JP2006156821A - Resin composite, resin layer and carrier material/circuit board with resin layer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composite that has a good electrical characteristic and enables fine via holes to be created on the resin layer of a circuit board by laser, a resin layer that has a good electrical characteristic and enables fine via holes to be created by laser, and a carrier material/circuit board that employ the resin layer. <P>SOLUTION: A resin composite constitutes a circuit board insulated layer where via holes are created by exposure and development, and comprises a circular olefin resin with a functional group doubly-bonded to a side chain and a polymerization initiator. In addition, a resin layer is composed of the above-mentioned resin composites. A carrier material with a resin layer is provided with the above-mentioned resin layer formed at least at either side of the material. A circuit board has the above-mentioned resin layer. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

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

  With the recent demand for higher functionality and lighter and thinner electronic devices, electronic components have been increasingly integrated and packaged, and high-speed transmission of electrical signals is required. However, as the density of electronic components increases, speeding up has progressed to such a state that electrical performance such as delay of electrical signals cannot be secured, so deterioration of electrical signals is an issue for high-speed transmission. It has become. The deterioration of the electric signal is the sum of the loss of the electric signal from the conductor and the loss of the electric signal from the dielectric. In particular, the loss of the electric signal from the dielectric due to the interlayer insulating material increases remarkably with the increase in the frequency of the electric signal, and is a main factor for the deterioration of the electric signal at frequencies in the GHz band. . For this reason, generally used epoxy resin, polyimide resin, etc. as interlayer insulation materials for electronic devices such as multilayer wiring boards have insufficient electrical properties such as dielectric constant and dielectric loss tangent, and support high-speed transmission of electrical signals. May be difficult to do.

  Furthermore, in the manufacture of multilayer wiring boards, to increase the area of fine circuits and electrical wiring for high-speed transmission of electrical signals, and to reduce the degradation of electrical signals, electrical wiring is connected in a multilayer straight line ( Stack via) is desired.

  In high-density mounting of the above electronic components, it is necessary to form fine via holes and circuit patterns. The formation method includes dry etching using laser and plasma, etching methods such as chemical etching, and interlayer insulating materials. Examples thereof include a method of selectively exposing and developing using a photosensitive resin. Among these, the method of forming a fine via hole by exposure / development can easily form a fine via hole or circuit pattern without damaging the resin simply by changing the mask during exposure. It is.

  Examples of resins having a low dielectric constant and excellent electrical characteristics include polynorbornene, which is a cyclic cycloolefin polymer (see, for example, Non-Patent Document 1). The adhesiveness of was insufficient.

NiCOLE R.M. GROVE et al. Journal of Polymer Science: part B, Polymer Physics, Vol. 37, 3003-3010 (1999)

An object of the present invention is a resin having a low dielectric constant, excellent electrical characteristics, and excellent adhesion when formed as a resin layer of a circuit board, and capable of forming fine via holes and circuit patterns by photosensitive and developing. It is to provide a composition.
Another object of the present invention is to provide a resin layer that is excellent in electrical characteristics, excellent in adhesion, and capable of forming fine via holes and circuit patterns by photosensitivity and development, and a carrier material with a resin layer using the resin layer, and It is to provide a circuit board.

（６） 前記ノルボルネン系樹脂は、側鎖に重合性二重結合を有する官能基を有するノルボルネン型モノマーと、下記式（２）で表されるモノマーとの付加共重合体を含むものである第（２）項ないし第（５）項のいずれかに記載の樹脂組成物。

（７） 前記重合開始剤は、光および／または熱により重合を開始させるものである第（１）項ないし第（６）項のいずれかに記載の樹脂組成物。
（８） 前記重合開始剤は、光酸発生剤である第（７）項に記載の樹脂組成物。
（９） 前記樹脂組成物は、さらに無機充填材を含むものである第（１）項ないし第（８）項のいずれかに記載の樹脂組成物。
（１０） 第（１）項ないし第（９）項のいずれかに記載の樹脂組成物で構成されていることを特徴とする樹脂層。
（１１） 第（１０）項に記載の樹脂層が、キャリア材料の少なくとも片面に形成されていることを特徴とする樹脂層付きキャリア材料。
（１２） 第（１１）項に記載の樹脂層を有することを特徴とする回路基板。 Such an object is achieved by the present invention described in the following (1) to (12).
(1) A resin composition constituting an insulating layer of a circuit board for forming a via hole and / or a circuit pattern by a photolithography method, and a cyclic olefin resin having a functional group having a polymerizable double bond in a side chain; A resin composition comprising a polymerization initiator.
(2) The resin composition according to item (1), wherein the cyclic olefin-based resin includes a norbornene-based resin.
(3) The resin composition according to (1) or (2), wherein the norbornene-based resin is an addition polymer of a norbornene-type monomer.
(4) The resin according to any one of (1) to (3), wherein the functional group having a polymerizable double bond is a (meth) acryloyl group or an organic group having a (meth) acryloyl group. Composition.
(5) The resin composition according to any one of (2) to (4), wherein the norbornene-based resin has a repeating unit represented by the following formula (1).

(6) The norbornene-based resin contains an addition copolymer of a norbornene-type monomer having a functional group having a polymerizable double bond in the side chain and a monomer represented by the following formula (2) (2 The resin composition according to any one of items (5) to (5).

(7) The resin composition according to any one of (1) to (6), wherein the polymerization initiator is one that initiates polymerization by light and / or heat.
(8) The resin composition according to item (7), wherein the polymerization initiator is a photoacid generator.
(9) The resin composition according to any one of (1) to (8), wherein the resin composition further includes an inorganic filler.
(10) A resin layer comprising the resin composition according to any one of items (1) to (9).
(11) A carrier material with a resin layer, wherein the resin layer according to item (10) is formed on at least one side of the carrier material.
(12) A circuit board comprising the resin layer according to item (11).

According to the present invention, there is provided a resin composition having excellent electrical characteristics, excellent adhesion, and capable of forming fine via holes and circuit patterns by photosensitivity and development when used as a resin layer of a circuit board. be able to.
Further, according to the present invention, a resin layer having excellent electrical characteristics, excellent adhesion, and capable of forming fine via holes and circuit patterns by photosensitivity and development, and a carrier material with a resin layer using the resin layer, and A circuit board can be provided.
Further, when the norbornene resin is used as the cyclic olefin resin, the electrical characteristics are particularly excellent.
Moreover, when the norbornene-type monomer addition polymer is used as the norbornene-based resin, the heat resistance is particularly excellent.

Hereinafter, the resin composition, resin layer, carrier material with a resin layer, and circuit 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 circuit board that forms fine via holes and circuit patterns by photolithography, and has a functional group having a polymerizable double bond in a side chain It contains a cyclic olefin resin and a polymerization initiator. The photolithographic method is a technology for transferring a fine pattern drawn on a glass mask using light. Through the mask, the surface on which the resin layer is applied is irradiated with light, and the pattern is transferred onto the resin layer. To do. Since the wavelength of light to be used is short, this is an effective method for forming a fine pattern.
Moreover, the resin layer of this invention is comprised by the above-mentioned resin composition, It is characterized by the above-mentioned.
The carrier material with a resin layer of the present invention is characterized in that the above-mentioned resin layer is formed on at least one side of the carrier material.
The circuit board of the present invention is characterized by having the above-described resin layer.

First, the resin composition will be described.
The resin composition of the present invention is a resin composition that constitutes a resin layer of a circuit board that is excellent in adhesion to a substrate and that can form fine via holes and fine circuit patterns with high accuracy by photosensitivity and development. is there.

The resin composition includes a cyclic olefin resin having a functional group having a polymerizable double bond in a side chain.
Examples of the cyclic olefin-based resin include monocyclic compounds such as cyclohexene and cyclooctene, norbornene, norbornadiene, dicyclopentadiene, dihydrodicyclopentadiene, tetracyclododecene, tricyclopentadiene, dihydrotricyclopentadiene, and tetracyclopentadiene. And those composed of cyclic olefin monomers such as polycyclic compounds such as dihydrotetracyclopentadiene. Substitutes in which a functional group is bonded to these monomers can also be used. The cyclic olefin-based resin having a functional group having a polymerizable double bond in the side chain is composed of a resin having a functional group having a polymerizable double bond in the cyclic olefin monomer.

  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. Of these, polymers obtained by polymerizing norbornene-type monomers (particularly addition (co) polymerization) are preferred, but the present invention is not limited thereto.

  Examples of 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 of norbornene type monomers and non-conjugated dienes, and other monomers as required. These resins can be obtained by all known polymerization methods.

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, and t-butyl hydrogen peroxide.

  Examples of the ring-opening polymer of the cyclic olefin resin include, for example, (4) a ring-opening (co) polymer of a norbornene-type monomer, and a resin obtained by hydrogenating the (co) polymer if necessary, (5) norbornene Ring-opening copolymer of type monomers and ethylene or α-olefins, and a resin obtained by hydrogenating the (co) polymer if necessary, (6) norbornene type monomers and non-conjugated dienes, or other monomers 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 obtained by ring-opening (co) polymerizing at least one or more norbornene-type monomers by a known ring-opening polymerization method using titanium or a tungsten compound as a catalyst. A co) polymer, and then, if necessary, a hydrogenated carbon-carbon double bond in the ring-opened (co) polymer by a conventional hydrogenation method to produce a thermoplastic saturated norbornene resin. Obtained by.

  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 benzene, toluene, xylene and mesitylene, but are not limited thereto. Diethyl ether, tetrahydrofuran, ethyl acetate, ester, lactone, ketone, amide can also be used. These solvents can be used alone or as a polymerization solvent.

  The molecular weight of the cyclic olefin resin of the present invention can be controlled by changing the ratio of the initiator to 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.

The cyclic olefin resin has a functional group having a polymerizable double bond in a side chain. Thereby, when a resin layer is formed from the said resin composition, adhesiveness with a base material can be improved. Examples of the functional group include vinyl groups, allyl groups, acryloyl groups, methacryloyl groups, and the like, and organic groups having these groups. 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. Among these groups, a (meth) acryloyl group and an organic group having the same are preferable. The cyclic olefin-based resin having a functional group having a polymerizable double bond is a polymer of a cyclic olefin monomer having a functional group having a polymerizable double bond in the side chain as described below, or other polymer It may be a copolymer with a cyclic olefin monomer.
Specific examples of the cyclic olefin having a functional group having a polymerizable double bond in the side chain include 5-vinyl-2-norbornene, 5-allyl-2-norbornene, and 5- (meth) acrylic acid-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) actyl ester Such as Le acid 5-norbornene-2-decyl ester. 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 amount of substitution of the functional group having a polymerizable double bond is not particularly limited, but is preferably 3 to 70 mol%, particularly preferably 5 to 40 mol%, based on the total cyclic olefin resin. When the substitution amount is within the above range, the dielectric constant is particularly excellent. In addition, the cyclic olefin resin having a functional group having a polymerizable double bond in such a side chain is, for example, 1) a modification reaction of a compound having a functional group having a polymerizable double bond in the cyclic olefin resin. 2) by polymerizing a monomer having a functional group having a polymerizable double bond, and 3) using a monomer having a functional group having a polymerizable double bond as a copolymer component. It can be obtained by copolymerizing with other components.

  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, C2-C20 ethylene or α-olefin, such as 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc. , 4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, non-conjugated dienes such as 1,7-octadiene, etc. That.

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

  The norbornene-based resin having a functional group having a polymerizable double bond in the side chain further comprises a norbornene monomer having a functional group having a polymerizable double bond in the side chain, and the following formula (2): It is preferable that it is an addition copolymer with the monomer represented by these. Thereby, it is possible to obtain a resin layer that is particularly excellent in the balance between adhesion and electrical characteristics.

  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 a cyclopentyl group, a cyclohexyl group and a cyclooctyl group, and specific examples of the aryl group include a phenyl group, a naphthyl group and an anthracenyl group. Specific examples of the aralkyl group include a benzyl group and a phenethyl group. Is, the present invention is in no way limited thereto.

An addition copolymer composed of a norborn-type monomer having a functional group having a polymerizable double bond and a monomer represented by the above formula (2) includes a functional group having a polymerizable double bond and a substituent R ₁ . R ₂ , R ₃ , and R ₄ should have favorable characteristics by adjusting the types of functional groups and substituents and the ratio of repeating units having the functional groups and substituents according to the purpose. Can do. For example, the norborn type monomer having a functional group having a polymerizable double bond has a (meth) acryloyl group, thereby improving patterning accuracy by photosensitivity and adhesion to a metal such as copper. , Curing by heating becomes possible, and heat resistance is also improved. As a monomer represented by formula (2), X in formula (2) is —CH ₂ —, R _{1 to} R ₃ are hydrogen, n is 0, R ₄ , for example, when the alkyl group is introduced, norbornene having a methyl group in the side chain is particularly preferable, and a resin film having excellent solvent solubility and excellent electrical characteristics can be obtained when making a varnish. preferable. In this case, the norbornene repeating unit composed of a norborn type monomer having a functional group having a polymerizable double bond is preferably in the range of 5 to 80 mol%. More preferably, it is 5-50 mol%.

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 heat resistance, the smoothness of the surface of the molded article and the like are excellent in balance.
The weight average molecular weight can be evaluated in terms of polystyrene measured by, for example, 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 the case of a cyclic olefin resin whose weight average molecular weight or molecular weight distribution cannot be measured by the above method, it is possible to use a resin having a melt viscosity and a degree of polymerization that can form a resin layer by an ordinary melt processing method. it can. 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.

  The content of the cyclic olefin-based resin having a functional group having a polymerizable double bond in the side chain is not particularly limited, but is preferably 3 to 70% by weight, particularly 5 to 40% by weight of the entire resin composition. preferable. If the content is less than the lower limit, the adhesion to the substrate may be reduced, and if the content exceeds the upper limit, the dielectric constant may be reduced.

The resin composition includes a polymerization initiator. Thereby, the cyclic olefin resin having a polymerizable double bond in the side chain can be subjected to a crosslinking reaction.
The polymerization initiator preferably includes a polymerization initiator that initiates polymerization by light and / or heating, and a photoacid generator.

Examples of the photo and / or thermal polymerization initiator include benzophenones such as benzophenone, benzoylbenzoic acid, 4-phenylbenzophenone and hydroxybenzophenone, benzoin, benzoin ethyl ether, benzoin isopropyl ether and benzoin butyl ether, benzoin isobutyl ether, and the like. Benzoin alkyl ethers, 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- Mention may be made of organic peroxides such as ethyl hexanoate, dicumyl peroxide, t-butyl cumyl peroxide and t-butyl hydroperoxide.
Preferred photoacid generators are onium salts, halogen compounds, sulfates and mixtures thereof. For example, examples of onium salts include diazonium salts, ammonium salts, iodonium salts, sulfonium salts, phosphates, arsonium 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 the counter anion include, but are not limited to, boric acid, arsonium acid, phosphoric acid, antimonic acid, sulfate, carboxylic acid and its chloride. Examples of onium salt photoacid generators include triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluoroborate, triphenylsulfonium tetrafluoroarsenate, triphenylsulfonium tetrafluorophosphate, triphenylsulfonium tetrafluoro. Sulfate, 4-thiophenoxydiphenylsulfonium tetrafluoroborate, 4-thiophenoxydiphenylsulfonium tetrafluoroantimonate, 4-thiophenoxydiphenylsulfonium tetrafluoroarsenate, 4-thiophenoxydiphenylsulfonium tetrafluoro Phosphate, 4-thiophenoxydiphenylsulfonium tetrafluorosulfonate, 4-t-butylphenol Rudiphenylsulfonium tetrafluoroborate, 4-t-butylphenyldiphenylsulfonium tetrafluorosulfonium, 4-t-butylphenyldiphenylsulfonium tetrafluoroantimonate, 4-t-butylphenyldiphenylsulfonium Trifluorophosphonate, 4-t-butylphenyldiphenylsulfonium trifluorosulfonate, Tris (4-methylphenyl) sulfonium trifluoroborate, Tris (4-methylphenyl) sulfonium tetrafluoroborate, Tris ( 4-methylphenyl) sulfonium hexafluoroarsenate, tris (4-methylphenyl) sulfonium hexafluorophosphate, tris (4-methylphenyl) sulfonium hex Fluorosulfonate, tris (4-methoxyphenyl) sulfonium tetrafluoroborate, tris (4-methylphenyl) sulfonium hexafluorantimonate, tris (4-methylphenyl) sulfonium hexafluorophosphate, tris (4-methylphenyl) sulfonium trifluorosulfonate, triphenyliodonium tetrafluoroborate, triphenyliodonium hexafluoroantimonate, triphenyliodonium hexafluoroarsenate, triphenyliodonium hexafluorophosphate, triphenyliodonium trifluoros Ruphonate, 3,3-dinitrodiphenyliodonium tetrafluoroborate, 3,3-dinitrodiphenyliodonium hexa Fluoroantimonate, 3,3-dinitrodiphenyliodonium hexafluoroarsenate, 3,3-dinitrodiphenyliodonium trifluorosulfonate, 4,4-dinitrodiphenyliodonium tetrafluoroborate, 4,4-dinitrodiphenyliodonium hexafluoroantimonate 4,4-dinitrodiphenyliodonium hexafluoroarsenate and 4,4-dinitrodiphenyliodonium trifluorosulfonate may be used alone or in combination. Examples of acid generators containing halogen include 2,4,6-tris (trichloromethyl) triazine, 2-allyl-4,6-bis (trichloromethyl) triazine, α, β, α-tribromo. Methylphenylsulfone, α, α-2,3,5,6-hexachloroxylene, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) -1,1,1,3,3,3-hexa Fluoroxylene, 1,1,1-tris (3,5-dibromo-4-hydroxyphenyl) ethane and mixtures thereof. Examples of the sulfonate-based acid generator include 2-nitrobenzyl tosylate, 2,6-dinitrobenzyl tosylate, 2,4-dinitrobenzyl tosylate, 2-nitrobenzyl methyl sulfonate, 2-nitrobenzyl acetate, 9 , 10-Dimethoxyanthracene-2-sulfonate, 1,2,3-tris (methanesulfonylroxy) benzene, 1,2,3-tris (ethanesulfonylroxy) benzene, 1,2,3-tris (propanesulfonylroxy) Although it is benzene etc., it is not limited to this. Preferably, the acid generator includes 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-butylphenyl) sulfonyltetrakis (Pentafluorophenyl) borate, (4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrakis (pentafluorophenyl) borate and mixtures thereof.

Although content of the said polymerization initiator is not specifically limited, 0.1-10 weight part is preferable with respect to 100 weight part of said cyclic olefin resin, and 0.5-5 weight part is especially preferable. When the content is within the above range, the heat resistance is particularly excellent.
In order to adjust the polymerization start temperature, a plurality of the polymerization initiators may be mixed and used.

Although the said resin composition is not specifically limited, It is preferable that an inorganic filler is included. Thereby, the thermal expansion coefficient of the resin layer can be lowered, and thereby the fatigue resistance reliability can be improved.
Examples of the inorganic filler include talc, fired clay, unfired clay, silicates such as mica and glass, oxides such as titanium oxide, alumina, silica and fused silica, calcium carbonate, magnesium carbonate and hydrotalcite. Carbonates such as aluminum hydroxide, magnesium hydroxide and calcium hydroxide, sulfates or sulfites such as barium sulfate, calcium sulfate and calcium sulfite, zinc borate, barium metaborate, aluminum borate, Examples thereof include borates such as calcium borate and sodium borate, and nitrides such as aluminum nitride, boron nitride and silicon nitride. Among these, silica is preferable. Thereby, especially the dielectric constant of the resin layer can be lowered. Examples of the silica include a silica filler synthesized by a sol-gel method, a silica filler synthesized by a gas phase method, a fused silica filler, and a crystalline silica filler. In particular, a silica filler synthesized by a gas phase method and a silica filler synthesized by a sol-gel method are preferable.

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

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

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

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

  The resin composition contains a cyclic olefin resin having a functional group having a polymerizable double bond in the side chain, a polymerization initiator, and optionally an inorganic filler, but does not contradict the purpose of the present invention. In addition to the said component, other additives, such as a compatibilizer, a leveling agent, an antifoamer, surfactant, an organic filler, antioxidant, a sensitizer, can be contained. These additives can be used alone or in admixture of two or more. Although it does not specifically limit as content of the said additive, 0.01-200 weight part is preferable with respect to 100 weight part of cyclic olefin resin, Especially 0.1-100 weight part is preferable, Most 0.5- 50 parts by weight is preferred.

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

  The resin layer 3 is comprised with the resin composition mentioned above. Thereby, it is possible to obtain a resin layer that is excellent in electrical characteristics such as a low dielectric constant and excellent in the formation of fine via holes by light exposure and development.

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

  As a method for producing the resin layer 3, for example, an inorganic filler solution in which an inorganic filler is dispersed in a solvent, and a cyclic olefin-based resin, an ultrasonic dispersion method, a high-pressure collision dispersion method, a high-speed rotation dispersion method, and the like. A resin varnish obtained by mixing using various mixers such as a bead mill method, a high-speed shear dispersion method, and a rotation and revolution dispersion method can be obtained by a method of applying to a carrier material. 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 using a vacuum printer and a dill pencer. Among these, a method using a die coater is preferable. Thereby, a resin layer having a predetermined thickness can be stably produced. Moreover, after apply | coating the resin layer 3 to a dummy base material etc., it can also obtain in the state of a dry film.

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

  Examples of the carrier material 2 include metal foil made of metal such as copper or copper-based alloy and aluminum or aluminum-based alloy, polyethylene, fluorine-based resin, (aromatic) polyimide resin, polybutylene terephthalate, and polyethylene terephthalate. Examples thereof include a resin film composed of a polyester resin or the like. Among these, a resin film composed of a polyester resin is most preferable. This makes it particularly easy to peel from the resin layer with an appropriate strength. Furthermore, it has excellent stability against reactive diluents. Furthermore, it is possible to prevent the resin composition component dissolved in the reactive diluent and the solvent from migrating to the carrier material.

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

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

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

  As a method for manufacturing such a circuit board, for example, a core board (for example, a board having a double-sided copper foil layer of FR-4) 5 is opened with a drill machine and an opening 51 is provided. A plating process is performed on the opening 51 by electroplating to achieve conduction on both surfaces of the core substrate 5. Then, the conductor circuit 52 is formed by etching the copper foil.

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

Next, the resin layer 3 is formed so as to cover the conductor circuit 52. As a method for forming the resin layer 3, the above-mentioned carrier material with a resin layer is pressed, and the carrier material with a resin layer is laminated using a vacuum press, an atmospheric laminator, a vacuum laminator, a Becquerel type laminating apparatus, or the like. And a method of forming the resin layer 3.
When a metal layer is used as the carrier material, the metal layer can be processed as a conductor circuit.

After peeling off the carrier material, the resin layer 3 is irradiated with light through a glass mask to form the opening 31. As the light, UV light or the like can be used. Formation of the opening 31 by the light exposure can easily form the fine opening 31 by changing the glass mask. Therefore, it is particularly preferable when the resin layer 3 needs to be finely processed.
Next, the formed resin layer 3 is heated and cured. The temperature for heating and curing is preferably in the range of 150 ° C to 300 ° C. In particular, 150-250 degreeC is preferable. Further, the first resin layer 3 is heated and semi-cured, and one or more resin layers 3 are further formed on the resin layer 3, and the semi-cured resin layer 3 is heat-cured again to such an extent that there is no practical problem. By doing so, the adhesion between the resin layers 3 and between the resin layer 3 and the conductor circuit 52 can be improved. The semi-curing temperature in this case is preferably 100 ° C to 250 ° C, more preferably 150 ° C to 200 ° C.
Next, the conductor circuit 32 is formed. The conductive circuit 32 can be formed by a known method such as a semi-additive method. A circuit board can be obtained by these methods.
In addition, the adhesion between the resin layers 3 and between the resin layer 3 and the conductor circuit 52 can be improved by performing plasma treatment on the surface of the resin layer 3 after forming the resin layer 3. As a gas for plasma treatment, oxygen, argon, fluorine, carbon fluoride, nitrogen, or the like can be used singly or in combination. Further, the plasma treatment may be performed a plurality of times.

EXAMPLES Hereinafter, although this invention is demonstrated based on an Example and a comparative example, this invention is not limited to this.
Example 1
1. Preparation of resin varnish Addition polymerization type cyclic olefin resin (Abaterol, manufactured by Promeras Co., Ltd.) comprising 80 mol% of 5-methyl-2-norbornene and 20 mol% of 5- (meth) acrylic acid-2-norbornene obtained by a known method Polyolefin conversion Mw = 177,000, Tg: 360 ° C.) 100 parts by weight, 2 parts by weight of dicumyl peroxide (manufactured by NOF Corporation) as a polymerization initiator, and 1,3,5-trimethylbenzene It melt | dissolved and the cyclic olefin resin solution (A) of 40% of solid content was obtained.

Next, silica filler (average particle size 20 to 30 nm, nanotec, manufactured by CI Kasei Co., Ltd.), ethyltriethoxysilane, and 1,3,5-trimethylbenzene, which are synthesized by a gas phase method, are sheared at high speed. A silica filler solution (B) mixed and dispersed by a dispersion type mixer (manufactured by Nara Machinery Co., Ltd., Micros MICROS-0 type) was obtained.
Next, the silica filler solution (B) is added to the cyclic olefin-based resin solution (A) obtained above so as to be 40 parts by weight of the silica filler with respect to 100 parts by weight of the resin, and mixed by the same mixer as described above. Thus, a resin varnish was obtained.

2. Production of Carrier Material with Resin Layer The resin varnish obtained above was formed with a die coater on a polyester film as a carrier material to a thickness of 20 μm to obtain a carrier material with a resin layer.

3. 3. Production of Circuit Board 3.1 Formation of Inner Layer Circuit and Resin Layer 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 was used to drill After opening with a machine, conduction between the upper and lower copper foils was achieved by electroless 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 and sulfuric acid (Tech SO-G manufactured by Asahi Denka Kogyo Co., Ltd.) to form irregularities by roughening treatment. The resin layer of the obtained carrier material with a resin layer is aligned with the inner layer conductor circuit, and the inner layer conductor circuit is embedded using a vacuum laminator to form a resin layer.

3.2 Formation of vias by exposure / development and formation of outer layer circuit Next, after positioning the resin layer using a chromium-deposited glass mask (manufactured by Towa Process Co., Ltd.) with a via hole pattern formed thereon Then, an opening (blind via hole) having a diameter of 40 μm was formed by exposure and development using an exposure apparatus (UX-1100SM-AJN01 manufactured by Ushio Electric Co., Ltd.). Then, the baking process for 60 minutes was performed at 200 degreeC, and the resin layer was hardened. Next, 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-1211 manufactured by Sumitomo Bakelite Co., Ltd.) was formed on the circuit surface while embedding the circuit with a vacuum laminator, and finally a circuit board was obtained.

(Example 2)
Addition polymerization type cyclic olefin resin consisting of 70 mol% of 5-butyl-2-norbornene and 30 mol% of 5- (meth) acrylic acid-2-norbornene as a cyclic olefin resin (Probatas, abaterol, polyolefin conversion Mw = 257,000) , Tg: 380 ° C.).
(Example 3)
Addition polymerization type cyclic olefin resin consisting of 80 mol% of 5-methyl-2-norbornene and 20 mol% of (meth) acrylic acid 5-norbornene-2-methyl ester as a cyclic olefin resin (Promerus, Abaterol, Mw = 124 in terms of polyolefin) , 000, Tg: 370 ° C.).

Example 4
The same procedure as in Example 1 was performed except that the amount of the polymerization initiator was changed as follows.
Dicumyl peroxide (made by Nippon Oil & Fats) was 0.5 weight part with respect to 100 weight part of cyclic olefin resin.

(Example 5)
The same procedure as in Example 1 was performed except that the amount of the polymerization initiator was changed as follows.
Dicumyl peroxide (manufactured by NOF Corporation) was 5.0 parts by weight with respect to 100 parts by weight of the cyclic olefin resin.

(Example 6)
The procedure was the same as Example 1 except that the following polymerization initiator was used.
(4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrakis (pentafluorophenyl) borate (manufactured by Rhodia Japan)) was used as a polymerization initiator.

(Example 7)
Example 1 was repeated except that the following were used as the cyclic olefin-based resin.
As the cyclic olefin-based resin, 6-methyl-1,4: 5,8-dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene and dicyclopentadiene (molar ratio of 70 / 30) A cyclic olefin resin (polystyrene equivalent Mw = 60,000, Tg: 140 ° C.) obtained by ring-opening polymerization was used.

(Comparative Example 1)
The procedure was the same as Example 1 except that no polymerization initiator was added.

(Comparative Example 2)
The same procedure as in Example 1 was conducted except that the following cyclic olefin-based resin was used.
As a cyclic olefin-based resin, an addition polymerization type cyclic olefin resin (Promerus, Abaterol, Mw = 1,040,000 in terms of polyolefin, Tg: 260 ° C.) composed of 25 mol% of n-hexyl norbornene and 75 mol% of n-norbornene is used. Using.

The following evaluation was performed about the resin layer and circuit board which were obtained above. The evaluation items are shown together with the contents. The obtained results are shown in Table 1.
1. Photosensitivity / developability The SEM observation evaluated the photosensitivity and developability at the time of producing a circuit board. Each code is as follows.
A: There is no resin residue at the bottom of the via, and a good via can be formed.
○: Resin residue is observed at the bottom of the via (the plating property is not affected).
X: A via cannot be formed.

2. Dielectric constant The dielectric constant was evaluated by the perturbation method.

3. Dielectric loss tangent Dielectric loss tangent was evaluated by the perturbation method.

4). Heat resistance Heat resistance was evaluated with a differential thermothermal gravimetric simultaneous measurement device (temperature with a weight loss rate of 100%).

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

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

As is apparent from Table 1, Examples 1 to 7 had a low dielectric constant and dielectric loss tangent, and were excellent in photosensitivity and developability.
Moreover, Examples 1-5 were excellent also in heat resistance.
Moreover, Examples 1-4 were excellent also in adhesiveness especially.
Moreover, Examples 1-4 were excellent also in crack resistance.

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

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

Explanation of symbols

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

Claims (12)

  A resin composition constituting an insulating layer of a circuit board for forming a via hole and / or a circuit pattern by photolithography, a cyclic olefin resin having a functional group having a polymerizable double bond in a side chain, and a polymerization initiator And a resin composition characterized by comprising:   The resin composition according to claim 1, wherein the cyclic olefin-based resin includes a norbornene-based resin.   The resin composition according to claim 1, wherein the norbornene-based resin is an addition polymer of a norbornene-type monomer.   4. The resin composition according to claim 1, wherein the functional group having a polymerizable double bond is a (meth) acryloyl group or an organic group having a (meth) acryloyl group. The resin composition according to any one of claims 2 to 4, wherein the norbornene-based resin has a repeating unit represented by the following formula (1).

6. The norbornene-based resin includes an addition copolymer of a norbornene-type monomer having a functional group having a polymerizable double bond in a side chain and a monomer represented by the following formula (2). The resin composition in any one.

  The resin composition according to any one of claims 1 to 6, wherein the polymerization initiator is one that initiates polymerization by light and / or heat.   The resin composition according to claim 7, wherein the polymerization initiator is a photoacid generator.   The resin composition according to claim 1, wherein the resin composition further contains an inorganic filler.   A resin layer comprising the resin composition according to claim 1.   11. A carrier material with a resin layer, wherein the resin layer according to claim 10 is formed on at least one surface of the carrier material.   A circuit board comprising the resin layer according to claim 11.

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