JP4862259B2 - Resistive paste and multilayer wiring board - Google Patents

Description

  The present invention relates to a resistance paste and a multilayer wiring board.

  In order to cope with the downsizing of electronic devices and the speeding up of circuits, the resistor mounted on the electronic substrate has been improved in performance and has a structure built into the electronic substrate (for example, Patent Documents). 1).

  Conventionally, as a method of forming a resistor on a printed wiring board, a conductive paste such as silver, copper and carbon is used, and a resistance paste mixed with a thermosetting resin and a solvent in a paste form is applied or applied. A method of printing is generally known.

  Furthermore, conventional resistance pastes are generally manufactured by mixing and kneading thermosetting resins such as epoxy resins and phenol resins having a specific structure and average molecular weight, conductive powders, organic solvents, and additives. ing. (For example, refer to Patent Document 2).

JP 7-335403 A JP-A-5-175004

  However, a resistance paste including a thermosetting resin such as an epoxy resin and a phenol resin having a specific structure and an average molecular weight is, for example, 30- In the curing time of about 60 minutes, unreacted groups of the thermosetting resin remain even when a curing accelerator is used. Therefore, the resistance change rate is determined by a test process such as a solder heat resistance test or a boiling test of a wiring board. There is a disadvantage that the value of fluctuates greatly. As a countermeasure, there is a method of increasing the curing time by using a highly acidic or alkaline curing accelerator and increasing the amount thereof, but this method does not provide a sufficient effect. It was.

An object of the present invention is to provide a resistance paste having a small change in resistance change rate due to a solder heat resistance test, a boiling test or the like, and having excellent reliability.
Another object of the present invention is to provide a resistor having a small change in resistance change rate due to a solder heat resistance test, a boiling test or the like, and having excellent reliability.
In addition, it is possible to provide a multilayer wiring board with good stability and reliability of electrical characteristics.

（２）前記導電性粒子は、炭素材料粉末および／または金属粉末である第（１）項に記載の抵抗ペースト。
（３）前記導電性粒子は、カーボンブラックである第（１）項または第（２）項に記載の抵抗ペースト。
（４）前記ポリノルボルネン樹脂の共重合体は、ブチル基を有するノルボルネン９０ｍｏｌ％とトリエトシキシシリル基を有するノルボルネン１０ｍｏｌ％とからなる第（１）項ないし第（３）項のいずれかに記載の抵抗ペースト。
（５）前記抵抗ペーストは、０．１Ｐａ・ｓ以上１００Ｐａ・ｓ以下の粘度を有するものである第（１）項ないし第（４）項のいずれかに記載の抵抗ペースト。
（６）第（１）項ないし第（５）項のいずれかに記載の抵抗ペーストで構成される抵抗体を内蔵した多層配線板。
Such an object is achieved by the present invention described in the following (1) to ( 6 ).
(1) Cyclic olefin type which is a copolymer of polynorbornene resin composed of norbornene having a butyl group represented by the following chemical formula (1) and norbornene having a triethoxysilyl group represented by the following chemical formula (2) A resistance paste obtained by dispersing conductive particles having a particle diameter of 5 nm to 25 μm and silica filler having a particle diameter of 5 nm to 25 μm as an inorganic filler in a resin.

(2) The resistance paste according to item (1), wherein the conductive particles are carbon material powder and / or metal powder.
(3) The resistance paste according to (1) or (2), wherein the conductive particles are carbon black.
( 4 ) The copolymer of polynorbornene resin according to any one of items (1) to (3), comprising 90 mol% of norbornene having a butyl group and 10 mol% of norbornene having a triethoxysilyl group. Resistance paste.
( 5 ) The resistive paste according to any one of (1) to (4) , wherein the resistive paste has a viscosity of 0.1 Pa · s to 100 Pa · s.
( 6 ) A multilayer wiring board incorporating a resistor composed of the resistor paste according to any one of (1) to (5) .

ADVANTAGE OF THE INVENTION According to this invention, the resistance paste with the small change of the value of resistance change by a solder heat test, a boiling test, etc. can be provided, and it was excellent in reliability.
In addition, the present invention can provide a resistor having a small change in resistance change rate due to a solder heat resistance test, a boiling test, etc., and excellent in reliability. Also, the present invention incorporates the resistor. As a result, the resistance change due to the thermal history in the manufacturing process of the multilayer wiring board can be reduced, so that it is possible to provide a multilayer wiring board having excellent stability and reliability of electrical characteristics having a resistor as initially set.

  The present invention is a resistance paste in which conductive particles are dispersed in a cyclic olefin-based resin. In the present invention, by using a cyclic olefin resin as the binder resin, a resistance paste excellent in heat resistance, hygroscopicity, and reliability can be obtained.

  Examples of the cyclic olefin resin used in the present invention include monocyclic compounds such as cyclohexene and cyclooctene, norbornene, norbornadiene, dicyclopentadiene, dihydrodicyclopentadiene, tetracyclododecene, tricyclopentadiene, dihydrotricyclopentadiene, tetra Examples thereof include polymers of cyclic olefin monomers such as polycyclic compounds such as cyclopentadiene and dihydrotetracyclopentadiene, and substituted products in which a functional group is bonded to these monomers.

  Such polymers of cyclic olefin monomers include, for example, (co) polymers of cyclic olefin monomers, copolymers of cyclic olefin monomers and other monomers capable of copolymerization such as α-olefins, and the like. Examples thereof include hydrogenated products of these copolymers. Examples of these known polymers include random copolymers, block copolymers, and alternating copolymers. These cyclic olefin-based resins can be produced by a known polymerization method, and examples of the polymerization method include an addition polymerization method and a ring-opening polymerization method. Among the cyclic olefin-based resins, generally, norbornene-based resins have low hygroscopicity because their main chain skeleton has an alicyclic structure.

  Examples of addition polymers of cyclic olefin resins include (1) addition (co) polymers of norbornene monomers obtained by addition (co) polymerization of norbornene monomers, (2) norbornene monomers and ethylene or α -Addition copolymers with olefins, (3) addition copolymers with norbornene monomers and nonconjugated dienes, and other monomers as required. These resins can be obtained by all known polymerization methods. Among these, polymers obtained by polymerizing norbornene-based monomers (particularly addition (co) polymerization) are preferred, but the present invention is not limited thereto.

Such an addition polymer of a cyclic olefin resin is obtained by coordination polymerization or radical polymerization using a metal catalyst. 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 (1998).
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, t-butyl hydrogen peroxide, and the like.

  Examples of the ring-opening polymer of the cyclic olefin resin include, for example, (4) a ring-opening (co) polymer of a norbornene-based monomer, and a resin obtained by hydrogenating the (co) polymer if necessary, (5) norbornene A ring-opening copolymer of an ethylene monomer and ethylene or α-olefins, and a resin obtained by hydrogenating the (co) polymer if necessary, (6) a norbornene monomer and a non-conjugated diene, or another monomer And a resin obtained by hydrogenating the (co) polymer if necessary. These resins can be obtained by all known polymerization methods.

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

  Examples of the polymerization solvent used for the addition polymerization and ring-opening polymerization include hydrocarbons and aromatic solvents. Examples of the hydrocarbon solvent include pentane, hexane, heptane, and cyclohexane, but are not limited thereto. Examples of the aromatic solvent include, but are not limited to, benzene, toluene, xylene and mesitylene. Diethyl ether, tetrahydrofuran, ethyl acetate, esters, lactones, ketones and amides can also be used. These solvents can be used alone or as a polymerization solvent.

  The molecular weight of the cyclic olefin resin in the present invention 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 through the use of a chain transfer catalyst. In the present invention, α-olefins such as ethylene, propylene, 1-hexane, 1-decene and 4-methyl-1-pentene are suitable for controlling the molecular weight.

As the cyclic olefin resin, one having a polymerizable functional group in the side chain can be used. Further, the polymerizable functional group may be an organic group containing these functional groups, and examples thereof include a group composed of the functional group and a group such as an alkyl group, an ether group, and an ester group. . Thereby, when a resin layer is formed from the said dielectric paste, characteristics, such as adhesiveness with a base material and heat resistance, can be improved.
Examples of the functional group include a hydroxyl group, a carboxyl group, an ester group, an acryloyl group, a methacryloyl group, a silyl group, and an epoxy group (glycidyl ether group). The cyclic olefin-based resin having a polymerizable functional group in the side chain is a polymer of a cyclic olefin monomer having a polymerizable functional group in the side chain described below, or other cyclic olefin monomer. A copolymer may also be used.

  Specific examples of the cyclic olefin monomer having a polymerizable functional group in the side chain include 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-no Boronene-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-hydroxyethyl 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- Norbornene-2-methyl t-butyl Carbonate, 5-methoxy-2-norbornene, (meth) acrylic acid 5-norbornene-2-methyl ester, (meth) acrylic acid 5-norbornene-2-ethyl ester, (meth) acrylic acid 5-norbornene-2 -N-butyl ester, (meth) acrylic acid 5-norbornene-2-n-propyl ester, (meth) acrylic acid 5-norbornene-2-i-butyl ester, (meth) acrylic acid 5-norbornene-2-i -Propyl ester, (meth) acrylic acid 5-norbornene-2-hexyl ester, (meth) acrylic acid 5-norbornene-2-octyl ester, (meth) acrylic acid 5-norbornene-2-decyl ester, 5-trimethoxy Silyl-2-norbornene, 5-triethoxysilyl-2-norbornene, 5- (2 -Trimethoxysilylethyl) -2-norbornene, 5- (2-triethoxysilylethyl) -2-norbornene, 5- (3-trimethoxypropyl) -2-norbornene, 5- (4-trimethoxybutyl)- Examples include 2-norbornene, 5-trimethylsilylmethyl ether-2-norbornene, and 5-methylglycidyl ether-2-norbornene. Most preferred are addition polymers obtained by polymerizing these cyclic olefin monomers, and addition copolymers of these cyclic olefin monomers with other cyclic olefin monomers. Thereby, it can be more excellent in heat resistance.

  The substitution amount of the polymerizable functional group is not particularly limited, but is preferably 3 to 70 mol%, particularly preferably 5 to 40 mol%, based on the entire cyclic olefin resin. When the substitution amount is within the above range, the dielectric constant is particularly excellent. In addition, the cyclic olefin-based resin having a functional group polymerizable in such a side chain is, for example, 1) by introducing a compound having a functional group capable of initiating polymerization into the cyclic olefin-based resin by a modification reaction. By polymerizing a monomer having a functional group capable of initiating polymerization, 3) by copolymerizing a monomer having a functional group capable of initiating polymerization with other components as a copolymer component, or 4) It can be obtained by copolymerizing a monomer having a polymerizable functional group such as an ester group as a copolymerization component and then hydrolyzing the ester group.

  Further, unsaturated monomers copolymerizable with cyclic olefin monomers include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3- Ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, Ethylene or α-olefin having 2 to 20 carbon atoms such as 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicocene; Non-conjugated dienes such as 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene and 1,7-octadiene And the like.

Next, the addition (co) polymer of norbornene resin will be described.
Specifically, the norbornene-based resin having a polymerizable functional group in the side chain preferably has a repeating unit represented by the following formula (1).

X in the formula (1) independently represents —CH ₂ —, —CH ₂ CH ₂ — or —O—. R _{1 to} R ₄ are each independently one selected from hydrogen or a hydroxyl group, carboxyl group, ester group, acryloyl group, methacryloyl group, silyl group, epoxy group, and an organic group containing these functional groups. The above groups are shown, and at least one of them represents a functional group or an organic group containing the functional group. n represents an integer of 0 to 5, and the repetition may be different. Examples of the organic group containing the functional group include groups composed of the functional group and groups such as an alkyl group, an ether group, and an ester group.

  The norbornene-based resin having a polymerizable functional group in the side chain further includes a norbornene-type monomer having a polymerizable functional group in the side chain and a monomer represented by the following formula (2): An addition copolymer is preferred. Thereby, it is possible to obtain a resin layer that is particularly excellent in the balance between adhesion and electrical characteristics.

X in formula (2) independently represents —CH ₂ —, —CH ₂ CH ₂ — or —O—. R _{1 to} R ₄ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, an alkenyl group, an alkynyl group, a vinyl group, an allyl group, an aralkyl group, a cyclic aliphatic group, or an aryl group. 1 or more substituents selected from a group are shown. n represents an integer of 0 to 5, and the repetition may be different.
Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and dodecyl group. Specific examples of the group include vinyl group, allyl group, butynyl group and cyclohexenyl group. Specific examples of the alkynyl group include ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group and the like. 2-butynyl group and the like, specific examples of the cycloaliphatic group include cyclohexyl group, cyclopentyl group and methylcyclohexyl group, and specific examples of the aryl group include phenyl group, naphthyl group and anthracenyl group. Specific examples of the aralkyl group include a benzyl group and a phenethyl group. But are lower, the present invention is in no way limited thereto.

The weight average molecular weight of the cyclic olefin resin is not particularly limited, but is preferably 1,000 to 1,000,000, particularly preferably 5,000 to 500,000, and most preferably 10,000 to 250,000. When the weight average molecular weight (Mw) is within the above range, the properties such as heat resistance and smoothness of the surface of the molded article are excellent in balance.
The weight average molecular weight can be evaluated, for example, in terms of polystyrene measured by gel permeation chromatography (GPC) using cyclohexane or toluene as an organic solvent.

The molecular weight distribution of the cyclic olefin-based resin [the ratio of the weight average molecular weight: Mw to the 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 is preferred. When the molecular weight distribution is within the above range, the electrical characteristics are particularly excellent.
As a method for measuring the molecular weight distribution, for example, it can be measured by GPC using cyclohexane or toluene as an organic solvent.
In addition, in the case of a cyclic olefin resin in which the weight average molecular weight and molecular weight distribution cannot be measured by the above method, those having a melt viscosity and a degree of polymerization that can form a resin layer are used by a normal melt processing method. be able to. Although the glass transition temperature of the said cyclic olefin resin can be suitably selected according to a use purpose, it is 50 degreeC or more normally, Preferably it is 70 degreeC or more, More preferably, it is 100 degreeC or more, More preferably, it is 125 degreeC or more.

In the norbornene-based resin having the structure represented by the general formula (1), the substituents R ₁ , R ₂ , R ₃ , and R ₄ have the type of the substituent and the substituent depending on the purpose. By adjusting the proportion of the repeating unit, the characteristics can be made preferable, and particularly when the above addition copolymer is used, a preferable one can be obtained. For example, when using the general formula (1), when X is —CH ₂ —, R _{1 to} R ₃ are hydrogen, and n is 0, as R ₄ , for example, repetition of introduction of the above alkyl group When it has a unit, since the polynorbornene resin film excellent in flexibility can be obtained, it is preferable. Moreover, it is preferable to have a repeating unit introduced with a silyl group such as a trimethoxysilyl group or a triethoxysilyl group as these substituents because adhesion with a metal such as copper is improved. However, when the ratio of triethoxysilyl group and trimethoxysilyl group is large, the dielectric loss tangent of the polynorbornene resin may increase, so the repeating unit of norbornene having a triethoxysilyl group and / or trimethoxysilyl group is In 1 molecule of norbornene represented by the general formula (1), it is preferably in the range of 5 to 80 mol%. More preferably, it is 5-50 mol%.

  In particular, in order to obtain a resin film having good flexibility, adhesion and dielectric properties, in the above addition polymer, norbornene having 90 mol% having an n-butyl group and norbornene having 10 mol% having a triethoxysilyl group can be used. Polynorbornene comprising 90 mol% unsubstituted (substituent is a hydrogen atom) norbornene having 10 mol% norbornene having a triethosylsilyl group, and polynorbornene having 25 mol% norbornene having 75 mol% unsubstituted norbornyl and n-hexyl group. preferable.

  Further, norbornene having an epoxy group in place of the triethoxysilyl group and trimethoxysilyl group in the side chain is used in a proportion of 5 to 95 mol%, preferably 20 to 80 mol%, more preferably 30 to 70%. In this case, the adhesion with the substrate can be improved.

Examples of the conductive particles used in the resistance paste of the present invention include carbon material powders such as carbon black such as acetylene black, furnace black, thermal black and ketjen black, and graphites such as natural graphite and artificial graphite, silver powder, and the like. And metal powders such as copper powder.
Among these, carbon black is preferable. Thereby, a resistor with a low rate of resistance change can be obtained.
The conductive particles preferably have a particle size of 5 nm to 25 μm, particularly preferably 30 nm to 5 μm. When the particle size is within the above range, the dispersibility in the resin is good, and the printability of the resistance paste is improved.

  The content of the conductive particles can be adjusted by the resistance value of the resistor to be produced. For example, the content of the conductive particles is 0.1 to 50 parts by weight with respect to 100 parts by weight of the resin solid component contained in the resistor paste of the present invention. Is more preferable, and the range of 2 to 10 parts by weight is more preferable. The resistance paste of the present invention can adjust the sheet resistance from 10 mΩ / □ to 100 MΩ / □.

  Examples of the inorganic filler used in the present invention include calcium carbonate, alumina, titanium oxide, magnesium oxide, mica, aluminum carbonate, aluminum hydroxide, magnesium silicate, aluminum silicate, aerosil, spherical silica, fused silica, crushed silica, There are various types of whiskers such as fumed silica, barium sulfate, short glass fibers, aluminum borate and silicon carbide, and these can be used alone or in combination of two or more. A preferred inorganic filler is a silica filler such as Aerosil.

  As a particle size of the said inorganic filler, 5 nm or more and 25 micrometers or less are preferable, More preferably, they are 30 nm-5 micrometers. When the particle size is less than 5 nm, the thickening effect is increased and it may be difficult to control the viscosity of the resistance paste. When the particle size is 25 μm or more, the surface smoothness of the resistance after printing may be impaired. .

  The content of the inorganic filler is preferably 2 to 60 parts by weight, more preferably 10 to 40 parts by weight with respect to 100 parts by weight of the resin solid component contained in the resistance paste of the present invention. The content is preferably equal to or higher than the lower limit in order to improve the resistance of the resistor and the resistance paste printing in the production of the resistor, and the upper limit in order to improve the adhesion between the resistor and the metal. The following is preferred.

The resistance paste of the present invention may contain a crosslinking agent, a coupling agent, a diluent, a flame retardant, etc. as components other than those described above.
Examples of the crosslinking agent include bisazides, peroxides, aliphatic polyamines, alicyclic polyamines, aromatic polyamines, acid anhydrides, dicarboxylic acids, polyhydric phenols and polyamides. For example, 4,4′-bisazide Benzal (4-methyl) cyclohexaneone, 4,4′-diazidochalcone, 2,6-bis (4′-azidobenzal) cyclohexanone, 2,6-bis (4′-azidobenzal) -4-methyl-cyclohexanone, Bisazides such as 4,4′-diazidodiphenylsulfone, 4,4′-diazidodiphenylmethane and 2,2′-diazidostilbene; α, α′-bis (t-butylperoxy) diisopropylbenzene, dicumylper Oxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, t-butylkumi Peroxides such as peroxide, di-t-butyl peroxide and 2,5-dimethyl-2,5-bis (t-butyl peroxide) hexyne-3; hexamethylenediamine, triethylenetetramine and diethylenetriamine, tetraethylenepenta aliphatic polyamines such as amine; diaminocyclohexane, 3 (4), 8 (9) - bis (aminomethyl) tricyclo [5,2,1,0 ^2,6] decane, 1,3- (diaminomethyl) cyclohexane, Cycloaliphatic polyamines such as mensendiamine, isophoronediamine, N-aminoethylpiperazine, bis (4-amino-3-methylcyclohexyl) methane and bis (4-aminocyclohexyl) methane; 4,4′-diaminodiphenyl ether Tellurium, 4,4′-diaminodiphenylmethane, , Α′-bis (4-aminophenyl) -1,3-diisopropylbenzene, α, α′-bis (4-aminophenyl) -1,4-diisopropylbenzene, 4,4′-diaminodiphenylsulfone and metaphenylene Aromatic polyamines such as diamines; phthalic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, nadic anhydride, 1,2-cyclohexanedicarboxylic anhydride, maleic anhydride modified polypropylene and maleic anhydride modified cyclic Acid anhydrides such as olefinic resins; dicarboxylic acids such as fumaric acid, phthalic acid, maleic acid, trimellitic acid and hymic acid; polyhydric phenols such as phenol novolac resin and cresol novolac resin; nylon 6, nylon-66, nylon-610, nylon-1 1, polyamides such as nylon-612, nylon-12, nylon-46, methoxymethylated polyamide, polyhexamethylenediamine terephthalamide, and polyhexamethyleneisophthalamide; These may be used alone or as a mixture of two or more. It is preferable because it can be dispersed uniformly.
Moreover, it is also possible to mix | blend a hardening adjuvant as needed and to raise the efficiency of a crosslinking reaction. The blending amount of the crosslinking agent is not particularly limited, but the weight of the cyclic olefin-based resin is 100 wt% from the viewpoint of the electrical properties of the resulting crosslinked product, physical properties such as water resistance and moisture resistance, and the like. The amount is preferably 0.1 to 50 parts by weight, more preferably 1 to 10 parts by weight with respect to parts.

  Examples of the coupling agent used in the present invention include all silane compounds having an alkoxysilyl group and an organic functional group such as an alkyl group, an epoxy group, a vinyl group, and a phenyl group in one molecule. Silanes having an alkyl group such as triethoxysilane, propyltriethoxysilane and butyltriethoxysilane; Silanes having a phenyl group such as phenyltriethoxysilane, benzyltriethoxysilane and phenethyltriethoxysilane; and butenyltriethoxysilane Silanes having vinyl groups such as propenyltriethoxysilane and vinyltrimethoxysilane; silanes having methacrylic groups such as γ- (methacryloxypropyl) trimethoxysilane; γ-aminopropyltriethoxysilane, N-β ( Ami Ethyl) -γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane and silanes having amino groups such as γ-ureidopropyltriethoxysilane; γ-glycidoxypropyltrimethoxysilane and β -(3,4-epoxycyclohexyl) ethyltrimethoxysilane and other silanes having an epoxy group; γ-mercaptopropyltrimethoxysilane and other silanes having a mercapto group; and the like. Absent. These may be used alone or in combination.

Examples of the diluent used in the present invention include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene and xylene; alcohols such as methanol, isopropanol and cyclohexanol; cyclohexane and methylcyclohexane Alicyclic hydrocarbons; petroleum solvents such as petroleum ether and petroleum naphtha; cellosolves such as cellosolve and butylcellosolve; carbitols such as carbitol, methylcarbitol and butylcarbitol; ethyl acetate, butyl acetate And acetic acid esters such as cellosolve acetate, butyl cellosolve acetate, carbitol acetate and butyl carbitol acetate.
Among these, at least one selected from carbitols and acetates is preferable. Thereby, the printability of the resistance paste and the surface smoothness of the cured product can be improved.

  As a method for producing the resistance paste of the present invention, for example, the above-mentioned various components other than the conductive particles and an appropriate amount of diluent are put into a mixing container, and sufficiently stirred until a uniform varnish is obtained. Particles are added and mixed to form a resin composition. The resin composition is divided into a high-pressure collision dispersion method, a roll mill method, a high-speed rotation dispersion method, a bead mill method, a high-speed shear dispersion method, and a rotation and revolution dispersion method. Although the method of making it disperse | distribute using a dispersion system is mentioned, It is not limited to these methods.

  The resistance paste obtained here preferably has a viscosity of 0.1 Pa · s to 100 Pa · s, whereby various printing methods can be applied in the production of the resistor. The viscosity in the present invention can be measured by a normal shear viscosity measured with an E-type viscometer.

The resistance paste of the present invention preferably has a sheet resistance of 10 mΩ / □ to 100 MΩ / □.
As a method for measuring the resistance value, the resistance value was measured using a precision impedance analyzer (manufactured by Agilent Technologies), and the sheet resistance was converted from the thickness / aspect ratio of the resistance element composed of the resistance paste of the present invention.

The resistor of the present invention, for example, on the lower copper electrode formed on the substrate, the resistor paste obtained above on the lower copper electrode formed on the substrate by a method such as a printing method or a coating method, A resistor layer can be formed in a desired thickness, and this can be heated and cured to produce.
Moreover, it can be set as a resistor element by forming a conductor layer (conductor electrode) in the both ends of the said resistor. In the resistor element, for example, a conductive paste such as a silver paste or a metal such as gold or copper may be vapor-deposited on the conductive layers on both sides. It is also possible to form a metal such as copper by plating.

Examples of the method for forming the resistor layer include a printing method such as screen printing and stencil printing, a coating method such as dispenser, spin coating, ink jetting, and spraying, an applicator, a bar coater, a knife coater, a curtain coater, a die coater, and a gravure coater. However, it is not limited to these.
There is no problem as long as the thickness of the resistor layer can secure a thickness that can withstand the voltage used in accordance with the use of the multilayer wiring board and a thickness that does not form a pinhole. The temperature at which the resistor is cured can be set in consideration of the curing temperature of the resistor resin system and the heat resistance of the multilayer wiring board. In the case of the resin system of the present invention, the temperature is 150 ° C to 300 ° C. Preferably, 160 ° C to 220 ° C is more preferable.

  For the resistor of the present invention obtained above, the dispersibility of the filler in the layer made of the resistance paste is processed with the cross section of the layer and the image obtained by measurement with a scanning electron microscope or transmission electron microscope. Thus, it is possible to quantify the volume ratio and the distance between the fillers.

Next, the manufacturing method of the multilayer wiring board which incorporated the resistor of this invention is demonstrated. FIG. 1 is a view for explaining an example of a method for manufacturing a multilayer wiring board according to an embodiment of the present invention, and FIG. 1 (e) is a cross-sectional view showing the structure of the resulting multilayer wiring board.
First, an insulating substrate 103 with a double-sided metal foil (copper foil) of FR-4 as a core substrate is provided with an opening 102 by opening with a drill machine, and then plated on the opening 102 by electroless plating. The conductive circuit layer 101 is formed by etching the metal foil to obtain a wiring-formed double-sided substrate 109 (FIG. 1A). . The material of the conductor circuit layer 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. Are preferably resistant to the chemicals used in this. Examples of the material of the conductor circuit layer 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 preferable for use as the conductor circuit layer 101 because not only electrolytic plated products and rolled products can be selected, but also various thicknesses can be easily obtained.

  Next, silver paste is printed at any position on the insulating substrate 103 as a resistor electrode to form an electrode 104 (FIG. 1A). Examples of the electrode forming method include a printing method such as screen printing and stencil printing, and a coating method such as dispenser, ink jet, and spray.

  Next, the resistor paste is printed on the electrode 104 to form the resistor 105 (FIG. 1B). Examples of the method of forming the resistor include a printing method such as a screen stencil, a dispenser, an inkjet, and a spray coating method.

Next, the insulating layer 106 is formed on the conductor circuit layer 101 using the resin composition for the insulating layer (FIG. 1C). Examples of a method for forming the insulating layer 106 include a coating method and a film lamination method. Examples of the coating method include a curtain coater, a bar coater, a comma coater, a knife coater, a gravure coater, a die coater, a spin coater, a printing machine, and a vacuum printing. Using an apparatus such as a machine and a dispenser, the insulating layer resin composition is applied to the surface on which the insulating layer is to be formed to form a coating film, and the coating film is applied to a dryer, a nitrogen dryer, and a vacuum dryer. Etc., and a method of forming an insulating layer by drying and curing. As the film laminating method, a coating film is formed on a substrate such as a polyester film using the resin composition for an insulating layer in the same manner as described above, and this is dried and a film with a supporting substrate (insulating) A film) is formed on the surface on which the insulating layer is formed using a vacuum press, a normal pressure laminator, a vacuum laminator, a Becquerel type laminating apparatus, or the like, to form an insulating layer. In addition, instead of a resin base material such as a polyester film, an insulating film is formed on a metal base material in the same manner as described above, and a film with a metal layer (insulating film) is produced and laminated. And a method of forming an insulating layer. In the film with a metal layer, the metal layer can be processed as a conductor circuit.
The insulating layer resin composition may be used for an insulating layer of a wiring board, and includes, for example, those containing an insulating resin such as the cyclic olefin resin, polyimide resin and epoxy resin, and required characteristics. For example, when properties such as heat resistance and dielectric constant are required, an addition (co) polymer of the norbornene-based resin is preferable.
The temperature for heat curing the insulating layer is preferably in the range of 150 ° C to 300 ° C. In particular, 150-250 degreeC is preferable. In the case where a plurality of insulating layers are provided, the first insulating layer is heated and semi-cured to form one or more insulating layers on the insulating layer. It is possible to improve the adhesion between the insulating layer and between the insulating layer and the conductor circuit by heating and curing again to such an extent that it does not occur. In this case, the semi-curing temperature is preferably 150 ° C to 250 ° C, more preferably 150 ° C to 200 ° C.
Further, after the insulating layer is formed, the surface of the insulating layer is subjected to plasma treatment, whereby the adhesion between the insulating layers and between the insulating layer and the conductor circuit can be improved. As the plasma treatment gas, one or a mixture of gases such as oxygen, argon, fluorine, carbon fluoride, and nitrogen can be used. Further, the plasma treatment may be performed a plurality of times.

  Next, the insulating layer 106 is irradiated with a laser to form a via hole 107 (FIG. 1D). As the laser, an excimer laser, a UV laser, a carbon dioxide gas laser, or the like can be used. When a via hole is opened by the laser, a fine via hole can be easily formed regardless of whether the material of the insulating layer is photosensitive or non-photosensitive. Since it can be formed, it is particularly preferable when microfabrication is required. As a method for forming the via hole 107, in addition to the laser irradiation method, dry etching, chemical etching, or the like using a laser or plasma can be used. In the case where the insulating layer 106 is made of a photosensitive resin, the via hole 107 can be formed by selectively exposing and developing the insulating layer 106.

  Next, the second conductor circuit layer 108 is formed (FIG. 1E). The second conductor circuit layer 108 can be formed by a known method such as a semi-additive method. A multilayer wiring board can be manufactured by these methods.

(Example)
EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example and a comparative example, this invention is not limited to this.

[Preparation of resin composition]
Copolymer of 1 g of conductive carbon black (average particle size 30 nm) and 5 g of spherical silica filler (average particle size 5 μm) at room temperature and 20 g of polynorbornene (manufactured by Promelas, abaterol (90 mol% of butyl norbornene and 10 mol% of triethoxysilane norbornene) )) And 20 g of diethylene glycol monomethyl ether, and pre-stirring was performed with a planetary rotary kneader. After the completion of stirring, the mixture was sufficiently kneaded with a three-roll mill to obtain a target resistance paste.

[Preparation of substrate for resistor evaluation]
2A and 2B are (a) a measurement terminal / electrode formation substrate and (b) an evaluation substrate with a resistor, respectively.
A FR-4 double-sided copper-clad laminate (ELC4765, manufactured by Sumitomo Bakelite Co., Ltd.) is laminated with a photosensitive resist film (AUS308, manufactured by Taiyo Ink Manufacturing Co., Ltd.), and a mask on which terminals and electrodes for measurement are formed is applied. Then, exposure was performed using an exposure machine.
After exposure, development was performed to remove excess resist. Thereafter, etching is performed to remove copper, and further to remove the resist, so that a copper terminal 201 for measurement and an electrode 202 for length 5 mm and width 2.5 mm resistor, 4 mm and width 2.0 mm for resistor A substrate (FIG. 2A) on which an electrode 204 for a resistor 203, 3 mm and a width 1.5 mm was formed was obtained.

The resistor paste obtained above is printed with a screen printer so as to coincide with the electrode of the substrate, and heated at 180 ° C. for 3 hours to cure the resin, and the conductor layer is formed on one side of the resistor layer. A substrate with a resistor 205 (FIG. 2B) was obtained. At this time, the thickness of the resistor was measured with a thickness meter so that the sheet resistance could be calculated later. In the case of this example, the thickness was 30 μm.
In this way, a resistor evaluation substrate was produced.

  Example 1 was performed except that graphite particles having a particle size of 24 μm were used as the conductive particles.

  The same procedure as in Example 1 was performed except that conductive carbon black having a particle size of 13 nm was used as the conductive particles.

  The same procedure as in Example 1 was performed except that a silica filler having an average particle size of 9 μm was used as the inorganic filler.

  The same procedure as in Example 1 was performed except that a silica filler having an average particle size of 0.5 μm was used as the inorganic filler.

(Comparative Example 1)
Example 1 was performed except that graphite having a particle size of 27 μm was used as the conductive particles.

(Comparative Example 2)
The same procedure as in Example 1 was performed except that conductive carbon black having a particle size of 3 nm was used as the conductive particles.

(Comparative Example 3)
The same procedure as in Example 1 was performed except that a silica filler having an average particle size of 30 μm was used as the inorganic filler.

(Comparative Example 4)
Example 1 was repeated except that a silica filler having an average particle diameter of 3 nm was used.

(Comparative Example 5)
A bisphenol F type liquid epoxy resin was used in place of the cyclic olefin resin, and the same procedure as in Example 1 was carried out except that 5-phenyl 4-methylimidazole was added as a curing accelerator to the epoxy resin.

The following evaluation was performed about the resistor obtained by each Example and the comparative example. The evaluation items are shown together with the contents. The obtained results are shown in Table 1.
[Solder heat resistance]
The resistor evaluation substrate prepared above was immersed in a solder bath heated to 260 ° C. for 5 seconds. After performing this operation for 5 cycles, the resistance change rate was measured. In addition, the area resistance value was measured with a Precision LCR meter 4284A (manufactured by Hewlett-Packard Company), and the resistance change rate was calculated.
[Boiling test]
The resistor evaluation substrate prepared above was immersed in boiling water boiled to 100 ° C. for 2 hours, and then allowed to stand at room temperature for 22 hours, which was taken as 5 cycles. Thereafter, the resistance change rate was measured.
[Hot oil test]
The resistor evaluation substrate prepared above was immersed in an oil tank heated to 260 ° C. for 10 seconds, and then immersed in a 20 ° C. water tank for 10 seconds for one cycle, and this was performed for 100 cycles. Thereafter, the resistance change rate was measured.

  As shown in Table 1, in Examples 1 to 5, the resistor of the present invention has a small resistance change rate by a solder heat resistance test, a boiling test, etc., and is excellent in reliability.

It is sectional drawing for demonstrating the multilayer wiring board of this invention, and its manufacturing method. It is the figure which looked at the board | substrate for resistor evaluation of this invention from the copper wiring side.

Explanation of symbols

DESCRIPTION OF SYMBOLS 101 Conductor circuit layer 102 Opening part 103 Insulating substrate 104 Resistor electrode 105 Resistor 106 Insulating layer 107 Via hole 108 2nd conductor circuit layer 109 Wiring formation double-sided board 201 Measuring terminal 202 For length 5mm and width 2.5mm resistor Electrode 203 4 mm long and 2.0 mm wide electrode 204 for resistor body 3 mm long and 1.5 mm wide electrode 205 for resistor body

Claims (6)

In a cyclic olefin resin which is a copolymer of a polynorbornene resin composed of norbornene having a butyl group represented by the following chemical formula (1) and norbornene having a triethoxysilyl group represented by the following chemical formula (2) A resistance paste obtained by dispersing conductive particles having a particle size of 5 nm to 25 μm and silica filler having a particle size of 5 nm to 25 μm as an inorganic filler.

  The resistance paste according to claim 1, wherein the conductive particles are carbon material powder and / or metal powder.   The resistance paste according to claim 1, wherein the conductive particles are carbon black. The resistance paste according to any one of claims 1 to 3 , wherein the copolymer of the polynorbornene resin comprises 90 mol% of norbornene having a butyl group and 10 mol% of norbornene having a triethoxysilyl group. The resistor paste is one which has a 100 Pa · s or less viscosity than 0.1 Pa · s according to claim 1 to the resistance paste according to any one of 4. A multilayer wiring board having a built-in resistor composed of the resistive paste according to any one of claims 1 to 5 .

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