parts by weight. Within this range, polymerization of the styrene group and crosslinking reaction can be promoted to obtain a cured product at a low temperature. Examples of curing catalysts that generate cations and radical active species capable of polymerizing and crosslinking styrene groups by heat and light are shown below. Examples of the cation-based catalyst include diallyl iodonium salts, triallyl sulfonium salts, and aliphatic sulfonium salts having BF ₄ , PF ₆ , AsF ₆ , and SbF ₆ as counter anions.
P-70, 172, CP-66, Nippon Soda CI-285
5,2823, Sanshin Chemical Industry SI-100L, SI-1
A commercially available product such as 50 L can be used. As the radical polymerization catalyst, benzoin compounds such as benzoin and benzoinmethyl, acetophenone compounds, acetophenone compounds such as 2,2-dimethoxy-2-phenylacetophenone, thioxanthone compounds such as thioxanthone and 2,4-diethylthioxanthone compounds. 4,
4′-diazidochalcone, 2,6-bis (4′-azidobenzal) cyclohexanone, bisazide compound such as 4,4′-diazidobenzophenone, azobisisobutyronitrile, 2,2-azobispropane, m , Azo compounds such as m'-azoxystyrene, hydrazones,
Organics such as 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, dicumyl peroxide Examples thereof include peroxides. In particular, it is desirable to add an organic peroxide or a bisazide compound capable of causing hydrogen abstraction of a compound having no functional group and forming a bridge between the crosslinking component and the high molecular weight product.

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 the total amount of the resin components is 100 parts by weight,
It is preferably 0.0005 to 5 parts by weight. Within this range, unnecessary polymerization reaction during storage can be suppressed, and no significant curing trouble is brought about during curing.
Examples of the polymerization inhibitor include quinones such as hydroquinone, p-benzoquinone, chloranil, trimethylquinone, and 4-t-butylpyrocatechol, and aromatic diols.

The resin composition of the present invention can be made into a liquid or solid resin composition depending on the phase states of the curable resin (A) and the curing component (B) to be blended. The solid resin composition can be dissolved in an organic solvent and used as a varnish.

The cured product of the present invention is a general-purpose curable resin (A).
It has a lower dielectric constant and dielectric loss tangent than when used alone, and since it is non-volatile, it can be stably reproduced with a low dielectric loss tangent, and thus can be suitably used as an insulator for electric circuits of various high-frequency devices. Specific examples include application to a potting resin used for embedding a gold wire wiring of an LSI in the case of a liquid composition, and application to a prepreg, a laminate, a printed circuit board in the case of a solid resin. .

As the curing component (B), a polyfunctional styrene compound having a hydrocarbon skeleton such as alkylene or arylene is preferable, and a cured product having a low dielectric constant and a low dielectric loss tangent that does not crack during curing is stabilized. You can get it. [Examples] The present invention will be specifically described below with reference to Examples and Comparative Examples. The resin composition ratios in the tables below are weight ratios.

The names of the reagents used in the examples and comparative examples, the synthesizing method, the varnish adjusting method, and the cured product evaluation method will be described below. (1) Synthesis: Synthesis of 1,2-bis (vinylphenyl) ethane (BVPE) 1,2-bis (vinylphenyl) ethane (BVPE)
Was synthesized by a known method. Granular magnesium for Grignard reaction (manufactured by Kanto Kagaku) in a 500 ml three-necked flask
5.36 g (220 mmol) was taken, 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. After cooling the solution to −5 ° C., 30.5 g (200 ml) of vinylbenzyl chloride (VBC, manufactured by Tokyo Kasei) was added dropwise using a dropping funnel over about 4 hours. After the completion of dropping, stirring was continued at 0 ° C./20 hours.
After completion of the reaction, the reaction solution was filtered to remove residual magnesium, and concentrated with an evaporator. Dilute the concentrated solution with hexane, wash once with 3.6% hydrochloric acid aqueous solution and three times with pure water,
Then, it was dehydrated with magnesium sulfate. The dewatered solution was purified by passing through a short column of silica gel (Wako gel C300 manufactured by Wako Pure Chemical Industries) / hexane, and vacuum dried to obtain BVPE.
The obtained BVPE was a mixture of m-m body, m-p body (liquid) and p-p body (crystal), and the yield was 90%. When the structure was examined by 1H-NMR, the value was in agreement with the literature value (6
H-vinyl: α-2H, 6.7, β-4H, 5.7, 5.2; 8H-aromatic: 7.1-7.35; 4H-methylene: 2.9). The cured product obtained by curing the BVPE under a nitrogen stream had a dielectric constant of 2.5 and a dielectric loss tangent of 0.001 at 10 GHz. This BVPE
Was used as the curing component (B). (2) Purification of Liquid Crosslinking Component BVPE synthesized previously was dissolved in methanol and recrystallized. The solid component was removed by filtration, and the filtrate was concentrated and vacuum dried to collect m-m and m-p liquid BVPE. The yield was 66%. A cured product obtained by curing the liquid BVPE under a nitrogen stream had a dielectric constant of 2.5 at 10 GHz and a dielectric loss tangent of 0.001. This liquid BVPE was used as the curing component (B) of the liquid resin composition. (3) Names of other reagents L-10: Cyanate ester resin (Aroc manufactured by Asahi Ciba)
y @ L-10); Curable resin A component of Comparative Example 1 and Examples 1 to 3.

CL2021A: Alicyclic epoxy resin (Celoxide 2021A) manufactured by Daicel Industries Ltd .; curable resin A component of Comparative Example 2 and Examples 4-6.

Ep828: Bisphenol A type epoxy resin manufactured by Yuka Shell (Epicoat Ep828); Comparative Example 3
And the curable resin A component of Examples 7 to 9.

R684: Nippon Kayaku acrylate resin (KAYARAD R-684); curable resin A component of Comparative Example 4 and Examples 10-12.

KRM2650: Asahi Denka cresol novolac type epoxy resin; Comparative Examples 5 and 6 and Examples 13 to
One component of 15 curable resin A components.

PP1000: Phenol resin manufactured by Nippon Oil Co., Ltd .; Curable resin A of Comparative Examples 5 and 6 and Examples 13 to 15
One ingredient of ingredient.

1421: Dicyclopentadiene skeleton-containing epoxy acrylate resin manufactured by Dainippon Ink; Comparative Example 5,
One component of the curable resin A component of Example 6 and Examples 13 to 15.

5X: Silicon oxide filler manufactured by Tatsumori (Crystallite 5X); fillers of Comparative Examples 5 and 6 and Examples 13 to 15.

Co: cobalt naphthenate manufactured by Wako Pure Chemical Industries; curing catalyst of Comparative Example 1 and Examples 1 to 3.

CP66: Asahi Denka thermal acid generator; Comparative Example 2
~ 3 and curing catalysts of Examples 4-9.

25B: Radical polymerization initiator manufactured by NOF CORPORATION (Perhexa 25B); Comparative Examples 5 and 6 and Examples 13 to
One component of 15 hardeners.

SI100L: thermal acid generator manufactured by Sanshin Kagaku Kogyo; one component of the curing agent of Comparative Examples 5 and 6 and Examples 13 to 15.

Glass cloth: Nitto Boseki # 2116; prepreg base material of Example 17.

DVB: divinylbenzene; curing component (B) of Comparative Example 6. (3) Method for adjusting varnish Varnish by mixing predetermined amount of curable resin (A), curing component (B), curing catalyst, filler and solvent, and stirring to dissolve and disperse the curing catalyst and filler. Was produced. (4) Production of Resin Plate The solvent-free varnishes of Comparative Examples 1 to 4 and Examples 1 to 12 were injected and sealed between two glass plates having Teflon (registered trademark) spacers attached, and heated and cured. To produce a resin plate. Heating conditions are 120 ° C / 30 minutes, 150 ° C / 30
Minutes, 180 ° C./100 minutes multi-step heating. The resin plate was 70 × 70 × 1 mm.

Comparative Examples 5 and 6 and Examples 13 to 15 are MEKs.
Each resin was mixed as a varnish. The MEK varnish is applied on a polyethylene terephthalate film (PET), dried at room temperature for 1 hour and at 90 ° C. for 30 minutes, and then PE
The film sample was peeled from T to obtain a resin film for molding. As shown in FIG. 1, the molding film 2 was put into the Teflon spacer 1 via the end plate 4 and the release film 3 and heat-pressed under vacuum to prepare a resin plate. Pressure is
1.5 MPa, heating conditions are 120 ° C / 30 minutes, 150 ° C /
Multi-step heating was performed for 30 minutes and 180 ° C./100 minutes. The resin plate was 70 × 70 × 1 mm. (5) Measurement of dielectric constant and dielectric loss tangent The dielectric constant and dielectric loss tangent were measured at a value of 10 GHz by a cavity resonance method (Agilent Technology model 8722ES network analyzer, Kanto Electronics Application Development cavity resonator). Comparative Example 1 Comparative Example 1 is a cyanate ester resin L-1.
It is a cured product of 0. The composition and dielectric properties are shown in Table 1.
The dielectric constant was 2.85 and the dielectric loss tangent was 0.016. The dielectric loss tangent of this cured product was rather high, and it could not be sufficiently applied to the insulators of electric parts that correspond to high frequency signals. [Examples 1 to 3] Examples 1 to 3 are examples of liquid varnishes obtained by adding liquid BVPE to the cyanate ester resin L-10 of Comparative Example 1. By adding BVPE, the values of the dielectric constant and the dielectric loss tangent decreased, and the dielectric constant became 2.71 to 2.60 and the dielectric loss tangent became 0.009 to 0.005. Since the dielectric characteristics (particularly the dielectric loss tangent) can be reduced, it is possible to manufacture an electric component having an insulator with a smaller dielectric loss than the conventional Comparative Example 1. The varnishes of Examples 1 to 3 were vacuum-dried at 5 mmHg / room temperature for 30 minutes and then cured, but the dielectric properties of the cured products did not change. This confirmed that there was no change in the dielectric properties due to volatilization of the liquid BVPE.

[0045]

[Table 1] [Comparative Example 2] Comparative Example 2 is an alicyclic epoxy resin CL202.
It is a cured product of 1A. The composition and dielectric properties are shown in Table 1. The dielectric constant was 2.86 and the dielectric loss tangent was 0.039. The dielectric loss tangent of this cured product was rather high, and it could not be sufficiently applied to the insulators of electric parts that correspond to high frequency signals. [Examples 4 to 6] Examples 4 to 6 are alicyclic epoxy resin C.
It is an example of a liquid varnish obtained by adding liquid BVPE to L2021A. The composition and dielectric properties are shown in Table 2. BVPE
The addition of the above decreases the values of the dielectric constant and the dielectric loss tangent, the dielectric constant is 2.80 to 2.65, and the dielectric loss tangent is 0.029 to 0.0.
It became 17. Since the dielectric characteristics (particularly the dielectric loss tangent) can be reduced, it is possible to manufacture an electric component having an insulator with a smaller dielectric loss than the conventional comparative example 2.

[0046]

[Table 2] Comparative Example 3 Comparative Example 3 is a cured product of a bisphenol A type epoxy resin Ep828. The composition and dielectric properties are shown in Table 3.
It was shown to. The dielectric constant was 2.78 and the dielectric loss tangent was 0.037. The dielectric loss tangent of this cured product was rather high, and it could not be sufficiently applied to the insulators of electric parts that correspond to high frequency signals. [Examples 7 to 9] Examples 7 to 9 are examples of liquid varnish obtained by adding liquid BVPE to bisphenol A type epoxy resin Ep828. The composition and dielectric properties are shown in Table 3.
The addition of BVPE lowers the values of dielectric constant and dielectric loss tangent. The dielectric constant is 2.74 to 2.61 and the dielectric loss tangent is 0.01.
It became 7-0.010. Since the dielectric characteristics (particularly the dielectric loss tangent) can be reduced, it is possible to manufacture an electric component having an insulator with a smaller dielectric loss than the conventional Comparative Example 3.

[0047]

[Table 3] Comparative Example 4 Comparative Example 4 is a cured product of acrylate resin R684. The composition and dielectric properties are shown in Table 4. The dielectric constant was 2.66 and the dielectric loss tangent was 0.019. The dielectric loss tangent of this cured product was rather high, and it could not be sufficiently applied to the insulators of electric parts that correspond to high frequency signals. [Examples 10 to 12] Examples 10 to 12 are examples of liquid varnish obtained by adding liquid BVPE to acrylate resin R684. The composition and dielectric properties are shown in Table 4. BVPE
The addition of the above decreases the values of the dielectric constant and the dielectric loss tangent, the dielectric constant is 2.61 to 2.56 and the dielectric loss tangent is 0.017 to 0.0
It became 07. Since the dielectric characteristics (particularly the dielectric loss tangent) can be reduced, it is possible to manufacture an electric component having an insulator with a smaller dielectric loss than the conventional comparative example 4.

[0048]

[Table 4] [Comparative Example 5] Comparative Example 5 is an epoxy resin Ep828, KR.
It is a cured product obtained by dissolving and dispersing the indicated substances such as M2650, epoxy acrylate resin 1421, and phenol resin PP1000 in MEK, and then drying and curing. Dielectric constant is 2.
84 and the dielectric loss tangent was 0.022. The dielectric loss tangent of this cured product was rather high, and it could not be sufficiently applied to the insulators of electric parts that correspond to high frequency signals. Comparative Example 6 Comparative Example 6 is a cured product of a resin composition obtained by adding DVB as a crosslinking component to Comparative Example 5. The composition and dielectric properties are shown in Table 5. Since it was cured after being dried in the same manner as in Example 5, DVB was evaporated and a sufficient low dielectric loss tangent was not achieved. Dielectric constant is 2.84,
The dielectric loss tangent was 0.021. [Examples 13 to 15] Examples 13 to 15 are examples of solid resin compositions obtained by adding BVPE to the resin composition of Comparative Example 5. The composition and dielectric properties are shown in Table 5. The addition of BVPE lowers the values of dielectric constant and dielectric loss tangent, and the dielectric constant is 2.
67-2.52 and the dielectric loss tangent were 0.015-0.007. Since the dielectric characteristics (particularly the dielectric loss tangent) can be reduced, it is possible to manufacture an electric component having an insulator with a smaller dielectric loss than the conventional Comparative Example 5.

[0049]

[Table 5] Example 16 An example of making a semiconductor device using the resin composition of the present invention as an insulating layer will be described below with reference to FIG.

In FIG. 2, 5 is a shield, 6 is a substrate electrode, 7 is a substrate, 8 is gold wire wiring, 9 is an aluminum electrode, 1
0 indicates an IC chip, 11 indicates a die bond resin, and 12 indicates a low dielectric loss tangent resin cured product. (A) A liquid leakage preventing shield 5 is formed around the IC chip 10 of the semiconductor device manufactured by the wire bonding method. (B) Wire wiring 8
Low dielectric loss tangent resin composition 12 of Example 3 for protecting the
(Potting) and under vacuum (approx. 5 mmH
g), 120 ° C / 30 minutes, 150 ° C / 30 minutes, 180 ° C
Cured by multi-step heating for 100 minutes. No residual air bubbles around the wire wiring 8, foaming of the resin composition 12, disconnection of the wire wiring 8, short circuit, or the like occurred. As described above, a semiconductor device compatible with high frequency signals was manufactured. Since this semiconductor device covers the periphery of the wiring with an insulating layer having a low dielectric constant and a low dielectric loss tangent, the semiconductor device has a small loss of electric signals. Example 17 A glass cloth was dipped in the MEK varnish of the resin composition of Example 14 and dried at room temperature for 1 hour at 90 ° C./60 minutes to prepare a prepreg. This prepreg was heated and pressed under vacuum to prepare a simulated substrate. The heating condition is 12
0 ° C / 30 minutes, 150 ° C / 30 minutes, 180 ° C / 100
Min., Multi-step heating with a press pressure of 1.5 MPa. The simulated substrate has a resin content of about 35 wt% and a size of 70x70.
× 0.15 mm. The permittivity of this simulated substrate is 3.2,
The dielectric loss tangent was 0.012, which was a good dielectric property. [Example 18] Rough surfaces of electrolytic copper foil were attached to both surfaces of the prepreg produced in Example 17, and heated and pressed under vacuum to produce a double-sided copper-clad laminate. Heating condition is 120 ℃ / 30
Minutes, 150 ° C./30 minutes, 180 ° C./100 minutes, and multi-stage heating with a pressing pressure of 1.5 MPa. The copper foil and the prepreg showed good adhesion. This made it possible to fabricate a multilayer printed circuit board. [Example 19] Fig. 3 shows an example of manufacturing a multilayer printed circuit board according to the present invention.
Shown in. (A) A photoresist (Hitachi Chemical Co., Ltd. H on the surface of the copper foil 13 on one side of the double-sided copper-clad laminate (resin substrate 14 and electrolytic copper foils 13 provided on both sides thereof) produced in Example 17
S425) 15 was laminated and exposed over the entire surface. Then, a photoresist (HS manufactured by Hitachi Chemical Co., Ltd.) is formed on the surface of the remaining copper foil 13.
425) 15 was laminated to expose the test pattern, and the unexposed portion of the photoresist 15 was developed with a 1% sodium carbonate solution. (B) The exposed copper foil 13 was removed by etching with an etching solution containing 5% sulfuric acid and 5% hydrogen peroxide to form conductor wiring on one surface of the double-sided copper-clad laminate.
(C) The remaining photoresist 15 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 17 was sandwiched between the wiring-side surfaces of two wiring boards, and heated and pressed under vacuum to form a multilayer structure. The heating condition is 1
20 ° C / 30 minutes, 150 ° C / 30 minutes, 180 ° C / 100
Min., Multi-step heating with a press pressure of 1.5 MPa.
(E) A photoresist (HS425 manufactured by Hitachi Chemical Co., Ltd.) 15 was laminated on the exterior copper surface of the produced multilayer board to expose a test pattern, and the unexposed portion of the photoresist 15 was developed with a 1% sodium carbonate solution. (F) The exposed copper foil 13 was removed by etching with an etching solution containing 5% sulfuric acid and 5% hydrogen peroxide, and the remaining photoresist 15 was removed with a 3% sodium hydroxide solution to form the exterior wiring 18.
(G) A through hole 19 for connecting the exterior wiring 18 and the inner layer wiring 17 was produced by drilling. (H) Immerse the wiring board in the colloidal solution of the plating catalyst to form the through hole 19
Of these, a catalyst was applied to the substrate surface. (I) After the activation treatment of the plating catalyst, electroless plating (CUST20 manufactured by Hitachi Chemical
00) provided a seed film 21 of about 1 μm. (J) Photoresist (HN920 manufactured by Hitachi Chemical) 15 was laminated on both surfaces of the wiring board. (K) The through hole 19 and the end of the wiring board were masked, exposed, and then developed with 3% sodium carbonate to form an opening 22. (L) The electrode 23 was placed at the end of the wiring board, and plated copper 24 was formed to 18 μm in the through hole by electrolytic plating. (M) The electrode 23 portion was cut and removed, and the remaining photoresist 15 was removed with a 5% sodium hydroxide solution. (N) Immerse the wiring board in an etching solution of 5% sulfuric acid and 5% hydrogen peroxide, and
The multilayer film was manufactured by removing the seed film 21 by μm etching. The insulating layer of the present multilayer wiring board is a wiring board which has a lower dielectric constant and a lower dielectric loss tangent than ordinary epoxy resin compositions and can reduce the dielectric loss of high frequency signals.

[0051]

Industrial Applicability According to the present invention, a low dielectric loss tangent having a dielectric loss tangent at 10 GHz of less than 0.002 at a cured product obtained by curing a general-purpose curable resin (A) at 180 ° C. for 100 minutes. Of the curable component (B) at the time of curing, by blending the curable component (B) having both properties and a non-volatile property that the vapor pressure at 52 ° C. is 1 hPa or less, as will be apparent from the description of Examples below. It is possible to reduce the dielectric loss tangent of the curable resin composition while suppressing the variation in the dielectric properties due to volatilization.

As the above-mentioned curing component (B), a polyfunctional styrene compound having a hydrocarbon skeleton such as alkylene or arylene is preferable, and a cured product having a low dielectric constant and a low dielectric loss tangent that does not crack during curing is stabilized. You can get it.

Further, by using the low dielectric loss tangent resin composition as an insulator of an electric component, an electric component having a small dielectric loss can be manufactured.

[Brief description of drawings]

FIG. 1 is a layout view of a jig when manufacturing a resin plate.

FIG. 2 is a schematic cross-sectional view of a semiconductor device manufactured by a wire bonding method.

FIG. 3 is a schematic view showing a process for manufacturing a multilayer printed circuit board.

[Explanation of symbols]

1 ... Spacer, 2 ... Molding film, 3 ... Release film, 4 ... End plate, 5 ... Shield, 6 ... Substrate electrode, 7 ... Substrate, 8 ... Gold wire wiring, 9 ... Aluminum electrode, 10 ... IC chip, 11 ... Die bond resin, 12 ... Low dielectric loss tangent resin cured product, 13 ... Electrolytic copper foil, 14 ... Resin substrate, 15 ... Photoresist, 16 ... Prepreg, 17 ... Inner layer wiring, 18 ...
Outer layer wiring, 19 ... through hole, 20 ... plating catalyst, 2
1 ... Seed film, 22 ... Open hole part, 23 ... Electrode, 24 ... Plated copper.

Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) // C08L 51:00 C08L 51:00 (72) Inventor Keiro Ishikawa 7-1 Omika-cho, Hitachi-shi, Ibaraki Hitachi Ltd., Hitachi Research Laboratory (72) Inventor Akio Takahashi 7-1-1, Omika-cho, Hitachi City, Ibaraki Prefecture F-term inside Hitachi Laboratories Hitachi Research Laboratory (reference) 4F072 AB02 AB08 AB28 AB29 AD03 AD09 AD11 AD13 AD23 AD23 AD52 AG03 AL13 4F100 AB17 AB33 AK12A AR00B AR00C BA02 BA03 BA07 BA10B BA10C BA15 DH01A GB43 JG01B JG01C 4J026 AA20 AA45 AA57 AB01 AB04 AB05 AB37 AC19 BA07 BB01 GG17FF15 DD15FF17 FF15 DD17FF15 DD13 FF17 DD15 DD07 DD15 DD02 DD44 DD12 DD12 DD02 DD12 DD02 DD12 DD02 DD12 DD12 DD12 DD02 DD02 DD12 DD02 DD12 DD02 DD12 DD02 DD12 DD02 DD12 DD12 DD02 DD12 DD12 DD12 DD02 DD02 DD12 DD02 DD02 DD12 DD02 DD12 DD02 DD12 DD12 DD12 DD12 DD02 DD12 DD02 DD12 DD12 DD12 DD12 DD12 DD12 DD12 DD12 DD12 DD12 DD12 DD12 DD12 DD12 DD12 DD12 DD12 DD12 DD12 DD12 DD12 DD12 DD12 DD12 DD12 DD12 DD12 DD12 DD12 DD12 DD12 DD12 DD12 DD12 DD12 DD12 DD12 DD12 DD12 DD12 DD12 DD12 DD04 DD12 DD44 DD12 DD16 GG28 HH06

Claims (10)

[Claims] 1. A curable resin (A) having a dielectric loss tangent of 0.002 or more at 10 GHz at 180 ° C. and a cured product obtained by curing at 180 ° C. for 1 hP at 52 ° C.
A method for reducing dielectric loss tangent, which comprises adding a curing component (B) which is a or less and has a dielectric loss tangent of less than 0.002 at 10 GHz of a cured product obtained by curing at 180 ° C. for 100 minutes. 2. The curing component (B) has the following general formula: (In the formula, R represents a hydrocarbon skeleton which may have a substituent, and R ² , R ³ and R ⁴ may be the same or different,
Represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, R ⁵ ,
R ⁶ , R ⁷ , and R ⁸ may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and n represents an integer of 2 or more. The low dielectric loss tangent method according to claim 1, which is a compound having a plurality of styrene groups and having a weight average molecular weight of 1,000 or less. 3. A curable resin (A) having a dielectric loss tangent at 10 GHz of not less than 0.002 at 10 GHz, which is obtained by curing at 180 ° C. for 100 minutes, and the following general formula: (In the formula, R represents a hydrocarbon skeleton which may have a substituent, and R ² , R ³ and R ⁴ may be the same or different,
Represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, R ⁵ ,
R ⁶ , R ⁷ , and R ⁸ may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and n represents an integer of 2 or more. ) A composition containing a curing component (B) having a plurality of styrene groups and having a weight average molecular weight of 1000 or less. 4. The curable resin (A) contains at least one curable resin selected from an epoxy resin, a phenol resin, a cyanate ester resin, a maleimide resin, an acrylate resin and a methacrylate resin. Item 4. The composition according to Item 3. 5. The dielectric loss tangent at 10 GHz of a cured product obtained by curing at 180 ° C. for 100 minutes is 0.001 to 0.0.
The composition according to claim 3, wherein the composition is 1. 6. A cured product of the composition according to any one of claims 3 to 5. 7. An electric component comprising the cured product according to claim 6 as an insulating layer. 8. A curable resin (A) having a dielectric loss tangent at 10 GHz of not less than 0.002 at 10 GHz, which is obtained by curing at 180 ° C. for 100 minutes, and the following general formula: (In the formula, R represents a hydrocarbon skeleton which may have a substituent, and R ² , R ³ and R ⁴ may be the same or different,
Represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, R ⁵ ,
R ⁶ , R ⁷ , and R ⁸ may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and n represents an integer of 2 or more. ) The composition containing the curing component (B) having a plurality of styrene groups and having a weight average molecular weight of 1000 or less is impregnated into an organic or inorganic cloth or unwoven cloth,
A dried prepreg. 9. A laminated board having conductor layers provided on both sides or one side of the prepreg or the cured product thereof according to claim 8. 10. A multilayer printed circuit board obtained by applying wiring processing to a conductor layer of the laminated board according to claim 9, and laminating and adhering the laminated board via a prepreg.