WO2015040934A1

WO2015040934A1 - Method for manufacturing plastic article having metal pattern, and plastic article having metal pattern

Info

Publication number: WO2015040934A1
Application number: PCT/JP2014/068320
Authority: WO
Inventors: クリストファーコルドニエ; 義夫堀内; 本間　英夫
Original assignee: 学校法人関東学院
Priority date: 2013-09-19
Filing date: 2014-07-09
Publication date: 2015-03-26
Also published as: JP2015059244A; TWI563124B; TW201512455A

Abstract

Provided are a method for manufacturing a plastic article having a metal pattern, and a plastic article having a metal pattern; the method enabling the dimensional accuracy required for the plastic article to be satisfied and a fine metal pattern with high adhesiveness to be formed in a plastic article. In order to achieve the abovementioned objective, the method includes: a step for forming a metal pattern (21) on the surface of a pattern formation substrate (10) using electroless plating; a step for forming a resin composition film on the substrate (10) using a liquid resin composition and causing the composition to solidify or harden to obtain a resin layer (22) that adheres fast to the metal pattern (21); and a step for separating the resin layer (22) and the substrate (10) to obtain a plastic article (20) having a metal pattern.

Description

Manufacturing method of resin material with metal pattern and resin material with metal pattern

The present invention relates to a method for producing a resin material with a metal pattern and a resin material with a metal pattern, and more particularly to a method for producing a cycloolefin resin material in which a metal pattern is embedded and the cycloolefin resin material.

In recent years, small electronic devices such as smartphones and mobile phones have been remarkably advanced in functionality and performance, and with the integration of signal circuits mounted on these electronic devices, the speed and frequency of signals have also increased. ing. In response to such a flow, further miniaturization and higher density of the circuit are required for the printed wiring board. At the same time, a resin material having a low dielectric constant and excellent high-frequency characteristics is also required for the insulating layer of the printed wiring board. In recent years, polyphenylene resins, cycloolefin resins, and the like have been proposed as such resin materials in place of conventionally used fluororesins.

For example, Patent Document 1 describes that polyphenylene resin or cycloolefin resin is used as an interlayer insulating layer of a multilayer printed wiring board. In particular, since the cycloolefin resin is excellent in mechanical properties in addition to being excellent in the above electrical properties, Patent Document 1 describes that it is suitable as an interlayer insulating layer of a multilayer printed wiring board.

By the way, when a metal thin film is formed on the surface of an insulating base material such as a resin, generally, the surface of the insulating base material is roughened to obtain adhesion by an anchor effect. Moreover, when forming a metal thin film with a predetermined pattern, the metal pattern is formed using a photoresist made of a photo-curing resin or the like. That is, a metal layer and a photoresist are sequentially laminated on an insulating substrate, and the photoresist is partially cured by irradiating the photoresist with light in a pattern, and the uncured photoresist is dissolved and removed. The metal layer exposed from between the resists is removed by dissolution with an etching solution. In this method, finally, the cured photoresist is removed with a strong alkaline aqueous solution or the like (for example, see Patent Document 2).

However, in such a method using a photoresist, a photoresist made of a photo-curing resin may remain on the surface of the metal constituting the pattern even after treatment with a strong alkaline aqueous solution. When post-processing at a high temperature is performed to remove the remaining photoresist, the photoresist may ignite, and handling thereof requires caution. Further, when the metal layer is etched, the portion of the metal layer where the photoresist remains is also eroded in a tapered shape, and an accurate pattern with a rectangular cross section may not be obtained.

In view of such a problem, for example, in the invention described in Patent Document 3, a coating solution is formed by coating a coating solution containing a metal complex on a substrate, and selectively exposing the coating film. A method has been proposed in which development is performed by removing the region, the photosensitive metal complex contained in the coating film is changed to metal, and a pattern is formed by electroless plating using the metal as a catalyst.

JP 2002-9448 A JP 2004-302371 A JP 2012-203236 A

According to the method described in Patent Document 3 and the like, it is possible to accurately form a fine metal pattern having a rectangular cross section by a simple process. However, after developing the coating film, the photosensitive metal complex is subjected to a relatively high temperature heat treatment. For this reason, when a metal pattern is formed on a resin material, the resin material may shrink depending on the temperature during the heat treatment. In particular, thermoplastic resins such as cycloolefin resins are highly likely to shrink during heat treatment, and satisfy the dimensional accuracy required for resin materials when the method described in Patent Document 3 is applied. There was a case that I could not do.

Accordingly, the present invention provides a method for producing a resin material with a metal pattern, which can satisfy the dimensional accuracy required for the resin material and can form a fine metal pattern with good adhesion on the resin material, and It aims at providing the resin material with a metal pattern.

Therefore, as a result of intensive studies, the present inventors have achieved the above object by adopting the following manufacturing method.

The method for producing a resin material with a metal pattern according to the present invention includes a step of forming a metal pattern on the surface of a substrate for pattern formation by an electroless plating method, and a liquid on the substrate on which the metal pattern is formed. Forming a resin composition film using the resin composition, solidifying or curing the resin composition film to obtain a resin layer in close contact with the metal pattern, and peeling the resin layer and the substrate; And a step of obtaining a resin material with a metal pattern.

The method for producing a resin material with a metal pattern according to the present invention comprises forming a first metal pattern on the surface of a first base material for pattern formation by an electroless plating method, and forming a second base for pattern formation. A step of forming a second metal pattern on the surface of the material by an electroless plating method, and a first base material and a second base material, with the first metal pattern and the second metal pattern inside. A resin layer disposed opposite to each other at a predetermined interval, filled with a liquid resin composition between both substrates, and solidified or cured to be in close contact with the first metal pattern and the second metal pattern. And a step of peeling the resin layer from the first base material and the second base material to obtain a resin material provided with the first metal pattern and the second metal pattern on both sides. It is characterized by.

In the method for producing a resin material with a metal pattern according to the present invention, the resin composition includes a cycloolefin resin, a polyimide resin, an epoxy resin, an acrylic resin, an isocyanate resin, a urethane resin, a liquid crystal polymer, a melamine resin, a polyester resin, and a polyester resin. , Silicon resin, polyethylene, polypropylene, polystyrene, and precursors thereof are preferably included.

In the method for producing a resin material with a metal pattern according to the present invention, the resin material is a cycloolefin resin material, a polyimide resin material, an epoxy resin material, an acrylic resin material, an isocyanate resin material, a urethane resin material, a liquid crystal polymer, or a melamine resin material. , Polyester resin material, polyester resin material, silicon resin material, polyethylene material, polypropylene material, and polystyrene material.

In the method for producing a resin material with a metal pattern according to the present invention, the step of forming the metal pattern by an electroless plating method on the surface of the substrate is a catalyst application step of selectively applying a catalyst to the surface of the substrate. And an electroless plating step of immersing the substrate selectively provided with the catalyst in the electroless plating solution and depositing metal ions in the electroless plating solution in a predetermined pattern.

In the method for producing a resin material with a metal pattern according to the present invention, the catalyst application step includes a step of forming a photosensitive catalyst film on the surface of the substrate and selectively exposing the photosensitive catalyst film. It is preferable to include.

The resin material with a metal pattern according to the present invention is manufactured by the above-described method for manufacturing a resin material with a metal pattern.

In the resin material with a metal pattern according to the present invention, the metal pattern is embedded in the resin layer.

By adopting the method described in the present invention, even if it is a thermoplastic resin material or the like, it can satisfy the dimensional accuracy required for the resin material, and a fine metal pattern with good adhesion can be obtained. It can be formed on a resin material.

It is a schematic diagram for demonstrating the manufacturing method of the resin material with a metal pattern (resin material with a single-sided metal pattern) which concerns on this invention. It is a schematic diagram for demonstrating the manufacturing method of the resin material with a metal pattern (resin material with a double-sided metal pattern) which concerns on this invention. It is a microscope picture which shows the state which formed the metal pattern in the base material for pattern formation by the electroless-plating method. It is a microscope picture which shows the cycloolefin resin film with a copper plating pattern which is a resin material with a metal pattern of Example 1 of this invention. It is a microscope picture which shows the polyimide resin film with a copper plating pattern which is a resin material with a metal pattern of Example 2 of this invention. It is a microscope picture which shows the PDMS film with a copper plating pattern which is a resin material with a metal pattern of Example 3 of this invention. It is a microscope picture which shows another example of the PDMS film with a copper plating pattern which is a resin material with a metal pattern of Example 3 of this invention.

Hereinafter, preferred embodiments of a method for producing a resin material with a metal pattern and a resin material with a metal pattern according to the present invention will be described.

<Production method of resin material with metal pattern>
1. Method for Producing Resin Material with Single-sided Metal Pattern First, among methods for producing a resin material with a metal pattern according to the present invention, a method for producing a resin material with a metal pattern having a metal pattern on one side of the resin material is described with reference to FIG. explain. In the method for producing a resin material with a metal pattern according to the present invention, a step of forming a metal pattern 21 on the surface of a substrate 10 for pattern formation (see FIG. 1A) by an electroless plating method (FIG. 1B). And the metal pattern 21 is formed on the substrate 10 on which the metal pattern 21 is formed using a liquid resin composition, and the resin composition film is solidified or cured. The process of obtaining the closely adhered resin layer 22 (see FIG. 1C) and the process of separating the resin layer 22 and the substrate 10 to obtain the resin material 20 with a metal pattern shown in FIG. It is characterized by including. Hereinafter, each step will be described.

1-1. Patter formation process First, the process (henceforth a "pattern formation process") which forms the metal pattern 21 by the electroless-plating method on the surface of the base material 10 for pattern formation is demonstrated. In the present invention, the metal pattern 21 is not directly formed on the resin material, but the metal pattern 21 is formed on the substrate 10 for pattern formation, and the resin material (22) side is subjected to the process described later. The method of transferring to is adopted. For this reason, in the process of forming the metal pattern 21, it is necessary to perform various surface treatments such as roughening treatment and surface modification treatment on the base material 10, or to perform heat treatment on the base material 10. It is not necessary to perform these treatments on the resin material (22). For this reason, the resin material (22) is not affected by various processes performed in the process of forming the metal pattern 21, and can satisfy the required dimensional accuracy even with a thermoplastic resin material. Further, the smoothness of the surface can be maintained.

(1) Substrate In the present invention, the substrate 10 for pattern formation shown in FIG. 1 (a) refers to a substrate used only when forming the metal pattern 21, and is finally a resin on which the metal pattern 21 is provided. It is different from the material (22). The material of the substrate 10 for pattern formation is not particularly limited, and examples thereof include inorganic materials typified by glass, ceramics, quartz, silicon wafer, metal, and organic materials such as various plastics. May be. In the present invention, in particular, a glass substrate or a silicon wafer having heat resistance can be suitably used.

(2) Electroless plating method When the metal pattern 21 is formed on the surface of the substrate 10 for pattern formation by the electroless plating method, a pattern forming method by a conventionally known electroless plating method may be appropriately employed. The specific procedure of the pattern forming process is not particularly limited. For example, a catalyst is applied to the entire surface of the substrate 10, a metal film is formed by depositing metal on the entire surface by an electroless plating method, and then the metal film is selectively dissolved and removed according to the pattern by etching or the like. Accordingly, the predetermined metal pattern 21 may be formed. As another method, a catalyst is selectively applied to the surface of the substrate 10, the substrate 10 selectively applied with this catalyst is immersed in an electroless plating solution, and metal ions in the electroless plating solution are added. The predetermined metal pattern 21 may be formed by depositing. In any of these methods, as long as the metal pattern 21 is formed on the substrate 10 as shown in FIG. 1B, the specific method is not particularly limited. However, as described above, from the viewpoint that the fine metal pattern 21 having a rectangular cross section can be accurately formed by a simple process, in the present invention, the pattern forming process is performed by applying a catalyst to the surface of the substrate 10. A catalyst application step for selectively applying, and an electroless plating step for immersing the base material 10 to which the catalyst is selectively applied in an electroless plating solution to deposit metal ions in the electroless plating solution in a predetermined pattern. Are preferably included.

(A) Catalyst application step In order to selectively apply the catalyst to the surface of the substrate 10, a conventionally known method can be appropriately employed. However, the fine metal pattern 21 having a rectangular cross section can be accurately obtained by a simple process. From the viewpoint that it can be formed, any one of the following first catalyst application step to fourth catalyst application step is preferably employed.

i) 1st catalyst provision process As a 1st catalyst provision process, the following method can be mentioned, for example. First, a metal oxide film having a predetermined pattern shape is formed on one surface of the substrate 10, and then the metal oxide film is fired to obtain a sintered body of the metal oxide film. And by immersing the said sintered compact in a catalyst solution, a catalyst is selectively provided to the surface of the base material 10 according to a predetermined pattern shape.

Metal oxide film formation process: A metal oxide film is a film containing a metal oxide, such as physical vapor deposition (PVD), chemical vapor deposition (CVD), and liquid phase growth. The film can be formed by, for example. More specifically, as these film forming methods, examples of the physical vapor deposition method (PVD) include a vacuum deposition method, a sputtering method, an ion plating method, a molecular beam epitaxy method, and a laser ablation method. Examples of chemical vapor deposition (CVD) include thermal CVD, MOCVD (metal organic chemical vapor deposition), RF plasma CVD, ECR plasma CVD, photo CVD, laser CVD, and ALE (atomic layer epitaxy). It is done. Examples of the liquid phase growth method include an anodic oxidation method, electrodeposition method, coating method, and sol-gel method.

Examples of metal elements constituting the metal oxide contained in the metal oxide film include beryllium (Be), magnesium (Mg), aluminum (Al), silicon (Si), calcium (Ca), scandium (Sc), and titanium (Ti ), Vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), germanium (Ge) ), Strontium (Sr), zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), rhodium (Rh), indium (In), tin (Sn), barium (Ba), lanthanum (La) ), Cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (G ), Hafnium (Hf), tantalum (Ta), tungsten (W), iridium (Ir), lead (Pb), bismuth (Bi), polonium (Po), or any one selected from uranium (U) One or more metals may be mentioned.

The metal oxide contained in the metal oxide, together with the metal element, is lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), boron (B), phosphorus (P ), Sulfur (S), arsenic (As), selenium (Se), antimony (Sb) and the like.

In particular, in the present invention, the metal element is preferably any one or two or more metals selected from sodium, titanium, zinc, zirconium, niobium, molybdenum, hafnium, tantalum, and tungsten (W). .

Further, as metal oxides formed by the above metals, titanium oxide (TiO ₂ ), niobium oxide (Nb ₂ O ₅ ), tantalum oxide (Ta ₂ O ₅ ), zirconium oxide (ZrO ₂ ), hafnium oxide (HfO ₂ ). ), Molybdenum oxide (MoO ₃ ), tungsten oxide (WO ₃ ), zinc oxide (ZnO), or a salt or alloy thereof is desirable. As these salts, for example, sodium titanate _{_{_{(Na 2 O 7 Ti 3)}}} , sodium niobate (NaNbO _3), sodium tantalate (Tanao _3), sodium zirconate _(Na 2 ZrO _3), sodium hafnium (Na ₂ O ₇ Hf ₃ ), sodium molybdate (Na ₂ MoO ₄ ), sodium tungstate (Na ₂ O ₄ W), and the like. Among these, titanium oxide (TiO ₂ ), niobium oxide (Nb ₂ O ₅ ), and sodium niobate (NaNbO ₃ ) are preferable.

For example, a metal oxide film having a predetermined pattern shape can be formed by forming a metal oxide film from these metal oxides by a printing method such as offset printing or screen printing. Further, when forming a metal oxide film, first, a metal oxide film precursor film containing a photosensitizer is formed on the entire surface of the substrate 10, and then formed into a metal oxide film precursor film using a photomask or the like. A metal oxide film having a predetermined pattern shape can also be obtained by selectively irradiating ultraviolet light. However, the metal oxide film precursor film refers to a negative or positive photosensitive film capable of forming a pattern by development processing.

Baking step: Next, this metal oxide film is baked for 1 to 200 minutes under a temperature condition of 100 ° C. to the breakdown temperature of the substrate, whereby a metal oxide film sintered body can be obtained. What is necessary is just to adjust a calcination temperature so that it may become a suitable temperature suitably according to a composition of a metal oxide. By performing the heat treatment, the metal oxide film becomes a porous ceramic in which fine pores are formed.

Surface modification treatment step: Then, the metal oxide film sintered body is appropriately subjected to surface treatment as necessary to improve the adsorptivity with the catalyst in the subsequent catalyst application step, or patterning with high accuracy. The surface modification treatment is preferably performed so that Examples of such surface modification treatment include the following.

First, examples of the surface modification treatment include ultraviolet irradiation treatment. In the ultraviolet irradiation treatment, it is preferable to irradiate the surface of the metal oxide film sintered body with ultraviolet rays having a wavelength of about 180 to 400 nm with an irradiation intensity of about 1 to 50 mW / cm ² . At this time, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a black light, a sterilizing lamp, a DUV lamp, an excimer lamp, or the like can be used as the light source. By irradiating the surface of the metal oxide film sintered body with ultraviolet rays, the surface molecules of the sintered body are cut and ionized to generate hydrophilic groups. Thereby, the adsorptivity of the catalyst in the subsequent catalyst application step is improved.

Also, as the surface modification treatment, a surface modification solution immersion treatment may be mentioned. In the surface modification liquid immersion treatment, the metal oxide film sintered body is immersed in the surface modification liquid together with the substrate 10 to increase the polarity of the hydrophilic group on the surface and the surface roughness, thereby adsorbing with the catalyst. Can be improved. As the surface modifying solution, for example, a sodium hydroxide solution, a nonionic surfactant and / or an anionic surfactant can be used. More specifically, as the surface modification liquid, 2-aminothioethanol, polyethylene glycol, polyoxyethylene dodecyl ether, sodium dodecyl sulfate, sodium laurate, sodium dodecylbenzenesulfonate, tetramethylammonium hydroxide (TMAH), Trimethylphenylammonium hydroxide or the like can be used. The metal oxide film sintered body has fine pores formed by sintering as described above. An anchor effect is obtained by this pore. Therefore, if the metal oxide film sintered body is provided on the surface of the base material 10, it is basically unnecessary to perform the surface modification liquid immersion treatment, but may be appropriately performed as necessary.

Catalyst application process: In the catalyst application process, the palladium catalyst can be adsorbed to the sintered metal oxide film in which a large number of fine pores are formed by immersing the base material 10 together in the catalyst solution. As a method for catalysis, any method such as a catalyst-accelerator method, a sensitizing-activating method, an activating method, or the like may be used. Further, any material such as palladium, ruthenium, platinum or the like may be used as the catalyst substance. A catalyst is selectively given to the surface of the base material 10 by the said process.

ii) Second catalyst application step A catalyst may be selectively applied to the surface of the substrate 10 by a second catalyst application step that differs from the first catalyst application step in part. In the second catalyst application step, when the metal oxide film is formed, a photocatalytic film made of a metal oxide that exhibits a photocatalytic action described later is formed, and then the photocatalytic film is baked. Thus, a sintered body of the photocatalytic film is obtained. Then, a water-repellent coating film is provided on the surface of the sintered body, and ultraviolet light is selectively irradiated from above the water-repellent coating film through a photomask having a predetermined exposure pattern. Thereby, in a region irradiated with ultraviolet light, the photocatalyst is activated to decompose the water-repellent coating film. Therefore, the photocatalytic film is exposed according to the exposure pattern, and the surface of the unexposed area is covered with the water repellent coating film. Then, like the 1st catalyst provision process, a catalyst can be selectively given to the surface of substrate 10 according to a predetermined pattern shape by immersing substrate 10 together in a catalyst solution. Only the steps different from the first catalyst application step will be described below.

Film formation of photocatalytic film: Examples of metal oxides that exhibit photocatalytic action include titanium oxide (TiO ₂ ), iron oxide (Fe ₂ O ₃ ), tungsten oxide (WO ₃ ), tin oxide (SnO ₂ ), and bismuth oxide. (Bi ₂ O ₃ ), niobium oxide (Nb ₂ O ₅ ), nickel oxide (NiO), copper oxide (Cu ₂ O), zirconium oxide (ZrO ₂ ), zinc oxide (ZnO), strontium titanate (SrTiO ₃ ) And iron titanate (FeTiO ₃ ) or salts thereof. Among these, it is particularly preferable to form a photocatalytic film using titanium oxide (TiO ₂ ), niobium oxide (Nb ₂ O ₅ ), sodium niobate (NaNbO ₃ ), or the like.

These photocatalytic films can be formed by the general film forming method described above, and are particularly preferably formed by a sol-gel method, a sputtering method, a vapor deposition method, or the like. After forming the photocatalytic film, a firing process is performed in the same manner as in the first catalyst application process to obtain a sintered body of the photocatalytic film.

Water repellent coating film forming step: After obtaining a photocatalytic film sintered body, a water repellent coating film is provided on the surface of the photocatalytic film sintered body. Here, the water-repellent coating film is a film provided for modifying the surface of the photocatalytic film sintered body to be hydrophobic. A water-repellent coating film will not be specifically limited if it is a thin film comprised by the film | membrane component which has hydrophobicity. In particular, from the viewpoint of improving pattern formation accuracy, it is preferable to provide a self-assembled monomolecular film such as octadecyltrimethoxysilane (ODS), octadecyltrichlorosilane (OTS), octadecylphosphonic acid (ODP), or the like.

Exposure Step: Next, ultraviolet light or the like is selectively exposed from above the water repellent coating film through a photomask having a predetermined exposure pattern. At this time, it is preferable to irradiate the surface of the water-repellent coating film with ultraviolet rays having a wavelength of about 180 to 400 nm with an irradiation intensity of about 1 to 50 mW / cm ² . As the light source, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a black light, a sterilization lamp, a DUV lamp, an excimer lamp, or the like can be used. By performing the exposure step, the photocatalyst can be activated only in the exposed region to decompose the self-assembled monolayer. On the other hand, the photocatalytic film is exposed according to the exposure pattern, and the surface of the unexposed area is covered with a water repellent coating film.

The subsequent catalyst application step can be performed in the same manner as the first catalyst application step. In the catalyst application step, when the substrate 10 is immersed in the catalyst solution, the catalyst can be selectively applied only to the region where the photocatalytic film is exposed. In addition, after forming the photocatalytic film, in any stage from application of the catalyst, surface modification treatment similar to the first catalyst application process can be performed as necessary.

iii) Third catalyst application step As the third catalyst application step, which is further different from the first and second catalyst application steps, a catalyst is selectively applied to the surface of the substrate 10 by the following method, for example. It may be given. In the third catalyst application step, when the metal oxide film is formed, a water-repellent photocatalytic film containing a hydrophobic substance having hydrophobicity is formed on the photocatalytic film. Specifically, when the photocatalytic film is formed by a sol-gel method, ODS, OTS, ODP, or the like that can form the self-assembled monolayer is mixed with the sol solution containing the photocatalytic substance. A water-repellent photocatalytic film can be formed using a photosensitive sol solution. This water-repellent photocatalytic film is fired to obtain a water-repellent photocatalytic film sintered body, and then selectively irradiated with ultraviolet light through a photomask having a predetermined exposure pattern as in the second catalyst application step. Etc., the photocatalyst can be activated only in the exposed region to decompose the self-assembled monomolecule. On the other hand, since the surface of the unexposed area maintains water repellency, the catalyst can be selectively applied only to the exposed area in the catalyst application step. In addition, after forming the photocatalytic film on the surface of the substrate 10, the water-repellent photocatalytic film may be laminated. A calcination process, a catalyst provision process, etc. can be performed similarly to a 1st catalyst provision process and a 2nd catalyst provision process. Further, surface modification treatment can be appropriately performed as necessary. According to the third catalyst application step, by using the photocatalyst sol solution, a step of separately forming a water-repellent coating film can be omitted after the photocatalytic film is provided.

iv) Fourth catalyst application step When the catalyst is selectively applied to the surface of the substrate 10, the following fourth catalyst application step may be employed. In the fourth catalyst application step, for example, an organic compound of a first metal that does not serve as a catalyst for an electroless plating reaction, a second metal compound that serves as a catalyst for an electroless plating reaction, and a photosensitizer that forms a complex with the first metal. A photosensitive catalyst solution containing a photosensitive photosensitive compound is prepared, and this catalyst solution is applied to the surface of the substrate 10 to form a coating film. When this coating film is selectively irradiated with ultraviolet light through a photomask having a predetermined exposure pattern and developed with an alkaline solution or the like, the region irradiated with the ultraviolet light is dissolved, and the coating film having a predetermined pattern shape is obtained. Is obtained. Next, heat treatment is performed to decompose the photosensitive compound into a metal oxide, and this coating film is used as a photosensitive catalyst precursor film. Then, the ions of the second metal are reduced to metal, and the photosensitive catalyst precursor film is used as a catalyst film having a predetermined pattern shape.

Photosensitive catalyst solution preparation step: First, a solution preparation step for preparing a photosensitive catalyst solution will be described. The catalyst solution includes an organic compound of the first metal M1 that does not serve as a catalyst for the electroless plating reaction, a compound of the second metal M2 that serves as a catalyst for the electroless plating reaction, and a photosensitive compound that forms a metal complex with the first metal M1. A solution containing

As the first metal M1, Mg, Ca, Sr, Ba, Sc, Y, La-Lu, Ti, Zr, Hf, Nb, Ta, Mo, W, Zn, Al, Si, Ni, In, or Sn are used. Use. As the second metal M2, Ru, Co, Rh, Ni, Pt, Cu, Ag, Fe, Pd, or Au is used.

When titanium (Ti) is selected as the first metal M1, it is preferable to use titanium alkoxide represented by titanium tetraisopyropoxide as the organic compound. As titanium alkoxide, specifically, titanium tetraisopropoxide, tetrabutoxy titanium, tetraethoxy titanium, alkoxides composed of condensates such as dimers, trimers, and tetramers, titanyl bisacetylacetonate, Examples thereof include chelates such as dibutoxytitanium acetylacetonate and isopropoxytitanium triethanolaminate, and organic acid salts such as titanium stearate and titanium octylate.

When gold (Au) is selected as the second metal M2, it is preferable to use an Au inorganic salt typified by sodium chloroaurate as the compound. Specific examples of the Au inorganic salt include chloroauric acid, gold bromide, tetrachlorogold, gold sulfite, gold hydroxide, sodium hydroxide goldate (NaAu (OH) ₄ ), gold acetate, or a sodium salt thereof. Or a potassium salt etc. are mentioned.

When silver (Ag) is selected as the second metal M2, it is preferable to use an Ag inorganic salt typified by silver nitrate as the compound. Specific examples of the Ag inorganic salt include silver chloride, silver bromide, silver acetate, silver sulfate, and silver carbonate.

When copper (Cu) is selected as the second metal M2, it is preferable to include a metal ion-soluble organic solvent typified by 2-methoxyethoxyacetic acid for improving the solubility of Cu ions.

Examples of the photosensitive compound that forms a metal complex with the first metal M1 include 4- (4,5-Dimethoxy-2-nitrobenzoylcarbonyl) catechol (NVOC-CAT), naphthoquinonediazide compound (NQD), β-diketone, α- In addition to the photosensitive compounds disclosed in Japanese Patent Application Laid-Open No. 2011-20769 such as hydroxyketone, 1-hydroxycyclohexyl, phenyl ketone (HPK), known photosensitive compounds that form metal complexes with the first metal M1 can be used. .

By preparing a photosensitive catalyst solution (photosensitive metal complex solution) containing the organic compound of the first metal M1, the second metal compound, and the photosensitive compound, for example, a photosensitive metal such as NBOC-TiCu. A complex can be obtained.

Coating film forming step: After preparing the photosensitive catalyst solution, a coating film is formed on the surface of the substrate 10 by a coating method such as spin coating, slit coating, dip coating, or spray coating.

Exposure and development step: In this step, as in the second and third catalyst application steps, ultraviolet light is selectively irradiated from above the coating film via a photomask having a predetermined exposure pattern. In the region irradiated with ultraviolet rays, the metal complex becomes readily soluble in the alkaline developer, and the unexposed region remains insoluble in the alkaline developer. Therefore, after the exposure, development is performed using an alkaline developer, whereby only the exposed portion is removed and a pattern is formed. As the developer, a developer for semiconductor / liquid crystal lithography can be used.

Heat treatment step: When a heat treatment is performed by a method such as baking the coating film having a predetermined pattern shape in the same manner as in the first to third catalyst application steps, the photosensitive metal complex can be changed to a metal oxide. . Thereby, the catalyst precursor film | membrane which consists of a metal oxide thin film pattern can be obtained. The catalyst precursor film has a structure in which the second metal M2 ions are dispersed in an inorganic binder made of the first metal oxide.

Reduction process: When the catalyst precursor film is immersed together with the base material 10 in an aqueous solution containing a reducing agent such as tetrahydroboric acid, hypophosphorous acid, hydrazine, borohydride, dimethylamine borane, etc., the second metal M2 ion Is reduced to the second metal M. By passing through this step, a catalyst film in which fine particles of the second metal having a catalytic function of electroless plating reaction are dispersed in the film can be obtained.

(B) Electroless plating step After selectively applying a catalyst to the surface of the substrate 10 by the above-described catalyst applying step or the like, activation treatment or the like is performed as necessary, and then the substrate 10 is electrolessly plated. A predetermined metal pattern 21 can be obtained by immersing in the solution to deposit metal ions contained in the electroless plating solution. Examples of metals deposited by the electroless plating include nickel (Ni), phosphorus (P), boron (B), gold (Au), silver (Ag), copper (Cu), palladium (Pd), and these These alloys are mentioned.

The electroless plating step can be appropriately performed using a known method or the like, and is not particularly limited. The above activation treatment is an optional step, and as the activation treatment liquid, one containing hydrochloric acid, sulfuric acid, hydrazine, tin chloride, formalin, hypophosphorous acid, boron hydroxide compound, amine borane compound or the like should be used. Can do. Further, as the electroless plating solution, a known electroless plating solution can be appropriately used depending on the metal to be deposited.

Through the above steps, the metal pattern 21 is formed on the surface of the substrate 10 for pattern formation by the electroless plating method.

1-2. Resin Layer Forming Step In the resin layer forming step, first, a resin composition film is formed on the base material 10 on which the metal pattern 21 is formed using a liquid resin composition.

The resin composition is not particularly limited as long as the resin composition can be obtained in a liquid form and can be solidified or cured, and the thermoplastic resin composition and the thermosetting resin composition are not limited. Any of the objects may be used. In the present invention, in particular, cycloolefin resin, polyimide resin, epoxy resin, acrylic resin, isocyanate resin, urethane resin, liquid crystal polymer, melamine resin, polyester resin, polyester resin, silicon resin, polyethylene, polypropylene, polystyrene, and precursors thereof. It is preferable to include at least one of the bodies, and by using the liquid resin composition, cycloolefin resin material, polyimide resin material, epoxy resin material, acrylic resin material, isocyanate resin material, urethane resin material, It is preferable to obtain at least one of a liquid crystal polymer, a melamine resin material, a polyester resin material, a polyester resin material, a silicon resin material, a polyethylene material, a polypropylene material, and a polystyrene material. By applying these liquid resin compositions onto the base material 10, a resin composition film can be formed so as to cover the surface of the base material 10 and the metal pattern 21.

Next, the resin composition film is solidified or cured by evaporating the solvent in the resin composition film or by thermosetting or photocuring to obtain the resin layer 22. Thereby, as shown in FIG.1 (c), it will be in the state by which the metal pattern 21 was embed | buried in the resin layer 22 solidified or hardened | cured. When evaporating the solvent, the solvent may be evaporated at room temperature, but heat treatment may be performed in a temperature range of 50 ° C. to 150 ° C. depending on the type of resin.

1-3. Peeling process After obtaining the resin layer 22, the resin layer 22 and the base material 10 are peeled. Here, as shown in FIG. 1C, when the adhesion area between the metal pattern 21 and the substrate 10 and the adhesion area between the metal pattern 21 and the resin layer 22 are compared, the metal pattern 21 and the resin layer 22 are Since both sides of the metal pattern 21 are in close contact with each other, the latter is larger and the adhesion is increased. For this reason, when the resin layer 22 and the base material 10 are physically peeled, the metal pattern 21 is transferred from the base material 10 to the resin layer 22 side, and the resin material 20 with a metal pattern can be obtained.

When the metal pattern 21 is formed on the surface of the substrate 10 by the above steps, even when heat treatment or surface modification treatment such as baking treatment or roughening treatment is performed in the catalyst application step, after the metal pattern 21 is formed. Since the resin layer 22 is formed, even if a thermoplastic resin material is manufactured, the dimensional accuracy required for the resin material can be satisfied, and a fine metal pattern with good adhesion to the resin layer 22 21 can be formed.

2. 2. Manufacturing method of resin material with double-sided metal pattern Next, in the manufacturing method of resin material with metal pattern according to the present invention, refer to FIG. While explaining. In the manufacturing method, the first metal pattern 41 is formed on the surface of the first substrate 31 for pattern formation by an electroless plating method, and the surface of the second substrate 32 for pattern formation is formed on the surface of the first substrate 31 for pattern formation. The step of forming the second metal pattern 42 by the electrolytic plating method (see FIGS. 2A and 2B), the first metal pattern 41 and the second metal pattern 42 are set inward, and the first substrate The material 31 and the second base material 32 are arranged to face each other with a predetermined interval, the liquid resin composition is filled between the

base materials

31 and 32, and this is solidified or cured, and the first A step of obtaining a resin layer 43 in close contact with the metal pattern 41 and the second metal pattern 42 (see FIG. 2C), the resin layer 43, the first base material 31, and the second base material 32. The first metal pattern 41 and the second metal pattern 42 are peeled off and the resin layer 43 is peeled off. Characterized in that it comprises a step of obtaining a resin material 50 provided on the side (see Figure 2 (d)). Hereinafter, each step will be described.

2-1. Pattern formation process In a pattern formation process, as shown to Fig.2 (a), the 1st base material 31 for pattern formation and the 2nd base material 32 for pattern formation are prepared, and each base material 31, Metal patterns (a first metal pattern 41 and a second metal pattern 42) are respectively formed on 32 (see FIG. 2B). When the metal patterns 41 and 42 are formed on the

respective base materials

31 and 32, the same pattern forming process as applied when the metal pattern 21 is formed on the base material 10 in the resin material 20 with a single-sided metal pattern. Since it can be performed by a process, description thereof is omitted here.

2-2. Resin Layer Forming Step In the resin layer forming step, the first base material 31 and the second base material 32 are opposed to each other with a predetermined interval with the first metal pattern 41 and the second metal pattern 42 facing inside. It arrange | positions and it fills with a liquid resin composition between both the

base materials

31 and 32, and forms a resin composition film | membrane. The resin composition may be the same as the liquid resin composition used when forming the resin composition film on the substrate 10 in the resin material 20 with a single-sided metal pattern. And like the manufacturing method of the resin material with a single-sided metal pattern, the 1st metal pattern 41 and the 2nd metal pattern 42 are obtained by evaporating the solvent in a resin composition film, or thermosetting or photocuring. The resin layer 43 solidified or hardened in a state where is embedded is obtained (see FIG. 2C).

2-3. Peeling step In the peeling step, the resin layer 43 is physically peeled from the first base material 31 and the second base material 32. When the adhesion area between each metal pattern 41, 42 and each

base material

31, 32 and the adhesion area between each metal pattern 41, 42 and the resin layer 43 are compared, each metal pattern 41, 42 is similar to the above. The contact area with the resin layer 43 is larger, and the adhesion force is increased. For this reason, when the resin layer 43 and each of the

base materials

31 and 32 are physically separated, the first metal pattern 41 and the second metal pattern 42 are transferred to both sides of the resin layer 43, and these metal patterns 41 are transferred. , 42 can be obtained as a double-sided metal-patterned resin material 40 embedded in the resin layer 43 (see FIG. 3D).

<Resin material with metal pattern>
The resin material with a metal pattern according to the present invention is manufactured by the method for manufacturing a resin material with a metal pattern according to the present invention, and the resin material with a single-sided metal pattern (see FIG. 1 (d)) or both surfaces It is the resin material 40 with a metal pattern (refer FIG.2 (d)).

The resin material 20 (40) with a metal pattern according to the present invention has the metal pattern 21 (41, 42) embedded in the resin layer 22 (43) as described above. For this reason, when the resin material 20 (40) with a metal pattern according to the present invention is applied to, for example, a flexible printed wiring board or the like, the metal pattern 21 (41, 42) serving as a wiring pattern is formed on the resin layer 22 (43). Since it does not protrude outward from the surface, the wiring pattern portion can be protected, and the risk of migration or short-circuiting can be reduced.

In the present invention, the resin material constituting the resin material 20 (40) is not particularly limited as long as it is a resin material that can be obtained by solidifying or curing a liquid resin composition. For example, it is preferably applied to the various resin materials listed above, and is particularly suitable for thermoplastic resin materials such as cycloolefin resin materials. In the present invention, the shape of the resin material is not particularly limited. By changing the shape of the base material 10 (31, 32) or the like, not only the film-like and plate-like resin materials, but also so-called casting is used. Various shaped resin materials that can be molded by the method can be obtained.

Adhesion if the above-mentioned catalyst application process (first catalyst application process to fourth catalyst application process) is adopted when forming a metal pattern on the surface of a thermoplastic resin material by a conventional electroless plating method. A favorable metal pattern can be formed. However, if a metal pattern is formed directly on the surface of the resin material by this conventional electroless plating method, there is a risk of shrinkage in the case of a thermoplastic resin during the heat treatment in the above-described catalyst application step, etc. The accuracy may not be satisfied. In addition, if the surface of the resin material is roughened or subjected to surface modification treatment by irradiating ultraviolet rays, the surface roughness of the resin material increases, and the required translucency is required for transparent resin films. In some cases, the sex cannot be satisfied.

In contrast, in the resin material with metal pattern 20 (40) manufactured by the method according to the present invention, the metal pattern 21 (41, 42) is in close contact with the resin layer 22 (43), and the metal pattern 21 In the formation step of (41, 42), the resin layer 22 (43) is not subjected to any heat treatment or surface modification treatment, and is not exposed to various chemicals such as electroless plating solution. Therefore, even if the metal pattern-attached resin material 20 (40) is a thermoplastic transparent resin material such as a cycloolefin resin material, the required dimensional accuracy and transparency can be satisfied. For this reason, this invention is suitable for the thermoplastic transparent resin material used for uses, such as a transparent conductive film base material for touchscreens, an organic EL illumination base material, a flexible print base material, and an insulating film.

Next, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the following examples, and it is needless to say that the present invention can be appropriately changed without departing from the gist of the present invention.

In Example 1, a resin material with a metal pattern was manufactured as follows.

(1) Pattern formation process First, the metal pattern was formed by the electroless-plating method on the surface of the base material for pattern formation. In Example 1, as a base material for pattern formation, a plate borosilicate glass (Tempax Float (registered trademark)) made by Schott Akgel Gesellshaft (manufactured by SCHOTT AG) having a thickness of 50 mm × 50 mm and 0.7 mm is used. It was.

And a catalyst is selectively given to the surface of the above-mentioned base material, the base material to which this catalyst was selectively given is immersed in an electroless copper plating solution, and copper ions in the electroless copper plating solution are deposited. Thus, a copper wiring pattern was formed on the surface of the substrate.

a) Catalyst application step In Example 1, in accordance with the fourth catalyst application step described in the above embodiment, a photosensitive catalyst solution preparation step, a coating film formation step, an exposure development step, a heat treatment step, and a reduction are performed as follows. The process was performed and the catalyst film of the predetermined pattern shape was provided on the surface of the base material.

Photosensitive catalyst solution preparation step: In the photosensitive catalyst solution preparation step, a photosensitive catalyst solution containing titanium as the first metal M1, copper as the second metal M2, and NBOC-CAT as the photosensitive compound ( NBOC-TiCu) was prepared.
First, NBOC-CAT was synthesized by esterifying 3,4-dihydroxybenzoic acid with a 2-nitrobenzyl alcohol derivative. Then, NBOC-CAT (2.46 g) was dissolved in ethyl lactate (12 ml) and N, N′-dimethylacetamide (2 ml), tetraisopropoxide titanium (1.04 ml) was added, and “solution A Was prepared. On the other hand, 2-methoxyethoxyacetic acid (0.171 ml) and anhydrous copper acetate (0.272 g) were dissolved in N, N′-dimethylacetamide (2 ml) at 100 ° C. to prepare “Solution B”. Then, “Solution A” and “Solution B” were mixed and heated at 100 ° C. for 1 hour to obtain a photosensitive metal complex solution (NBOC-TiCu). Note that the photosensitive metal complex (NBOC-TiCu) is a metal complex having a so-called positive photosensitivity that greatly increases the solubility in an alkali developer upon receiving short-wavelength light.

Coating film forming step: 0.35 ml of the photosensitive metal complex solution was spin-coated at 1000 revolutions on the surface of the substrate. And the base material with which the said coating film was provided on the hotplate was mounted, and it dried at 100 degreeC for 1 hour.

Exposure and development process: Next, a photomask having a predetermined exposure pattern is placed on the coating film, and the coating film is placed on the coating film via a photomask by an ultrahigh pressure mercury lamp (ModuleX (registered trademark)) manufactured by Ushio Spex. A parallel light source (UXM-500SX, 500 W lamp) manufactured by Co., Ltd. was used to expose 313 nm ultraviolet light to 2500 mJ / cm 2. Thereafter, the film was immersed in a 0.25 wt% tetramethylammonium hydroxide (TMAH) developer for 30 seconds for development. Thereby, the exposed area | region melt | dissolves and the coating film of a predetermined pattern shape is obtained.

Heat treatment step: Next, the base material provided with the coating film having a predetermined pattern shape was placed in an electric furnace and baked at 300 ° C. for 1 hour. By performing the heat treatment step, the photosensitive metal complex is changed to a metal oxide, and the catalyst precursor film can be obtained.

Reduction process: Then, as a reducing solution, it was immersed in an aqueous NaBH ₄ solution 2 g / l at 50 ° C. for 2 minutes. Through this step, CuO in the catalyst precursor film is reduced to Cu having catalytic activity, and a catalyst film is obtained.

b) Electroless plating step The substrate selectively provided with the catalyst in the above step was immersed in electroless copper plating (PB-506 manufactured by JCU) to deposit copper with a thickness of about 0.2 μm. . The copper plating pattern shown in FIG. 3 (a grid pattern with a line width of 5 μm and an interval of 100 μm, a sheet resistance of 2Ω / sq) was obtained by this process.

(2) Resin composition film forming step 3 ml of a liquid cycloolefin resin composition was hung on a substrate on which a copper plating pattern was formed, and spread with a pipettor chip to form a resin composition film.

(3) Resin layer forming step Then, the solvent was evaporated under a temperature atmosphere of 80 ° C. to solidify the resin composition film to obtain a cycloolefin resin layer.

Then, the cycloolefin resin layer was physically peeled from the substrate to obtain a cycloolefin resin film (resin material with a metal pattern) in which the copper plating pattern shown in FIG. 4 was embedded.

In Example 2, when forming a resin composition film, instead of using a liquid cycloolefin resin composition, 3 ml of a commercially available liquid polyimide resin composition (trade name: aldrich575771 (Sigma-Aldrich Sakai Japan Co., Ltd.)) was used. A polyimide resin film with a copper plating pattern (resin material with a metal pattern) was obtained in the same manner as in Example 1 except that the solvent was volatilized at 100 ° C. and the resin composition film was cured at 200 ° C. (FIG. 5). reference). The copper plating pattern embedded in the polyimide film is a lattice pattern with a line width of 5 μm and an interval of 100 μm, as in Example 1, and the sheet resistance is 2Ω / sq.

In Example 3, the copper plating pattern was formed except that an L-shaped pattern (see FIG. 6) having a line / space (L / S) width of 100 μm and a cross pattern (see FIG. 7) having a line width of 200 μm were formed. An electroless copper plating pattern was formed on the substrate in the same manner as in 1. In addition, when forming the resin composition film, instead of using the liquid cycloolefin resin composition, liquid dimethyl produced by Shin-Etsu Chemical Co., Ltd. was used. Using 3 ml of a polysiloxane composition (PDMS (trade name: SIM-240 / CAT-240)), the solvent was volatilized at 100 ° C. to cure the resin composition film. 1 was performed to obtain a PDMS film with a copper plating pattern (resin material with a metal pattern).

The resin films with copper plating patterns produced in Examples 1 to 3 are all highly transparent and have a smooth surface. The copper plating pattern is embedded in the film, and the copper plating pattern adheres to the film. The property was also excellent. Further, a fine copper plating pattern with a narrow line width can be obtained in a rectangular cross section, and a high-definition wiring pattern can be formed by a simple method.

By adopting the method described in the present invention, even if it is a thermoplastic resin material or the like, it can satisfy the dimensional accuracy required for the resin material, and a fine metal pattern with good adhesion can be obtained. It can be formed on a resin material. Moreover, since this invention does not give a roughening process etc. to the surface of a resin material, it is the heat | fever used for uses, such as a transparent conductive film base material for touchscreens, an organic EL lighting base material, a flexible printed base material, and an insulating film. Suitable for plastic transparent resin material

DESCRIPTION OF SYMBOLS 10 ... Base material 20 ... Resin material with a single-sided metal pattern 21 ... Metal pattern 22 ... Resin layer 31 ... First base material 32 ... Second base material 40 ... Resin material with double-sided metal pattern 41... First metal pattern 42... Second metal pattern 43.

Claims

Forming a metal pattern on the surface of the substrate for pattern formation by an electroless plating method;
A step of forming a resin composition film using a liquid resin composition on a substrate on which the metal pattern is formed, and solidifying or curing the resin composition film to obtain a resin layer in close contact with the metal pattern When,
Peeling the resin layer and the substrate to obtain a resin material with a metal pattern;
The manufacturing method of the resin material with a metal pattern characterized by including.
A first metal pattern is formed on the surface of the first substrate for pattern formation by electroless plating, and a second metal is formed on the surface of the second substrate for pattern formation by electroless plating. Forming a pattern;
The first metal pattern and the second metal pattern are inside, the first base material and the second base material are arranged to face each other at a predetermined interval, and a liquid resin composition is provided between the two base materials. And solidifying or curing this to obtain a resin layer in close contact with the first metal pattern and the second metal pattern;
Peeling the resin layer from the first base material and the second base material to obtain a resin material provided on both sides with the first metal pattern and the second metal pattern;
The manufacturing method of the resin material with a metal pattern characterized by including.
The resin composition includes cycloolefin resin, polyimide resin, epoxy resin, acrylic resin, isocyanate resin, urethane resin, liquid crystal polymer, melamine resin, polyester resin, polyester resin, silicon resin, polyethylene, polypropylene, polystyrene, and precursors thereof. The manufacturing method of the resin material with a metal pattern of Claim 1 or Claim 2 containing at least any one among these.
The resin material is cycloolefin resin material, polyimide resin material, epoxy resin material and acrylic resin material, isocyanate resin material, urethane resin material, liquid crystal polymer, melamine resin material, polyester resin material, polyester resin material, silicon resin material, polyethylene The method for producing a resin material with a metal pattern according to any one of claims 1 to 3, which is at least one of a material, a polypropylene material, and a polystyrene material.
The step of forming the metal pattern by the electroless plating method on the surface of the base material,
A catalyst application step of selectively applying a catalyst to the surface of the substrate;
An electroless plating step of immersing a substrate selectively provided with a catalyst in an electroless plating solution, and depositing metal ions in the electroless plating solution in a predetermined pattern;
The method for producing a resin material with a metal pattern according to any one of claims 1 to 4, comprising:
6. The metal according to claim 5, wherein the catalyst application step includes a step of forming a photosensitive catalyst film on the surface of the substrate and selectively exposing the photosensitive catalyst film. Manufacturing method of resin material with a pattern.
A resin material with a metal pattern produced by the method for producing a resin material with a metal pattern according to any one of claims 1 to 6.