JP2012153924A - Method of manufacturing metal pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing a metal pattern having a high sensitivity to electroless plating, having an excellent homogeneity of a plated film, and retaining a high adhesion to a substrate even after a long-term storage under the condition of high temperature and high humidity.SOLUTION: The method of forming the metal pattern includes the steps of: forming an anchor layer on the substrate; applying ink containing electroless plating catalyst or a precursor thereof onto the anchor layer; then forming the metal pattern by an electroless plating process; wherein the anchor layer is formed by, after applying a polymerizable composition onto the substrate, polymerizing the polymerizable composition by photo-polymerization or thermopolymerization, and the gel fraction of the anchor layer by the acetone extraction is 95% or higher.

Description

  The present invention relates to a novel metal pattern manufacturing method capable of forming a metal pattern excellent in plating suitability and durability.

  Conventionally, as a manufacturing method for forming a metal pattern, a metal-clad laminate in which a metal foil is pasted on a substrate is used. The most common method is a printed circuit board in which an adhesive layer is provided between the substrate and a metal (mainly copper) foil, and this adhesive layer employs a resin that has adhesion and flexibility characteristics ( For example, see Patent Document 1.) However, in this method, after the adhesive layer is formed, a process of laminating the metal foil with a hot press, a process of forming a metal pattern with photolithography, and the like are required. Since the resin and the metal foil are edged, there is a problem that man-hours and costs are excessive.

  In recent years, attention has been focused on a metal pattern forming method in which a metal pattern is directly drawn using an ink containing a so-called metal nanoparticle having an average particle size of 100 nm or less, using a screen printing method, an ink jet printing method, or the like.

  This metal pattern formation method is a method of forming a circuit by firing at a temperature of about 200 to 300 ° C. utilizing the fact that the melting point is lowered by minimizing the particle size of the metal nanoparticles. Although this technology certainly has advantages such as reduced man-hours and improved utilization efficiency of raw materials, it is difficult to completely fuse metal nanoparticles together, and in post-processing to lower the electrical resistance in the fired metal pattern The problem of severe restrictions on temperature and conditions remained.

  There is a method of forming a conductive pattern from a solution containing a reducing agent having a reducing property under heating by using a metal salt in the form of metal ions in an ink without using metal nanoparticles. However, since the complexing agent that coordinates and stabilizes the metal salt does not have sufficient performance, the reduction reaction of the metal salt tends to proceed and the solution storage stability is poor.

  On the other hand, as a means for forming and depositing metal under mild conditions, a method of forming a metal pattern by utilizing an electroless plating technique has also been proposed. For example, as a method of forming a copper pattern without using an etching process in a photolithography process, an initiator pattern of a printed wiring board is formed by an ink jet printer using aqueous ink, and then electroless plating is performed to form a metal A method of forming a (conductor) pattern has been proposed (see, for example, Patent Document 2).

  However, the method described in Patent Document 2 is a method in which a latent image is formed by directly applying catalyst ink droplets onto an insulating substrate that has no liquid absorption property. Adhesion was insufficient. Several other methods for applying a catalyst pattern on an ink-receiving layer or adhesive layer on a substrate have also been proposed. In order to obtain performance as an electronic circuit, such as subsequent plating properties, adhesion, and heat resistance. Still have challenges. By applying a polymerizable composition such as an acrylic monomer or epoxy monomer as an anchor layer and plating on this, abnormal plating deposition, deterioration of physical properties of the plating film, adhesion after long-term storage at high temperature and high humidity, etc. There was a problem.

  On the other hand, a method of forming a metal pattern by electroless plating after placing a patterned polymer layer as an anchor layer on a substrate and immersing it in a catalyst solution is also disclosed (see, for example, Patent Document 3). .

  In this method, a photosensitive resin composition having a group interacting with a catalyst and a polymerizable group is patterned by exposure, and immersed in a catalyst solution in the patterned photosensitive resin composition to form a metal film by electroless plating. By forming the catalyst in the surface region of the anchor layer using a catalyst solution, a printed circuit board imparted with adhesion and catalyst adsorption (electroless plating) is realized. However, since the catalyst solution containing a large amount of expensive metal is immersed in the entire substrate and unnecessary edging treatment of the metal portion is required later, the manufacturing cost is very high.

  In addition, this method requires a special exposure apparatus for patterning, so it lacks simplicity and has problems such as insufficient peel strength when stored in a high temperature and high humidity environment for a long period of time. .

JP 2006-265444 A JP 7-131135 A JP 2010-138475 A

  The present invention has been made in view of the above problems, and its purpose is to form a metal pattern in a simple and inexpensive process using a printing process such as inkjet, high electroless plating sensitivity, and uniform plating film. An object of the present invention is to provide a method for producing a metal pattern, which is excellent and can obtain a metal pattern having high adhesion to a substrate even when stored in a high temperature and high humidity environment for a long period of time.

  The above object of the present invention is achieved by the following configurations.

  1. In the method for producing a metal pattern, an anchor layer is formed on a substrate, an ink containing an electroless plating catalyst or a precursor thereof is applied on the anchor layer, and then a metal pattern is formed by an electroless plating process. The anchor layer is formed by applying the polymerizable composition onto the substrate and then polymerizing the polymerizable composition by a photopolymerization method or a thermal polymerization method, and the anchor layer has a gel fraction of 95 by the acetone extraction method. % Or more, The manufacturing method of the metal pattern characterized by the above-mentioned.

  2. 2. The method for producing a metal pattern according to 1, wherein the polymerizable composition contains a polymerizable monomer having an epoxy group as a polymerizable group and a latent catalyst.

  3. The polymerizable composition contains a polymerizable monomer having an ethylenically unsaturated group as a polymerizable group, and is applied on the substrate, and then heated at a temperature of 100 ° C. or higher for 1 minute or longer. 2. The method for producing a metal pattern according to 1 above, wherein

  4). 1. The method according to claim 1, further comprising an activation step of activating the electroless plating catalyst or a precursor thereof between the step of forming an anchor layer on the substrate and the step of performing electroless plating. 4. The method for producing a metal pattern according to any one of items 1 to 3.

  According to the present invention, a metal pattern can be formed by a simple and inexpensive process using a printing process such as inkjet, high electroless plating sensitivity, excellent uniformity of the plating film, and stored for a long time in a high temperature / high humidity environment. Moreover, the metal pattern manufacturing method which can obtain the metal pattern with high adhesiveness with respect to a board | substrate was able to be provided.

  Hereinafter, embodiments for carrying out the present invention will be described in detail.

  As a result of intensive studies in view of the above problems, the present inventor formed an anchor layer on a substrate, applied an electroless plating catalyst or an ink containing a precursor thereof on the anchor layer, and then electrolessly formed the anchor layer. In the method for producing a metal pattern in which a metal pattern is formed by plating, the anchor layer is obtained by polymerizing the polymerizable composition by a photopolymerization method or a thermal polymerization method after applying the polymerizable composition on the substrate. By the metal pattern manufacturing method, wherein the anchor layer is formed and the gel fraction by an acetone extraction method is 95% or more, the electroless plating sensitivity is high, the uniformity of the plating film is high, the high temperature and the high The inventors have found that a metal pattern manufacturing method capable of obtaining a metal pattern with high adhesion to a substrate even when stored for a long time in a humid environment can be realized, and the present invention is completed. It is up that led to.

  The metal pattern according to the present invention is mainly formed by the following process.

1) forming an anchor layer on the substrate;
2) A step of applying a catalyst ink containing an electroless plating catalyst or a precursor thereof to the formed anchor layer,
3) When the catalyst ink is a catalyst precursor, an activation treatment for conversion (reduction) into a catalyst;
4) An electroless plating process for generating metal with an electroless plating solution,
Consists of.

  Among the above steps, when forming an anchor layer to be a plating underlayer on the substrate which is the process 1), if the polymerization is insufficient, a low molecular weight polymerizable composition, or a polymerizable property It has been found that the monomers remain and these unreacted components adversely affect the formation of the metal pattern during the electroless plating process in the above process 4). Further, it has been found that the metal pattern formed in such a state has a marked decrease in adhesion between the substrate and the metal pattern when stored for a long period of time in a high temperature and high humidity environment.

  As a result of investigations in view of the above problems, the present inventor has selected and formed an anchor layer forming material (type of polymerizable monomer, additive, etc.) when forming the anchor layer on the substrate. Or by selecting the processing conditions after forming the anchor layer (post-cure conditions such as heating) so that the gel fraction of the formed anchor layer by the acetone extraction method is 95% or more. It has been found that the unreacted low molecular weight polymerizable monomer having a functional group can be reduced, and as a result, the above-mentioned problem can be solved by the method for producing a metal pattern defined by the present photographic pattern.

The gel fraction (monomer reaction rate) by the acetone extraction method referred to in the present invention is that after an anchor layer polymerized by photopolymerization or thermal polymerization is isolated and subjected to extraction treatment at 25 ° C. for 12 hours in an acetone solution. When the mass of the anchor layer before treatment is W ₁ (g) and the mass of the anchor layer after acetone extraction is W ₂ (g), the gel fraction can be obtained by the following equation.

Gel fraction (%) = (W ₂ / W ₁ ) × 100
More specifically, in the method for producing a metal pattern of the present invention, when an anchor layer composed of a polymerizable composition is polymerized, the low molecular weight component polymerizable composition or the unreacted polymerizable monomer component is reduced. Is effective in maintaining excellent plating sensitivity, plating film physical properties, and high adhesion strength when stored in a high temperature and high humidity environment.

  Therefore, even when a photopolymerizable radical polymerizable composition, a photopolymerizable cationic polymerizable composition, or an epoxy crosslinking composition is used as the polymerizable composition, residual monomer components and low molecular weight components are reduced. It is necessary to form an anchor layer under optimum conditions for each.

  For example, when a photopolymerizable radically polymerizable composition is used as the polymerizable composition, polymerization is inhibited by oxygen, and the degree of polymerization tends to decrease on the surface of the anchor layer. This tendency is more likely to occur as the anchor layer is thinner. Therefore, as a polymerizable composition, as a combination of compounds that are not easily affected by oxygen inhibition, together with radically polymerizable monomers, N-containing compounds such as amines, prepolymerization of polymerizable components, and high internal curing photopolymerization start A polymerizable composition is preferably used in combination with an agent. In addition, in order to prevent oxygen inhibition, a method of preventing oxygen from diffusing into the anchor layer by irradiating with high-intensity light is also effective. is there. However, as the polymerization proceeds, the mobility of the reactive site decreases, and the pass-through rate of the functional group is difficult to increase. Therefore, in the present invention, when the anchor layer is formed using a polymerizable monomer having an ethylenically unsaturated group as a polymerizable group as a polymerizable monomer constituting the photopolymerizable radical polymerizable composition. After the anchor layer is polymerized by irradiation with active energy rays or the like, it is preferable to use a means for increasing the reaction pass-through rate by heat treatment on the anchor layer. As this heat treatment (post-cure treatment), it is preferable to perform a heat treatment at 100 ° C. or more for 1 minute or more, more preferably at a heating temperature of 100 ° C. or more and 250 ° C. or less, and a heating time of 1 minute or more, 10 hours or less, more preferably heating temperature is 100 ° C. or more and 250 ° C. or less, heating time is 1 minute or more and 5 hours or less. The heating temperature depends on the material (heat resistance) of the substrate to be used. It is preferable to select the optimum condition within the above temperature range in consideration.

  In addition, as a polymerizable composition, a cationic polymerizable composition containing a photopolymerizable cationic polymerizable monomer has a high polymerization pass-through rate because a protonic acid which is a reactive species is not deactivated, and is one of preferable configurations. It is. However, moisture and base components prevent the pass-through rate of the cationic polymerizable monomer from increasing, so it is preferable to reduce the water content of the reaction system as much as possible by removing the bases that inhibit polymerization and controlling the environmental humidity. .

  Moreover, it is preferable that the epoxy crosslinking composition containing the monomer which has an epoxy group as a polymeric composition removes an acid component and a water | moisture content similarly to the said photopolymerizable cation polymeric composition. In particular, from the viewpoint of improving the pass-through rate of the monomer having an epoxy group, a latent catalyst and a catalytic initiator such as imidazole are effective. In this case, the polymerization temperature of the polymerizable monomer having an epoxy group is preferably a polymerization condition at a relatively high temperature as compared with polymerization with amines.

  Hereinafter, the manufacturing method of the metal pattern of this invention and the detail of the component of a metal pattern are demonstrated.

  In the method for producing a metal pattern of the present invention, after applying a polymerizable composition on a substrate, the polymerizable composition is polymerized by photopolymerization or thermal polymerization to form an anchor layer, and electroless plating is performed on the anchor layer. After applying the ink containing the catalyst or its precursor, a metal pattern is formed by electroless plating.

"substrate"
In the method for producing a metal pattern of the present invention, the substrate on which the metal pattern is formed is not particularly limited as long as it has insulating properties. For example, from a highly rigid material such as glass or ceramics, PET ( Polyethylene terephthalate) and a film-like material composed of a resin such as polyimide.

  In the board | substrate used for this invention, you may perform a surface modification process from a viewpoint of adhesiveness improvement or the installation improvement of an anchor layer. Specific examples include plasma treatment, corona discharge treatment, UV irradiation treatment, silane coupling agent treatment, and the like.

《Anchor layer》
The anchor layer according to the present invention is formed by applying a polymerizable composition on a substrate and then photocuring or thermosetting the polymerizable composition under a condition that the gel fraction by an acetone extraction method is 95% or more. It is characterized by doing.

  The polymerizable composition is mainly composed of a polymerization initiator, various polymers, various additives, a solvent and the like in addition to the polymerizable monomer.

  Furthermore, in the present invention, one of the polymerizable compositions is preferably a constitution containing a polymerizable monomer having an epoxy group as a polymerizable group and a latent catalyst. As a preferred embodiment, it contains a polymerizable monomer having an ethylenically unsaturated group as a polymerizable group, is applied on a substrate, and then heated at a temperature of 100 ° C. or higher for 1 minute or longer (both post-heating and post-cure). An embodiment in which the anchor layer is formed by performing the above is preferable.

(Polymerizable composition)
The polymerizable composition according to the present invention is a composition that can be polymerized and crosslinked by application of active energy rays such as ultraviolet rays, electron beams, or visible light, or application of thermal energy such as heating, and is generally photocured. A composition called a curable resin or a thermosetting resin can be used. After applying these polymerizable compositions onto a substrate, a three-dimensional cross-linked structure having a strong and high polymerization rate (gel fraction) can be obtained by polymerizing by the above means. Solvent resistance and water resistance can be obtained.

  As a method for forming a resin layer having such a high degree of polymerization, there is a method in which a polymer composition having a high degree of polymerization having a gel fraction of 95% or more is previously applied to a substrate, but a resin component that is three-dimensionally crosslinked is extremely High viscosity or poor solubility in solvents, etc., making it difficult to form a film uniformly applied to the substrate, and thinning a polymerization composition with a high degree of polymerization with a gel fraction of 95% or more in advance Then, there is a method of forming by thermal transfer as a sheet on the substrate, but all methods are extremely insufficient as adhesion to the substrate and uniformity of the film to be formed, and are required in the present invention. It is far from quality. Therefore, from the viewpoint of forming a uniform anchor layer with high adhesion to the substrate, after applying the photocurable or thermosetting polymerizable monomer coating liquid to the substrate stably in a low viscosity state, A method of curing the anchor layer with a high gel fraction is preferred.

  The polymerizable group that the polymerizable monomer applied to the anchor layer according to the present invention has is a functional group that can be polymerized by energy application (for example, light energy, thermal energy), specifically, vinyl group, vinyloxy group. , Allyl group, acryloyl group, methacryloyl group, oxetane group, epoxy group, isocyanate group, functional group containing active hydrogen, active group in azo compound, and the like. As the polymerizable compound, monomers, oligomers, and polymers having these functional groups can be used.

  Specific photocurable resins include radically polymerizable compositions and cationic polymerizable compositions, and thermosetting resins are generally phenol resins, melamine resins, unsaturated polyester resins, epoxy resins, and diallyl phthalate resins. Any type can be used in the present invention.

  In the present invention, in particular, as a polymerizable compound, a photocurable radical polymerizable compound, a photocurable cationic polymerizable compound, and a thermosetting epoxy resin have adhesion to a substrate and a metal pattern, and heat resistance. From the viewpoints of various physical properties such as insulation properties and ease of handling of the curing process.

  Hereinafter, the photopolymerizable radical polymerizable compound, the photocurable cationic polymerizable compound, and the thermosetting epoxy resin, which are typical polymerizable compositions, will be described in detail.

(Photo-curable polymerizable composition)
<Radically polymerizable composition>
In the present invention, it is preferable to use a radical polymerizable composition as one of the photocurable polymerizable compositions. The radical polymerizable composition is mainly composed of a radical polymerizable monomer and a photopolymerization initiator. Specifically, it is composed of a monomer / oligomer / polymer having an ethylene addition polymerizable unsaturated group (polymerizable group) such as a vinyl group, an allyl group, or a (meth) acryl group, and a photopolymerization initiator that generates radical species. Is done.

  Examples of the compound having an ethylene addition polymerizable unsaturated group (polymerizable group) include a diene monomer, (meth) acrylate, polyester acrylate, urethane acrylate, epoxy acrylate, unsaturated polyester, maleimide, vinyl ether, enthiol, and allyl ether. Etc. Among these, it is preferable to add an unsubstituted alkyl acrylic monomer as a constituent monomer from the viewpoint of obtaining excellent adhesion to the substrate. Specifically, tertiary butyl acrylate, 2-ethylhexyl acrylate, butyl acrylate, cyclohexyl acrylate, benzyl methacrylate and the like can be preferably used. Moreover, when the polymeric compound which has CN group is contained, it is preferable from a viewpoint which adhesiveness with plating improves.

  The photopolymerization initiator has a function of generating radicals (active species) upon irradiation with ultraviolet energy and reacting with a reactive group of a monomer or oligomer to initiate polymerization. Although various compounds can be mentioned as the photopolymerization initiator, it is preferable to use a benzophenone-based, benzoin-based, acetophenone-based, or thioxanthone-based initiator.

  In the formation of the anchor layer according to the present invention, as a means for reducing polymerization inhibition due to oxygen and improving the gel fraction after polymerization, an α-hydroxyacetophenone initiator or N-containing photopolymerization initiation which is less susceptible to oxygen inhibition It is preferable to use an agent and to use maleimide in combination as a polymerizable monomer.

<Cationically polymerizable composition>
In the present invention, it is preferable to use a cationic polymerizable composition as one of the photocurable polymerizable compositions. The cationic polymerizable composition is mainly composed of a cationic polymerizable monomer and a photopolymerization initiator. Specifically, it is composed of a monomer / oligomer / polymer having a cationic polymerizable group such as epoxy, oxetane, vinyl ether, and a photopolymerization initiator that generates an acid.

  Examples of the compound having a cationically polymerizable group include glycidyl ethers, glycidyl esters, glycidyl amines, oxides of unsaturated compounds, oxetane compounds having an alicyclic epoxy group, a bisphenol-based epoxy group, and the like. . Among these, it is preferable to add bisphenol glycidyl ether as a constituent monomer from the viewpoint of obtaining excellent heat resistance and adhesion. Specifically, the jER series made by Mitsubishi Chemical (former Japan Epoxy Resin) can be mentioned.

  The photopolymerization initiator generates a strong acid (active species) upon irradiation with ultraviolet energy, and this reacts with a reactive group of a monomer or oligomer to initiate polymerization. Examples of the photopolymerization initiator include aromatic diazonium salts, aromatic sulfonium salts, aromatic iodonium salts, metallocene compounds, silicon compounds / aluminum complexes, and the like, for example, using triarylsulfonium salts and diaryliodonium salts. Can do.

  In cationic polymerization, polymerization inhibition is generally caused by moisture or a base. Therefore, as a means for reducing polymerization inhibition and reaching the gel fraction after polymerization to the conditions specified in the present invention, the cationic polymerization composition contains It is preferable that water is removed and a basic compound is not contained. In addition, it is preferable to use an oxetane compound together from a viewpoint of improving the gel fraction after hardening.

(Thermosetting polymerizable composition)
<Epoxy crosslinking composition>
In the present invention, it is preferable to use a thermosetting epoxy crosslinked composition as one of the polymerizable compositions constituting the anchor layer. The epoxy crosslinking composition is mainly composed of an epoxy compound and a polymerization initiator or a curing agent.

  Details of the epoxy compound applicable to the present invention and the polymerization initiator or curing agent are described in detail in “Review Epoxy Resin Basics I” (issued on November 19, 2003, first edition) published by the Epoxy Technology Association. Can refer to them.

  In the present invention, the epoxy compound (epoxy resin) can be polymerized and crosslinked by reacting with various functional groups, curing agents and catalysts.

  Examples of the epoxy resin applicable to the present invention include 1) Bis-A type, Bis-F type, High-Br type, novolak type, and alcohol type as glycidyl ether type. 2) Glycidylamine Examples of the type include aromatic amine type and aminophenol type. 3) Examples of the glycidyl ester type include hydrophthalic acid type and dimer acid type. In forming the anchor layer according to the present invention, it is preferable to use an aromatic amine type glycidyl ether type from the viewpoint of obtaining excellent heat resistance and adhesion.

  On the other hand, the polymerization initiator or the curing agent can be selected according to the reaction type. The reaction between the epoxy group and the active hydrogen compound is as follows: 1) addition reaction with amino group, carboxyl group, phenol group, thiol group, 2) copolycondensation reaction between epoxy group and acid anhydride group, 3) epoxy group Self-polymerization with a basic or acidic catalyst can be mentioned.

  In the cation polymerizable composition of the photopolymerization, an example in which an onium salt that generates an acid by light irradiation is used as a photopolymerization initiator has been described, but this type of polymerization initiator is a type belonging to the above 3). is there.

  In the present invention, the addition reaction type by amino group, carboxyl group, phenol group and thiol group shown in 1) is preferable from the viewpoint of obtaining good adhesion, and further the basicity of the epoxy group shown in 3). Alternatively, it is particularly preferable to use a self-polymerization type using an acidic catalyst in view of reducing the unreacted epoxy group and achieving the gel fraction defined in the present invention.

  In the present invention, the curing agent and accelerator that can be used in combination with the epoxy resin include an unmodified aliphatic polyamine, a modified aliphatic polyamine, an unmodified aromatic polyamine, a modified aromatic polyamine, and an unmodified alicyclic polyamine. , Modified alicyclic polyamines, unmodified polyaminoamides, modified polyaminoamides, mixtures of amine curing agents, tertiary amines, condensates of amine derivatives and formaldehyde, unmodified fatty acids and acid anhydrides, unmodified alicyclic acids and Acid anhydrides, unmodified aromatic acids and acid anhydrides, modified acids and acid anhydrides, halogenated acids and acid anhydrides, hydrazide derivatives, dicyandiamide and its derivatives, boron halide complexes, organometallic complexes, onium salts, polythiols, Phenol formaldehyde condensate, phenol and its derivatives, hydroxyl group-containing compounds, isocyanates Include a blocked isocyanate, ketimine, imidazole and derivatives thereof.

  Among the above classifications, polyamine-based curing agents can be preferably used, and examples include aliphatic polyamines, alicyclic polyamines, and aromatic polyamines. Among them, aliphatic polyamines can be crosslinked at a relatively low temperature. An aromatic amine can obtain excellent heat resistance.

  Specific examples of polyamine curing agents include aliphatic polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, m-xylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, and diethylaminopropylamine. Examples of alicyclic polyamines include isophorone diamine, 1,3-bisaminomethylcyclohexane, bis (4-aminocyclohexyl) methane, norbornene diamine, 1,2-diaminocyclohexane, and lalomine (manufactured by BASF). Examples of aromatic polyamines include diaminodiphenylmethane, metaphenylenediamine, and diaminodiphenylsulfone. Others include polyoxypropylenediamine and polyoxypropylene. Ntoriamin, polycyclohexyl polyamine mixture, may be mentioned N- aminoethylpiperazine and the like.

  In the present invention, in the formation of the anchor layer, it is preferable to use a polymerizable composition containing a latent catalyst together with a polymerizable monomer having an epoxy group as a polymerizable group.

  The latent catalyst (latent curing agent) referred to in the present invention can be stored for a long time in a state of being mixed in advance with an epoxy resin, and the curing reaction is caused by external stimuli such as heat, light, pressure and moisture. Catalyst (curing agent) to start. By using such a latent catalyst (latent curing agent), a one-component epoxy resin composition can be constituted.

  Examples of the latent catalyst that can be suitably used in the present invention include a basic catalyst, and more specifically, tertiary amines and imidazoles.

  Specific latent catalysts include 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, 2-4-diamino-6- [2 -Methylimidazolyl- (1)] ethyl-s-triazine, 2-phenylimidazoline, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, tris (dimethylaminomethyl) phenol, benzyldimethylamine, And compounds such as 1,8-diazabicyclo (5,4,0) undecene-7.

  The imidazoles having secondary amines and tertiary amines mentioned above are particularly preferable from the viewpoint of not only acting as a basic catalyst but also reacting with an epoxy group so that the gel fraction can be improved. .

[Other additives]
In addition to the polymerizable composition, the anchor layer according to the present invention can be added for adjusting physical properties, such as a solvent, a polymer compound, an inorganic filler, and a surfactant, as necessary.

(solvent)
In the method for producing a metal pattern of the present invention, when forming an anchor layer on a substrate, the polymerizable composition is dissolved and diluted in an appropriate solvent, applied using a wet coating method, dried, and then photopolymerized or It can be formed by thermal polymerization.

  Solvents applicable to the present invention include alcohol solvents such as methanol, ethanol, propanol, ethylene glycol, glycerin, propylene glycol monomethyl ether, acids such as acetic acid, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Amide solvents such as formamide, dimethylacetamide and N-methylpyrrolidone, nitrile solvents such as acetonitrile and propyronitrile, ester solvents such as methyl acetate and ethyl acetate, carbonate solvents such as dimethyl carbonate and diethyl carbonate, toluene And aromatic hydrocarbon solvents such as xylene.

(Polymer compound)
In the anchor layer according to the present invention, together with the polymerizable composition according to the present invention, a polymer can be contained within a range that does not impair the object effects of the present invention. For example, polycarbonate, polyacrylonitrile, polystyrene, polyacrylic acid, Examples thereof include polymethacrylic acid, polyacrylic acid ester, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyester, polyamide, polyether, polyurethane, and phenol resin, and their copolymers and salts thereof.

These polymers include:
1) Good adhesion between the substrate and the anchor layer polymer;
2) The electroless plating catalyst or its precursor in the ink and the polymer of the anchor layer have adsorptivity (coordination);
It is preferable to select from.

  In order to improve the adhesion between the substrate and the anchor layer, the polymer of the anchor layer preferably has a functional group that interacts with the substrate. Specific examples include a carboxyl group, an amino group, and a hydroxyl group.

  Examples of the functional group that can be adsorbed (coordinated) to the catalyst or its precursor in the ink include a carboxyl group, a hydroxyl group, a sulfonic acid group, an amino group, a cyano group, and an amide group.

  Furthermore, it is preferable that the anchor layer according to the present invention further contains a compound having an adsorptivity (coordination property) to the catalyst or its precursor.

  Examples of the compound having a high adsorptivity (coordination property) to a catalyst, for example, a palladium metal salt, include compounds capable of forming a complex. Such a compound specifically includes an organic acid having a carboxyl group, and examples thereof include acetic acid, oxalic acid, malonic acid, succinic acid, adipic acid, maleic acid, tartaric acid, and citric acid.

  Furthermore, in the present invention, polymer fine particles (latex) can be used as the polymer used in the step of forming the anchor layer. By using polymer fine particles for forming the anchor layer, the area of the polymer ink comes into contact with the catalyst ink, but the catalyst or precursor of electroless plating is more easily penetrated into the polymer. Polymer fine particles (latex) that can be used in the present invention include polycarbonate, polyacrylonitrile, polystyrene, polyacrylic acid, polymethacrylic acid, polyacrylic ester, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyester, Examples thereof include polymer fine particles (latex) composed of polyamide, polyether, polyurethane, epoxy resin, phenol resin, and the like. The average particle size of the polymer fine particles is preferably 0.01 μm to 20 μm, more preferably 0.1 μm to 5 μm. In addition, additives such as an inorganic filler, a rubber component, an antioxidant, and a surfactant can be appropriately added to the composition of the anchor layer for adjusting physical properties.

  As a film thickness of an anchor layer, 0.05-20 micrometers is preferable and 0.1-10 micrometers is more preferable. If the thickness is less than 0.05 μm, the adhesion with the substrate is reduced. If the thickness is more than 20 μm, the anchor layer is liable to be deteriorated due to cohesive failure of the polymer.

(Means for forming anchor layer)
As a method for forming a polymer anchor layer, a polymer solution (dispersion) can be used, which can be appropriately selected from known coating methods, coated on a substrate and dried. Examples of the coating method include a roll coating method, a rod bar coating method, an air knife coating method, a spray coating method, and a dip method.

[Catalyst ink]
One of the characteristics of the ink used in the method for producing a metal pattern of the present invention is that it contains an electroless plating catalyst or a precursor thereof and a solvent.

  In the method for producing a metal pattern of the present invention, when the catalyst ink is applied to the anchor layer, the anchor layer is preferably swollen or dissolved by the catalyst ink. Swelling or dissolution here refers to swelling when the anchor layer is immersed in the catalyst ink and when the volume of the anchor layer is increased or white turbidity is observed after immersion, and when the mass of the anchor layer is decreased after immersion. It is determined. Therefore, as a criterion for determining whether the ink swells or dissolves the anchor layer, the anchor layer is immersed in the catalyst ink at 25 ° C. for 3 minutes, and then the determination is made by mass change before and after immersion, volume change, and visual observation. be able to.

(Electroless plating catalyst or its precursor)
The electroless plating catalyst contained in the catalyst ink according to the present invention is a metal that forms itself as a reaction active nucleus in the electroless plating treatment step. Specifically, palladium, silver, copper, nickel , Metals such as aluminum and iron.

  Moreover, the precursor of the electroless plating catalyst according to the present invention means a compound before being modified into an electroless plating catalyst, and can be a catalyst by an activation treatment step. Specifically, it is a metal salt compound, which becomes a zero-valent metal upon activation, for example, palladium metal salt, silver metal salt, copper metal salt, nickel metal salt, aluminum metal salt, iron metal salt Among them, palladium metal salts are preferable. In addition, when a zerovalent metal is used, it is preferable to use a nano-sized dispersion or a nano colloid. Alternatively, a palladium metal complex in which a palladium metal salt is complexed with a complexing agent may be used.

  Examples of the palladium metal salt applicable to the present invention include palladium fluoride, palladium chloride, palladium bromide, palladium iodide, palladium nitrate, palladium sulfate, palladium acetate, palladium acetoacetate, palladium trifluoroacetate, palladium hydroxide. , Palladium oxide, palladium sulfide and the like.

  Among the catalysts according to the present invention, a compound having a high solubility in the solvent used in the ink has good storage stability as an ink, and has a low mist and excellent discharge stability when discharged from an ink jet recording head. Particularly preferred. Specific examples of the catalyst include palladium salts such as palladium acetate and palladium acetoacetate, copper salts such as copper (II) acetate, and silver carboxylates such as silver behenate. Among these, palladium acetate has a high solubility in a solvent and is unlikely to precipitate during low-temperature storage, so that ink nozzle clogging hardly occurs and stable ink-jet drawing can be performed.

  Furthermore, it is preferable to use a catalyst nucleus that does not dissolve in the treatment liquid used in the surface treatment step and electroless plating treatment step described later. The term “not dissolved” as used in the present invention means that the solubility in these treatment solutions is 5.0% by mass or less, preferably 1.0% by mass or less.

  In particular, the catalyst core is dissolved in the electroless plating treatment step, and plating thickness due to bleeding of the catalyst pattern can be suppressed. Of the catalyst nuclei excellent in solubility in the solvent of the ink, those having no water solubility (in the alkali to acid region) are preferable. Among these, palladium acetate is particularly preferable from the viewpoint of high solubility in the ink solvent and almost no water solubility.

  For example, when a palladium metal salt is used as the catalyst nucleus, the content of the palladium metal salt in the catalyst ink is preferably 0.01% by mass or more and 1.0% by mass or less. If the concentration of the palladium metal salt is 0.01% by mass or more, the necessary activity of the electroless plating reaction as the next step can be obtained, and if it is 1.0% by mass or less, the palladium metal in the ink is obtained. This is preferable in that the stability of the salt can be maintained.

  In the present invention, as a method for applying the catalyst ink on the anchor layer, a catalyst ink containing an electroless plating catalyst or a precursor thereof is applied uniformly or in a pattern on the anchor layer using an ink jet recording head. .

  The inkjet head that can be used in the present invention is not particularly limited, and an electro-mechanical conversion method (for example, a single cavity type, a double cavity type, a vendor type, a piston type, a shear mode type, a shared wall type, etc.), Electro-thermal conversion method (for example, thermal ink jet type, bubble jet (registered trademark) type, etc.), electrostatic attraction method (for example, electric field control type, slit jet type, etc.), discharge method (for example, spark jet type, etc.), etc. Inkjet heads can be mentioned. From the viewpoint of the cost and productivity of the inkjet head, it is preferable to use an electro-mechanical conversion type or an electro-thermal conversion type head.

  In the method for producing a metal pattern of the present invention, it is preferable to heat the anchor layer including the substrate when applying the catalyst ink on the anchor layer. When recording by heating, the surface temperature of the substrate is preferably 40 ° C. or higher and 70 ° C. or lower. By setting the temperature to 40 ° C. or higher, drying of the catalyst ink is promoted to suppress liquid drift, and the reproducibility of the metal pattern is easily improved. Moreover, the heat damage with respect to a base material can be suppressed because heating temperature shall be 70 degrees C or less.

(Complexing agent)
Examples of the complexing agent applicable to the ink according to the present invention include compounds capable of forming a complex with the palladium metal salt. Examples of the compound include organic acids having a carboxyl group, and examples include acetic acid, oxalic acid, malonic acid, succinic acid, adipic acid, maleic acid, tartaric acid, and citric acid.

  Other compounds are preferably amine compounds or nitrogen-containing heterocyclic compounds. An amine compound is a compound in which one or more hydrogen atoms of ammonia are substituted with a hydrocarbon residue R, and is a complexing agent for Pd ions. Here, ammonia is also included. The amine retains an unshared electron pair on the N atom and tends to complex with palladium ions. As amines, ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, butylamine, dibutylamine, tributylamine, pyridine, 2-aminopyridine, 3-aminopyridine , 4-aminopyridine, ethylenediamine, ethanolamine, triethanolamine, linear amine compounds such as ethylenediaminetetraacetic acid, and cyclic amine compounds. Examples of the nitrogen-containing heterocyclic compound include pyridine, bipyridine, phenanthroline and the like.

(solvent)
In the catalyst ink according to the present invention, the electroless plating catalyst or its precursor in the catalyst ink is poorly soluble in water. In particular, in a palladium metal salt, it is difficult to dissolve the content necessary for electroless plating. Therefore, since the storage stability is poor even if dissolved by pH or additives, it is preferable not to contain water as the solvent of the catalyst ink according to the present invention. In the catalyst ink according to the present invention, from the viewpoint of catalyst solubility, ink storage stability, and ink emission property, a non-aqueous catalyst in which an organic solvent is contained by 70% by mass or more and an electroless plating catalyst or a precursor thereof is dissolved. Ink is preferred. Furthermore, it is preferable to select a solvent having good solubility and storage stability with respect to the catalyst or catalyst precursor.

  Examples of the organic solvent used in the catalyst ink according to the present invention include a solvent in which all alcohol ends are esterified or etherified with a polyhydric alcohol, a tertiary alcohol, an N-based organic solvent having no reducing group, and a polar aprotic solvent. Among them, the following solvent groups are particularly preferable.

  For example, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol diacetate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether , Diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol diacetate, tetraethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol diacetate Dipropylene glycol dimethyl ether, dipropylene glycol monomethyl ether acetate, t-butanol, ethylene carbonate, propylene carbonate, 1,3-dimethyl-2-imidazolidinone, 3-methyl-2-oxazolidone, N-methylformamide, N , N-dimethylformamide, N-methylacetamide, N-ethylacetamide, N, N-dimethylacetamide, 2-pyrrolidone, N-methylpyrrolidone, N-ethylpyrrolidone, 2-piperidone, 1-methyl-2-piperidone, ε -Caprolactam, N-ethylmorpholine, urea, ethyl acetoacetate, thiodiglycol, γ-butyrolactone, γ-valerolactone, γ-hexanolactone, δ-valerolactone, δ-hexanolactone, ε-caprolactone, tetrahydro Thiophene-1,1-dioxide, dimethyl sulfoxide, isobutyric acid, ethyl lactate, butyl lactate, butyl acetate, cyclopentanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, 4-ethylcyclohexanone, 2 , 5-dimethylcyclohexanone, 2,6-dimethylcyclohexanone, 3,4-dimethylcyclohexanone, 3,5-dimethylcyclohexanone, 3,5,5-trimethylcyclohexanone, 2-cyclohexen-1-one, 3-methyl-2- Examples include cyclohexen-1-one, 3,5,5-trimethyl-2-cyclohexen-1-one, and cycloheptanone.

  Furthermore, among the above preferable solvent group, it is preferable to contain 70% by mass or more of the total mass of the catalyst ink with a solvent in which the alcohol terminals are all etherified or esterified with a polyhydric alcohol. With this configuration, drying of the catalyst ink on the anchor layer, printing image quality, ejection stability as ink, and storage stability can be improved.

(Other various additives)
The ink according to the present invention can contain various conventionally known additives in other metal pattern forming inks as required. For example, fluorescent brighteners, antifoaming agents, lubricants, preservatives, thickeners, antistatic agents, matting agents, water-soluble polyvalent metal salts, acid bases, pH adjusters such as buffers, antioxidants, surfaces Tension modifiers, non-resistance modifiers, rust inhibitors, inorganic pigments and the like can be mentioned.

《Metallic pattern manufacturing process》
The method for producing a metal pattern of the present invention includes a step of forming an anchor layer on a substrate using a polymerizable composition, and a step of applying an electroless plating catalyst or an ink containing a precursor thereof to the substrate. Basically, an electroless plating process for forming a metal pattern by electroless plating, and an electroplating process for thickening the metal film formed in the electroless plating process to form a plating layer (conductive film, final metal pattern) In addition, the following steps are appropriately provided. For example, having a drying process after the ink application process, having an activation process between the drying process and the electroless plating process, and having a surface treatment process between the drying process and the activation process. Can be mentioned.

  Hereinafter, a typical process of the metal pattern manufacturing method of the present invention will be described.

As described above, the metal pattern manufacturing method of the present invention mainly includes:
(1) forming an anchor layer having a gel fraction of 95% or more on a substrate using a polymerizable compound;
(2) a step of applying a catalyst ink containing a catalyst for electroless plating or a precursor thereof;

(3) Surface treatment step for modifying the catalyst ink surface or anchor layer surface (4) When the catalyst ink contains a catalyst precursor, an activation treatment step for converting (reducing) the catalyst precursor into a catalyst,
(5) An electroless plating process for generating metal with an electroless plating solution,
(6) In the electroplating step, the step of increasing the thickness of the metal pattern portion,
Thus, a metal pattern is formed. At this time, the formation of the metal pattern may be a method of forming a pattern only on a necessary portion, or a method of forming a metal pattern on the entire anchor layer.

  Hereafter, the manufacturing method flow of the metal pattern of this invention is further demonstrated.

[1: Anchor layer forming step]
As described above, as the anchor layer forming step, the anchor layer coating solution is applied and dried on the substrate using the coater, and the anchor layer is formed on the entire surface.

[2: Catalyst ink application step]
Next, as a step of applying the catalyst ink, the catalyst ink is applied to the entire surface of the anchor layer using a coater. Further, a method of applying a catalyst ink so as to form a separated region on the anchor layer using a coater (for example, an ink jet recording head) may be applied.

  As a method for applying the catalyst ink according to the present invention, a printing method can be used. Specific examples include screen printing, letterpress printing, gravure printing, offset printing, dispenser printing, and ink jet printing. As long as the catalyst ink can be applied to the anchor layer, it is not limited to the printing method, and can be applied by roll coating, reverse coating, wire bar coating, dip coating, or the like.

The amount of the catalyst ink applied is selected in consideration of the concentration of the electroless plating catalyst in the ink or the precursor concentration, the boiling point of the solvent, the drying property, and the electroless plating property. The application amount of a specific catalyst ink ^is preferably ^{0.5ml / m 2 ~50ml / m 2} , more preferably from ^{2.0ml / m 2 ~30ml / m 2} . If the applied amount is 0.5 ml / m ² or more, the electroless plating property (metal forming property) is sufficient, and if it is 50 ml / m ² or less, the uniformity and drying property of the catalyst ink is ensured. Can do.

  After applying the catalyst ink, it is preferable to provide a drying step, and the drying method is preferable from the viewpoint of shortening the time such as heating and blowing and simplifying the step.

  In the present invention, a step in which the catalyst ink component swells or dissolves the anchor layer may be provided. That is, the catalyst ink applied on the anchor layer may penetrate into the anchor layer to form a region where the anchor layer swells or dissolves.

[3: Surface treatment process]
Next, before performing the electroless plating treatment step (activation step in the case of a catalyst precursor), the anchor layer or the catalyst ink application region is hydrophilized so as to improve the surface wettability with respect to the plating solution or the activation solution. It is preferable to modify the surface by performing a surface treatment such as the above.

  Since the plating treatment solution or the activation treatment solution is usually an aqueous treatment solution, the improvement in wettability here means a surface treatment step for increasing the wettability of the anchor layer surface to water.

  If the contact angle of the anchor layer with respect to water decreases before and after the surface treatment step, it is effective as the surface treatment. Specifically, a treatment in which the contact angle with water is reduced by 20% or more before and after the surface treatment step is preferable. As the surface treatment method, there are a method of treating with a liquid containing a cation, nonion, and anionic surfactant, and a method of improving wettability to a plating solution by a surface treatment process such as plasma, corona, flame, and UV irradiation. Among these, liquid treatment with a surfactant is preferable because it is simple and highly effective.

[4: Activation treatment process]
Next, when the catalyst ink contains a catalyst precursor, an activation treatment is performed to convert the catalyst precursor into a catalyst capable of electroless plating. That is, when the catalyst ink contains a precursor of an electroless plating catalyst, the activation treatment step is performed before the electroless plating treatment step in order to denature it into an electroless plating catalyst.

  When a metal salt compound is used as a precursor of the electroless plating catalyst, it is a step of reacting with a zero-valent metal by a reduction reaction, and this activation step can become an electroless plating catalyst.

  In the activation step, it is necessary to select an appropriate method depending on the type of the catalyst, and examples thereof include application of an acid, heating, and application of a reducing agent. As a preferable reducing agent, a boron-based compound is preferable, and specifically, sodium borohydride, trimethylamine borane, dimethylamine borane (DMAB) and the like are preferable. As a reduction method, an activation treatment can be performed by immersing a substrate provided with a catalyst ink in a solution of a reducing agent.

[5: Electroless plating process]
Next, an electroless plating process is performed on the catalyst to form a metal part and a metal film in the anchor layer.

  The electroless plating process according to the present invention will be described.

  Usually, it is a step of immersing in an electroless plating solution (bath) and forming a metal by an electroless plating reaction at a portion of the anchor layer provided with a catalyst ink.

  The electroless plating solution mainly contains 1) metal ions, 2) complexing agent for electroless plating solution, and 3) reducing agent. Examples of the metal formed by electroless plating include gold, silver, copper, palladium, nickel, and alloys thereof, and copper, nickel, and alloys thereof are preferable from the viewpoint of adhesion and conductivity. Also as a metal ion used for an electroless plating bath, a metal ion corresponding to the above metal is contained. The complexing agent and reducing agent for the electroless plating solution are also selected to be suitable for metal ions. Examples of the complexing agent include ethylenediaminetetraacetic acid (hereinafter abbreviated as EDTA), Rochelle salt, D-mannitol, D-sorbitol, dulcitol, iminodiacetic acid, trans-1,2-cyclohexanediaminetetraacetic acid, and the like. EDTA is preferred. Examples of the reducing agent include formaldehyde, potassium tetrahydroborate, dimethylamine borane, glyoxylic acid and sodium hypophosphite, and formaldehyde is preferred.

  The electroless plating step can control the metal formation speed and film thickness by controlling the temperature, pH, immersion time, and metal ion concentration of the plating bath.

[6: Electroplating process]
Finally, for the purpose of forming a plating layer (conductive film) by increasing the film thickness of the metal film formed by the electroless plating process, an electroplating process is further performed.

  In the electroplating step, after the electroless plating treatment of item 5, the metal film formed by the electroless plating treatment step can be used as an electrode for further electroplating. Thus, a conductive film (plating layer) having an arbitrary thickness can be easily formed on a metal film having excellent adhesion to the base material. By adding this step, the conductive film can be formed to a thickness according to the purpose, and the conductive film thus formed is suitable for various applications that require high conductivity. .

  As a method of electroplating applicable to the present invention, a conventionally known method can be used. In addition, as a metal used for the electroplating of this process, copper, chromium, lead, nickel, gold, silver, tin, zinc, etc. are mentioned. From the viewpoint of conductivity, copper, gold, and silver are preferable. More preferred.

  About the film thickness of the electrically conductive film obtained by electroplating, it changes according to a use, It can control by adjusting the metal density | concentration contained in a plating bath, immersion time, or current density. In addition, from the viewpoint of conductivity, the film thickness when used for general electric wiring or the like is preferably 0.3 μm or more, and more preferably 3 μm or more.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "part by mass" or "mass%" is represented.

Example 1
<< Preparation of substrate with anchor layer >>
(Preparation of substrate 1 with anchor layer)
<Synthesis of polymerizable compound 1 having an ethylenically unsaturated group>
A polymerizable compound 1 having an ethylenically unsaturated group as a polymerizable group was synthesized according to the following procedure. To a 500 ml three-necked flask, 20 ml of ethylene glycol diacetate, 7.43 g of hydroxyethyl acrylate, and 32.08 g of cyanoethyl acrylate are added, and the temperature is raised to 80 ° C. Then, an oil-soluble azo polymerization initiator is added thereto. As a mixture, 0.737 g of V-601 (dimethyl-2,2′-azobis (2-methylisopropionate)) and 20 ml of ethylene glycol diacetate were added dropwise over 4 hours. Reacted for hours.

  In the above reaction solution, 0.32 g of di-tert-butylhydroquinone, 1.04 g of neostan U-600 (bismuth octylate, manufactured by Nitto Kasei), Karenz AOI (acryloxyethyl isocyanate, Showa) as a photocurable resin additive 21.87 g of Denko Co., Ltd.) and 22 g of ethylene glycol diacetate were added and reacted at 55 ° C. for 6 hours. Thereafter, 4.1 g of methanol was added to the reaction solution, and the reaction was further performed for 1.5 hours. After completion of the reaction, reprecipitation was performed with water, and a solid was taken out to obtain a polymerizable compound 1 having a nitrile group as an interactive group.

  The polymerizable compound 1 was a repeating unit containing a polymerizable group (ethylenically unsaturated group): a repeating unit containing a nitrile group = 22: 78 (molar ratio). Moreover, molecular weight was Mw = 82,000 (Mw / Mn = 3.4) in polystyrene conversion.

<Preparation of anchor layer coating solution 1>
10 parts by mass of the prepared polymerizable compound 1 and 90 parts by mass of acetonitrile were mixed and stirred to prepare an anchor layer coating solution 1 having a solid content of 10% by mass.

<Formation of anchor layer 1>
A polyimide film (Toray Film Processing Co., Ltd., Kapton 100EN film thickness 25 μm) was used as the substrate, and after the surface was subjected to oxygen plasma treatment, the anchor layer coating solution 1 was dried to have a film thickness of 1.0 μm. Then, it was applied by spin coating and dried at 80 ° C. for 30 minutes.

<Hardening treatment of anchor layer 1>
Next, using a UV irradiation lamp (model number: UVF-502S, lamp: UXM-501MD) manufactured by Mitsunaga Electric, an irradiation power of 1.5 mW / cm ² (Ushio Electric UV integrated light meter UIT150-light receiving sensor UVD-S254). The anchor layer 1 was cured by irradiating with ultraviolet rays under the condition that the integrated light quantity was 500 mJ / cm ² . This curing condition is referred to as condition A.

The anchor layer 1 cured under the above condition A is isolated, subjected to extraction treatment at 25 ° C. for 12 hours in an acetone solution, the weight of the anchor layer before treatment is set to W ₁ (g), and the anchor after acetone extraction When the mass of the layer was W ₂ (g), the gel fraction was determined by the following formula. As a result of the measurement, the gel fraction of the anchor layer 1 was 93%.

Gel fraction (%) = (W ₂ / W ₁ ) × 100
(Preparation of substrate 2 with anchor layer)
A substrate 2 with an anchor layer was produced in the same manner as in the production of the substrate 1 with an anchor layer, except that the anchor layer 1 was changed to an anchor layer 2 formed according to the following method.

<Formation of anchor layer 2>
In the formation of the anchor layer 1, a cured anchor layer 2 was formed in the same manner except that the irradiation power of the UV irradiation lamp was changed to 100 mW / cm ² and the integrated light quantity was changed to 250 mJ / cm ² . This forming method is referred to as condition B. The gel fraction of the anchor layer 2 measured by the above method was 95%.

(Preparation of substrate 3 with anchor layer)
A substrate 3 with an anchor layer was produced in the same manner as in the production of the substrate 1 with an anchor layer, except that the anchor layer 1 was changed to an anchor layer 3 formed according to the following method.

<Formation of anchor layer 3>
In the formation of the anchor layer 1, irradiation with a UV irradiation lamp was performed in the same manner as the formation conditions of the anchor layer 1 to cure the anchor layer, and then a heat treatment (post cure) at 90 ° C. for 30 minutes was performed. An anchor layer 3 was formed in the same manner except that. This forming method is referred to as condition C. The gel fraction of the anchor layer 3 measured by the above method was 94%.

(Preparation of substrate 4 with anchor layer)
A substrate 4 with an anchor layer was produced in the same manner as in the production of the substrate 1 with an anchor layer, except that the anchor layer 1 was changed to an anchor layer 4 formed according to the following method.

<Formation of anchor layer 4>
In the formation of the anchor layer 1, irradiation with a UV irradiation lamp was performed in the same manner as the formation conditions of the anchor layer 1 to cure the anchor layer, and then a heat treatment (post cure) at 100 ° C. for 30 minutes was performed. An anchor layer 4 was formed in the same manner except that. This forming method is referred to as condition D. The gel fraction of the anchor layer 4 measured by the above method was 96%.

(Preparation of substrate 5 with anchor layer)
A substrate 5 with an anchor layer was produced in the same manner as in the production of the substrate 1 with an anchor layer, except that the anchor layer 1 was changed to an anchor layer 5 formed according to the following method.

<Formation of anchor layer 5>
In the formation of the anchor layer 1, irradiation with a UV irradiation lamp was performed in the same manner as the formation conditions of the anchor layer 1 to cure the anchor layer, and then a heat treatment (post cure) at 120 ° C. for 30 minutes was performed. An anchor layer 5 was formed in the same manner except that. This forming method is referred to as condition E. The gel fraction of the anchor layer 5 measured by the above method was 97%.

(Preparation of substrate 6 with anchor layer)
A substrate 6 with an anchor layer was produced in the same manner as in the production of the substrate 1 with an anchor layer, except that the anchor layer 1 was changed to an anchor layer 6 formed according to the following method.

<Formation of anchor layer 6>
In the formation of the anchor layer 1, irradiation with a UV irradiation lamp was performed in the same manner as the formation conditions of the anchor layer 1 to cure the anchor layer, and then a heat treatment (post cure) was performed at 100 ° C. for 30 seconds. An anchor layer 6 was formed in the same manner except that. This forming method is referred to as condition F. The gel fraction of the anchor layer 6 measured by the above method was 94%.

(Preparation of substrate 7 with anchor layer)
A substrate 7 with an anchor layer was produced in the same manner as in the production of the substrate 1 with an anchor layer, except that the anchor layer 1 was changed to an anchor layer 7 formed according to the following method.

<Formation of anchor layer 7>
In the formation of the anchor layer 1, irradiation with a UV irradiation lamp was performed in the same manner as the formation conditions of the anchor layer 1 to cure the anchor layer, and then a heat treatment (post cure) was performed at 100 ° C. for 1 minute. An anchor layer 7 was formed in the same manner except that. This forming method is referred to as condition G. The gel fraction of the anchor layer 7 measured by the above method was 95%.

(Preparation of substrate 8 with anchor layer)
A substrate 8 with an anchor layer was produced in the same manner as in the production of the substrate 1 with an anchor layer, except that the anchor layer 1 was changed to an anchor layer 8 formed according to the following method.

<Formation of anchor layer 8>
In the formation of the anchor layer 1, irradiation with a UV irradiation lamp was performed in the same manner as the formation conditions of the anchor layer 1 to cure the anchor layer, and then a heat treatment (post cure) at 100 ° C. for 1 hour was performed. An anchor layer 8 was formed in the same manner except that. This forming method is referred to as condition H. The gel fraction of the anchor layer 8 measured by the above method was 97%.

(Preparation of substrate 9 with anchor layer)
A substrate 9 with an anchor layer was produced in the same manner as in the production of the substrate 1 with an anchor layer, except that the anchor layer 1 was changed to an anchor layer 9 formed according to the following method.

<Formation of anchor layer 9>
In the formation of the anchor layer 1, irradiation with a UV irradiation lamp was performed in the same manner as the formation conditions of the anchor layer 1 to cure the anchor layer, and then a heat treatment (post cure) was performed at 100 ° C. for 5 hours. An anchor layer 9 was formed in the same manner except that. This formation method is referred to as Condition I. The gel fraction of the anchor layer 9 measured by the above method was 97%.

(Preparation of substrate 10 with anchor layer)
A substrate 10 with an anchor layer was produced in the same manner as in the production of the substrate 1 with an anchor layer, except that the anchor layer 1 was changed to an anchor layer 10 formed according to the following method.

<Formation of Anchor Layer 10>
In the formation of the anchor layer 1, irradiation with a UV irradiation lamp was performed in the same manner as the formation conditions of the anchor layer 1 to cure the anchor layer, and then a heat treatment (post cure) at 100 ° C. for 10 hours was performed. An anchor layer 10 was formed in the same manner except that. This forming method is referred to as condition J. The gel fraction of the anchor layer 10 measured by the above method was 97%.

<Production of metal pattern>
[Production of Metal Pattern 1]
The metal pattern 1 was produced according to the following metal pattern formation process using the produced substrate 1 with an anchor layer.

(Metal pattern formation process)
1: Catalyst ink application process 2: Drying process 3: Surface treatment process 4: Activation process 5: Electroless plating process 6: Electroplating process (1: Catalyst ink application process)
<Preparation of catalyst ink 1>
Catalyst ink 1 was prepared by mixing the following additives.

Electroless plating catalyst precursor: 0.05% by mass of palladium acetate
Ethylene diacetate 79.95% by mass
t-Butyl alcohol 20% by mass
<Application of catalyst ink 1>
The prepared catalyst ink 1 was drawn on the anchor layer of the formed anchor layer substrate 1 by using an ink jet recording head, and each line and space pattern of 75 μm, 100 μm, 150 μm, and 200 μm was drawn. Was made.

  The ink jet recording head used was a 512S head manufactured by Konica Minolta IJ, which can eject 4 pl size ink droplets by a piezo method.

(2: Drying process)
After the catalyst ink 1 was applied, hot air at 50 ° C. was blown onto the catalyst ink application surface for 10 minutes and dried.

(3: Surface treatment process)
A surface treatment method was applied to the dried sample 1 according to the following method.

<Surface treatment method>
The sample 1 was immersed in a 10% by mass solution of a plating conditioner containing a nonionic surfactant (trade name: PC-321, manufactured by Meltac Corporation) at 60 ° C. for 5 minutes for surface treatment.

  As a result of measuring the contact angle with respect to water of the sample 1 subjected to the surface treatment and the untreated sample, it was confirmed that the contact angle was reduced by 20% or more by the surface treatment.

(4: Activation process)
Next, the sample 1 subjected to the surface treatment was immersed in the following activation liquid at 35 ° C. for 10 minutes to perform the activation treatment.

<Activation liquid>
Alcup MRD2-A (Uemura Kogyo Co., Ltd.) 18ml
Alcup MRD2-C (manufactured by Uemura Kogyo Co., Ltd.) 60ml
Finished to 1000 ml with pure water.

(5: Electroless plating process)
After adjusting the pH of the following electroless copper plating solution to 13.0 with sodium hydroxide, the sample 1 subjected to 5: activation treatment was subjected to electroless plating treatment at a temperature of 50 ° C. A copper plating layer having a thickness of 2 μm was formed.

<Electroless copper plating solution>
Melplate CU-5100A (Meltex) 60ml
Melplate CU-5100B (Meltex) 55ml
Melplate CU-5100C (Meltex) 20ml
Melplate CU-5100M (Meltex) 40ml
Finished to 1000 ml with pure water.

  The electroless copper plating solution has a copper concentration of 2.5 mass%, a formalin concentration of 1 mass%, and an ethylenediaminetetraacetic acid (EDTA) concentration of 2.5 mass%.

(6: Electroplating process)
Sample 1 subjected to the above electroless plating treatment is immersed in an electroplating bath, a copper plate is used as an anode, and electroplating is performed at a current density of 1.5 A / dm ² to form a copper film having a thickness of about 15 μm. 1 was produced.

<Preparation of electroplating bath>
Copper sulfate pentahydrate 60g
190g of sulfuric acid
Chloride ion 50mg
Copper Gream PCM (Meltex) 5ml
Finished to 1000 ml with pure water.

[Production of metal patterns 2 to 10]
In the formation of the metal pattern 1, metal patterns 2 to 10 were produced in the same manner except that the substrates 2 to 10 with anchor layers were used instead of the substrate 1 with anchor layers, respectively.

<Evaluation of metal pattern>
The following evaluations were performed on each of the fabricated metal patterns.

[Evaluation of plating sensitivity]
About the sample which processed to the electroless-plating process of each metal pattern, the time until the copper film thickness formed by electroless plating grew to 0.3 micrometer was measured, and plating sensitivity was evaluated according to the following standard. .

A: Formation of a copper film thickness of 0.3 μm is less than 5 minutes ○: Formation of a copper film thickness of 0.3 μm is 5 minutes or more and less than 10 minutes Δ: Copper film thickness of 0.3 μm Formation is 10 minutes or more and less than 20 minutes x: Formation of a copper film thickness of 0.3 μm is 20 minutes or more or cannot be formed [Evaluation of plating quality]
The 75 μm, 100 μm, 150 μm, and 200 μm line & space patterns drawn on the samples processed up to the electroless plating process of each metal pattern were visually observed, and the image quality was evaluated according to the following criteria.

○: The line & space pattern after completion of electroless plating has no abnormal deposition outside the printed part, and it has good quality with no degradation of plating gloss or cracks. △: Line & space after completion of electroless plating In the space pattern, slight abnormal deposition outside the printed area occurs, but no degradation of plating gloss or cracks are observed. ×: In the line & space pattern after electroless plating is completed, abnormal deposition outside the printed area. , Plating gloss reduction, or crack generation has occurred. [Evaluation of durability (adhesion resistance) under high temperature and high humidity]
Each metal pattern prepared above was stored for 7 days in a high-temperature and high-humidity environment at 80 ° C. and 90% RH, and then immediately subjected to heat treatment on a hot plate at 240 ° C. and 260 ° C. The adhesion (the presence or absence of occurrence of blisters) was visually observed, and the durability (adhesion resistance) was evaluated according to the following criteria.

○: Even when heated to 260 ° C. on the hot plate, no blistering is observed between the substrate and the copper plating pattern. Δ: Even when heated to 240 ° C. on the hot plate, between the substrate and the copper plating pattern. No blistering was observed, but some blistering was observed when heated at 260 ° C. ×: When heated to 240 ° C on a hot plate, blistering was clearly observed between the substrate and the copper plating pattern. Table 1 shows the results obtained as described above.

  As is clear from the results shown in Table 1, the metal pattern formed according to the metal pattern manufacturing method of the present invention has a plating sensitivity, plating quality, and durability under high-temperature and high-humidity environments (adhesion) with respect to the comparative example. It can be seen that it is excellent in resistance.

Example 2
<< Preparation of substrate with anchor layer >>
(Preparation of substrate 11 with anchor layer)
<Preparation of anchor layer coating solution 11>
The following additives were mixed and dissolved to prepare anchor layer coating solution 11 having a solid content of 20% by mass.

Epoxy resin: Epicoat 828EL (bisphenol A type epoxy resin, epoxy equivalent 186 g / eq, manufactured by Japan Epoxy Resin Co., Ltd.) 6.0% by mass
Curing agent: Amine compound 1 (4,4-diaminophenylmethane) 2.0% by mass
Polymer: SG-P3 (epoxy group-containing acrylic copolymer, manufactured by Nagase ChemteX Corporation)
12% by mass
Methyl ethyl ketone 40% by mass
Toluene 40% by mass
<Formation of anchor layer 11>
As a substrate, a polyimide film (Toray Film Processing Co., Ltd., Kapton 100EN film thickness 25 μm) was used, and after the surface was subjected to oxygen plasma treatment, the anchor layer coating solution 11 was dried to have a film thickness of 5.0 μm. The anchor layer was cured by applying a wire bar coating method, followed by heat treatment at 150 ° C. for 1 hour.

  The anchor layer 11 cured under the above conditions was isolated, and the gel fraction was measured in the same manner as in the method described in Example 1. As a result, it was 65%.

(Preparation of anchor layer-attached substrates 12 to 20)
<Preparation of Anchor Layer Coating Solutions 12-20>
In the preparation of the anchor layer coating solution 11, the addition amount of the epoxy resin, the type and addition amount of the amine compound, the type and addition amount of the latent catalyst, and the addition amount of the polymer were changed as shown in Table 2, respectively. In the same manner, anchor layer coating solutions 12 to 20 were prepared.

  In addition, the detail of each additive described by the abbreviation in Table 2 is as follows.

<Epoxy resin>
828EL: Epicoat 828EL (bisphenol A type epoxy resin, epoxy equivalent 186 g / eq, manufactured by Japan Epoxy Resin Co., Ltd.)
<Curing agent>
Amine compound 1: 4,4-diaminophenylmethane Amine compound 2: Dicyandiamide <Latent catalyst>
Latent catalyst 1: 2-ethyl-4-methylimidazole Latent catalyst 2: 2-phenylimidazole <Polymer>
SG-P3: Epoxy group-containing acrylic copolymer, manufactured by Nagase ChemteX Corporation <Preparation of substrate with anchor layer>
In the production of the anchor layer-provided substrate 11, the anchor layer-coated substrates 12 to 20 were produced in the same manner except that the anchor layer coating solutions 12 to 20 were used in place of the anchor layer coating solution 11.

<Production of metal pattern>
In the production of the metal pattern 1 described in Example 1, metal patterns 11 to 20 were produced in the same manner except that the produced substrates 11 to 20 with anchor layers were used instead of the substrate 1 with anchor layers.

<Measurement of gel fraction of anchor layer>
About the anchor layer which comprises each board | substrate with an anchor layer, it carried out similarly to the method of Example 1, measured the gel fraction, and Table 3 shows the result obtained.

<Evaluation of metal pattern>
For each metal pattern produced above, in the same manner as described in Example 1, evaluation of plating sensitivity, evaluation of plating quality, and evaluation of durability (adhesion resistance) under high temperature and high humidity environment, The obtained results are shown in Table 3.

  As is apparent from the results shown in Table 3, the metal pattern formed according to the method for producing a metal pattern of the present invention has a plating sensitivity, plating quality, and durability under high-temperature and high-humidity environments (adhesion) compared to the comparative example. It can be seen that it is excellent in resistance.

Claims (4)

  In the method for producing a metal pattern, an anchor layer is formed on a substrate, an ink containing an electroless plating catalyst or a precursor thereof is applied on the anchor layer, and then a metal pattern is formed by an electroless plating process. The anchor layer is formed by applying the polymerizable composition onto the substrate and then polymerizing the polymerizable composition by a photopolymerization method or a thermal polymerization method, and the anchor layer has a gel fraction of 95 by the acetone extraction method. % Or more, The manufacturing method of the metal pattern characterized by the above-mentioned.   The method for producing a metal pattern according to claim 1, wherein the polymerizable composition contains a polymerizable monomer having an epoxy group as a polymerizable group and a latent catalyst.   The polymerizable composition contains a polymerizable monomer having an ethylenically unsaturated group as a polymerizable group, and is applied on the substrate, and then heated at a temperature of 100 ° C. or higher for 1 minute or longer. The metal pattern manufacturing method according to claim 1, wherein the metal pattern is a metal pattern.   2. An activation step of activating the electroless plating catalyst or a precursor thereof between the step of forming an anchor layer on the substrate and the step of performing electroless plating treatment. The manufacturing method of the metal pattern of any one of 1-3.