JP2014101399A - Cyanate ester-based resin composition, and prepreg and laminate plate using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cyanate ester-based resin composition which can impart excellent dielectric characteristics in a high-frequency region to a printed wiring board while sufficiently securing compatibility with a resin component.SOLUTION: A resin composition contains (A) a saturation type thermoplastic elastomer having a styrene skeleton, (B) a cyanate ester compound, (C) monofunctional phenol, and (D) an epoxy resin. A mass ratio of the styrene with respect to the mass of the whole (A) components is 10% to 70%.

Description

  The present invention relates to a cyanate ester resin composition and a prepreg and a metal-clad laminate produced using the cyanate ester resin composition.

  In recent years, electronic devices related to mobile communication are required to process a large amount of information at high speed, and the frequency of electric signals handled here is increasing. However, since the strength of the signal tends to attenuate as the frequency becomes higher, a substrate material with low transmission loss is desired for the printed wiring board used in this field. That is, it is necessary to use a resin material having a low relative dielectric constant and low dielectric loss tangent in a high frequency band.

  Further, in electronic devices such as computers, in order to process a large amount of information in a short time, development of a high-speed microprocessor having an operating frequency exceeding several GHz and an increase in signal frequency are progressing. In devices that handle such high-speed pulse signals, delay on the printed wiring board has become a problem. Since the signal delay time in the printed wiring board becomes longer in proportion to the square root of the relative dielectric constant of the insulator around the wiring, a resin material for a substrate having a low relative dielectric constant is required for the wiring board used in computers and the like. .

  Corresponding to the higher frequency of signals as described above, conventionally thermoplastic resin materials such as fluororesins with low relative permittivity and dielectric loss tangent have been used in this field, but fluidity is insufficient due to high melt viscosity. However, there remains a problem that a high temperature and a high pressure are necessary at the time of press molding, and a disadvantage that the dimensional stability and the adhesion to metal plating are inferior. Therefore, a composition comprising a cyanate ester and an epoxy resin disclosed in Patent Document 1 as a composition of a cyanate ester compound known as one of the resins having the lowest relative dielectric constant and dielectric loss tangent among thermosetting resin materials And a method using a composition comprising a bismaleimide, a cyanate ester and an epoxy resin disclosed in Patent Document 2 have been proposed.

  Moreover, as a thing which improves a high frequency characteristic using a thermoplastic resin, the resin composition of the polyphenylene ether (PPO or PPE) shown in patent document 3 and a crosslinkable polymer / monomer, and patent document 4 show. Among the heat-resistant thermoplastic resins, there is a method of using a polyphenylene ether-based resin composition having good dielectric properties such as a resin composition of a polyphenylene ether having a specific curable functional group and a crosslinking monomer.

  Further, as a resin composition comprising a cyanate ester compound and polyphenylene ether having good dielectric properties, the resin composition of cyanate ester / bismaleimide and polyphenylene ether disclosed in Patent Document 5 is disclosed as an improvement in high-frequency characteristics. , A method of using a resin composition of cyanate ester / epoxy resin and polyphenylene ether shown in Patent Document 6, and a resin composition of phenol-modified resin / cyanate ester reaction product and polyphenylene ether shown in Patent Document 7 There is. Furthermore, as a heat-resistant molding material having good high-frequency characteristics, there is a resin composition in which a cyanate ester compound is kneaded with polyphenylene ether as disclosed in Patent Document 8.

  In addition, a metal-clad laminate (see Patent Document 3) prepared using a polyphenylene oxide-based resin composition, a crosslinkable polymer and a crosslinkable monomer, a resin composition containing a flame retardant or a flame retardant aid, and A film obtained by appropriately crosslinking a specific cured polyphenylene ether resin containing a saturated group is also disclosed (see Patent Document 9). Further, in addition to a modified cyanate ester resin film using a polyphenylene ether resin and a cyanate ester compound (see Patent Document 10), a resin film in which an elastomer is blended with a polyphenylene ether-containing modified cyanate ester compound is also disclosed. (See Patent Document 11).

  On the other hand, Patent Document 12 discloses a film adhesive using a cyanate ester compound and various thermoplastic resins such as a styrene elastomer.

Japanese Patent Publication No.46-41112 Japanese Patent Publication No.52-31279 Japanese Examined Patent Publication No. 5-77705 Japanese Patent Publication No. 6-92533 Japanese Patent Publication No. Sho 63-33506 Japanese Examined Patent Publication No. 4-57696 Japanese Patent Laid-Open No. 5-311071 Japanese Patent Publication No. 61-18937 JP-A-7-188362 Japanese Patent Laid-Open No. 11-124451 JP 2003-138133 A JP-A-9-279121

However, even the above-described resin composition is not sufficient to achieve the dielectric properties (low relative dielectric constant and low dielectric loss tangent) in the high frequency region required for printed wiring boards for millimeter waves. . In particular, in a resin composition containing an acrylic rubber or a modified polybutadiene-based elastomer as described in Patent Document 12, adverse effects in the high frequency region become significant. In addition, even when blended with a styrene-based elastomer as described in Patent Document 12, since the elastomer used is only a polar group-containing type, not only high-frequency characteristics, but also moisture resistance, heat discoloration resistance, etc. Slightly insufficient. On the other hand, according to the study by the present inventors, in the case of the resin composition described in the previous period, from the viewpoint of ensuring compatibility with the main component polyphenylene ether, the type of resin used and the blending amount thereof are limited. Therefore, it has also been found that the degree of freedom of composition that can be practically used is small.
Therefore, the present invention has been made in view of such circumstances, and a resin capable of imparting good dielectric properties in a high frequency region to a printed wiring board while sufficiently ensuring the compatibility of resin components. An object is to provide a composition.

As a result of intensive studies to achieve the above object, the present inventor has found that a styrene weight ratio is specific in a cyanate ester resin composition having a saturated thermoplastic elastomer having a styrene skeleton and a cyanate ester compound. It has been found that the above-described problems can be solved by using a saturated thermoplastic elastomer in the range.
That is, the present invention
[1] (A) A saturated thermoplastic elastomer having a styrene skeleton, (B) a cyanate ester compound, (C) a monofunctional phenol, and (D) an epoxy resin, and the total weight of the component (A) A cyanate ester-based resin composition having a mass ratio of styrene to 10% to 70%,

[2] The cyanate ester resin composition of [1], wherein the component (A) is a saturated thermoplastic elastomer containing a styrene-ethylene-butylene copolymer.
[3] The cyanate ester resin composition according to [2], wherein the styrene-ethylene-butylene copolymer is obtained by hydrogenating a double bond group of a butadiene portion of a styrene-butadiene copolymer.
[4] The cyanate ester resin composition according to any one of [1] to [3], wherein the component (A) contains a saturated thermoplastic elastomer having a number average molecular weight of 40,000 or more and 70,000 or less. .
[5] The cyanate ester system according to the above [4], wherein the content ratio of the saturated thermoplastic elastomer having a number average molecular weight of 40,000 or more and 70,000 or less is 50% by mass or more based on the total mass of the component (A). Resin composition.
[6] The above-mentioned [5], wherein the saturated thermoplastic elastomer contains an elastomer having a number average molecular weight of 40,000 or more and 60,000 or less and an elastomer having a number average molecular weight of more than 60,000 and 70,000 or less. ] Cyanate ester-based resin composition.
[7] The cyanate ester system according to any one of the above [1] to [6], wherein the component (B) contains a phenol-modified cyanate ester prepolymer obtained by reacting a cyanate ester compound with a monofunctional phenol compound. Resin composition.

[8] A prepreg obtained by coating the base material with the cyanate ester resin composition according to any one of [1] to [7] above,
[9] A resin-coated film obtained by coating the cyanate ester resin composition according to any one of [1] to [7] on a support film,
[10] A laminate obtained by stacking one or more prepregs of the above [8], placing a metal foil on one or both sides thereof, and heating and pressing the laminate,
[11] A laminate obtained by stacking one or more films with resin of [9] above, placing a metal foil on one or both sides thereof, and heating and pressing,
About.
[12] A wiring board obtained by forming wiring on the laminated board of [10] or [11],
[13] A multilayer wiring board having at least one wiring board according to [12].

  ADVANTAGE OF THE INVENTION According to this invention, the cyanate ester-type resin composition which can provide the favorable dielectric characteristic in a high frequency area | region to a printed wiring board can be provided, ensuring the compatibility of a resin component fully.

Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.
[Cyanate ester resin composition]
The cyanate ester resin composition according to the embodiment of the present invention includes (A) a saturated thermoplastic elastomer having a styrene skeleton, (B) a cyanate ester compound, (C) a monofunctional phenol, and (D) an epoxy resin. The mass ratio of styrene to the mass of the entire component (A) is 10% to 70%.

The component (A) is not particularly limited as long as it is a saturated thermoplastic elastomer having a styrene skeleton in the molecule, but from the viewpoint of improving the high-frequency characteristics, it is saturated containing a styrene-ethylene-butylene copolymer (SEBS). The mold type thermoplastic elastomer is preferred.
As the styrene-ethylene-butylene copolymer, those obtained by a method of hydrogenating the unsaturated double bond portion of the butadiene block of the styrene-butadiene copolymer are preferable.
That is, the saturated thermoplastic elastomer in the present embodiment refers to those in which an aliphatic hydrocarbon portion other than the aromatic hydrocarbon portion (styrene block) is composed of a saturated bonding group. The component (A) may contain a chemically modified saturated thermoplastic elastomer having a maleic anhydride group at the side chain or terminal.

The component (A) preferably contains a saturated thermoplastic elastomer having a number average molecular weight of 40,000 to 70,000. If the number average molecular weight of the saturated thermoplastic elastomer of component (A) is 40,000 or more, the thermophysical properties such as Tg and high-frequency characteristics are improved by increasing the elongation and interaction between molecules as an elastomer. If it is 1,000 or less, the compatibility and moldability will be good due to the interaction between molecules. In addition, the weight average molecular weight in this invention is measured by the gel permeation chromatography (GPC) method (polystyrene conversion) using tetrahydrofuran as an eluent.
The number average molecular weight of the saturated thermoplastic elastomer is more preferably from 45,000 to 65,000, further preferably from 50,000 to 60,000.
The component (A) preferably contains a saturated thermoplastic elastomer having a number average molecular weight of 40,000 or more and 60,000 or less and a saturated thermoplastic elastomer greater than 60,000 and 70,000 or less. The saturated thermoplastic elastomer having a number average molecular weight of 40,000 or more and 60,000 or less has good compatibility with the component (B), the component (C) and the component (D), and the number average molecular weight is 60,000. Larger saturated thermoplastic elastomers of 70,000 or less have good heat resistance and high-frequency characteristics but have poor compatibility. By mixing a saturated thermoplastic elastomer having a number average molecular weight of 40,000 or more and 60,000 or less with a saturated thermoplastic elastomer having a number average molecular weight of more than 60,000 but not more than 70,000, compatibility, thermophysical properties and high-frequency characteristics are improved. A good resin composition is obtained.

  Here, examples of the saturated thermoplastic elastomer include non-modified SEBS (manufactured by Asahi Kasei Chemicals Corporation, Tuftec H1041, H1051, H1043, H1053, and the like). On the other hand, SEBS (manufactured by Asahi Kasei Chemicals Corporation, Tuftec M1911, M1913, M1943, etc.) modified with maleic anhydride can be used as the chemically modified saturated thermoplastic elastomer.

  (B) As a component, the cyanate ester compound shown by General formula (1) is mentioned.

（式中、Ｒ¹は、下記式で表されるものである。Ｒ²及びＲ³は、互いに同一でも異なっていてもよく、水素またはメチル基を表す）

(In the formula, R ¹ is represented by the following formula. R ² and R ³ may be the same as or different from each other and represent hydrogen or a methyl group)

  Moreover, what used together the (C) component mentioned later to a cyanate ester compound, or the phenol modified cyanate ester compound previously modified | denatured by (C) component can also be used. As a result, the dielectric properties, moisture resistance, and heat resistance can be improved more effectively.

  Specific examples of the component (B) are not particularly limited as long as they are cyanate ester compounds having two or more cyanato groups in the molecule. For example, 2,2-bis (4-cyanatophenyl) propane, bis (4-cyanatophenyl) ethane, bis (3,5-dimethyl-4-cyanatophenyl) methane, 2,2-bis (4- Cyanatophenyl) -1,1,1,3,3,3-hexafluoropropane, α, α′-bis (4-cyanatophenyl) -m-diisopropylbenzene, cyanate ester of phenol-added dicyclopentadiene polymer Examples include compounds, phenol novolac type cyanate ester compounds, and cresol novolac type cyanate ester compounds. These may be used alone or in combination of two or more.

  When a cyanate ester compound is used as the component (B), a curing agent or a curing accelerator for the cyanate ester compound may be included. For example, a monofunctional phenol compound, a polyfunctional phenol compound, an amine compound, an acid anhydride, and Organic metal compounds such as 2-ethylhexanoate such as manganese, iron, cobalt, nickel, copper, and zinc, naphthenate, and acetylacetone complex. In consideration of high-frequency characteristics, moisture resistance, heat resistance, etc., it is more preferable to use a monofunctional phenol compound and an organometallic compound in combination.

(C) As a component, the phenol compound shown by General formula (2) is mentioned, for example.

（式中、Ｒ⁴及びＲ⁵は、互いに同一でも異なっていてもよく、水素原子または炭素数１〜４の低級アルキル基を表し、ｎは、１または２である）

(Wherein R ⁴ and R ⁵ may be the same as or different from each other, and represent a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms, and n is 1 or 2)

  As specific examples of the component (C), pt-octylphenol, p-phenylphenol, and p- (α-cumyl) phenol are preferably used, and the compounding amount of the monofunctional phenol compound is the cyanate group of the cyanate ester compound. The equivalent ratio of the hydroxyl group of the phenol compound to 0.01 to 1.00 is preferable from the viewpoints of dielectric properties, moisture resistance, and heat resistance.

  Moreover, when using a cyanate ester compound and a monofunctional phenol compound, it is possible to react the cyanate ester compound and the monofunctional phenol compound in advance to prepolymerize and use the appearance and handleability of the uncured (B stage) film and the cured film. It is preferable from the viewpoint of curability. The monofunctional phenol compound to be blended may be blended in all of the prescribed amount at the time of prepolymerization, or the prescribed amount may be blended separately before and after the prepolymerization, but from the viewpoint of storage stability of the varnish, It is preferable to mix them separately. Here, the prepolymer is a reaction that has been stopped before gelation, and is reacted to such an extent that it does not gel.

  (D) Any epoxy resin may be used as long as it has two or more epoxy groups in the molecule. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, fat Cyclic epoxy resin, aliphatic chain epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, naphthalene skeleton type epoxy resin, bifunctional biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, Examples include dicyclopentadiene type epoxy resins, dihydroanthracene type epoxy resins, diglycidyl etherified products of phenols, diglycidyl etherified products of alcohols, and alkyl-substituted products and halides thereof. May be used in combination it is. In consideration of high frequency characteristics, it is more preferable to use a naphthalene skeleton type epoxy resin, a bifunctional biphenyl type epoxy resin, a biphenyl aralkyl type epoxy resin, or a dicyclopentadiene type epoxy resin. Furthermore, a cresol novolac type epoxy resin is more preferable.

  In addition to the epoxy resin, a curing agent or curing accelerator for the epoxy resin may be contained. For example, a polyfunctional phenol compound, an amine compound, an imidazole compound, an acid anhydride, an organic phosphorus compound, and a halide thereof. Is mentioned.

  In addition, the cyanate ester resin composition according to the present embodiment includes handling properties, dielectric properties, heat resistance, adhesion to conductors and other resin materials, moisture resistance, glass transition point (Tg), thermal expansion properties, and the like. If necessary, a flame retardant, various additives, an inorganic filler, and the like may be further blended in a blending amount within a range not deteriorating the amount. Although it does not specifically limit as various additives, For example, a silane coupling agent, a titanate coupling agent, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a pigment, a coloring agent, a lubricant, etc. are mentioned. Each may be used alone or in combination of two or more.

  Although it does not specifically limit as a flame retardant, Flame retardants, such as a bromine type, a phosphorus type, and a metal hydroxide, are used suitably. More specifically, brominated flame retardants include brominated epoxy resins such as brominated bisphenol A type epoxy resin and brominated phenol novolac type epoxy resin, hexabromobenzene, pentabromotoluene, ethylenebis (pentabromophenyl). , Ethylenebistetrabromophthalimide, 1,2-dibromo-4- (1,2-dibromoethyl) cyclohexane, tetrabromocyclooctane, hexabromocyclododecane, bis (tribromophenoxy) ethane, brominated polyphenylene ether, brominated Brominated flame retardants such as polystyrene and 2,4,6-tris (tribromophenoxy) -1,3,5-triazine, tribromophenyl maleimide, tribromophenyl acrylate, tribromophenyl methacrylate, tetrabromide Bisphenol A dimethacrylate, brominated reactive flame retardant unsaturated double bond-containing, such as pentabromobenzyl acrylate and brominated styrene.

  Phosphorus flame retardants include aromatic phosphoric acids such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl di-2,6-xylenyl phosphate and resorcinol bis (diphenyl phosphate) Esters, phosphonic esters such as divinyl phenylphosphonate, diallyl phenylphosphonate and bis (1-butenyl) phenylphosphonate, phenyl diphenylphosphinate, methyl diphenylphosphinate, 9,10-dihydro-9-oxa-10-phos Phosphinic acid esters such as faphenanthrene-10-oxide derivatives, phosphazene compounds such as bis (2-allylphenoxy) phosphazene, dicresyl phosphazene, melamine phosphate, melamine pyrophosphate, Phosphorus flame retardants such as melamine phosphate, melam polyphosphate, ammonium polyphosphate, phosphorus-containing vinylbenzyl compounds and red phosphorus can be exemplified, and examples of metal hydroxide flame retardants include magnesium hydroxide and aluminum hydroxide. . Moreover, the above-mentioned flame retardant may be used individually by 1 type, and may be used in combination of 2 or more types.

  The blending ratio of the flame retardant is not particularly limited, but is preferably 10 to 200 parts by mass, and preferably 15 to 150 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B). Is more preferable, and it is still more preferable to set it as 20-100 mass parts. If the blending ratio of the flame retardant is less than 10 parts by mass, the flame resistance tends to be insufficient, and if it exceeds 200 parts by mass, the heat resistance, adhesiveness, film-forming ability, and moldability tend to decrease.

  The inorganic filler is not particularly limited to the following materials, but spherical silica that has been surface-treated with an amino-based silane coupling agent in advance is preferable. That is, after blending the spherical silica in the resin containing the component (A) and the component (B), the surface treatment agent is added to the resin composition. Alternatively, a method in which the surface treatment is performed in a wet manner and then used as it is or in a slurry state at the time of blending is preferable.

  The amino-based silane coupling agent that is a surface treatment agent for silica is not particularly limited, and N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl)- 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine and its partial hydrolyzate, 3-trimethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine and its partial hydrolyzate, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, etc. Can be mentioned. Among them, N-phenyl-3-aminopropyl represented by the formula (3) from the viewpoint of dispersibility of silica in the resin containing the component (A) and the component (B), reactivity with the resin, and adhesiveness Trimethoxysilane is particularly preferably used. By using the above-mentioned inorganic filler treatment method and these amino-based silane coupling agents, it is possible not only to suppress defects such as silica agglomeration, but also to improve the resin curability and the reactivity between silica and resin. In addition, the adhesiveness can be improved, and high chemical resistance against various acidic and basic aqueous solutions used in the printed wiring board manufacturing process can be exhibited while improving high-frequency characteristics and thermal expansion characteristics and high heat resistance.

  The average particle diameter of the spherical silica is preferably from 0.01 to 30 μm, and the resin film obtained within this range has good moldability (inner layer circuit fillability). Moreover, it is especially preferable that the average particle diameter of spherical silica is 0.1-10 micrometers, and it is still more preferable that it is 0.3-7 micrometers.

  In this embodiment, it is preferable that the mixture ratio of an inorganic filler is 10-1000 mass parts with respect to 100 mass parts of total amounts of (A) component and (B) component, and if it exists in this range The resulting resin film has good moldability (inner layer circuit fillability), handleability, low thermal expansion, heat resistance, adhesion to conductors and core substrates, and the like.

  Further, the amount of the amino-based silane coupling agent as the inorganic filler is not particularly limited, but it is preferable that the surface treatment is performed at 0.1 to 5% by mass with respect to the mass of the spherical silica to be blended, If it is this range, the characteristic by said inorganic filler can be exhibited effectively, without impairing heat resistance.

  When preparing the cyanate ester-type resin composition which concerns on this embodiment, the mixing method of (A) component, (B) component, (C) component, and (D) component is not specifically limited. In addition to the above components, the method for mixing the curing agent, curing accelerator, crosslinking agent, flame retardant, inorganic filler and various additives is not particularly limited. It is preferable to use in the form of a resin varnish which is added with an organic solvent and stirred, dissolved and dispersed by a known method. The solvent used in this case is not particularly limited, but specific examples include alcohols such as methanol, ethanol and butanol, ethyl cellosolve, butyl cellosolve, ethylene glycol monomethyl ether, carbitol, butyl carbitol and the like. Ethers, acetone, methyl ethyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone, aromatic hydrocarbons such as toluene, xylene, mesitylene, esters such as methoxyethyl acetate, ethoxyethyl acetate, butoxyethyl acetate, ethyl acetate, N , N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone-containing solvents and the like. (A) When a mixed solvent of aromatic hydrocarbons such as toluene, xylene and mesitylene or aromatic hydrocarbons and ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, which is a good solvent of component (A), is used as a film This is desirable because of its good appearance. Moreover, these may be used individually by 1 type and may be used in combination of 2 or more types.

By using the cyanate ester-based resin composition according to this embodiment described above, a laminate in which the prepreg, the resin film, and the metal foil according to the present invention are arranged can be manufactured by a known method.
For example, a prepreg can be obtained by impregnating a cyanate ester resin composition into a substrate made of reinforcing fibers such as glass fibers and organic fibers, and then drying in a drying furnace or the like. Moreover, after arrange | positioning the resin composition which concerns on this invention on a support film, a film with resin is obtained by making it dry.
One or a plurality of the prepregs are stacked, a metal foil is disposed on one side or both sides thereof, and heated and / or pressurized under predetermined conditions to obtain a double-sided or single-sided metal-clad laminate. Similarly, a metal-clad laminate is obtained from the resin-coated film. By using the prepreg and metal-clad laminate produced as described above, by performing a hole forming process, a metal plating process, a circuit forming process such as etching a metal foil, and a multi-layer bonding process by a known method, A multilayer printed wiring board is obtained.

  The present invention is not limited to the above-described embodiment, and can be arbitrarily changed and modified within a range not departing from the object of the invention.

Next, the present invention will be described in more detail with reference to the following examples, but these examples do not limit the present invention.
[Preparation of resin varnish]
A resin varnish was prepared according to the following procedure and the blending amount of Table 1 or Table 2.
<Preparation Example 1>
Into a 1 liter separable flask equipped with a thermometer, reflux condenser, vacuum concentrator and stirrer, toluene, methyl isobutyl ketone, and hydrogenated styrene-butadiene copolymer (Tuftec) as component (A) H1041, styrene content ratio: 30%, Mn: 58,000, manufactured by Asahi Kasei Chemicals Co., Ltd.), and the temperature in the flask was set to 80 ° C. and dissolved by stirring. Next, 2,2-bis (4-cyanatophenyl) propane (BADCY, manufactured by Lonza Japan Co., Ltd.) as the component (B), naphthalene cresol novolak type epoxy resin (NC-7000, manufactured by DIC) as the component (D) And p-((alpha) -cumyl) phenol (made by Tokyo Chemical Industry) was mix | blended as (C) component, and the dissolution was confirmed, and the flask was cooled to room temperature. Thereafter, as an inorganic filler, spherical silica (SC2050-KNK, average particle diameter) pretreated by surface treatment with N-phenyl-3-aminopropyltrimethoxysilane (KBM-573, manufactured by Shin-Etsu Chemical Co., Ltd.) at a treatment amount of 1% by mass. : 0.5 μm, manufactured by Admatechs) (dispersion medium: methyl isobutyl ketone, solid content: 70% by mass, forced dispersion treatment performed by a nanomizer disperser) was blended, and 2-ethyl-4- was used as a curing accelerator. After adding methylimidazole (2E4MZ, manufactured by Shikoku Chemicals), methyl ethyl ketone was blended and stirred to prepare a resin varnish having a solid content concentration of about 45% by mass.

<Preparation Example 2>
Into a 1-liter separable flask equipped with a thermometer, reflux condenser, vacuum concentrator, and stirrer, toluene, (B) component, 2,2-bis (4-cyanatophenyl) propane (BADCY, Lonza Japan) Co., Ltd.), p- (α-cumyl) phenol (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as component (C), and after confirming dissolution, the liquid temperature was kept at 110 ° C. and then manganese naphthenate (Japanese Koganei Pharmaceutical Co., Ltd.) was blended and heated for about 3 hours to obtain a phenol-modified cyanate prepolymer solution. Next, the reaction solution was cooled, and when the internal temperature reached 80 ° C., naphthalene cresol novolac type epoxy resin (NC-7000, manufactured by DIC) was used as component (D), and hydrogen of styrene-butadiene copolymer was used as component (A). Additives (Tuftec H1041, styrene content ratio: 30%, Mn: 58,000, manufactured by Asahi Kasei Chemicals Co., Ltd.), toluene and methyl ethyl ketone were mixed, and after confirming dissolution, the flask was cooled to room temperature. Thereafter, as an inorganic filler, spherical silica (SC2050-KNK, average particle diameter) pretreated by surface treatment with N-phenyl-3-aminopropyltrimethoxysilane (KBM-573, manufactured by Shin-Etsu Chemical Co., Ltd.) at a treatment amount of 1% by mass. : 0.5 μm, manufactured by Admatechs) slurry (dispersion medium: methyl isobutyl ketone, solid content: 70% by mass, forced dispersion treatment with nanomizer disperser), blended with zinc naphthenate (Wako Pure) A resin varnish having a solid content concentration of about 45% by mass was prepared by blending with Yakuhin Kogyo Co., Ltd.

<Preparation Example 3>
In Preparation Example 2, component (A) Tuftec H1041 was replaced with a hydrogenated styrene-butadiene copolymer having a number average molecular weight of 50,000 or less (Tuftec H1043, styrene content ratio: 67%, Mn: 47,000, Asahi Kasei. A resin varnish was prepared in the same manner as in Preparation Example 2 except that the chemical varnish was used.

<Preparation Example 4>
In Preparation Example 3, component (A) Tuftec H1043 was replaced with a hydrogenated styrene-butadiene copolymer having a number average molecular weight of 60,000 or more (Tuftec H1051, styrene content ratio: 42%, Mn: 66,000, Asahi Kasei. A resin varnish was prepared in the same manner as in Preparation Example 2 except that the chemical varnish was used.

<Preparation Example 5>
In Preparation Example 4, (A) component Tuftec H1051 was replaced with a hydrogenated styrene-butadiene copolymer having a number average molecular weight of 60,000 or more (Tuftec H1052, styrene content ratio: 20%, Mn: 66,000, Asahi Kasei. A resin varnish was prepared in the same manner as in Preparation Example 4 except that the chemical varnish was replaced.

<Preparation Example 6>
In Preparation Example 5, component (A) Tuftec H1052 was replaced with a hydrogenated styrene-butadiene copolymer having a number average molecular weight of 60,000 or more (Tuftec H1053, styrene content ratio: 30%, Mn: 66,000, Asahi Kasei. A resin varnish was prepared in the same manner as in Preparation Example 5 except that it was replaced with Chemicals).

<Preparation Example 7>
In Preparation Example 6, a part of (A) component Tuftec H1053 was added to a hydrogenated maleic acid-modified styrene-butadiene copolymer (Tuftec M1913, styrene content ratio: 30%, Mn: 63,000, maleimide modification amount. A resin varnish was prepared in the same manner as in Preparation Example 6 except that it was replaced with 10 mg CH ₃ ONa / g (manufactured by Asahi Kasei Chemicals Corporation) and blended in the blending amounts shown in Table 1.

<Preparation Example 8>
In Preparation Example 7, a part of (A) component Tuftec M1913 was added to a hydrogenated maleic acid-modified styrene-butadiene copolymer (Tuftec M1911, styrene content ratio: 30%, Mn: 63,000, maleimide modification amount. A resin varnish was prepared in the same manner as in Preparation Example 7 except that the amount was changed to 2 mg CH ₃ ONa / g (manufactured by Asahi Kasei Chemicals Corporation) and blended in the blending amounts shown in Table 1.

<Preparation Example 9>
In Preparation Example 8, a part of (A) component Tuftec M1911 was mixed with a hydrogenated maleic acid-modified styrene-butadiene copolymer (Tuftec M1943, styrene content ratio: 20%, Mn: 63,000, maleimide modified amount. A resin varnish was prepared in the same manner as in Preparation Example 8 except that it was replaced with 10 mg CH ₃ ONa / g (manufactured by Asahi Kasei Chemicals Corporation) and blended in the blending amounts shown in Table 1.

<Preparation Example 10>
In Preparation Example 1, a resin varnish was prepared in the same manner as in Preparation Example 5 except that the diluent solvent was only toluene and the materials used were blended in the blending amounts shown in Table 1.

<Preparation Example 11>
(Production of phenol-modified cyanate prepolymer)
Into a 1-liter separable flask equipped with a thermometer, reflux condenser, vacuum concentrator, and stirrer, toluene, (B) component, 2,2-bis (4-cyanatophenyl) propane (BADCY, Lonza Japan) Co., Ltd.), p- (α-cumyl) phenol (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as component (C), and after confirming dissolution, the liquid temperature was kept at 110 ° C. and then manganese naphthenate (Japanese Kogure Pharmaceutical Co., Ltd.) was blended and reacted by heating for about 3 hours, and then the reaction solution was cooled to obtain a phenol-modified cyanate prepolymer solution.

(Preparation of resin varnish)
Spherical silica (SC2050-KNK) obtained by surface-treating N-phenyl-3-aminopropyltrimethoxysilane (KBM-573, manufactured by Shin-Etsu Chemical Co., Ltd.) in an amount of 1% by mass in 1 liter of polybin as an inorganic filler. The slurry (dispersion medium: methyl isobutyl ketone, solid content: 70% by mass, forcible dispersion treatment with a nanomizer disperser) was added, and then the component (A) A hydrogenated product of styrene-butadiene copolymer previously dissolved in toluene (Tuftec H1041, styrene content ratio: 30%, Mn: 58,000, manufactured by Asahi Kasei Chemicals Corporation, solid content: 23% by mass) was blended. Next, the phenol-modified cyanate prepolymer solution prepared above and a naphthalene cresol novolak type epoxy resin (NC-7000, manufactured by DIC) as a component (D) are mixed and stirred in this solution, and zinc naphthenate is used as a curing accelerator. (Wako Pure Chemical Industries, Ltd.) and methyl ethyl ketone were blended to prepare a resin varnish having a solid concentration of about 45% by mass.

<Comparative Preparation Example 1>
Toluene and polyphenylene ether resin (S202A, manufactured by Asahi Kasei Chemicals Co., Ltd., Mn: 16000) are charged into a 1-liter separable flask equipped with a thermometer, a reflux condenser, and a stirring device, and the temperature in the flask is set to 90 ° C. And dissolved with stirring. Subsequently, triallyl isocyanurate (TAIC, manufactured by Nippon Kasei Co., Ltd.) was blended, and after confirming that it was dissolved or uniformly dispersed, it was cooled to room temperature. Next, after cooling to room temperature with stirring, spherical silica in which N-phenyl-3-aminopropyltrimethoxysilane (KBM-573, manufactured by Shin-Etsu Chemical Co., Ltd.) is surface-treated in advance at a treatment amount of 1% by mass as an inorganic filler. (SC2050-KNK, average particle size: 0.5 μm, manufactured by Admatechs) slurry (dispersion medium: methyl isobutyl ketone, solid content: 70 mass%, forced dispersion treatment performed by nanomizer disperser) 1, 1 as a curing accelerator After adding 1′-bis (t-butylperoxy) diisopropylbenzene (Perbutyl P, manufactured by NOF Corporation), methyl ethyl ketone was blended to prepare a resin varnish (solid content concentration of about 45% by mass).

<Comparative Preparation Example 2>
In Preparation Example 1, a resin varnish (solid content concentration of about 45% by mass) was prepared in the same manner as Preparation Example 1 except that polyphenylene ether resin (S202A) was used instead of Tuftec H1041.

<Comparative Preparation Example 3>
A resin varnish (solid content concentration of about 45% by mass) was prepared in the same manner as in Preparation Example 1 except that SC6000 was used instead of KBM-573 in Preparation Example 1.

<Comparative Preparation Example 4>
Toluene and polyphenylene ether resin (S202A, manufactured by Asahi Kasei Chemicals Co., Ltd., Mn: 16000) are charged into a 1-liter separable flask equipped with a thermometer, a reflux condenser, and a stirring device, and the temperature in the flask is set to 90 ° C. And dissolved with stirring. Subsequently, 2,2-bis (4-cyanatophenyl) propane (BADCY, manufactured by Lonza Japan Co., Ltd.) and p-tert-octylphenol (manufactured by Wako Pure Chemical Industries, Ltd.) were added and dissolved, and then manganese naphthenate (Japanese sum) Kogure Pharmaceutical Co., Ltd.) was blended and heated for about 3 hours. Subsequently, toluene and methyl ethyl ketone were mixed with stirring, the flask was cooled to room temperature, and then 3-glycidoxypropyltrimethoxy (KBM-403), manufactured by Shin-Etsu Chemical Co., Ltd.) was preliminarily surfaced at a treatment amount of 1% by mass. Blended slurry of treated spherical silica (SO-25R, average particle size: 0.5 μm, manufactured by Admatechs) (dispersion medium: methyl isobutyl ketone, solid content: 70% by mass, forced dispersion treatment with nanomizer disperser) And the resin varnish (solid content concentration = 45 mass%) was manufactured by mix | blending zinc naphthenate (made by Wako Pure Chemical Industries) as a hardening accelerator.

<Comparative Preparation Example 5>
In Comparative Preparation Example 2, a resin varnish (solid content) was obtained in the same manner as in Comparative Preparation Example 5 except that an epoxy-modified polybutadiene elastomer (manufactured by Daicel Chemical Industries, Ltd., PB-3600) was additionally added in the amount shown in Table 1. A concentration of about 45% by weight) was prepared.

<Comparative Preparation Example 6>
A resin varnish (solid content concentration of about 45% by mass) was prepared in the same manner as in Preparation Example 5 except that vinyltrimethoxysilane (KBM-1003) was used instead of KBM-573.

<Comparative Preparation Example 7>
In Preparation Example 2, a resin varnish (solid content concentration of about 45% by mass) was prepared in the same manner as in Preparation Example 5 except that 3-glycidoxypropyltrimethoxy (KBM-403) was used instead of KBM-573. Prepared.

<Comparative Preparation Example 8>
In Preparation Example 2, a resin varnish (solid content concentration of about 45% by mass) was prepared in the same manner as Preparation Example 5 except that 3-methacryloxypropyltrimethoxy (KBM-503) was used instead of KBM-573. did.

  Table 1 shows the amount of each raw material used in the preparation of the resin varnishes of Preparation Examples 1 to 10. In addition, Table 2 shows the amount of each raw material used for preparing the resin varnishes of Comparative Preparation Examples 1 to 8.

[Preparation of cured resin]
The resin varnishes obtained in Preparation Examples 1 to 11 and Comparative Preparation Examples 1 to 8 were coated on a film, dried at a drying temperature of 170 ° C., and pressure cured with a press to produce a cured resin. In addition, the resin cured material produced using the resin varnish of Preparation Examples 1-11 is Examples 1-11, and the resin cured material produced using the resin varnish of Comparative Preparation Examples 1-8 is Comparative Examples 1-8, respectively. Equivalent to.

[Evaluation method]
<Compatibility of varnish>
The compatibility of the varnish was measured visually and classified as follows.
○: No precipitate or precipitate Δ: Minor precipitate ×: Precipitate and precipitate <Measurement of dielectric properties (dielectric constant Dk, dielectric loss tangent Df)>
Dielectric characteristics were measured by cavity resonator perturbation method after etching an outer layer copper foil of a cured resin. The conditions were a frequency: 10 GHz and a measurement temperature: 25 ° C.
<Measurement of copper foil peeling strength>
The copper foil peeling strength was measured in accordance with the copper clad laminate test standard JIS-C-6481.
<Measurement of thermal characteristics>
Thermal characteristics were measured by TMA after etching the outer layer copper foil of the cured resin. Thermal characteristics were evaluated by the glass transition point Tg. Tg of the outer layer copper foil of the cured resin was etched by TMA.

[Evaluation results]
The cured resin products prepared using the resin varnishes of Preparation Examples 1 to 11 were evaluated by the above evaluation methods. Moreover, the resin cured material produced using the resin varnish of Examples 1-11 and Comparative preparation examples 1-8 is corresponded to Comparative Examples 1-8, respectively.

The cyanate ester resin composition according to the present invention has a high frequency characteristic of about 3.0 or less, a dielectric constant equivalent to that of a fluororesin substrate material containing an inorganic filler, a low dielectric loss tangent, and a liquid crystal polymer. Also exhibits good dielectric properties. Therefore, the transmission loss characteristic is exhibited even in a high frequency band exceeding the millimeter wave band, and it has a high Tg and a good copper foil peeling strength.
Therefore, components and parts for printed wiring boards used in mobile communication devices that handle high-frequency signals of 1 GHz or higher, base station devices, network-related electronic devices such as servers and routers, and various electric and electronic devices such as large computers. Useful as.
The resin composition according to the present invention has an operation frequency of several hundreds of MHz, such as a filter and other components incorporated in a wireless communication-related terminal device that requires a low signal loss in a high frequency band, a radio base station antenna, or a microprocessor. It is suitable for manufacturing a substrate for a printed wiring board used for a high-speed computer exceeding

Claims (13)

(A) a saturated thermoplastic elastomer having a styrene skeleton;
(B) a cyanate ester compound;
(C) a monofunctional phenol;
(D) The cyanate ester-type resin composition which contains an epoxy resin and whose mass ratio of styrene with respect to the mass of the said (A) component whole is 10%-70%.   The cyanate ester resin composition according to claim 1, wherein the component (A) is a saturated thermoplastic elastomer containing a styrene-ethylene-butylene copolymer.   The cyanate ester resin composition according to claim 2, wherein the styrene-ethylene-butylene copolymer is obtained by hydrogenating a double bond group of a butadiene portion of a styrene-butadiene copolymer.   The cyanate ester resin composition according to any one of claims 1 to 3, wherein the component (A) contains a saturated thermoplastic elastomer having a number average molecular weight of 40,000 or more and 70,000 or less.   The cyanate ester-based resin composition according to claim 4, wherein the content ratio of the saturated thermoplastic elastomer having a number average molecular weight of 40,000 or more and 70,000 or less is 50% by mass or more based on the total mass of the component (A). object.   The cyanate according to claim 5, wherein the saturated thermoplastic elastomer contains an elastomer having a number average molecular weight of 40,000 or more and 60,000 or less and an elastomer having a number average molecular weight of more than 60,000 and 70,000 or less. Ester resin composition.   The cyanate ester resin composition according to any one of claims 1 to 6, wherein the component (B) contains a phenol-modified cyanate ester prepolymer obtained by reacting a cyanate ester compound with a monofunctional phenol compound. object.   A prepreg obtained by coating the base material with the cyanate ester-based resin composition according to claim 1.   The film with resin formed by coating the cyanate ester-type resin composition in any one of Claims 1-7 on a support film.   A laminate obtained by stacking one or more prepregs according to claim 8, placing a metal foil on one or both sides, and heating and pressing.   A laminate obtained by stacking one or more films with a resin according to claim 9, placing a metal foil on one side or both sides, and heating and pressing.   The wiring board obtained by forming wiring in the laminated board of Claim 10 or 11.   A multilayer wiring board having at least one wiring board according to claim 12.