TW202020222A - Method for producing molded body having metal pattern - Google Patents

Abstract

The present invention provides a method for producing a molded body having a metal pattern, which is characterized by comprising: a step 1 for forming a metal layer (M1), which contains metal particles, on an insulating molded body (A); a step 2 for forming a patterned metal layer (PM1) by removing a part of the metal layer (M1); and a step 3 for forming a metal plating layer (PM2) on the patterned metal layer (PM1) by means of a plating method. The present invention alternatively provides the production method wherein a primer layer (B) is formed before the formation of the metal layer (M1), which contains metal particles, on the insulating molded body (A). This production method is able to form a metal pattern having high adhesion without roughening the surface of the molded body, and is also capable of producing a molded body that has a metal pattern on the surface without requiring a vacuum apparatus or a special device.

Description

Method for manufacturing shaped body with metal pattern

The invention relates to a method for manufacturing a molded body having a metal pattern on a planar or three-dimensional insulating molded body.

Previously, as a method of forming a metal pattern on an insulating molded body, for example, it has been known to form a patterned region and a non-patterned region on the surface by performing two-color molding using two materials having different plating precipitation properties, and reuse The method of forming metal patterns due to the difference in plating precipitation. This method requires two forming steps. Therefore, not only is the process complicated and costly, but also it is difficult to express the minute patterns by forming. In addition, there may be plating solution penetration, The problem remains at the interface between the two resin materials.

On the other hand, as a method that does not perform two-color molding, a method of using a plating seed layer formed on the entire surface of the molded body is disclosed (for example, refer to Patent Document 1). In this method, the plastic molded body is immersed in an etching solution to roughen the surface, and then the metal catalyst core is attached to the surface of the roughened shaped body, immersed in the electroless plating solution, and on the outer peripheral surface An electroless plating layer is formed. After irradiating the formed electroless plating layer with laser light to remove a part of the electroless plating layer, the remaining electroless plating layer is used to perform electrolytic plating to form a pattern on the molded body.

However, the technique of Patent Document 1 is to ensure the adhesion between the substrate and the plating film by roughening the surface of the molded body. For example, for substrates where transparency is important, or chemical resistance is low or vice versa. Substrates that are too high and difficult to roughen cannot be used. In addition, because this technology roughens the surface of the molded body, the surface of the coating film will also reflect the rough surface of the molded body and will easily become a surface with irregularities. Therefore, in order to obtain a glossy surface, it is necessary to increase the thickness of the coating film and extend the plating time. Therefore, there are disadvantages of reduced productivity, increased cost, and increased weight of the molded body. Furthermore, this technique removes the electroless plating layer by laser light irradiation, but in order to cut and remove the continuous metal film, burrs are generated at the peripheral edge of the removal area, or the peripheral edge of the pattern is swelled due to thermal damage, or the pattern is not Neat topics.

In addition, as a method of improving the adhesion without roughening the surface of the molded body, and without using a vacuum device, a method of using a plastic molded body in which fine particles containing metal elements are scattered on the surface is disclosed (for example, refer to Patent Document 2). As a method for obtaining a plastic molded body in which particles containing metal elements are scattered on the surface, the following method is disclosed: the plastic molded body is impregnated with alcohol or a reducing agent, and then brought into contact with high-pressure carbon dioxide containing metal complexes; The high-pressure carbon dioxide containing the metal complex is dissolved in the molten resin in the plasticizing cylinder for injection molding of the plastic molded body, and then the dissolved molten resin is injected into the mold to form the plastic molded body. In this method, the metal element-containing fine particles are formed on the surface of the plastic molded body, so the following problems exist: a special device using high-pressure carbon dioxide is needed, and the operation of impregnating the surface portion of the plastic molded body with the metal element causes the surface and the main body to have different physical properties Wait. [Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 5-65687 [Patent Document 2] Japanese Patent Application Publication No. 2010-80495

[Problems to be solved by the invention]

The problem to be solved by the present invention is to provide a metal pattern with high adhesion without roughening the surface of the molded body, and without a vacuum device or a special device, the molded body with the metal pattern on the surface can be manufactured The manufacturing method of the shaped body. [Technical means to solve the problem]

In order to solve the above-mentioned problems, the present inventors have made intensive studies and found that a metal layer containing metal particles is formed on the surface of the molded body, and a metal layer containing metal particles is formed by removing the pattern-free part of the metal layer The pattern is subjected to a plating process, whereby without roughening and without special equipment, a metal pattern with high adhesion can be formed on various molded bodies, and the present invention is completed.

That is, the present invention provides a method for manufacturing a molded body having a metal pattern, which is characterized by the following steps: Step 1, which forms a metal layer (M1) containing metal particles on an insulating molded body (A); Step 2, It forms a patterned metal layer (PM1) by removing part of the metal layer (M1); Step 3, which forms metal plating on the patterned metal layer (PM1) by plating Layer (PM2).

Moreover, the present invention provides a method for manufacturing a molded body having a metal pattern, which is characterized by the following steps: Step 1', which forms an undercoat layer (B) on an insulating molded body (A), and then the undercoat layer (B) forming a metal layer (M1) containing metal particles; step 2, which forms a patterned metal layer (PM1) by removing part of the metal layer (M1); step 3, which is formed by plating The coating method forms a metal plating layer (PM2) on the patterned metal layer (PM1). [Effect of invention]

The method for manufacturing a molded body having a metal pattern of the present invention does not require complicated two-color molding or complicated operations such as exposure and development in a dark room using a photoresist, and does not require the use of special equipment, and can be manufactured on various molding bases. The smooth substrate of the material has a flat or three-dimensional three-dimensional shaped body with high adhesion and good metal patterns. Therefore, by adopting the technology of the present invention, it is possible to provide a molded circuit with a high-density and high-performance printed wiring board and three-dimensional wiring on various materials, various shapes and sizes of substrates that are difficult to roughen the surface at a low cost Parts (MID, Molded Interconnect Device), etc., so it is highly applicable in the related industries of the printed wiring field. The method for manufacturing a molded body with a metal pattern of the present invention can be used for various electronic components having a patterned metal layer on the surface of a substrate, such as connectors, electromagnetic wave shielding, RFID (Radio Frequency Identification) antennas, etc. Wait.

Moreover, the molded body with a metal pattern manufactured by the method for manufacturing a molded body with a metal pattern of the present invention can be used not only for electronic components, but also for a patterned metal layer on a substrate of various shapes and sizes Functional parts, decorative plating purposes.

The invention is a method for manufacturing a molded body with a metal pattern, which is characterized by the following steps: Step 1, which forms a metal layer (M1) containing metal particles on an insulating molded body (A); Step 2, which is borrowed A patterned metal layer (PM1) is formed by removing part of the metal layer (M1); Step 3, which forms a metal plating layer (PM1) on the patterned metal layer (PM1) by plating PM2).

Furthermore, a more preferred aspect of the present invention is a method for manufacturing a molded body having a metal pattern, which is characterized by the following steps: Step 1', after forming an undercoat layer (B) on an insulating molded body (A) , Forming a metal layer (M1) containing metal particles on the undercoat layer (B); step 2, which forms a patterned metal layer (PM1) by removing a part of the metal layer (M1); step 3 , Which forms a metal plating layer (PM2) on the patterned metal layer (PM1) by a plating method.

Examples of the material of the above-mentioned insulating molded body (A) used in step 1 or step 1'of the present invention include, for example, polyimide resin, polyimide amide imide resin, polyamide resin, and polyparaphenylene Ethylene dicarboxylate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, polycarbonate resin, acrylonitrile-butadiene-styrene (ABS) resin, polyarylate resin, Acrylic resins such as polyacetal resin, polymethyl (meth)acrylate, polyvinylidene fluoride resin, polytetrafluoroethylene resin, polyvinyl chloride resin, polyvinylidene chloride resin, chlorine copolymerized with acrylic resin Vinyl resin, polyvinyl alcohol resin, polyethylene resin, polypropylene resin, urethane resin, cyclic olefin resin, polystyrene, liquid crystal polymer (LCP), polyether ether ketone (PEEK) resin, polybenzene Thioether (PPS), polyphenylene oxide (PPSU), cellulose nanofiber, silicon, silicon carbide, gallium nitride, sapphire, ceramics, glass, diamond-like carbon (DLC), alumina, etc.

In addition, as the insulating molded body (A), a resin base material containing a thermosetting resin and an inorganic filler can also be preferably used. Examples of the above thermosetting resins include epoxy resins, phenol resins, unsaturated amide imide resins, cyanate resins, isocyanate resins, benzoxane resins, oxetane resins, amine-based resins, and Saturated polyester resin, allyl resin, dicyclopentadiene resin, polysiloxane resin, three resins, melamine resin, etc. On the other hand, examples of the inorganic filler include silica, alumina, talc, mica, aluminum hydroxide, magnesium hydroxide, calcium carbonate, aluminum borate, and borosilicate glass. These thermosetting resins and inorganic fillers may be used alone or in combination of two or more.

As the form of the insulating molded body (A), any of a flexible material, a rigid material, and a rigid-flexible material can be used. More specifically, the above-mentioned insulating molded body (A) may be a commercially available material formed into a film, sheet, or plate shape, or may be formed into an arbitrary three-dimensional shape using a solution, melt, or dispersion of the above various resins. The material obtained from the shape. In addition, the above-mentioned insulating molded body (A) may be a base material in which the above-mentioned various resins and other materials are formed on a conductive molding material such as metal.

In addition, in the step 2 of the present invention, when the electromagnetic wave is used to remove a part of the metal particle-containing metal layer (M1), the heat resistance and mechanical strength of the insulating molded body (A) in the target use environment may not be impaired Within the range of insulation properties, the above-mentioned insulating molded body (A) contains graphite or carbon, cyanine compound, phthalocyanine compound, dithiol metal complex, naphthoquinone compound, diya Light-absorbing pigments or pigments such as ammonium compounds and azo compounds are used as light absorbers. These pigments or pigments may be appropriately selected according to the wavelength of the electromagnetic waves used above. In addition, these pigments or pigments may be used alone or in combination of two or more. Furthermore, when a commercially available resin material is used as the material of the insulating molded body (A), a coloring resin material commercially available as a colored grade may also be used. If the insulating molded body (A) contains a pigment or a pigment that absorbs the electromagnetic wave, the electromagnetic wave is absorbed on the surface of the insulating molded body (A), and the metal layer (M1 ) Removed, so better.

Step 1 of the method for manufacturing a molded body having a metal pattern of the present invention is a step of forming a metal layer (M1) containing metal particles on the insulating molded body (A). The above-mentioned metal layer (M1) becomes the plating base layer when the metal plating layer (PM2) is formed by the plating method in the following step 3. The metal layer (M1) is a metal layer containing metal particles. Examples of the metal particles constituting the layer include silver, gold, platinum, palladium, ruthenium, tin, copper, nickel, iron, cobalt, titanium, indium, and iridium. Wait for metal particles. These metal particles may be used alone or in combination of two or more. In addition, in the following plating step, when the above metal layer (M1) is used as the plating base layer of electroless plating, the activity as a plating catalyst is high, and the above metal layer (M1) is used as the electrolysis In the case where the plating base layer is plated, the resistance value is sufficiently low, the surface is not easily oxidized when stored in the atmosphere, and the price is relatively low. The metal particles are preferably silver particles.

In the case of using a plurality of kinds of metal particles as the above-mentioned metal particles, as long as the ratio of the metal particles other than the main metal particles can be formed, as long as the above-mentioned metal layer (M1) can be formed and the plating in the following step 3 can be carried out without problems, There is no particular limitation. From the viewpoint of the uniformity stability of the plating precipitation, the content of the particles of other metal species is preferably 5 parts by mass or less, more preferably 2 with respect to 100 parts by mass of the particles of the main metal species Below mass parts.

As a method of forming the metal layer (M1), for example, a method of applying a dispersion liquid of metal particles on the insulating molded body (A) may be mentioned. The coating method of the above metal particle dispersion liquid is not particularly limited as long as the metal layer (M1) can be formed satisfactorily, and various coating methods are appropriately selected according to the shape, size, degree of rigidity, etc. of the insulating molded body (A) used That's it. Specific coating methods include, for example, gravure method, offset method, flexographic method, pad printing method, gravure offset method, relief method, relief inversion method, screen method, micro-touch method, reverse roll method, pneumatic Including coating method, blade coating method, air knife coating method, extrusion coating method, impregnating coating method, transfer roller coating method, contact coating method, coating casting method, spray coating method, inkjet Method, die coating method, spin coating method, bar coating method, dip coating method, etc.

In addition, as a method of applying the metal particle dispersion liquid to both surfaces of the above-mentioned insulating molded body (A) in the form of a film, a sheet, or a plate, as long as the metal layer (M1) can be formed satisfactorily, it is not particularly limited and may be appropriately selected. The coating method exemplified above may be sufficient. In this case, the metal layers (M1) may be formed on both surfaces of the insulating molded body (A) at the same time, or the metal layer (M1) may be formed on one surface of the insulating molded body (A) and then formed on the other surface. Furthermore, in the case where the insulating molded body (A) is a three-dimensional shaped molded body, the coating method exemplified above may be appropriately selected according to the size and shape of the molded body, preferably a spray coating method, an inkjet method, or a dip coating Buffalo etc.

For the purpose of improving the coatability of the metal particle dispersion liquid and the adhesion of the metal plating layer (PM2) formed in step 3 to the substrate, the insulating molded body (A) may be applied before the metal particle dispersion liquid Surface treatment. The surface treatment method of the above-mentioned insulating molded body (A) is not particularly limited as long as there is no problem with micropitch pattern formability due to increased surface roughness or signal transmission loss due to rough surface. Just choose various methods. Examples of such surface treatment methods include UV treatment, gas-phase ozone treatment, liquid-phase ozone treatment, corona treatment, and plasma treatment. These surface treatment methods may be performed by one method, or two or more methods may be used in combination.

After the dispersion of the metal particles is coated on the insulating molded body (A), the coating film is dried, and the solvent contained in the metal particle dispersion is volatilized to fix the metal particles to the insulating molded body ( A) Up.

The drying temperature and time may be appropriately selected according to the heat-resistant temperature of the base material used, or the selected steps, productivity, etc., preferably within a temperature range of 20 to 350° C. for about 1 to 200 minutes, below In the case of performing the electroless plating method in the above step 3, it is preferable to set the drying temperature to the range of 20 to 300°C, and it is more preferable to set the aspect of improving the electroless plating precipitation It is in the range of 20～250℃. In the case where the electrolytic plating method is directly performed in the above-mentioned step 3, the drying temperature is preferably in the range of 80 to 350°C, and more preferably in the range of 100 to 300°C.

After coating and drying the metal particle dispersion on the insulating molded body (A), if necessary, curing or annealing may be performed for the purpose of improving the adhesion with the metal plating layer (PM2) described below. The temperature and time of aging or annealing may be appropriately selected according to the heat-resistant temperature, required steps, productivity, etc. of the above-mentioned insulating molded body (A), and it is preferable to perform electroless plating in the following step 3 In order to perform the said insulating molded body (A) in which the said metal layer (M1) was formed in the temperature range of 60-200 degreeC for 30 minutes-2 weeks. In addition, when electrolytic plating is performed in the following step 3, it is preferably performed within a temperature range of 80 to 250° C. for 5 minutes to 1 hour.

In addition, the insulating molded body (A) after step 1 or step 1'of the present invention and step 2 below is stored at a temperature range from room temperature to about 60°C and then used in step 3 below Special question.

The above-mentioned drying, aging or annealing may be carried out with air blowing, or may be carried out without particular air blowing. In addition, drying, aging or annealing may be performed in the atmosphere, or may be performed in a replacement environment of inert gas such as nitrogen or argon, or under a gas flow, or may be performed under vacuum.

When the above-mentioned insulating molded body (A) is a single-piece film, sheet, plate, or three-dimensional three-dimensional shaped molded body, in addition to natural drying at the coating site, it can be used in a dryer such as a blower, a constant temperature dryer, etc. The above drying, aging or annealing is performed. In addition, when the insulating molded body (A) is a roll-shaped film or roll-shaped sheet, the roll-shaped material can be dried by continuously moving the roll-shaped material in the non-heated or heated space provided after the coating step. As a heating method for drying at this time, for example, a method using an oven, a hot air type drying furnace, an infrared drying furnace, laser irradiation, microwave, light irradiation (flash irradiation device), etc. may be mentioned. One type of these heating methods may be used, or two or more types may be used in combination.

In terms of making it possible to make a more excellent plating base layer in the following step 3, the thickness of the metal layer (M1) is preferably in the range of 10 to 500 nm. Moreover, in the case of performing electroless plating in the following step 3, the thickness of the metal layer (M1) is preferably in the range of 10 to 500 nm, and from the viewpoint of reducing the material cost, it is more preferably 10 to 150 nm Scope. In addition, in the case where electrolytic plating is performed in the following step 3, the thickness of the metal layer (M1) is preferably in the range of 50 to 500 nm, to ensure conductivity and materials for performing electrolytic plating with better efficiency From the viewpoint of cost, the range of 60 to 250 nm is more preferable.

In the case where electrolytic plating is performed in the following step 3, it is preferable that the metal layer (M1) has metal particles that are in close contact with each other and bonded to have high conductivity. In addition, the voids between the metal particles can also be filled with the plating metal constituting the metal plating layer (PM2) by the plating method in step 3 below. When the gap between the metal particles is filled with plated metal, the adhesion between the insulating molded body (A) and the metal pattern is improved.

The metal particle dispersion used to form the metal layer (M1) is one in which metal particles are dispersed in a solvent. The shape of the metal particles is not particularly limited as long as the metal layer (M1) is formed satisfactorily, and metal particles of various shapes such as spherical, lenticular, polyhedral, flat, rod-shaped, and linear can be used. One type of these metal particles may be used in a single shape, or two or more types of different shapes may be used in combination.

When the shape of the metal particles is spherical or polyhedral, the average particle diameter is preferably in the range of 1 to 20,000 nm. In addition, in the case of forming a fine metal pattern, the homogeneity of the metal layer (M1) is further improved. In terms of the following step 2, the removal property by electromagnetic waves can be further improved, and its average particle diameter is more preferable It is in the range of 1 to 200 nm, and more preferably in the range of 1 to 50 nm. In addition, the "average particle diameter" of nano-sized particles is the volume average value of the above-mentioned silver particles diluted with a good dispersion solvent by dynamic light scattering method. For the measurement, "Nanotrac UPA-150" manufactured by Microtrac can be used.

On the other hand, in the case where the metal particles have a lens-like, rod-like, linear, etc. shape, the shorter diameter is preferably in the range of 1 to 200 nm, more preferably in the range of 2 to 100 nm, and more preferably It is in the range of 5 to 50 nm.

The metal particle dispersion liquid used to form the metal layer (M1) is one in which metal particles are dispersed in various solvents. The particle size distribution of the metal particles in the dispersion liquid may be monodispersion with uniform particle size, or it may be A mixture of particles within the above average particle size range.

As the solvent used in the dispersion liquid of the above-mentioned metal particles, an aqueous medium or an organic solvent can be used. Examples of the aqueous medium include distilled water, ion-exchanged water, pure water, and ultrapure water. In addition, examples of the organic solvent include alcohol compounds, ether compounds, ester compounds, and ketone compounds.

Examples of the alcohol solvent or ether solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, second butanol, third butanol, pentanol, hexanol, and octanol. , Nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecyl alcohol, stearyl alcohol, allyl alcohol, cyclohexanol, terpineol, terpineol, dihydropine Oleyl alcohol, 2-ethyl-1,3-hexanediol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, 1,2-butanediol, 1, 3-butanediol, 1,4-butanediol, 2,3-butanediol, glycerin, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether , Diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol monopropyl ether, dipropylene glycol mono Propyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, etc.

Examples of the ketone solvent include acetone, cyclohexanone, and methyl ethyl ketone. In addition, examples of the ester solvent include ethyl acetate, butyl acetate, 3-methoxybutyl acetate, 3-methoxy-3-methyl-butyl acetate, and the like. Furthermore, examples of other organic solvents include hydrocarbon solvents such as toluene, and particularly hydrocarbon solvents having 8 or more carbon atoms.

Examples of the hydrocarbon solvent having 8 or more carbon atoms include octane, nonane, decane, dodecane, tridecane, tetradecane, cyclooctane, xylene, symmetrical xylene, and ethylbenzene. , Non-polar solvents such as dodecylbenzene, naphthalene, trimethylbenzene cyclohexane, etc., can be used in combination with other solvents as needed. Furthermore, a solvent such as mineral spirits and solvent naphtha which are mixed solvents may be used in combination.

As long as the metal particles are stably dispersed, the metal layer (M1) is formed well on the insulating molded body (A) or on the undercoat layer (B) formed on the insulating molded body (A) described below. The solvent is not particularly limited. Moreover, the said solvent can use 1 type or 2 or more types together.

The content rate of the metal particles in the metal particle dispersion liquid is adjusted to have a viscosity corresponding to the best coating adaptability of the coating method described above, preferably in the range of 0.5 to 90% by mass, more preferably 1 The range of ~60% by mass, further preferably the range of 2~10% by mass.

The metal particle dispersion liquid preferably maintains the dispersion stability of the metal particles in the various solvents for a long time without aggregation, fusion, or precipitation, and preferably contains a dispersant for dispersing the metal particles in the various solvents. As such a dispersing agent, a dispersing agent having a functional group coordinated to the metal particles is preferred, and examples thereof include a carboxyl group, an amine group, a cyano group, an acetoacetyl group, a group containing a phosphorus atom, a thiol group, Dispersant for thiocyanate group, glycine group and other functional groups.

As the dispersant, a commercially available or self-synthesized low molecular weight or high molecular weight dispersant can be used, depending on the type of solvent for dispersing the metal particles or the type of the above-mentioned insulating molded body (A) for coating the metal particle dispersion, etc., The purpose can be selected appropriately. For example, dodecanethiol, 1-octanethiol, triphenylphosphine, dodecylamine, polyethylene glycol, polyvinylpyrrolidone, polyethylenimine, polyvinylpyrrolidone; Fatty acids such as myristic acid, caprylic acid and stearic acid; polycyclic hydrocarbon compounds with carboxyl groups such as cholic acid, glycyrrhizic acid and rosinic acid. Here, in the case where the above-mentioned metal layer (M1) is formed on the following undercoat layer (B), it is preferable to use an undercoat layer ( B) The reactive functional group [X] of the resin used has a reactive functional group [Y] that forms a bond.

As the compound having a reactive functional group [Y], for example, an amine group, an amide group, an alkanol group amide group, a carboxyl group, an anhydrous carboxyl group, a carbonyl group, an acetylacetoyl group, an epoxy group, an alicyclic Compounds such as epoxy groups, oxycyclobutane rings, vinyl groups, allyl groups, (meth)acryloyl groups, (blocked) isocyanate groups, (alkoxy) silane groups, silsesquioxane compounds Wait. In particular, in terms of further improving the adhesion between the undercoat layer (B) and the metal layer (M1), the reactive functional group [Y] is preferably a group containing a basic nitrogen atom. Examples of the basic nitrogen atom-containing group include imine groups, primary amine groups, and secondary amine groups.

One or more of the above basic nitrogen atom-containing groups may be present in one molecule of the dispersant. By containing a plurality of basic nitrogen atoms in the dispersant, part of the base containing basic nitrogen atoms contributes to the dispersion stability of the particles by interacting with the metal particles, and the remaining base containing basic nitrogen atoms Helps improve the adhesion to the insulating molded body (A). In addition, in the case where a resin having a reactive functional group [X] is used in the undercoat layer (B) below, the basic nitrogen atom-containing group in the dispersant can form a bond with the reactive functional group [X] In addition, the adhesion of the following metal plating layer (PM2) to the insulating molded body (A) can be further improved, which is preferable.

The dispersant is preferably a dispersant in terms of the stability of the dispersion liquid of the metal particles, the coatability, and the formation of the metal layer (M1) exhibiting good adhesion on the insulating molded body (A). A polymer dispersant. As the polymer dispersant, polyalkyleneimines such as polyethylenimine and polypropyleneimine are preferred, and polyoxyalkylene is added to the polyalkyleneimine. Alkyl compounds, etc.

As a compound for adding polyoxyalkylene to the polyalkyleneimine, the polyethylenimine and polyoxyalkylene may be linearly bonded, or may be a compound Ethylene imine is the main chain and the side chain is grafted with polyoxyalkylene.

As a specific example of a compound in which polyoxyalkylene is added to the above polyalkyleneimine, for example, a block copolymer of polyethylenimine and polyoxyethylene; polyethylenimine A part of the imine group present in the main chain undergoes an addition reaction with ethylene oxide to introduce a polyoxyethylene structure; the amine group possessed by the polyalkyleneimine and the hydroxyl group possessed by the polyoxyethylene glycol It is obtained by reacting with epoxy group of epoxy resin.

Examples of the commercially available products of the polyalkyleneimine include “PAO2006W”, “PAO306”, “PAO318”, and “PAO718” of the “EPOMIN (registered trademark) PAO series” manufactured by Japan Catalyst Co., Ltd. .

The number average molecular weight of the polyalkyleneimine is preferably in the range of 3,000 to 30,000.

The amount of the dispersing agent required to disperse the metal particles is preferably in the range of 0.01 to 50 parts by mass relative to 100 parts by mass of the metal particles, and can be used in the insulating molded body (A ) In terms of forming the above-mentioned metal layer (M1) exhibiting good adhesion on the undercoat layer (B) or below, it is preferably in the range of 0.1 to 10 parts by mass relative to 100 parts by mass of the above-mentioned metal particles, Furthermore, in terms of improving the conductivity of the metal layer (M1), it is more preferably in the range of 0.1 to 5 parts by mass.

The method for producing the dispersion liquid of the metal particles is not particularly limited, and various methods can be used. For example, the metal particles produced by the gas phase method such as low vacuum gas evaporation method can be dispersed in the solvent or the liquid phase The metal compound is reduced to directly prepare a dispersion of metal particles. Both the gas phase and liquid phase methods can appropriately change the solvent composition of the dispersion liquid at the time of manufacture and the dispersion liquid at the time of application by solvent exchange or solvent addition as appropriate. Among the gas-phase and liquid-phase methods, the liquid-phase method can be particularly preferably used in terms of the stability of the dispersion liquid or the simplicity of the manufacturing steps. As the liquid phase method, for example, it can be produced by reducing metal ions in the presence of the above-mentioned polymer dispersant.

If necessary, organic compounds such as surfactants, leveling agents, viscosity modifiers, film-forming aids, defoamers, preservatives and the like can be further blended into the dispersion of the metal particles.

Examples of the surfactant include polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene sorbitol tetraoleate, and polyoxyethylene-poly Nonionic surfactants such as oxypropylene copolymers; fatty acid salts such as sodium oleate, alkyl sulfate ester salts, alkylbenzene sulfonates, alkyl sulfosuccinates, naphthalene sulfonates, polyoxyethylene alkyl groups Sulfate, alkane sulfonate sodium salt, alkyl diphenyl ether sulfonate sodium salt and other anionic surfactants; alkyl amine salt, alkyl trimethyl ammonium salt, alkyl dimethyl benzyl ammonium salt, etc. Cationic surfactants, etc.

As the above-mentioned leveling agent, general leveling agents can be used, and examples thereof include polysilicone-based compounds, acetylene glycol-based compounds, and fluorine-based compounds.

As the viscosity adjuster, general tackifiers can be used, for example, acrylic polymers that can be thickened by adjusting to alkaline, synthetic rubber latex, and amine ester resins that can be thickened by molecular association. , Hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, polyvinyl alcohol, hydrogenated castor oil, amide wax, oxidized polyethylene, metal soap, dibenzylidene sorbitol, etc.

As the above-mentioned film-forming aid, general film-forming aids can be used, and examples thereof include anionic surfactants such as dioctyl sulfosuccinate sodium salt, and hydrophobic nonionic systems such as sorbitan monooleate. Surfactant, polyether modified silicone, polysiloxane oil, etc.

As the antifoaming agent, general antifoaming agents can be used, and examples thereof include polysiloxane-based antifoaming agents, nonionic surfactants, polyethers, higher alcohols, and polymer surfactants.

As the above-mentioned preservatives, general preservatives can be used, and examples thereof include isothiazoline-based preservatives, tri-based preservatives, imidazole-based preservatives, pyridine-based preservatives, azole-based preservatives, and pyridinethione-based preservatives. Wait.

In addition, as a better aspect of the present invention, there is a method (step 1'): before forming a metal layer (M1) containing metal particles on the insulating shaped body (A), precede the insulating shaped body (A) An undercoat layer (B) is formed thereon, and then a metal layer (M1) containing metal particles is formed on this layer. The method of providing the undercoat layer (B) can further improve the adhesion of the metal plating layer (PM2) to the above-mentioned insulating molded body (A), which is preferable.

The undercoat layer (B) can be obtained by applying a primer to a part of or the entire surface of the insulating molded body (A) to remove solvents such as an aqueous medium and an organic solvent contained in the primer form. Here, the primer is used for the purpose of improving the adhesion of the metal plating layer (PM2) to the insulating molded body (A), and is a liquid state obtained by dissolving or dispersing the following various resins in a solvent Composition.

The method for applying the primer to the insulating molded body (A) is not particularly limited as long as the undercoat layer (B) can be formed satisfactorily, depending on the shape and size of the insulating molded body (A) used , The degree of rigidity and flexibility, etc., can be appropriately selected for various coating methods. Specific coating methods include, for example, gravure method, offset method, flexographic method, pad printing method, gravure offset method, relief method, relief inversion method, screen method, micro-touch method, reverse roll method, pneumatic Including coating method, blade coating method, air knife coating method, extrusion coating method, impregnating coating method, transfer roller coating method, contact coating method, coating casting method, spray coating method, inkjet Method, die coating method, spin coating method, bar coating method, dip coating method, etc.

In addition, as a method of applying the above-mentioned primer on both surfaces of the above-mentioned insulating molded body (A) in the form of a film, a sheet, or a plate, as long as the undercoat layer (B) can be formed well, it is not particularly limited and is suitable. It is sufficient to select the coating method illustrated above. In this case, the undercoat layer (B) may be formed on both sides of the insulating molded body (A) at the same time, or the undercoat layer (B) may be formed on one surface of the insulating molded body (A) and then another One side is formed. Furthermore, in the case where the insulating molded body (A) is a three-dimensional shaped molded body, the coating method exemplified above may be appropriately selected according to the size and shape of the molded body, preferably a spray coating method, an inkjet method, or a dip coating Buffalo etc.

For the purpose of improving the coatability of the primer or the adhesion of the metal plating layer (PM2) to the substrate, the above-mentioned insulating molded body (A) may also be applied before the primer (step 1') Surface treatment. As the surface treatment method of the insulating molded body (A), the same method as the above-mentioned surface treatment method in the case of forming the metal plating layer (PM2) containing silver particles on the insulating molded body (A) can be used.

As a method of forming the undercoat layer (B) by applying the above primer on the surface of the insulating molded body (A) and then removing the solvent contained in the coating layer, for example, it is generally dried by using a dryer to make the above The method of solvent evaporation. The drying temperature may be set to a temperature within a range that can volatilize the solvent without adversely affecting the insulating molded body (A), and may be drying at room temperature or heating. The specific drying temperature is preferably in the range of 20 to 350°C, and more preferably in the range of 60 to 300°C. In addition, the drying time is preferably in the range of 1 to 200 minutes, and more preferably in the range of 1 to 60 minutes.

The above-mentioned drying may be carried out with air blowing, or may be carried out without particular air blowing. In addition, drying can be performed in the atmosphere, or in a replacement environment such as nitrogen or argon, or under a gas flow, or under vacuum.

When the above-mentioned insulating molded body (A) is a single-piece film, sheet, plate, or three-dimensional shaped molded body, in addition to natural drying at the coating site, it can be carried out in a dryer such as a blower, a constant temperature dryer, etc. dry. In addition, when the insulating molded body (A) is a roll-shaped film or roll-shaped sheet, the roll-shaped material can be dried by continuously moving the roll-shaped material in the non-heated or heated space provided after the coating step.

The film thickness of the undercoat layer (B) may be appropriately selected according to the specifications and uses of the molded body having a metal pattern manufactured by the present invention, and the insulating molded body (A) and the metal plating layer can be further improved In terms of the adhesiveness of (PM2), it is preferably in the range of 10 nm to 30 μm, more preferably in the range of 10 nm to 10 μm, and further preferably in the range of 10 nm to 5 μm.

Regarding the resin forming the undercoat layer (B), in the case where the dispersant of the metal particles contains a reactive functional group [Y], it is preferable to contain a reactive function reactive toward the reactive functional group [Y] Base [X] resin. Examples of the reactive functional group [X] include, for example, amine group, amide group, alkylol amide group, carboxyl group, anhydrous carboxyl group, carbonyl group, acetoacetyl group, epoxy Group, alicyclic epoxy group, oxycyclobutane ring, vinyl group, allyl group, (meth)acryloyl group, (blocked) isocyanate group, (alkoxy) silane group, etc. In addition, a silsesquioxane compound can also be used as a compound for forming the undercoat layer (B).

Especially in the case where the reactive functional group [Y] in the above dispersant is a group containing a basic nitrogen atom, the adhesion of the metal plating layer (PM2) on the above-mentioned insulating molded body (A) can be further improved. In terms of aspect, the resin forming the undercoat layer (B) preferably contains a carboxyl group, a carbonyl group, an acetylacetoyl group, an epoxy group, an alicyclic epoxy group, an alkanol group amide group, an isocyanate group, a vinyl group, (Meth) acrylamide and allyl as reactive functional groups [X].

Examples of the resin for forming the undercoat layer (B) include urethane resin, acrylic resin, core-shell composite resin with urethane resin as the shell and acrylic resin as the core, epoxy resin, amide imine Resin, amide resin, melamine resin, phenol resin, urea formaldehyde resin, blocked isocyanate polyvinyl alcohol, polyvinyl pyrrolidone obtained by reacting a blocking agent such as polyisocyanate and phenol. Furthermore, a core-shell composite resin having an urethane resin as a shell and an acrylic resin as a core is obtained, for example, by polymerizing an acrylic monomer in the presence of an urethane resin. In addition, these resins can be used alone or in combination of two or more.

Among the resins forming the above-mentioned undercoat layer (B), in order to further improve the adhesion of the metal plating layer (PM2) on the insulating molded body (A), it is preferable to generate reducibility by heating Compound resin. Examples of the reducing compound include phenol compounds, aromatic amine compounds, sulfur compounds, phosphoric acid compounds, and aldehyde compounds. Among these reducing compounds, phenol compounds and aldehyde compounds are preferred.

When a resin that generates a reducing compound by heating is used as a primer, reducing compounds such as formaldehyde and phenol are generated in the heating and drying step when forming the undercoat layer (B). Specific examples of resins that generate reducing compounds by heating include, for example, resins obtained by polymerizing monomers containing N-alkanol (meth)acrylamide, urethane resins as shells, and The resin containing N-alkanol (meth)acrylamide polymerized as the core-shell composite resin, urea-formaldehyde-methanol condensate, urea-melamine-formaldehyde-methanol condensate, poly Formaldehyde adducts of N-alkoxymethylol (meth)acrylamide, poly(meth)acrylamide, melamine resins, etc. generate formaldehyde by heating; phenol resin, phenol blocked isocyanate, etc. Resins that produce phenol compounds by heating. Among these resins, from the viewpoint of improving the adhesiveness, it is preferable to use an urethane resin as a shell and a resin obtained by polymerizing a monomer containing an N-alkanol group (meth)acrylamide as a core Core-shell composite resin, melamine resin, phenol blocked isocyanate.

Furthermore, in the present invention, the term "(meth)acrylamide" refers to one or both of "methacrylamide" and "acrylamide", and the term "(meth)acrylic acid" refers to One or both of "methacrylic acid" and "acrylic acid".

The resin that generates a reducing compound by heating can be obtained by polymerizing a monomer having a functional group that generates a reducing compound by heating by a polymerization method such as radical polymerization, anionic polymerization, or cationic polymerization.

Examples of the monomer having a functional group that generates a reducing compound by heating include N-alkanol vinyl monomers, and specifically, N-methylol (meth)acrylamide, N -Methoxymethyl(meth)acrylamide, N-ethoxymethyl(meth)acrylamide, N-propoxymethyl(meth)acrylamide, N-isopropoxy Methyl (meth) acrylamide, N-n-butoxymethyl (meth) acrylamide, N-isobutoxymethyl (meth) acrylamide, N-pentyloxymethyl ( Meth) acrylamide, N-ethanol (meth) acrylamide, N-propanol (meth) acrylamide, etc.

In addition, in the production of the resin that generates the reducing compound by heating, other various monomers such as alkyl (meth)acrylate and the monomer having a functional group that generates the reducing compound by heating may be performed together Copolymerization.

In the case of using the above-mentioned blocked isocyanate as the resin for forming the above-mentioned undercoat layer (B), the uretdione bond is formed by the self-reaction between the isocyanate groups, or the isocyanate group forms a bond with the functional group possessed by other components, thereby Form a primer layer (B). The bond formed at this time may be formed before coating the metal particle dispersion liquid, or may not be formed before coating the metal particle dispersion liquid, but may be formed by heating after coating the metal particle dispersion liquid.

Examples of the blocked isocyanate include functional groups formed by blocking isocyanate groups with a blocking agent.

The blocked isocyanate is preferably one having the above functional groups in an average range of 350 to 600 g/mol per mole of blocked isocyanate.

From the viewpoint of improving adhesion, it is preferable that the blocked isocyanate has 1 to 10 of the above functional groups in one molecule, and more preferably 2 to 5.

The number average molecular weight of the blocked isocyanate is preferably in the range of 1,500 to 5,000, and more preferably in the range of 1,500 to 3,000, from the viewpoint of improving adhesion.

Furthermore, from the viewpoint of further improving adhesion, the blocked isocyanate preferably has an aromatic ring. Examples of the aromatic ring include phenyl and naphthyl.

Furthermore, the blocked isocyanate can be produced by reacting a part or all of the isocyanate group possessed by the isocyanate compound with a blocking agent.

Examples of the isocyanate compound that becomes the raw material of the blocked isocyanate include: 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, and carbodiimide modified diphenyl Methane diisocyanate, crude diphenylmethane diisocyanate, benzene diisocyanate, toluene diisocyanate, naphthalene diisocyanate and other polyisocyanate compounds with aromatic rings; hexamethylene diisocyanate, amine diisocyanate, cyclohexane diisocyanate , Isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate and other aliphatic polyisocyanate compounds or polyisocyanate compounds having an alicyclic structure, etc. Moreover, the biuret body, isocyanurate body, addition object etc. of the said polyisocyanate compound can also be mentioned.

Moreover, as said isocyanate compound, the polyisocyanate compound exemplified above and the compound which has a hydroxyl group or an amine group, etc. are obtained by making it react, and can also be mentioned.

When introducing an aromatic ring into the blocked isocyanate, it is preferable to use a polyisocyanate compound having an aromatic ring. In addition, among the polyisocyanate compounds having an aromatic ring, 4,4'-diphenylmethane diisocyanate, toluene diisocyanate, 4,4'-diphenylmethane diisocyanate isocyanurate, The isocyanurate body of toluene diisocyanate.

Examples of the blocking agent used for the production of the blocked isocyanate include phenol compounds such as phenol and cresol; ε-caprolactam, δ-valerolactam, and γ-butyrolamide. Compounds; formamide oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketoxime, methyl isobutyl ketone oxime, cyclohexanone oxime and other oxime compounds; 2-hydroxypyridine, butyl cycloxane, propylene glycol mono Methyl ether, benzyl alcohol, methanol, ethanol, n-butanol, isobutanol, dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, acetone acetone, butyl sulfide Alcohol, dodecanethiol, acetanilide, acetamide, succinimide, maleimide, imidazole, 2-methylimidazole, urea, thiourea, ethidium urea, diphenylaniline, Aniline, carbazole, ethyleneimine, polyethylenimine, 1H-pyrazole, 3-methylpyrazole, 3,5-dimethylpyrazole, etc. Among these, the blocking agent capable of dissociating to form isocyanate groups by heating in the range of 70 to 200°C is preferred, and the blocking end capable of dissociating to generate isocyanate groups by heating in the range of 110 to 180°C is more preferred化剂。 Chemical agent. Specifically, it is preferably a phenol compound, an internal amide compound, or an oxime compound, and in particular, it is more preferably a phenol compound in terms of becoming a reducing compound when the blocking agent is removed by heating.

Examples of the method for producing the blocked isocyanate include a method of mixing and reacting the isocyanate compound and the blocking agent prepared in advance, and the blocking agent and the raw material for manufacturing the isocyanate compound. The method of mixing and reacting together.

More specifically, the blocked isocyanate can be produced by reacting the polyisocyanate compound with a compound having a hydroxyl group or an amine group to produce an isocyanate compound having an isocyanate group at the terminal, and then, the isocyanate compound and the blocked The terminating agent is mixed and reacted.

The content ratio of the blocked isocyanate obtained by the above method in the resin forming the undercoat layer (B) is preferably in the range of 50 to 100% by mass, more preferably in the range of 70 to 100% by mass.

Examples of the above-mentioned melamine resin include mono- or polymethylol melamine formed by adding 1 to 6 mol of formaldehyde to 1 mol of melamine; trimethoxymethylol melamine and tributyloxymethyl melamine , Ether of hexamethoxymethylolmelamine (poly)methylolmelamine (any degree of etherification); urea-melamine-formaldehyde-methanol condensate, etc.

In addition to the method of using a resin that generates a reducing compound by heating as described above, a method of adding a reducing compound to the resin can also be mentioned. In this case, examples of the added reducing compound include phenol-based antioxidants, aromatic amine-based antioxidants, sulfur-based antioxidants, phosphoric acid-based antioxidants, vitamin C, vitamin E, sodium ethylenediamine tetraacetate, Sulfite, hypophosphorous acid, hypophosphite, hydrazine, formaldehyde, sodium borohydride, dimethylamine borane, phenol, etc.

In the present invention, the method of adding a reducing compound to the resin may eventually leave a low-molecular-weight component or an ionic compound, resulting in the possibility of lowering electrical characteristics, so it is more preferable to use a resin that generates a reducing compound by heating .

From the viewpoint of coatability and film formability, the primer used to form the undercoat layer (B) is preferably one containing 1 to 70% by mass of the above resin in the primer, and more preferably 1~20% by mass.

In addition, examples of solvents that can be used for the above primer include various organic solvents and aqueous media. Examples of the organic solvent include toluene, ethyl acetate, methyl ethyl ketone, and cyclohexanone. Examples of the aqueous medium include water, organic solvents mixed with water, and these mixtures.

Examples of the organic solvent mixed with water include alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, ethyl carbitol, ethylcellosolve, and butylcellosolve; acetone , Methyl ethyl ketone and other ketone solvents; ethylene glycol, diethylene glycol, propylene glycol and other alkylene glycol solvents; polyethylene glycol, polypropylene glycol, polytetramethylene glycol and other polyalkylene glycol Solvent; N-methyl-2-pyrrolidone and other acetamide solvents, etc.

Furthermore, the resin forming the above-mentioned undercoat layer (B) may have functional groups that contribute to the crosslinking reaction, such as alkoxysilyl groups, silanol groups, hydroxyl groups, and amine groups, if necessary. Regarding the cross-linked structure formed by these functional groups, the cross-linked structure may be formed before the step of forming the metal layer containing silver particles (M1) described below, or the metal layer containing metal particles may be formed below ( After the step of M1), a cross-linked structure is formed. In the case where a cross-linked structure is formed after the step of forming a metal layer (M1) containing metal particles, the above-mentioned undercoat layer (B) may be formed into a cross-linked structure before the above-mentioned metal plating layer (PM2) is formed. After the metal plating layer (PM2), for example, the undercoat layer (B) is formed into a cross-linked structure by aging.

If necessary, a known agent such as a pH adjusting agent represented by a cross-linking agent, a film-forming auxiliary agent, a leveling agent, a thickener, a water-repellent agent, a defoaming agent, etc. may be appropriately added and used in the above-mentioned undercoat layer (B).

Examples of the crosslinking agent include metal chelate compounds, polyamine compounds, aziridine compounds, metal salt compounds, and isocyanate compounds. Examples include crosslinking at a relatively low temperature of about 25 to 100°C. Thermal cross-linking agent of structure, melamine-based compound, epoxy-based compound, oxazoline compound, carbodiimide compound, blocked isocyanate compound is a thermal cross-linking agent that reacts to form a cross-linked structure at a relatively high temperature equal to or higher than 100°C Or various photocrosslinking agents.

The amount of the cross-linking agent used varies depending on the type. From the viewpoint of improving the adhesion of the metal plating layer (PM2) on the insulating molded body (A), relative to the resin contained in the primer The total amount is 100 parts by mass, preferably 0.01 to 60 parts by mass, more preferably 0.1 to 10 parts by mass, and further preferably 0.1 to 5 parts by mass.

In the case of using the above-mentioned cross-linking agent, the cross-linked structure may have been formed before the step of forming the metal layer (M1) containing metal particles in the subsequent step, or it may be used in the step of forming the metal layer (M1) containing metal particles After that, a cross-linked structure is formed. In the case where a cross-linked structure is formed after the step of forming a metal layer (M1) containing metal particles, the above-mentioned undercoat layer (B) may be formed into a cross-linked structure before the above-mentioned metal plating layer (PM2) is formed. After the metal plating layer (PM2), for example, the undercoat layer (B) is formed into a cross-linked structure by aging.

In step 1'of the present invention, a method of forming a metal layer (M1) containing metal particles on the undercoat layer (B) and forming a metal layer (M1) containing metal particles on an insulating molded body (A) The method is the same.

The above-mentioned undercoat layer (B) may contain the following absorption of the above-mentioned electromagnetic waves within a range that does not impair the heat resistance, mechanical strength, insulating properties, adhesion, etc. in the target use environment, similar to the above-mentioned insulating molded body (A) The pigment or pigment acts as a light absorber.

In addition, the undercoat layer (B) may be similar to the insulating molded body (A) by improving the coatability of the metal particle dispersion liquid or improving the metal plating layer (PM2) on the insulating molded body ( A) For the purpose of adhesion, surface treatment is performed before applying the metal particle dispersion.

In step 2 of the present invention, a patterned metal layer (PM1) is formed by removing a part of the metal layer (M1). The patterned metal layer (PM1) is the remaining portion of the metal layer (M1) on the insulating molded body (A).

As a method of removing the metal layer (M1), a method of mechanically shaving the metal layer (M1) or a method of removing by irradiation of electromagnetic waves, etc. may be mentioned. For the method of mechanically cutting the metal layer (M1), for example, a substrate processing machine of IPtronics can be used. In addition, as a method of removing the irradiated electromagnetic wave, a method using X-rays, a pulse flash lamp, a laser, etc. can be mentioned.

Among the above methods of removing the metal layer (M1), in terms of high resolution of pattern formation, or easy adaptability to various shapes of shaped bodies, and high productivity, the method of removing electromagnetic waves and the method of radiating electromagnetic waves are preferred Among them, in terms of high irradiation energy and easy removal of the metal layer (M1), which is convenient for industrial applications, it is preferable to use laser.

As the laser to be used, well-known infrared lasers, visible lasers, and ultraviolet lasers may be used, which may be continuous oscillation lasers or pulse lasers. Examples of the infrared laser include carbon dioxide (CO ₂ ) laser, Nd:YAG laser, Er:YAG laser, Yb:YAG laser, Tm:YAG laser, Nd:YLF laser, and Nd: Glass laser, Nd: YVO ₄ laser, Cr magnesium silicate laser, titanium sapphire laser, alexandrite laser, etc. Moreover, examples of the visible laser include glass laser, ruby laser, copper vapor laser, pigment laser, and second harmonic of various infrared lasers. Furthermore, examples of ultraviolet lasers include third harmonics and fourth harmonics of nitrogen lasers, excimer lasers, and various infrared lasers. Furthermore, semiconductor lasers of various wavelengths and higher harmonics of semiconductor lasers can be selected according to the purpose.

In order to irradiate the laser light along the desired pattern shape, the laser for removing the metal layer (M1) preferably has a laser beam capable of moving the laser light on the metal layer (M1) at high speed using a galvanometer scanner or optical fiber, etc. Scanning system of the irradiation department. Such a scanning system can be produced by combining a laser oscillator, a galvanometer scanner, and an optical fiber, or a commercially available laser processing machine, laser marking machine, etc. can be used.

Among the above lasers, carbon dioxide (CO ₂ ) laser, Nd: YAG laser, Er: YAG laser, Yb: YAG laser, Tm: YAG laser, Nd: YLF laser, Nd: glass laser , Nd: YVO ₄ laser, and semiconductor lasers are commercially available as laser processing machines or laser engraving machines, so they are suitable for industrial use.

In step 2, the laser light is irradiated to the part of the metal layer (M1) that does not form the following metal plating layer (PM2) by irradiating the laser light to remove the metal layer (M1) A patterned metal layer (PM1) is formed as a residual portion of the metal layer (M1). In addition, when removing the metal layer (M1), the surface of the insulating molded body (A) or the surface of the undercoat layer (B) under the metal layer (M1) irradiated with laser may be removed, or the above The surface of the undercoat layer (B) and the above-mentioned insulating molded body (A) are simultaneously removed.

In step 3 of the present invention, the patterned metal layer (PM1) formed in the above step 2 is plated as a plating base layer, thereby being formed on the patterned metal layer (PM1) Metal coating (PM2). The metal plating layer (PM2) becomes a metal pattern formed on the insulating molded body (A) to obtain a molded body having a metal pattern.

Examples of the plating method implemented in step 3 include electrolytic plating, electroless plating, and a combination method of electroless plating and electrolytic plating. In the case of performing electroless plating as the plating method, the patterned metal layer (PM1) is used as a catalyst seed. The above-mentioned metal plating layer (PM2) of a thick film can be formed only by electroless plating, or the metal plating film formed by electroless plating can be used as a conductive seed crystal, and then electrolytic plating is performed to form Thick film of the above metal plating layer (PM2). Furthermore, in the case of performing electroless plating directly without performing electroless plating, the above-mentioned patterned metal layer (PM1) is used as a conductive seed crystal.

In the case of forming a metal plating layer (PM2) by electroless plating, examples of the plating metal include copper, nickel, chromium, cobalt, cobalt-tungsten, cobalt-tungsten-boron, and tin. In the case where the metal plating layer (PM2) is a conductor circuit pattern, among these metals, it is preferable to use copper in terms of lower resistance value. In addition, as described above, the metal plating layer (PM2) may be formed by electrolytic plating after electroless plating. If electrolytic plating is used in combination, the plating precipitation speed can be accelerated, which contributes to higher manufacturing efficiency.

In the case where electroless plating and electrolytic plating are used together in step 3 of the present invention to form a metal plating layer (PM2), the precipitated metals of electroless plating and electrolytic plating may be the same or different. For example, a combination of electrolytic copper plating after electroless copper plating, electrolytic copper plating after electroless nickel plating, electrolytic nickel plating after electroless nickel plating, and electrolytic copper plating after electroless nickel plating. In the case where the metal plating layer (PM2) is a circuit pattern, as the main metal constituting the metal plating layer (PM2), in terms of lower resistance value, it is preferable to use copper. The combination of electrolytic cobalt and the like can suppress the diffusion of copper to the substrate, and thus can improve the long-term reliability of the printed wiring board.

In the case of using electroless plating and electrolytic plating together in step 3 of the present invention to form a metal plating layer (PM2), the thickness of the electroless plating layer may be appropriately selected as needed, in order to ensure that it is suitable for electrolytic plating The conductivity of the coating is preferably in the range of 0.1 μm to 2 μm, and from the viewpoint of improving productivity, the range of 0.15 μm to 1 μm is more preferable.

In the case where electrolytic plating is directly performed in step 3, examples of the plating metal constituting the metal plating layer (PM2) include copper, nickel, chromium, zinc, tin, gold, silver, rhodium, palladium, and platinum. . Among these metals, in the case where the formed metal pattern is a circuit pattern, as described above, in terms of low cost and low resistance, copper is preferred, and the metal plating is preferably formed by electrolytic copper plating Cladding (PM2). The electrolytic copper plating may be performed by a well-known method, preferably a copper sulfate plating method using a copper sulfate bath.

In the case where the electrolytic plating method is directly implemented, the plating metal constituting the metal plating layer (PM2) may use one of the above-mentioned metals, or a combination of plural kinds. For example, in the case where the formed metal pattern is a decorative pattern, in order to relax the stress of the plated metal, copper plating is performed on the lowermost nickel-chromium plating layer. For the copper plating performed at this time, electrolytic nickel plating can be performed on the patterned metal layer (PM1), followed by electrolytic copper plating, and then electrolytic nickel plating and electrolytic chromium plating can also be performed on the patterned metal layer (PM1) electrolytic copper plating, followed by electrolytic nickel plating and electrolytic chromium plating.

The metal plating layer (PM2) obtained by the above method is mainly for the purpose of protecting the metal layer, and it can be further coated with other metal layers by electroless plating on the surface layer. For example, when the formed metal pattern is a conductor circuit pattern, Ni/Au plating, Ni/Pd/Au plating, and Pd/Au plating may be appropriately performed on the metal plating layer (PM2) formed of copper as needed.

By the above-described method for manufacturing a molded body having a metal pattern of the present invention, it is not necessary to perform complicated two-color molding or complicated operations such as exposure and development in a dark room using a photoresist, and does not require the use of special equipment, and can be manufactured in The smooth substrates of various forming substrates have flat or three-dimensional shaped bodies with high adhesion and good metal patterns. Therefore, by adopting the technology of the present invention, it is possible to provide a molded circuit with a high-density and high-performance printed wiring board and three-dimensional wiring on various materials, various shapes and sizes of substrates that are difficult to roughen the surface at a low cost Parts (MID, Molded Interconnect Device), etc., so it is highly applicable in the related industries of the printed wiring field. The method for manufacturing a molded body having a metal pattern of the present invention can be used for various electronic components having a patterned metal layer on the surface of a substrate, for example, it can also be applied to connectors, electromagnetic wave shielding, antennas such as RFID, and the like. Moreover, the molded body with a metal pattern manufactured by the method for manufacturing a molded body with a metal pattern of the present invention can be used not only for electronic components, but also for a patterned metal layer on a substrate of various shapes and sizes Functional parts, decorative plating purposes. [Example]

Hereinafter, the present invention will be described in detail by examples.

[Production Example 1: Production of primer (B-1)] In a nitrogen-replaced vessel equipped with a thermometer, nitrogen introduction tube, and agitator, polyester polyol (polyester polyol obtained by reacting 1,4-cyclohexanedimethanol with neopentyl glycol and adipic acid) ) 100 parts by mass, 2,7.6 parts by mass of 2,2-dimethylolpropionic acid, 21.7 parts by mass of 1,4-cyclohexanedimethanol, and 106.2 parts by mass of dicyclohexylmethane-4,4′-diisocyanate in methyl The reaction was carried out in a mixed solvent of 178 parts by mass of ethyl ketone, thereby obtaining an amine ester prepolymer solution having an isocyanate group at the terminal.

Next, 13.3 parts by mass of triethylamine was added to the above amine ester prepolymer solution to neutralize the carboxyl group possessed by the above amine ester prepolymer, and then 380 parts by mass of water was added and stirred well to obtain an amine ester prepolymer The aqueous dispersion.

The amine ester prepolymer chain was extended by adding 8.8 parts by mass of a 25% by mass ethylenediamine aqueous solution to the aqueous dispersion of the amine ester prepolymer obtained above and stirring. Then, aging and desolvation were performed, thereby obtaining an aqueous dispersion of the urethane resin (30% by mass of non-volatile content). The weight average molecular weight of the urethane resin is 53,000.

Next, add 140 parts by mass of deionized water to the reaction vessel equipped with a stirrer, a reflux cooling tube, a nitrogen introduction tube, a thermometer, a dropping funnel for dropping monomer mixture, and a dropping funnel for polymerization catalyst dropping. 100 parts by mass of the aqueous dispersion of the urethane resin was heated to 80°C while blowing nitrogen. Thereafter, while maintaining the temperature in the reaction vessel at 80°C for 120 minutes while stirring, 60 parts by mass of methyl methacrylate, 30 parts by mass of n-butyl acrylate and N-n-butoxy were added dropwise from different dropping funnels A monomer mixture composed of 10 parts by mass of methacrylamide and 20 parts by mass of an aqueous solution of 0.5% by weight of ammonium persulfate.

After the dropwise addition, the mixture was further stirred at the same temperature for 60 minutes, and the temperature in the reaction vessel was cooled to 40°C, diluted with deionized water so that the nonvolatile content became 20% by mass, and then filtered through a 200-mesh filter cloth. To obtain an aqueous dispersion of the resin composition for the undercoat layer of the core-shell composite resin, the core-shell composite resin using the urethane resin as the shell layer, in which methyl methacrylate and the like are provided The raw material vinyl resin is used as the core layer. Then, isopropyl alcohol and deionized water were added to the aqueous dispersion in such a manner that the mass ratio of isopropyl alcohol to water was 7/3 and the nonvolatile content was 2% by mass, and mixed to obtain a primer (B -1).

[Production Example 2: Production of primer (B-2)] Add 350 parts by mass of deionized water and surfactant ("Latemul E-118B" manufactured by Kao Co., Ltd.: 25 parts of active ingredient to a reaction vessel equipped with a stirrer, reflux cooling tube, nitrogen introduction tube, thermometer, and dropping funnel) %) 4 parts by mass, while blowing nitrogen, the temperature is raised to 70°C.

A vinyl monomer mixture consisting of 47.0 parts by mass of methyl methacrylate, 5.0 parts by mass of glycidyl methacrylate, 45.0 parts by mass of n-butyl acrylate, and 3.0 parts by mass of methacrylic acid was added to the reaction vessel with stirring, Part of the monomer pre-emulsion obtained by mixing surfactant ("AQUALON KH-1025" manufactured by First Industrial Pharmaceutical Co., Ltd.: 25% by mass of active ingredient) and 15 parts by mass of deionized water (5 Parts by mass), followed by adding 0.1 parts by mass of potassium persulfate, and maintaining the temperature in the reaction vessel at 70°C for 60 minutes for polymerization.

Secondly, while maintaining the temperature in the reaction vessel at 70°C, the remaining monomer pre-emulsion (114 parts by mass) and the aqueous solution of potassium persulfate (active ingredient 1.0% by mass) were separately added dropwise using a different dropping funnel for 180 minutes. ) 30 parts by mass. After the dropwise addition, the mixture was stirred at the same temperature for 60 minutes.

The temperature in the above reaction vessel was cooled to 40°C, and then deionized water was used so that the non-volatile content became 10.0% by mass, followed by filtration with a 200-mesh filter cloth, thereby obtaining the resin for undercoat layer used in the present invention Composition. Then, water was added to this resin composition for dilution and mixing, thereby obtaining a primer (B-2) having a solid content of 5% by mass.

[Production Example 3: Production of primer (B-3)] Introduce nitrogen into a reaction vessel equipped with a thermometer, nitrogen introduction tube, and mixer, and add 830 parts by mass of terephthalic acid, 830 parts by mass of isophthalic acid, 685 parts by mass of 1,6-hexanediol, and neopentyl glycol 604 parts by mass and 0.5 parts by mass of dibutyltin oxide were subjected to a polycondensation reaction at 230°C for 15 hours until the acid value of 180 to 230°C became 1 or less to obtain a polyester polyol having a hydroxyl value of 55.9 and an acid value of 0.2. 1,000 parts by mass of the above polyester polyol was dehydrated at 100°C under reduced pressure, and after cooling to 80°C, 883 parts by mass of methyl ethyl ketone was added, stirred well to dissolve, and 2,2-dimethylolpropionic acid was added 80 parts by mass, followed by the addition of 244 parts by mass of isophorone diisocyanate, reacted at 70°C for 8 hours.

After the above reaction was completed, it was cooled to 40°C, 60 parts by mass of triethylamine was added for neutralization, and then mixed with 4,700 parts by mass of water to obtain a transparent reaction product.

The methyl ethyl ketone was removed from the above reaction product under a reduced pressure of 40 to 60°C, and then water was mixed to obtain a primer (B-3) with a solid content of 10% by mass.

[Preparation Example 1: Preparation of silver particle dispersion] Using a compound obtained by adding polyoxyethylene to polyethylenimine as a dispersant, the silver particles with an average particle diameter of 30 nm are dispersed in a mixed solvent of 45 parts by mass of ethylene glycol and 55 parts by mass of ion-exchanged water. Thus, a dispersion containing silver particles and a dispersant is prepared. Then, ion-exchanged water, ethanol, and surfactant were added to the obtained dispersion to prepare a silver particle dispersion liquid of 5 mass%.

[Preparation Example 2: Preparation of black colored primer (B-4)] With respect to 100 parts by mass of the primer (B-3) obtained in Production Example 3 above, 2 parts by mass of a black colorant ("Dilac Black HS9530" manufactured by DIC Corporation) was added, and then isopropyl alcohol was added and stirred. As a result, a black colored primer (B-4) with a solid content of 6% by mass was prepared.

[Production Example 1: Production of polyphenylene sulfide (PPS) molded body] 100 parts by mass of linear polyphenylene sulfide (MFR according to ASTM D1238-86: 600 g/10 min), chopped glass fiber ("FT562" manufactured by Asahi Fiber Glass Co., Ltd., fibrous inorganic filler) 58.8 parts by mass Parts, zinc ion type ethylene-methacrylic acid copolymer ("Himilan 1855" manufactured by Mitsui Dupont Chemical Co., Ltd.) 8.4 parts by mass and montanic acid composite ester wax ("Licolub WE40" manufactured by Clariant Japan Co., Ltd.) 0.8 mass After the parts were uniformly mixed, a 35 mmϕ biaxial extruder was used for melt-kneading at 290~330°C to obtain a polyphenylene sulfide resin composition. The obtained polyphenylene sulfide resin composition was molded using an injection molding machine, thereby producing a PPS molded body having a size of 50 mm×105 mm×2 mm.

(Example 1) Using a small desktop coater ("K Printing Proofer" manufactured by RK Print-Coat Instruments), the polyimide film (manufactured by TORAY-DUPONT Co., Ltd.) was so dried that the average thickness became 20 nm. "Kapton 150EN-C", with a thickness of 38 μm) was coated with the silver particle dispersion obtained in Preparation Example 1. Next, a hot air dryer was used to dry at 120°C for 5 minutes, thereby forming a metal layer containing silver particles on the surface of the polyimide film (Figure 1).

Using a laser plotting device ("MD-V9900A" manufactured by KEYENCE Co., Ltd.: YVO4 laser, wavelength 1,064 nm), at a laser intensity of 50%, a drawing speed of 500 mm/sec, and a frequency of 100 kHz, the metal containing silver particles Laser irradiation is performed on the layer, and the metal layer containing silver particles in the irradiated portion is removed, thereby forming a patterned metal layer with L/S=500/500 μm (Fig. 2-3).

Then, it was immersed in an electroless copper plating solution ("THRU-CUP PEA-6" manufactured by Uemura Industrial Co., Ltd.) at 36°C for 90 minutes, and a metal plating layer was formed by electroless copper plating (thickness 3 μm) In order to obtain a shaped body with a copper stripe pattern with L/S=500/500 μm on the polyimide substrate (Figure 3).

(Example 2) After patterning by laser as in Example 1, the immersion time in the electroless copper plating solution was changed from 90 minutes to 10 minutes to form an electroless copper plating film (film thickness 0.4 μm). Then, the surface of the obtained electroless copper plating film was set as the cathode, and the phosphorus-containing copper was used as the anode, and an electrolytic plating solution containing copper sulfate (copper sulfate 70 g/L, sulfuric acid 200 g/L, chloride ion) was used. 50 mg/L, additive ("Top Lucina SF-M" manufactured by Aoye Pharmaceutical Industry Co., Ltd.)), electrolytic plating at a current density of 2.5 A/dm ² for 20 minutes, thereby forming metal plating using electrolytic copper plating Layer (film thickness 10 μm), and a molded body having a copper stripe pattern with L/S=500/500 μm on a polyimide substrate is obtained.

(Example 3) In the same manner as in Example 1, the silver particle dispersion liquid was coated on the polyimide film using a desktop coater so that the average thickness after drying became 100 nm. Then, a hot air dryer was used to dry at 200° C. for 30 minutes, thereby forming a metal layer containing silver particles on the surface of the polyimide film. Then, as in Example 1, a patterned metal layer with L/S=500/500 μm was formed using a laser drawing device. The surface of the patterned metal layer obtained above was set as a cathode, and phosphorus-containing copper was used as an anode, and electrolytic plating was performed in the same manner as in Example 2, thereby forming a metal plating layer (film thickness of 10 μm) by electrolytic copper plating ), and a molded body having a copper stripe pattern with L/S=500/500 μm on a polyimide substrate is obtained.

(Example 4) Using a desktop-type small coater ("K Printing Proofer" manufactured by RK Print-Coat Instruments), the polyimide film (manufactured by TORAY-DUPONT Co., Ltd.) was dried to a thickness of 100 nm. Kapton 150EN-C", thickness 38 μm) is coated on the surface with the primer (B-1) obtained in Production Example 1. Then, a hot air dryer was used to dry at 80°C for 5 minutes, thereby forming an undercoat layer on the surface of the polyimide film.

Next, in the same manner as in Example 3, a silver particle dispersion liquid was coated on the surface of the undercoat layer so that the average thickness after drying became 100 nm, and a metal layer containing silver particles was formed on the surface of the undercoat layer. After the metal layer was formed, a molded body having a copper stripe pattern with L/S=500/500 μm on a polyimide substrate was obtained in the same manner as in Example 3.

(Example 5) Using the PPS molded body obtained in Production Example 1 above, immersed in the primer (B-2) obtained in Production Example 2 for 10 seconds, the PPS molded body was taken out, and after standing for 1 minute, the hot air dryer was used at 200 After drying at ℃ for 5 minutes, an undercoat layer (thickness 130 nm) was formed on the PPS molded body.

Then, the PPS shaped body formed with the undercoat layer was immersed in the silver particle dispersion liquid (1) obtained in Preparation Example 1 for 10 seconds. Thereafter, the PPS molded body was taken out, and after standing for 1 minute, it was dried at 200° C. for 5 minutes using a hot air dryer to form a metal layer (film thickness of 100 nm) containing silver particles on the undercoat layer. After the metal layer was formed, a molded body having a copper stripe pattern with L/S=500/500 μm on the PPS molded body was obtained in the same manner as in Example 4.

(Example 6) A transparent polycarbonate (hereinafter abbreviated as "PC") forming plate (polycarbonate plate "PC-1600" manufactured by CITAKIRON Co., Ltd., thickness 2 mm) was used instead of the PPS molded body used in Example 5 The primer (B-3) obtained in Example 3 replaced the primer (B-2), the drying temperature was changed to 80°C, and the drying temperature after the silver particle dispersion liquid was applied was changed to 100°C. A metal layer containing silver particles is formed on the surface of the layer. After the metal layer was formed, a molded body having a copper stripe pattern with a film thickness of 10 μm of L/S=500/500 μm on a PC formed plate was obtained in the same manner as in Example 2.

(Example 7) Using the black primer (B-4) prepared in Preparation Example 2 instead of the primer (B-3) used in Example 6, the laser intensity of the laser drawing device was changed from 50% to 30%, except Otherwise, a molded body having a copper stripe pattern with a film thickness of 10 μm of L/S=500/500 μm on a PC forming plate formed with a black undercoat layer was obtained in the same manner as in Example 6.

(Example 8) A black PC forming plate ("Iupilon NF2000VC" manufactured by Mitsubishi Engineering-Plastics Co., Ltd., 1.5 mm thick) was used instead of the transparent PC forming body used in Example 6, and the laser intensity of the laser drawing device was changed from 50% to 30%, except for this, a molded body having a copper stripe pattern with a film thickness of 10 μm of L/S=500/500 μm on a black PC formed plate was obtained in the same manner as in Example 6.

(Example 9) Electroless nickel-boron plating ("Top Chem Alloy 66-LF" manufactured by Okino Pharmaceutical Co., Ltd.) was used instead of the electroless copper plating solution ("THRU-CUP PEA" manufactured by Uemura Industrial Co., Ltd.) used in Example 8. -6"), after forming a nickel-boron plated layer with a thickness of 0.2 μm at 65° C. for 2 minutes, electrolytic copper plating is performed to obtain a film thickness of L/S=500/500 μm on a black PC forming plate Shaped body of 10 μm copper stripe pattern.

(Example 10) The copper stripe pattern of the molded body with a copper stripe pattern obtained in Example 8 was set as the cathode, and electrolytic nickel plating was performed at a current density of 2 A (nickel sulfate 280 g/L, nickel chloride 50 g/L, boric acid 30 g/L), and a nickel layer with a thickness of 10 μm is formed on the copper stripes.

(Example 11) According to Synthesis Example 36 of International Publication No. 2014/045972, a 16% by mass aqueous dispersion of copper particles having an average particle diameter of 108 nm measured by dynamic light scattering method was obtained. Isopropyl alcohol was added to this aqueous dispersion to prepare a 5% by mass copper particle dispersion, which was applied to the PPS molded body with the undercoat layer formed in the same manner as in Example 5 so that the average thickness after drying became 60 nm. surface. Then, using a hot air dryer to dry at 200° C. for 30 minutes under a nitrogen flow, thereby forming a metal layer containing copper particles on the surface of the undercoat layer, the L/S obtained on the PPS molded body was obtained in the same manner as in Example 5. = 500/500 μm copper striped pattern shaped body.

(Comparative example 1) On the surface of the polyimide film ("Kapton 150EN-C" manufactured by TORAY-DUPONT Co., Ltd., thickness 38 μm), a nickel-chromium layer (film thickness 30 nm, nickel/chromium mass ratio= 8/2) After that, a copper layer (thickness 100 nm) is formed by sputtering, and a metal layer composed of nickel-chromium sputtering film/copper sputtering film is produced.

A patterned metal layer with L/S=500/500 μm was formed on the metal layer prepared above using a laser drawing device as in Example 1. As a result, the metal layer formed by the sputtering method was a continuous film, Therefore, the metal layer at the edge of the laser processing swelled up, and the edge of the metal pattern swelled in the electrolytic plating in the subsequent steps, and the pattern was uneven.

(Comparative example 2) After the nickel layer (thickness 300 nm) was formed by sputtering on the surface of the PPS molded body obtained in Production Example 1, a copper layer (thickness 100 nm) was formed by sputtering, to produce a nickel sputtering film/ A metal layer composed of a copper sputtering film.

A patterned metal layer with L/S=500/500 μm was formed on the metal layer prepared above using a laser drawing device as in Example 1. As a result, the metal layer formed by the sputtering method was a continuous film, Therefore, the metal layer at the edge of the laser processing swelled up, and the edge of the metal pattern swelled in the electrolytic plating in the subsequent steps, and the pattern was uneven.

(Comparative example 3) After the nickel layer (film thickness 15 nm) was formed by sputtering on the surface of the transparent PC forming board used in Example 6, a copper layer (film thickness 100 nm) was formed by sputtering to produce a nickel-sputtered film /Metal layer composed of copper sputtering film.

A patterned metal layer with L/S=500/500 μm was formed on the metal layer prepared above using a laser drawing device as in Example 1. As a result, the metal layer formed by the sputtering method was a continuous film, Therefore, the metal layer at the edge of the laser processing swelled up, and the edge of the metal pattern swelled in the electrolytic plating in the subsequent steps, and the pattern was uneven.

[Measurement of peel strength] In the above Examples 2 to 8 and Comparative Examples 1 to 3, after the metal layer was formed, a linear pattern formation region with a line width of 1 cm was formed in the same manner as above to produce a metal pattern with a copper plating film thickness of 15 μm Of test piece. For Example 1, after electroless copper plating with a film thickness of 3 μm, electrolytic plating was performed to adjust the film thickness to 15 μm. Using the "Multi-bond Tester SS-30WD" manufactured by Xijin Commercial Co., Ltd., a 90°-direction peel test was performed on the produced test piece to measure the peel strength.

Table 1 summarizes the measurement results of the molded bodies having metal patterns obtained in Examples 1 to 8 and Comparative Examples 1 to 3.

[Table 1]

1: Insulated molded body 2: Metal layer containing metal particles 3: Patterned metal layer 4: metal plating

FIG. 1 is a schematic view of a metal layer containing metal particles formed on an insulating molded body. FIG. 2 is a schematic diagram of a part of a metal layer containing metal particles removed to form a patterned metal layer. FIG. 3 is a schematic diagram of a metal plating layer formed on a patterned metal layer by a plating method.

1: Insulated molded body

3: Patterned metal layer

4: metal plating

Claims (12)

A method for manufacturing a shaped body with a metal pattern, which has the following steps: Step 1, forming a metal layer (M1) containing metal particles on the insulating molded body (A); Step 2, which forms a patterned metal layer (PM1) by removing a part of the metal layer (M1); In step 3, a metal plating layer (PM2) is formed on the patterned metal layer (PM1) by a plating method. A method for manufacturing a shaped body with a metal pattern, which has the following steps: Step 1', after forming an undercoat layer (B) on the insulating molded body (A), a metal layer (M1) containing metal particles is formed on the undercoat layer (B); Step 2, which forms a patterned metal layer (PM1) by removing a part of the metal layer (M1); In step 3, a metal plating layer (PM2) is formed on the patterned metal layer (PM1) by a plating method. The method for manufacturing a molded body having a metal pattern according to claim 1 or 2, wherein the plating method in the above step 3 is an electroless plating method, or a combination of an electroless plating method and an electrolytic plating method. The method for manufacturing a molded body having a metal pattern according to claim 1 or 2, wherein the plating method in the above step 3 is an electrolytic plating method. The method for manufacturing a molded body having a metal pattern according to any one of claims 1 to 4, wherein in step 2 above, a method of partially removing the metal layer (M1) is a method of irradiating electromagnetic waves. The method for manufacturing a molded body having a metal pattern according to claim 5, wherein in the method for manufacturing the molded body according to claim 2, the undercoat layer (B) contains a substance that absorbs the electromagnetic waves. The method for manufacturing a molded body having a metal pattern according to any one of claims 1 to 6, wherein the metal particles are silver particles. The method for manufacturing a molded body having a metal pattern according to any one of claims 1 to 7, wherein the metal particles are coated with a polymer dispersant. The method for manufacturing a molded body having a metal pattern according to claim 8, wherein in the method for manufacturing the molded body according to claim 2, the undercoat layer (B) uses a reactive functional group [X] For the resin, the polymer dispersant uses a reactive functional group [Y], and forms a bond between the reactive functional group [X] and the reactive functional group [Y]. The method for manufacturing a molded body having a metal pattern according to claim 9, wherein the reactive functional group [Y] is a group containing a basic nitrogen atom. The method for manufacturing a molded body having a metal pattern according to claim 9, wherein the polymer dispersant having a reactive functional group [Y] is selected from the group consisting of polyalkyleneimine and having an oxyethylene unit One or more of the groups consisting of polyalkyleneimines of polyoxyalkylene structure. The method for manufacturing a molded body having a metal pattern according to any one of claims 9 to 11, wherein the reactive functional group [X] is selected from the group consisting of a ketone group, an acetoacetyl group, an epoxy group, and a carboxyl group , N-alkylol group (N-alkylol), isocyanate group, vinyl group, (meth)acryloyl group, allyl group at least one group.

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