JP2017128757A - Metal wiring forming composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition capable of forming fine metal wiring having an excellent adhesion and a homogeneous thickness for an insulation substrate surface conveniently and precisely but without lowering the insulation of said substrate.SOLUTION: A composition for forming a metal wiring over an insulating substrate of the invention contains a chemical compound (A), in which metal ions are arranged on a coordination group of a chemical compound having said coordination group, and a chemical compound (B) having a reactivity with coordination groups of said chemical compound (A). A carboxyl group is preferred as the coordination group of said chemical compound (A).SELECTED DRAWING: None

Description

  The present invention relates to a composition for forming metal wiring on an insulating substrate, a method of forming metal wiring using the composition, and a method of manufacturing a wiring board using the method.

  A printed wiring board used for the purpose of forming an electronic circuit by fixing electronic parts to the surface and connecting the parts with wiring is insulated by a dry process (vacuum deposition method, sputtering method, etc.). A metal layer formed on the entire surface of the substrate is used as a starting material, and unnecessary portions of the metal layer of the starting material are etched using a mask formed using a photolithographic method. A method (subtractive method) for forming a metal wiring by removing a mask is known. However, in recent years, printed wiring boards are required to form finer wiring patterns in order to cope with the higher density of wiring boards as electronic devices become smaller and have higher functionality. It was difficult to form a wiring pattern with high accuracy.

  An additive method is known as a method for forming a finer wiring pattern. In this method, a resin layer having a wiring pattern-shaped recess is formed on the surface of an insulating substrate using a photolithographic method, and then a metal layer is formed in the recess by plating, and then the resin layer is removed. To form a metal wiring. According to this method, a fine wiring pattern can be formed with excellent productivity. However, the problem is that the adhesion between the insulating substrate and the metal wiring is weak and easy to peel off.

  As a method for improving the adhesion between the insulating substrate and the metal wiring, Patent Document 1 discloses that the surface of a polyimide substrate as an insulating substrate is treated with an alkaline aqueous solution to generate carboxyl groups, and metal ions are generated on the generated carboxyl groups. After coordination to form a metal salt of a carboxyl group, a metal thin film is formed by reducing metal ions by irradiating with ultraviolet rays, and then the surface of the metal thin film is plated to increase the thickness of the metal. A method of forming a wiring has been proposed. Patent Document 2 discloses that a thin resin layer is formed on the surface of a resin layer made of a polyamic acid coordinated with metal ions to form a thin metal layer, and the surface of the thin metal layer is further plated to increase the film thickness. A method of forming a metal wiring is proposed.

JP 2001-73159 A JP 2007-100134 A

  As a result of studies by the present inventors, in the inventions described in Patent Documents 1 and 2, free carboxyl groups present on the surface of the insulating substrate are obtained after reducing the metal ions coordinated to the carboxyl groups and precipitating the metal. As a result, it was found that the insulation properties deteriorated, causing problems such as leakage and short circuit. In order to prevent the insulation from deteriorating, it is necessary to convert the polyamic acid to polyimide by heat treatment. However, for polyimidization, it is necessary to heat at a high temperature close to 400 ° C. It turns out that it deteriorates.

  In addition, a method of forming metal wiring by discharging ink containing metal nanoparticles onto an insulating substrate by an ink jet method and then baking the metal nanoparticle is easy to agglomerate. It is difficult to hold the metal nanoparticles in a highly dispersed state, and it is difficult to form a metal wiring having a uniform film thickness by aggregation of the metal nanoparticles. In addition, the discharged metal nanoparticles are bonded to each other by firing to form conductive wiring. However, if the number of metal nanoparticles is insufficient, the wiring is disconnected, and if it is excessive, the thickness of the wiring is not good. It is difficult to control the number of metal nanoparticles within an appropriate range such as being uniform.

Accordingly, an object of the present invention is to form a fine metal wiring having excellent adhesion to the surface of an insulating substrate and a uniform thickness simply and accurately without reducing the insulating properties of the substrate. It is to provide a composition that can.
Another object of the present invention is to provide a method for forming a metal wiring on an insulating substrate using the composition.
Another object of the present invention is to provide a method for producing a wiring board using the composition.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have determined that a compound having a configuration in which a metal ion is coordinated to a coordinating group (A) has a group having reactivity with the coordinating group. The composition obtained by blending the prepared compound (B) contains a metal component as an ion, so that the state in which the metal component is highly dispersed can be stably maintained over time, and an insulating substrate can be obtained by imprinting or printing. It is possible to form a fine wiring pattern thereon, and free coordinating groups that cause a decrease in insulation even when metal ions coordinated to the compound (A) are precipitated as a metal. It disappears by reacting with the reactive group which (B) has, and also the reaction of the free coordinating group of the said compound (A) and the reactive group which the compound (B) has compared with the polyimidation of polyamic acid. Mild Therefore, it is possible to solve the problem of deterioration of insulation without heating at a high temperature. After that, by performing plating treatment as necessary, excellent adhesion to the insulating substrate surface and uniform It has been found that a fine metal wiring having a thickness can be formed with high accuracy. The present invention has been completed based on these findings.

  That is, the present invention is a group having reactivity between a compound (A) in which a metal ion is coordinated to the coordinating group of a compound having a coordinating group and the coordinating group of the compound (A). A composition for forming a metal wiring on an insulating substrate, comprising a compound (B) comprising:

  The present invention also provides the above composition, wherein the compound (A) is a compound in which a metal ion is coordinated to the coordinating group of the compound having a coordinating group and a polymerizable group.

  The present invention also provides the above composition, wherein the coordinating group of the compound (A) is a carboxyl group.

  The present invention also provides the above composition, wherein the compound (A) is a compound having a carboxyl group coordinated with a metal ion and a carbon-carbon double bond.

  The present invention also provides the above composition, wherein the compound (A) is a (meth) acrylic acid ester having a carboxyl group coordinated with a metal ion.

  The present invention also provides the above composition, wherein the group having reactivity with the coordinating group in the compound (B) is an epoxy group, an oxetane group, an isocyanate group, or an amino group.

The present invention also provides a method for forming a metal wiring having the following steps.
Step 1: Forming a coating film having a wiring pattern using the above composition Step 2: Curing the coating step 3: Depositing metal ions present on the coating surface as metal

  The present invention also provides the method for forming a metal wiring as described above, wherein in step 1, a coating film having a wiring pattern shape is formed using an imprint method or a printing method.

  The present invention also provides the above-described method for forming a metal wiring in which metal ions are precipitated as metal by reducing metal ions in step 3.

  The present invention also provides a method for manufacturing a wiring board, characterized in that metal wiring is formed on an insulating substrate by the metal wiring formation method described above.

  Since the composition of the present invention contains the metal component in an ionic state, the metal component does not aggregate and the composition can be kept uniform. Therefore, when the composition of the present invention is used, a highly accurate wiring pattern can be easily and inexpensively formed on an insulating substrate by an imprint method, a printing method, or the like. And even if it is not heated at a high temperature, it does not cause deterioration of the insulating properties of the substrate, and has a uniform thickness and excellent adhesion to the insulating substrate by performing plating treatment as necessary. Fine metal wiring can be formed with high accuracy. Since it has the above effect together, if the composition of this invention is used, generation | occurrence | production of a short circuit and an electrical leakage will be suppressed and a small and highly functional electronic device which has high reliability can be manufactured.

FIG. 1 is a schematic view showing an example of a method for forming a pattern of the composition of the present invention using an imprint method. FIG. 2 is a schematic diagram showing an example of a method for patterning the composition of the present invention using an imprint (letter plate transfer) method.

[Composition for forming metal wiring on insulating substrate]
The composition of the present invention is a composition for forming a metal wiring on an insulating substrate, the compound (A) in which a metal ion is coordinated to the coordination group of the compound having a coordination group, And a compound (B) having a group having reactivity with the coordinating group of the compound (A).

  The composition of this invention may contain 1 type, or 2 or more types of other components as needed besides the compound (A) and the compound (B). Other components include, for example, a monomer having a polymerizability with the compound (A) (for example, a radical curable monomer), a polymerization initiator, a photosensitizer, a reaction catalyst, a solvent, a filler (for example, talc, silica). Metal oxides, etc.).

(Compound (A))
The compound (A) in the present invention is a compound in which a metal ion is coordinated to the coordinating group of the compound having a coordinating group.

  The compound (A) contains one or more groups as a coordinating group. The coordinating group is a group having a property of coordinating with a metal ion, and examples thereof include a carboxyl group, a phenol group, and a sulfonic acid group. In the present invention, in particular, the cured product has excellent electrical characteristics and excellent reliability of electrical characteristics. More specifically, the reactivity with the reactive group of the compound (B) is particularly excellent, and the compound (B ) Can be stably maintained with the reactive group over time, so that it is possible to suppress a decrease in insulation due to a free coordinating group (specifically, a carboxyl group, a phenol group, a sulfonic acid group, etc.). In addition, it is possible to prevent a decrease in insulation due to cleavage of the bond over time and generation of free coordinating groups (specifically, carboxyl groups, phenol groups, sulfonic acid groups, etc.). A carboxyl group is preferred.

  In addition, the compound (A) has a polymerizable group together with a coordinating group coordinated with a metal ion. At room temperature, the wiring pattern can be transferred with high accuracy using an imprint method or a printing method, and at the same time, cured. Is preferable in that a metal wiring excellent in heat resistance, weather resistance, and electrical characteristics can be formed. The number of polymerizable groups provided in one molecule of the compound (A) is, for example, 1 to 50.

  Examples of the polymerizable group include a radical polymerizable group and a cationic polymerizable group. As the compound (A) in the present invention, a compound having a radically polymerizable group as a polymerizable group is preferable in terms of excellent reactivity, reaction rate, and versatility. Compounds with a heavy bond are preferred.

  The compound (A) is a compound in which a metal ion is coordinated to the coordination group of a compound having a coordination group (preferably a compound having a coordination group and a polymerizable group). A compound (A ′) having a coordinate group (preferably a compound having a coordination group and a polymerizable group) (referred to as “compound (A ′)”) and a metal ion-containing aqueous solution are mixed. It can manufacture by coordinating a metal ion to this coordinating group. After the metal ions are coordinated, unreacted metal ions are preferably removed by washing with water or the like.

Examples of the compound (A ′) include (meth) acrylic acid esters [for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, (Meth) acrylic acid C _1-10 alkyl esters such as hexyl (meth) acrylate; benzyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, adamantyl (meth) acrylate, cyclopentenyl (meth) acrylate, Isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, 2- (dicyclopentenyloxy) ethyl (meth) acrylate, 2- (dicyclopentanyloxy) (Meth) acrylic acid ester having a cyclic structure (aliphatic cyclic structure or aromatic cyclic structure) in the molecule such as ethyl (meth) acrylate], a styrene compound [for example, styrene, vinyltoluene, α-methylstyrene, Or a compound in which a coordinating group is bonded to vinyl naphthalene], a vinyl ether compound [for example, a compound in which a coordinating group is bonded to methyl vinyl ether, butyl vinyl ether, or phenyl vinyl ether], or the like, an oligomer or a polymer thereof Etc. “(Meth) acrylic acid” means “acrylic acid” or “methacrylic acid”. “(Meth) acrylate” means “acrylate” or “methacrylate”.

  The acid value of the compound (A ′) is, for example, preferably 10 mgKOH / g or more, more preferably 50 mgKOH / g or more, further preferably 100 mgKOH / g or more, further preferably 300 mgKOH / g or more, particularly preferably 400 mgKOH. / G or more, most preferably 600 mgKOH / g or more. The upper limit of the acid value is, for example, about 800 mgKOH / g. Therefore, the compound (A) is preferably a compound having a coordinating group and having a metal ion coordinated to the coordinating group of the compound having an acid value of 10 mgKOH / g or more. Use of a compound (A) obtained by coordinating a metal ion to a compound (A ′) having an acid value in the above range is preferable in that a metal wiring having excellent adhesion can be formed. Further, a metal ion is coordinated to the compound (A ′) having a higher acid value (for example, 300 to 800 mgKOH / g, preferably 400 to 800 mgKOH / g, particularly preferably 600 to 800 mgKOH / g) in the above range. If the composition containing the compound (A) obtained in this way is used, a sufficient metal thin film can be obtained even with a thinner coating, and metal wiring with excellent adhesion can be formed. It becomes possible to cope with further downsizing and higher density of electronic devices. On the other hand, when the compound (A) obtained by coordinating the metal ion to the compound (A ′) having an acid value lower than the above range is used, the metal ion concentration in the composition is low. As a result, it is difficult to obtain a sufficient metal thin film, and it tends to be difficult to form a metal wiring having excellent adhesion even after plating.

  As the metal ions, metal ions that can form conductive wiring are preferably used. For example, gold ions, silver ions, copper ions, tungsten ions, tantalum ions, titanium ions, tin ions, indium ions. , Cadmium ions, vanadium ions, chromium ions, manganese ions, aluminum ions, iron ions, cobalt ions, nickel ions, zinc ions, and metal ions derived from complexes such as platinum ammine complexes and palladium ammine complexes. These can be used alone or in combination of two or more.

  As described above, the compound (A) is preferably a compound in which a metal ion is coordinated to the coordinating group of a compound having a coordinating group and a polymerizable group, and more preferably a coordination in which a metal ion is coordinated. A radical curable compound having a functional group, more preferably a compound having a coordinating group coordinated with a metal ion and a carbon-carbon double bond, more preferably a coordinating group coordinated with a metal ion. (Meth) acrylic acid ester provided, particularly preferably a radical curable compound having a carboxyl group coordinated with a metal ion, particularly preferably a carboxyl group coordinated with a metal ion and a carbon-carbon double bond A compound, most preferably a (meth) acrylic acid ester having a carboxyl group coordinated with a metal ion.

(Compound (B))
In the compound (B) in the present invention, one or more groups having a reactivity with the coordinating group of the compound (A) (in this specification, sometimes referred to as “reactive group”) are used. It is a compound provided.

  Examples of the reactive group include an epoxy group, an oxetane group, an isocyanate group, and an amino group. In addition, the number of the reactive groups provided in one molecule of the compound (B) is a cured product (excellent in heat resistance, weather resistance, and electrical properties (for example, insulating property) by forming a highly crosslinked structure ( Or 2 or more are preferable at the point from which a metal wiring) is obtained, and 2-4 are especially preferable.

  In particular, the composition of the present invention preferably contains a compound having two or more epoxy groups (oxirane rings) as the compound (B), and particularly contains a compound having two or more glycidyl groups. preferable. When the composition of the present invention contains these compounds as the compound (B), the surface functional group of the insulating substrate and the epoxy group, or the hydroxyl group generated after the epoxy group reacts with the coordinating group, or A coating film (or metal wiring) that is particularly excellent in adhesion to the insulating substrate can be formed because the affinity with the insulating substrate is increased by the epoxy group or the hydroxyl group.

  The compound (B) may have a curable group (for example, a radical polymerizable group such as a carbon-carbon double bond) together with the reactive group. That is, the compound (B) may be a radical curable compound.

  Examples of the compound (B) having an epoxy group include an epoxy-modified siloxane compound, an alicyclic epoxy compound, an aromatic epoxy compound, an aliphatic epoxy compound, and a heterocyclic epoxy compound.

<Epoxy-modified siloxane compound>
Examples of the epoxy-modified siloxane compound include epoxy-modified silicone and epoxy-modified polyorganosilsesquioxane.

  The epoxy-modified silicone is a compound in which an epoxy group is introduced into at least one of a terminal and a side chain of a dimethyl silicone skeleton.

  The epoxy-modified polyorganosilsesquioxane is a polysiloxane compound having a silsesquioxane structure and an epoxy group bonded to the silsesquioxane structure. The silsesquioxane structure includes a random structure, a cage structure, and a ladder. Includes type structure.

<Alicyclic epoxy compound>
As said alicyclic epoxy compound, the compound (glycidyl ether type epoxy compound) etc. which have an alicyclic ring and a glycidyl ether group in a molecule | numerator can be mentioned, for example. More specifically, for example, 2,2-bis [4- (2,3-epoxypropoxy) cyclohexyl] propane, 2,2-bis [3,5-dimethyl-4- (2,3-epoxypropoxy) Compound obtained by hydrogenating bisphenol A type epoxy compound such as cyclohexyl] propane (hydrogenated bisphenol A type epoxy compound); bis [o, o- (2,3-epoxypropoxy) cyclohexyl] methane, bis [o , P- (2,3-epoxypropoxy) cyclohexyl] methane, bis [p, p- (2,3-epoxypropoxy) cyclohexyl] methane, bis [3,5-dimethyl-4- (2, 3-epoxypropoxy) cyclohexyl] Compound obtained by hydrogenating bisphenol F-type epoxy compound such as methane (hydrogenated bisphenol F-type epoxy compound) Hydrogenated biphenol type epoxy compound; hydrogenated phenol novolak type epoxy compound; hydrogenated cresol novolac type epoxy compound; hydrogenated cresol novolak type epoxy compound of bisphenol A; hydrogenated naphthalene type epoxy compound; epoxy compound obtained from trisphenolmethane And hydrogenated compounds.

<Aromatic epoxy compound>
Examples of the aromatic epoxy compound include epibis type glycidyl ether type epoxy resins obtained by condensation reaction of bisphenols [for example, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, etc.] and epihalohydrin; High molecular weight epibis type glycidyl ether type epoxy resin obtained by addition reaction of bis type glycidyl ether type epoxy resin with the above bisphenols; phenols [eg, phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, bisphenol S, etc.] and aldehyde [eg, formaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, salicy A novolak alkyl type glycidyl ether type epoxy resin obtained by further condensing a polyhydric alcohol obtained by a condensation reaction with an aldehyde etc. with an epihalohydrin; two phenol skeletons are bonded to the 9-position of the fluorene ring. In addition, an epoxy compound in which a glycidyl group is bonded to an oxygen atom obtained by removing a hydrogen atom from the hydroxy group of the phenol skeleton, either directly or via an alkyleneoxy group.

<Aliphatic epoxy compound>
Examples of the aliphatic epoxy compound include a glycidyl ether of an alcohol having no q-valent cyclic structure (q is a natural number); a glycidyl ester of a monovalent or polyvalent carboxylic acid; an epoxidized product of an oil or fat having a double bond An epoxidized product of polyolefin (including polyalkadiene) such as epoxidized polybutadiene; Examples of the alcohol having no q-valent cyclic structure include monovalent alcohols, divalent alcohols, and trihydric or higher polyhydric alcohols. The alcohol having no q-valent cyclic structure may be polyether polyol, polyester polyol, polycarbonate polyol, polyolefin polyol, or the like.

<Heterocyclic epoxy compound>
The heterocyclic epoxy compound is a compound containing at least nitrogen as a heteroatom such as a triazine ring, an isocyanuric ring, a hydantoin ring, or a glycoluril ring, and an epoxy group (for example, a glycidyl group) is substituted on the nitrogen atom. A compound etc. can be mentioned. Specific examples include 1,3,4,6-tetraglycidyl glycoluril, triglycidyl isocyanurate and the like.

  In the composition of the present invention, the content of the compound (B) (the total amount when containing two or more) is the reactivity in the compound (B) with respect to 1 mol of the coordinating group of the compound (A). For example, the range of 0.5 to 3 mol, particularly 0.8 to 1.5 mol, especially 0.9 to 1.2 mol, of the group is sufficient to suppress a decrease in insulation properties of the insulating substrate. It is preferable in that it can be performed. When content of a compound (B) is less than the said range, suppression of the insulation fall may become difficult. On the other hand, when the content of the compound (B) is excessive, the content of the compound (A) is relatively decreased, and the amount of metal ions introduced is decreased, so that it is difficult to obtain a sufficient metal thin film. Even if the treatment is performed, it tends to be difficult to form a metal wiring having excellent adhesion.

(Radical curable monomer)
The composition of the present invention may contain a radical curable monomer in addition to the compound (A) and the compound (B). Examples of the radical curable monomer include ethyl (meth) acrylate, (meth) Monofunctional monomers such as butyl acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hexanediol di (meth) acrylate, (poly) ethylene glycol Di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate Dipentaerythritol hexa (meta Acrylate, epoxy acrylate, polyester acrylate, a polyfunctional monomer such as urethane acrylate. These can be used alone or in combination of two or more.

  In the present invention, it is particularly preferable to use a polyfunctional monomer from the viewpoint of obtaining a cured product (or metal wiring) having more excellent heat resistance and weather resistance by improving the crosslinking density of the cured product. On the other hand, if the crosslink density of the cured product becomes too high, it may be brittle and easily broken, but in that case, it is preferable to add a monofunctional monomer. Thereby, a crosslinking density can be reduced moderately, toughness can be provided to the hardened | cured material obtained, and brittleness can be improved.

  The amount of the radical curable monomer used (when two or more are contained, the total amount thereof) is, for example, about 0 to 300 parts by weight with respect to 100 parts by weight of the compound (A), and the upper limit is preferably 200 parts by weight. Particularly preferred is 100 parts by weight, and most preferred is 60 parts by weight. The lower limit is preferably 1 part by weight, particularly preferably 5 parts by weight, and most preferably 10 parts by weight. When the composition of the present invention contains a radical curable monomer in the above range, a wiring board having excellent heat resistance and electrical characteristics can be formed. In addition, when transferring the wiring pattern shape by the imprint method, it is preferable in that it is excellent in releasability from the mold and can suppress a decrease in yield due to defective release.

  The composition of the present invention may contain other curable compounds in addition to the compound (A), the compound (B), and the radical curable monomer as the curable compound. The proportion of the total content of the compound (A), the compound (B) and the radical curable monomer in the curable compound is preferably, for example, 60% by weight or more, more preferably 70% by weight or more, and particularly preferably. 80% by weight or more, most preferably 90% by weight or more. The upper limit is 100% by weight. If the content of the other curable compound is excessive, the effect of the present invention tends to be difficult to obtain.

  The proportion of the total content of the compound (A), the compound (B), and the radical curable monomer in the total amount of the nonvolatile components contained in the composition of the present invention is, for example, 70% by weight or more, preferably 80%. % By weight, particularly preferably 90% by weight or more, and most preferably 95% by weight or more.

(Polymerization initiator)
The polymerization initiator includes a photo radical polymerization initiator and a thermal radical polymerization initiator. These can be used alone or in combination of two or more.

  Examples of the photo radical polymerization initiator include benzophenone, acetophenone benzyl, benzyl dimethyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, dimethoxyacetophenone, dimethoxyphenylacetophenone, diethoxyacetophenone, diphenyldisulfite, ortho Benzoyl methyl benzoate, ethyl 4-dimethylaminobenzoate (Nippon Kayaku Co., Ltd., trade name “Kayacure EPA”, etc.), 2,4-diethylthioxanthone (Nippon Kayaku Co., Ltd., trade name “ Kayacure DETX ”etc.), 2-methyl-1- [4- (methyl) phenyl] -2-morpholinopropanone-1 (Ciba-Geigy Co., Ltd., trade name“ Irgacure 907 ”etc.), 1-hydroxycyclohexyl 2-amino-2-benzoyl-1-phenyl such as phenyl ketone (Ciba-Geigy Co., Ltd., trade name “Irgacure 184”, etc.), 2-dimethylamino-2- (4-morpholino) benzoyl-1-phenylpropane, etc. Aminobenzene derivatives such as alkane compounds, tetra (t-butylperoxycarbonyl) benzophenone, benzyl, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 4,4′-bis (diethylamino) benzophenone, 2,2′-bis (2-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole (made by Hodogaya Chemical Co., Ltd., trade name “B-CIM”) ) And the like, 2,6-bis (trichloromethyl) -4- (4-methoxynaphthalen-1-yl) -1,3,5-to Halomethyl triazines compounds such as azine, 2-trichloromethyl-5- (2-benzofuran-2-yl - ethenyl) -1,3,4 oxadiazole, and the like halomethyl oxadiazole compounds, and the like.

  Examples of the thermal radical polymerization initiator include organic peroxides. Examples of the organic peroxides include hydroperoxide, dialkyl peroxide, peroxyester, diacyl peroxide, peroxydicarbonate, peroxyketal, and ketone peroxide (specifically, benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di (2-ethylhexanoyl) peroxyhexane, t-butylperoxybenzoate, t-butylperoxide, cumene hydro Peroxide, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-dibutylperoxyhexane, 2,4-dichlorobenzoyl peroxide, 1,4-di (2-t- Butylperoxyisopropyl) benzene, 1,1 Bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, methyl ethyl ketone peroxide, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate and the like).

  Furthermore, together with the thermal radical polymerization initiator, naphthenic acid such as cobalt naphthenate, manganese naphthenate, zinc naphthenate, cobalt octenoate and the like, and metal salts such as cobalt, manganese, lead, zinc and vanadium of octenoic acid Can do. Similarly, tertiary amines such as dimethylaniline can be used.

  The use amount (blending amount) of the polymerization initiator is a radical curable compound (compound (A) and compound (B) when the compound (B) is a radical curable compound) contained in the composition of the present invention, For example, about 0.01 to 5 parts by weight, preferably 0.1 to 3 parts by weight with respect to 100 parts by weight of the radical curable monomers.

(solvent)
The composition of the present invention may contain a solvent for the purpose of adjusting the viscosity. Examples of the solvent include hydrocarbon solvents such as xylene, toluene and cyclohexane; ketone solvents such as cyclohexanone and methyl isobutyl ketone; methyl cellosolve, cellosolve, butyl cellosolve, methyl carbitol, carbitol, butyl carbitol, diethyl carbitol Ether solvents such as Tol, propylene glycol monomethyl ether; ester solvents such as n-butyl acetate, isobutyl acetate, n-amyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate (PGMEA), 3-methoxybutyl acetate; Alcohol systems such as butyl alcohol, sec-butyl alcohol, isobutyl alcohol, cyclohexanol, 2-ethylhexanol, 3-methyl-3-methoxybutanol Mention may be made of the medium, and the like. These can be used alone or in combination of two or more.

  As a usage-amount of a solvent, the solid content density | concentration in the composition of this invention is the range used as about 25-100 weight%, for example.

[Metal wiring formation method]
The metal wiring formation method of the present invention includes the following steps.
Step 1: Forming a coating film having a wiring pattern using the composition of the present invention Step 2: Curing the coating step 3: Depositing metal ions present on the coating surface as a metal

  Examples of methods for forming a wiring pattern-shaped coating film (including a coating film having a wiring pattern-shaped recess) using the composition in Step 1 include a printing method (for example, gravure printing method, screen printing). Method, ink jet printing method, etc.), or a method of applying the composition in the form of a wiring pattern on the insulating substrate by letterpress transfer, or applying the composition to the surface of the insulating substrate by roller coating, bar coating, spray coating, etc. It is possible to employ a method of coating to form a coating film, and then transferring the wiring pattern shape to the coating film by imprinting.

  Since the composition of the present invention contains the metal component in an ionic state, the metal component does not aggregate and the composition can be kept uniform. Therefore, a highly accurate wiring pattern can be easily and inexpensively formed on the insulating substrate by imprinting or printing.

  In the imprint method, (1) the composition of the present invention is applied onto an insulating substrate to form a coating film, and a mold having a wiring pattern shape projection is pressed against the coating film to transfer the wiring pattern shape. A method of forming a coated film (= coating film having a wiring pattern-shaped recess), or (2) a composition adhered to the convex part of a mold having a wiring pattern-shaped convex part. A method of forming a wiring pattern-shaped coating film by pressing an object on an insulating substrate (letter-plate transfer method) is included.

  In the gravure printing method, the composition of the present invention is used as an ink, and the ink is applied to a concave portion of a plate having a concave portion having a wiring pattern shape, and then transferred onto an insulating substrate. Form.

  In the screen printing method, a coating film having a wiring pattern shape is formed by applying the composition of the present invention on an insulating substrate through a stencil having holes having a wiring pattern shape.

  In the inkjet printing method, a coating film having a wiring pattern shape is formed by using the composition of the present invention as an ink and spraying and applying the ink onto an insulating substrate. As the ink jet printing method, a thermal method, a piezo method, or the like can be adopted.

  In the present invention, the use of the imprint method is advantageous in terms of cost because it can form high-resolution wiring and can form wiring with a small number of steps. Is preferable.

  In the case where a radical curable compound is used as the compound (A) and / or the compound (B) in the composition of the present invention, or when the radical curable monomer is contained in the composition of the present invention, in step 1 When forming a coating film having a wiring pattern shape (for example, when a coating film is formed by imprinting, the mold is pressed on an insulating substrate), the radical curable compound and / or radical curable property is used. It is preferable to advance the radical curing reaction of the monomer in that a highly accurate wiring pattern can be formed.

  And when the composition of this invention contains radical photopolymerization initiator as a polymerization initiator, radical hardening reaction can be advanced by irradiating with an ultraviolet-ray. Moreover, when it contains a thermal radical polymerization initiator, radical curing reaction can be advanced by heat-processing.

The ultraviolet light source may be any light source that can cause radical curing reaction to proceed by irradiating light, such as a UV lamp, a mercury lamp such as a low, medium or high pressure mercury lamp, or a mercury xenon lamp. Metal halide lamps, tungsten lamps, arc lamps, excimer lamps, excimer lasers, semiconductor lasers, YAG lasers, laser systems in which lasers and nonlinear optical crystals are combined, high-frequency induced ultraviolet ray generators, and the like can be used. The ultraviolet irradiation amount (integrated light amount) is, for example, about 10 to 2000 mJ / cm ² .

  When the heat treatment is performed, the heating temperature is about 25 to 150 ° C., and the heating time is about 1 second to 5 minutes.

  Curing of the coating film in step 2 is performed by reacting the coordinating group of compound (A) with the reactive group of compound (B). In the composition of the present invention, the compound (B) reacts with the coordinating group of the compound (A) (the metal ion is removed and becomes free), for example, the reactive group is an epoxy group or an oxetane group. In the case where the coordinating group is esterified, and when the reactive group is an isocyanate group or an amino group, the coordinating group is amidated, so that the insulating property of the insulating substrate can be maintained. Since the free coordinating group exhibits conductivity, if it remains on the surface of the insulating substrate, the insulating property is deteriorated.

  The reaction between the coordinating group of the compound (A) and the reactive group of the compound (B) is carried out by applying a heat treatment under conditions milder than the heating temperature (about 400 ° C.) required for polyamic acid polyimidation. The heating temperature is about 100 to 250 ° C., and the heating time is about 1 to 30 minutes.

As a method for precipitating metal ions present on the coating film surface as metal in Step 3, for example, metal ions can be reduced. And reduction of a metal ion can be performed by the method of following (1) or (2), for example.
(1) A method of treating a coating film surface with a solution containing a reducing agent (2) A method of subjecting the coating film surface to a heat treatment in an atmosphere of a reducing gas or an inert gas

  In the case of (1), as the reducing agent, it is preferable to use one or more selected from, for example, sodium borohydride, hypophosphorous acid and salts thereof, dimethylamine borane, and the like. It is preferable to immerse the hardened | cured material of the coating film obtained through process 2 for about 1 to 30 minutes in the solution containing this.

  In the case of (2), as the reducing gas, for example, hydrogen gas, hydrogen-nitrogen mixed gas, borane-nitrogen mixed gas or the like can be used. Moreover, as inert gas, nitrogen gas, argon gas, etc. can be used, for example.

  After the reduction treatment, it is preferable to wash with distilled water or the like. Thereby, metal ions remaining on the surface of the coating film can be removed, and deterioration of insulation due to the presence of metal ions can be suppressed.

  By depositing a metal in step 3, a metal thin film having a thickness of about 10 to 500 nm can be formed on the surface of the coating film. Since the metal thin film formed in this way is partially embedded in the coating film on the surface of the insulating base material, it has excellent adhesion to the surface of the insulating base material due to the anchor effect. .

  The metal wiring preferably has a thickness of μm from the viewpoint of electric resistance and noise reduction. For this reason, when it is necessary to increase the thickness of the metal thin film, the surface of the metal thin film formed in step 3 is further subjected to plating treatment (electroless plating and / or electrolytic plating treatment) to form a plating film. It is preferable to provide a step of providing. The plated film thus formed has excellent adhesion to the metal thin film, and the metal thin film has excellent adhesion to the surface of the insulating base as described above. Excellent.

  Furthermore, after the plating film is formed, it is preferable to remove the excess plating film, and for example, it can be removed by a method such as chemical mechanical polishing (CMP).

As a method for forming a metal wiring of the present invention, for example, a method (imprint method) shown in FIG.
(1) A coating film is formed by applying the composition of the present invention to the surface of an insulating substrate.
(2) A mold having a wiring pattern shape convex portion is pressed against the coating film to transfer the wiring pattern to the coating film, and the mold is removed after being irradiated with ultraviolet rays.
(3) The coating film is cured.
(4) A metal thin film is formed on the surface of the cured coating film by treating the surface of the cured coating film with a reducing agent to precipitate a metal.
(5) A plating process is performed to form a plating film.
(6) Remove excess plating film.

In addition, the method for forming a metal wiring of the present invention includes a method shown in FIG.
(1) The composition of this invention is made to adhere to the convex part of the mold which has a convex part of wiring pattern shape.
(2) The composition adhering to the convex part of the mold is pressed against the surface of the insulating substrate, irradiated with ultraviolet rays, and then the mold is removed to form a wiring pattern-shaped coating film on the surface of the insulating substrate.
(3) The coating film is cured.
(4) A metal thin film is formed on the surface of the cured coating film by treating the surface of the cured coating film with a reducing agent to precipitate a metal.
(5) A plating process is performed to form a plating film.

The metal wiring formed by the above method has excellent adhesion to the surface of the insulating substrate. Further, the metal wiring is excellent in electrical conductivity, and the electric resistance value is, for example, 1 × 10 ⁻² Ωcm or less, preferably 1 × 10 ⁻³ to 1 × 10 ⁻⁵ Ωcm.

[Method of manufacturing a wiring board]
The method for manufacturing a wiring board according to the present invention is characterized in that metal wiring is formed on an insulating substrate by the above-described metal wiring formation method. According to the present invention, it is possible to form a wiring board having a highly accurate fine metal wiring having a uniform thickness and excellent adhesion to an insulating substrate. Furthermore, a circuit board (for example, a circuit board such as a flexible circuit board, a flex-rigid circuit board, a TAB carrier, etc.) can be formed by connecting various components such as a capacitor to the obtained wiring board. The electronic device provided with a small size, high function, and high reliability by suppressing the occurrence of short circuit and electric leakage.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited by these Examples.

Preparation Example 1
Acrylic oligomer represented by the following formula (1) [trade name “Cyclomer P (ACA) Z320” (manufactured by Daicel Ornex Co., Ltd.), average molecular weight (Mw): 23000, acid value 120 mgKOH / g], 50 mM concentration By mixing the CuSO ₄ aqueous solution, copper ions are coordinated to the carboxyl groups of the acrylic oligomer, the gel-like copper ion-containing acrylic oligomer is separated by centrifugation, and excess copper ions are removed with distilled water. Thus, a gel-like copper ion-containing acrylic oligomer was obtained. The obtained gel-like copper ion-containing acrylic oligomer was dissolved in PGMEA (manufactured by Daicel Corporation) to obtain a copper ion-containing acrylic oligomer solution.

  114 g of the obtained copper ion-containing acrylic oligomer solution (non-volatile content), 47 g of bisphenol A glycidyl ether (manufactured by Tohto Kasei Co., Ltd.) in 1 mol of carboxyl group in the copper ion-containing acrylic oligomer, 1 mol of epoxy group), 50 g of trimethylolpropane triacrylate (manufactured by Daicel Ornex Co., Ltd.), and 2 g of a photo radical polymerization initiator (trade name “Irgacure 184”, manufactured by BASF) are mixed to obtain a solid content concentration. 50% by weight of composition (A) was obtained.

Preparation Example 2
20 g of copper (II) acrylate (manufactured by Alfa Aesar, acid value of acrylic acid: 779 mg KOH / g) was dissolved in 120 g of cyclohexanone, and the solution was passed through a filter (pore size: 0.25 μm) 70 g (nonvolatile) In terms of fraction), 1,3,4,6-tetraglycidylglycoluril (manufactured by Shikoku Kasei Kogyo Co., Ltd.) 20 g (per mole of carboxyl group in copper (II) acrylate) 6-tetraglycidyl glycoluril (epoxy group 1.1 mol), trimethylolpropane triacrylate (manufactured by Daicel Ornex Co., Ltd.), and radical photopolymerization initiator (trade name “Irgacure 184”, manufactured by BASF) 0.6 g was mixed to obtain a composition (B) having a solid content concentration of 33% by weight.

Example 1
(Pattern formation by imprint method)
On the silicon wafer, the composition (A) obtained in Preparation Example 1 was applied using a spin coater (Dry) to form a 10 μm thick coating film. Next, using a computer-controlled imprint apparatus (trade name “NM-0401”, manufactured by Myeongchang Kiko Co., Ltd.), the mold was pressed against the coating film to transfer the pattern, and the mold was pressed against the coating film. The pattern was formed by irradiating with ultraviolet rays. As the mold, a PDMS mold having an L / S (line width / line interval) of 2 μm was used.
(Curing)
The coating film on which the pattern was formed was put in an oven (at 200 ° C. for 5 minutes), and a carboxyl group and an epoxy group in the coating film were reacted to obtain a hard cured coating film.
(reduction)
Next, when the obtained cured coating film was immersed in an aqueous solution of DMAB (dimethylaminoborane, manufactured by Wako Pure Chemical Industries, Ltd.) for 5 minutes and then washed with distilled water, a copper thin film was deposited on the surface of the cured coating film. It was observed that
(plating)
Next, the cured coating film on which the copper thin film was deposited was immersed in an electroless nickel plating bath (trade name “Top Nicolon TOM-S”, manufactured by Okuno Pharmaceutical Co., Ltd.) for 30 seconds at 80 ° C. A nickel layer serving as a base for copper plating was formed. Furthermore, electroplating was performed at an electric density of 3.5 A / dm ^{2 in} an electric copper plating bath.
Finally, the surface was subjected to CMP grinding to obtain a metal wiring having a line width and thickness of 2 μm.

Example 2
In the same manner as in Example 1 except that the composition (B) obtained in Preparation Example 2 was used in place of the composition (A) obtained in Preparation Example 1 (pattern formation by imprint method) to (reduction) It was observed that a copper thin film was deposited on the surface of the cured coating film. Furthermore, when (plating) treatment was performed in the same manner as in Example 1, a metal wiring having a line width and thickness of 2 μm was obtained.

Example 3
(Pattern formation by imprint method)
A coating film was simulated by letterpress printing using the composition (A) obtained in Preparation Example 1. Specifically, a PDMS mold having a convex wiring pattern (L / S: 5 μm) was set on an imprint apparatus (trade name “NM-0401”, manufactured by Myeongchang Kiko Co., Ltd.) controlled by a computer. .
The composition (A) was applied onto a silicon wafer using a spin coater (Dry) to form a coating film having a thickness of 300 nm.
At room temperature, the mold provided in the imprint apparatus is brought into contact with the coating film, the coating film is attached to the mold, and then the coating film attached to the mold is brought into contact with the glass substrate, thereby the glass substrate. And the pattern was formed by irradiating with ultraviolet rays while the mold was in contact with the glass substrate.
Then, about the coating film in which the pattern was formed, when the process from (hardening) to (reduction) was performed similarly to Example 1, it was observed that the copper thin film precipitated on the coating-film surface.
Further, the same (plating) treatment as in Example 1 was performed. When the thickness of the metal wiring was 5 μm, the line width was about 5.9 μm.

Example 4
Pattern formation by imprint (letterplate transfer) method as in Example 3 except that the composition (B) obtained in Preparation Example 2 was used instead of the composition (A) obtained in Preparation Example 1 ) To (reduction), it was observed that a copper thin film was deposited on the surface of the coating film.
Further, the same (plating) treatment as in Example 3 was performed. When the thickness of the metal wiring was 5 μm, the line width was 5.5 μm.

Example 5
In the same manner as in Example 4, (reduction) treatment was performed from (pattern formation by imprint (letter transfer) method) to deposit a copper thin film on the coating film surface. The copper thin film had a thickness of 100 nm and a line width of 5 μm, and a wiring pattern having the same shape as the mold could be formed.
Thereafter, the obtained coating film (coating having a copper thin film on the surface) was immersed in a neutral electroless copper plating bath (pH: 6.75) having a temperature adjusted to 50 ° C. for 3 hours.
When the electroless copper plating bath was performed in this way, copper was deposited on the surface of the copper thin film, and a uniform electroless copper plating film having a thickness of 5 μm was obtained. The electric resistance value of the electroless copper plating film was 3 × 10 ⁻⁵ Ωcm, and an electronic circuit board circuit excellent in conductivity could be formed.
<Neutral electroless copper plating bath composition>
CuCl ₂ : 0.05M
Ethylenediamine: 0.60M
Co (NO ₃ ) ₂ : 0.15M
Ascorbic acid: 0.01M
2,2′-bipyridyl: 20 ppm

Example 6
(Pattern formation by inkjet printing method)
Using an ink jet printing apparatus with an ultraviolet irradiation device, the ink cartridge was filled with the composition (B) obtained in Preparation Example 2, and a pattern was formed by drawing a wiring pattern having a line width of 10 μm on the glass substrate surface. .
Then, about the coating film in which the pattern was formed, when the process from (hardening) to (reduction) was performed similarly to Example 1, it was observed that the copper thin film precipitated on the coating-film surface.
Further, the same (plating) treatment as in Example 1 was performed. When the thickness of the metal wiring was 5 μm, the line width was about 5.9 μm.

DESCRIPTION OF SYMBOLS 1 Mold which has convex part of wiring pattern shape 2 Coating film which consists of composition of this invention 3 Insulating substrate 4 Cured material (cured coating film) of composition of this invention
5 Metal thin film 6 Plating film

Claims (10)

  Compound (B) comprising a group having a reactivity between the compound (A) in which a metal ion is coordinated to the coordinating group of the compound having a coordinating group and the coordinating group of the compound (A) And a composition for forming a metal wiring on an insulating substrate.   The composition according to claim 1, wherein the compound (A) is a compound in which a metal ion is coordinated to the coordinating group of the compound having a coordinating group and a polymerizable group.   The composition according to claim 1 or 2, wherein the coordinating group of the compound (A) is a carboxyl group.   The composition according to claim 1, wherein the compound (A) is a compound having a carboxyl group coordinated with a metal ion and a carbon-carbon double bond.   The composition according to claim 1, wherein the compound (A) is a (meth) acrylic acid ester having a carboxyl group coordinated with a metal ion.   The composition according to any one of claims 1 to 5, wherein the group having reactivity with the coordinating group in the compound (B) is an epoxy group, an oxetane group, an isocyanate group, or an amino group. A metal wiring forming method including the following steps.
Step 1: Forming a coating film in the form of a wiring pattern using the composition according to any one of claims 1 to 6 Step 2: Curing the coating film 3: Metal ions present on the surface of the coating film To deposit as a metal   The method of forming a metal wiring according to claim 7, wherein in step 1, the coating film having a wiring pattern shape is formed by using an imprint method or a printing method.   The method for forming a metal wiring according to claim 7 or 8, wherein in step 3, the metal ions are reduced to be precipitated as metal.   A method for manufacturing a wiring board, comprising forming a metal wiring on an insulating substrate by the method for forming a metal wiring according to any one of claims 7 to 9.

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