WO2019142570A1 - Organic insulator, metal-clad laminate sheet, and wiring board - Google Patents

Abstract

This organic insulator 3 is formed of a resin material including, as a main component, a cyclic olefin copolymer. When the resin material is analyzed by time-of-flight secondary ion mass spectrometry, a peak of a hydrocarbon compound is detected in a region of 340-350 molecular weight. In this organic insulator 3, the hydrocarbon compound has at least one functional group selected from acryl group, methacryl group, vinyl group, amino group, and epoxy group. The resin material further comprises a peroxide having a benzene ring. The metal-clad laminate sheet is provided with the organic insulator 3 and a metal foil 5 laminated on at least one surface of the organic insulator 3. The wiring board 10 is provided with multiple insulating layers 11 and conductor layers 13 disposed between the insulating layers 11. The insulating layers 11 are formed of the organic insulator 3.

Description

Organic insulator, metal-clad laminate and wiring board

The present disclosure relates to an organic insulator, a metal-clad laminate and a wiring substrate.

In recent years, speeding up of LSI, high integration, and large capacity of memory have progressed. Along with this, the miniaturization, weight reduction and thickness reduction of various electronic components are rapidly advancing. Heretofore, as an organic insulator material of a wiring substrate used in the field of such electronic components, for example, cyclic olefin copolymers are known (see, for example, Patent Document 1). Such an organic insulator is used for a copper-clad substrate in which a copper foil is adhered to the surface and a wiring substrate for high frequency.

Unexamined-Japanese-Patent No. 2010-100843

The organic insulator of the present disclosure is made of a resin material containing a cyclic olefin copolymer as a main component, and the molecular weight of the surface of the resin material is analyzed using time-of-flight secondary ion mass spectrometry. The peak of the hydrocarbon compound is detected in the region of 340 or more and 350 or less.

The metal-clad laminate of the present disclosure includes the above-described organic insulator and a metal foil laminated on at least one of the organic insulator.

The wiring substrate of the present disclosure includes a plurality of insulating layers and a conductor layer disposed between the insulating layers, and the insulating layer is made of the above-described organic insulator.

It is a sectional view showing an example of a metal tension laminate sheet. It is a sectional view showing an example of a wiring board. Sample No. of Example. 1 shows the results of analysis by time-of-flight secondary ion mass spectrometry (TOF-SIMS) for No.1. Sample No. of the example. 2 shows the results of analysis by time of flight secondary ion mass spectrometry (TOF-SIMS) for No. 2.

Resin materials based on cyclic olefin copolymers are usually used as materials for organic insulators. Such organic insulators are used for wiring boards. Among wiring boards, in particular, wiring boards compatible with high frequencies are required to reduce the surface roughness of metal foils such as copper foils used for organic insulators in order to improve high frequency characteristics. However, when the surface roughness of the metal foil is reduced, the adhesion strength between the metal foil and the organic insulator is reduced.

The organic insulator of the present disclosure is composed of a resin material containing a cyclic olefin copolymer as a main component. The resin material is mainly composed of a cyclic olefin copolymer. Thereby, the relative dielectric constant and the dielectric loss tangent in the high frequency region can be lowered. This is because when the atoms constituting the cyclic olefin copolymer are constrained to one another, they have a stable molecular structure in which the relative positions of the atoms do not easily change.

In addition, when this organic insulator is analyzed using time-of-flight secondary ion mass spectrometry with respect to the resin material constituting the same, the peak of the hydrocarbon compound is in the region of molecular weight 340 or more and 350 or less Is detected. That is, on the surface of this organic insulator, a hydrocarbon compound having a specific molecular weight detected by the above analysis is present. When a hydrocarbon compound having a specific molecular weight is present on the surface of the organic insulator, the adhesive strength between the surface and the metal foil such as copper foil provided on the surface of the resin material can be enhanced. Here, the hydrocarbon compound refers to a compound in which at least two or more carbon atoms (C) are bonded and in which a plurality of hydrogen atoms (H) are contained. For example, alkenes, alkanes and alkynes and cyclo-types which are structural variants of these can be mentioned.

Here, having the cyclic olefin copolymer as the main component means that the ratio of the cyclic olefin copolymer contained in the organic insulator is 60% by mass or more when the inorganic filler is removed. The molecular weight (weight-average molecular weight) of the cyclic olefin copolymer is the same as the molecular weight (tens of thousands to hundreds of thousands) of polymers of ordinary polymer compounds.

Examples of cyclic olefins include norbornene monomers, cyclic diene monomers, and vinyl alicyclic hydrocarbon monomers. Specifically, examples of cyclic olefins include norbornene, vinyl norbornene, phenyl norbornene, dicyclopentadiene, tetracyclododecene, cyclopropene, cyclobutene, cyclopentene, cyclohexene, cyclohexadiene, cyclooctadiene and the like. These cyclic olefins may be used alone or in combination of two or more.

The cyclic olefin copolymer may also be a polyolefin copolymer having a cyclic structure. When the cyclic olefin copolymer is a polyolefin copolymer, it may be a copolymer of a cyclic olefin and another monomer copolymerizable with the cyclic olefin.

As another monomer which can be copolymerized with cyclic olefin, for example, chain olefin, acrylic acid methacrylic acid, acrylic acid ester, methacrylic acid ester, aromatic vinyl compound, unsaturated nitrile, aliphatic conjugated diene and the like can be mentioned. Specifically, as such monomers, ethylene, propylene, butene, acrylic acid, methacrylic acid, fumaric acid, fumaric anhydride, maleic acid, maleic anhydride, methyl acrylate, ethyl acrylate, acrylic acid n- Propyl, isopropyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, styrene, vinyl toluene, acrylonitrile, methacrylonitrile, 1,3-butadiene, 2-methyl-1,3-butadiene And 2,3-dimethyl-1,3-butadiene and the like. These other monomers may be used alone or in combination of two or more.

Furthermore, the cyclic olefin copolymer may have a crosslinkable functional group in the molecule. As the crosslinkable functional group, it is preferable that a crosslinking reaction proceeds by a peroxide having a benzene ring. As the functional group, for example, at least one selected from a vinyl group, an allyl group, an acryl group, a methacryl group and the like is preferable. Among them, a vinyl group is preferable as the functional group in that the heat resistance is high and the dielectric loss tangent described later can be lowered. As such a cyclic olefin copolymer, for example, LCOC-4 manufactured by Mitsui Chemicals, Inc. can be mentioned.

In the case of the cyclic olefin copolymer, the crosslinking site of the cyclic olefin copolymer and the radical species derived from the peroxide having a benzene ring in the molecule are easily miscible and preferentially reactive. From the viewpoint of such reactivity, it is preferable to use a peroxide having at least two benzene rings in the molecule as the peroxide.

As a peroxide having a benzene ring in the molecule, for example, t-butylperoxybenzoate, α, α'-di- (t-butylperoxy) diisopropylbenzene, t-butylcumyl peroxide, dicumyl peroxide and the like Can be mentioned. These compounds are commercially available, for example, as “Percure VS”, “Perbutyl P”, “Perbutyl C”, “Parkyl D” (all from NOF Corporation), and the like in the order described above.

The peroxide having a benzene ring in the molecule may be contained in a proportion of 1 to 8 parts by mass, based on 100 parts by mass of the total of the cyclic olefin copolymer and the peroxide. By including a peroxide having a benzene ring in the molecule in such a proportion, the crosslinking reaction of the cyclic olefin copolymer can proceed efficiently, and in particular, the dielectric loss tangent can be further reduced.

The resin material containing a cyclic olefin copolymer as a main component thus obtained is usually thermosetting, but in this case, the heat formed by reducing the proportion of peroxide having a benzene ring in the organic insulating layer Plastic cyclic olefin copolymers may be included. The inclusion of the thermoplastic cyclic olefin copolymer in the organic insulating layer can lower the dielectric constant and the dielectric loss tangent in the high frequency region of the organic insulator.

Resin materials based on thermosetting cyclic olefin copolymers have peaks of loss tangent and loss elastic modulus obtained by dynamic viscoelasticity test, and temperature at which storage elastic modulus sharply decreases (hereinafter, storage elastic modulus It may be said that the change point is 100 ° C. or more and 150 ° C. or less. When a thermoplastic cyclic olefin copolymer is included therein to form a complex, the loss tangent, storage elastic modulus and loss elastic modulus peak is lower than 100 ° C. in addition to the range of 100 ° C. or more and 150 ° C. or less Peaks of these loss tangent, storage elastic modulus and loss elastic modulus are also confirmed in the temperature range (50 ° C. to 100 ° C.). That is, in the case of a composite of a thermosetting cyclic olefin copolymer and a thermoplastic cyclic olefin copolymer, loss tangent, storage elastic modulus and loss elastic modulus peaks appear respectively in different temperature regions.

The organic insulator of the present disclosure, as described above, when a resin material is analyzed using time-of-flight secondary ion mass spectrometry, the hydrocarbon compound has a molecular weight of 340 or more and 350 or less. The peak is detected. Here, the fact that the hydrocarbon compound is recognized when TOF-SIMS analysis is performed on the surface of the organic insulating layer appears on the chart when, for example, TOF-SIMS analysis is performed under the following conditions: It refers to one in which the peak number of the hydrocarbon compound is 200 or more. In this case, the maximum value of the peak count number of the hydrocarbon compound can be 3000 or less as a standard. Examples of conditions for TOF-SIMS analysis include the following conditions when TRIFT III (manufactured by ULVAC-PHI) is used. The conditions are that the primary ion is ¹⁹⁷ Au 1 cluster ion, the amount of primary ion current is 900 pA (aperture: 3), the measurement area is about 100 μm × 100 μm, and the measurement time is 2 min. A charge correction electron gun is used for measurement.

In this case, the hydrocarbon compound is an acrylic silane compound (molecular weight (MW): 234), a methacrylic silane compound (molecular weight (MW): 248), a vinylsilane compound (molecular weight (MW): 190), an aminosilane compound (molecular weight (MW) : 222) and an epoxysilane compound (molecular weight (MW): 236), preferably including functional groups derived from respective low molecular weight silane compounds. Here, the low molecular weight is preferably equivalent to the molecular weight of the above-mentioned silane compound. Specifically, 180 or more and 300 or less are good.

Moreover, as a functional group contained in a hydrocarbon compound, the acryl group derived from each above-mentioned silane compound, methacryl group, a vinyl group, an amino group, and an epoxy group become a suitable thing. Among these, at least one of an acryl group, a methacryl group and a vinyl group is particularly preferable in that the adhesive strength between the organic insulating layer and the metal foil can be further enhanced.

In addition, even if the above-mentioned hydrocarbon compound is contained in the resin material, when the TOF-SIMS analysis is performed, the peak number of the peak of the hydrocarbon compound appearing in the chart of the TOF-SIMS analysis is noise at the time of analysis If at the level (less than 200), the adhesion strength between the organic insulator and the metal foil remains low.

The organic insulator of the present disclosure may contain additives such as a flame retardant and a stress relaxation agent as needed, as long as the effect of the organic insulator is not impaired.

The flame retardant is not particularly limited. For example, melamine phosphate, melam polyphosphate, melem polyphosphate, melamine pyrophosphate, ammonium polyphosphate, red phosphorus, aromatic phosphate ester, phosphonate ester, phosphinate ester, phosphine oxide, Phosphazene, melamine cyanate, ethylenebispentabromobenzene, ethylenebistetrabromophthalimide and the like can be mentioned. These flame retardants may be used alone or in combination of two or more. From the viewpoints of dielectric loss tangent, flame resistance, heat resistance, adhesion, moisture resistance, chemical resistance, reliability and the like, melamine pyrophosphate, melamine polyphosphate, melam polyphosphate or ammonium polyphosphate is preferable.

The flame retardant is preferably contained in a proportion of 15 to 45 parts by mass, based on 100 parts by mass of the total of the cyclic olefin copolymer and the peroxide. By including the flame retardant in such a proportion, the flame resistance can be further improved with almost no influence on the dielectric loss tangent, the adhesion and the moisture resistance.

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

As the stress relaxation agent, one having an average particle diameter of 10 μm or less may be used. By using a stress relaxation agent having such an average particle diameter, adhesion to a metal foil can be further improved when the resin composition is used, for example, for a metal-clad substrate or the like. The stress relaxation agent may be contained in a proportion of 1 to 10 parts by mass, based on 100 parts by mass of the total of the cyclic olefin copolymer and the peroxide. When the stress relaxation agent is contained in such a ratio, when the organic insulator 1 is applied to, for example, a wiring board or the like, adhesion to a metal foil to be a wiring layer and moisture absorption resistance are further improved. be able to. In addition, connection reliability of through holes can also be improved.

Furthermore, as additives other than flame retardants and stress relaxation agents that can be contained in organic insulators, for example, antioxidants, heat stabilizers, light stabilizers, antistatic agents, plasticizers, pigments, dyes And colorants. Specific examples of the additive include, for example, R-42 (manufactured by Sakai Chemical Co., Ltd.) as a pigment, IRGANOX 1010 (manufactured by BASF) as a heat stabilizer, and CHIMASSORB 944 (manufactured by Ciba) as a light stabilizer. be able to.

The organic insulator can be obtained by using a general manufacturing method from a resin composition containing a cyclic olefin copolymer as a main component. As the sheet molding method, an extrusion molding method, an injection molding method, a doctor blade method or the like can be used. The resin composition is formed into a sheet by such a sheet forming method. Thereafter, a silane compound is applied to the surface of the produced sheet-like compact. Then, after volatilizing an unnecessary solvent from a sheet-like molded object, pressure heating is performed on predetermined conditions. The cyclic olefin copolymer contained in the sheet-like molded product reacts with the silane compound. An organic insulator can be obtained through such a process.

In the organic insulator of the present disclosure, an inorganic filler may be contained in the resin material as long as the dielectric properties and the adhesive strength are not impaired. When preparing a resin composition, it is good to add an inorganic filler in the range which enables sheet forming. Examples of the inorganic filler include silica, talc, mica, clay, calcium carbonate, titanium oxide, barium titanate, carbon black, glass beads, glass hollow spheres and the like. For example, as silica, crushed silica, fused silica, etc. may be mentioned, and one or more kinds may be mixed and used. In this case, the inorganic filler preferably has an average particle size of 10 nm to 10 μm. The content of the inorganic filler is preferably 5 to 40 parts by mass based on 100 parts by mass of the cyclic olefin copolymer.

FIG. 1 is a cross-sectional view showing an example of a metal-clad laminate. The metal-clad laminate 1 includes the above-described organic insulator 3 and a metal foil 5 laminated on at least one of the organic insulator 3. In the metal-clad laminate 1, when TOF-SIMS analysis is performed on the surface of the organic insulator 3 on the metal foil 5 side, peaks of hydrocarbon compounds are observed in the region of molecular weights of 340 to 350 in the chart. Be When the metal-clad laminate 1 has such a configuration, a metal-clad laminate having high adhesion strength between the organic insulator 3 and the metal foil 5 can be obtained. In this case, in the TOF-SIMS analysis, for example, the metal foil 5 is etched from the upper surface of the metal-clad laminate 1 to expose the organic insulator 3 and the surface of the organic insulator 3 is analyzed.

Such a metal-clad laminate 1 is prepared, for example, by preparing a resin composition to be the above-described organic insulator 3, molding the resin composition into a sheet, and forming a semi-cured insulating sheet (organic insulator A step of forming a precursor), a step of forming a metal-clad laminate precursor by applying a silane compound to the surface of the insulating sheet, and depositing a metal foil 5 under a predetermined condition (a metal-clad laminate precursor) It can obtain through the process of heating and pressurizing at temperature, pressure and atmosphere. In this case, the metal foil 5 can be produced in the same manner even in a configuration in which the metal foil 5 is attached to both sides of the organic insulator 3. In addition, when manufacturing the metal-clad laminated board 1, it is good to apply | coat a silane compound on the adhesion surface side with the organic insulator 3 of the metal foil 5. FIG. In this case, a method of immersing the metal foil 5 in a silane compound may be employed. In this case, the silane compound reacts with the cyclic olefin copolymer contained in the insulating sheet by pressure heating and adheres to the metal foil 5.

It does not specifically limit as metal foil 5, For example, Copper foils, such as an electrolytic copper foil and a rolled copper foil, aluminum foil, the composite foil etc. which laminated | stacked these metal foils 5 etc. can be mentioned. Also, the thickness of the metal foil 5 is not particularly limited. For example, it is good that they are 5 micrometers or more and 105 micrometers or less. The surface roughness (Sa) of the metal foil 5 is preferably 0.5 μm or less, and more preferably 0.05 μm or more and 0.3 μm or less.

Next, the wiring board 10 according to the present disclosure will be described based on FIG. The wiring substrate 10 of the present disclosure includes a plurality of insulating layers 11 (organic insulators 3) and a conductor layer 13 made of a metal foil 5 disposed on the insulating layers 11. In this case, the insulating layer 11 is constituted by the organic insulator 3 described above. In addition to the multilayer wiring board in which the insulating layers 11 and the conductor layers 13 are alternately multi-layered, the wiring board 10 can be similarly applied to the wiring board 10 having a cavity structure.

According to the wiring substrate 10 of the present disclosure, since the above-described organic insulator 1 is applied as the insulating layer 11, the relative dielectric constant and the dielectric loss tangent are low in the high frequency region. Further, the wiring substrate 10 has high adhesion strength between the insulating layer 11 and the conductor layer 13. Also in this case, the surface roughness (Sa) of the metal foil 5 is preferably 0.5 μm or less, and more preferably 0.05 μm or more and 0.3 μm or less. When the surface roughness (Sa) of the metal foil 5 is in the above range, it is possible to lower the interface conductivity between the organic insulator 3 as the insulating layer 11 and the metal foil 5 as the conductor layer 13 It becomes useful as the wiring board 10 for high frequency.

Such a wiring board 10 is prepared, for example, in the step of preparing a resin composition to be the above-described organic insulator 3, the step of forming the resin composition into a sheet, and forming a semi-cured sheet-like compact; A step of adhering a metal foil 5 to be a conductor layer on the surface of the sheet-like formed body, a step of etching the metal foil 5 into a predetermined pattern to form a conductor layer 13, a sheet-like formation on which a conductor layer 13 is formed It can be obtained through the process of heating and pressurizing the body under predetermined conditions (temperature, pressure and atmosphere). In the manufacture of the wiring substrate 10, it is preferable to perform plating treatment or the like on the surface of the conductor layer 13 as necessary. Also in this case, the silane compound reacts with the cyclic olefin copolymer contained in the insulating sheet by pressure heating and adheres to the metal foil 5. Even in the case of manufacturing the wiring substrate 10, as a method of applying the hydrocarbon compound between the insulating layer 11 and the conductor layer 13, it is preferable to adopt the same method as the metal-clad laminate 1.

Hereinafter, the above embodiments will be specifically described by way of examples, but the present invention is not limited to these examples.

The components used in the examples are as follows.
(Cyclic olefin copolymer)
Thermosetting COC (LCOC-4): Cyclic olefin copolymer having a crosslinkable functional group (manufactured by Mitsui Chemicals, Inc.)
(Peroxide with benzene ring)
Park Mill D: Dicumyl Peroxide (manufactured by NOF Corporation, with benzene ring)
(Other additives)
As other additives, silica particles having an average particle diameter of 1 μm and a flame retardant (brominated) were added.

As a flame retardant, "SAYTEX 8010 (manufactured by Albemarle)" was used.

Next, these raw materials were blended so as to have the following composition, and stirred at room temperature (25 ° C.) to obtain a resin composition.

The following composition of the resin composition was 94% by mass of thermosetting COC which is a cyclic olefin copolymer, and 6% by mass of perbutyl D which is a peroxide. The flame retardant (SAYTEX 8010) was 30 parts by mass with respect to 100 parts by mass of the total amount of the cyclic olefin copolymer and the perbutyl D. The amount of the silica particles was 20 parts by mass with respect to 100 parts by mass of the total amount of the cyclic olefin copolymer and the perbutyl D.

Next, the obtained resin composition was dissolved in xylene to obtain a resin varnish. The mass ratio of the resin composition to xylene was 40:60. Next, the obtained resin varnish was formed into a sheet using a bar coater, and dried at 150 ° C. for 4 minutes to obtain a sheet-like formed product having a thickness of 15 μm.

Next, the prepared sheet-like compact is cut into small pieces, eight sheets are stacked and stacked to form a semi-cured insulating sheet (precursor of organic insulator), and surface roughness is applied to both sides of this insulating sheet. A metal-clad laminate precursor was produced by laminating a copper foil having a thickness of 18 μm (Sa: average value) at 0.2 μm (the maximum value (Sz) of surface roughness is 1.7 μm). At this time, the silane compound shown in Table 1 was applied to the surface of the copper foil. In addition, the sample (sample No. 1) which does not apply | coat a silane compound on the surface of copper foil was also produced, and the same evaluation was performed. In the case of the sample (sample No. 1) which does not apply | coat a silane compound on the surface of copper foil, the silane compound was used as a surface treatment agent of a silica particle.

Thereafter, the metal-clad laminate precursor was heated at 200 ° C. for 120 minutes under a pressure of 4 MPa to obtain a metal (copper) -clad laminate having a thickness of 0.8 mm.

Next, the copper foil of the obtained metal (copper) -clad laminate was peeled off, and the relative dielectric constant and dielectric loss tangent at 30 GHz were measured by a balanced disk resonator method at room temperature (25 ° C.). The relative dielectric constant was 2.7, and the dielectric loss tangent was 0.002.

Moreover, the interface conductivity of the metal (copper) -clad laminate was measured using the following method. First, the produced metal (copper) -clad laminate was processed to have an area of 50 mm × 50 mm. Next, one of the copper foils on both sides of this processed metal (copper) -clad laminate is etched to expose the organic insulator, and a sample of the metal (copper) -clad laminate having copper foil on one side is etched. Made. A peroxydisulfate (microclean: manufactured by MacDermid) was used for etching the copper foil. Two metal (copper) -clad laminates having a copper foil on one side were prepared for each sample.

Next, two prepared metal (copper) -clad laminates were placed on both sides of a dielectric cylinder (sapphire) so that the copper foil side was on the outside. In this case, the dielectric cylinder is smaller than the diameter of the metal (copper) -clad laminate as a measurement sample. At the time of measurement, two coaxial cables used as input and output conductors were placed outside the dielectric cylinder and at a position where they were sandwiched between two metal (copper) -clad laminates. Thereafter, using a network analyzer, the specific conductivity (interface conductivity) was measured at a frequency of 30 GHz. The interfacial conductivity of the copper foil of the prepared sample was 2 × 10 ⁷ Ω ^-1 · m ^-1 for all samples regardless of whether the silane compound was applied between the insulating layer and the copper foil . In addition, about evaluation of interface conductivity, when the surface roughness (Sa) of copper foil manufactured the sample about each sample using the thing of 0.34 micrometers, as for the interface conductivity measured on the same conditions, all were 0. It was 2 × 10 ⁷ Ω ⁻¹ · m ⁻¹ .

In addition, an organic insulator processed into a size of 70 mm long × 8 mm wide is produced from the organic insulator obtained by peeling the copper foil from the obtained metal (copper) -clad laminate, and dynamic viscoelasticity measurement (DMA) is performed. The behavior of loss tangent, storage modulus and loss modulus was evaluated. The loss tangent and the peak of the loss modulus, and the change point of the storage modulus were both 100 ° C. or more and 150 ° C. or less.

In addition, the copper foil of the obtained metal (copper) -clad laminate was pulled perpendicularly to the organic insulator, and the peel strength when peeling off the copper foil was measured by an autograph, and the results are shown in Table 1. The

In addition, the copper foil was etched with peroxydisulfate (Microclean: manufactured by MacDermid), and TOF-SIMS analysis was performed on the surface of the exposed organic insulator on the copper foil side. As an analyzer, TRIFT III (manufactured by ULVAC-PHI) is used. As conditions, primary ion is ¹⁹⁷ Au 1 cluster ion, primary ion current amount is 900 pA (aperture: 3), measurement area is about 100 μm × 100 μm, measurement The time was 2 min, and a charge correction electron gun was used for measurement. The sample No. of Example is shown in FIG. The results of TOF-SIMS analysis for 1 are shown. The sample No. of Example is shown in FIG. The results of TOF-SIMS analysis for 2 are shown.

Among the prepared samples, for the samples (samples No. 2 to 6) in which the silane compound was applied to the surface of the copper foil, in the chart of TOF-SIMS, the peak derived from hydrocarbon compound in the region of molecular weight 340 to 350 It was observed. The peak counts in the 340-350 region were 600-2200 for all samples. For the sample (sample No. 1) in which the silane compound was not applied to the surface of the copper foil, only the output of the noise level (150 or less) was observed.

The adhesive strength of each sample is, as apparent from the results in Table 1, the surface of the copper foil is not coated with a silane compound and the adhesive strength of a sample (sample No. 1) in which a hydrocarbon compound is not present on the surface is 0. Although it was 25 kN / m, samples (sample Nos. 2 to 6) produced by applying a silane compound between the insulating layer and the copper foil were 0.46 kN / m or more. Among these samples, samples using acrylic silane, methacrylic silane and vinylsilane as the silane compound (samples Nos. 2 to 4) had an adhesive strength of 0.77 kN / m or more.

1 · · · metal-clad laminate 3 · · · organic insulator 5 · · · metal foil 10 · · wiring board 11 · · insulating layer 13 · · conductor layer

Claims (6)

1. It is composed of a resin material containing a cyclic olefin copolymer as a main component, and when the resin material is analyzed using time-of-flight secondary ion mass spectrometry, hydrocarbons in the region of molecular weight 340 or more and 350 or less Organic insulators where compound peaks are detected.
2. The organic insulator according to claim 1, wherein the hydrocarbon compound has at least one functional group of an acryl group, a methacryl group, a vinyl group, an amino group and an epoxy group.
3. The organic insulator according to claim 1, wherein the resin material further contains a peroxide having a benzene ring.
4. A metal-clad laminate comprising the organic insulator according to any one of claims 1 to 3 and a metal foil laminated on at least one of the organic insulators.
5. The metal-clad laminate according to claim 4, wherein the surface roughness of the metal foil on the organic insulator side is 0.05 μm or more and 3 μm or less.
6. A wiring board comprising a plurality of insulating layers and a conductor layer disposed between the insulating layers, wherein the insulating layer is made of the organic insulator according to any one of claims 1 to 3.

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