JP6749055B2 - Resin composition, prepreg, metal-clad laminate and wiring board - Google Patents

Description

The present invention relates to a resin composition, a prepreg using the resin composition, a metal-clad laminate, and a wiring board.

2. Description of the Related Art In recent years, the speed and integration of LSIs have increased, and the capacity of memories has increased, and along with that, various electronic components have rapidly become smaller, lighter, and thinner. Therefore, superior heat resistance, dimensional stability, and electrical characteristics are required in terms of materials.

In recent years, as a resin composition for a printed wiring board, by using a polyphenylene ether-based resin or a cyclic olefin-based resin or the like instead of the conventionally used epoxy resin, an improvement for exerting various performances in a balanced manner has been achieved. (See, for example, Patent Documents 1 and 2).

Special table 2004-523615 gazette JP, 2010-100843, A

However, the resin compositions disclosed in Patent Documents 1 and 2 still have a problem that when they are cured, they have a large dielectric loss tangent or a low glass transition point (Tg).

An object of the present invention is to provide a resin composition having a low dielectric loss tangent and a high glass transition point (Tg), a prepreg, a metal-clad laminate, and a wiring board.

The resin composition of the present invention comprises, as the component (A), a polyphenylene ether having hydroxyl groups at both ends modified by an ethylenically unsaturated compound, and as the component (B), a plurality of crosslinkable double bonds in the side chain portion. It contains the cyclic olefin copolymer which has, at least 1 sort(s) of triallyl isocyanurate and triallyl cyanurate as a component (C), and an organic peroxide as a component (D).

The prepreg of the present invention comprises the above resin composition and a base material.

The metal-clad laminate of the present invention includes a metal foil on the surface of the prepreg.

Wiring board of the present invention includes a plurality of insulating layers; and a and insulating interlayer disposed conductor layer, the insulating layer is a polymer body including cured product obtained from the above resin composition base material Is to have.

According to the present invention, a resin composition having a small dielectric loss tangent and a high glass transition point (Tg), a prepreg, a metal-clad laminate, and a wiring board can be obtained.

Hereinafter, the present invention will be described based on an embodiment of the resin composition. The resin composition of the present disclosure comprises, as component (A), polyphenylene ether in which hydroxyl groups at both ends are modified with an ethylenically unsaturated compound, and as component (B), a crosslinkable carbon-carbon double bond in a side chain portion. A cyclic olefin copolymer having a plurality of:, at least one of triallyl isocyanurate and triallyl cyanurate as the component (C), and an organic peroxide as the component (D).

When the resin composition contains the component (A), the component (B), the component (C) and the component (D) as described above, the dielectric loss tangent (frequency: 10 GHz) is 0.0030 or less, A cured product having a glass transition point (Tg) of 190° C. or higher can be obtained. In this case, the dielectric constant at the same frequency is also 3.0 or less.

Here, the hardened body means a state in which the resin composition containing the above-mentioned four components is formed after being heated or heated and pressed.

Here, each component of the component (A), the component (B), the component (C), and the component (D) will be described. As the component (A), for example, a compound represented by the following structural formula (I): Can be mentioned.

Here, the organic compound represented by the structural formula (I) has a functional group based on a hydroxyl group at both ends of the main chain of polyphenylene ether. In this polyphenylene ether, an ethylenically unsaturated compound is bonded to the hydrogen atom portion of the functional group based on the hydroxyl group. In the structural formula (I), R _{1 to} R ₂₂ are each independently a hydrogen atom or a functional group (substituent) shown below. Examples of the functional group include a linear or branched alkyl group having 1 to 8 carbon atoms, a linear or branched alkenyl group having 2 to 8 carbon atoms, and a linear or branched alkynyl group having 2 to 8 carbon atoms. , And an aryl group having 6 to 10 carbon atoms are preferable. Specific examples of the substituent include a carboxyl group, an aldehyde group, a hydroxyl group, an amino group and the like. X, Y, Z are each independent and a carbonyl group (> C = O), thiocarbonyl (> C = S), methylene _(-CH 2 -), ethylene group (dimethylene group) (- CH ₂ -CH ₂ -), isopropenyl _{(-C (CH 3) 2 -} ) trimethylene _{(-CH 2 -CH 2 -CH 2 -} ) or tetramethylene group _{(-CH 2} -CH ₂ -CH ₂ -CH ₂ −) is shown. n is an integer of 1 to 100.

In this case, the molecular weight of the component (A) is preferably in the range of 1000 to 5000, particularly 1000 to 3000 from the viewpoint of improving the miscibility with the cyclic olefin polymer which is the component (B).

Next, as the component (B), a cyclic olefin copolymer having a plurality of the following structural formulas (II) in the molecule can be mentioned.

In structural formula (II), R23 to R42 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, or an alkyl group having 3 to 15 carbon atoms. It is a cycloalkyl group or an aromatic hydrocarbon group having 6 to 20 carbon atoms, in which R39 to R42 have one or more substituents having a crosslinkable double bond. Examples of the substituent include a vinyl group, an alkenyl group, an acryl group, and a methacryl group. These functional groups allow the crosslinking reaction to proceed between the crosslinkable double bonds of the cyclic olefin copolymer or with other molecules having a similar structure by radicals derived from the peroxide. Specific examples thereof include LCOC-4 manufactured by Mitsui Chemicals.

Next, at least one of the triallyl isocyanurate (TAIC) and the triallyl cyanurate (TAC) listed as the component (C) is mainly crosslinked to the component (A) and the component (B). It acts as an agent.

Next, the component (D), an organic peroxide (hereinafter, sometimes referred to as a peroxide) acts as a radical initiator. That is, the component (D) is obtained by radically reacting the component (A), the component (B), and the component (C) to obtain a crosslinked product of the component (A), the component (B), and the component (C). Used for. Examples of the component (D) include di-t-butyl peroxide, 2,5-dimethyl-2,5-di(t-butyl peroxide)hexane, and 2,5-dimethyl-2,5-di(t-). Butyl peroxide) hexyne-3 and the like are mentioned, but not particularly limited. Note that these compounds are commercially available, for example, as "Perbutyl D", "Perhexa 25B", "Perhexin 25B" (all manufactured by NOF Corporation). As the component (D), it is preferable to use an organic peroxide containing no benzene ring.

Here, the background of the four-component structure will be described. In recent years, in an insulating material for a high-frequency substrate or an antenna substrate, in order to achieve high-speed transmission, a resin used in an insulating layer has a low dielectric constant and a low dielectric constant. Tangentization is desired. In this field, even lower dielectric constants and dielectric loss tangents are required than the epoxy resins and polyphenylene ether resins used conventionally. Therefore, the applicant has focused on a cyclic olefin resin as the candidate material.

However, even if these polyphenylene ether-based resins and cyclic olefin-based resins are combined, the conventional polyphenylene ether-based resin and the cyclic olefin-based resin originally have almost no miscibility (compatibility). It has not been possible to obtain a resin composition capable of simultaneously exhibiting the advantages of the base resin and the cyclic olefin resin component.

Therefore, the present applicant uses polyphenylene ether (component (A)) in which hydroxyl groups at both ends are modified with an ethylenically unsaturated compound as the polyphenylene ether-based resin, and the side chain portion is used as the cyclic olefin-based resin. A cyclic olefin copolymer having a plurality of crosslinkable double bonds (component (B)) was combined. A crosslinking agent (component (C)) and a peroxide serving as a curing catalyst (component (D)) were combined and added thereto.
In this way, the resin composition of the present disclosure and the cured product obtained thereby could be obtained.

In this case, the component (A) used had a molecular weight in the range of 1,000 to 5,000. Further, a method of preparing a mixture of the component (B) and the component (C) in advance and then mixing the component (A) and the component (D) therein was adopted. As a result, miscibility (compatibility) between the component (A) and the component (B) was enhanced, and a resin composition (cured product) having the advantages of the component (A) and the component (B) was obtained.

When the composition of the above-mentioned four components is limited, various characteristics can be improved. For example, the component (A) is limited to 42 to 66% by mass, the component (B) to 4 to 28% by mass, the component (C) to 20 to 28% by mass, and the component (D) to 2 to 10% by mass. In some cases, a cured product having a dielectric constant of 2.9 or less, a dielectric loss tangent of 0.0029 or less, and a glass transition point (Tg) of 191° C. or more can be obtained.

Further, the resin composition in this composition range can also improve the adhesiveness to the copper foil which is smooth and has a small anchoring effect. For example, the surface roughness (Ra) of the copper foil is MD (Machine Direction)
) Direction and TD (Transverse direction) direction both are 0.2 μm or less, and even in a copper foil having a thickness of 0.15 to 0.19 μm, the peel strength of the copper foil from the cured product can be 0.52 kN/m or more. ..

Further, in the case of this resin composition, the component (A) is 42 to 56% by mass, the component (B) is 14 to 28% by mass, the component (C) is 22 to 26% by mass, and the component (D) is 4 to 8%. When each is limited to mass %, the dielectric constant is 2.8 or less, the dielectric loss tangent is 0.0026 or less, the glass transition point (Tg) is 192° C. or more, and the peel strength from the copper foil is 0.62 kN. It is possible to obtain a cured product having a hardness of /m or more.

The resin composition of the present disclosure may contain silica, a flame retardant, a stress relaxation agent, and the like, if necessary, within a range that does not impair the effects of the resin composition. Examples of silica include pulverized silica and fused silica, which may be used alone or in admixture of two or more. Specifically, methacrylsilane-treated fused silica: SFP-130MC (manufactured by Denki Kagaku Kogyo Co., Ltd.), FUSELEX E-2, Adma FineSO-C5, PLV-3 (all manufactured by Tatsumori Co., Ltd.) and the like can be mentioned. To be

As the silica, silica particles having an average particle diameter of 5 μm or less are preferably used. By using the silica particles having such an average particle diameter, when the resin composition is used in, for example, a metal-clad laminate, it is possible to improve the adhesion to the metal foil. In this case, silica may be contained in a proportion of 5 to 40 parts by mass when the total amount of the components (A), (B), (C) and (D) is 100 parts by mass. it can. By including silica in such a ratio, the melt fluidity of the resin composition is improved. Furthermore, when the resin composition is used in, for example, a metal-clad laminate, the adhesion with the metal foil can be improved and the connection reliability of the through holes can be improved.

The flame retardant is not particularly limited and includes, for example, melamine phosphate, melam polyphosphate, melem polyphosphate, melamine pyrophosphate, ammonium polyphosphate, red phosphorus, aromatic phosphate ester, phosphonate ester, phosphinate ester, phosphine oxide, Examples include phosphazene, melamine cyanolate, ethylenebispentabromobenzene, ethylenebistetrabromophthalimide and the like. These flame retardants may be used alone or in combination of two or more. In this case, from the viewpoints of dielectric properties, flame resistance, heat resistance, adhesion, moisture resistance, chemical resistance, reliability, etc., melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, ammonium polyphosphate, ethylenebispentabromo Benzene is preferably used.

The flame retardant can be contained in a proportion of 15 to 45 parts by mass when the total amount of the components (A), (B), (C) and (D) is 100 parts by mass. When the flame retardant is contained in such a ratio, the flame resistance can be improved with almost no influence on the dielectric properties, adhesion and moisture resistance.

The stress relaxation agent is not particularly limited, and examples thereof include silicone resin particles. Examples of the silicone resin particles include KMP-597 (manufactured by Shin-Etsu Chemical Co., Ltd.) and X-52-875 (manufactured by Shin-Etsu Chemical Co., Ltd.) as silicone rubber powder, and KMP-590 (Silicone resin powder). Shin-Etsu Chemical Co., Ltd. product, X-52-1621 (Shin-Etsu Chemical Co., Ltd. product), etc. are mentioned. These stress relaxation agents may be used alone or in combination of two or more kinds.

As the stress relaxation agent, those having an average particle diameter of 10 μm or less can be used. By using the stress relaxation agent having such an average particle diameter, the adhesiveness with the metal foil can be improved when the resin composition is used for, for example, a metal-clad laminate. By including the stress relaxation agent in such a ratio, when the resin composition is used, for example, in a metal-clad laminate, it is possible to improve the adhesion with the metal foil and the moisture absorption resistance, and to improve the through hole. Connection reliability can also be improved.

In addition to the above components, the resin composition of the present disclosure may be appropriately added with a filler, an additive, or the like depending on the application. Examples of the filler include carbon black, titanium oxide, barium titanate, glass beads, glass hollow spheres and the like. Examples of the additive include an antioxidant, a heat stabilizer, an antistatic agent, a plasticizer, a pigment, a dye and a colorant. Specific examples of the additive include R-42 (manufactured by Sakai Chemical Industry Co., Ltd.) and IRGANOX1010 (manufactured by BASF). The fillers and additives may be used alone or in combination of two or more.

Furthermore, at least one of a thermoplastic resin and a thermosetting resin may be added to the resin composition of the present disclosure. Examples of the thermoplastic resin include GPPS (general-purpose polystyrene), HIPS (impact-resistant polystyrene), polybutadiene, and styrene-butadiene block copolymer. Examples of the thermosetting resin include epoxy resin. These resins may be used alone or in combination of two or more.

The resin composition of the present disclosure can be obtained, for example, by mixing the above-mentioned components (A) to (D) as described above, and then by mixing other components as necessary, as a mixing method. Examples thereof include a solution mixing method in which each component is uniformly dissolved or dispersed in a solvent, and a melt blending method in which heating is performed by an extruder or the like. Examples of the solvent used in the solution mixing method include aromatic solvents such as benzene, toluene and xylene, tetrahydrofuran and cyclohexane. These solvents may be used alone or in combination of two or more.

Next, the prepreg of the present disclosure will be described. The prepreg of the present disclosure includes the resin composition of the present disclosure and a base material. For example, it is obtained by applying or impregnating a substrate with the resin composition of the present disclosure according to a conventional method, and then drying. Examples of the base material include woven or non-woven fabric of fibers such as glass and polyimide, and paper. Examples of the material of glass include ordinary E glass, D glass, S glass, and quartz glass.

The proportion of the base material in the prepreg may be 20 to 80 mass% in the entire prepreg. In the prepreg of the present disclosure, a coupling agent such as a silane coupling agent or a titanate coupling agent may be applied to a base material and used as necessary.

The resin composition (component) and content in the prepreg are gas chromatography mass spectrometry (GC-MS) and nuclear magnetic resonance analysis ( ¹ H-NMR and ¹³ C-NMR), Fourier transform infrared absorption spectrum analysis (FT-). It can be confirmed by analysis by quantitative analysis of thermal decomposition products by IR) and thermal decomposition gas chromatography.

The method for producing the prepreg of the present disclosure is not particularly limited, and, for example, the resin composition of the present disclosure is uniformly dispersed in a solvent (for example, the aromatic solvent described above, a ketone solvent such as methyl ethyl ketone, etc.) as necessary. Examples thereof include a method of dissolving or dispersing in a base material, coating or impregnating the base material, and then drying.

Alternatively, the resin composition may be melted and impregnated into the base material. The coating method and the impregnation method are not particularly limited, and for example, a method of applying a solution or dispersion of the resin composition using a spray, a brush, a bar coater, or the like, a substrate for the solution or dispersion of the resin composition is used. Examples include a method of dipping (dipping). The application or impregnation can be repeated a plurality of times as necessary. Alternatively, the application or impregnation can be repeated using a plurality of solutions or dispersions having different resin concentrations.

The prepreg of the present disclosure is subjected to, for example, thermoforming to be processed into a laminated plate. The laminated plate can be obtained, for example, by stacking a plurality of prepregs in accordance with a desired thickness and heat-pressing. Furthermore, a thicker laminate can be obtained by combining the obtained laminate with another prepreg. The lamination molding and curing are usually performed simultaneously using a hot press machine, but both may be performed separately.

That is, it is possible to first laminate and mold to obtain a semi-cured laminate, and then treat with a heat treatment machine to completely cure. The heat and pressure molding can be performed under a pressure of 80 to 300° C. and a pressure of 0.1 to 50 MPa for about 1 minute to 10 hours. Moreover, it can also be performed under 150-250 degreeC and 0.5-10 MPa pressurization for about 30 minutes-5 hours.

Next, the metal-clad laminate of the present disclosure will be described. The metal-clad laminate of the present disclosure includes a metal foil on the surface of the prepreg of the present disclosure. For example, the metal-clad laminate of the present disclosure can be obtained by stacking the prepreg and the metal foil of the present disclosure on each other and molding with heating and pressing. The metal foil is not particularly limited, and examples thereof include electrolytic copper foil, copper foil such as rolled copper foil, aluminum foil, and composite foil obtained by stacking these metal foils. Among these metal foils, copper foil is preferable. The thickness of the metal foil is not particularly limited, and one having a thickness of about 5 to 105 μm can be used. The metal-clad laminate of the present disclosure can also be obtained by stacking a desired number of the prepreg and the metal foil of the present disclosure on each other and heat-pressing. In this case, in the metal-clad laminate, the resin composition in the prepreg has at least two kinds selected from the group of the above-mentioned component (A), component (B), component (C) and component (D). It will contain a polymer obtained from the combination. In this case, the polymer preferably has at least one crosslinkable functional group selected from the group consisting of a vinyl group, a propenyl group and a methacryl group, and in particular, these functional groups are preferably a cycloalkyl group and an ether group. What you have between and is good. Thus, the metal-clad laminate of the present disclosure has the above-mentioned cured body, and has a low dielectric constant and dielectric loss tangent, high heat resistance, and is used for a printed circuit board excellent in adhesiveness with a copper foil. Will be possible.

Next, the wiring board of the present disclosure will be described. The wiring board of the present disclosure includes a plurality of insulating layers and a conductor layer disposed between the insulating layers, and the insulating layer includes a cured body containing a polymer obtained from the resin composition of the present disclosure and a base material. It is formed by and.

A wiring board according to the present disclosure includes, for example, a metal-clad laminate of the present disclosure, an inner layer board having a circuit and a through hole formed thereon, and a prepreg, and a conductive metal foil is laminated on the surface of the prepreg and then heated. Obtained by pressure molding. Furthermore, a circuit and a through hole may be formed in the conductive metal foil on the surface to form a multilayer printed wiring board.

According to the resin composition of the present disclosure, a cured product having a low dielectric constant and a low dielectric loss tangent can be obtained. Further, by using such a resin composition, it is possible to obtain a prepreg and a metal-clad laminate having a low dielectric constant and dielectric loss tangent, and a wiring board having excellent high frequency characteristics.

Hereinafter, the resin composition of the present disclosure will be specifically described with reference to examples, but the resin composition of the present disclosure is not limited to these examples.

The components used in the sample are as follows.

SA9000: Methacryl-modified polyphenylene ether (molecular weight: 2300) (manufactured by Savix)
LCOC-4: a cyclic olefin copolymer having a plurality of crosslinkable double bonds in the side chain (
(Mitsui Chemicals)
LCOC-3: Cyclic olefin copolymer having no crosslinkable double bond in the side chain (Mitsui Chemicals)
TAIC: triallyl isocyanurate (manufactured by Nippon Kasei Co., Ltd.)
Perbutyl D: di-t-butyl peroxide (without benzene ring) (NOF Corporation)
Silica particles: SFP-130MC (average particle size 5 μm) (manufactured by Denki Kagaku Kogyo Co., Ltd.)
Copper foil: EXP-WS (thickness=18 μm, Ra=0.18 μm)
(Sample Nos. 1 to 11)
The components shown in Table 1 were mixed in the proportions shown in Table 1, and "SAYTEX 8010" (manufactured by Albemarle Asano Co., Ltd.) was added as a flame retardant to the components (A), (B), (C) and (D). 30 parts by mass was added to 100 parts by mass of the total amount) and stirred at room temperature (25° C.) to obtain a resin composition. The obtained resin composition was dissolved in toluene to obtain a resin varnish. The mass ratio of the resin composition and toluene was 50:50.

The obtained resin varnish was molded on a PET film (carrier film) using a bar coater and then dried at 170° C. for 4 minutes to obtain a resin film.

The obtained resin film was repeatedly laminated with a laminator and the carrier film was peeled off to prepare a resin plate.

Next, both sides of the obtained resin plate were sandwiched between copper foils having a thickness of 18 μm and heated and pressed at a pressure of 4 MPa and a temperature of 200° C. for 120 minutes to produce a copper clad laminate having a thickness of about 1 mm.

Next, the obtained copper clad laminate was processed into a desired size to prepare a sample, and the characteristics were evaluated.

The dielectric constant and the dielectric loss tangent were measured by the disk resonator method using an impedance analyzer. The measurement frequency was 10 GHz. A resin plate after peeling the copper foil from the copper-clad laminate was used as a sample. The size of the measurement sample was 50 mm square and the thickness was 0.95 mm. As the impedance analyzer, a scalar network analyzer manufactured by Keysight, Inc. was used.

Next, the glass transition point (Tg) of the resin plate was determined by dynamic viscoelasticity (DMA) analysis. For this measurement, a sample cut into a length of 30 mm, a width of 5 mm, and a thickness of 0.95 mm was heated in the atmosphere from room temperature to 260° C. under the conditions of a heating rate of 5° C./min and an acceleration frequency of 1 Hz to determine the mechanical properties. Measured in bending mode. As the dynamic viscoelasticity measuring device, SIIDMS110, manufactured by Hitachi High-Tech Science Co., Ltd.) was used.

The peel strength of the copper foil was measured by a 90° peel test at room temperature using a sample obtained by cutting the produced copper-clad laminate into a length of 150 mm, a width of 5 mm, and a thickness of 1 mm.
The results are shown in Table 1.

From Table 1, sample No. containing no component (B). No. 10 had a glass transition point of 190° C., but had a dielectric constant of 3.1 and a dielectric loss tangent of 0.0032. On the other hand, sample No. containing no component (A). No. 11 had a dielectric constant of 2.7 and a dielectric loss tangent of 0.0028, but had a glass transition point of 157°C.

On the other hand, the range of the component (A) is 42 to 66 mass %, the component (B) is 4 to 28 mass %, the component (C) is 20 to 28 mass %, and the component (D) is 2 to 10 mass %. Sample No. Nos. 1 to 9 have a dielectric constant of 2.9 or less, a dielectric loss tangent of 0.0029 or less, a glass transition point (Tg) of 191° C. or more, and a copper foil peel strength of 0.52 kN/m or more. Met.

Furthermore, sample No. 4 which made the component (A) 42-56 mass %, the component (B) 14-28 mass %, the component (C) 22-26 mass %, and the component (D) 4-8 mass %. In Nos. 2 to 5, the dielectric constant was 2.8, the dielectric loss tangent was 0.0026 or less, the glass transition point (Tg) was 192° C. or higher, and the peel strength from the copper foil was 0.62 kN/m or higher. ..

Claims (7)

As component (A), a polyphenylene ether having hydroxyl groups at both ends modified with an ethylenically unsaturated compound,
As the component (B), a cyclic olefin copolymer having a plurality of crosslinkable double bonds in the side chain portion,
As component (C), at least one of triallyl isocyanurate and triallyl cyanurate;
As a component (D), an organic peroxide,
A resin composition comprising: 42 to 66% by mass of the component (A),
The component (B) is 4 to 28% by mass,
20 to 28% by mass of the component (C),
2 to 10% by mass of the component (D),
The resin composition according to claim 1, wherein the resin composition is contained in the following ratio. 42 to 56% by mass of the component (A),
14-28% by mass of the component (B),
22 to 26 mass% of the component (C),
4 to 8 mass% of the component (D),
The resin composition according to claim 1 or 2, wherein the resin composition is contained in the following ratio. A prepreg comprising the resin composition according to claim 1 and a base material. A metal-clad laminate comprising the surface of the prepreg according to claim 4 and a metal foil. The resin composition in the prepreg is a polymer obtained from a combination of at least two selected from the group consisting of the component (A), the component (B), the component (C) and the component (D). The metal-clad laminate according to claim 5, which contains. And a plurality of insulating layers and conductive layer disposed on the insulating interlayer, and the insulating layer according to claim 1 including curing body polymeric object obtained from the resin composition according to any one of the three A wiring board having a base material .