JPS63227785A - Pattern forming method - Google Patents

Abstract

PURPOSE:To obtain an accurate metallic pattern having high bonding strength to a substrate by forming an ink layer having a required pattern on the substrate, roughening the surface of the ink layer by etching, immersing the substrate in an electroless plate soln. and forming a metallic layer on the roughened surface by electroless plating. CONSTITUTION:An ink layer 3 having a required pattern is formed on the pattern forming surface 2 of a substrate 1 of glass or the like and the surface of the printed ink layer 3 is roughened 4 by etching with sulfuric acid or the like. The substrate 1 is then immersed in an electroless plating soln. and a layer 5 of a metal such as Ni is formed on the roughened surface 4 by electroless plating to obtain a metallic pattern. The ink layer 3 is desirably made of radiation-curing ink and irradiated with natural light, UV or electron beams. By this method, the accurate metallic pattern having high bonding strength to the substrate 1 can be obtd. without requiring the forming or removal of a resist film.

Description

DETAILED DESCRIPTION OF THE INVENTION (1) Industrial Field of Application The present invention is applicable to, for example, electronic components such as printed circuit boards,
Regarding a pattern forming method for forming a metal coating on a plastic substrate such as a dash board or an emblem, I am particularly interested in a pattern forming method that can increase the bonding strength between the substrate and the metal coating.

(b) Conventional technology Conventionally, as a method for forming a metal pattern layer on an electrically insulating plastic substrate, a metal pattern layer is deposited on the substrate by a chemical reduction method, and if necessary, the metal pattern layer is Electric plating? +已2+ 1similar II'h1
The demand has not yet been met.

When a metal pattern layer is formed on a plastic substrate by electroless plating, the metal pattern layer is often formed to draw a special pattern.

For example, in the case of electronic parts such as printed circuit boards, the conductive wires that connect the elements mounted on the board or between the elements and external circuits are formed of metal coatings, and in the case of the dash board of a self-driving car, etc. If so, trimming lines surrounding instruments, indicator lamps, instrument panels, etc. are formed with a metal pattern and layer, and in the case of decorative emblems, a metal pattern layer is used especially in areas where metallic luster is required for the design. is formed.

As a method for forming a metal pattern layer on a portion of a substrate as described above, rlI. The so-called etched wheel method and additive method, which can form a dense metal pattern layer, are the mainstream.

The etched wheel method consists of a metal film forming process in which a metal film is formed by electroless plating on the entire surface of the patterned surface of the substrate, and an etched wheel method that involves forming a metal film on the entire surface of the pattern-forming surface of the substrate by electroless plating, and an etched wheel method that involves forming a metal film on the entire surface of the pattern-forming surface of the substrate. There is no need to immerse the substrate that has gone through the above metal film formation process and resist film formation process in an etching solution and remove unnecessary parts of the metal film that are not covered with the etching resist film by etching. The process consists of a partial etching process and a resist removal process in which the etching lens nost film is removed from the surface of the metal wave film from which unnecessary parts have been removed in the unnecessary part etching process.

The additive method involves forming a resist film on the pattern-forming surface of the substrate with a negative pattern corresponding to the unnecessary portions of the metal coating, and immersing the substrate after this resist film formation process in an electroless plating solution. , a metal coating formation step in which a metal coating is deposited and adhered over the entire surface thereof, and an unnecessary portion removal step in which unnecessary portions of the metal coating and plating layer are removed from the substrate to which the metal coating is attached in the metal coating formation step. It consists of

In addition, in order to increase the adhesion between the film formed on the surface of the substrate by the etched wheel method or the additive method, the surface of the substrate is made of thermoplastic plastic, and the bond between the substrate and the substrate is increased. A method of adhering a metal film attached to the surface by applying heat and pressure has already been proposed (Japanese Unexamined Patent Publication No. 145997/1983).

(C) Problems to be solved by the invention In the above etched wheel method or additive method,
A resist film forming process for forming an etching renost film or a plating renost film and a renost film removal process for removing the renost film are required, which is disadvantageous in reducing the number of steps and reducing costs.

In addition, in the etched wheel method, etching progresses to the bottom a of the resist film at the periphery of the etching resist film.
There is a problem that the required pattern becomes thinner, that is, so-called bite occurs.

Since such digging affects the electrical characteristics such as the resistance value required for the pattern, it must be prevented as much as possible in electronic components such as printed circuit boards.

In the additive method, if the removal of the resist film is incomplete, the electrical properties such as the dielectric constant between adjacent patterns will be affected, and when the Lenost film is removed, the peripheral edges of the desired patterns will peel off, causing the above-mentioned problem. Similar to biting, electrical characteristics such as resistance value are affected.

Furthermore, since the surface of the substrate is usually formed as a smooth surface, this is disadvantageous in terms of increasing the affinity between the metal wave film and the substrate, and thus the adhesion strength of the metal coating to the substrate.

According to a technique in which the substrate is made of thermoplastic plastic and a metal pattern layer formed on the surface of the substrate is bonded by heating and pressure, the substrate and the metal wave film are firmly bonded by adhesion. However, in reality, it was found that metal curling occurs due to the difference in thermal expansion coefficient or thermal contraction coefficient between the metal coating and the substrate, resulting in lack of g-tilt.

The present invention has been made in consideration of the above circumstances, and by forming a metal layer in an accurate pattern, the bonding strength between the metal pattern layer and the substrate is extremely high, and the reliability is also increased. We promise to provide a method for forming patterns that allows

(d) Means for solving the problem formula, i.e. this Hfj
The invention of S1 includes a pattern forming step (A) in which an ink layer having a desired pattern is formed on the pattern forming surface of the substrate, and the surface of the ink layer printed in the pattern forming step (A) is roughened by etching. an etching step (B) to form a metal pattern; a metal pattern forming step (C) in which the substrate obtained through the etching step (B) is immersed in an electroless plating solution to form a metal layer on the rough surface; It is characterized by the following.

Also, this IE [! The invention of ff12 includes a pattern forming step (A) of printing an ink layer, the above pattern An etching step (to form a rough surface by etching the surface of the In-A layer printed in the forming step (A))
B), a metal pattern forming step (C) in which the substrate that has not been etched in the etching step (B) is crushed in an electroless plating solution and a metal plating layer is formed on the rough surface; ), an electroplating step (D) in which a metal of the same kind or a different kind as the metal plating layer is deposited by electrolytic plating on the metal plating layer formed on the surface of the ink layer.

Furthermore, the third invention of the present application includes: a pattern forming step (A) of printing a conductive ink layer having a desired pattern on the pattern forming surface of the substrate; Etching process ([3
), a metal pattern forming step (C) in which a metal of the same kind or different kind as the metal in the conductive ink is deposited on the substrate obtained in the etching step ([3)] by electrolytic plating. be.

Hereinafter, first, the first invention of Book II will be explained in detail.

In the present invention, first, the step (A) of forming an ink layer having a desired pattern on the pattern formation surface of the substrate is performed.

In the present invention, the material used for the substrate is not particularly limited (eg, glass, plastics, or composite materials thereof, but specifically, for example, polyester resin, polyimide resin, etc.). , lath epoxy resin, glass Teflon resin, polyamideimide resin, polyvinyl chloride resin, polyethylene ω
Examples include plastics such as 1-glue resin, and composite materials such as plastics and glass.

Further, the form of the substrate is not particularly limited as long as it can form an ink layer, which will be described later, and may be any form such as a film, sheet, or plate.

In the above pattern forming step, the ink layer formed is not particularly limited, but in order to prevent corrosion of the substrate due to etching in the etching step, the ink layer may have inferior chemical resistance to etching agents than that of the substrate. is necessary.

As for the material of the ink layer, to give a specific example, it is recommended to use radiation-curable ink, which is cured without heat generation or heating and has excellent compatibility with plastic substrates. be done.

In addition, the radiation-curable ink is not limited to 13 as long as it is sensitive and hardened by irradiation with radiation such as natural light, ultraviolet rays, or electron beams, but the energy consumption in this curing process is particularly high. UV curable ink is recommended.

Ultraviolet curable ink usually consists of a colorant, a prepolymer, a monomer added as necessary, and a photoinitiator.

The color should be selected taking into consideration the storage stability of the ink. For example, organic pigments, extender pigments, carbon black, titanium white, etc.
Metal powder etc. are used.

As the prepolymer, acrylic synthetic resins such as polyol 7 acrylate 0, epoxy acrylate, urethane acrylate, polyester acrylate, alkyd acrylate, and polyether acrylate are used.

Examples of the polyol acrylate include pentaerythritol triacrylate, pentaerythritol-containing triacrylate, noventaerythritol hexaacrylate, notrimethylolpropane tetraacrylate, and the like.

Epoxy acrylates include epoxidized drying oil acrylate, bisphenol A type noglycinol acrylate, modified bisphenol A type epoxy acrylate, /
Examples include borac type epoxy acrylate and aliphatic epoxy acrylate.

Urethane 7-I+ rate, 1-L f I+-polycarbo-wood acrylate, hydroxyl group-containing acrylate, reaction product of noisocyanate and hydroxyl group-containing substance (alkyd, drying oil, polyester, etc.)? An example is P.

Polyester acrylate is oil, modified alkyd υI
They are based on resins, modified polyester resins, etc., have acryloyl groups introduced into them, and are further made into urethanes, and are rich in variety.

Moamer is used as a diluent to lower the viscosity, and those with a high crosslinking density due to acryloyl groups have high speed curing properties and are also used to adjust rheology.

Many of the mowers mentioned above affect the blanket, roller, and printing plate, so care must be taken when selecting them.

As the above moamer, acrylic moamer, methacrylate, vinyl ether, itaconic acid ester, etc. are used, and N-vinylpyrrolidone is particularly recommended as a low viscosity reactive diluent.

As an acrylic moamer, for example, monoacrylic
The monoacrylates used include hydroxybutyl acrylate, dicyclopentanediacrylate, 1. Examples include C-hexanediol monoacrylate and cyclohexyl acrylate.

Examples of noacrylates include 1,6-hexanenoolnoacrylate, neopentylglycolnoacrylate, triethyleneglyfurnoacrylate, ethylene glycol diacrylate, trinotyrolbrovanoacrylate, and tripropylene glycolnoacrylate. Can be mentioned.

Furthermore, examples of the triacrylate include trimethylolpropane triacrylate and pentaerythritol triacrylate.

A photoinitiator here refers to a substance that absorbs ultraviolet light to initiate a polymerization reaction, and is distinguished from a sensitizer that acts as a promoter. The rfA starter is cost 1
It is necessary to select a hydrogen abstraction type in consideration of absorption spectrum, solubility, color tone, photoactivity, toxicity, stability, and reactivity.As a standard, a hydrogen abstraction type among radical reaction types, such as an allyl ketone type, is selected. used. Benzophenone and its derivatives are used as allyl ketone type photoinitiators, and amines and thiols are added as hydrogen donors.

Additives include anti-mist agents, slip agents, antioxidants,
A desiccant, a wet waste, a viscosity improver, a wax, and a polymerization inhibitor to prevent dark polymerization and storage polymerization are used. Select a polymerization inhibitor that does not reduce the curing properties of the ink.
For example, benzoquinone, hydroquinone, methoquinone, etc. are recommended.

In addition, soluble fillers such as calcium carbonate, aluminum oxide, zinc oxide, or metal salts are added to the above ink, and when forming a rough surface as described later, this is eluted with water, acid, or alkali to form a rough surface. It is also possible to make it easier to form.

By the way, when the ink layer is formed of radiation-curable ink, either a printing method or a photographic method is employed as a method for forming an ink layer having a desired pattern on the pattern-forming surface of the substrate. be able to.

That is, in the printing method, the pattern forming step includes a printing step of printing an ink layer on the substrate in a desired pattern, and a step of curing the In-A layer printed on the substrate in this printing step. This printing method can be employed even when the ink forming the ink layer is not a radiation-curable ink.

The printing method can be a conventional printing method using a normal printing device. For example, when printing a circuit pattern of an electronic component such as a printed circuit board, a silk screen, which is a type of formal wear, can be used. Printing may be performed using a silk screen printing method.

In addition, in the photographic method, the pattern forming step includes a coating film forming step in which an ink layer is applied over the entire surface of the pattern forming surface of the substrate, and a pattern forming a desired pattern in the ink layer formed by the coating film forming step. The process consists of a pattern curing process in which the pattern part is cured by irradiating the part with radiation, and an excess ink layer removal process in which the pattern part cured in the pattern curing process is removed (the ink layer part). .

Excess ink layer removal process may include, for example, washing with water or elution with an organic solvent. 1i work is enough.

In the case where the above ink layer is formed of an ultraviolet curable ink, examples of the ultraviolet ray generation source include xenon lamps, high pressure mercury lamps, metal halide lamps, ultraviolet fluorescent lamps, etc., and the irradiation time of ultraviolet rays is from several seconds to a few seconds. A few minutes is sufficient.

In the present invention, next, an etching step 1) is carried out in which the surface of the ink layer printed in the above step (A) is formed into a rough surface by etching.

The etching solution C↓ used in this etching step (B) is not particularly limited as long as it corrodes to the extent that it does not eat away at the substrate and roughens the surface of the ink layer, for example, sulfuric acid. , chromic acid, or a mixture thereof can be used.

In the present invention, finally, a metal pattern forming step (C) in which the substrate obtained through the above step (B) is immersed in an N&electrolytic solution to form a metal plating layer on the rough surface.
Implement.

The material of the metal plating layer formed in this metal pattern forming step (C) is not particularly limited as long as it is a metal deposited by electroless plating, and examples include gold, silver, copper, nickel, tin, cadmium, and cobalt. Examples include zinc, zinc, and alloys containing these as matrices.
Among these, nickel is preferred because it is inexpensive and relatively stable.

The following will explain the case of forming nickel plating as an example, but the composition and hydrogen ion concentration of the electroless angle etchant will be determined as appropriate, taking into account the plating speed, working temperature, purity of the deposited 2nd and 7th layer, etc. Select "r".

The electroless plating solution used in the pattern forming process (such as nickel on metals) may be immersed in an acid bath, an alkaline bath, or a neutralization tower.

Examples of the acidic bath include glyfuric acid bath, succinic acid bath, and the like. Examples of the alkaline bath include an ammonia alkaline bath and a caustic alkaline bath.

Among these immersion species, the deposited metal contains nickel)N.
An ammonia alkaline bath is recommended as it contains relatively few impurities such as phosphorus.

For reduction in the methane solution, known reducing agents such as hypophosphite, borohydride compounds, and hydrazine may be used.

Products that use hypophosphite are often used at high temperatures of 80°C or higher, but products that allow relatively high plating speeds to be achieved at low temperatures in order to eliminate heat and effects on the substrate as much as possible. It is preferable to use, for example, formulations shown in Table 1 can be used.

(Left below) Since the rate of oxidation of boron hydride compounds and their transparent conductors in aqueous solutions is somewhat faster than that of hypophosphite, a reduced layer and soot at the pore temperature are more preferable. An example of this type of electroless nickel plating 2 solution is one with a formulation as shown in m2a.

(The following is a blank space) Metsu A solution using hydrazine as a reducing agent has a slow plating speed, but is advantageous in that the resulting metal plating layer has a high purity. Electroless nickel metal that uses hydrazine as a reducing agent! It: Examples of the liquid include those shown in Table 3.

(The following is a blank space) Also, six Mf5s will be elaborated in detail regarding the second invention of the present application.
The invention No. 2 is an improvement of the invention No. 1 of the present application, and its main points are: a pattern forming step (A) in which an ink layer having a desired pattern is printed on a pattern forming surface of a substrate; ) printed in! An etching step (D) in which the surface of the f-layer is formed into a rough surface by etching, the substrate obtained in the above etching step (B) is crushed in an electroless plating solution, and a metal plating layer is formed on the rough surface. (C), an electrolytic method in which the same or different metal as the metal plating layer is deposited by electrolytic plating on the metal plating layer formed on the surface of the ink layer in the metal pattern forming step (C). / Ki process (D), It is characterized by consisting of the following.

That is, the second invention of the present application is t3 in the first invention of the present M,
In order to increase the film thickness of the electroless plating layer obtained in the metal pattern forming step (C) and improve the t&density of the metal plating layer, the surface of the ink layer is removed after the metal pattern forming step (C). An electrolytic 2-ki process (D) is added to the metal plating layer formed by electrolytic plating to deposit a metal of the same kind or a different kind as the metal plating layer.

In this case, electric angle plating does not require any special conditions, and is carried out using a normal electrolytic plating solution under normal electrolytic conditions.

Specifically, the concentration of the metal salt is generally 10 to 300, /
1. The electrical angle temperature is room temperature to 85°C, the pI is 11 to 13, and the current density is 0.5 to 120 A/dm2.

During this electrolytic plating, the substrate obtained in the metal pattern forming step (C) is used as a l'2 pole, a conductive plate such as a metal plate or a carbon plate is used as a positive abrasive, and a predetermined electrolytic solution is flowed thereon.
By performing electrolysis under predetermined electrolytic conditions while showering, it is possible to form a desired metal pattern without π, which causes the problem of so-called fading.

By the way, in this invention, depositing the same type of metal or 'A type metal as the metal plating layer formed by electroless plating means, for example, first forming a nickel plating layer by electroless method, and then depositing the same type of metal as the metal plating layer formed by electroless method. This refers to cases in which a nickel plating layer is formed on top of the nickel plating layer, or a copper plating layer is formed on the nickel plating layer formed by M electrolysis. The same gold R layer (including alloys) or a different metal WI on the layer (including alloys)
(including alloys) is formed by electrolytic plating.

In the present invention, in order to promote or suppress the formation of the metal J+ layer on the rough surface obtained in the etching process before forming the metal pattern, a known catalyst for electroless plating may be attached. It is.

Catalysts that increase the plating speed are not particularly limited as long as they increase metal ion reduction, improve metal ion adsorption, or have both of these characteristics. Catalysts that retard the metal ions in the electroless plating solution are used when forming the metal plating layer with particularly precise thickness, when increasing the purity of the metal coating, and when the metal ions in the electroless plating solution
! If the reducing property is too high,
It is used in very special cases such as.

Furthermore, the third invention of the present invention will be explained in detail.

The invention of Mf53 is an improvement of the invention of MfjG1, and its main point 1a is pattern formation in which a conductive ink layer having a desired pattern is printed on the pattern formation surface of the substrate. W (A), the above pattern forming step (A)
an etching step (B) in which the surface of the conductive ink layer printed in step (13) is formed into a rough surface by etching to expose the metal in the conductive ink; Metal in conductive ink and l1iiF! by electrolytic plating! ! or a metal pattern forming step (C) in which different metals are deposited;
It is characterized by:

That is, in the third invention of the present application, a conductive ink layer is formed on the pattern-forming surface of the substrate, and the conductive ink layer is roughened by etching to expose the metal in the conductive ink layer. It efficiently forms metal patterns by applying electricity.

In this case, electrolytic fIY plating does not require a special strip f↑, and is carried out in the same manner as in the invention of Moto 111fjS2.

The above-mentioned conductive ink is composed of an ink base material and a metal, and the metal is not limited to (but not limited to).

Also, as for the blending ratio of the ink base material and metal, the ink base material is ! [Depending on the adhesion to the metal, the metal accounts for 5~
50111%, preferably 10-3om%, especially 1
It is desirable to set it as 5-25 weight percent.

In this invention, depositing a metal of the same kind or a different kind as the metal in the conductive ink means, for example, when the metal in the conductive ink layer is copper, copper or a metal other than the copper base (shell alloy) is deposited by electrolytic plating. and other alloys).

(e) Function In the pattern forming method according to the present invention, as described above,
In! printed on the pattern forming surface during the pattern forming process! + The surface of the layer is shaped into a rough surface by the etching process +l!
, will be done. This rough surface has a much larger surface area than the original smooth surface, and the concentration of metal ions in that area is extremely high. Therefore, in the subsequent metal pattern forming step, the metal J+ layer is formed only on the rough surface of the ink layer. As a result, the metal pattern layer can be formed very precisely.

In addition, 'kR is deposited on the four parts of the uneven ink layer formed on the rough surface, and the metal plating layer is mechanically bonded to the ink layer by the so-called anchoring effect.
It has the effect of firmly bonding to the ink layer.

Moreover, there is no need to form a renost film before the etching process or metal pattern forming process, and there is no need to form a resist film after the metal pattern forming process or etching process.
Since there is no need to peel off the film, the number of steps can be reduced and productivity can be improved.

Further, when the conductive ink layer formed on the patterned surface of the substrate is roughened by etching to expose the metal therein, when electricity is applied to this conductive ink layer, plating occurs using the exposed metal as a core. It has the ability to grow and form a uniform metal pattern.

(f) Examples Hereinafter, the present invention will be explained in detail based on Examples, but the present invention is not limited thereto.

Embodiment 1 Figures f51 to 3 are schematic diagrams showing the order of steps in an embodiment of the present invention, and the pattern forming method according to this embodiment is as shown in Fig. 1. An ink layer (
As shown in FIG.
) to form a rough surface (4) by etching, and as shown in FIG. (1) is immersed in an electroless plating solution (not shown) to form a metal coating layer (5) on the rough surface (4) (metal pattern forming step (C)).

The plastics used for the above substrate (1) include:
For example, polyester resins, polyimide resins, plus epoxy resins, glass Teflon resins, polyamideimide resins, polyvinyl chloride resins, polyethylene thread trimmers, etc., or composite materials such as plastics and glass. However, here we will use a relatively inexpensive polyethylene terephthalate sheet as a substrate (
1) is formed.

In the pattern forming step (A), the ink layer (3) formed does not corrode the substrate (1) in the etching step (B), although it is not particularly limited. It is necessary to select a material whose chemical resistance to etching agents is inferior to that of the substrate (1) so that only the back surface of the substrate (1) is corroded.

In addition, it is recommended that the material of the ink layer (3) is made of radiation-curable ink that is cured without heat generation or heating and is compatible with plastic substrates. In this case, ultraviolet curable ink is preferred because it consumes less energy in the curing process.

In this example, a commercially available ultraviolet curable ink (trade name:
4100 medium acrylate UV curing resin, 1-Jo Kako Co., Ltd.? ! The ink layer (3) is formed using

When the ink layer (3) is made of radiation-curable ink such as ultraviolet-curable ink, the ink layer (3) having a desired pattern is formed on the pattern-forming surface (2) of the substrate (1). As a forming method, either a printing method or a photographic method can be adopted, and the printing method was adopted here.

That is, in the printing method, the pattern forming step (A) includes a printing step (A1) in which the ink layer (3) is printed in a desired pattern on the substrate (1), and a printing step (A1) in which the ink layer (3) is printed on the substrate (1) in a desired pattern.
) is a step (A2) of curing the ink IrIJ (3) printed on the paper. This printing method can be employed even when the ink forming the ink layer (3) is not a radiation-curable ink.

Further, as the printing method, a normal printing method using a normal printing device can be adopted, and for example, printing may be performed by a screen printing method using a screen which is a type of stencil.

Examples of screens used for screen printing include silk screens and plastic screens, but here a Tetron screen (300 mesh), which has excellent durability, was used.

In addition, in the photographic method, instead of the above embodiment, although not shown, the pattern forming step (A) is a step in which an ink layer (3) is applied over the entire surface of the pattern forming surface (2) of the substrate (1). Film forming step (A3) and the above coating film forming step (A3
), a pattern curing step (A4) in which a pattern portion forming a required pattern of the ink layer (3) formed by irradiation is irradiated with radiation to harden this pattern portion, and a pattern curing step (A・t) described above. A method comprising an excess ink removal step (A5) of removing a portion of the ink layer excluding the hardened pattern portion is also adopted.

The excess ink layer removal step (A5) may be a simple operation such as washing with water or elution with a solvent.

The etching solution used in the above etching step (B) does not corrode the substrate (1), and the etching solution is ink/! (3) There is no particular limitation as long as it corrodes to the extent that the surface becomes rough. In this example, concentrated sulfur Nt in 1 liter of pure water
An etching solution containing 330 g S chromic anhydride and 340 g is used. In this case, the temperature of the etching solution is 67° C. and the processing time is 10 minutes.

The etched substrate (1) is washed with running water and then immersed in an aqueous hydrochloric acid solution (50 ml/N) for 30 to 60 seconds.

Furthermore, after washing with water again, the next metal pattern forming process (
Move on to C).

The material of the metal plating layer formed in this metal pattern forming step (C) is not particularly limited as long as it is a metal, for example, gold, copper, nickel, tin, or an alloy containing these as a matrix. An example of this is:

In this example, a nickel plating layer is formed, so below we will discuss the case of forming a nickel plating layer as an example, but even when forming a plating layer of the same metal, the composition of the electroless plating solution and hydrogen ion concentration, etc.
It may be selected appropriately in consideration of the plating speed, working temperature, purity of the deposited metal film, etc.

The immersion type of the electroless plating solution used in the metal pattern forming step (C) may be an acidic bath, an alkaline bath, or a medium-A13 bath.

Examples of the acidic bath include a glycolic acid bath and a succinic acid bath. Examples of the alkaline bath include an ammonia alkaline bath and a caustic alkaline bath.

Among these immersion types, an ammonia alkaline bath is recommended because it contains relatively few impurities such as precipitated metal coatings and phosphorus.

As the reducing agent in the plating solution, known reducing agents such as hypophosphite, hydrogenated boric acid compound, hydrazine, etc. may be used.

In this example, a commercially available product (trade name: T M r' nickel plating solution, Okuno Pharmaceutical Co., Ltd. 5j) was used as the electroless plating solution, and the treatment was carried out at a solution temperature of about 40° C. for 15 minutes.

By following these steps, the ink layer (3) having the desired pattern is formed in the pattern forming step (A).
In the etching process (B), the surface of this ink layer (3) is formed into a rough surface (4), which has a much larger surface area than the original smooth surface, and metal ions are adsorbed. It's getting easier. Therefore, when the substrate (1) is immersed in the electroless plating solution in the metal pattern forming step (C), the metal ions in the plating solution are concentratedly absorbed on the rough surface (4) with high ion adsorption; This makes it difficult for metal ions to adhere to the surface of the substrate (1), which has a low ion adsorption property and is smooth. As a result, the ink layer (3) is a rough surface (4).
) The metal layer A layer (5) can be formed only on the surface of the metal plated layer (5), and the pattern of the metal plating layer (5) can be formed very accurately.

Example 2 The substrate (1) is composed of a polyimide sheet, and the above Example 1
Using the same procedure as above, apply the nickel metal layer (5) having the desired pattern to the patterned surface (2) of the substrate (1).
was formed.

Example 3 After carrying out the pattern forming step (A) and etching step (B) in the same manner as in Example 1, a metal film forming step (C
), it is possible to obtain the shell film (4) only on the surface of the ink layer (3) by using a commercially available electroless plating solution (trade name: Kagakudo 100, manufactured by Okuno Pharmaceutical Co., Ltd.). Ta.

Example 4 After carrying out the pattern forming step (A), etching step (B), and metal pattern forming step (C) in the same manner as in Example 2 above, an electric angle was formed on the metal pattern obtained in step (C). A thick and dense nickel plating layer (4) was obtained using the nickel plating method.

In this case, the Nikermetsu liquid and electric heating conditions are as follows:
Nickel sulfate 2408/1, nickel chloride 30g/l,
Nickel acetate 45g/l, boric acid 30kI/N, ammonium sulfate 2.5ε/1, formaldehyde 1g/l,
p112~4, temperature 60~70℃, current density 2~4A/
(11112 for 15 minutes.

Comparative Examples 1 to 4 were the same as Examples 1 to 4 except that the respective etching steps were removed.

The adhesion strength of the metal plating layer to the substrate in each of the above examples was 530 g/cUa or more, while that of the comparative example was 150 to 250 g/c111, which indicates that the adhesion of the metal plating layer of the present invention is extremely good. Admitted.

Further, when each of the comparative examples was heat-treated at a temperature of 80 to 200°C, curling occurred and peeling was observed at the edge portion of the metal pattern layer.

Furthermore, each comparative example product obtained by heat treatment with each example product was subjected to an atmosphere of a temperature of 20°C and a temperature of 60°C and a relative humidity of 85%.
When a thermal cycle test was carried out for 500 hours, no ``A'' was observed in the samples of the Examples, but curling became more severe in the samples of the Comparative Examples, and progression of peeling was observed.

[Brief explanation of the drawing]

Figures 1 to 3 are diagrams showing the order of steps in an embodiment of the present invention, with Figure 1 being a schematic diagram of the pattern forming process, and Figure 2 being a two-dimensional diagram of the etching process. , FIG. 3 is a schematic diagram of the metal pattern forming process. (1)...Substrate, (2)...Pattern formation surface, (3
)... Ink layer, (4 rough, (5)... Metal plating layer. 4・-・斌f-■ 5・・-31SazLノ・ツa()11 Fig. 7 Fig. 2 Fig. 3

Claims (11)

[Claims] (1) Pattern forming step (A) of forming an ink layer having a desired pattern on the pattern forming surface of the substrate, forming the surface of the ink layer printed in the above pattern forming step (A) into a rough surface by etching. Etching process (
B), a metal pattern forming step (C) in which the substrate obtained through the etching step (B) is immersed in an electroless plating solution to form a metal plating layer on the rough surface. How to form a pattern. (2) The pattern forming method according to claim 1, wherein in the pattern forming step (A), the ink layer is formed of a radiation-curable ink. (3) The pattern forming step (A) includes a printing step (A1) of printing an ink layer on a substrate in a desired pattern, and a step (A2) of curing the ink layer printed on the substrate in this printing step (A1). ), The pattern forming method according to claim 1 or 2, comprising: (4) The pattern forming step (A) is formed by the coating film forming step (A3) of applying an ink layer made of radiation-curable ink over the entire pattern forming surface of the substrate, and the coating film forming step (A3) described above. A pattern curing step (A4) in which the part of the ink layer that forms the desired pattern is irradiated with radiation to harden the part of the ink layer that forms the pattern, the pattern cured in the pattern curing step (A4). 3. The method for forming a pattern according to claim 1 or 2, comprising: a surplus ink layer removing step (A5) of removing a portion of the ink layer excluding the portion of the ink layer. (5) The pattern forming method according to any one of claims 2 to 4, wherein the irradiation radiation is natural light, ultraviolet rays, or electron beam. (6) Pattern forming step (A) in which an ink layer having a desired pattern is printed on the pattern forming surface of the substrate, and etching in which the surface of the ink layer printed in the pattern forming step (A) is formed into a rough surface by etching. Process (B)
, a metal pattern forming step (C) in which the substrate obtained in the etching step (B) is immersed in an electroless plating solution to form a metal plating layer on the rough surface; A method for forming a pattern, comprising: (D) an electrolytic plating step (D) of depositing a metal of the same kind or a different kind as the metal plating layer on the metal plating layer formed on the surface of the ink layer by electrolytic plating. (7) The pattern forming method according to claim 6, wherein in the pattern forming step (A), the ink layer is formed of a radiation-curable ink. (8) The pattern forming step (A) includes a printing step (A1) in which an ink layer is printed on a substrate in a desired pattern, and a curing step in which the ink layer printed on the substrate in this printing step (A1) is hardened. (A2) The method for forming a pattern according to claim 6 or 7, comprising: (9) A coating film forming step (A3) in which the pattern forming step (A) applies an ink layer made of radiation-curable ink over the entire pattern forming surface of the substrate; A pattern curing step (A4) of curing the part of the ink layer forming the pattern by irradiating the part of the ink layer forming the required pattern with radiation; The process of removing parts of the ink layer except for the
A5) A method for forming a pattern according to claim 6 or 7, which comprises: (10) The pattern forming method according to any one of claims 7 to 9, wherein the irradiation radiation is natural light, ultraviolet rays, or electron beam. (11) Pattern forming step (A) in which a conductive ink layer having a desired pattern is printed on the pattern forming surface of the substrate, and the surface of the conductive ink layer printed in the pattern forming step (A) is roughened by etching. Etching step (B) to expose the metal in the conductive ink
, a metal pattern forming step (C) in which a metal of the same type or different type as the metal in the conductive ink is deposited on the substrate obtained in the etching step (B) by electrolytic plating. .