JP4894138B2 - Resin composition, resin layer, carrier material with resin layer, and circuit board - Google Patents

Description

  The present invention relates to a resin composition, a resin layer, a carrier material with a resin layer, and a circuit board.

  With recent demands for higher functionality and lighter and thinner electronic devices, electronic components such as circuit boards have been increasingly integrated and densely packaged. Along with the increase in the density of electronic components, electrical signals are also required to be transmitted at high speed.

  However, in order to increase the electrical signal transmission speed as described above, it is necessary to reduce the electrical loss from the conductor portion and the insulating layer constituting the circuit board. In particular, the loss of the electric signal due to the insulating layer increases remarkably with an increase in the frequency of the electric signal, and becomes a main factor for deterioration of the electric signal in the GHz band.

As a material constituting the insulating layer of the circuit board, epoxy resin and polyimide resin have been mainly used (for example, refer to Patent Document 1).
However, epoxy resin, etc. has insufficient electrical characteristics such as dielectric constant and dielectric loss tangent to meet the demands for high-speed electrical signals as described above, and can respond to high-speed transmission of electrical signals that have been required in recent years. May be difficult.

JP-A-5-121396

An object of the present invention is to provide a resin composition that is excellent in electrical characteristics and less deteriorated in electrical signals when used as a resin layer of a circuit board.
Another object of the present invention is to provide a resin layer and a carrier material with a resin layer that are excellent in electrical characteristics and have little deterioration of electrical signals.
Another object of the present invention is to provide a circuit board capable of high-speed transmission of electrical signals.

（２）前記置換基は、下記式（I）で表されるヘテロレプティックPOSS[(RSiO_1.5)₇(XSiO_1.0)₁]_Σ8である上記（１）に記載の樹脂組成物。

（３）前記置換基を有するノルボルネン型モノマーの繰り返し単位の含有量は、前記付加共重合体の５〜８０モル％である上記（１）または（２）に記載の樹脂組成物。
（４）前記第２の環状オレフィン系樹脂の重量平均分子量は、前記第１の環状オレフィン系樹脂の重量平均分子量よりも大きいものである上記（１）ないし（３）のいずれかに記載の樹脂組成物。
（５）前記第１の環状オレフィン系樹脂の重量平均分子量は、１０，０００〜５００，０００である上記（１）ないし（４）のいずれかに記載の樹脂組成物。
（６）前記第２の環状オレフィン系樹脂の重量平均分子量は、１００，０００〜７００，０００である上記（１）ないし（５）のいずれかに記載の樹脂組成物。
（７）上記（１）ないし（６）のいずれかに記載の樹脂組成物で構成されていることを特徴とする樹脂層。
（８）上記（７）に記載の樹脂層が、キャリア材料の少なくとも片面に形成されていることを特徴とする樹脂層付きキャリア材料。
（９）上記（７）に記載の樹脂層を有していることを特徴とする回路基板。 Such an object is achieved by the present invention described in the following (1) to (9).
(1) A resin composition constituting a resin layer of a circuit board,
Heteroleptic POSS [(RSiO _1.5 ) ₇ (XSiO _1.0 ) ₁ ] _Σ8 , functionalized heteroleptic POSS [(RSiO _{1.5 ) 4 (RXSiO 1.5) 3]} Σ7 and functionalized heteroleptic _{POSS [(RSiO 1.5) 4 (} RXSiO 1.0) 2 (RX'SiO 1.0) 1] in the side chain as a substituent of any one of _Shiguma7 A first cyclic olefin-based resin which is an addition copolymer of a norbornene-type polymer repeating unit and a norbornene-type monomer represented by the following formula (II):
A second cyclic olefin-based resin that is a polymer having a repeating unit represented by the following formula (V), different from the first cyclic olefin-based resin,
The content of the first cyclic olefin resin is 1 to 50% by weight of the whole resin composition, and the content of the second cyclic olefin resin is 50 to 50% of the whole resin composition. 99% by weight of a resin composition.

(2) The resin composition according to (1), wherein the substituent is heteroleptic POSS [(RSiO _1.5 ) ₇ (XSiO _1.0 ) ₁ ] _Σ8 represented by the following formula (I).

(3) The resin composition according to the above (1) or (2), wherein the content of the repeating unit of the norbornene monomer having a substituent is 5 to 80 mol% of the addition copolymer.
(4) The resin according to any one of (1) to (3), wherein a weight average molecular weight of the second cyclic olefin resin is larger than a weight average molecular weight of the first cyclic olefin resin. Composition.
(5) The resin composition according to any one of (1) to (4), wherein the first cyclic olefin-based resin has a weight average molecular weight of 10,000 to 500,000.
(6) The resin composition according to any one of (1) to (5), wherein the second cyclic olefin-based resin has a weight average molecular weight of 100,000 to 700,000.
(7) A resin layer comprising the resin composition according to any one of (1) to (6) above.
(8) A resin material with a resin layer, wherein the resin layer according to (7) is formed on at least one surface of the carrier material.
(9) A circuit board having the resin layer according to (7).

ADVANTAGE OF THE INVENTION According to this invention, when it is set as the resin layer of a circuit board, the resin composition which is excellent in an electrical property and has little deterioration of an electrical signal can be obtained.
In addition, according to the present invention, it is possible to obtain a resin layer and a carrier material with a resin layer that are excellent in electrical characteristics and have little deterioration of electrical signals.
In addition, according to the present invention, a circuit board capable of high-speed transmission of electrical signals can be obtained.
Further, when the side chain has a substituent represented by any one of formulas (I) to (III), the elastic modulus can be improved and the linear expansion coefficient can be lowered.
In addition, when the weight average molecular weight of the second cyclic olefin resin is larger than that of the first cyclic olefin resin, the film formability of the resin layer can be improved.

Hereinafter, the resin composition, resin layer, carrier material with a resin layer, and circuit board of the present invention will be described in detail.
The resin composition of the present invention is a resin composition that constitutes a resin layer of a circuit board, and is mainly composed of silicon and oxygen, and at least partly has a substituent having a cyclic structure in the side chain. And a second cyclic olefin resin different from the first cyclic olefin resin.
Moreover, the resin layer of this invention is comprised by the resin composition as described above, It is characterized by the above-mentioned.
The carrier material with a resin layer of the present invention is characterized in that the resin layer described above is formed on at least one side of the carrier material.
Moreover, the circuit board of the present invention is characterized by having the resin layer described above.

First, the resin composition will be described.
The resin composition of this invention comprises the resin layer of a circuit board. This is to provide a resin layer with excellent electrical characteristics on a circuit board that requires high-speed transmission of electrical signals.

The resin composition includes a first cyclic olefin resin mainly composed of silicon and oxygen, and having a substituent having a cyclic structure in at least a part in a side chain. Thereby, the adhesiveness of a board | substrate and the resin layer comprised with the said resin composition can be improved, maintaining the outstanding electrical property (low dielectric constant and low dielectric loss tangent).
Although the said substituent is not specifically limited, It is preferable that it has a silsesquioxane structure, and it is preferable that the said silsesquioxane structure forms the polyhedral structure (saddle-type structure) especially. Thereby, especially dynamic characteristics, such as an elastic modulus and an expansion coefficient, can be improved.
Specific examples of the substituent include heteroleptic POSS [(RSiO _1.5 ) ₇ (XSiO _1.0 ) ₁ ] _Σ8 (formula I below), functionalized heteroleptic POSS [(RSiO _1.5 ) ₄ (RXSiO _1.5 ) ₃ ] _Σ7 (formula III below), functionalized heteroleptic POSS [(RSiO _1.5 ) 4 (RXSiO _1.0 ) ₂ (RX′SiO _1.0 ) ₁ ] _Σ7 (formula IV below) and the like.

  It is preferable that the first cyclic olefin-based resin has a side chain specifically represented by the following formula (I) among the substituents. Thereby, especially dynamic characteristics, such as an elastic modulus and an expansion coefficient, can be improved.

  Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group. Examples of the cycloalkyl group include (C3-C15) cycloalkyl groups such as a cyclohexyl group, a cyclopentyl group, and a methylcyclohexyl group. Examples of the alkoxysilyl group include alkoxysilyl groups such as a trimethoxysilyl group, a triethoxysilyl group, and a triethoxysilylethyl group.

  Examples of the cyclic olefin monomer constituting the first cyclic olefin-based resin include, for example, a monocyclic product such as cyclohexene and cyclooctene, norbornene, norbornadiene, dicyclopentadiene, dihydrodicyclopentadiene, tetracyclododecene, tricyclopentadiene, Examples include polycyclic compounds such as dihydrotricyclopentadiene, tetracyclopentadiene, and dihydrotetracyclopentadiene. Furthermore, as described later, monomers in which a substituent (functional group) is bonded to these cyclic olefin monomers can also be used.

  Such polymers of cyclic olefin monomers include, for example, (co) polymers of cyclic olefin monomers, copolymers of cyclic olefin monomers and other copolymerizable monomers such as α-olefins, and copolymers thereof. Examples thereof include a hydrogenated product of a polymer. Examples of these known polymers include random copolymers, block copolymers, and alternating copolymers. These cyclic olefin-based resins can be produced by a known polymerization method, and examples of the polymerization method include an addition polymerization method and a ring-opening polymerization method. Of these, polymers obtained by polymerizing norbornene-type monomers (particularly addition (co) polymerization) are preferred, but the present invention is not limited thereto.

  Examples of the addition polymer of the first cyclic olefin resin include (1) addition (co) polymer of norbornene type monomer obtained by addition (co) polymerization of norbornene type monomer, and (2) norbornene type monomer and ethylene. And addition copolymers with α-olefins, (3) addition copolymers with norbornene type monomers and non-conjugated dienes, and other monomers as required. These resins can be obtained by all known polymerization methods.

  Examples of the ring-opening polymer of the first cyclic olefin-based resin include (4) a ring-opening (co) polymer of a norbornene-type monomer, and a resin obtained by hydrogenating the (co) polymer if necessary (5) ) A ring-opening copolymer of norbornene-type monomer and ethylene or α-olefins, and a resin obtained by hydrogenating the (co) polymer if necessary, (6) norbornene-type monomer and non-conjugated diene, or other Examples thereof include a ring-opening copolymer with a monomer, and a resin obtained by hydrogenating the (co) polymer if necessary. These resins can be obtained by all known polymerization methods. Among these, (1) addition (co) polymers obtained by addition (co) polymerization of norbornene type monomers are preferred, but the present invention is not limited to these.

The addition polymer of the first cyclic olefin resin is obtained by coordination polymerization using a metal catalyst or radical polymerization. Among them, in coordination polymerization, a polymer is obtained by polymerizing a monomer in a solution in the presence of a transition metal catalyst (NiCOLE R. GROVE et al. Journal of Polymer Science: part B, Polymer Physics, Vol. 37, 3003-3010 (1999)).
Representative nickel and platinum catalysts as metal catalysts for coordination polymerization are described in PCT WO 9733198 and PCT WO 00/20472. Examples of metal catalysts for coordination polymerization include (toluene) bis (perfluorophenyl) nickel, (mesylene) bis (perfluorophenyl) nickel, (benzene) bis (perfluorophenyl) nickel, bis (tetrahydro) bis ( Known metal catalysts such as perfluorophenyl) nickel, bis (ethyl acetate) bis (perfluorophenyl) nickel, and bis (dioxane) bis (perfluorophenyl) nickel may be mentioned.

The radical polymerization technique is described in Encyclopedia of Polymer Science, John Wiley & Sons, 13, 708 (1988).
Generally, in radical polymerization, the temperature is raised to 50 to 150 ° C. in the presence of a radical initiator, and the monomer is reacted in a solution. Examples of the radical initiator include azobisisobutyronitrile (AIBN), benzoyl peroxide, lauryl peroxide, azobisisocapronitrile, azobisisoleronitrile, t-butyl hydrogen peroxide, and the like.

  The ring-opening polymer of the first cyclic olefin-based resin is formed by ring-opening (co) polymerizing at least one or more norbornene-type monomers by a known ring-opening polymerization method using titanium or a tungsten compound as a catalyst. A co) polymer, and then, if necessary, a hydrogenated carbon-carbon double bond in the ring-opened (co) polymer by a conventional hydrogenation method to produce a thermoplastic saturated norbornene resin. Obtained by.

  Suitable solvents for polymerizing such first cyclic olefin-based resin include, for example, hydrocarbons and aromatic solvents. Specific examples of the hydrocarbon solvent include pentane, hexane, heptane, and cyclohexane, but are not limited thereto. Specific examples of the aromatic solvent include benzene, toluene, xylene and mesitylene, but are not limited thereto. Diethyl ether, tetrahydrofuran, ethyl acetate, ester, lactone, ketone, amide can also be used. These solvents can be used alone or as a polymerization solvent.

  The molecular weight of the first cyclic olefin resin can be controlled by changing the ratio of the initiator and the monomer or changing the polymerization time. When the above-mentioned coordination polymerization is used, US Pat. As disclosed in US Pat. No. 6,136,499, the molecular weight can be controlled through the use of a chain transfer catalyst. In the present invention, α-olefins such as ethylene, propylene, 1-hexane, 1-decene, 4-methyl-1-pentene are suitable for controlling the molecular weight.

  Among such first cyclic olefin resins, norbornene resins are preferably used, and addition (co) polymers of norbornene resins are particularly preferable. Thereby, the electrical characteristics (for example, dielectric constant is low) of the resin layer obtained are especially excellent. That is, it is preferable that the resin composition includes a first norbornene-based resin mainly composed of silicon and oxygen and having a substituent having a cyclic structure in at least a part in a side chain. Thereby, in addition to preventing the deterioration of the electric signal, the heat resistance can also be improved. As the substituent, the same ones as described above can be used.

Hereinafter, the first norbornene-based resin that is mainly composed of silicon and oxygen and has a substituent having a cyclic structure in at least a part in the side chain will be described in more detail.
Such a first norbornene-based resin mainly composed of silicon and oxygen and having a substituent in the side chain at least partially has a cyclic structure is not particularly limited, but the norbornene having the substituent in the side chain is not particularly limited. An addition copolymer of a repeating unit of a type monomer and a norbornene type monomer represented by the following formula (II) is particularly preferable.

  Examples of the alkyl group include (C1-C20) alkyl groups having a side chain such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group. Examples of the alkenyl group include a (C3-C10) alkenyl group. Examples of the alkynyl group include (C2-C20) alkynyl groups such as ethynyl group, propenyl group, hexenyl group, octenyl group and heptenyl group. Examples of the aryl group include (C6-C40) aryl groups such as a phenyl group, a tolyl group, a naphthyl group, and a phenylethynyl group. Examples of the aralkyl group include a benzyl group and a (C7-C15) aralkyl group. Examples of the ester group include ester groups such as a methyl ester group, an ethyl ester group, an n-butyl ester group, a t-butyl ester group, and an n-propyl ester group. Examples of the (meth) acryl group include a (meth) acryl group such as a methacryloxymethyl group. Examples of the epoxy group include an epoxy group such as a glycidyl ether group.

  The content of the repeating unit of the norbornene-type monomer having the substituent in the side chain in the addition copolymer is not particularly limited, but is preferably 5 to 80 mol% of the entire addition copolymer, particularly 20 to 70 mol% is preferable. When the content is within the above range, the balance between adhesion and heat resistance is particularly excellent.

  Now, the content of the substituent in the first cyclic olefin resin is preferably 1 to 80 mol%, particularly preferably 5 to 75 mol%, based on the entire first cyclic olefin resin. If the content is less than the lower limit, the effect of improving adhesion may be reduced, and if the content exceeds the upper limit, the effect of improving electrical characteristics may be reduced.

  Although the weight average molecular weight of the 1st cyclic olefin resin which has the said substituent in a side chain is not specifically limited, 10,000-500,000 are preferable and 50,000-300,000 are especially preferable. When the weight average molecular weight is within the above range, the crack resistance is particularly excellent. The weight average molecular weight can be measured by GPC using, for example, cyclohexane or toluene as an organic solvent.

  The molecular weight distribution of the first cyclic olefin-based resin having the above substituent in the side chain [ratio of weight average molecular weight: Mw and number average molecular weight: Mn (Mw / Mn)] is not particularly limited, but 2.0 -6.0 is preferable, and 3.0-5.0 is particularly preferable. When the molecular weight distribution is within the above range, the electrical characteristics are particularly excellent. As a method for measuring the molecular weight distribution, for example, it can be measured by GPC using cyclohexane or toluene as an organic solvent.

  Although content of the 1st cyclic olefin resin which has the said substituent in a side chain is not specifically limited, 1 to 50 weight% of the whole said resin composition is preferable, and 10 to 45 weight% is especially preferable. When the content is within the above range, the electrical characteristics are particularly excellent.

The resin composition includes a second cyclic olefin resin different from the first cyclic olefin resin. Thereby, the film formability of the resin layer can be improved.
As said 2nd cyclic olefin resin, the cyclic olefin resin which comprises the 1st cyclic olefin resin mentioned above can be used.
Examples thereof include (co) polymers of cyclic olefin monomers, copolymers of cyclic olefin monomers and other monomers capable of copolymerization such as α-olefins, and hydrogenated products of these copolymers. Examples of these known polymers include random copolymers, block copolymers, and alternating copolymers. These cyclic olefin-based resins can be produced by a known polymerization method, and examples of the polymerization method include an addition polymerization method and a ring-opening polymerization method. Of these, polymers obtained by polymerizing norbornene-type monomers (particularly addition (co) polymerization) are preferred, but the present invention is not limited thereto.

  As the method for polymerizing the second cyclic olefin-based resin and the constituent monomer, the same methods and monomers as those for the first cyclic olefin-based resin can be used.

Among these second cyclic olefin resins, addition (co) polymers of norbornene resins are preferable.
Hereinafter, the second norbornene resin will be described.
The second norbornene resin is not particularly limited, but preferably has a repeating unit represented by the following formula (V). Thereby, a linear expansion coefficient can be reduced.

  Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, etc. Specific examples of the alkenyl group include vinyl group, allyl group, butynyl group, cyclohexenyl group and the like. Specific examples of the alkynyl group include ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl. Group, 2-butynyl group and the like, specific examples of the cycloaliphatic group include cyclopentyl group, cyclohexyl group, cyclooctyl group and the like, and specific examples of the aryl group include phenyl group and naphthyl group. Anthracenyl group and the like, and specific examples of the aralkyl group include a benzyl group and a phenethyl group. Invention is in no way limited to these.

  The second norbornene-based resin is preferably an addition copolymer having a repeating unit represented by the following formula (VI). Thereby, adhesiveness can be improved.

  Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, etc. Specific examples of the alkenyl group include vinyl group, allyl group, butynyl group, cyclohexenyl group and the like. Specific examples of the alkynyl group include ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl. Group, 2-butynyl group and the like, specific examples of the cycloaliphatic group include cyclopentyl group, cyclohexyl group, cyclooctyl group and the like, and specific examples of the aryl group include phenyl group and naphthyl group. Anthracenyl group and the like, and specific examples of the aralkyl group include a benzyl group and a phenethyl group, Specific examples of the ryl group may have a substituent such as a silyl group, an alkyl group such as a methyl group and an ethyl group, an alkoxy group such as a trimethoxy group and a triethoxy group, and an aromatic group such as a phenyl group. Although a silyl group is mentioned, this invention is not limited to these at all.

  The content of the repeating unit represented by the following formula (V) in the addition copolymer is not particularly limited, but is preferably 50 to 95% by weight, particularly preferably 60 to 90% by weight, based on the whole addition copolymer. . When the content is within the above range, the dielectric properties are particularly excellent.

The weight average molecular weight of the second cyclic olefin resin is not particularly limited, but is preferably larger than the weight average molecular weight of the first cyclic olefin resin having a substituent in the side chain. Thereby, crack resistance can be improved.
Specifically, the weight average molecular weight of the second cyclic olefin-based resin is preferably 100,000 to 700,000, particularly 200,000 to 500,000. When the weight average molecular weight is within the above range, the crack resistance is particularly excellent. The weight average molecular weight can be measured by GPC using cyclohexane or toluene as an organic solvent.

  The molecular weight distribution of the second cyclic olefin-based resin [weight average molecular weight: Mw and number average molecular weight: ratio of Mn (Mw / Mn)] is not particularly limited, but is preferably 2.0 to 5.0, In particular, 2.0 to 3.0 is preferable. When the molecular weight distribution is within the above range, the electrical characteristics are particularly excellent. As a method for measuring the molecular weight distribution, for example, it can be measured by GPC using cyclohexane or toluene as an organic solvent.

  Although content of the said 2nd cyclic olefin resin is not specifically limited, 50 to 99 weight% of the whole said resin composition is preferable, and 30 to 80 weight% is especially preferable. When the content is within the above range, the film formability is particularly excellent.

The resin composition contains other additives such as an inorganic filler, a compatibilizer, a leveling agent, an antifoaming agent, a surfactant, an organic filler, and an antioxidant as long as they do not contradict the purpose of the present invention. Can do. These additives can be used alone or in admixture of two or more.
Examples of the inorganic filler include talc, calcined clay, unfired clay, silicates such as mica and glass, oxides such as titanium oxide, alumina, silica and fused silica, calcium carbonate, magnesium carbonate and hydrotalcite. Carbonates, hydroxides such as aluminum hydroxide, magnesium hydroxide and calcium hydroxide, sulfates or sulfites such as barium sulfate, calcium sulfate and calcium sulfite, zinc borate, barium metaborate, aluminum borate, boron Examples thereof include borates such as calcium oxide and sodium borate, and nitrides such as aluminum nitride, boron nitride and silicon nitride. Among these, silica is preferable. Thereby, especially the dielectric constant of the resin layer can be lowered. Examples of the silica include a silica filler synthesized by a sol-gel method, a silica filler synthesized by a gas phase method, a fused silica filler, and a crystalline silica filler. In particular, a silica filler synthesized by a gas phase method and a silica filler synthesized by a sol-gel method are preferable.

The average particle size of the inorganic filler is not particularly limited, but is preferably 800 nm or less, particularly preferably 600 nm or less, more preferably 100 nm or less, and most preferably 1 to 50 nm. If the average particle diameter exceeds the upper limit, it may be difficult to smoothly form a resin layer having a thickness of about several tens of μm. If the average particle diameter is less than the lower limit, the effect of setting a low linear expansion coefficient is reduced. There is a case.
The average particle diameter of the inorganic filler can be measured, for example, with a dynamic light scattering particle size distribution measuring apparatus.

  The content of the inorganic filler is not particularly limited, but is 5 to 200 parts by weight with respect to 100 parts by weight of the cyclic olefin resin (the total of the first cyclic olefin resin and the second cyclic olefin resin). Particularly preferred is 10 to 150 parts by weight, and most preferred is 15 to 60 parts by weight. If the content is less than the lower limit, the effect of reducing the thermal expansion coefficient may be reduced, and if the content exceeds the upper limit, the dielectric constant may increase or the film characteristics may be reduced.

The inorganic filler is not particularly limited, but is preferably surface-treated with a silane coupling agent. Thereby, the dispersibility of a filler can be improved.
Examples of the silane coupling agent include silane compounds having an alkoxysilyl group and an organic functional group such as an alkyl group, an epoxy group, a vinyl group, or a phenyl group in one molecule. Specifically, silanes having an alkyl group such as ethyltriethoxysilane, propyltriethoxysilane, and butyltriethoxysilane, silanes having a phenyl group such as phenyltriethoxysilane, benzyltriethoxysilane, and phenethyltriethoxysilane, Silanes having vinyl groups such as tenenyltriethoxysilane, propenyltriethoxysilane, vinyltrimethoxysilane, silanes having methacrylic groups such as γ- (methacryloxypropyl) trimethoxysilane, γ-aminopropyltriethoxysilane, N- Silanes having amino groups such as β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, γ-glycidoxypropyltri Examples include, but are not limited to, silanes having epoxy groups such as toxisilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and silanes having mercapto groups such as γ-mercaptopropyltrimethoxysilane. is not. These may be used alone or in combination.

  The addition amount of the silane coupling agent is not particularly limited, but is preferably 0.01 to 30 parts by weight, more preferably 0.05 to 10 parts by weight, and still more preferably 0. 0 to 100 parts by weight with respect to 100 parts by weight of the inorganic filler. 1 to 5.0 parts by weight is preferred.

Next, the resin layer and the carrier material with the resin layer will be described.
FIG. 1 is a cross-sectional view showing a carrier material 1 with a resin layer in which a resin layer 3 composed of the above-described resin composition is formed on one side of a carrier material 2.

  The resin layer 3 is comprised with the resin composition mentioned above. Thereby, it is possible to obtain a resin layer that is excellent in electrical characteristics such as a low dielectric constant and has little deterioration of electrical signals.

  Although the thickness of the resin layer 3 is not specifically limited, 0.1-60 micrometers is preferable and especially 1-40 micrometers is preferable. If the thickness of the resin layer 3 is less than the lower limit value, the effect of improving the insulation reliability may be reduced. If the thickness exceeds the upper limit value, it may be difficult to reduce the thickness of the circuit board.

  As a method for producing the resin layer 3, for example, a first cyclic olefin resin and a second cyclic olefin resin are mixed with an ultrasonic dispersion method, a high-pressure collision dispersion method, a high-speed rotation dispersion method, a bead mill method, a high-speed method. It can be obtained by a method of applying a resin varnish obtained by mixing using various mixers such as a shear dispersion method and a rotation and revolution dispersion method to a carrier material. Examples of the coating method include a roll coater, a bar coater, a knife coater, a gravure coater, a die coater, a curtain coater, a spraying method, a dipping method, a printing machine, a vacuum printing machine, and a dip dispenser. The method to use etc. are mentioned. Among these, a method using a die coater is preferable. Thereby, the resin layer 3 having a predetermined thickness can be stably produced. Moreover, after apply | coating the resin layer 3 to a dummy base material etc., it can also obtain in the state of a dry film.

  The solvent only needs to be able to dissolve the cyclic olefin-based resin. For example, an aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent, a ketone solvent, an ether solvent, an ethyl acetate or an ester solvent, Examples include lactone solvents and amide solvents, and among them, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, ketone solvents, and ether solvents are preferable. Examples of the hydrocarbon solvent include pentane, hexane, heptane, and cyclohexane. Examples of the aromatic solvent include benzene, toluene, xylene, and mesitylene. Examples of the ketone solvent include methyl ethyl ketone and the like. Examples of the ether solvent include diethyl ether and tetrahydrofuran. These solvents can be used alone or in combination. Of these, 1,3,5-trimethylbenzene is particularly preferable.

  Examples of the carrier material 2 include metal foils made of copper or copper alloys, aluminum or aluminum alloys, polyethylene, fluorine resins, (aromatic) polyimide resins, polybutylene terephthalate, polyester resins such as polyethylene terephthalate, etc. The resin film comprised by these is mentioned. Among these, a resin film composed of a polyester resin is most preferable. Thereby, it becomes easy to peel the carrier material 2 from the resin layer 3 with an appropriate strength. Furthermore, it has excellent stability against reactive diluents. Therefore, migration of the resin composition component dissolved in the reactive diluent and the solvent to the carrier material 2 can also be prevented.

  Although the thickness of the carrier material 2 is not specifically limited, 10-200 micrometers is preferable and 20-100 micrometers is especially preferable. When the thickness is within the above range, the flatness of the resin layer 3 is particularly excellent on the circuit.

  As a method for producing the carrier material 1 with a resin layer, for example, a solution obtained by dissolving the above resin composition in a solvent is applied to the carrier material 2 with a thickness of about 1 to 100 μm, and the applied layer is, for example, 80 to 200 ° C. And a method of drying for 20 seconds to 30 minutes. Thus, the carrier material 1 with a resin layer in which the resin layer 3 is laminated on the carrier material 2 can be obtained. At this time, the residual solvent amount is preferably 0.5% by weight or less. The heat curing temperature of the resin composition is not particularly limited, but is preferably 150 to 300 ° C, particularly preferably 170 to 250 ° C.

Next, the circuit board will be described.
FIG. 2 is a cross-sectional view showing an example of the circuit board of the present invention.
As shown in FIG. 2, the circuit board 10 includes a core substrate 5 and a resin layer 3 provided on both surfaces of the core substrate 5.
The core substrate 5 is formed with an opening 51 opened by a drilling machine. Conductor circuits 52 are formed on both surfaces of the core substrate 5.
The inside of the opening 51 is plated, and the conductor circuits 52 on both surfaces of the core substrate 5 are electrically connected.

The resin layer 3 is provided on both surfaces of the core substrate 5 so as to cover the conductor circuit 52. An opening 31 formed by laser processing is formed in the resin layer 3.
Conductor circuits 32 are formed on both surfaces of the resin layer 3.
The inside of the opening 31 is plated, and the conductor circuit 52 and the conductor circuit 32 are electrically connected.

  As a method of manufacturing such a circuit board 10, for example, a core substrate (for example, FR-4 double-sided copper foil) 5 is opened with a drill machine to provide an opening 51, and then the opening is formed by electroless plating. The inside of 51 is subjected to a plating process so as to make both surfaces of the core substrate 5 conductive. Then, the conductor circuit 52 is formed by etching the copper foil.

  The material of the conductor circuit 52 may be any material as long as it is suitable for this manufacturing method, but is preferably removable by a method such as etching or peeling in the formation of the conductor circuit. Those having resistance to the chemicals used for this are preferred. Examples of the material of the conductor circuit 52 include copper, copper alloy, 42 alloy, nickel, and the like. In particular, the copper foil, the copper plate, and the copper alloy plate are most preferable for use as the conductor circuit 52 because not only electrolytic plated products and rolled products can be selected, but also various thicknesses can be easily obtained.

Next, the resin layer 3 is formed on the conductor circuit 52. As a method of forming the resin layer 3, the above-described method of pressing the carrier material 1 with a resin layer, and laminating the carrier material 1 with a resin layer using a vacuum press, an atmospheric laminator, a vacuum laminator, a Becquerel type laminating apparatus, or the like. And a method of forming the resin layer 3.
Moreover, when a metal layer is used as the carrier material 2, the metal layer can be processed as a conductor circuit.

After the carrier material 2 is peeled off, the formed resin layer 3 is heated and cured. The temperature for heating and curing is not particularly limited, but is preferably 150 to 300 ° C, particularly preferably 160 to 250 ° C.
Further, one or more resin layers 3 are formed on the resin layer 3 obtained by heating and semi-curing the first resin layer 3, and the semi-cured resin layer 3 is heat-cured again to such an extent that there is no practical problem. Thereby, the adhesiveness between the resin layers 3 and between the resin layer 3 and the conductor circuit 52 can be improved. The semi-curing temperature in this case is not particularly limited, but is preferably 100 to 250 ° C, and more preferably 150 to 200 ° C.
Further, after the resin layer 3 is formed, the surface of the resin layer 3 is subjected to plasma treatment, whereby the adhesion between the resin layers 3 and between the resin layer 3 and the conductor circuit 52 can be improved. As the plasma treatment gas, for example, oxygen, argon, fluorine, carbon fluoride, nitrogen, or the like can be used singly or in combination. The plasma treatment may be performed a plurality of times.

Next, the resin layer 3 is irradiated with a laser to form the opening 31. Examples of the laser that can be used include an excimer laser, a UV laser, and a carbon dioxide gas laser. Formation of the opening 31 by the laser can easily form the fine opening 31 regardless of whether the material of the resin layer 3 is photosensitive or non-photosensitive. Therefore, it is particularly preferable when the resin layer 3 needs to be finely processed. Then, the opening 31 is plated by electroless plating.
Next, the conductor circuit 32 is formed. The conductor circuit 32 can be formed by a known method such as a semi-additive method. A circuit board can be obtained by these methods.

EXAMPLES Hereinafter, although this invention is demonstrated based on an Example and a comparative example, this invention is not limited to this.
Example 1
1. Synthesis of a first cyclic olefin-based resin mainly composed of silicon and oxygen and having a substituent having a cyclic structure in at least a part of the side chain. Reaction in which the atmosphere of the polymerization system is sufficiently filled with an inert gas nitrogen In a container, 51.4 g (0.075 mol) of Norbornenylylethyl-POSS (manufactured by Hybrid Plastics LLC), 0.095 g (0.025 mol) of 5-butyl-2-norbornene, and then a transition metal catalyst (η ⁶ -toluene) After 0.12 g (1.00 × 10 ⁻³ mol) of nickel bis (perfluorophenyl) and 76.0 g of toluene were encapsulated, the mixture was reacted at 80 ° C. for 3 hours while stirring with a magnetic stirrer. Reprecipitated in 1.50 kg of methanol, mainly composed of silicon and oxygen, and a small amount 26.0 g of 1st cyclic olefin resin (A) which has the substituent which has a cyclic structure in part at least in a side chain was obtained.
It was confirmed by gel permeation chromatography (GPC) measurement that the obtained first cyclic olefin-based resin had a polystyrene equivalent weight average molecular weight of 1.05 × 10 ⁵ ). Further, it was confirmed by nuclear magnetic resonance (NMR) measurement that the composition of Norbornenylylethyl-POSS / 5-butyl-2-norbornene was 24/76 (mol%).

2. Preparation of Resin Varnish 3.00 g (30% by weight) of the first cyclic olefin resin (A) obtained above was used as a second cyclic olefin resin, 90 mol% butyl norbornene and 10 mol% triethoxysilane norbornene. To the copolymer solution (Abaterol EPM manufactured by PROMERUS LLC, solid content 22.3% by weight, weight average molecular weight 3.05 × 10 ⁵ ) 31.82 g (70% by weight) And mixed to obtain a resin varnish.

3. Production of Carrier Material with Resin Layer The resin varnish obtained above is formed with a die coater on a polyester film (T-100G-25, manufactured by Diafoil Text Co., Ltd., thickness 25 μm) as a carrier material with a thickness of 20 μm. Thus, a carrier material with a resin layer was obtained.

4). 4.1 Production of Circuit Board 4.1 Formation of Inner Layer Circuit and Resin Layer Open a double-sided copper-clad laminate (ELC-4781 manufactured by Sumitomo Bakelite Co., Ltd.) with a total thickness of 0.3 mm and a copper foil thickness of 12 μm using a drilling machine. After hole formation, conduction between the upper and lower copper foils was achieved by electroless plating in the opening. And the inner layer conductor circuit was formed in both surfaces by etching the said copper foil of both surfaces.
Next, the inner layer conductor circuit is sprayed with a chemical solution mainly composed of hydrogen peroxide and sulfuric acid (Tech SO-G manufactured by Asahi Denka Kogyo Co., Ltd.) to form irregularities by roughening treatment. The obtained carrier material with a resin layer was filled with wiring using a vacuum laminator and baked at 200 ° C. for 60 minutes to form a resin layer.

4.2 Laser processing and formation of outer layer circuit Next, a UV-YAG laser device (ML605LDX manufactured by Mitsubishi Electric Corporation) was used to form a φ40 μm opening (blind via hole), and desmear treatment (Nippon McDermid ( Then, electroless copper plating (Ulmura Koru Sulcup PRX) was performed for 15 minutes to form a 0.5 μm thick power supply layer. Next, an ultraviolet photosensitive dry film (AQ-2558 manufactured by Asahi Kasei Co., Ltd.) having a thickness of 25 μm is pasted on the surface of the power supply layer by a hot roll laminator, and a pattern having a minimum line width / line spacing of 20/20 μm is drawn. Using the chrome vapor deposition mask (made by Towa Process Co., Ltd.), alignment and exposure were performed using an exposure apparatus (UX-1100SM-AJN01 made by Ushio Electric Co., Ltd.). Development was performed with a sodium carbonate aqueous solution to form a plating resist.

Next, electrolytic copper plating (Okuno Pharmaceutical Co., Ltd. 81-HL) was performed at 3 A / dm ² for 30 minutes using the power feeding layer as an electrode to form a copper wiring having a thickness of about 20 μm. Here, the plating resist was peeled off using a two-stage peeling machine. Each chemical solution consists of a monoethanolamine solution (R-100 manufactured by Mitsubishi Gas Chemical Co., Inc.) for the first-stage alkaline aqueous solution layer, and potassium permanganate and sodium hydroxide for the second-stage oxidizing resin etchant. An aqueous solution (Mc. Dither 9275, 9276 manufactured by Nippon McDermid Co., Ltd.) as the main component and an acidic amine aqueous solution (Mc. Dicer 9279 manufactured by Nippon McDermid Co., Ltd.) were used for neutralization.

  Next, the power feeding layer was immersed in an aqueous ammonium persulfate solution (AD-485 manufactured by Meltex Co., Ltd.) to remove it by etching and ensure insulation between the wirings. Finally, a dry film type solder resist (CFP-1121 manufactured by Sumitomo Bakelite Co., Ltd.) was formed on the circuit surface while embedding the circuit with a vacuum laminator, and finally a circuit board having the structure shown in FIG. 2 was obtained. .

(Example 2)
The same procedure as in Example 1 was performed except that the mixing ratio of the first cyclic olefin resin (A) and the second cyclic olefin resin was as follows.
3.0 g (24 wt%) of the first cyclic olefin resin and 41.9 g (76 wt%) of the second cyclic olefin resin (Abaterol EPM solution: solid content 22.3% wt) were used.

(Example 3)
The same procedure as in Example 1 was performed except that the mixing ratio of the first cyclic olefin resin (A) and the second cyclic olefin resin was as follows.
3.0 g (50 wt%) of the first cyclic olefin resin and 13.5 g (50 wt%) of the second cyclic olefin resin (Abaterol EPM solution: solid content 22.3% wt) were used.

Example 4
The same procedure as in Example 1 was performed except that the mixing ratio of the first cyclic olefin resin (A) and the second cyclic olefin resin was as follows.
3.0 g (5 wt%) of the first cyclic olefin resin and 255.6 g (95 wt%) of the second cyclic olefin resin (Abaterol EPM solution: solid content 22.3% wt) were used.

(Example 5)
As 1st cyclic olefin resin, it carried out similarly to Example 1 except having used the following.
When synthesizing the first cyclic olefin-based resin, 28.3 g of the first cyclic olefin-based resin (B) was obtained by using 79.0 g of Norbornenylylcyclopropyl-POSS instead of 51.4 g of Norbornenylylethyl-POSS.
The obtained first cyclic olefin-based resin (B) was confirmed to have a polystyrene-reduced weight average molecular weight of 4.80 × 10 ⁵ by gel permeation chromatography (GPC) measurement. Moreover, it was confirmed from nuclear magnetic resonance (NMR) measurement that the composition of Norbornenylylcyclopropyl-POSS / 5-butyl-2-norbornene was 24/76 (mol%).

(Example 6)
Except that the reaction time was 30 minutes when the first cyclic olefin resin was synthesized, and the weight average molecular weight of the first cyclic olefin resin was changed to obtain the first cyclic olefin resin (C). Same as Example 1.
The weight average molecular weight of the first cyclic olefin-based resin (C) was 4.50 × 10 ⁴ (polystyrene conversion from GPC measurement).
Further, it was confirmed by NMR measurement that the composition of Norbornenylylcyclopentyl-POSS / 5-butyl-2-norbornene was 26/74 (mol%).

(Example 7)
As 2nd cyclic olefin resin, it carried out similarly to Example 1 except having obtained the resin varnish using the following.
The second cyclic olefin resin (D) obtained by the method described in US Pat. No. 5,468,819 as the second cyclic olefin resin (99 mol% 2-norbornene and decyl-2-norbornene 1 (Mol%, polystyrene equivalent weight average molecular weight 3.31 × 10 ⁵ ) 7.00 g was dissolved in 40.0 g of a toluene solution.

(Example 8)
As 2nd cyclic olefin resin, it carried out similarly to Example 1 except having obtained the resin varnish using the following.
The second cyclic olefin resin (E) obtained by the method described in US Pat. No. 5,468,819 as the second cyclic olefin resin (76 mol% of 2-norbornene and decyl-2-norbornene 24) (Mol%, polystyrene-reduced weight average molecular weight 1.67 × 10 ⁵ ) 7.00 g was dissolved in 40.0 g of a toluene solution.

(Comparative Example 1)
Example 1 was repeated except that only the second cyclic olefin resin was used without using the first cyclic olefin resin.

(Comparative Example 2)
The same procedure as in Example 1 was performed except that only the first cyclic olefin resin was used without using the second cyclic olefin resin.
The obtained resin varnish was applied and dried on a 25 μm-thick PET substrate (T-100G-25, manufactured by Diafoil Text Co., Ltd.) in the same manner as in Example 1, but the film was cracked to obtain a film. I couldn't.

The circuit board obtained in each example and comparative example was evaluated as follows. The evaluation items are shown together with the contents. The obtained results are shown in Table 1.
1. Measurement of dielectric constant and dielectric loss tangent From the carrier material with a resin layer, the resin layer was peeled off and dried in nitrogen at 220 ° C. for 1 hour. The obtained 20 μm-thick film was cut into 2 mm × 80 mm, and the dielectric constant and dielectric loss tangent were measured by a perturbation method using a cylindrical cavity resonator (Agilent Technology Microwave Network Analyzer HP8510B) (measurement) The frequency was 10 GHz).

2. Degradation of electrical signal For degradation of electrical signal, transmission loss was measured using a triplate stripline resonator method. (The measurement frequency was 10 GHz.)

3. Heat resistance Heat resistance was evaluated with a differential thermothermal gravimetric simultaneous measurement apparatus (temperature with a weight loss rate of 5%).

4). Crack resistance The crack resistance was evaluated by conducting a temperature cycle test of -55 ° C to 125 ° C 1,000 times, observing the surface and cross-section of the circuit board, and visually evaluating the presence or absence of cracks in the resin layer. Each code is as follows.
◎: More than 500 times in the temperature cycle test and no cracks in the resin layer up to 1,000 times ○: More than 200 times in the temperature cycle test and no cracks in the resin layer up to 500 times △: 50 in the temperature cycle test There are no cracks in the resin layer up to 200 times. ×: Cracks occur in the resin layer up to 50 times in the temperature cycle test.

5). Adhesiveness Adhesiveness was evaluated by a cross cut test (JIS K5400-1900).
A: Each cut is thin and smooth on both sides, and there is no peeling between the intersection and the square at a glance.
○: There is a slight peeling at the intersection of the cuts, there is no peeling at a glance, and the area of the defect is within 5% of the total square area.
Δ: There are peeling at both sides of the cut and at the intersection, and the area of the defect is 5% or more ×: the area of the peeling is 65% or more

As is clear from Table 1, Examples 1 to 8 had a low dielectric constant and dielectric loss tangent, and there was little deterioration of electrical signals.
Moreover, Examples 1-8 were excellent also in heat resistance.
Examples 1 to 5, 7 and 8 were particularly excellent in crack resistance.
Moreover, Examples 1-3, 5 and 6 were particularly excellent in adhesion.

The resin layer obtained using the resin composition of the present invention is suitable for applications such as circuit boards, printed wiring boards, multilayer wiring boards, semiconductor devices, and liquid crystal display devices. Since the resin composition of the present invention has excellent dielectric properties in the GHz band and excellent heat resistance, it has mounting reliability and interlayer connection reliability, and also has excellent laser processability. It is.
When the resin composition of the present invention is used as an interlayer insulating film of a circuit board, a method such as pressing a carrier film with a resin layer applied onto a circuit board or a carrier film can be considered. Therefore, it is preferable to form a resin layer on the carrier film and embed the carrier film with the resin layer by pressing.

It is sectional drawing which shows an example of the carrier material with a resin layer of this invention. It is sectional drawing which shows an example of the circuit board of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Carrier material with resin layer 2 Carrier material 3 Resin layer 31 Opening part 32 Conductor circuit 5 Core substrate 51 Opening part 52 Conductor circuit 10 Circuit board

Claims (9)

A resin composition constituting a resin layer of a circuit board,
Heteroleptic POSS [(RSiO _1.5 ) ₇ (XSiO _1.0 ) ₁ ] _Σ8 , functionalized heteroleptic POSS [(RSiO _{1.5 ) 4 (RXSiO 1.5) 3]} Σ7 and functionalized heteroleptic _{POSS [(RSiO 1.5) 4 (} RXSiO 1.0) 2 (RX'SiO 1.0) 1] in the side chain as a substituent of any one of _Shiguma7 A first cyclic olefin-based resin which is an addition copolymer of a norbornene-type polymer repeating unit and a norbornene-type monomer represented by the following formula (II):
A second cyclic olefin-based resin that is a polymer having a repeating unit represented by the following formula (V), different from the first cyclic olefin-based resin,
The content of the first cyclic olefin resin is 1 to 50% by weight of the whole resin composition, and the content of the second cyclic olefin resin is 50 to 50% of the whole resin composition. 99% by weight of a resin composition.

The resin composition according to claim 1, wherein the substituent is heteroleptic POSS [(RSiO _1.5 ) ₇ (XSiO _1.0 ) ₁ ] _Σ8 represented by the following formula (I).

  The resin composition according to claim 1 or 2, wherein the content of the repeating unit of the norbornene-type monomer having a substituent is 5 to 80 mol% of the addition copolymer.   4. The resin composition according to claim 1, wherein a weight average molecular weight of the second cyclic olefin-based resin is larger than a weight average molecular weight of the first cyclic olefin-based resin.   The resin composition according to any one of claims 1 to 4, wherein the first cyclic olefin-based resin has a weight average molecular weight of 10,000 to 500,000.   The resin composition according to any one of claims 1 to 5, wherein the second cyclic olefin-based resin has a weight average molecular weight of 100,000 to 700,000.   A resin layer comprising the resin composition according to claim 1.   A carrier material with a resin layer, wherein the resin layer according to claim 7 is formed on at least one surface of the carrier material.   A circuit board comprising the resin layer according to claim 7.

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