JP2007103683A - Resin composition, laminated body, wiring board, and manufacturing method therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition excellent in electrical properties and adhesiveness when a resin layer of a wiring board is formed, a laminated body excellent in machinability, the wiring board excellent in electrical properties, and a wiring board manufacturing method. <P>SOLUTION: The resin composition is that constituting an insulating layer of the wiring board. A norbornene-based resin and spherical silica having an average particle size of ≤2 μm are used as essential components. Its thermal expansion rate at -50 to 150°C is ≤60 ppm. The resin composition has the spherical silica of ≥50 wt.%, and is subjected to surface treatment beforehand. The laminated body is a laminated body used for the wiring board and composed by laminating a carrier film and a resin layer made of the resin composition. The wiring board manufacturing method includes a step for forming the insulating layer by using the resin composition, a step for forming a circuit layer, and a step for boring holes by irradiating the insulating layer with a laser beam. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a resin composition, a laminate, a wiring board, and a method for producing a wiring board.

    In recent use of electronic devices, high-speed transmission is performed for information transmission, and deterioration of electrical signals is a problem in high-speed transmission. The deterioration of the electric signal is represented by the sum of conductor loss and dielectric loss. In particular, the dielectric loss due to the dielectric characteristics of the interlayer insulating material of the multilayer wiring board increases remarkably in the high frequency region necessary for high-speed transmission. For this reason, the dielectric characteristics are the main cause of electrical signal degradation at frequencies in the GHz band. In order to solve this problem, it is required to use a material having low dielectric constant and low dielectric loss tangent as the insulating material.

  Against this background, epoxy resins and polyimide resins that have been used as insulating materials for electronic parts such as wiring boards may have insufficient electrical characteristics such as dielectric constant and dielectric loss tangent, and are compatible with high-speed transmission. Is difficult.

  On the other hand, addition-type norbornene resin, which is a cyclic olefin resin, is a high heat resistant resin having a high glass transition temperature, and has a dielectric constant of 2.2 to 2.8 and a dielectric loss tangent in a frequency range of GHz band. Since it is 0.001 to 0.006 and shows excellent electrical characteristics, it is expected as an insulating resin for wiring boards for high frequencies.

However, addition-type norbornene-based resins have low mechanical strength and a high coefficient of thermal expansion, so when used for electronic parts, fillers and other fillers are added to increase the mechanical strength or decrease the coefficient of thermal expansion. The technique of letting you do is shown. (For example, refer to Patent Document 1) Further, since the addition type norbornene resin has very low polarity, it is very difficult to uniformly disperse the filler in the resin. For this reason, an example (for example, see Patent Document 2) in which the filler is highly filled or an insulating resin for a wiring board using a filler having a low dispersibility with an average particle diameter of 2 μm or less is shown. Such high filling and dispersibility of the filler were not satisfactory. In addition, since the adhesion of the addition type norbornene resin to various adherends is low, mounting reliability and connection reliability are also problems. In order to improve the adhesion of such a cyclic olefin-based resin, there is a method of applying a primer treatment to the surface of the adherend (see, for example, Patent Document 3). It was difficult and insufficient.
JP 11-43566 A JP-A-11-502083 Japanese Patent Laid-Open No. 2003-73631

The objective of this invention is providing the resin composition which is excellent in adhesiveness, a low thermal expansion coefficient, and an electrical property, when the resin layer of the said wiring board is formed.
Moreover, the objective of this invention is providing the laminated body which is excellent in workability.
Moreover, the objective of this invention is providing the wiring board excellent in the electrical property, and its manufacturing method.

Such an object is achieved by the present invention described in the following [1] to [18].
[1] A resin composition constituting an insulating layer of a wiring board,
(A) Addition-type norbornene represented by the following formula (1) having at least one crosslinkable group selected from the group consisting of a cyclic ether group, an organic group having a reactive double bond, and an alkoxysilyl group A norbornene-based resin composition, characterized in that an essential resin is (B) spherical silica having an average particle size of 2 μm or less, and the coefficient of thermal expansion at −50 to 150 ° C. is 60 ppm or less.

［式（１）中のＸは、−ＣＨ₂−、−ＣＨ₂ＣＨ₂−、または−Ｏ−を示し、Ｒ₁、Ｒ2、Ｒ3、Ｒ₄はそれぞれ独立して水素原子、炭化水素基、炭素数１〜１２の極性基を示し、または該極性基を含む基を示す。Ｒ₁、Ｒ₂、Ｒ₃およびＲ₄は、少なくとも１つが炭素数１〜１２の環状エーテル基、反応性二重結合を有する有機基、又はアルコキシシリル基を含む基である。ｎは０から２の整数を示し、その繰り返しは異なっていても良い。］

[Equation (1) X in _{the, -CH 2 -, - CH 2} CH 2 -, or -O- and _{shown, R 1, R2, R3,} R 4 are each independently a hydrogen atom, a hydrocarbon group, A polar group having 1 to 12 carbon atoms is shown, or a group containing the polar group. R ₁ , R ₂ , R ₃ and R ₄ are groups each including at least one of a cyclic ether group having 1 to 12 carbon atoms, an organic group having a reactive double bond, or an alkoxysilyl group. n represents an integer of 0 to 2, and the repetition may be different. ]

[2] The resin composition according to item [1], wherein the addition-type norbornene-based resin includes an addition polymer of a norbornene-based monomer represented by the following general formula (2).

［式（２）中のＸは、−ＣＨ₂−、−ＣＨ₂ＣＨ₂−、または−Ｏ−を示し、Ｒ₁、Ｒ₂、Ｒ₃およびＲ₄は、それぞれ独立して、水素原子、炭化水素基、炭素数１〜１２の極性基または該極性基を含む基を示す。Ｒ₁、Ｒ₂、Ｒ₃およびＲ₄は、少なくとも１つが炭素数１〜１２の環状エーテル基、反応性二重結合を有する有機基、又はアルコキシシリル基を含む基である。ｎは０から２の整数を示す。］

Expression (2) X in _{the, -CH 2 -, - CH 2} CH 2 -, or -O- and _{shown, R 1, R 2, R} 3 and R ₄ are each independently a hydrogen atom, A hydrocarbon group, a polar group having 1 to 12 carbon atoms or a group containing the polar group is shown. R ₁ , R ₂ , R ₃ and R ₄ are groups each including at least one of a cyclic ether group having 1 to 12 carbon atoms, an organic group having a reactive double bond, or an alkoxysilyl group. n represents an integer of 0 to 2. ]

[3] The norbornene-based resin composition according to the item [1] or [2], wherein the spherical silica is 50% by weight or more.
[4] The norbornene-based resin composition according to any one of [1] to [3], wherein the spherical silica is surface-treated in advance.
[5] The surface treatment agent for pre-treating the spherical silica has at least two functional group-containing silanes, cyclic oligosiloxanes, organohalosilanes, organoalkoxysilanes, alkylsilazanes, and repeating units of siloxane bonds. The norbornene-based resin composition according to any one of [1] to [4], which is at least one compound selected from the group consisting of silicone oils having an alkoxy group.
[6] The group in which the functional group-containing silane is composed of epoxy silane, (meth) acryl silane, mercapto silane, amino silane, vinyl silane, isocyanate silane, ureido silane, (5-norbornene-2-yl) alkyl silane, and phenyl silane. The norbornene-based resin composition according to item [5], which is selected from:
[7] The norbornene-based resin composition according to the item [5], wherein the organohalosilane is selected from the group consisting of trimethylchlorosilane, dimethyldichlorosilane, and methyltrichlorosilane.
[8] The alkylsilazane is selected from the group consisting of hexamethyldisilazane, 1,3-divinyl-1,1,3,3, -tetramethyldisilazane, octamethyltrisilazane, and hexamethylcyclotrisilazane. The norbornene-based resin composition according to item [5].
[9] The norbornene-based resin composition according to any one of [1] to [8], wherein the cyclic ether group is oxirane or oxetane.
[10] The organic group having a reactive double bond is selected from the group consisting of a vinyl group, an allyl group, an acryloyl group, and a methacryloyl group. The norbornene group according to any one of items [1] to [9] Resin composition.
[11] A laminate used for a wiring board, wherein a resin layer composed of the resin composition according to any one of [1] to [10] and a carrier film are laminated. Laminated body.
[12] A step of forming an insulating layer using the resin composition according to any one of [1] to [10], a step of forming a circuit layer, and a step of opening the insulating layer by laser irradiation A method of manufacturing a wiring board including:
[13] The method for manufacturing a wiring board according to item [12], wherein the step of forming the insulating layer is performed by applying the resin composition.
[14] The method for manufacturing a wiring board according to [12] or [13], wherein the step of forming the insulating layer is formed by laminating a film obtained using the resin composition.
[15] The method for manufacturing a wiring board according to item [14], wherein the film in the step of forming the insulating layer is a film with a metal layer.
[16] The method for manufacturing a wiring board according to any one of [12] to [15], including a step of heat-curing the insulating layer.
[17] A wiring board obtained by the method for manufacturing a wiring board according to any one of [12] to [16].
[18] A wiring board comprising a resin layer formed using the laminate according to the item [11].

ADVANTAGE OF THE INVENTION According to this invention, when the resin layer of a wiring board is formed, the resin composition which is excellent in adhesiveness, a low linear expansion coefficient, and an electrical property can be provided.
Moreover, according to this invention, the laminated body excellent in workability can be provided.
Moreover, according to this invention, the wiring board excellent in the electrical property and its manufacturing method can be provided.

Hereinafter, the resin composition, laminate and wiring board of the present invention will be described.
The resin composition of the present invention is a resin composition constituting an insulating layer of a wiring board, and is at least one selected from the group consisting of a cyclic ether group, an organic group having a reactive double bond, and an alkoxyl group. An addition-type norbornene-based resin having various types of crosslinkable groups and spherical silica having an average particle diameter of 2 μm or less are essential components, and a thermal expansion coefficient at −50 to 150 ° C. is 60 ppm or less.
The laminate of the present invention is characterized in that the resin composition described above is formed on at least one surface of a carrier film (carrier material).
Moreover, the wiring board of this invention comprises an insulating layer with the resin composition as described above.

Hereinafter, the resin composition will be described.
The resin composition of the present invention constitutes an insulating layer of a wiring board. This is to provide an insulating layer with excellent electrical characteristics for a wiring board that requires high-speed transmission of electrical signals.
The resin composition is represented by the following formula (1) having at least one crosslinkable group selected from the group consisting of a cyclic ether group, an organic group having a reactive double bond, and an alkoxysilyl group. Includes addition-type norbornene resin. Thereby, when an insulating layer is formed, heat resistance and electrical characteristics are excellent.
The resin composition contains spherical silica having an average particle size of 2 μm or less. Thereby, since the resin layer whose thermal expansion coefficient of -50-150 degreeC is 60 ppm or less is obtained, the generated stress by the thermal expansion coefficient difference between conductor wiring can be reduced. In addition, it has heat resistance that can withstand a lead-free reflow process. Furthermore, it is possible to reduce the thickness of the insulating layer to accommodate fine pitch wiring. Therefore, the mounting reliability and the connection reliability are excellent in a high-density and thin circuit board.

［式（１）中のＸは、−ＣＨ₂−、−ＣＨ₂ＣＨ₂−、または−Ｏ−を示し、Ｒ₁、Ｒ2、Ｒ3、Ｒ₄はそれぞれ独立して水素原子、炭化水素基、炭素数１〜１２の極性基を示し、または該極性基を含む基を示す。Ｒ₁、Ｒ₂、Ｒ₃およびＲ₄は、少なくとも１つが炭素数１〜１２の環状エーテル基、反応性二重結合を有する有機基、又はアルコキシシリル基を含む基である。ｎは０から２の整数を示し、その繰り返しは異なっていても良い。］

[Equation (1) X in _{the, -CH 2 -, - CH 2} CH 2 -, or -O- and _{shown, R 1, R2, R3,} R 4 are each independently a hydrogen atom, a hydrocarbon group, A polar group having 1 to 12 carbon atoms is shown, or a group containing the polar group. R ₁ , R ₂ , R ₃ and R ₄ are groups each including at least one of a cyclic ether group having 1 to 12 carbon atoms, an organic group having a reactive double bond, or an alkoxysilyl group. n represents an integer of 0 to 2, and the repetition may be different. ]

Examples of the polar group include a hydroxyl group, a carboxyl group, an ester group, an acryloyl group, a methacryloyl group, an aryl group, an aralkyl group, a silyl group, an epoxy group, and an organic group containing these polar groups. As the organic group containing the polar group, the polar group is bonded by a linear or branched alkyl group, alkenyl group, alkynyl group, vinyl group, allyl group, aralkyl group, cyclic aliphatic group, aryl group, or ether group. It may be what was done.
Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group and a dodecyl group. Examples include vinyl group, allyl group, butynyl group, and cyclohexenyl group. Specific examples of alkynyl group include ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, and 2-butynyl group. However, as specific examples of the cycloaliphatic group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, etc., as specific examples of the aryl group, a phenyl group, a naphthyl group, an anthracenyl group, etc., and as a specific example of the aralkyl group, benzyl Group, phenethyl group, etc., as specific examples of silyl group, trimethoxysilyl group, trieth Specific examples of epoxy groups include alkoxysilyl groups such as sisilyl groups and triethoxysilylethyl groups, silyl groups, trimethoxypropylsilyl groups, trimethylsilylmethyl ether groups, diphenylmethylsilyl groups, and the like. Examples thereof include glycidyl-ether groups, but the present invention is not limited thereto.

  The amount of the polar group introduced is not particularly limited, but is preferably 3 to 70 mol%, particularly preferably 5 to 40 mol% of the whole norbornene-based resin. When the introduction amount is within the above range, the adhesion and electrical characteristics are particularly excellent. Further, the norbornene-based resin having a polar group in such a side chain can be obtained by, for example, 1) introducing a compound having the polar group into the norbornene-based resin by a modification reaction, and 2) a monomer having the polar group. 3) by copolymerizing the monomer having the polar group as a copolymer component with other components, or 4) copolymerizing the monomer having the polar group such as an ester group. After copolymerization as a component, it can be obtained by hydrolyzing the ester group.

The addition-type norbornene-based resin is obtained by coordination polymerization using a metal catalyst or radical polymerization. Among them, in coordination polymerization, a polymer is obtained by polymerizing monomers 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. 1). 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 ° C. 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, and t-butyl hydrogen peroxide.

  Suitable polymerization solvents for the above-described polymerization system include hydrocarbon solvents and aromatic solvents. Examples of the hydrocarbon solvent include, but are not limited to, pentane, hexane, heptane, and cyclohexane. Examples of the aromatic solvent include, but are not limited to, benzene, toluene, xylene and mesitylene. Diethyl ether, tetrahydrofuran, ethyl acetate, ester, lactone, ketone, amide can also be used. Even if these solvents are used alone or in combination, they can be used as polymerization solvents.

  The molecular weight of the addition-type norbornene resin can be controlled by changing the ratio of the initiator and the monomer or changing the polymerization time. When the above coordination polymerization is used, US Pat. As disclosed in US Pat. No. 6,136,499, the molecular weight can be controlled by using 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.

In the present invention, the weight average molecular weight of the addition-type norbornene-based resin is preferably 10,000 to 500,000, more preferably 30,000 to 300,000, and still more preferably 50,000 to 200,000. The weight average molecular weight can be measured, for example, by gel permeation chromatography (GPC) using standard polystyrene with cyclohexane or tetrahydrofuran as an organic solvent. (Conforms to ASTM D3536-91)
The molecular weight distribution of the addition-type norbornene-based resin [ratio of weight average molecular weight: Mw and number average molecular weight: Mn (Mw / Mn)] is not particularly limited, but is preferably 5 or less, particularly preferably 4 or less, particularly 1-3 are preferable. When the molecular weight distribution is within the above range, the mechanical strength is particularly excellent.
In addition, in the case of an addition-type norbornene-based resin whose weight average molecular weight and molecular weight distribution cannot be measured by the above method, use one having a melt viscosity and a degree of polymerization that can form a resin layer by an ordinary melt processing method. Can do. The glass transition temperature of the addition-type norbornene resin can be appropriately controlled according to the purpose of use, but is preferably 150 ° C. or higher, more preferably 200 ° C. or higher, and further preferably 250 ° C. or higher.

  Such an addition-type norbornene-based resin has a high glass transition temperature and excellent heat resistance compared to a ring-opening-type norbornene-based resin and a copolymer with another copolymerizable α-olefin, and therefore uses lead-free solder. It is particularly preferable for environment-friendly wiring board applications.

  In the present invention, the addition type norbornene resin has at least one kind of crosslinkable group selected from the group consisting of a cyclic ether group, an organic group having a reactive double bond, and an alkoxysilyl group. When the insulating layer of the resin composition is formed, it is possible to improve the adhesion and heat resistance with the conductor circuit and the insulating layer.

  The cyclic ether group refers to a cyclic hydrocarbon group having a 3- to 8-membered ether bond, and examples thereof include a 3-membered oxirane and a 4-membered oxetane. These cyclic ethers can be easily opened by an acid or base and crosslinked with other cyclic ethers. By cross-linking, it is particularly excellent in heat resistance and mechanical strength. Moreover, the hydroxyl group produced | generated by ring-opening can anticipate adhesiveness with the metal of conductor circuits, such as copper, nickel, and gold. Of these, highly reactive oxiranes are particularly preferred. This oxirane is commonly called an epoxy group.

  The organic group having a reactive double bond refers to alkenes such as vinyl group and allyl group, and unsaturated carboxylic acids such as acryloyl group and methacryloyl group. These reactive double bonds can be easily initiated and cross-linked by radicals or cations. By cross-linking, it is particularly excellent in heat resistance and mechanical strength.

  The alkoxysilyl group includes a silicon compound that can be easily hydrolyzed to generate an active silanol group, and the active silanol groups are cross-linked with each other or the silanol groups on the silica surface of the filler. Can interact with and chemically bond with. Therefore, heat resistance and mechanical strength are particularly excellent.

  As the monomer used for producing the addition-type norbornene-based resin used in the present invention, a norbornene-based monomer represented by the general formula (2) is preferable.

［式（２）中のＸは、−ＣＨ₂−、−ＣＨ₂ＣＨ₂−、または−Ｏ−を示し、Ｒ₁、Ｒ₂、Ｒ₃およびＲ₄は、それぞれ独立して、水素原子、炭化水素基、炭素数１〜１２の極性基または該極性基を含む基を示す。Ｒ₁、Ｒ₂、Ｒ₃およびＲ₄は、少なくとも１つが炭素数１〜１２の環状エーテル基、反応性二重結合を有する有機基、又はアルコキシシリル基を含む基である。ｎは０から２の整数を示す。］

Expression (2) X in _{the, -CH 2 -, - CH 2} CH 2 -, or -O- and _{shown, R 1, R 2, R} 3 and R ₄ are each independently a hydrogen atom, A hydrocarbon group, a polar group having 1 to 12 carbon atoms or a group containing the polar group is shown. R ₁ , R ₂ , R ₃ and R ₄ are groups each including at least one of a cyclic ether group having 1 to 12 carbon atoms, an organic group having a reactive double bond, or an alkoxysilyl group. n represents an integer of 0 to 2. ]

  Examples of the norbornene-based monomer having a cyclic ether group include 5-methylglycidyl ether-2-norbornene, 5-ethyl glycidyl ether-2-norbornene, and 5-propyl glycidyl ether-2-norbornene. The present invention is not limited to these.

  Examples of the norbornene-based monomer having an organic group having a reactive double bond include 5-vinyl-2-norbornene, 5-allyl-2-norbornene, 5-ethylidene-2-norbornene, (meth) acrylic acid (5- Norbornen-2-yl) methyl ester, (meth) acrylic acid 2- (5-norbornen-2-yl) ethyl ester, (meth) acrylic acid 4- (5-norbornen-2-yl) n-butyl ester, ( (Meth) acrylic acid 3- (5-norbornen-2-yl) n-propyl ester, (meth) acrylic acid 2- (5-norbornen-2-yl) -1-methylethyl ester, (meth) acrylic acid 6- (5-Norbornen-2-yl) n-hexyl ester, (meth) acrylic acid 8- (5-norbornen-2-yl) n-octyl Ester, and (meth) can be exemplified acrylic acid 10- (5-norbornene-2-yl) n- decyl ester, the present invention is in no way limited thereto.

  Examples of the norbornene-based monomer having an alkoxysilyl group include 5-trimethoxysilyl-2-norbornene, 5-triethoxysilyl-2-norbornene, 5- (2-trimethoxysilylethyl) -2-norbornene, 5- ( 2-triethoxysilylethyl) -2-norbornene, 5- (3-trimethoxypropyl) -2-norbornene, 5- (4-trimethoxybutyl) -2-norbornene, 5-trimethylsilylmethyl ether-2-norbornene, And dimethylbis ((5-norbornen-2-yl) methoxy)) silane and the like, but the present invention is not limited thereto.

  The norbornene-based resin used in the present invention is used in a range that does not impair the object of the present invention other than norbornene-based nomers having a crosslinkable group such as a cyclic ether group, an organic group having a reactive double bond, and an alkoxysilyl group. can do. For example, as having an alkyl group, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-propyl-2-norbornene, 5-butyl-2-norbornene, 5-pentyl-2-norbornene, 5 -Hexyl-2-norbornene, 5-heptyl-2-norbornene, 5-octyl-2-norbornene, 5-nonyl-2-norbornene, 5-decyl-2-norbornene and the like, and those having an alkenyl group, 5-allyl-2-norbornene, 5-ethylidene-2-norbornene, 5-isopropylidene-2-norbornene, 5- (2-propenyl) -2-norbornene, 5- (3-butenyl) -2-norbornene, 5 -(1-Methyl-2-propenyl) -2-norbornene, 5- (4-pentenyl) -2- Rubornene, 5- (1-methyl-3-butenyl) -2-norbornene, 5- (5-hexenyl) -2-norbornene, 5- (1-methyl-4-pentenyl) -2-norbornene, 5- (2 , 3-Dimethyl-3-butenyl) -2-norbornene, 5- (2-ethyl-3-butenyl) -2-norbornene, 5- (3,4-dimethyl-4-pentenyl) -2-norbornene, 5- (7-octenyl) -2-norbornene, 5- (2-methyl-6-heptenyl) -2-norbornene, 5- (1,2-dimethyl-5-hexenyl) -2-norbornene, 5- (5-ethyl -5-hexenyl) -2-norbornene and 5- (1,2,3-trimethyl-4-pentenyl) -2-norbornene and the like, and those having an alkynyl group include Ru-2-norbornene and the like, and those having a silyl group include 1,1,3,3,5,5-hexamethyl-1,5-dimethylbis ((2- (5-norbornene-2-yl) Ethyl) trisiloxane 5-trimethylsilylmethyl ether-2-norbornene and the like, and those having an aryl group include 5-phenyl-2-norbornene, 5-naphthyl-2-norbornene and 5-pentafluorophenyl-2-norbornene. Examples of those having an aralkyl group include 5-benzyl-2-norbornene, 5-phenethyl-2-norbornene, 5-pentafluorophenylmethane-2-norbornene, 5- (2-pentafluorophenylethyl) 2-norbornene and 5- (3-pentafluorophenylpropyl ) -2-norbornene and the like having a polar group include, for example, 5-hydroxy-2-norbornene, 5-norbornene-2-methanol, acetic acid 5-norbornene-2-methyl ester, propionic acid 5-norbornene- 2-methyl ester, butyric acid 5-norbornene-2-methyl ester, valeric acid 5-norbornene-2-methyl ester, caproic acid 5-norbornene-2-methyl ester, caprylic acid 5-norbornene-2-methyl ester, capric acid 5-norbornene-2-methyl ester, lauric acid 5-norbornene-2-methyl ester, stearic acid 5-norbornene-2-methyl ester, oleic acid 5-norbornene-2-methyl ester, linolenic acid 5-norbornene-2- Methyl ester, 5-norbornene 2-carboxylic acid, 5-norbornene-2-carboxylic acid methyl ester, 5-norbornene-2-carboxylic acid ethyl ester, 5-norbornene-2-carboxylic acid t-butyl ester, 5-norbornene-2-carboxylic acid i -Butyl ester, 5-norbornene-2-carboxylic acid trimethylsilyl ester, 5-norbornene-2-carboxylic acid triethylsilyl ester, 5-norbornene-2-carboxylic acid isobornyl ester, 5-norbornene-2-carboxylic acid 2-hydroxy Ethyl ester, 5-norbornene-2-methyl-2-carboxylic acid methyl ester, cinnamic acid 5-norbornene-2-methyl ester, 5-norbornene-2-methylethyl carbonate, 5-norbornene-2-methyl n-butyl carbonate, 5-norbo Nene -2-methyl t- Buchirukarubone - DOO, and 5-methoxy-2-norbornene the like can be mentioned, the present invention is in no way limited thereto.

Moreover, as what consists of a tetracyclo ring, for example, 8-methoxycarbonyl tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-n-propylcarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-i-propylcarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8- (2-methylpropoxy) carbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8- (1-methylpropoxy) carbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-t-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-cyclohexyloxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8- (4′-t-butylcyclohexyloxy) carbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-phenoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-tetrahydrofuranyloxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-tetrahydropyranyloxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-i-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8- (2-methylpropoxy) carbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8- (1-methylpropoxy) carbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-t-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-cyclohexyloxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8- (4′-t-butylcyclohexyloxy) carbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-phenoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-tetrahydrofuranyloxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-tetrahydropyranyloxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-methyl-8-acetoxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,9-di (methoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,9-di (ethoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,9-di (n-propoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,9-di (i-propoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,9-di (n-butoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,9-di (t-butoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,9-di (cyclohexyloxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,9-di (phenoxyloxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,9-di (tetrahydrofuranyloxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8,9-di (tetrahydropyranyloxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8,9-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene-8-carboxylic acid, 8-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene-8-carboxylic acid, 8-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyltetracyclo [4.4.0.1 ^2,5 . 0 ^1,6 ] dodec-3-ene, 8-ethylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^7,12] Dodekku-3-ene, and 8-ethylidene tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 0 ^1,6 ] dodec-3-ene and the like can be mentioned, but the present invention is not limited thereto.

  As content of addition type norbornene-type resin used for this invention, 10 to 60 weight% with respect to a resin composition is preferable, and 20 to 50 weight% is especially preferable. If the content is less than the lower limit, the adhesion and electrical characteristics may be reduced, and if the content exceeds the upper limit, the coefficient of thermal expansion may be deteriorated.

  The resin composition contains spherical silica having an average particle size of 2 μm or less. As the spherical silica, those obtained by a known method can be used without limitation. Examples of the spherical silica include dry silica, wet silica, and sol-gel silica.

  The dry silica is generally obtained by burning a silicon compound such as silicon tetrachloride in an atmosphere containing oxygen. Generally, it is also called fumed silica. The spherical silica used in the present invention is preferably a true spherical particle having an average particle diameter of 0.05 to 2 μm, and more preferably a true spherical particle having an average particle diameter of 0.05 to 1 μm. Thereby, it can be set as the resin composition which forms the insulating layer suitable for the wiring board of a fine conductor circuit, a thin multilayer wiring board, and an interposer.

    The wet silica is typically precipitated silica in which silica is precipitated in a solution by neutralizing sodium silicate with a mineral acid.

  The sol-gel silica can be produced by hydrolyzing an alkoxysilane such as tetramethoxysilane or tetraethoxysilane in an acidic or alkaline water-containing organic solvent, and extremely high purity silica can be obtained. There is a feature.

Further, hollow or porous silica produced by the above dry, wet and sol-gel methods can be used as required. Also in this case, it is preferable that an average particle diameter is 2 micrometers or less.

  The spherical silica having an average particle size of 2 μm or less may be surface-treated in advance. By performing a surface treatment in advance, silica aggregation can be suppressed. Accordingly, the dispersibility in the norbornene resin is excellent. In addition, since the adhesion between the norbornene resin and the silica surface is improved, the mechanical strength is excellent.

  The treating agent for pre-treating the spherical silica is a functional group-containing silane, cyclic oligosiloxane, organohalosilane, organoalkoxysilane, alkylsilazane, two or more repeating units of siloxane bond, and an alkoxy group. At least one compound selected from the group consisting of silicone oils having The said processing agent can be selected according to the crosslinkable group of the norbornene-type resin to be used.

  Examples of the functional group-containing silanes include epoxy silane, (meth) acryl silane, mercapto silane, amino silane, vinyl silane, isocyanate silane, ureido silane, (5-norbornen-2-yl) alkyl silane, and phenyl silane. However, epoxy silane, (meth) acryl silane, and (5-norbornen-2-yl) alkyl silane are more preferable.

  Examples of the cyclic oligosiloxane include hexamethylcyclotrisiloxane and oritamethylcyclotetrasiloxane.

  Examples of the organohalosilanes include trimethylchlorosilane, dimethyldichlorosilane, and methyltrichlorosilane, and dimethyldichlorosilane is more preferable.

    Examples of the alkylsilazanes include hexamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, octamethyltrisilazane, and hexamethylcyclotrisilazane. Disilazane is more preferred.

  The method of surface-treating spherical silica used in the present invention can be performed by a known method. For example, it can be carried out by putting silica powder in a mixer, spraying the treatment agent while stirring in a nitrogen atmosphere, and maintaining the mixture at a predetermined temperature for a certain time. The treatment agent to be sprayed may be dissolved in a solvent in advance. In addition, in the solvent together with the treatment agent, stirring, heating, adding a small amount of water, or using an acid or alkali to promote the reaction between the silanol on the silica surface and the coupling agent This is known to those skilled in the art and is included in the present invention. There is also a method for surface treatment by directly contacting the vapor of the treating agent with spherical silica.

  Although the temperature at the time of the treatment depends on the kind of the treatment agent, it is necessary to perform the treatment at a temperature lower than the decomposition temperature of the treatment agent. On the other hand, if the treatment temperature is too low, the bonding strength between the treatment agent and the raw silica powder is low, and the treatment effect cannot be obtained. Therefore, it is necessary to perform the treatment at an appropriate temperature according to the treatment agent. Furthermore, the holding time depends on the type of processing agent and the processing temperature.

  Further, when the surface treatment of silica is performed using organohalosilanes and alkylsilazanes, it is suitable for hydrophobizing the silica surface and is excellent in dispersibility of silica in the norbornene resin used in the present invention. Of course, it can be used alone or in combination with a normal functional group-containing silane and the above-mentioned organohalosilane or alkylsilazane. When using in combination, either may be used first for surface treatment, but using organohalosilanes or alkylsilazanes first will give organic surface affinity to the silica surface, and the following surface treatment will be effective. Therefore, it is preferable. The ratio of the normal functional group-containing silane used here and the amount of the organohalosilane or alkylsilazane used is preferably 500/1 to 5/1 (weight ratio). If it is out of this range, the combined effect may be reduced.

  The content of the spherical silica having an average particle size of 2 μm or less is preferably 40 to 90% by weight, particularly 50 to 80% by weight, based on the resin composition. If the content is less than the lower limit value, the thermal expansion coefficient of −50 to 150 ° C. may not be 60 ppm or less, and if the content exceeds the upper limit value, electrical characteristics may be deteriorated.

  In addition to the norbornene-based resin used in the present invention, other components can be used in combination in order to improve adhesion and connection reliability. For example, acrylic monomer, vinyl ether monomer, epoxy resin, vinyl monomer, bisphenol A type phenoxy resin, polyester resin, polyurethane resin, polyimide resin, polybutadiene, polypropylene, styrene-butadiene-styrene copolymer, polyacetal resin, polyvinyl butyral resin, butyl rubber , Chloroprene rubber, polyamide resin, acrylonitrile-butadiene copolymer, acrylonitrile-butadiene-methacrylic acid copolymer, acrylonitrile-butadiene-styrene copolymer, acrylic copolymer, polyvinyl acetate resin, nylon, styrene-isoprene copolymer A polymer, a styrene-butylene-styrene block copolymer, or the like can be used, or a single type or a mixture of two or more types may be used.

  Furthermore, in the present invention, an additive such as a coupling agent can be separately used for the resin composition, if necessary, in addition to the surface treatment agent. Examples of coupling agents that can be used in the present invention include silane-based, titanate-based, and aluminum-based coupling agents. For example, N-phenyl-γ-aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-amino Ethyl) aminopropyltriethoxysilane, γ-anilinopropyltrimethoxysilane, γ-anilinopropyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane and N-β Aminosilane compounds such as-(N-vinylbenzylaminoethyl) -γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane and β- (3,4-epoxy (Cyclohexyl) ethyltrimethoxysila As other epoxy silane compounds such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylvinylethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ- Examples include ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, (5-norbornen-2-yl) ethyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane. The blending amount of the coupling agent is preferably 0.01 to 5 parts by weight, more preferably 0.01 to 2.5 parts by weight, based on 100 parts by weight of the resin composition. This is because the spherical silica has been surface-treated in advance, so that a sufficient effect can be obtained with a small amount.

  Furthermore, in the present invention, fluorine particles can be blended in the resin composition as necessary. Excellent electrical characteristics by blending fluorine particles. As the fluorine particles, particles having an average particle diameter of 5 μm or less are preferable. When the average particle diameter exceeds 5 μm, when an insulating layer composed of a resin composition is formed, the fluorine particles may cause non-uniform electrical characteristics between the wirings due to the bridge between the wirings, and may cause a decrease in adhesion. Reliability may be reduced.

  Examples of the fluororesin constituting the particles composed of the fluororesin include polytetrafluoroethylene (PTFE), tetrafluoroethylene, polyvinylidene fluoride, polychlorotrifluoroethylene (PCTFE), and tetrafluoroethylene-perfluoroalkyl vinyl ether. Examples thereof include a polymer (PFA), a tetrafluoroethylene-hexafluoropropylene copolymer (FEP), and a tetrafluoroethylene-ethylene copolymer (ETFE), and polytetrafluoroethylene (PTFE) is preferable. Polytetrafluoroethylene (PTFE) includes only units derived from tetrafluoroethylene, or one or more monomers that can be copolymerized with units derived from tetrafluoroethylene, such as hexa A unit comprising units derived from fluoropropylene, perfluorovinyl ether, hexafluoroisobutylene, vinylidene fluoride, or olefin, and units other than units derived from tetrafluoroethylene in the case of the above copolymer The ratio is up to 20%, preferably up to 5%, more preferably 2% or less. The crystallinity of PTFE is at least 50% or more, preferably 60% or more, and more preferably 70% to 90%.

An arbitrary latent catalyst can be further added to the resin composition used in the present invention. Thereby, the heat curing performed after the insulating layer is applied, dried, laminated, or press formed can be set to a temperature of 200 ° C. or less and a temperature of 2 hours or less.
As the latent catalyst, for example, a catalyst that does not promote the crosslinking reaction of the addition-type norbornene-based resin having a crosslinkable group at a temperature lower than 120 ° C., but can accelerate the crosslinking reaction at 120 ° C. or higher is used. be able to. More specifically, the gel time on a hot plate at 150 ° C. can be set to 1 minute 30 seconds or more.
Examples of such latent catalysts include phosphine compounds and imidazole derivatives. Phosphine compounds include triphenylphosphine, tricyclohexylphosphine, triisopropylphosphine, tetraphenylphosphonium phenoate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenoxyborate, tetraphenylphosphonium tetraalkoxyborate, tetraphenylphosphonium tetraalkylborate. And tetraphenylphosphonium. Examples of imidazole derivatives include 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-ethylimidazole, 1-benzyl-2-ethyl-5-methylimidazole, and 2-phenyl-4. -Methyl-5-hydroxydimethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-undecylimidazole, 1-benzyl-2-phenylimidazole, 2,4-diamino-6- [2'-methyl- Examples include imidazolyl- (1 ′)]-ethyl-s-triazine, 1-cyanoethyl-2-undecylimidazole, and the like. Among these, 2,4-diamino-6- [2′-methyl-imidazolyl- (1 ′)]-ethyl-s-triazine and 1-cyanoethyl-2-undecylimidazole are particularly preferable. Thereby, the latency of the catalyst is particularly improved.
Furthermore, the phosphine compound is preferably a phosphonium salt. Thereby, it can have sufficient latency and curability. These may be used alone or in combination of two or more.

Examples of other latent catalysts include benzophenones such as benzophenone, benzoylbenzoic acid, 4-phenylbenzophenone, and hydroxybenzophenone, benzoin alkyl ethers such as benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, and benzoin isobutyl ether. , Acetophenones such as 4-phenoxydichloroacetophenone, and diethoxyacetophenone, thioxanthones such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, and 2,4-dimethylthioxanthone, ethyl anthraquinone, and Examples include alkyl anthraquinones such as butyl anthraquinone.
Also, azobisisobutyronitrile, isobutyryl peroxide, diisopropyl peroxydicarbonate, t-hexylperoxy-2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxy-2- Organic peroxidation such as ethyl hexanoate, dicumyl peroxide, 2,5-dimethyl-2,5 di (t-butylperoxy) hexyne-3, t-butylcumyl peroxide, and t-butyl hydroperoxide You can list things.

  Further, when a photoacid generator is used as a light and / or thermal polymerization initiator as another latent catalyst, the epoxy group is crosslinked and the adhesion to the substrate is improved by subsequent curing. Preferred photoacid generators are onium salts, halogen compounds, sulfates and mixtures thereof. Examples of onium salts include diazonium salts, ammonium salts, iodonium salts, sulfonium salts, phosphate salts, and oxonium salts. There is no limitation on the counter anion as long as it is a compound capable of forming a counter anion with the onium salt. Examples of counter anions include, but are not limited to, boric acid, phosphoric acid, antimonic acid, sulfate, carboxylic acid and its chloride. Examples of photoacid generators for onium salts include triphenylsulfonium tetrafluorophosphate, triphenylsulfonium tetrafluorosulfate, 4-thiophenoxydiphenylsulfonium tetrafluoroborate, and 4-thiophenoxydiphenylsulfonium tetrafluoroantimony. 4-t-butylphenyldiphenylsulfonium tetrafluoroantimonate, 4-t-butylphenyldiphenylsulfonium trifluorophosphonate, tris (4-methylphenyl) sulfonium trifluoroborate, tris (4- Methylphenyl) sulfonium tetrafluoroborate, tris (4-methylphenyl) sulfonium hexafluoroarsenate, tris (4-methylphenyl) sulfur Nitrohexafluorophosphate, Tris (4-methylphenyl) sulfonium hexafluorosulfonate, Tris (4-methoxyphenyl) sulfonium tetrafluoroborate, Tris (4-methylphenyl) sulfonium hexafluoroantimonate , Tris (4-methylphenyl) sulfonium hexafluorophosphate, triphenyliodonium hexafluorophosphate, triphenyliodonium trifluorosulfonate, 3,3-dinitrodiphenyliodonium tetrafluoroborate, 3,3-dinitrodiphenyliodonium Trifluorosulfonate, 4,4-dinitrodiphenyliodonium tetrafluoroborate, 4,4-dinitrodiphenyliodonium hexafluoroer Neato, 4,4-dinitrodiphenyliodonium trifluorosulfonate, 4,4'-di-t-butylphenyliodonium triflate, 4,4 ', 4' '-tris (t-butylphenyl) sulfonium triflate , Diphenyliodonium tetrakis (pentafluorophenyl) borate, triphenylsulfonium diphenyliodonium tetrakis (pentafluorophenyl) borate, 4,4′-di-t-butylphenyliodonium tetrakis (pentafluorophenyl) borate, tris (t-butyl) Phenyl) sulphonium tetrakis (pentafluorophenyl) borate, (4-methylphenyl) (4- (1-methylethyl) phenyl) iodonium tetrakis (pentafluorophenyl) borate, and 4 -(2-methylpropyl) phenyl (4-methylphenyl) iodonium hexafluorophosphate and mixtures thereof. These may be used alone or in combination.

Among these latent catalysts, those described below are particularly preferable.
Dicumyl peroxide, 2,5-dimethyl-2,5 di (t-butylperoxy) hexyne-3,4,4'-di-t-butylphenyliodonium triflate, 4,4 ', 4''- Tris (t-butylphenyl) sulfonium triflate, diphenyliodonium tetrakis (pentafluorophenyl) borate, triphenylsulfonium diphenyliodoniumtetrakis (pentafluorophenyl) borate, 4,4′-di-t-butylphenyliodonium tetrakis (Pentafluorophenyl) borate, tris (t-butylphenyl) sulfonyl tetrakis (pentafluorophenyl) borate, (4-methylphenyl) (4- (1-methylethyl) phenyl) iodonium tetrakis (pentafluorophenyl) borate And 4- (2-methylpropyl) phenyl (4-methylphenyl) iodonium hexafluorophosphate and mixtures thereof.

  The content of the latent catalyst is not particularly limited, but is preferably 0.1 to 10% by weight, particularly preferably 0.5 to 5% by weight, based on the resin component of the resin composition. When the content is less than the lower limit, the insulating layer is insufficiently cured, and when the content exceeds the upper limit, the storage stability may be lowered.

  In addition, the resin composition of the present invention has various additives such as leveling agents, antioxidants, UV absorbers, non-reactive dilutions, in order to improve various properties such as resin compatibility, stability, and workability. Agents, reactive diluents, thixotropic agents, thickeners and the like may be added as appropriate.

  As a method for producing the resin composition of the present invention, first, the norbornene-based resin, spherical silica having an average particle size of 2 μm or less, and any latent catalyst or additive are mixed with methyl ethyl ketone, toluene, mesitylene, decahydronaphthalene, acetic acid. Various organic solvents such as ethyl, cyclohexane, heptane, cyclohexanone, tetrahydrofuran and anisole, such as ultrasonic dispersion method, high-pressure collision dispersion method, high-speed rotation dispersion method, bead mill method, high-speed shear dispersion method, and rotation and revolution dispersion method A varnish can be obtained by mixing and stirring using a mixer and applied 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, and a curtain coater, a spin coating method, a spraying method, a dipping method, a printing machine, Examples include a method using a vacuum printer and a dill pencer. Among these, a method using a die coater or a knife coater is preferable. It is also possible to form an insulating layer by spin coating directly on the circuit. A wiring board or multilayer wiring board obtained by forming an insulating layer using the resin composition thus obtained is excellent in electrical characteristics / workability and reliability.

  Since the resin composition of the present invention has excellent electrical characteristics and workability, it is suitable not only for printed wiring boards and multilayer wiring boards but also for insulators such as semiconductor devices and liquid crystal display devices. In particular, when used in an insulating layer of a multilayer wiring board that requires uniformity in thickness and surface smoothness in an interlayer insulating layer, the multi-wiring board has stable high-speed transmission characteristics because of excellent circuit embedding and surface smoothness. Can be provided. In addition, since it has excellent adhesion to each adherend such as a copper circuit, silicon, organic materials, etc., and low moisture absorption, it is possible to provide a multilayer wiring board having high mounting reliability and connection reliability. it can.

Next, a laminated body is demonstrated.
FIG. 1 is a cross-sectional view schematically showing an example of the laminate of the present invention.
The laminate 1 is formed by laminating a resin layer 3 composed of the above resin composition and a carrier film 2.
The resin layer composed of the resin composition enables high-speed transmission of electronic devices. Further, it can be used as an insulating layer having characteristics excellent in electrical characteristics and laser processability.
Although the thickness of the resin layer 3 comprised with a resin composition is not specifically limited, 0.1-60 micrometers is preferable and 1-40 micrometers is especially preferable. The thickness of the resin layer composed of the resin composition is preferably not less than the lower limit for improving insulation reliability, and not more than the upper limit for achieving thinning which is one of the purposes in a multilayer wiring board. Is preferred.

  The carrier film 2 is preferably a metal foil that can be used as a conductor layer such as copper or aluminum, or a resin film that can be easily peeled off from the resin layer 2 composed of a resin composition with an appropriate strength. Examples of the resin film include films made of polyester, aromatic polyimide, polyethylene, and the like. Among these carrier films, a film made of polyester is most preferable. Thereby, it becomes particularly easy to peel the resin layer 3 composed of the resin composition with an appropriate strength. It also has excellent stability against reactive diluents. Furthermore, migration of the resin composition component dissolved in the reactive diluent and the solvent to the carrier film can be prevented. Moreover, although the thickness of the carrier film 3 is not specifically limited, 10-200 micrometers is preferable and 20-100 micrometers is especially preferable. When the thickness of the carrier film is within the above range, the flatness of the resin layer on the circuit in the wiring board is particularly excellent.

  As a method of laminating the resin layer 3 composed of the resin composition on the carrier film 2, for example, the resin composition is dissolved in a solvent or the like to form a varnish, and this is applied to the carrier film 3 to form a resin layer. And the like. Examples of the application method include, for example, a method of applying or casting using a roll coater, bar coater, knife coater, gravure coater, die coater and curtain coater, a spraying method, a dipping method, a printing machine, Examples include a method of drawing with a vacuum printer and a dispenser, and optionally spin coating. Among these, a method using a die coater is preferable. Thereby, the laminated body 1 which has predetermined | prescribed thickness can be produced stably.

  Specifically, as a method for producing the laminate 1, for example, a resin composition dissolved in a solvent is applied to the carrier film 2 with a thickness of about 1 to 100 μm, and the coating layer is formed, for example, 80 to 200 Dry at 20 ° C. for 20 seconds to 30 minutes so that the residual solvent amount is 1.0% by weight or less. Thereby, the laminated body 1 by which the resin layer 3 comprised by the resin composition was laminated | stacked on the carrier film 2 can be obtained (FIG. 1).

  The resin layer thus obtained is excellent in workability and electrical characteristics. For example, the height difference of surface irregularities of 1.0 μm or less, a dielectric constant of 3.0 or less at 1 GHz, and a dielectric of 0.006 or less. Tangent can be achieved.

Next, the wiring board will be described.
FIG. 2 is a cross-sectional view showing an example of the wiring board of the present invention.
As illustrated in FIG. 2, the wiring 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 conducted.

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.
In addition, second conductor circuits 32 are formed on both surfaces of the resin layer 3.
The conductor circuit 52 and the conductor circuit 32 are electrically connected via the opening 31.

  A method of manufacturing such a wiring board will be described with reference to FIG. 3. For example, after opening the opening 102 by drilling a core board (for example, FR-4 double-sided copper foil) 107 with a drilling machine. Then, the opening 102 is plated by electroless plating so that both surfaces of the core substrate 107 are electrically connected. Then, the conductor circuit 101 is formed by etching the copper foil (FIG. 3A).

  The material of the conductor circuit 101 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 in this are preferred. Examples of the material of the conductor circuit 101 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 101 because not only electrolytic plated products and rolled products can be selected, but also various thicknesses can be easily obtained.

Next, a resin layer 104 is formed so as to cover the conductor circuit 101 (FIG. 3B). As a method of forming the resin layer 104, a method of directly applying the resin composition of the present invention to the insulating layer forming surface, a method of pressing the above-described carrier material with a resin layer, a vacuum with a carrier material with a resin layer, Examples thereof include a method in which the resin layer 104 is formed by laminating using a press, a normal pressure laminator, a vacuum laminator, a Becquerel type laminating apparatus, and the like.
When a metal layer is used as the carrier material, the metal layer can be processed as a conductor circuit.

  Next, when a carrier material with a resin layer is used for the resin layer formation, the formed resin layer 104 is heated and cured after peeling off the carrier material. The temperature for heating and curing is preferably in the range of 150 ° C to 300 ° C. In particular, 150-250 degreeC is preferable. Also, the first resin layer 104 is heated and semi-cured, and one or more resin layers 104 are further formed on the resin layer 104, and the semi-cured resin layer 104 is again heat-cured to such an extent that there is no practical problem. Thus, the adhesion between the resin layers 104 and between the resin layer 104 and the conductor circuit 101 can be improved. The semi-curing temperature in this case is preferably 100 ° C to 250 ° C, more preferably 150 ° C to 200 ° C.

  Next, the resin layer 104 is irradiated with a laser to form an opening 105 (FIG. 3C). As the laser, an excimer laser, a UV laser, a carbon dioxide gas laser, or the like can be used. Formation of the opening 105 by the laser can easily form a fine opening 105 regardless of whether the resin layer 104 is photosensitive or non-photosensitive. Therefore, it is particularly preferable when the resin layer 104 needs to be finely processed.

Next, the conductor circuit 106 is formed (FIG. 3D). The conductive circuit 106 can be formed by a known method such as a semi-additive method.
Next, a conductor post is formed (FIG. 3E). As a method of forming the conductor post 107, it can be formed by a known method such as electrolytic plating. For example, copper electroplating can be performed using the conductive circuit 106 as a lead for electrolytic plating, and the copper post can be formed by filling with copper. By this method, a wiring board can be obtained.
In the step of obtaining the wiring board, a multilayer wiring board can be obtained by repeating the steps shown in FIGS. 3 (a) to 3 (d).

Example 1
An addition copolymer of 2-norbornene / 5-methylglycidyl ether-2-norbornene (70/30) monomer (Polymer A, Mw = 200,000) was used as the norbornene-based resin. In addition, norbornene-type resin (polymer A) was synthesize | combined with the following method.
[Synthesis of Polymer A]
In a reaction vessel in which the atmosphere of the polymerization system is sufficiently filled with an inert gas nitrogen, 13.2 g (0.14 mol) of 2-norbornene, 10.8 g (0.06 mol) of 5-methylglycidyl ether-2-norbornene, As a polymerization solvent, 170 g of ethyl acetate and 147 g (0.53M) of cyclohexane were charged. Subsequently, a catalyst solution in which 1.39 g (2.86 × 10 ⁻³ mol) of a transition metal catalyst (η ⁶ -toluene nickel bis (pentafluorophenyl)) was dissolved in 10 g of toluene was charged into the reaction vessel at room temperature for 4 hours. After stirring and polymerizing, the polymerization solution was put into a mixed solution of 94 ml of glacial acetic acid, 174 ml of 30% hydrogen peroxide water and 600 ml of pure water, and stirred for 2 hours. The organic layer was washed several times with pure water, and the resin solution was poured into methanol to precipitate a norbornene-based resin, which was filtered and dried under reduced pressure. Polymer A was obtained by removing the solvent.

  Surface treatment using 10 g of the obtained norbornene resin (Polymer A), β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and (5-norbornene-2-yl) ethyltrimethoxysilane as surface treatment agents 12.2 g of spherical silica (manufactured by Admatechs, SE-2030, average particle size 0.5 μm, 3 μm coarse particle cut), (4-methylphenyl) (4- (1-methylethyl) phenyl as a latent catalyst ) 0.1 g of iodonium tetrakis (pentafluorophenylborate) and 0.15 g of 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole as UV absorber in a mesitylene solvent To 35%. In this case, the silica content is about 55% by weight based on the resin composition. Subsequently, silica was dispersed using a high-speed shear dispersion type mixer (manufactured by Nara Machinery Co., Ltd., Micros MICROS-0 type) to prepare a resin solution.

  The above-mentioned resin solution was applied as a carrier film onto a polyester film (Diafoil, MRX-50, thickness 50 μm) with a roll coater so as to have a thickness of 25 μm. Then, it dried at 80 degreeC for 10 minutes and 140 degreeC for 10 minutes, laminated | stacked with the carrier film, and obtained the laminated body which consists of a resin layer with a carrier film.

  The following evaluation was performed about the laminated body obtained by each Example and the comparative example. The evaluation items are shown together with the contents. The results are shown in Table 1.

(1) Thermal expansion coefficient of −50 to 150 ° C., and glass transition temperature Thermal strain measuring device (manufactured by Seiko Instruments Inc., EXSTAR6000 TMA / SS), load 20 mN, temperature rising rate 5 ° C./min, temperature Measurements were made in the range −50 to 350 ° C. The thermal expansion coefficient at −50 to 150 ° C. was evaluated by calculating the average thermal linear expansion coefficient at −50 to 0 ° C., 0 to 50 ° C., 50 to 100 ° C., and 100 to 150 ° C., and calculating the average value. The inflection point was taken as the glass transition temperature. In addition, the carrier film was removed from the laminate, and then a resin composition that was heat-treated at 200 ° C. for 1 hour with a dryer in a nitrogen atmosphere was used as a sample.
Each code is as follows.
◎: Less than 30 ppm ○: 30 to 60 ppm or less △: 60 to 90 ppm or less ×: 90 ppm or more

(2) Dielectric constant measurement Dielectric characteristics at a frequency of 2.45 GHz were measured. As a measuring instrument, a cylindrical cavity resonator (manufactured by Agilent Technologies, microwave network analyzer HP8510B) was used. In addition, the carrier film was removed from the laminate, and then a resin composition that was heat-treated at 200 ° C. for 1 hour with a dryer in a nitrogen atmosphere was used as a sample.

(Example 2)
The same as Example 1 except that the content of silica was 75% by weight.

(Example 3)
Example 1 was the same as Example 1 except that the following were used as the surface treatment agents for norbornene resin and silica.
An addition copolymer of 2-norbornene / 5-trimethoxysilyl-2-norbornene (90/10) monomer (polymer B, Mw = 200,000) was used as the norbornene-based resin. Polymer B was synthesized by the following method. (5-norbornen-2-yl) ethyltrimethoxysilane was used as a surface treatment agent for silica.
[Synthesis of Polymer B]
In a reaction vessel in which the atmosphere of the polymerization system is sufficiently filled with an inert gas nitrogen, 16.95 g (0.18 mol) of 2-norbornene, 4.3 g (0.02 mol) of 5-trimethoxysilyl-2-norbornene, As a polymerization solvent, 170 g of ethyl acetate and 147 g (0.53M) of cyclohexane were charged. Subsequently, a catalyst solution in which 1.39 g (2.86 × 10 ⁻³ mol) of a transition metal catalyst (η ⁶ -toluene nickel bis (pentafluorophenyl)) was dissolved in 10 g of toluene was charged into the reaction vessel at room temperature for 4 hours. After stirring and polymerizing, the polymerization solution was put into a mixed solution of 94 ml of glacial acetic acid, 174 ml of 30% hydrogen peroxide water and 600 ml of pure water, and stirred for 2 hours. The organic layer was washed several times with pure water, and the resin solution was poured into methanol to precipitate a norbornene-based resin, which was filtered and dried under reduced pressure. Polymer B was obtained by removing the solvent.

Example 4
Example 1 was the same as Example 1 except that the following were used as the surface treatment agents for norbornene resin and silica.
Addition weight of 5-methyl-2-norbornene / (2-norbornene-5-yl) methyl acrylate / 5- (2-trimethoxysilylethyl) -2-norbornene (85/10/5) monomer as norbornene resin A coalescence (polymer C, Mw = 200,000) was used. Polymer C was synthesized by the following method. Further, hexamethyldisilazane was used as a silica surface treatment agent.
[Synthesis of Polymer C]
In a reaction vessel in which the atmosphere of the polymerization system was sufficiently filled with an inert gas nitrogen, 45.98 g (0.425 mol) of 5-methyl-2-norbornene and 9.62 g of (2-norbornene-5-yl) methyl acrylate ( 0.05 mol), 5- (2-trimethoxysilylethyl) -2-norbornene 6.06 g (0.025 mol), and 192 g of toluene as a polymerization solvent were charged. Next, transition metal catalyst [(acetyl) bis (triisopropylphosphine) (acetonitrile) palladium] [tetrakis (perfluorophenyl) borate] 0.0482 g (4.0 × 10 ⁻⁵ mol), dimethylphenylammonium tetrakis as Lewis acid 0.0641 g (8.0 × 10 ⁻⁵ mol) of (perfluorophenyl) borate and 0.291 g of triethoxysilane as a molecular weight regulator were dissolved in 10 g of toluene, and the catalyst solution was charged into the reaction vessel. After stirring and polymerizing at 70 ° C. for 3 hours, the resin solution was put into methanol to precipitate a norbornene resin. The solid content was filtered and then dried under reduced pressure to remove the solvent and obtain polymer C.

(Example 5)
It carried out like Example 4 except having used the following as norbornene-type resin.
An addition copolymer of 5-methyl-2-norbornene / (2-norbornene-5-yl) methyl acrylate (90/10) monomer (polymer D, Mw = 200,000) was used as the norbornene resin. Polymer D was synthesized by the following method.
[Synthesis of Polymer D]
In a reaction vessel in which the atmosphere of the polymerization system was sufficiently filled with an inert gas nitrogen, 16.23 g (0.15 mol) of 5-methyl-2-norbornene, 9.62 g of (2-norbornene-5-yl) methyl acrylate ( 0.05 mol) and 115 g of mesitylene as a polymerization solvent were charged. Next, transition metal catalyst [(acetyl) bis (triisopropylphosphine) (acetonitrile) palladium] [(acetyl) bis (triisopropylphosphine) (acetonitrile) palladium] 0.0193 g (1.60 × 10 ⁻⁵ mol), Lewis 0.0256 g (3.20 × 10 ⁻⁵ mol) of dimethylphenylammonium tetrakis (perfluorophenyl) borate as an acid and 0.116 g of triethoxysilane as a molecular weight regulator are dissolved in 1 g of toluene, and the catalyst solution is dissolved in a reaction vessel. It was thrown into. After stirring and polymerizing at 70 ° C. for 3 hours, the resin solution was put into methanol to precipitate a norbornene resin. After filtering the solid content, the polymer D was obtained by drying under reduced pressure to remove the solvent.

(Example 6)
The same as Example 5 except that the content of silica was 75% by weight.

(Example 7)
Example 6 was the same as Example 6 except that the following methacrylsilane compound was used as the surface treatment agent for silica.
As the methacrylic silane compound, 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-503) was used.

(Example 8)
Example 6 was the same as Example 6 except that the following norbornene-based silane compound was used as the silica surface treatment agent.
(5-Norbornen-2-yl) ethyltrimethoxysilane (Promerus LLC) was used as the methacrylsilane compound.

(Comparative Example 1)
The same procedure as in Example 6 was used except that an addition polymer (polymer E) of 2-norbornene having no crosslinkable group was used as the norbornene-based resin. Polymer E was synthesized by the following method.
[Synthesis of Polymer E]
In a reaction vessel in which the atmosphere of the polymerization system was sufficiently filled with an inert gas nitrogen, 18.8 g (0.20 mol) of 2-norbornene, 170 g of ethyl acetate and 147 g of cyclohexane (0.53 M) as polymerization solvents were charged. Subsequently, a catalyst solution in which 1.39 g (2.86 × 10 ⁻³ mol) of a transition metal catalyst (η ⁶ -toluene nickel bis (pentafluorophenyl)) was dissolved in 10 g of toluene was charged into the reaction vessel at room temperature for 4 hours. After stirring and polymerizing, the polymerization solution was put into a mixed solution of 94 ml of glacial acetic acid, 174 ml of 30% hydrogen peroxide water and 600 ml of pure water, and stirred for 2 hours. The organic layer was washed several times with pure water, and the resin solution was poured into methanol to precipitate a norbornene-based resin, which was filtered and dried under reduced pressure. Polymer E was obtained by removing the solvent.

(Comparative Example 2)
Example 6 was the same as Example 6 except that the following were used as the surface treatment agents for norbornene resin and silica.
As norbornene resin, tetracyclo [4.4.2 0.1 ^{2, 5.1 7, 10]} ring-opening polymerization by a known method dodecene, was hydrogenated, those epoxy-modified (polymer F, Mw = 85000 ) Was used. Polymer A was synthesized by the following method. As a surface treating agent for silica, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-303)
[Synthesis of Polymer F]
Add 100 parts of tetracyclo [4.4.0.12, 5.17, 10] dodecene, 300 parts of toluene and 13 parts of 1-hexene to a reaction vessel sufficiently filled with an inert gas nitrogen. While heating to 80 ° C. Add 0.9 parts of 0.1 mol / L toluene solution of paraaldehyde, 1.5 parts of 0.5 mol / L toluene solution of diethylaluminum chloride, and 1 part of 0.05 mol / L chlorobenzene solution of hexachlorotungsten. The reaction was carried out at 0 ° C. for 3 hours. After the completion of the polymerization, the polymerization solution was dropped into a large amount of methanol to precipitate a polymer, separated by filtration and vacuum dried. 100 parts of this polymer is dissolved in 2000 parts of tetrahydrofuran, palladium catalyst (activated carbon catalyst) is added, and hydrogenation reaction is performed by heating in an autoclave at a hydrogen gas pressure of 150 kg / cm ² and a reaction temperature of 150 ° C. for 4 hours. It was. After completion of the reaction, the catalyst was filtered off and precipitated in a large amount of methanol and recovered. 50 parts of the resulting ring-opening hydrogenated polymer was dissolved in 1000 parts of xylene at 130 ° C. Subsequently, 10 parts of allyl glycidyl ether and 5 parts of 2,5-dimethyl-2,5 (t-butylperoxy) hexyne-3 were added and melt-kneaded at 230 ° C. to obtain an epoxy modification. (Mw = 85000)

Next, examples of the wiring boards and comparative examples will be described using the laminate (resin layer with a carrier film) obtained above.
Example 1A
1. Formation of inner layer circuit and insulating layer After opening with a drilling machine using a double-sided copper-clad laminate (ELC-4781 manufactured by Sumitomo Bakelite Co., Ltd.) having a total thickness of 0.3 mm and a copper foil thickness of 12 μm, Conduction between the upper and lower copper foils was achieved by electrolytic plating, and the inner layer conductor circuits were formed on both sides by etching the copper foils on both sides.
Next, the inner layer conductor circuit is sprayed with a chemical solution mainly composed of hydrogen peroxide solution and sulfuric acid (Tech SO-G manufactured by Asahi Denka Kogyo Co., Ltd.) to form irregularities by roughening treatment. Example 1 The resin solution obtained in (1) was applied by spin coating, dried at 80 ° C. for 10 minutes and 140 ° C. for 10 minutes, and then baked at 200 ° C. for 60 minutes to form an insulating layer.

2. Laser processing and formation of outer layer circuit Next, an opening (blind via hole) with a diameter of 40 μm is formed using a UV-YAG laser device (ML605LDX manufactured by Mitsubishi Electric Corporation), and desmear treatment (manufactured by Nihon McDermid Co., Ltd.) After applying the Macudizer series, electroless copper plating (Sulcup PRX manufactured by Uemura Kogyo Co., Ltd.) was performed for 15 minutes to form a power feeding layer having a thickness of 0.5 μm. 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 wiring board was obtained.

(Examples 2A to 8A)
Instead of the resin solution obtained in Example 1, wiring boards were obtained in the same manner as in Example 1A, using the resin solutions obtained in Examples 2-4.

(Comparative Examples 1A to 2A)
A wiring board was obtained in the same manner as in Example 1A using the resin solutions obtained in Comparative Examples 1 and 2 instead of the laminate obtained in Example 1.

  The following evaluation was performed about the wiring board obtained by each Example and the comparative example. The evaluation items are shown together with the contents. The results are shown in Table 1.

(1) Connection reliability Connection reliability was determined by leaving the sample at -30 hours at 30 ° C and 70% humidity for 196 hours followed by 3 reflows at 260 ° C and a temperature cycle test (-40 ° C, 125 ° C for 30 minutes, no exposure) ), And a continuity test was conducted every 100 cycles, and evaluation was made on the failure occurrence cycle.
Each code is as follows.
◎: 800 cycles or more ○: 500 to 800 cycles Δ: 100 to 500 cycles ×: less than 100 cycles

(2) Insulation reliability test (PCBT)
The insulation reliability is the insulation resistance value between conductors after being left for 100 hours using a substrate with a voltage of DC 5 V and a wiring pitch of 20 μm (L / S = 20/20) in an atmosphere of a temperature of 100 ° C. and a humidity of 85%. The digital insulation resistance value was evaluated. Each code is as follows.
◎: Insulation resistance value 10 ¹⁰ Ω or more ○: Insulation resistance value 10 ⁸ to 10 ⁹ Ω
Δ: Insulation resistance value 10 ⁷ to 10 ⁸ Ω
×: less than the insulation resistance of 10 ⁷

As apparent from Table 1, Examples 1 to 8 were excellent in dielectric constant, coefficient of thermal expansion of −50 to 150 ° C., and glass transition temperature. Moreover, it was shown that Examples 1 and 3-5 are particularly excellent in dielectric constant. Moreover, it was shown that Example 2 and 6-8 are excellent in especially a thermal expansion coefficient. On the other hand, the comparative example 2 was inferior in the thermal expansion coefficient of -50-150 degreeC. In Comparative Example 2, the glass transition temperature was extremely low and inferior.
Furthermore, as is clear from Table 1, Examples 1A to 8A were excellent in connection reliability and insulation reliability. In particular, Examples 2 and 6 to 8 were very excellent in connection reliability and insulation reliability. This is due to the excellent thermal expansion coefficient of -50 to 150 ° C.
On the other hand, Comparative Examples 1A to 2A were inferior in connection reliability and insulation reliability. Since Comparative Example 1A had no crosslinkable group and its adhesion to silica was reduced and mechanical strength was greatly inferior, Comparative Example 2A was inferior in thermal expansion coefficient and glass transition temperature of −50 to 150 ° C. Both connection reliability and insulation reliability were greatly inferior.

  According to the present invention, since it is possible to obtain a resin composition having both high reliability and workability required for an insulating layer, as an insulating material such as a semiconductor mounting substrate that requires electrical characteristics and fine processing. Can be used. In addition, this makes it possible to obtain a wiring board having excellent electrical characteristics, particularly dielectric characteristics, and thus can be applied to multilayer wiring boards for electronic devices that require miniaturization of parts and high-speed signal transmission.

It is sectional drawing which shows an example of the laminated body of this invention. It is sectional drawing which shows an example of the wiring board of this invention. It is sectional drawing which shows an example of the manufacturing method of the wiring board of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Laminated body 2 Carrier film 3 Resin layer 5 Core board 10 Wiring board 31 Opening part of resin layer 32 Conductor circuit 51 Opening part of core board 52 Conductor circuit 101 Conductor circuit 102 Opening part 103 Core substrate 104 Resin layer 105 Opening part 106 Conductor Circuit 107 Conductor post

Claims (18)

A resin composition constituting an insulating layer of a wiring board,
(A) Addition-type norbornene represented by the following formula (1) having at least one crosslinkable group selected from the group consisting of a cyclic ether group, an organic group having a reactive double bond, and an alkoxysilyl group A norbornene-based resin composition, characterized in that an essential resin is (B) spherical silica having an average particle size of 2 μm or less, and the coefficient of thermal expansion at −50 to 150 ° C. is 60 ppm or less.

[X in the formula (1) _{may, -CH 2 -, - CH 2} CH 2 -, or -O- and _{shown, R 1, R 2, R3} , R 4 are each independently a hydrogen atom, a hydrocarbon group Represents a polar group having 1 to 12 carbon atoms, or represents a group containing the polar group. R ₁ , R ₂ , R ₃ and R ₄ are groups each including at least one of a cyclic ether group having 1 to 12 carbon atoms, an organic group having a reactive double bond, or an alkoxysilyl group. n represents an integer of 0 to 2, and the repetition may be different. ] The resin composition according to claim 1, wherein the addition-type norbornene-based resin includes an addition polymer of a norbornene-based monomer represented by the following general formula (2).

Expression (2) X in _{the, -CH 2 -, - CH 2} CH 2 -, or -O- and _{shown, R 1, R 2, R} 3 and R ₄ are each independently a hydrogen atom, A hydrocarbon group, a polar group having 1 to 12 carbon atoms or a group containing the polar group is shown. R ₁ , R ₂ , R ₃ and R ₄ are groups each including at least one of a cyclic ether group having 1 to 12 carbon atoms, an organic group having a reactive double bond, or an alkoxysilyl group. n represents an integer of 0 to 2. ] The norbornene-based resin composition according to claim 1 or 2, wherein the spherical silica is 50% by weight or more. The norbornene-based resin composition according to any one of claims 1 to 3, wherein the spherical silica is surface-treated in advance. The surface treatment agent for pre-treating the spherical silica is a functional group-containing silane, cyclic oligosiloxane, organohalosilane, organoalkoxysilane, alkylsilazane, and two or more repeating units of siloxane bond and alkoxy. The norbornene-based resin composition according to any one of claims 1 to 4, which is at least one compound selected from the group consisting of silicone oils having a group. The functional group-containing silane is selected from the group consisting of epoxy silane, (meth) acryl silane, mercapto silane, amino silane, vinyl silane, isocyanate silane, ureido silane, (5-norbornen-2-yl) alkyl silane and phenyl silane. The norbornene-based resin composition according to claim 5, which is a product. The norbornene-based resin composition according to claim 5, wherein the organohalosilane is selected from the group consisting of trimethylchlorosilane, dimethyldichlorosilane, and methyltrichlorosilane. The alkylsilazanes are selected from the group consisting of hexamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, octamethyltrisilazane and hexamethylcyclotrisilazane. The norbornene-based resin composition according to claim 5. The norbornene-based resin composition according to any one of claims 1 to 8, wherein the cyclic ether group is oxirane or oxetane. The norbornene-based resin composition according to any one of claims 1 to 9, wherein the organic group having a reactive double bond is selected from the group consisting of a vinyl group, an allyl group, an acryloyl group, and a methacryloyl group. It is a laminated body used for a wiring board, Comprising: The laminated body formed by laminating | stacking the resin layer comprised from the resin composition in any one of Claim 1 thru | or 10, and a carrier film. A wiring board comprising a step of forming an insulating layer using the resin composition according to any one of claims 1 to 10, a step of forming a circuit layer, and a step of opening the insulating layer by laser irradiation. Production method. The method for manufacturing a wiring board according to claim 12, wherein the step of forming the insulating layer is performed by applying the resin composition. The method for manufacturing a wiring board according to claim 12 or 13, wherein the step of forming the insulating layer is formed by laminating a film obtained using the resin composition. The method for manufacturing a wiring board according to claim 14, wherein the film in the step of forming the insulating layer is a film with a metal layer. The method for manufacturing a wiring board according to claim 12, comprising a step of heat-curing the insulating layer. The wiring board obtained by the manufacturing method of the wiring board in any one of Claim 12 thru | or 16. A wiring board comprising a resin layer formed using the laminate according to claim 11.

Images