WO2014162867A1

WO2014162867A1 - Method for manufacturing wiring board

Info

Publication number: WO2014162867A1
Application number: PCT/JP2014/057266
Authority: WO
Inventors: 加納　丈嘉; 考浩加藤
Original assignee: 富士フイルム株式会社
Priority date: 2013-04-01
Filing date: 2014-03-18
Publication date: 2014-10-09
Also published as: JP2014203848A

Abstract

The purpose of the present invention is to provide a method for manufacturing a wiring board in which the wiring layer pattern-formability is excellent and the adhesion performance with respect to an insulation layer laminated thereon remains extremely stable over time. This method for manufacturing a wiring board has: a step (A) for imparting energy to a region representing a part of the wettability variation layer of the board and converting the region into a water-repellent region, and forming a wettability pattern comprising the water-repellent region and a hydrophilic region on the wettability variation layer; a step (B) for imparting a wiring-layer-forming composition containing at least metal particles and/or metal oxide particles on the wettability variation layer and forming a coating on the water-repellent region or the hydrophilic region; and a step (C) for simultaneously or separately performing a step (C1) for imparting energy to the coating and forming a wiring layer and a step (C2) for imparting energy to the hydrophilic region and converting the hydrophilic region into a water-repellent region.

Description

Wiring board manufacturing method

The present invention relates to a method for manufacturing a wiring board, and more particularly to a method for manufacturing a wiring board using a wettability changing layer in which the wettability changes so that the contact angle with water increases when energy is applied.

In recent years, as a method of manufacturing a wiring substrate, a method of forming a pattern using a difference in wettability of a substrate surface has been proposed for improving pattern formation.
For example, in Patent Document 1, the pattern forming portion of the substrate is hydrophobized using a hydrophobic processing agent that can be hydrophilized by exposure, and then the pattern forming portion is exposed in a pattern shape to make the exposed portion hydrophilic, A hydrophilic solution of a metal compound is applied to a pattern, and the metal compound is deposited to form a wiring layer (metal) in a pattern.

Japanese Patent No. 3430632

In the method of Patent Document 1, a hydrophobic surface is exposed to make it hydrophilic, and a wiring layer is formed on the hydrophilic region. Therefore, the hydrophilic region remains in the formed wiring board.
In recent years, electronic devices have been improved in performance and size, and accordingly, further improvement in adhesion between a wiring board and an insulating layer provided on the wiring board is required.
The present inventor formed a wiring substrate using a wettability changing layer that changes from hydrophobicity to hydrophilicity described in Patent Document 1, and provided an insulating layer on the wiring substrate, and examined its adhesion. However, it has been found that the adhesiveness of the insulating layer decreases with time.

In view of the above circumstances, an object of the present invention is to provide a method of manufacturing a wiring board that is excellent in pattern formation of a wiring layer and excellent in temporal stability of the adhesion of laminated insulating layers.

As a result of earnestly examining the problems of the prior art, the present inventors can solve the above-mentioned problems by using a wettability changing layer in which the wettability changes so that the contact angle with water is increased by applying energy. I found.
That is, it has been found that the above object can be achieved by the following configuration.

(1) A wettability changing layer of a substrate having a support and a wettability changing layer that is disposed on the support and changes wettability so that a contact angle with water increases when energy is applied. Applying energy to a partial region to convert the hydrophilic region to a water-repellent region, and forming a wettability pattern comprising the water-repellent region and the hydrophilic region on the wettability changing layer (A);
Step (B) of applying a composition for forming a wiring layer containing at least metal particles and / or metal oxide particles on the wettability changing layer to form a coating film on the water-repellent region or the hydrophilic region. When,
The step (C1) of applying energy to the coating film to form a wiring layer and the step (C2) of applying energy to the hydrophilic region remaining in the wettability changing layer and converting it to a water repellent region, or simultaneously A method for manufacturing a wiring board, comprising the step (C) of performing separately.
(2) The method for manufacturing a wiring board according to (1), wherein a coating film is formed on the water-repellent region.
(3) The method for manufacturing a wiring board according to (1) or (2), wherein the application of energy is a light irradiation treatment.
(4) The method for manufacturing a wiring board according to any one of (1) to (3), wherein the wettability changing layer is a layer in which the wettability is changed by decarboxylation by application of energy.
(5) The wettability changing layer is selected from the group consisting of a nitrophenylacetic acid structure, a β-keto acid structure, and an acetic acid structure having an O element, an N element, or an S element at the β position with respect to the carboxyl group. The method for manufacturing a wiring board according to any one of (1) to (4), comprising a compound having at least one.
(6) The method for manufacturing a wiring board according to any one of (1) to (5), wherein the step (C1) and the step (C2) are performed simultaneously.

According to the present invention, it is possible to provide a method of manufacturing a wiring board that is excellent in pattern formation of a wiring layer and excellent in the temporal stability of the adhesion of laminated insulating layers.

It is typical sectional drawing which shows each process of the manufacturing method of this invention. It is typical sectional drawing which shows the suitable embodiment of a wettability change layer. It is the schematic which shows the evaluation method of the pattern formation property in the Example column.

Below, the suitable aspect of the manufacturing method of the wiring board of this invention is explained in full detail.
First, the feature point compared with the prior art of this invention is explained in full detail.
As described above, the feature of the present invention is that the wettability changing layer whose wettability changes so that the contact angle with water is increased by applying energy, and the hydrophilic region does not remain in the wettability changing layer. In this way, the step of applying energy (fixing step) is performed. The present inventor has found that the adhesiveness of the insulating layer in the prior art is lowered because the hydrophilic region remains, so that moisture adsorbs near the interface between the wiring board and the insulating layer over time. As a result, it was found that the adhesiveness between the two deteriorated. Therefore, in the present invention, by using a wettability changing layer in which the wettability changes so as to increase the contact angle, that is, the wettability changing layer in which the surface characteristics change from hydrophilic to water repellent (hydrophobic), I found that the problem could be solved. More specifically, in the present invention, the wiring layer is formed with high pattern accuracy using the wettability changing layer, and the entire region of the wettability changing layer is formed so that the hydrophilic region does not remain finally. It changes to water repellency, suppresses moisture adsorption, and ensures the adhesion of the insulating layer.

Hereinafter, the method for manufacturing a wiring board according to the present invention will be described in detail with reference to FIG.
The production method of the present invention includes steps (A) to (C). Below, the material and member used for every process, and the procedure of a process are explained in full detail.

<Process (A) (Wettability pattern formation process)>
In the step (A), energy is imparted to a partial area of the wettability changing layer in the substrate to convert the hydrophilic area into the water repellent area, and the water repellent area and the hydrophilic area are formed on the wettability changing layer. Forming a wettability pattern. In addition, a board | substrate has a support body and the wettability change layer which is arrange | positioned on a support body and wettability changes so that a contact angle with water will increase when energy is provided.
More specifically, as shown in FIG. 1A, first, a substrate 10 is prepared. The substrate 10 includes a support 12 and a wettability changing layer 14. The wettability changing layer 14 is in a state before energy application and has a hydrophilic region 14a. Energy is applied to the wettability changing layer 14 in a pattern to form a water repellent region 14b, and the hydrophilic region 14a and the water repellent property are formed on the wettability changing layer 14 as shown in FIG. A wettability pattern including the region 14b is formed.
In the present specification, the water repellent region and the hydrophilic region are words indicating that there is a difference in wettability between the two, and do not indicate the size of the contact angle of each region. Further, in this specification, a region of the wettability changing layer before energy application is referred to as a hydrophilic region, and a region where energy is applied and the contact angle with water is increased is referred to as a water repellent region.
Below, the material and member used at this process A are explained in full detail, and the procedure of the process A is explained in full detail after that.

(substrate)
A board | substrate has a support body and the wettability change layer arrange | positioned on a support body. Each will be described in detail below.

A support body is a board | substrate which supports the wettability change layer mentioned later.
The kind in particular of support body is not restrict | limited, A well-known support body is used. For example, a resin substrate, a glass substrate, a metal substrate, a semiconductor substrate, etc. are mentioned. Among these, it is preferable to use a resin substrate (particularly an insulating resin substrate) from the viewpoint of excellent handleability.

The wettability changing layer is a layer that is disposed on a support and changes wettability so that the contact angle with water increases when energy such as heat, ultraviolet rays, electron beams, plasma, or the like is applied. That is, it is a layer whose wettability changes more hydrophobicly when energy is applied.
By applying energy to a part of the wettability changing layer, patterns having different surface wettability composed of a water-repellent region (high surface energy region) and a hydrophilic region (low surface energy region) are formed. be able to. In other words, regions having different contact angles with respect to water can be formed. Therefore, the composition for forming a wiring layer, which will be described later, selectively adheres to a water-repellent region or a hydrophilic region on the basis of its property (hydrophobicity) and solidifies this, thereby selectively on one region. A wiring layer can be formed.

In the hydrophilic region of the wettability changing layer, the contact angle with water is preferably 60 ° or less, more preferably 40 ° or less, and even more preferably 20 ° or less.
In the water-repellent region of the wettability changing layer, the contact angle with water is preferably more than 90 °, preferably 100 ° or more, and more preferably 110 ° or more.
The difference in contact angle between the hydrophilic region and the water-repellent region with water is not particularly limited, but 30 ° or more is preferable and 50 ° or more is preferable in that the pattern forming property of the wiring layer is better and jaggy bulge is less likely to occur. More preferred. The upper limit is not particularly limited, but is usually 150 ° or less in many cases.
As a method for measuring the contact angle with water, a tangential method using two points of contact between the top of the dropped water and the wettability changing layer is used.

The thickness of the wettability changing layer is not particularly limited, but is preferably from 0.01 to 2 μm, more preferably from 0.01 to 1 μm, from the viewpoint of better pattern formation of the wiring layer.

The kind of material which comprises a wettability change layer is not restrict | limited in particular, It may consist of a single material and may be comprised from 2 or more types of materials. When the wettability changing layer is composed of two or more kinds of materials, it is preferable to mix an insulating material (for example, an insulating resin) and a material whose wettability changes.
As a material whose wettability changes by applying energy contained in the wettability changing layer (hereinafter also referred to as wettability changing material), the degree of change in wettability is large, and it is more excellent in pattern formation of the wiring layer. It has at least one selected from the group consisting of a nitrophenylacetic acid structure, a β-keto acid structure, a quaternary ammonium salt structure, and an acetic acid structure having an O, N, or S element at the β-position with respect to the carboxyl group Compounds are preferred. The compound may be a low molecular compound (a compound having a molecular weight of 1000 or less) or a high molecular compound (a compound having a molecular weight of more than 1000).
The content of the wettability changing layer in the wettability changing layer is not particularly limited, but 80% by mass or more based on the total mass of the wettability changing layer in that the change in the contact angle of water in the wettability changing layer is larger. Is preferable, and 90 mass% or more is more preferable. The upper limit is not particularly limited, but is preferably 100% by mass.

More specifically, the nitrophenylacetic acid structure is preferably a structure represented by the following formula (1). In the formula (1), * 1 and * 2 indicate bonding positions, and it is sufficient that they are bonded to the compound at any one position. In addition, a hydrogen atom couple | bonds with the carbon atom which is not a coupling | bonding position among the carbon atoms located in * 1 or * 2.

When energy (particularly light energy) is imparted to the nitrophenylacetic acid structure, the carboxyl group part undergoes a decarboxylation reaction and is decomposed and removed, resulting in more water repellency (hydrophobicity).
In formula (1), M represents an ion having a positive charge. Specific examples include sodium ions, potassium ions, ammonium ions, lithium ions, and the like, including hydrogen ions.

More specifically, the β-keto acid structure is preferably a structure represented by the following formula (2). In the formula (2), * 3 represents a bonding position. M in the formula (2) has the same definition as above.

When energy (particularly thermal energy) is applied to this β-keto acid structure, the carboxyl group part undergoes a decarboxylation reaction, which is decomposed and removed, resulting in more water repellency (hydrophobicity). .

More specifically, the quaternary ammonium salt structure is preferably a structure represented by the following formula (3). In formula (3), * 4 represents a bonding position.

When energy is imparted to the quaternary ammonium salt structure, the ammonium structure is decomposed and removed, resulting in more water repellency (hydrophobicity).
In formula (3), Z represents a halogen anion (for example, chlorine ion, bromine ion, etc.). R represents an alkyl group.

An acetic acid structure having an O element (oxygen element), an N element (nitrogen element), or an S element (sulfur element) in the β position with respect to the carboxyl group (hereinafter also simply referred to as an acetic acid structure X) is more specifically described. Is preferably a structure represented by the following formula (4). In the formula (4), * 5 indicates a bonding position.

When energy (particularly thermal energy) is imparted to the acetic acid structure X, the carboxyl group part undergoes a decarboxylation reaction and is decomposed and removed, resulting in more water repellency (hydrophobicity).
In the formula (4), X represents —O—, —S—, —Se—, —NR ³ —, —CO—, —SO—, —SO ₂ —, —PO—, —SiR ³ R ⁴ —, — CS-
R ¹ , R ² , R ³ and R ⁴ each independently represents a hydrogen atom or a substituent.
Specific examples of R ¹ , R ² , R ³ , R ⁴ include —F, —Cl, —Br, —I, —CN, —R ¹⁰ , —OR ¹⁰ , —OCOR ¹⁰ , —OCOOR ¹⁰ , —OCONR. ¹⁰ R ¹¹ , —OSO ₂ R ¹⁰ , —COR ¹⁰ , —COOR ¹⁰ , —CONR ¹⁰ R ¹⁴ , —NR ¹⁰ R ¹¹ , —NR ¹⁰ —COR ¹¹ , —NR ¹⁰ —COOR ¹¹ , —NR ¹⁰ —CONR ¹¹ R ¹² , —SR ¹⁰ , —SOR ¹⁰ , —SO ₂ R ¹⁰ , —SO ₃ R ^{10 and the} like can be mentioned.
R ¹⁰ , R ¹¹ , and R ¹² each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, or an alkynyl group.
Among these, preferred as R ¹ , R ² , R ³ and R ⁴ are specifically a hydrogen atom, an alkyl group, an aryl group, an alkynyl group and an alkenyl group.
M is an ion having a positive charge, and the definition is as described above.

As a preferred embodiment of the material whose wettability changes, a polymer having a repeating unit including any one selected from the group consisting of the nitrophenylacetic acid structure, the β-ketoic acid structure, and the acetic acid structure X is used. Can be mentioned. More specifically, a polymer having a repeating unit represented by the following formula (5) is preferable.

In the formula (5), R ²⁰ represents a hydrogen atom or an alkyl group (preferably a methyl group or an ethyl group).
L represents a single bond or a divalent linking group. Examples of the divalent linking group include a divalent aliphatic hydrocarbon group (preferably having 1 to 8 carbon atoms), a divalent aromatic hydrocarbon group (preferably having 6 to 12 carbon atoms), —O—, —S. —, —SO ₂ —, —N (R) — (R: alkyl group), —CO—, —NH—, —COO—, —CONH—, or a combination thereof (eg, alkyleneoxy group, alkylene Oxycarbonyl group, alkylenecarbonyloxy group, etc.).
Examples of the divalent aliphatic hydrocarbon group (for example, an alkylene group) include a methylene group, an ethylene group, a propylene group, or a butylene group.
Examples of the divalent aromatic hydrocarbon group include a phenylene group and a naphthylene group.

In formula (5), Y represents any one selected from the group consisting of a nitrophenylacetic acid structure, a β-keto acid structure, and an acetic acid structure X.

The content of the repeating unit in the polymer is not particularly limited, but is preferably 60 mol% or more, more preferably 80 mol% or more with respect to all repeating units in the polymer in terms of a greater change in wettability. preferable. The upper limit is not particularly limited, but is 100 mol%.

The weight average molecular weight of the polymer is not particularly limited, but is preferably 5000 to 100,000, more preferably 10,000 to 50,000 in terms of greater change in wettability and excellent handleability.

The wettability changing layer may contain a photothermal conversion substance.
If the energy to be applied is light energy such as IR laser, it is preferable that a photothermal conversion substance for converting the light energy into heat energy is contained in the wettability changing layer. Further, a photothermal conversion substance-containing layer may be separately provided on the wettability changing layer and contained therein.
As the photothermal conversion substance, any substance that absorbs light such as ultraviolet light, visible light, infrared light, white light and can be converted into heat can be used. For example, carbon black, carbon graphite, pigment, phthalocyanine pigment, iron powder Graphite powder, iron oxide powder, lead oxide, silver oxide, chromium oxide, iron sulfide, chromium sulfide and the like. Particularly preferred are dyes, pigments or metal fine particles having a maximum absorption wavelength from 760 nm to 1200 nm, which is the exposure wavelength of an infrared laser used for energy application.

As a preferred embodiment of the wettability changing layer, a layer in which the wettability is changed by decarboxylation by application of energy can be mentioned. Examples of such a layer include a layer containing a compound having at least one selected from the group consisting of the above-described nitrophenylacetic acid structure, β-keto acid structure, and acetic acid structure X.
The reason why the above layer is suitable will be described with reference to FIG.
When wettability changes with decarboxylation, the volume of the region decreases with decarboxylation, resulting in a difference in height between adjacent regions (non-energy imparted regions). More specifically, as shown in FIG. 2, the water-repellent region 14b, which is an energy application portion, decreases with decarboxylation and becomes lower than the adjacent hydrophilic region 14a. As a result, as shown in FIG. 2B, when a wiring layer forming composition 20 described later is applied on the water repellent region 14b, a step between the water repellent region 14b and the hydrophilic region 14a The wiring layer forming composition 20 is likely to stay on the water-repellent region 14b, and the pattern forming property of the wiring layer is further improved.

In addition, the method in particular of forming a wettability change layer on a support body is not restrict | limited, A well-known method is employable. For example, the wettability change layer forming composition containing the material which forms a wettability change layer is apply | coated on a support body, and the method of giving a drying process as needed is mentioned.
In addition, the composition for wettability change layer formation may contain the solvent as needed.

(Procedure of step (A))
The method for applying energy to a partial region of the wettability changing layer in the step (A) is not particularly limited, and an optimal method is appropriately selected according to the type of energy.
As the energy applying means, for example, heat treatment or light irradiation treatment such as exposure can be used. Specifically, for example, light irradiation with a UV lamp, visible light, or the like, heating with a laser, or the like is possible.
Examples of the light source include a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, and a carbon arc lamp. Also, g-line, i-line, and Deep-UV light can be used.
The time required for energy application varies depending on the material used, but is preferably 1 second to 10 minutes from the viewpoint of productivity.
The details of the heat treatment and the light irradiation treatment will be described in detail in the step (C) described later.

<Process (B): Coating film forming process>
In the step (B), a composition for forming a wiring layer containing at least metal particles and / or metal oxide particles is applied to the wettability changing layer obtained in the step (A), and the water repellent region or This is a step of forming a coating film on the hydrophilic region. By implementing this process, the coating film which is a precursor layer of a wiring layer can be formed on one area | region on a water-repellent area | region or a hydrophilic area | region.
Below, the material (composition for wiring layer formation) used by this process (B) is explained in full detail, and the procedure of this process (B) is explained in full detail after that.

(Composition for wiring layer formation)
The composition for forming a wiring layer contains metal particles and / or metal oxide particles. The metal particles and / or metal oxide particles become a material for forming the wiring layer in the step (C) described later.
The type of metal atom contained in the metal particle and metal oxide particle is not particularly limited, but a copper atom, a silver atom, or a gold atom is preferable, and a copper atom or a silver atom is more preferable in that the conductivity of the wiring layer is more excellent. preferable. That is, metal copper particles, copper oxide particles, metal silver particles, and silver oxide particles are preferable.

The shape of the metal particles and the metal oxide particles is not particularly limited, and examples thereof include a spherical shape, an ellipsoid shape, a rod shape, a wire shape, a plate shape, and a tree shape.
The average particle diameter of the metal particles and metal oxide particles is not particularly limited, but is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 500 nm or less. Although a minimum in particular is not restrict | limited, 1 nm or more is preferable.
An average particle size of 1 nm or more is preferable because the activity on the particle surface does not become too high, does not dissolve in the composition, and is easy to handle. Moreover, if it is 10 micrometers or less, it will become easy to form patterns, such as wiring by various printing methods, using the composition for wiring layer formation as an inkjet ink composition or a paste composition for screen printing, and use a composition as a conductor. Is preferable because the resulting wiring layer has good conductivity.
In addition, an average particle diameter points out an average primary particle diameter. The average particle diameter is determined by measuring the particle diameter (diameter) of at least 50 metal particles or metal oxide particles by observation with a transmission electron microscope (TEM) or scanning electron microscope (SEM), and calculating the arithmetic average of them. And ask. In addition, when the shape of a metal copper particle or a copper oxide particle is not a perfect circle shape in an observation figure, a major axis is measured as a diameter.

The composition for forming a wiring layer may contain components other than the metal particles and metal oxide particles.
For example, the wiring layer forming composition may contain a resin binder.
The type of the resin binder is not particularly limited, and examples thereof include thermoplastic resins such as vinyl resins, acrylic resins, styrene resins, polyolefin resins, and polyamide resins; epoxy resins, urethane resins, polyimide resins, non-plastic resins, and the like. Examples thereof include curable resins such as saturated polyester resins. These resins may be used alone or in combination of two or more.
More specifically, examples include polyvinyl pyrrolidone, polyvinyl alcohol, and polyalkylene glycol (for example, polyethylene glycol).

Moreover, the composition for wiring layer formation may contain the solvent. The solvent functions as a dispersion medium for metal particles and metal oxide particles.
The type of the solvent is not particularly limited. For example, water, alcohols (eg, methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol), ethers (eg, diethyl ether, diisobutyl ether, dibutyl ether) , Methyl-t-butyl ether), esters (for example, methyl formate, ethyl formate, butyl formate, methyl acetate) and the like can be used.
As will be described later, it is possible to control whether the wiring layer forming composition is disposed on the water-repellent region or the hydrophilic region depending on the type of the solvent. That is, when a solvent having a surface energy close to the surface energy of the water-repellent region (water-repellent solvent) is used, the wiring layer forming composition is disposed on the water-repellent region and has a surface close to the surface energy of the hydrophilic region. When the solvent (hydrophilic solvent) which has energy is used, the composition for wiring layer formation is arrange | positioned on a hydrophilic region.

(Procedure of step (B))
The method for applying the wiring layer forming composition on the wettability changing layer is not particularly limited, and examples thereof include spin coating, dip coating, screen printing, offset printing, and ink jet method. In order to be easily affected by the surface energy of the property change layer, an ink jet method capable of supplying smaller droplets is preferable.

As shown in FIG. 1C, the coating film 16 can be formed by applying the wiring layer forming composition onto the wettability changing layer.
In FIG. 1C, the coating film 16 is formed on the water-repellent region 14b. By selecting the type of solvent in the wiring layer forming composition, the coating film is formed on any region. Can form or control. That is, in the case of a wiring layer forming composition containing a water-repellent solvent, the composition is easily disposed on the water-repellent region 14b, and as a result, the embodiment shown in FIG. 1C is formed.
On the other hand, when the wiring layer forming composition containing a hydrophilic solvent is used, the composition is easily disposed on the hydrophilic region 14a, and as a result, the coating film 16 is disposed on the hydrophilic region 14a. .

In this step, if necessary, the wiring layer forming composition may be applied to the wettability changing layer and then dried to remove the solvent. By removing the remaining solvent, it is possible to suppress the generation of minute cracks and voids due to the vaporization and expansion of the solvent in the step (C) described later, and to change the conductivity of the wiring layer and the wettability of the wiring layer. It is preferable in terms of adhesion to the layer.
As a method for the drying treatment, for example, a hot air dryer or the like can be used, and an optimal temperature is appropriately selected as the temperature depending on the material to be used. It is more preferable to perform the treatment, and it is more preferable to perform the heat treatment at 70 ° C. or higher and lower than 100 ° C. In the case of using metal oxide particles, conditions that suppress oxidation are preferable, and for example, an inert gas atmosphere such as nitrogen or argon is more preferable, and drying is preferably performed in a reducing gas atmosphere such as hydrogen.

<Process (C): Wiring layer forming process>
In step (C), energy is applied to the coating produced in step (B) to form a wiring layer (C1), and energy is applied to the hydrophilic region remaining in the wettability changing layer. In this step, the step (C2) of converting to the water-repellent region is performed simultaneously or separately.
More specifically, in the step (C), as shown in FIG. 1 (D), energy is applied to the coating film 16 in FIG. 1 (C) to form the wiring layer 18 and the wettability changing layer 14. In this step, energy is imparted to the hydrophilic region 14a remaining therein to convert it into the water repellent region 14b.
First, each procedure of a process (C1) and a process (C2) is explained in full detail.

(Process (C1): Firing process)
Step (C1) is a step of forming a wiring layer by applying energy to the coating film produced in step (B).
Examples of the energy application method include heat treatment and / or light irradiation treatment as described in the step (A).
When metal particles are contained in the coating film, by performing heat treatment and / or light irradiation treatment, the metal particles are fused to each other to form grains, and the grains are further bonded and fused to each other. A wiring layer containing a metal is formed.
When the metal oxide particles are contained in the coating film, the metal oxide particles are reduced to metal particles by heat treatment and / or light irradiation treatment, and the generated metal particles are fused to each other. Then, the grains are formed, and the grains are bonded and fused together to form a wiring layer containing metal.

As the conditions for the heat treatment, optimum conditions are appropriately selected depending on the types of metal particles and metal oxides used. Among them, the heating temperature is preferably 100 to 300 ° C., more preferably 150 to 250 ° C., and the heating time is 5 to 120 minutes in that a wiring layer having better conductivity can be formed in a short time. Preferably, 10 to 60 minutes are more preferable.
The heating means is not particularly limited, and known heating means such as an oven and a hot plate can be used.

Unlike the above-described heat treatment, the light irradiation treatment can be sintered by irradiating light on a portion to which a coating film has been applied at room temperature for a short time, and deterioration of the substrate due to prolonged heating occurs. Therefore, the adhesion between the wiring layer and the substrate becomes better.

The light source used in the light irradiation treatment is not particularly limited, and examples thereof include a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, and a carbon arc lamp. Examples of radiation include electron beams, X-rays, ion beams, and far infrared rays. Also, g-line, i-line, deep-UV light, and high-density energy beam (laser beam) are used.
Specific examples of preferred embodiments include scanning exposure with an infrared laser, high-illuminance flash exposure such as a xenon discharge lamp, and infrared lamp exposure.

The light irradiation is preferably light irradiation with a flash lamp, and more preferably pulsed light irradiation with a flash lamp. Irradiation with high-energy pulsed light can heat the surface of the portion provided with the coating film in a very short time, so that the influence of heat on the substrate can be made extremely small.
The irradiation energy of the pulse light is preferably 1 ~ 100J / cm ^2, more preferably 1 ~ 30J / cm ^2, preferably from 1μ sec ~ 100 m sec as a pulse width, and more preferably 10μ sec ~ 10 m sec. The irradiation time of the pulsed light is preferably 1 to 100 milliseconds, more preferably 1 to 50 milliseconds, and further preferably 1 to 20 milliseconds.

The above heat treatment and light irradiation treatment may be performed alone or both may be performed simultaneously. Moreover, after performing one process, you may perform the other process further.

The atmosphere in which the heat treatment and the light irradiation treatment are performed is not particularly limited, and examples include an air atmosphere, an inert atmosphere, or a reducing atmosphere. The inert atmosphere is, for example, an atmosphere filled with an inert gas such as argon, helium, neon, or nitrogen, and the reducing atmosphere is a reducing gas such as hydrogen or carbon monoxide. It refers to the atmosphere.

(Process (C2): Fixing process)
Step (C2) is a step of applying energy to the hydrophilic region to convert it into a water-repellent region.
Examples of the energy application method include the heat treatment and the light irradiation treatment described in the step (C1). For example, in FIG. 1C, the hydrophilic region 14a can be converted to the water-repellent region 14b by performing light irradiation treatment.

The step (C1) and the step (C2) described above may be performed simultaneously or separately. Especially, it is preferable to implement simultaneously at the point which can shorten a manufacturing process more.
As a method of carrying out simultaneously, for example, in the embodiment of FIG. 1 (C), the entire surface of the wettability changing layer 14 is subjected to light irradiation treatment, thereby forming the wiring layer 18 from the coating film 16 and the hydrophilic region. Conversion from 14a to the water repellent region 14b can be performed simultaneously. Further, instead of the light irradiation treatment, the laminate including the support 12, the wettability changing layer 14 and the coating film 16 in the embodiment of FIG. Step (C1) and step (C2) can also be performed simultaneously.
Note that light irradiation may be performed from the coating film 16 side of FIG. 1C or from the support 12 side of FIG. In particular, when forming a coating film on the hydrophilic region and performing light irradiation in the step (C2), it is preferable to carry out from the support 12 side.

Moreover, a process (C1) and a process (C2) can also be implemented separately.
For example, after the step (C1) is performed, the step (C2) can be performed, or after the step (C2) is performed, the step (C1) can be performed.

In the wettability changing layer in the wiring board obtained through the steps (A) to (C), the hydrophilic region does not substantially remain. As a result, moisture hardly enters the interface between the insulating layer disposed on the wiring board and the wiring board, and the temporal stability of the adhesiveness of the insulating layer is excellent.

The thickness of the wiring layer is not particularly limited, and the optimum film thickness is appropriately adjusted according to the intended use. Of these, 0.01 to 1000 μm is preferable and 0.1 to 100 μm is more preferable from the viewpoint of printed wiring board use.
The thickness is a value (average value) obtained by measuring three or more thicknesses at arbitrary points on the wiring layer and arithmetically averaging the values.
The volume resistance value of the wiring layer is preferably less than 5 × 10 ⁻⁴ Ωcm, more preferably less than 1 × 10 ⁻⁴ Ωcm, from the viewpoint of conductive characteristics.
The volume resistance value can be calculated by multiplying the obtained surface resistance value by the film thickness after measuring the surface resistance value of the wiring layer by the four-probe method.

The pattern of the wiring layer is not particularly limited, and can take various pattern shapes (stripe shape, lattice shape, etc.).
An insulating layer (insulating resin layer, interlayer insulating film, solder resist) may be further laminated on the wiring layer of the wiring board. Further, a further wiring (metal pattern) may be formed on the surface.
The wiring board obtained above can be used for various applications. For example, a printed wiring board, TFT, FPC, RFID, etc. are mentioned.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

(Synthesis Example 1: Synthesis of Polymer 1)
The following intermediate 1-1 was synthesized by the method described in Journal of the Chemical Society, 1945, p630-633. Intermediate 1-1 (21.5 g, 100 mmol) was dissolved in 50 mL of dichloromethane, triethylamine (11.1 g, 110 mmol) was added thereto, and acrylic acid chloride (11.4 g, 110 mmol) was kept at 5 ° C. It was added dropwise over 20 minutes. The temperature was raised to room temperature and reacted for 2 hours. Water (100 mL) and ethyl acetate (300 mL) were added to the reaction solution, and the mixture was separated and washed with water. The ethyl acetate layer was evaporated and purified by column chromatography to obtain 8 g of Intermediate 1-2.
Dimethylacetamide (22 g) was charged into a three-necked flask and heated to 80 ° C. Into the solution, a solution of intermediate 1-2 (13 g) and dimethylacetamide (22 g) was added dropwise over 2 hours. Thereafter, the reaction was further continued for 2 hours to polymerize the intermediate 1-2. Next, the following polymer 1 (5 g) was obtained by reprecipitation purification of the obtained reaction solution.

(Synthesis Example 2: Synthesis of Polymer 2)
Intermediate 2-1 was synthesized according to the method described in Chemical Pharmaceutical Bulletin, 1982, p2590-2594, using 4-aceto-styrene (manufactured by aldrich). Next, intermediate 2-1 was synthesized according to the method described in Journal of Chemical Society, Parkin transaction I, 1982, p2477-2486.
Next, dimethylacetamide (15 g) was charged into a three-necked flask and heated to 80 ° C. A solution of intermediate 2-2 (9.5 g) and dimethylacetamide (15 g) was added dropwise to the solution over 2 hours. Thereafter, the reaction was further continued for 2 hours to polymerize the intermediate 2-2. Next, the obtained reaction solution was purified by reprecipitation to obtain polymer 2 (8 g).

(Synthesis Example 3: Synthesis of Compound 3)
Compound 3 was synthesized according to the method described in Tetrahedron Letters 1995 p2377-2378.

(Synthesis Example 4: Synthesis of Polymer 4)
Intermediate 4-1 was synthesized according to the method described in US3962230.
Next, dimethylacetamide (20 g) was charged into a three-necked flask and heated to 80 ° C. A solution of intermediate 4-1 (12.5 g) and dimethylacetamide (20 g) was dropped into the solution over 2 hours. Thereafter, the reaction was further continued for 2 hours to polymerize the intermediate 4-1. Next, the obtained reaction solution was purified by reprecipitation to obtain polymer 4 (6 g).

(Synthesis Example 5: Synthesis of Polymer 5)
Dimethylacetamide (17 g) was charged into a three-necked flask and heated to 80 ° C. A solution of 4- (methyltrimethylammonium chloride) -styrene (10.6 g) and dimethylacetamide (17 g) was dropped into the solution over 2 hours. Then, it was made to react for further 2 hours and superposed | polymerized. Next, polymer 5 (7 g) was obtained by reprecipitation purification of the obtained reaction solution.

(Synthesis Example 6: Synthesis of Comparative Polymer 1)
The following comparative polymer 1 was synthesized according to the method described in the Example column of JP-A-2008-227294.

<Example 1>
A composition 1 for forming a wettability changing layer having the following composition was applied on a polyimide support.
(Composition 1 for forming a wettability changing layer)
・ Polymer 1 1g
・ Methyl ethyl ketone 0.5g

The following composition for forming a photothermal conversion layer was further applied on the wettability changing layer. The obtained substrate was exposed (1 J / cm ² ) in a pattern (L / S = 30 μm / 30 μm) with an IR laser (exposed with a Trendsetter 3244VFS manufactured by Creo equipped with a water-cooled 40 W infrared semiconductor laser). The photothermal conversion layer was removed by washing with water to make the exposed portion water repellent.
(Photothermal conversion layer forming composition)
・ Photothermal conversion agent A 1g
・ Water 0.7g
・ 0.3g of 1-methoxy-2-propanol

Then, when a hydrophilic silver nano ink (prepared by the method described in JP 2010-265543 A) was applied on the wettability changing layer using an inkjet apparatus (DMP2831 manufactured by Daimatics), the ink was used in the water repellent region. It was repelled and ink was deposited on the hydrophilic area to form a coating.
Next, the obtained substrate with a coating film is subjected to a heat treatment at 250 ° C. for 15 minutes to form a wiring layer from the coating film, and to remove the hydrophilic region remaining in the wettability changing layer. It converted into the area and the wiring board was obtained.

(Pattern formability evaluation)
The wiring layer of the wiring board was observed from above with an optical microscope, the linearity of the edge part (end part) of the pattern of the wiring layer was confirmed, and evaluated according to the following criteria. In addition, the deviation width W of the position of the etched portion below is a schematic diagram of the wiring board observed from the upper surface, as shown in FIG. 3, how much the etched portion of the wiring layer is displaced in the width direction. It is a measure to show.
“A”: The deviation width of the etched portion of the wiring layer is within 3 μm “B”: The deviation width of the etched portion of the wiring layer is more than 3 μm and within 10 μm “C”: The deviation width of the etched portion of the wiring layer Is over 10μm

(Durability evaluation)
Solder resist is placed and protected on the wiring layer side of the obtained wiring board, and after leaving for 7 days at 40 ° C. and 85 RH%, the peeling of the wiring layer and the solder resist is confirmed, and the following criteria are met. And evaluated.
"A": There was no peeling.
“B”: The peeled portions were 2 or less.
“C”: There were 3 or more peeled portions.

<Example 2>
A wiring board was manufactured according to the same procedure as in Example 1 except that copper nano ink (solvent: decane) manufactured by Tateyama Machine was used instead of silver nano ink, and various evaluations were performed.
In Example 2, the coating film was formed on the water-repellent region in the step (B).

<Example 3>
A wiring board was produced according to the same procedure as in Example 1 except that polymer 2 was used instead of polymer 1, and various evaluations were performed.

<Example 4>
A wiring board was produced according to the same procedure as in Example 3 except that copper nano ink (solvent: decane) manufactured by Tateyama Machine was used instead of the silver nano ink, and various evaluations were performed.
In Example 4, the coating film was formed on the water-repellent region in the step (B).

<Example 5>
A procedure similar to that of Example 2 was used except that Compound 3 was used instead of Polymer 1 and UV exposure (1 J / cm ² ) was performed using a photomask instead of pattern exposure with an IR laser. A wiring board was manufactured and subjected to various evaluations.

<Example 6>
Instead of heat treatment at 250 ° C. for 15 minutes, flash lamp exposure (Xenon's photosintering apparatus Sinteron 2000, irradiation energy: 5 J / m ² , pulse width: 2 msec) is performed to form a wiring layer from the coating film, Example 5 except that the hydrophilic region remaining in the wettability changing layer was converted to a water-repellent region, the following composition A was used instead of the silver nanoink, and a dispenser was used instead of the ink jet device. According to the same procedure, a wiring board was manufactured and various evaluations were performed.
In Example 6, the coating film was formed on the water-repellent region in the step (B).
(Composition A)
The following ingredients were mixed by bead mill dispersion to produce a composition.
・ Isopar C 18g
・ CuO 1g
・ Polyethylene oxide 1g

<Example 7>
A wiring board was produced according to the same procedure as in Example 6 except that polymer 4 was used instead of compound 3 and benzophenone (0.2 g) was further added to the wettability variable layer forming composition. Evaluation was performed.

<Example 8>
A wiring board was produced according to the same procedure as in Example 2 except that the wettability variable layer forming composition 2 was used instead of the wettability variable layer forming composition 1, and various evaluations were performed.
In addition, the layer obtained by the composition 2 for forming a wettability changing layer is not a layer in which the wettability is changed by decarboxylation by applying energy.
(Composition 2 for forming wettability changing layer)
・ Polymer 5 1g
・ Methanol / water = 3/1 9g
・ Photothermal conversion agent A 0.2g

<Example 9>
A wiring board was produced according to the same procedure as in Example 6 except that the following compound X was used instead of compound 3, and various evaluations were performed.

<Comparative Example 1>
A wiring board was manufactured according to the same procedure as in Example 2 except that the wettability changing layer was not used, and various evaluations were performed.

<Comparative example 2>
An attempt was made to produce a wiring board according to the same procedure as in Example 5 except that Comparative Polymer 1 was used instead of Compound 3.
However, even when UV light was exposed to 1 J / cm ² , the pattern of the hydrophilic region and the water repellent region was not formed.
The comparative polymer 1 is a wettability changing material whose wettability changes so that the contact angle with water decreases when energy is applied.

<Comparative Example 3>
Except that performed UV exposure (10J / cm ²⁾ in place of the UV exposure (1 J / cm ^2), in accordance with the same procedure as in Comparative Example 2, to produce a wiring board was carried out various evaluations.

<Comparative example 4>
Instead of subjecting the obtained coated substrate to heat treatment at 250 ° C. for 15 minutes, only the coating portion was exposed to flash lamp (Xenon's photosintering apparatus Sinteron 2000, irradiation energy: 5 J / m ² , pulse width : 2 msec), a wiring board was manufactured according to the same procedure as in Example 2 except that the wiring layer was formed, and various evaluations were performed.
In Comparative Example 4, the step (C2) is not performed.

In Table 1 below, “hydrophilic ink” is intended for the silver nano ink (described in Example 1), “hydrophobic ink 1” is intended for copper nano ink manufactured by Tateyama Machine, and “hydrophobic ink 2” is Composition A above is contemplated.
In Table 1, “heat” in the “baking step” column and “fixing step” column means heat treatment, and “light” means light irradiation treatment (flash lamp exposure).
In addition, the “time required for firing / fixing” intends the time until a wiring layer having a predetermined conductivity is obtained.

According to the manufacturing method of the present invention, the obtained wiring board was excellent in the pattern formation property of the wiring layer and also in the temporal stability of the adhesiveness of the insulating layer.
In particular, as can be seen from the comparison between Examples 1 and 2, it was confirmed that the pattern formation was superior when the coating film was formed on the water-repellent region.
Further, as can be seen from the comparison between Examples 5 and 6, it was confirmed that when the light irradiation treatment was performed in the firing step and the fixing step, the time until the wiring layer was obtained was further shortened.
Further, as can be seen from a comparison between Example 8 and Example 2, it was confirmed that Example 2 using a layer in which wettability was changed by decarboxylation by application of energy was superior in pattern formability. .

On the other hand, in the comparative example 1 which did not use a wettability change layer, it was inferior to pattern formation.
Further, when Comparative Polymer 1 which is a wettability changing material whose wettability changes so that the contact angle with water is lowered when energy is applied, the wettability is small in Comparative Example 2 with a small amount of energy irradiation. The change of the change layer did not proceed sufficiently and the pattern formation was poor. In Comparative Example 3 in which the amount of energy irradiation was increased, a pattern was formed, but the durability was inferior because a hydrophilic region remained. Further, in Comparative Example 4 in which the fixing step (C2) was not performed, the pattern was formed, but the durability was inferior because the hydrophilic region remained.

DESCRIPTION OF SYMBOLS 10 Board | substrate 12 Support body 14 Wetting property change layer 14a Hydrophilic area | region 14b Water-repellent area | region 16 Coating film 18 Wiring layer 20 Composition for wiring layer formation

Claims

One of the wettability changing layers of the substrate having a support and a wettability changing layer which is disposed on the support and changes wettability so that a contact angle with water increases when energy is applied. Applying energy to the region of the part to convert from a hydrophilic region to a water-repellent region, and forming a wettability pattern comprising a water-repellent region and a hydrophilic region on the wettability changing layer (A);
A step of applying a composition for forming a wiring layer containing at least metal particles and / or metal oxide particles on the wettability changing layer to form a coating film on the water-repellent region or the hydrophilic region. (B) and
A step (C1) of applying energy to the coating film to form a wiring layer, and a step (C2) of applying energy to the hydrophilic region remaining in the wettability changing layer and converting it to a water-repellent region. The manufacturing method of a wiring board provided with the process (C) performed simultaneously or separately.
The method for manufacturing a wiring board according to claim 1, wherein a coating film is formed on the water-repellent region.
The method for manufacturing a wiring board according to claim 1 or 2, wherein the application of energy is a light irradiation treatment.
The method for manufacturing a wiring board according to any one of claims 1 to 3, wherein the wettability changing layer is a layer in which wettability is changed by decarboxylation by application of energy.
The wettability changing layer is at least one selected from the group consisting of a nitrophenylacetic acid structure, a β-keto acid structure, and an acetic acid structure having an O element, an N element, or an S element at the β position with respect to a carboxyl group. The method for manufacturing a wiring board according to any one of claims 1 to 4, comprising a compound having two.
The method for manufacturing a wiring board according to any one of claims 1 to 5, wherein the step (C1) and the step (C2) are performed simultaneously.