JP2011231170A - Insulator ink, and insulating layer, composite layer, circuit board and semiconductor package using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide insulator ink, which enables formation of a flat wiring layer for forming fine wiring lines by a printing method with high accuracy and which gives adhesive force with wiring lines printed on a flat insulating material, and to provide an insulating layer, a composite layer, a circuit board and a semiconductor package using the insulator ink.SOLUTION: The insulator ink comprises at least one of resin among an epoxy resin, phenol resin, polyimide resin, polyamide resin and polyamideimide resin having a molecular weight of 200 or more and 50,000 or less and containing a glycol ether having a molecular weight of 40 or more and less than 1,000. The ink preferably contains at least one of an epoxy resin, phenol resin, polyimide resin, polyamide resin and polyamide imide resin having a molecular weight of 200 or more and 50,000 or less, and a curing agent and a solvent.

Description

  The present invention relates to an insulating ink, a curable insulating resin insulating layer formed using the insulating ink, a composite layer of the insulating layer and a wiring layer, a circuit board and a semiconductor package using the composite layer.

  From the advantages of low energy, low cost, high throughput, on-demand production, etc., the formation of wiring patterns by the printing method is considered promising. This object is realized by forming a pattern by a printing method using an ink paste containing a metal element and then imparting metal conductivity to the printed wiring pattern. Conventionally, a conductive paste in which flaky silver or copper is mixed with a binder of a thermoplastic resin or a thermosetting resin together with an organic solvent, a curing agent, a catalyst, or the like has been used. This conductive paste is used by applying it to an object by dispenser or screen printing and drying at room temperature or by heating to about 150 ° C. to cure the binder resin to form a conductive film. It was. However, since the material for forming a conductive film made of such a conventional conductive paste contains a binder resin, it is difficult to obtain a low resistance film because the contact of particles is hindered. Further, in the conventional silver paste, since the silver particles are in the form of flakes having a particle diameter of 1 to 100 μm, it is impossible in principle to print a wiring having a line width equal to or smaller than the particle diameter of the flake-like silver particles. For this reason, an ink using particles having a particle size of 500 nm or less has been demanded. From these points, the conventional conductive paste is not suitable for forming a fine wiring pattern.

  In order to overcome such drawbacks of the conductive paste, a wiring pattern forming method using metal nanoparticles has been studied, and a method using gold or silver nanoparticles has been studied. Specifically, a dispersion containing gold or silver nanoparticles of 100 nm or less is coated on a substrate with a very fine circuit pattern by a printing method, and then sintered between metal nanoparticles to form a sintered body mold. A wiring layer is obtained.

  Therefore, in recent years, a method for forming a wiring pattern by an ink jet printing method as described in Patent Document 1 and a method for manufacturing a printed wiring board by an offset printing method as described in Patent Document 2 have been proposed. Patent Document 3 proposes a method of manufacturing a multilayer printed wiring board by forming an insulating layer having a hole on a substrate by a printing method and further forming a conductor layer by a printing method.

  According to these production methods, it is possible to produce a multilayer printed wiring board without using large-scale equipment such as press equipment and plating equipment. In addition, since the conductor ink or the insulator ink can be printed only in a necessary place, there is an advantage that the material use efficiency is very high.

  However, printing is usually performed on a flat resin in order to form fine wiring with high accuracy by a printing method. Until now, when producing a wiring board using copper foil, such as the subtractive method or the semi-additive method, the adhesive force between the substrate and the wiring is improved by using the anchor effect of the roughened copper foil. However, with the printing method as described above, it was extremely difficult to obtain an adhesive force due to the anchor effect.

  In addition, when metal nanoparticles such as gold and silver are used alone, a nano-size melting point drop occurs alone. Therefore, when used as printing ink, the metal nanoparticles are covered with an organic protective film to prevent fusion. This is the current situation (for example, Patent Document 4). For this reason, it was necessary to remove the organic protective film in order to obtain a low resistance. Furthermore, in the wiring formed from silver nanoparticles, it is expected that there will be a problem that as the inter-wiring space becomes narrower, the insulation between the circuits is likely to deteriorate due to electrochemical migration. Therefore, as a metal nanoparticle dispersion for forming fine wiring, it is expected to use copper, which has less electrochemical migration and has a lower unit price of the material itself than gold or silver.

JP 2003-80694 A JP-A-11-58921 JP 2003-110242 A JP 2005-81501 A

In recent years, the frequency of electrical signals flowing on the substrate has increased, but even if the wiring is uneven, it leads to a delay in the electrical signal propagation speed, so it is desirable to form a wiring layer that is as flat as possible. It is rare. For this reason, it was a big subject for the printing method application to propose the method which can provide adhesive force even if it is the wiring printed on the flat insulating material.
The present invention provides an insulating ink capable of forming a flat wiring layer for forming fine wiring with high accuracy by a printing method, and obtaining adhesive force with wiring printed on a flat insulating material. The insulating layer, composite layer, circuit board, and semiconductor package used are provided.

  As a result of the study, as a means for forming a flat wiring layer, the substrate surface is flattened by forming a cured insulating resin on the substrate, and the wiring layer is adhered while providing a wiring forming surface having a uniform surface state. I found a method. That is, the present invention is as follows.

  The present invention is [1] an epoxy resin, a phenol resin, a polyimide resin, a polyamide resin, or a polyamideimide resin having a molecular weight of 200 or more and less than 50,000 containing a glycol ether having a molecular weight of 40 or more and less than 1000. Insulator ink containing

  The present invention also provides [2] epoxy resins, phenol resins, polyimide resins, polyamide resins, and polyamideimide resins having a molecular weight of 200 or more and less than 1000 and having a molecular weight of 200 or more and 50,000 or less. The present invention relates to an insulating ink containing at least one of them.

  The present invention also provides [3] the above [1] comprising at least one of epoxy resins having a molecular weight of 200 or more and 50,000 or less, phenol resins, polyimide resins, polyamide resins, and polyamideimide resins, a curing agent, and a solvent. Or it relates to the insulator ink according to [2].

The present invention also relates to [4] the insulating ink according to the above [3], wherein the vapor pressure of the solvent is less than 1.34 × 10 ³ Pa (25 ° C.).

  Further, the present invention is [5] formed by a printing method using the insulating ink according to any one of [1] to [4], and cured by one or both of heat and light irradiation. It relates to an insulating layer (curable insulating resin).

  The present invention also relates to [6] The insulating layer according to [5], wherein the printing method is a printing method using an inkjet device or a dispenser device.

  The present invention also provides [7] at least one element of Cu, Ag, Au, Al, Ni, Co and / or an oxide thereof on the insulating layer according to [5] or [6]. The present invention relates to a composite layer of a wiring layer and an insulating layer formed by applying a wiring ink containing metal nanoparticles of the above by a printing method and imparting electrical conductivity. The metal nanoparticles of the elements and / or their oxides may be any of Pd, Sn, Pb, In, Ga, or a combination thereof.

  [8] The present invention also relates to a circuit board using the composite layer of the wiring layer and the insulating layer according to [8] and [7] as a part for or all of the circuit for electric conduction.

  [9] The present invention also relates to a semiconductor package using the composite layer of the wiring layer and the insulating layer according to [9] and [7] as part or all of the circuit for electric conduction.

  According to the present invention, when a wiring layer is formed on a substrate by a printing method such as an inkjet printing method, an insulating layer (curable insulating resin) is formed using the same printing method, and a wiring is formed thereon. In this way, the adhesion between the wiring layer and the substrate can be increased, and the excellent insulation of the insulating layer (curable insulating resin) enables high insulation reliability between the substrate and the wiring layer, and the conductivity of the wiring layer. In addition, it is possible to easily form all circuit boards and semiconductor packages having adhesion reliability by a printing method.

It is a cross-sectional photograph which shows the external appearance of the composite layer of the insulating layer and wiring layer with high adhesive force of this invention. It is a photograph which shows an example of the wiring layer which did not have an insulating layer and peeled from the board | substrate.

  Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

(Insulator ink)
In the present invention, the insulating material contains at least one of epoxy resin, phenol resin, polyimide resin, polyamide resin, and polyamideimide resin having a molecular weight of 200 or more and 50,000 or less, including glycol ether having a molecular weight of 40 or more and less than 1,000. Use body ink. The molecular weight of 200 to 50,000 is the weight average molecular weight (Mw), which is a value measured by GPC (gel permeation chromatography) and converted to standard polystyrene.
The glycol ether used in the insulator ink is a monomer or oligomer diol having a molecular weight of 40 or more and less than 1000. For example, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1 , 2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 2, 3-pentanediol, 2,4-pentanediol, 3,4-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol, 1,5 -Hexanediol, 2,3-hexanediol, 2,4-hexanediol, 2,5-hexanediol, 3,4-hexanediol, 1,6-hexanediol, 1,2-heptanediol, 1,3- Heptanediol, 1,4-heptanediol, 1,5-heptane All, 1,6-heptanediol, 1,7-heptanediol, 2,3-heptanediol, 2,4-heptanediol, 2,5-heptanediol, 2,6-heptanediol, 3,4-heptanediol 3,5-heptanediol, octanediols,
It is a terminally modified product with a double bond-containing diol such as butenediol or hexenediol, a cyclic diol, a polymer thereof, and / or an alkyl group such as a methyl group or an ethyl group. Further, when the molecular weight is 40 or more and less than 1000, there are many chemically reactive groups for the curing treatment at the time of forming the insulating layer, which is more preferable as the curable insulating resin. When the molecular weight is 40 or more and less than 500, particularly less than 200, the number of chemically reactive groups is further increased, which is more preferable as a curable insulating resin.

  Further, the material (resin) used for the insulator ink in combination with the above may be any material as long as it generally exhibits electrical insulation, for example, epoxy resin, phenol resin, polyimide resin, polyamide resin, polyamideimide resin, Although there are silicone-modified polyamideimide resin, polyester resin, cyanate ester resin, BT resin, acrylic resin, melamine resin, urethane resin, alkyd resin, etc., there is no particular limitation. These may be used alone or in combination of two or more. When these resins are used for printed wiring boards, it is preferable to use thermosetting resins from the viewpoints of insulation reliability, connection reliability, and heat resistance, and epoxy resins and phenol resins are particularly preferable because they have good mechanical properties. Polyimide resin, polyamide resin, and polyamideimide resin are preferable.

  Examples of the epoxy resin contained in the insulator ink include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenol type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, and glycidyl. Ester-type epoxy resins, or glycidyl etherified products of phenols, cresols, alkylphenols, catechols, phenols such as bisphenol F, bisphenol A, and bisphenol S and aldehydes such as formaldehyde and salicylaldehyde, and other bifunctional phenols There are glycidyl ethers, glycidyl ethers of bifunctional alcohols, glycidyl ethers of polyphenols, hydrogenated products, halides, etc. Glycidyl ethers of and connection condensates of reliability from the viewpoint phenols and aldehydes are preferred, can be used in combination several types.

Moreover, the epoxy resin containing one or more glycol ether structures is a structure in which the unit structure and the glycol ether structure in the epoxy resin are appropriately repeated. Examples of the unit structure in the epoxy resin include a bisphenol A structure, a bisphenol F structure, a bisphenol S structure, a biphenol structure, an alicyclic structure, an aliphatic chain, and a glycidyl ester structure. Examples of the glycol ether structure include a diol structure having a molecular weight of 40 or more and less than 1000, such as 1,2-ethanediol ether, 1,2-propanediol ether, 1,3-propanediol ether, 1 , 2-butanediol ether, 1,3-butanediol ether, 2,3-butanediol ether, 1,4-butanediol ether, 1,2-pentanediol ether, 1,3-pentanediol ether, 1,4 -Pentanediol ether, 2,3-pentanediol ether, 2,4-pentanediol ether, 3,4-pentanediol ether, 1,5-pentanediol ether, 1,2-hexanediol ether, 1,3-hexane Diol ether, 1,4-hexanediol ether, 1,5-hexanediol ether, 2,3-hexanediol ether, 2,4-hexanediol ether 2,5-hexanediol ether, 3,4-hexanediol ether, 1,6-hexanediol ether, 1,2-heptanediol ether, 1,3-heptanediol ether, 1,4-heptanediol ether, 1 , 5-heptanediol ether, 1,6-heptanediol ether, 1,7-heptanediol ether, 2,3-heptanediol ether, 2,4-heptanediol ether, 2,5-heptanediol ether, 2,6 -Heptanediol ether, 3,4-heptanediol ether, 3,5-heptanediol ether, octanediol ethers,
It is a terminally modified product with a double bond-containing diol ether such as butenediol ether or hexenediol ether, a cyclic diol ether, a polymer thereof, and / or an alkyl group such as a methyl group or an ethyl group. In addition, when the molecular weight of the glycol ether structure portion is 40 or more and less than 1000, there are many chemically reactive groups for the curing treatment at the time of forming the insulating layer per resin, and the occurrence of curing failure can be suppressed. Preferred as a resin. When the molecular weight is 40 or more and less than 500, the number of the chemically reactive groups is further increased, which is more preferable as the curable insulating resin, and when the molecular weight is 40 or more and less than 200, the heat resistance can be further improved.

The insulator ink of the present invention preferably contains an epoxy resin having a molecular weight of 200 or more and 50,000 or less, a phenol resin, a polyimide resin, a polyamide resin, or a polyamideimide resin, a curing agent, and a solvent.
Examples of the curing agent used together with the epoxy resin contained in the curable insulating resin ink include amines such as diethylenetriamine, triethylenetetramine, metaxylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, m-phenylenediamine, and dicyandiamide, phthalic anhydride Acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl nadic anhydride, pyromellitic anhydride, trimellitic anhydride, etc. acid anhydrides, imidazole, 2-ethyl Imidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 4 5-diphenylimidazole, 2-methylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline, 2-heptadecylimidazoline, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-phenyl-4-methylimidazole, 2- Imidazoles such as ethylimidazoline, 2-isopropylimidazoline, 2,4-dimethylimidazoline, 2-phenyl-4-methylimidazoline, and imino groups are acrylonitrile, phenylene diisocyanate, toluidine isocyanate, naphthalene diisocyanate, methylene bisphenyl isocyanate, melamine acrylate Such as imidazoles, bisphenol F, bisphenol A, bisphenol S, and polyvinylphenol Lumpur acids, and phenol, cresol, alkylphenol, catechol, bisphenol F, bisphenol A, and condensates and their halides and aldehydes such as phenol with formaldehyde and salicylaldehyde, such as bisphenol S. Some of these compounds can be used in combination.

  Among the above-mentioned curing agents, a condensate of a phenol compound having a phenolic hydroxyl group and an aldehyde compound is preferable from the viewpoint of heat resistance and connection reliability. Examples of such condensates are condensates of phenolic compounds such as hydroquinone, resorcinol, catechol, bisphenol A, bisphenol F, bisphenol S, naphthalene diols, biphenols and the like, and phenol novolac resins, resole resins, Examples thereof include bisphenol A novolak resins, cresol novolak resins, and their condensates such as halides, alkyl group-substituted products, and nitrogen-containing group-substituted products. These can be used alone or in combination of two or more.

  When using the said epoxy resin (a) and the condensate (b) of the said phenolic compound and an aldehyde compound in combination, both compounding quantity is an equivalent ratio (epoxy equivalent) of an epoxy equivalent and a hydroxyl equivalent from a sclerosing | hardenable viewpoint. / Hydroxyl equivalent) is preferably 0.70 / 0.30 to 0.30 / 0.70, and 0.65 / 0.35 to 0.35 / 0.65 from the viewpoint of solvent resistance and mechanical properties. More preferably, it is 0.60 / 0.40 to 0.40 / 0.60 from the viewpoint of connection reliability, and 0.55 / 0.45 to 0.00 from the viewpoint of heat resistance. The ratio is particularly preferably 45 / 0.55. If the blending amount of both is out of the above equivalent ratio range, the curability tends to be insufficient.

  As the phenol resin contained in the insulator ink, a condensate of a phenol compound having a phenolic hydroxyl group and an aldehyde compound is preferable from the viewpoint of heat resistance and connection reliability. Such a condensate is, for example, a condensate of a phenol compound such as hydroquinone, resorcinol, catechol, bisphenol A, bisphenol F, bisphenol S, naphthalene diols, biphenols, phenol novolac resin, resole resin, and the like, and an aldehyde compound, Bisphenol A novolak resins, cresol novolac resins and their halides, alkyl group-substituted products, or nitrogen-containing group-substituted products are exemplified. These can be used alone or in combination of two or more.

  A phenol resin containing at least one glycol ether structure is a structure in which a unit structure in a phenol resin and a glycol ether structure are repeated as appropriate. The unit structure in the phenol resin is, for example, a condensate of a phenol compound such as hydroquinone, resorcinol, catechol, bisphenol A, bisphenol F, bisphenol S, naphthalene diols, and biphenols with an aldehyde compound, a phenol novolac structure, and a resole. Examples include a structure, a bisphenol A novolak structure, and a cresol novolak structure. Examples of the glycol ether structure include a diol structure having a molecular weight of 40 or more and less than 1000, such as 1,2-ethanediol ether, 1,2-propanediol ether, 1,3-propanediol ether, 1 , 2-butanediol ether, 1,3-butanediol ether, 2,3-butanediol ether, 1,4-butanediol ether, 1,2-pentanediol ether, 1,3-pentanediol ether, 1,4 -Pentanediol ether, 2,3-pentanediol ether, 2,4-pentanediol ether, 3,4-pentanediol ether, 1,5-pentanediol ether, 1,2-hexanediol ether, 1,3-hexane Diol ether, 1,4-hexanediol ether, 1,5-hexanediol ether, 2,3-hexanediol ether, 2,4-hexanediol ether 2,5-hexanediol ether, 3,4-hexanediol ether, 1,6-hexanediol ether, 1,2-heptanediol ether, 1,3-heptanediol ether, 1,4-heptanediol ether, 1 , 5-heptanediol ether, 1,6-heptanediol ether, 1,7-heptanediol ether, 2,3-heptanediol ether, 2,4-heptanediol ether, 2,5-heptanediol ether, 2,6 -Heptanediol ether, 3,4-heptanediol ether, 3,5-heptanediol ether, octanediol ethers, butenediol ethers, hexenediol ethers and other double bond-containing diol ethers, cyclic diol ethers, etc. And / or a terminal modified product of an alkyl group such as a methyl group or an ethyl group. In addition, when the molecular weight of the glycol ether structure portion is 40 or more and less than 1000, there are many chemically reactive groups for the curing treatment at the time of forming the insulating layer per resin, and the occurrence of curing failure can be suppressed. Preferred as a resin. When the molecular weight is 40 or more and less than 500, the number of the chemically reactive groups is further increased, which is more preferable as a curable insulating resin.

  As the polyamideimide resin contained in the insulating ink, an aromatic polyamide resin containing a skeleton such as bisphenol A, bisphenol F, bisphenol S, or biphenol in the structure is preferable from the viewpoint of heat resistance and mechanical strength. These can be used alone or in combination of two or more.

  A polyamideimide resin containing one or more glycol ether structures is a structure in which a unit structure in a polyamideimide resin and a glycol ether structure are repeated as appropriate. Examples of the unit structure in the polyamideimide resin include aromatic polyamide resins containing a skeleton such as bisphenol A, bisphenol F, bisphenol S, and biphenol.

The polyamideimide resin is obtained by polymerizing an amine component composed of (1) a diamine compound and / or a diisocyanate compound and (2) a tribasic acid anhydride or a tribasic acid anhydride monochloride in a basic polar solvent. These (1) and (2) are obtained by polymerizing a diol compound or, if necessary, an acid component such as a tetrabasic acid dianhydride or a dicarboxylic acid.
The polyimide resin is obtained by polymerizing (1) an amine component composed of a diamine compound and / or a diisocyanate compound and (2) tetrabasic acid dianhydride in a basic polar solvent. ) And (2) are obtained by polymerizing a diol compound or, if necessary, an acid component such as a tribasic acid anhydride, a tribasic acid anhydride monochloride, or a dicarboxylic acid.
The polyamide resin is obtained by polymerizing (1) an amine component composed of a diamine compound and / or a diisocyanate compound, and (2) a dicarboxylic acid. These (1) and (2) are diol compounds, or If necessary, it is obtained by polymerizing tribasic acid anhydride, tribasic acid anhydride monochloride, and tetrabasic acid dianhydride acid components.
Examples of the diamine compound include tolidine, dihydroxybenzidine, dianisidine, diaminodiphenylmethane, dimethyldiaminodiphenylmethane, diaminodiethyldiphenylmethane, diaminodiphenyl ether, diaminodiphenylsulfone, phenylenediamine, xylylenediamine, toluenediamine, and bis (trifluoromethyl) diaminodiphenyl. , Tolidinesulfone, diaminobenzophenone, thiodianiline, sulfonyldianiline, diaminobenzanilide, bis (aminophenoxy) benzene, bis (aminophenoxy) biphenyl, bis (aminophenoxyphenyl) propane, bis [(aminophenoxy) phenyl] sulfone, bis [(Aminophenoxy) phenyl] hexafluoropropane, bis (amino Propyl) tetramethyl disiloxane, diaminobenzidine, polymethylene diamine having 1 to 18 carbon atoms, such as hexamethylenediamine, both terminal amine-modified products of polypropylene glycol and ethylene glycol. Examples of the diisocyanate compound include those obtained by replacing the amino group of the diamine compound with an isocyanate group. Examples thereof include polymethylene diisocyanate having a polymethylene group having 1 to 18 carbon atoms such as naphthalene diisocyanate, tolidine diisocyanate, diphenylmethane diisocyanate, phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate and the like.
Examples of the dicarboxylic acid compound include naphthalenedicarboxylic acid, isophthalic acid, terephthalic acid, sebacic acid, adipic acid, malonic acid, succinic acid, glutaric acid, brassic acid, oxalic acid (anhydride), itaconic acid, dodecanedioic acid, 3,3′-dithiodipropionic acid, 3,3′-thiodipropionic acid and the like can be mentioned.
Examples of the diol compound include resorcinol, hydroquinone, biphenyldiol, bisphenol A, naphthalene diol, aromatic polycarbonate diol, aromatic polycarbonate diol-chloroformate diester, and the like, ethylene glycol, 1,4- Examples thereof include derivatives of aliphatic polycarbonate diols such as butanediol, 1,6-hexanediol, aliphatic polycarbonate diol, and aliphatic polycarbonate diol-chloroformate diester.
Examples of the tribasic acid anhydride and tribasic acid anhydride monochloride include trimellitic anhydride and trimellitic anhydride chloride.
Examples of tetrabasic acid dianhydrides include biphenyl tetracarboxylic dianhydride, pyromellitic anhydride, oxydiphthalic dianhydride, benzophenone tetracarboxylic dianhydride, diphenyl sulfone tetracarboxylic dianhydride, (hexafluoro Isopropylidene) diphthalic dianhydride, terphenyl tetracarboxylic dianhydride and the like.

  Examples of the glycol ether structure include a diol structure having a molecular weight of 40 or more and less than 1000, such as 1,2-ethanediol ether, 1,2-propanediol ether, 1,3-propanediol ether, 1 , 2-butanediol ether, 1,3-butanediol ether, 2,3-butanediol ether, 1,4-butanediol ether, 1,2-pentanediol ether, 1,3-pentanediol ether, 1,4 -Pentanediol ether, 2,3-pentanediol ether, 2,4-pentanediol ether, 3,4-pentanediol ether, 1,5-pentanediol ether, 1,2-hexanediol ether, 1,3-hexane Diol ether, 1,4-hexanediol ether, 1,5-hexanediol ether, 2,3-hexanediol ether, 2,4-hexanediol ether 2,5-hexanediol ether, 3,4-hexanediol ether, 1,6-hexanediol ether, 1,2-heptanediol ether, 1,3-heptanediol ether, 1,4-heptanediol ether, 1 , 5-heptanediol ether, 1,6-heptanediol ether, 1,7-heptanediol ether, 2,3-heptanediol ether, 2,4-heptanediol ether, 2,5-heptanediol ether, 2,6 -Heptanediol ether, 3,4-heptanediol ether, 3,5-heptanediol ether, octanediol ethers, butenediol ethers, hexenediol ethers and other double bond-containing diol ethers, cyclic diol ethers, etc. And / or a terminal modified product of an alkyl group such as a methyl group or an ethyl group. In addition, when the molecular weight of the glycol ether structure portion is 40 or more and less than 1000, there are many chemically reactive groups for the curing treatment at the time of forming the insulating layer per resin, and the occurrence of curing failure can be suppressed. Preferred as a resin. When the molecular weight is 40 or more and less than 500, the number of the chemically reactive groups is further increased, which is more preferable as a curable insulating resin.

  In addition, the weight average molecular weight of the material (resin) used for the insulator ink makes the cross-linking points for the curing treatment dense, and provides good mechanical properties, heat resistance and environmental reliability. For example, when used as an insulating ink that can be applied to a plateless printing method such as ink jet, 200 or more and 35,000 or less are more preferable in order to stably secure ink jet nozzle discharge. In order to suppress an increase in the viscosity of the ink and to use it stably, it is more preferably from 200 to 20,000.

The solvent contained in the insulator ink is preferably a solvent having a vapor pressure at 25 ° C. of less than 1.34 × 10 ³ Pa. With such a solvent, an increase in ink viscosity due to the volatilization of the solvent can be suppressed. For example, when only a solvent having a vapor pressure of 25 ° C. of 1.34 × 10 ³ Pa or more is used, the ink viscosity is remarkably increased due to volatilization of the solvent. For example, in the ink jet printing method, droplets may be ejected from the nozzles of the ink jet head. In addition, the ink jet head tends to be clogged.

Note that a solvent having a vapor pressure of less than 1.34 × 10 ³ Pa and a solvent having a vapor pressure of 1.34 × 10 ³ Pa or more may be used in combination, but in that case, the vapor pressure is 1.34 × The blending ratio of the solvent of 10 ³ Pa or more is preferably 60% by mass or less based on the mass of the total amount of the solvent, and more preferably 50% by mass or less from the viewpoint of suppressing an increase in ink viscosity due to solvent volatilization. Further, it is more preferable that the content be 40% by mass or less from the viewpoint of the ability to eject droplets from the nozzles of the inkjet head. Various solvents can be used as long as the vapor pressure is in a desired range and the insulating resin is dispersed or dissolved.

The solvent having a vapor pressure at 25 ° C. of less than 1.34 × 10 ³ Pa may be any solvent that can dissolve the curable resin. Specifically, sulfolane, propylene carbonate, γ-butyrolactone, cyclohexanone, N-methyl -2-pyrrolidone, anisole, ethylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, triethylene glycol monomethyl ether, triethylene glycol dimethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol dimethyl ether, diacetone alcohol, 1,3-butylene glycol diacetate Propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, tetradecane, methyl lactate, ethyl lactate, etc. It is. Specific examples of the solvent having a vapor pressure at 25 ° C. of 1.34 × 10 ³ Pa or more include methyl ethyl ketone, methyl isobutyl ketone, toluene, isopropyl alcohol and the like. These solvents can be used alone or in combination of two or more.

  The content ratio of the solvent in the insulating ink is not particularly limited, and it is preferable to appropriately adjust the viscosity and surface tension of the ink at 25 ° C. to be within the ranges shown below. Thus, it is preferably 30 to 99% by mass.

  The viscosity of the insulator ink is preferably 50 mPa · s or less at 25 ° C. If the viscosity of the insulating ink is 50 mPa · s or less, it is possible to more reliably prevent the occurrence of non-ejection nozzles during inkjet printing and the occurrence of nozzle clogging. The viscosity of the insulator ink is more preferably 1 to 30 mPa · s at 25 ° C. By setting the viscosity of the insulating ink within this range, the droplet diameter can be reduced, the landing diameter of the insulating ink can be further reduced, and it is easy to cope with the formation of a fine pattern.

  The surface tension of the insulating ink at 25 ° C. is preferably 20 mN / m or more, and the surface tension can be adjusted with a surface conditioner. When the surface tension of the insulator ink is less than 20 mN / m, the droplet of the insulator ink wets and spreads after landing on the substrate, and there is a tendency that a flat thick film cannot be formed. The surface tension of the insulator ink is more preferably in the range of 20 to 80 mN / m. This is because when the surface tension of the insulating ink exceeds 80 mN / m, the inkjet nozzles tend to be clogged. From the viewpoint of flat film formation and stable inkjet discharge, it is more preferably 20 to 40 mN / m.

  As the surface conditioner to be added to the insulator ink, for example, one kind selected from silicone, vinyl, acrylic, and fluorine can be used alone, or two or more kinds can be used in combination. For example, such commercially available surface conditioners include BYK-300, BYK-302, BYK-306, BYK-310, BYK-315, BYK-320, BYK-322, BYK-323, BYK-325. BYK-330, BYK-331, BYK-333, BYK-337, BYK-340, BYK-344, BYK-370, BYK-375, BYK-377, BYK-350, BYK-352, BYK-354, BYK -355, BYK-358N, BYK-361N, BYK-392, BYK-UV3500, BYK-UV3510, BYK-3570, BYK-Silclean3700 (above, manufactured by BYK Japan Japan Co., Ltd., trade name), OX-880EF, OX- 881, OX-883, OX-883HF, X-70, OX-77EF, OX-60, OX-710, OX-720, OX-720EF, OX-750HF, LAP-10, LAP-20, LAP-30, 1970, 230, LF-1980, LF- 1982, LF-1983, LF-1984, LF-1985, LHP-90, LHP-91, LHP-95, LHP-96, 1711, 1751N, 1761, LS-001, LS-050 (above, Enomoto Kasei Co., Ltd.) Manufactured, trade name), SH200-100CS, SH7PA, 11ADDITIVE, SH28PA, SH-29PA, SH-30PA, ST80PA, ST83PA, ST86PA, ST90PA, ST97PA, ST105PA (trade name, manufactured by Toray Dow Corning Co., Ltd.), Polyflow No. . 3, Polyflow No. 7, Polyflow No. 50E, Polyflow No. 50EHF, Polyflow No. 54N, Polyflow No. 55, Polyflow No. 64, polyflow no. 75, Polyflow No. 77, Polyflow No. 85, Polyflow No. 85HF, Polyflow No. S, Polyflow No. 90, polyflow no. 90D-50, Polyflow No. 95, Polyflow No. 300, Polyflow No. 460, polyflow WS, polyflow WS-30, polyflow WS-314 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) and the like. These may be used alone or in combination of two or more.

  In addition to the above, additives such as a silane coupling agent can be appropriately added to the insulating ink.

(Method of forming insulating layer)
The insulating layer (hereinafter also referred to as curable insulating resin) formed in the present invention will be described. Usually, the curable insulating resin is formed by a printing method such as an inkjet printing apparatus or a dispenser apparatus. An insulator ink applicable to such a printing method is referred to as a curable insulating resin ink for printing method (hereinafter abbreviated as insulator ink).

  The insulating layer formed in the present invention is formed by the following process, for example. That is, a first step of forming an insulating ink on a substrate by a printing method, and if necessary, removing the solvent (for example, heat treatment and / or vacuum deaeration) and curing the insulating ink (for example, heat treatment or ultraviolet irradiation) Etc.) to form an insulating layer.

  The insulator ink contains glycol ether and / or a glycol ether structure-containing resin, and if necessary, contains a curing agent and a solvent. Moreover, you may mix | blend a hardening accelerator, a coupling agent, antioxidant, a filler, a surface conditioner, etc. The resin used for the insulator ink is obtained by dissolving a monomer, an oligomer, or the like in a solvent as necessary, and applying to the substrate, followed by heat treatment to remove the solvent and cure the resin to obtain a curable insulating resin (insulating layer). .

  Insulator ink printing methods include inkjet printing, super inkjet printing, screen printing, transfer printing, offset printing, jet printing, dispenser, jet dispenser, needle dispenser, comma coater, slit coater, die coater, gravure coater, letterpress printing, Intaglio printing, gravure printing, soft lithography, dip pen lithography, spray coater, spin coater, dip coater, electrodeposition coating can be used, among them inkjet printing, super inkjet printing, screen printing, transfer printing, offset printing, jet printing Any one selected from the group consisting of a method, a dispenser, a needle dispenser, a comma coater, a slit coater, a die coater, and a gravure coater It is preferred. Among them, the ink jet device or dispenser device can print a desired amount of ink at a desired position without using a special plate, and has features such as material utilization efficiency and ease of adapting to pattern design changes. preferable.

  As an inkjet printing method (inkjet apparatus), for example, a piezo method that discharges a liquid by vibration of a piezo element, a thermal method that discharges a liquid by utilizing the expansion of the liquid by rapid heating, and the like are generally reported. You can use the method. Among these, the piezo method is preferable from the viewpoint that the ink is not heated. In order to carry out such an ink jet printing method, for example, a normal ink jet apparatus can be used. The optimum nozzle diameter of the head that ejects ink can be selected depending on the desired droplet size.

  As a method of removing the solvent after applying the insulating ink to the substrate, a heat treatment method of heating the substrate or blowing hot air can be employed. Such heat treatment can be performed, for example, at a heating temperature of 80 to 200 ° C. and a heating time of 0.1 second to 2.0 hours. When a thermosetting resin is used as the resin, the resin can be cured after removing the solvent or simultaneously with removing the solvent. For example, in the case of an ultraviolet curable resin, the resin can be cured by irradiating ultraviolet rays after removing the solvent.

(Method for forming wiring layer and composite layer)
The wiring layer formed in the present invention is formed by the following process, for example. That is, the wiring layer is formed by a first step of forming wiring ink on the insulating layer by a printing method, and a second step of performing sintering and reduction treatment for removing the solvent and imparting conduction as necessary. A composite layer is formed by combining the insulating layer and the wiring layer. Then, as a third step, the composite layer may be formed by printing an insulating ink so as to be overlapped with the formed wiring. The formation of the insulating layer and the formation of the wiring layer described above are repeated, and a multilayer is formed. It can also be converted.

  The wiring layer formed in the present invention is characterized by containing at least one element of Cu, Ag, Au, Al, Ni, and Co.

  The wiring layer formed in the present invention is usually formed on a curable insulating resin (insulating layer) by a printing method. It is preferable that the wiring ink for printing methods applicable to such a printing method contains a metal nanoparticle and a solvent, and a commercially available metal nanoparticle dispersion ink can be applied. Moreover, the wiring ink applicable to a printing method can also be obtained by disperse | distributing a metal nanoparticle to a solvent.

  The metal nanoparticles used in the present invention will be described. As the metal nanoparticles, any of Cu, Ag, Au, Al, Ni, Co and oxides thereof can be used, and a metal salt and a metal complex may be contained as a small amount of impurities. The particles may be entirely metal, core-shell metal particles whose surroundings are oxides or almost all of them are oxides (for example, copper oxide), and other elements as long as they can exhibit electrical conductivity after normal processing or treatment. Or a compound thereof. In addition, particles having cuprous oxide and a core / shell structure are more preferable because they can be easily reduced. A commercial item may be used for these metal nanoparticles, and it is also possible to synthesize | combine using a well-known synthesis | combining method. These metal nanoparticles can be used individually by 1 type or in combination of 2 or more types, In order to prevent oxidation and aggregation of a particle, you may use the dispersing agent and the surface treating agent.

  When obtaining wiring ink applicable to the printing method by dispersing metal nanoparticles in a solvent, the metal generally has a large specific gravity, and when the particle size is large, it tends to settle by its own weight and keep the dispersion state stable. From the viewpoint of difficulty, the primary particle diameter of the metal nanoparticles is preferably 1 to 300 nm as an average particle diameter, and from 5 to 200 nm from the viewpoint of dispersibility when dispersed in a dispersion medium without using a dispersant. It is more preferable that the thickness is 10 to 100 nm because it is easy to make a conductor (lower resistivity) by continuing good dispersibility and reducing treatment described later. The average primary particle size is calculated by calculating the arithmetic average particle size from the particle size distribution of the volume fraction with respect to the particle size obtained from the intensity of scattered light measured at 25 ° C. by the laser diffraction scattering method, or the nitrogen adsorption BET When the average particle diameter is measured in the powder state, the specific surface area measured by the method is used to calculate the particle diameter based on the specific gravity of the primary particles and assuming that the particle shape is a true spherical particle. Is generally obtained by the latter method.

  When obtaining a wiring ink applicable to a printing method by dispersing metal nanoparticles in a solvent, the average dispersed particle size including secondary aggregates is preferably 500 nm or less. When the average dispersed particle size is 500 nm or less, for example, in the inkjet printing method, problems such as nozzle clogging hardly occur, which is more preferable. Although there may be particles having a dispersed particle diameter of 500 nm or more, it is preferable that the maximum dispersed particle diameter is 2 μm or less because clogging does not occur in ink jet printing.

  The content ratio of the solvent in the wiring ink for printing method is not particularly limited, and it is preferable to appropriately adjust the ink so that the viscosity and surface tension at 25 ° C. are within the ranges shown below. It is preferable to be 30 to 99% by mass with respect to the mass of the wiring ink for use.

  The viscosity of the wiring ink for printing method is preferably 50 mPa · s or less at 25 ° C. If the viscosity of the wiring ink for printing method is 50 mPa · s or less, it is possible to more reliably prevent the occurrence of non-ejection nozzles during nozzle printing and the occurrence of nozzle clogging. Further, the viscosity of the wiring ink for printing method is more preferably 1 to 30 mPa · s at 25 ° C. By setting the viscosity of the wiring ink for printing method within the above range, the diameter of the droplet can be reduced, and the landing diameter of the wiring ink for printing method tends to be further reduced. This facilitates formation of fine wiring.

The surface tension at 25 ° C. of the wiring ink for printing method is preferably 20 mN / m or more. When the surface tension of the printing method wiring ink is less than 20 mN / m, the printing method wiring ink droplet spreads on the curable insulating resin after landing and tends to be unable to form a flat thick film. The surface tension of the wiring ink for printing method is more preferably in the range of 20 to 80 mN / m. This is because when the surface tension of the wiring ink for printing method exceeds 80 mN / m, there is a tendency that ink jet nozzle clogging tends to occur. From the viewpoint of the formation of a flat thick film and stable inkjet discharge properties, it is more preferably 20 to 50 mN / m.
(Wiring formation method)

  As a printing method of the wiring ink for the printing method, a printing method similar to the formation of the insulating layer can be used. Inkjet printing, super inkjet printing, screen printing, transfer printing, offset printing, jet printing method, dispenser, jet dispenser, needle dispenser, comma coater, slit coater, die coater, gravure coater, letterpress printing, intaglio printing, gravure printing, particle deposition method , Soft lithograph, dip pen lithograph, spray coater, spin coater, dip coater, electrodeposition coating can be used. Among them, inkjet printing, super inkjet printing, screen printing, transfer printing, offset printing, jet printing method, dispenser, needle Any one selected from the group consisting of a dispenser, a comma coater, a slit coater, a die coater, and a gravure coater is preferable. In particular, the ink jet printing method and the super ink jet printing method can print a desired amount of ink at a desired position without using a special plate, and have characteristics such as material utilization efficiency and ease of adapting to pattern design changes. And more preferable.

  As the inkjet printing method, for example, a commonly-known ejection method such as a piezo method for ejecting a liquid by vibration of a piezo element or a thermal method for ejecting a liquid by utilizing the expansion of the liquid by rapid heating can be used. . Among these, the piezo method is preferable from the viewpoint that the ink is not heated. In order to carry out such an ink jet printing method, for example, a normal ink jet apparatus can be used. The optimum nozzle diameter of the head that ejects ink can be selected depending on the desired droplet size.

  As a method for removing the solvent after the wiring ink for printing method is deposited on the substrate, a heat treatment method in which the substrate is heated or hot air is blown can be employed. Such heat treatment can be performed, for example, at a heating temperature of 50 to 200 ° C. and a heating time of 0.1 second to 2.0 hours. In addition, the solvent can be removed in a vacuum environment.

(Conducting method)
A method for making the wiring layer into a conductor, for example, reduction treatment or sintering treatment may be any method suitable for each wiring layer, and is not particularly limited. The volume resistivity after the conductor is desirably 1 × 10 ⁻⁵ Ω · m or less. If the volume resistivity is higher than this, it may not be used as electrical wiring. From the viewpoint of electrical conductivity as electrical wiring, the volume resistivity is more preferably 1 × 10 ⁻⁶ Ω · m or less, and from the viewpoint of use as a suitable fine wiring with little electrical resistance loss, the volume resistivity is More preferably, it is 1 × 10 ⁻⁷ Ω · m or less.

  For example, in the case of a wiring layer using copper particles containing copper oxide as metal nanoparticles, a reducing method using atomic hydrogen or a reducing gas atmosphere such as hydrogen, ammonia, formic acid, etc. An example of this is the method of making the conductor heated below. Some of these conductorization methods can be used in combination.

Examples of the method for generating atomic hydrogen include a method using a hot wire apparatus. For example, the pressure in the apparatus is reduced to 10 ⁻³ Pa or less to remove the air in the system. Next, a raw material gas containing hydrogen such as hydrogen, ammonia or hydrazine is sent from a gas inlet to a shower head for diffusing the gas in the chamber. The gas diffused from the shower head passes through a high-temperature catalyst body (e.g., energized and heated to a high temperature, for example, 1700 ° C.) made of tungsten wire, for example, and the source gas is decomposed to generate atomic hydrogen. The copper oxide particles are reduced by the atomic hydrogen, and sintering proceeds. It is also possible to insert a shutter or a shielding plate with a gap that does not block the gas between the catalyst body heated to a high temperature and the sample substrate so that the substrate does not directly receive the radiant heat from the catalyst body. During this process, the temperature of the substrate is kept at 50 ° C. or lower unless directly receiving the radiant heat from the catalyst body or heating the substrate holder. Fusion progresses.
In the present invention, by forming the wiring (wiring layer) and imparting the metal conductivity at a low temperature of 200 ° C. or less, it is not necessary to require the substrate, the insulating layer, etc. to have a characteristic (heat resistance) that can withstand high temperature heating. ,preferable.

An example of a method for making a conductor heated in a reducing gas atmosphere is a treatment method using formic acid gas. As the processing gas, formaldehyde and methanol can be used because formaldehyde and methanol become formic acid when oxidized. For example, when formaldehyde is introduced, formic acid is generated by the reaction of reducing copper oxide, and as a result, the same effect as formic acid gas is obtained. For example, an inert gas such as nitrogen gas, argon gas, or carbon dioxide gas is used as a carrier gas, and a processing gas such as formic acid, formaldehyde, or methanol is introduced into the chamber and heated to 140 ° C. or higher to form metal nanoparticles. A wiring layer using copper particles containing copper oxide can be made into a conductor. Either the order of introduction of the processing gas into the chamber or heating may be first, but if liquid or mist of formic acid adheres to the wiring layer, conductorization does not proceed and the wiring layer dissolves in copper formate. Therefore, it is preferable to introduce the processing gas after preheating to 100 ° C. or higher which is the boiling point of formic acid, and it is more preferable to introduce the processing gas after heating to 140 ° C. or higher which is the processing temperature. Further, as a temperature condition, there is no significant difference in the effect even if the treatment is performed at a temperature exceeding 200 ° C. Therefore, the conductor treatment can be performed in a temperature range of 140 ° C. or more and 200 ° C. or less.
In the present invention, by forming the wiring (wiring layer) and imparting the metal conductivity at a low temperature of 200 ° C. or less, it is not necessary to require the substrate, the insulating layer, etc. to have a characteristic (heat resistance) that can withstand high temperature heating. Preferably, a reduced pressure environment for the purpose of advancing the conductor treatment reaction is unnecessary, and the treatment can be easily performed.

  In addition, it can be reduced by atomic hydrogen generated by a vacuum plasma apparatus or an atmospheric pressure plasma apparatus using RF or microwave. Other than this, alkylamine borane, hydrazine, hydrazine compound, formaldehyde, aldehyde compound, phosphorous acid compound, hypophosphorous acid compound, adipic acid, formic acid, alcohol, tin (II) compound, metallic tin, hydroxyamines, A wiring layer having a desired volume resistivity can be obtained by a reduction method using a reducing liquid selected from ascorbic acid. In any method, it is possible to form a wiring (wiring layer) and impart metal conductivity at a low temperature of less than 200 ° C.

  The composite layer of the insulating layer and the wiring layer of the present invention is suitable as a circuit board or a circuit for electrical conduction of a semiconductor package. It can be used as a circuit board or a part or all of a circuit for electric conduction of a semiconductor package.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example.

[Examples 1-8, Comparative Examples 1-4]
(Insulator ink adjustment)
Insulator ink was prepared for each of Examples 1 to 8 and Comparative Examples 1 and 2.
(Adjustment of insulator ink 1)
28.9 g of ethylene glycol chain-modified bisphenol A type epoxy resin (trade name “EXA4822”, manufactured by Dainippon Ink and Chemicals, Mw = 1800) and bisphenol A novolak resin (trade name “VH-4170” as a curing agent) 8.6 g manufactured by Dainippon Ink Chemical Co., Ltd., 0.03 g 2-ethyl-4-methylimidazole (manufactured by Tokyo Ohka Kogyo Co., Ltd.) which is a curing accelerator, and a silicone-based surface conditioner (trade name “ BYK307 ", manufactured by BYK Chemie), 0.05 g, is dissolved in 112.5 g of a solvent, γ-butyrolactone (vapor pressure at 25 ° C .: 3.4 × 10 ² Pa), and the viscosity is 10.6 mPa · s. An insulating ink having a surface tension of 25.0 mN / m was obtained. The viscosity is a value obtained by using a tuning fork type vibration viscometer (“SV-10”, manufactured by A & D) under the condition of 25 ° C., and the surface tension is determined by a platinum plate method. It is a value obtained by measurement under the condition of 25 ° C. using a surface tension meter (“CBVP-Z”, manufactured by Kyowa Interface Science Co., Ltd.) (the same applies hereinafter).

(Adjustment of insulator ink 2)
29.9 g of ethylene glycol chain-modified bisphenol A type epoxy resin (trade name “EXA4850-150”, Dainippon Ink & Chemicals, Inc. Mw = 900) and bisphenol A novolak resin (trade name “VH-4170” as a curing agent) ”, 7.6 g, manufactured by Dainippon Ink & Chemicals, Inc., 0.03 g of 2-ethyl-4-methylimidazole (manufactured by Tokyo Ohka Kogyo Co., Ltd.), which is a curing accelerator, and a silicone-based surface conditioner (trade name) “BYK307”, manufactured by BYK Chemie), 0.05 g) is dissolved in 112.5 g of γ-butyrolactone as a solvent, and the insulating ink has a viscosity of 10.2 mPa · s and a surface tension of 25.0 mN / m. Got.

(Adjustment of insulator ink 3)
1,6-hexanediol chain-modified bisphenol A type epoxy resin (trade name “EXA4816”, Dainippon Ink & Chemicals, Inc. Mw = 1800) 29.1 g and a curing agent bisphenol A novolak resin (trade name “VH”) -4170 ", manufactured by Dainippon Ink & Chemicals, Inc.) 8.3 g, 2-ethyl-4-methylimidazole (manufactured by Tokyo Ohka Kogyo Co., Ltd.) 0.03 g as a curing accelerator, and a silicone-based surface conditioner ( Insulation having a viscosity of 10.5 mPa · s and a surface tension of 25.0 mN / m by dissolving 0.05 g of a trade name “BYK307”, manufactured by BYK Chemie) in 112.5 g of γ-butyrolactone as a solvent. A body ink was obtained.

(Adjustment of insulator ink 4)
28.9 g of ethylene glycol chain-modified bisphenol A type epoxy resin (trade name “EXA4822”, manufactured by Dainippon Ink & Chemicals, Inc.) and bisphenol A novolac resin (trade name “VH-4170”, Dainippon Ink, Ltd.) which is a curing agent. 8.6 g manufactured by Chemical Industry Co., Ltd., 0.03 g of 2-ethyl-4-methylimidazole (manufactured by Tokyo Ohka Kogyo Co., Ltd.) which is a curing accelerator, and a silicone-based surface conditioner (trade name “Polyflow WS-314”). Insulator ink having a viscosity of 10.6 mPa · s and a surface tension of 25.0 mN / m is dissolved in 112.5 g of γ-butyrolactone as a solvent. Obtained.

(Adjustment of insulator ink 5)
20.2 g of ethylene glycol chain-modified bisphenol A type epoxy resin (trade name “EXA4822”, manufactured by Dainippon Ink & Chemicals, Inc.) and bisphenol A novolak type epoxy resin (trade name “N-865”, Dainippon Ink and Chemicals, Inc.) 7.3 g, bisphenol A novolak resin (trade name “VH-4170”, manufactured by Dainippon Ink & Chemicals, Inc.), which is a curing agent, and 2-ethyl-4, which is a curing accelerator. -0.03 g of methylimidazole (manufactured by Tokyo Ohka Kogyo Co., Ltd.) and 0.05 g of a silicone-based surface conditioner (trade names “BYK307”, BYK Chemie) were dissolved in 112.5 g of γ-butyrolactone as a solvent. Thus, an insulating ink having a viscosity of 11.0 mPa · s and a surface tension of 25.0 mN / m was obtained.

(Adjustment of insulator ink 6)
11.5 g of propylene glycol chain-modified polyamideimide resin (prototype, manufactured by Hitachi Chemical Co., Ltd., Mw = 33400) and bisphenol A novolac type epoxy resin (trade name “N-865”, Dainippon Ink and Chemicals, Inc. 1.4 g, 2-ethyl-4-methylimidazole (manufactured by Tokyo Ohka Kogyo Co., Ltd.) 0.001 g as a curing accelerator, and a silicone-based surface conditioner (trade names “BYK307”, BYK Chemie) 0.02 g was dissolved in 87.5 g of N-methyl-2-pyrrolidone (vapor pressure at 25 ° C .: 0.7 × 10 ² Pa) as a solvent, and the viscosity was 9.7 mPa · s and the surface tension was An insulator ink of 25.0 mN / m was obtained.

(Adjustment of insulator ink 7)
24.2 g of bisphenol A novolac type epoxy resin (trade name “N-865”, manufactured by Dainippon Ink & Chemicals, Inc.) and bisphenol A novolak resin (trade name “VH-4170”, Dainippon Ink Chemical Co., Ltd.) as a curing agent. 13.3 g manufactured by Kogyo Co., Ltd., 0.02 g of 2-ethyl-4-methylimidazole (manufactured by Tokyo Ohka Kogyo Co., Ltd.) as a curing accelerator, and a silicone-based surface conditioner (trade names “BYK307”, BYK Chemie) 0.05 g) is dissolved in 115.5 g of γ-butyrolactone (vapor pressure at 25 ° C .: 3.4 × 10 ² Pa) as a solvent, and the viscosity is 11.3 mPa · s and the surface tension is 25. An insulator ink of 0.0 mN / m was obtained.
Table 1 summarizes the composition of these insulator inks.

(Wiring ink)
As the wiring ink, a metal nanoparticle dispersion was prepared (wiring ink A). Metal nanoparticles (NanoTek CuO, manufactured by CIK Nanotech Co., Ltd., specific surface area 12 m ² / g, primary particle diameter 75 nm, copper oxide) 32.5 g and γ-butyrolactone (vapor pressure at 25 ° C .: 3.4 × 10 ² Pa) 97.5 g was mixed, treated with an ultrasonic homogenizer US-600CCVP manufactured by Nippon Seiki Seisakusho Co., Ltd. for 5 minutes at an output of 600 W, a frequency of 19.5 kHz, and an amplitude value of 26.5 μm, and 35 g was weighed into a 50 ml centrifugal sedimentation tube. Centrifugation was performed at 1500 rpm for 4 minutes, and the supernatant was used as wiring ink. The wiring ink had a viscosity of 5.0 mPa · s and a surface tension of 43.0 mN / m. Moreover, when the particle size distribution measurement was performed with a laser diffraction / scattering particle size distribution measuring apparatus (LS 13 320, manufactured by Beckman Coulter, Inc.), a well-dispersible wiring ink having an average particle size of 80 nm and a maximum particle size of 350 nm was obtained. As the wiring ink B, a silver ink (trade name “Ag1TeH”, manufactured by ULVAC Material Co., Ltd.), in which tetradecane is used as a solvent and stabilized by a dispersant, was used.

(Preparation of test specimen for evaluation)
(Examples 1-6, Comparative Example 1)
Insulator inks 1 to 7 were each printed on a glass plate having a size of 2.6 cm × 3.8 cm by using an inkjet printing apparatus. The printed insulator ink was cured by hot plate heating at 180 ° C. for 30 minutes to obtain an insulating layer. On the formed insulating layer, a pattern of 1 cm × 1 cm and a film thickness of about 2 μm was formed with the wiring ink A using an inkjet printing apparatus, and dried by hot plate heating at 60 ° C. for 15 minutes. As a conductor treatment, formic acid gas treatment was performed to obtain a copper wiring layer. Formic acid gas treatment is a formic acid saturated nitrogen gas generator by putting about 100 mL of formic acid into a washing bottle and bubbling nitrogen, aiming at uniform treatment temperature at the bottom of a flat bottom separable flask heated in an oil bath. A copper plate was laid and used as a treatment tank. The formic acid-saturated nitrogen gas generator and the treatment tank were connected with a polytetrafluoroethylene tube, and the formic acid-saturated nitrogen gas flow rate was adjusted with a purge flow meter with a needle valve. A test specimen for evaluation was set on a copper plate, and nitrogen gas was passed through the treatment tank for 15 minutes to replace the air inside with nitrogen. The mixture was heated for 15 minutes in an oil bath heated to 200 ° C. in advance, and was treated for 60 minutes while formic acid saturated nitrogen gas was passed through the treatment tank at 0.3 L / min. After the treatment, nitrogen gas was aerated for 15 minutes. A chromel alumel thermocouple was set on the glass substrate surface on the copper plate, and this temperature was used as the temperature of the test piece for evaluation. The temperature of the test piece for evaluation during formic acid gas treatment was in the range of 165 to 176 ° C. The formic acid gas treatment method for the test specimen for evaluation is the same as below.

(Examples 7 to 8)
Insulator inks 1 and 2 were respectively printed on a glass plate having a size of 2.6 cm × 3.8 cm by using an inkjet printing apparatus. The printed insulator ink was cured by hot plate heating at 180 ° C. for 30 minutes to obtain an insulating layer. On the formed insulating layer, a pattern of 1 cm × 1 cm and a film thickness of about 2 μm was formed with wiring ink B using an ink jet printing apparatus, and dried by hot plate heating at 120 ° C. for 15 minutes. Then, it sintered for 2 hours in 200 degreeC oven, and obtained the wiring layer of silver.

(Comparative Example 2)
A pattern of 1 cm × 1 cm and a film thickness of about 2 μm is formed with a wiring ink A on a glass plate having a size of 2.6 cm × 3.8 cm by using an ink jet printing apparatus, and heated at 60 ° C. for 15 minutes by hot plate heating. Dried. Thereafter, formic acid gas treatment was performed as a conductor treatment to obtain a copper wiring layer.

(Measurement of volume resistivity of wiring layer)
The coated substrate after the treatment was cut with a FIB (focused ion beam) apparatus, and the film thickness was measured by observing the cross section with SIM (scanning ion image). The surface resistivity of the film is measured with a four-probe method microresistance measuring device (Loresta MCP-T610, manufactured by Mitsubishi Chemical Corporation), and the measured value of the surface resistivity is converted into the volume resistivity using the measured value of the film thickness. If the value is 3 times or less (5.1 × 10 ⁻⁸ Ω · m or less) of the volume resistivity (1.7 × 10 ⁻⁸ Ω · m) of bulk copper, the conductivity is ◎, 3 If it is larger than 20 times and 20 times or less (3.4 × 10 ⁻⁷ Ω · m or less), the conductivity is ○, and if it is larger than 20 times and 10 ⁻⁵ Ω · m or less, the conductivity is Δ, 10 ⁻⁵ Ω -When exceeding m, electroconductivity was evaluated as x. The results are shown in Table 2.

(Adhesive strength evaluation)
A stripping tape ("adhesive tape CT-18", product name manufactured by Nichiban Co., Ltd.) was applied to the wiring layer of the test piece for evaluation, and it was brought into close contact with a finger, peeled off at once, and the state of the wiring layer after peeling was observed. . The case where there was no change in the wiring layer was evaluated as “◯”, the case where some peeling occurred, “Δ”, and the case where all peeling occurred, as “X”. The results are shown in Table 2.
FIG. 1 is a cross-sectional photograph showing the appearance of the composite layer of the insulating layer and the wiring layer obtained in Example 1 of the present invention. The tungsten protective film for cross-section processing is formed by depositing tungsten so that the cross-section can be easily processed. FIG. 2 shows a cross-sectional photograph of the wiring layer obtained in Comparative Example 2.

  As shown in Table 2, it can be seen that the insulating layer made of the insulating ink containing the glycol ether structure has a high adhesive force with respect to the wiring layer formed by the printing method and made into a conductor. In addition, by including an epoxy resin, a phenol resin and / or a polyamide-imide resin excellent in electrical insulation, heat resistance and chemical resistance, the insulation layer is formed by electrical insulation and heat treatment and / or reducing gas treatment. It turns out that the composite layer excellent in the electroconductivity of a wiring layer was obtained.

01 ... Tungsten protective film for cross-section processing 02 ... Wiring layer 03 ... Insulating layer 04 ... Glass

Claims (9)

  An insulating ink containing at least one kind of an epoxy resin, a phenol resin, a polyimide resin, a polyamide resin, and a polyamideimide resin having a molecular weight of 200 or more and 50,000 or less, including a glycol ether having a molecular weight of 40 or more and less than 1000.   Insulator ink containing at least one of epoxy resin, phenol resin, polyimide resin, polyamide resin, and polyamideimide resin having a molecular weight of 200 or more and 50,000 or less, containing at least one glycol ether structure having a molecular weight of 40 or more and less than 1000 .   The insulating ink according to claim 1 or 2, comprising at least one of epoxy resin, phenol resin, polyimide resin, polyamide resin, and polyamideimide resin having a molecular weight of 200 or more and 50,000 or less, a curing agent, and a solvent. . The insulating ink according to claim 3, wherein the vapor pressure of the solvent is less than 1.34 × 10 ³ Pa (25 ° C.).   An insulating layer formed by a printing method using the insulating ink according to any one of claims 1 to 4 and cured by one or both of heat and light irradiation.   The insulating layer according to claim 5, wherein the printing method is a printing method using an inkjet device or a dispenser device.   A wiring ink containing at least one element of Cu, Ag, Au, Al, Ni and Co and / or metal nanoparticles of their oxide is printed on the insulating layer according to claim 5 or 6. A composite layer of a wiring layer and an insulating layer formed by applying an electric conductivity and imparting electrical conductivity.   The circuit board which used the composite layer of the wiring layer and insulating layer of Claim 7 for the part or all as the circuit for electrical conduction.   A semiconductor package using the composite layer of the wiring layer and the insulating layer according to claim 7 as part or all of an electric conduction circuit.

Images