JP7269038B2 - Method for manufacturing plated parts - Google Patents

Description

The present invention relates to a method for manufacturing plated parts.

In recent years, inorganic substrates such as glass substrates and ceramic substrates have attracted attention as substrates for forming circuits and antenna patterns, and attempts have been made to form metal film patterns on the surfaces of such inorganic substrates ( For example, Patent Documents 1 and 2). Inorganic substrates such as glass substrates and ceramic substrates have high insulating properties and heat dissipation properties. A metal film pattern on an inorganic substrate can be formed, for example, by an electroless plated film or a combination of an electroless plated film and an electrolytic plated film.

Patent No. 6080873 JP 2019-9147 A

The electroless plated film must be formed only on predetermined regions of the circuit and antenna patterns. For example, when forming a circuit pattern, if an electroless plated film is deposited between wirings, a short circuit will occur in the wirings. Also, when forming an antenna with a plated film, sufficient antenna characteristics cannot be obtained if the plated film is deposited in a region other than a predetermined region. Therefore, there has been a demand for a technique capable of obtaining sufficient contrast between a portion having a plated film and a portion not having a plated film on an inorganic substrate such as glass or ceramics.

The present invention solves these problems, and provides a plated component capable of forming an electroless plated film only on a predetermined region by suppressing deposition of an electroless plated film on an inorganic base material other than the predetermined region. A manufacturing method is provided.

According to the present invention, there is provided a method for producing a plated component, wherein a catalytic activity hindering layer containing a catalyst deactivator is formed on the smooth surface of an inorganic substrate having a surface roughness (Ra) of 1 μm or less. irradiating a part of the catalytic activity hindering layer on the substrate with a laser beam; applying an electroless plating catalyst to the surface of the inorganic substrate irradiated with the laser beam; Provided is a method for producing a plated component, comprising contacting an electroless plating solution to the surface of the inorganic base material to which the electroless plating catalyst has been applied, and forming an electroless plating film on the region irradiated with the laser beam. .

After forming the electroless plating film, the surface of the inorganic substrate may be brought into contact with a solvent to remove the catalytic activity hindering layer from the surface of the inorganic substrate. Moreover, the inorganic substrate may have a smooth layer forming the smooth surface on its surface.

The method of manufacturing the plated component may further comprise applying a coupling agent onto the smooth surface of the inorganic substrate prior to forming the catalytic activity hindering layer. The coupling agent may be a silane coupling agent containing an epoxy group, an acryloxy group, a methacryloxy group or a styryl group.

The catalyst deactivator may be a polymer having at least one selected from the group consisting of amide groups, amino groups and dithiocarbamate groups. Further, the catalyst deactivator may be a hyperbranched polymer represented by the following formula (1).

式（１）において、Ａ^１は芳香環を含む基であり、Ａ^２はアミド基を含む基であり、Ａ^３は硫黄を含む基であり、Ｒ^０は、水素又は炭素数１～１０個の置換若しくは無置換の炭化水素基であり、ｍ１は０．５～１１であり、ｎ１は５～１００である。

In formula (1), A ¹ is a group containing an aromatic ring, A ² is a group containing an amide group, A ³ is a group containing sulfur, R ⁰ is hydrogen or has 1 to 10 carbon atoms is a substituted or unsubstituted hydrocarbon group, m1 is 0.5-11, and n1 is 5-100.

The wavelength of the laser light may be 200-380 nm. Also, the electroless plated film may form an electric circuit or an antenna pattern on the inorganic substrate.

The production method of the present invention can suppress deposition of an electroless plated film in areas other than a predetermined area on an inorganic substrate, and form an electroless plated film only in a predetermined area.

It is a flow chart which shows a manufacturing method of plated parts of a 1st embodiment. It is a flowchart which shows the manufacturing method of the plated components of 2nd Embodiment.

[First embodiment]
A method for manufacturing a plated component according to the present embodiment will be described according to the flowchart shown in FIG. The production method of the present embodiment includes forming a catalytic activity hindering layer containing a catalyst deactivator on a smooth surface of an inorganic substrate having a smooth surface having a surface roughness (Ra) of 1 μm or less (FIG. 1 step S1), irradiating a part of the catalytic activity hindering layer with a laser beam (step S2 in FIG. 1), and applying an electroless plating catalyst to the surface of the inorganic substrate irradiated with the laser beam (FIG. 1 step S3), the electroless plating solution is brought into contact with the surface of the inorganic substrate to which the electroless plating catalyst is applied, and an electroless plating film is formed in the region irradiated with the laser light (step S4 in FIG. 1). include.

(1) Formation of catalytic activity hindering layer First, a catalytic activity hindering layer containing a catalyst deactivator is formed on a smooth surface of an inorganic substrate having a surface roughness (Ra) of 1 μm or less (Fig. 1 step S1).

<Inorganic substrate>
The inorganic substrate (hereinafter sometimes simply referred to as "substrate" as appropriate) is not particularly limited as long as it is a substrate containing an inorganic material as a main component, and a circuit or antenna pattern is formed by an electroless plating film. In this case, glass substrates and ceramic substrates are preferable because they have excellent insulating properties and heat dissipation properties.

The glass substrate is not particularly limited as long as it contains glass, and can be appropriately selected according to the application of the plated part. Examples of glass substrates include glass substrates such as soda lime glass (soda glass), borosilicate glass, alkali-free glass, and quartz glass. The glass substrate may be transparent to visible light, or may be colored by including additives. The fact that the glass substrate is transparent to visible light means, for example, that the glass substrate has a transmittance of 60% or more for light with a wavelength of 400 nm to 800 nm (visible light region). When the transparency of the glass substrate is important, the transmittance of the glass substrate for light with a wavelength of 400 nm to 800 nm (visible light region) is preferably 65% or more, more preferably 85% or more. The glass substrate may be a commercially available product. Further, the glass substrate may be glass optical components such as lenses and prisms, and glass housings of electronic devices such as smartphones.

The ceramic substrate is not particularly limited as long as it contains ceramics, and can be appropriately selected according to the application of the plated part. Examples of ceramic substrates include ceramic substrates such as alumina, aluminum nitride, lead zirconate titanate (PZT), barium titanate, and silicon wafers.

The glass substrate may be made of glass only, or may contain general-purpose additives and the like as long as glass is the main component. Further, the ceramic base material may be formed only from ceramics, or may contain general-purpose additives and the like as long as ceramics is the main component.

The inorganic substrate has a smooth surface with a surface roughness (Ra) of 1 μm or less. The smooth surface may be the entire surface of the inorganic substrate or a portion of the surface of the inorganic substrate. In the plated component manufactured in this embodiment, the electroless plated film is formed on the smooth surface of the inorganic substrate. Here, "surface roughness" means arithmetic surface roughness (Ra). The surface roughness of the smooth surface is preferably 0.7 μm or less from the viewpoint of suppressing deposition of the electroless plating film on the inorganic base material other than the predetermined area. Moreover, the lower limit of the surface roughness of the smooth surface is not particularly limited, but from a practical point of view, it is, for example, 0.005 μm or more, or 0.01 μm or more.

The inorganic substrate itself may form a smooth surface. Moreover, the inorganic substrate may have a smooth layer on its surface, and the smooth layer may form a smooth surface. For example, some ceramic materials themselves have large surface roughness. Even a material having a surface roughness (Ra) of more than 1 μm can be used as the inorganic base material of the present embodiment by providing a smooth layer on the surface to make the surface smooth. That is, when the smooth layer forms a smooth surface, the inorganic base material of the present embodiment has an original base material that is an inorganic material and a smooth layer formed on the original base material. Since the surface roughness of the original substrate may be greater than 1 μm, the range of material selection for the inorganic substrate can be widened.

The smooth layer is preferably a thin film made of an inorganic material so as not to affect the insulating properties and heat dissipation properties of the original substrate. Examples thereof include thin films of silicon oxide, titanium oxide, and the like. The film thickness of the smooth layer is, for example, 0.01 μm to 1 μm, or 0.02 μm to 0.3 μm. In this embodiment, the inorganic substrate may be produced by forming a smooth layer on the original substrate before forming the catalytic activity hindering layer on the smooth surface. The smooth layer can be formed, for example, by a sol-gel method.

<Catalyst deactivator>
As the catalyst deactivator (catalytic activity inhibitor), any substance can be used as long as it prevents the electroless plating catalyst from exhibiting its catalytic ability and, as a result, suppresses the electroless plating reaction. can. The catalyst deactivator reacts directly with the electroless plating catalyst to poison the electroless plating catalyst, or even if it does not react directly with the electroless plating catalyst, the catalyst deactivator may be used in the electroless plating process at any stage of the catalyst application process. It is presumed that this prevents the catalyst from exhibiting its catalytic ability.

The catalyst deactivator includes, for example, zinc (Zn), lead (Pb), tin (Sn), bismuth (Bi), antimony (Sb) and other heavy metals and their compounds that poison the plating catalyst, iodine and its compounds, Catalyst deactivators disclosed in WO2016/013464 such as oxidizing agents such as peroxides may also be used. These catalyst deactivators can be mixed with a binder resin to form a catalytic activity hindering layer on the inorganic substrate.

Also, a polymer that interferes with catalyst activity may be used as a catalyst deactivator. When the catalyst deactivator is a polymer, it can form a catalytic activity hindering layer on the inorganic substrate by itself without using a binder resin. A polymer having an amide group, an amino group, or a dithiocarbamate group is preferred as the catalyst deactivator. It is presumed that these functional groups act on the metal ions that serve as electroless plating catalysts and prevent their catalytic activity from being exhibited. The polymer that is the catalyst deactivator is preferably a branched polymer containing these functional groups in its side chains, and more preferably a dendritic polymer such as a dendrimer or a hyperbranched polymer.

式（１）において、Ａ^１は芳香環を含む基であり、Ａ^２はアミド基を含む基であり、Ａ^３は硫黄を含む基であり、Ｒ^０は、水素又は炭素数１～１０個の置換若しくは無置換の炭化水素基であり、ｍ１は０．５～１１であり、ｎ１は５～１００である。 As the catalyst deactivator (catalytic activity hindrance), for example, a hyperbranched polymer represented by the following formula (1) described in WO 2018/131492 may be used.

In formula (1), A ¹ is a group containing an aromatic ring, A ² is a group containing an amide group, A ³ is a group containing sulfur, R ⁰ is hydrogen or has 1 to 10 carbon atoms is a substituted or unsubstituted hydrocarbon group, m1 is 0.5-11, and n1 is 5-100.

Although the mechanism by which the hyperbranched polymer represented by formula (1) hinders the catalytic activity of the electroless plating catalyst is not clear, it is presumed as follows. The amide groups of the hyperbranched polymer are adsorbed, coordinated, reacted, etc. with the electroless plating catalyst to form a complex, whereby the electroless plating catalyst is trapped in the hyperbranched polymer. The amide group of the hyperbranched polymer is contained in the side chain, so the degree of freedom is high, and one molecule of the hyperbranched polymer contains a large number of amide groups. Therefore, the hyperbranched polymer can efficiently and strongly trap the electroless plating catalyst with a plurality of amide groups. For example, a hyperbranched polymer can act as a multidentate ligand, with multiple amide groups coordinating to an electroless plating catalyst to form a chelate structure. The electroless plating catalyst trapped in this manner cannot exhibit catalytic activity. For example, when palladium is used as an electroless plating catalyst, the amide group of the hyperbranched polymer traps palladium in the form of palladium ions. Palladium ions are reduced to metallic palladium, which exhibits electroless plating catalytic activity. However, the palladium ions trapped in the hyperbranched polymer are not reduced even by the reducing agent, and cannot exhibit catalytic activity. As a result, formation of an electroless plated film is suppressed on the surface of the substrate to which the hyperbranched polymer represented by formula (1) is applied. However, this mechanism is only a guess, and the present invention is not limited to this.

Any group can be used for A ¹ as long as it contains an aromatic ring, but for example, a group represented by the following formula (2) is preferable.

When A ¹ is a group represented by formula (2), the hyperbranched structure of the hyperbranched polymer of the present embodiment has a styrene skeleton. When the hyperbranched structure has a styrene skeleton, the hyperbranched polymer has improved weather resistance and heat resistance.

A hyperbranched polymer has multiple end groups. In the terminal group of the hyperbranched polymer represented by formula (1) above, ^A2 is a group containing an amide group, and ^A3 is a group containing sulfur. In addition, m1 is the average value of the number (repeating number) m of groups (A ² ) containing an amide group in each terminal group. Therefore, m1 does not have to be an integer. The hyperbranched polymer of the present embodiment may have an average m1 of 0.5 to 11, and may have a terminal group that does not have an amide group-containing group (A ² ). The number (repeating number) m of groups (A ² ) containing an amide group in each terminal group is, for example, 0-11. m1 in formula (1) is the quotient obtained by dividing the total number of groups (A ² ) containing an amide group in the molecule (the total number of m in the molecule) by the number of terminal groups. The value of m1 can be quantified by NMR method or elemental analysis method.

In the above formula (1), A ² is not particularly limited as long as it contains an amide group, and the amide group contained in A ² is any of a primary amide group, a secondary amide group, and a tertiary amide group. may be In addition, ^A2 may be a group containing one amide group, or may be a group containing two or more amide groups. A ² is preferably a group represented by the following formula (3). When ^A2 is a group represented by the following formula (3), the hyperbranched polymer of the present embodiment has improved metal-trapping ability. As a result, the effect of suppressing electroless plating is enhanced.

式（３）において、Ｒ¹は炭素数が１～５である置換若しくは無置換のアルキレン基、又は単結合であり、Ｒ²及びＲ³は、それぞれ、炭素数が1～１０である置換若しくは無置換のアルキル基又は水素である。また、式（３）において、Ｒ¹は単結合であることが好ましく、Ｒ²は水素であることが好ましく、Ｒ^３はイソプロピル基であることが好ましい。

In formula (3), R ¹ is a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms or a single bond, and R ² and R ³ are each a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms. It is an unsubstituted alkyl group or hydrogen. In formula (3), R ¹ is preferably a single bond, R ² is preferably hydrogen, and R ³ is preferably an isopropyl group.

In the above formula (1), ^A3 is not particularly limited as long as it is a sulfur-containing group, and examples thereof include a dithiocarbamate group, a trithiocarbonate group, a sulfide group, a thiocyanate group, etc. Among them, dithiocarbamate It is preferably a group. When A ³ is a dithiocarbamate group, the hyperbranched polymer of the present embodiment is easy to synthesize and has improved metal trapping ability. Furthermore, A ³ is preferably a group represented by the following formula (4).

式（４）において、Ｒ^４及びＲ^５は、それぞれ、炭素数が１～５である置換若しくは無置換のアルキル基、又は水素である。また、式（４）において、Ｒ^４及びＲ^５はエチル基であることが好ましい。

In formula (4), R ⁴ and R ⁵ are each a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, or hydrogen. Moreover, in formula (4), R ⁴ and R ⁵ are preferably ethyl groups.

In the above formula (1), R ⁰ can be any hydrocarbon group as long as it is hydrogen or a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms. The hydrocarbon group may be a chain or cyclic saturated aliphatic hydrocarbon group, a chain or cyclic unsaturated aliphatic hydrocarbon group, or an aromatic hydrocarbon group. When R ⁰ is a substituted hydrocarbon group, the substituents include, for example, an alkyl group, a cycloalkyl group, a vinyl group, an allyl group, an aryl group, an alkoxy group, a halogen group, a hydroxy group, an amino group, an imino group, It may be a nitro group, a silyl group, an ester group, or the like. R ⁰ may also be an unsubstituted hydrocarbon group, such as a vinyl group or an ethyl group.

The hyperbranched polymer of the present embodiment may be a mixture of hyperbranched polymers with different R ⁰ in formula (1). For example, when R ⁰ has an unsaturated bond, a part of the unsaturated bond may undergo some addition reaction to become a saturated bond in the process of synthesizing the hyperbranched polymer. In this case, in the above formula (1), a mixture of a hyperbranched polymer in which R ⁰ is an unsaturated hydrocarbon group and a hyperbranched polymer in which R ⁰ is a saturated hydrocarbon group is obtained. The hyperbranched polymer of the present embodiment may be a mixture of a hyperbranched polymer in which R ⁰ is a vinyl group and a hyperbranched polymer in which R ⁰ is an ethyl group in the above formula (1).

The hyperbranched polymer of the present embodiment preferably has a number average molecular weight of 3,000 to 30,000, a weight average molecular weight of 10,000 to 300,000, and a number average molecular weight of 5,000. ~30,000, and more preferably a weight average molecular weight of 14,000 to 200,000. The weight-average molecular weight and number-average molecular weight of the hyperbranched polymer can be measured in terms of polystyrene by gel permeation chromatography (GPC), for example.

The method for synthesizing the hyperbranched polymer of the present embodiment is not particularly limited, and any method can be used for synthesis. For example, the hyperbranched polymer of the present embodiment may be synthesized using a commercially available hyperbranched polymer as a starting material. Alternatively, the hyperbranched polymer of the present embodiment may be synthesized by sequentially performing monomer synthesis, monomer polymerization, terminal group modification, and the like. The weight-average molecular weight and number-average molecular weight of the hyperbranched polymer of the present embodiment, m1 and n1 in formula (1) can be determined by adjusting the ratio of reagents used for synthesis, synthesis conditions, etc. by any method. can be adjusted within the range of

<Formation of catalytic activity hindering layer>
The catalytic activity hindrance layer (hereinafter sometimes simply referred to as "interference layer") contains a catalyst deactivator. The method for forming the catalytic activity impeding layer is not particularly limited, and for example, methods disclosed in WO2017/154470 and WO2018/131492 can be used as described below.

The catalytic activity hindering layer may be formed by mixing a catalyst deactivator with a binder resin and applying the mixture to the surface of the inorganic substrate. Alternatively, a resin layer made of a resin having no catalyst deactivation function may be formed on the inorganic substrate, and the formed resin layer may be brought into contact with the catalyst deactivator. The catalyst deactivator is supported by permeation, adsorption, etc. in the resin layer to form a catalyst activity hindering layer.

When the catalyst deactivator is a polymer, it can form a catalytic activity hindering layer by itself without using a binder resin. For example, first, a solution is prepared by dissolving or dispersing a resin, which is a catalyst deactivator, in a solvent. The catalytically active impeding layer may be formed by applying the solution to the substrate or by immersing the substrate in the solution. Specific forming methods include dip coating, screen coating, spray coating, and the like.

The catalytic activity hindrance layer is formed at least on the smooth surface of the inorganic substrate. Further, the catalytic activity hindering layer is preferably formed on a region of the surface of the inorganic substrate that comes into contact with the electroless plating solution in the electroless plating step described later, and more preferably formed on the entire surface of the inorganic substrate.

The catalytic activity hindrance layer is preferably thin so as not to affect the insulating properties and heat dissipation properties of the inorganic substrate. For example, it is preferably 5 µm or less, more preferably 1 µm or less, and even more preferably 0.3 µm or less. On the other hand, from the viewpoint of interfering with the catalytic activity of the electroless plating catalyst, for example, it is preferably 0.01 μm or more, more preferably 0.03 μm or more, and even more preferably 0.05 μm or more.

(2) Laser Light Irradiation Next, a part of the catalytic activity hindering layer is irradiated with laser light (step S2 in FIG. 1). The method of irradiating the laser beam is not particularly limited, and may be, for example, laser drawing in which the laser beam is irradiated according to a predetermined pattern.

The laser beam to be irradiated is not particularly limited, and a general-purpose laser device such as a _CO2 laser, a _YVO4 laser, and a YAG laser can be used for irradiation. The wavelength, intensity, etc. of the laser light can be determined based on the type of base material, the application of the plated part, and the like. For example, in applications where high adhesion strength of the electroless plated film is required, it is preferable that the roughness of the laser beam irradiated portion is large (high). In order to increase the roughness of the laser beam irradiated portion, for example, a laser beam having a wavelength that is highly absorbed by the inorganic substrate may be selected. On the other hand, for example, when an antenna pattern or the like is formed of an electroless plating film, it is preferable that the roughness of the laser beam irradiated portion is small in order to improve the antenna characteristics. In order to form a laser beam irradiated portion with a relatively small roughness on a glass substrate, the laser beam irradiated to the substrate is preferably an ultraviolet laser beam with a wavelength of 200 nm to 380 nm, and the wavelength is, for example, 355 nm. . For example, a catalytic activity hindering layer containing a hyperbranched polymer represented by formula (1) absorbs light (eg, ultraviolet light) of wavelengths in the above range, but glass does not easily absorb it. Therefore, laser light with a wavelength in the above range removes the hyperbranched polymer layer (catalytic activity hindering layer) represented by the formula (1) formed on the glass substrate, but hardly roughens the glass substrate. .

By irradiating a part of the surface of the base material with laser light, the light is converted into heat and the surface of the base material is heated. As a result, the interfering layer is removed in the laser beam irradiated portion. Here, "removal of the interfering layer" means, for example, the disappearance of the interfering layer in the laser beam irradiated portion due to evaporation or decomposition. By performing laser drawing of a predetermined pattern on the surface of the base material provided with the interference layer, it is possible to form a predetermined pattern of the interference layer-removed portion and the interference layer-remaining portion where the interference layer remains. In addition, in the interference layer-removed portion, which is the laser beam irradiation portion, the surface layer portion of the base material may be evaporated or decomposed to disappear together with the interference layer. "Removal of the interfering layer" includes not only complete disappearance of the interfering layer, but also the case where the interfering layer remains to such an extent that it does not affect the progress of the electroless plating process in the subsequent step. Even if the interfering layer remains, if it does not affect the subsequent electroless plating process, it means that the effect of interfering with the catalytic activity of the electroless plating catalyst has disappeared. Furthermore, in the present embodiment, "removal of the interference layer" also includes the case where the heated portion of the interference layer is denatured or deteriorated and no longer acts as the interference layer. For example, there is a case where the amide group of the hyperbranched polymer represented by Formula (1) is denatured or modified, and as a result, the hyperbranched polymer cannot trap the electroless plating catalyst. In this case, the heated portion of the interference layer does not disappear completely, but a modified substance (degraded substance) remains. This modification does not interfere with catalytic activity. Therefore, the portion where the interference layer is denatured or degraded acts in the same manner as the portion where the interference layer has disappeared.

(3) Application of Electroless Plating Catalyst Next, an electroless plating catalyst is applied to the surface of the inorganic substrate irradiated with the laser beam (step S3 in FIG. 1). The method of applying the electroless plating catalyst to the surface of the substrate is not particularly limited. For example, the electroless plating catalyst may be applied to the substrate by a general-purpose method such as a sensitizer-activator method or a catalyzer-accelerator method. Further, for example, an electroless plating catalyst may be applied to the surface of the substrate using a plating catalyst solution containing a metal salt such as palladium chloride disclosed in JP-A-2017-036486. A commercially available activator treatment liquid may be used as the plating catalyst liquid containing the metal salt.

When using a plating catalyst solution containing a metal salt, a polymer such as polyethyleneimine may be applied to the substrate as a pretreatment for applying the catalyst. A catalyst that is a metal ion derived from a metal salt is less likely to be adsorbed on a substrate than a non-ionized metal catalyst (having an oxidation number of 0 (zero)). Since polymers such as polyethyleneimine adsorb metal ions, the adsorption of metal ions derived from metal salts (electroless plating catalyst) to the substrate is promoted by adding polyethyleneimine or the like to the substrate in advance. be. The metal ions adsorbed on the substrate are reduced by the reducing agent in the electroless plating solution in the subsequent electroless plating process, for example, to exhibit electroless plating catalytic activity (electroless plating catalytic activity).

(4) Electroless Plating Next, the inorganic substrate is brought into contact with an electroless plating solution (step S4 in FIG. 1). On the surface of the inorganic substrate, there are an interference layer remaining portion where the interference layer remains and an interference layer removed portion with a predetermined pattern where the interference layer is removed by heating or the like. By applying an electroless plating catalyst to the surface of the substrate and contacting the substrate with an electroless plating solution, an electroless plating film can be formed only on the portion of the predetermined pattern from which the interfering layer has been removed.

As the electroless plating solution, any general-purpose electroless plating solution can be used according to the purpose. , an electroless nickel plating solution is preferred.

A different type of electroless plated film may be formed on the electroless plated film, or an electrolytic plated film may be formed by electroplating. By increasing the total thickness of the plated film on the substrate, the electrical resistance can be reduced when the plated film with a predetermined pattern is used as an electric circuit. From the viewpoint of lowering the electrical resistance of the plated film, the plated film laminated on the electroless plated film is preferably an electroless copper plated film, an electrolytic copper plated film, an electrolytic nickel plated film, or the like. In addition, since electroplating cannot be applied to an electrically isolated circuit, it is preferable to increase the total thickness of the plated film on the substrate by electroless plating in such a case. Also, in order to improve the solder wettability of the plated film pattern so as to be compatible with solder reflow, a plated film of tin, gold, silver, or the like may be formed on the outermost surface of the plated film pattern.

(5) Removal of Catalytic Activity Hindering Layer After forming the electroless plating film, the catalytic activity hindering layer may be removed from the surface of the inorganic substrate. By removing the catalytically active impeding layer, a plated part without the catalytically active impeding layer can be produced. For example, if the inorganic substrate is transparent, removal of the catalytic activity hindering layer allows the plated part to maintain the transparency of the inorganic substrate. In addition, if the catalytic activity hindering layer peels off from the base material, contamination may occur, which may contaminate the surroundings. By removing the catalytic activity hindrance layer, the occurrence of contamination can be prevented.

A method for removing the hyperbranched polymer represented by formula (1) from the inorganic substrate includes, for example, a method of contacting with a solvent (cleaning liquid) to wash the inorganic substrate. The solvent is not particularly limited as long as it can dissolve or disperse the hyperbranched polymer represented by formula (1) and does not alter the inorganic substrate. Examples include methyl ethyl ketone, tetrahydrofuran, propylene glycol monomethyl ether, and the like. These may be used alone or in combination of two or more. In addition, the solvent (cleaning liquid) may contain general-purpose additives such as surfactants, if necessary.

The plated component manufactured by the manufacturing method of this embodiment described above may be an electronic component in which an electroless plated film forms an electric circuit or an antenna pattern on an inorganic substrate.

The method for manufacturing a plated component according to this embodiment has, for example, the following effects. In the method for manufacturing a plated component according to the present embodiment, the catalyst deactivator is used to suppress the deposition of the electroless plating film in areas other than the predetermined area (the remaining portion of the interference layer where the interference layer remains). An electroless plated film can be formed only in the regions (laser light irradiated portions, interference layer removed portions). As described above, the catalytic activity hindering layer is preferably thin so as not to affect the physical properties of the inorganic substrate. However, when the surface roughness of the inorganic substrate on which the catalytic activity impeding layer is formed is large, it is difficult to uniformly form a thin catalytic activity impeding layer on the surface. Defects that expose the surface of the base material may occur in the catalytic activity hindering layer, and an electroless plating film may be deposited on the defects. In this embodiment, the catalytic activity hindering layer is formed on a smooth surface with a small surface roughness (Ra). Therefore, even a thin catalytic activity hindering layer can be uniformly covered, and the deposition of an electroless plating film can be sufficiently suppressed. As a result, in the method of manufacturing a plated component according to the present embodiment, a plated component with a clear contrast between the portion having the plated film and the portion not having the plated film can be manufactured.

In particular, when the hyperbranched polymer represented by formula (1) is used as the catalyst deactivator, the hyperbranched polymer sufficiently enhances the catalytic activity of the electroless plating catalyst even if the film thickness of the catalytic activity hindering layer is reduced. It has the ability to inactivate. Therefore, the catalytic activity hindering layer tends to be formed thinner. In the production method of the present embodiment, even when the hyperbranched polymer represented by formula (1) is used as the catalyst deactivator, the catalytic activity hindering layer can uniformly cover the substrate surface (smooth surface). It is possible to manufacture a plated part with a clear contrast between a portion with a plated film and a portion without a plated film.

In the method of manufacturing a plated component described above, a catalytic activity hindering layer is formed on an inorganic substrate (step S1 in FIG. 1), and then a part of the surface of the catalytic activity hindering layer is irradiated with a laser beam (FIG. 1 step S2). However, the present embodiment is not limited to this, for example, a part of the smooth surface of the substrate is irradiated with laser light (step S2 in FIG. 1), and then a catalytic activity hindering layer is applied to the substrate. (Step S1 in FIG. 1). Since the surface of the laser-written substrate is roughened, it is difficult to form an interference layer sufficient to suppress electroless plating. Therefore, a plated film can be selectively formed on the laser drawn portion.

[Second embodiment]
A method of manufacturing a plated component according to the present embodiment will be described according to the flowchart shown in FIG. In the production method of the present embodiment, a coupling agent is applied onto the smooth surface of the substrate before forming the catalytic activity hindering layer on the smooth surface (step S11 in FIG. 2). Otherwise, it is the same as the first embodiment described above. That is, the manufacturing method of the present embodiment includes applying a coupling agent onto a smooth surface of an inorganic substrate having a surface roughness (Ra) of 1 μm or less (step S11 in FIG. 2), and applying a coupling agent. Forming a catalytic activity hindering layer containing a catalyst deactivator on the inorganic substrate (step S1 in FIG. 2), irradiating a part of the catalytic activity hindering layer with laser light (step S2 in FIG. 2 ), applying an electroless plating catalyst to the surface of the inorganic substrate irradiated with laser light (step S3 in FIG. 2), and bringing an electroless plating solution into contact with the surface of the inorganic substrate to which the electroless plating catalyst has been applied. , forming an electroless plated film in the region irradiated with the laser light (step S4 in FIG. 2).

Only the step of applying the coupling agent to the smooth surface of the substrate (step S11 in FIG. 2) will be described below. Other steps (steps S1 to S4 in FIG. 2) are the same as in the first embodiment, and descriptions thereof are omitted.

The coupling agent used in this embodiment is not particularly limited, and for example, a silane coupling agent, a titanate coupling agent, or an aluminate coupling agent can be used, and among these, the silane coupling agent is preferable.

A silane coupling agent has, in its molecule, a structure that reacts or interacts with an inorganic material (hereinafter simply referred to as "a structure that reacts with an inorganic material") and a structure that reacts or interacts with an organic material (hereinafter, It is an organosilicon compound having both a structure that reacts with an organic material).

The structure of the silane coupling agent that reacts with the inorganic material is preferably a structure that generates a silanol group by hydrolysis (a structure containing a hydrolyzable silyl group). The generated silanol groups react or interact with the inorganic substrate. The structure that reacts with the inorganic material preferably includes, for example, a structure in which a halogen atom such as an alkoxy group, an acetoxy group, or a chlorine atom is bonded to a silicon element.

The structure of the silane coupling agent that reacts with the organic material is preferably a structure having an epoxy group, an acryloxy group, a methacryloxy group, or a styryl group, and more preferably a structure having an epoxy group. In particular, when the catalytic activity hindering agent is a hyperbranched polymer represented by formula (1), the silane coupling agent having the above functional group can further increase the adhesion strength between the inorganic substrate and the catalytic activity hindering layer. . Although this mechanism is unknown, it is speculated that these functional groups interact with the styrene skeleton of the hyperbranched polymer.

In the silane coupling agent, the structure that reacts with the inorganic material and the structure that reacts with the organic material may be linked by a single bond or by a hydrocarbon chain. When the structure that reacts with the inorganic material and the structure that reacts with the organic material are linked by a relatively long hydrocarbon chain, the adhesion strength between the inorganic substrate and the catalytic activity hindering layer is increased, and the adhesion strength is maintained over a long period of time. can be maintained The hydrocarbon chain is, for example, an alkylene group having 1 to 12 carbon atoms, preferably an alkylene group having 3 to 8 carbon atoms, and more preferably an alkylene group having 6 to 8 carbon atoms.

式（Ｓ）において、
Ｘ^１～Ｘ^３は、全てがアルコキシ基であるか、又は、２つがアルコキシ基であり、残りの１つがアルキル基であり、
Ｙは、グリシドキシ基、アクリロキシ基（アクリル基）、メタクリロキシ基（メタクリル基）又はスチリル基であり、
Ｒは、単結合又は炭素数１～１２個のアルキレン基である。 As the silane coupling agent, for example, a silane coupling agent represented by the following formula (S) may be used. The silane coupling agent represented by the formula (S) has a structure (X ^1-3 Si-) that reacts with an inorganic material and a structure (-Y) that reacts with an organic material, and these are single bonds or Linked by a hydrocarbon chain (-R-).

In formula (S),
all of X ¹ to X ³ are alkoxy groups, or two are alkoxy groups and the remaining one is an alkyl group;
Y is a glycidoxy group, an acryloxy group (acryl group), a methacryloxy group (methacryl group) or a styryl group;
R is a single bond or an alkylene group having 1 to 12 carbon atoms.

In formula (S), all of X ¹ to X ³ are preferably alkoxy groups, more preferably all methoxy groups. Y is preferably a glycidoxy group, and R is preferably an alkylene group having 3 to 8 or 6 to 8 carbon atoms.

A method for applying the coupling agent is not particularly limited, and a general-purpose method can be used. For example, a coupling agent solution may be prepared by dissolving a coupling agent in a solvent and applied to the inorganic substrate, or the inorganic substrate may be immersed in it. Specific methods include dip coating, screen coating, spray coating, and the like.

In the present embodiment described above, similarly to the first embodiment, a plated component with a clear contrast between the portion having the plating film and the portion not having the plating film can be manufactured. In addition, in the present embodiment, the adhesion strength between the inorganic substrate (inorganic material) and the catalytic activity hindering layer (organic material) can be increased by applying the coupling agent onto the smooth surface of the inorganic substrate. As a result, it is possible to more efficiently suppress the deposition of the electroless plated film in the region not irradiated with the laser beam (interfering layer residual portion where the interfering layer remains).

Further, when the hyperbranched polymer represented by the formula (1) is used as the catalyst deactivator, and the coupling agent is a silane coupling agent having an epoxy group, an acryloxy group, a methacryloxy group, or a styryl group, the silane coupling The agent can suppress deposition of an electroless plating film on the hyperbranched polymer (catalytic activity hindering layer) represented by formula (1) in the subsequent electroless plating step (step S4 in FIG. 2). This mechanism is presumed as follows. According to the studies of the inventors, it has been found that an electroless plating film is deposited on the hyperbranched polymer, which is a catalyst deactivator, depending on the type of silane coupling agent used. For example, when a silane coupling agent containing an amino group is used, the adhesion strength between the inorganic substrate and the hyperbranched polymer represented by formula (1) increases, but electroless A plating film is deposited. This is presumably because the amino group in the silane coupling agent reacts with the hyperbranched polymer and further traps (traps) the electroless plating catalyst applied thereon via the hyperbranched polymer. . The hyperbranched polymer, which is a catalyst deactivator, strongly traps the electroless plating catalyst, thereby preventing the electroless plating catalyst (for example, palladium ions) from being reduced and exhibiting catalytic activity. On the other hand, the amino group in the silane coupling agent traps the electroless plating catalyst with a relatively weak force. Therefore, it is presumed that the electroless plating catalyst captured by the silane coupling agent is reduced, the catalytic activity is developed, and an electroless plating film is deposited there. The present inventors have found that if the structure of the silane coupling agent that reacts with the organic material (hyperbranched polymer represented by formula (1)) contains an epoxy group, an acryloxy group, a methacryloxy group or a styryl group, It was found that although it reacts with the hyperbranched polymer, it hardly captures the electroless plating catalyst. By using such a silane coupling agent, the adhesion strength between the inorganic substrate and the hyperbranched polymer represented by formula (1) is increased, and the electroless plating film is prevented from being deposited on the hyperbranched polymer. can be suppressed. It should be noted that the mechanism described above is an assumption, and does not limit the present invention in any way. Moreover, from the viewpoint of suppressing deposition of an electroless plating film on the hyperbranched polymer, the silane coupling agent preferably does not contain an amino group.

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples and comparative examples.

Samples 1-34 (plated parts) were prepared as follows. The methods for producing samples 1 to 23, 33 and 34 correspond to examples of the present invention, and the methods for producing samples 24 to 32 correspond to comparative examples of the present invention.

[Sample 1]
(1) Application of Silane Coupling Agent As an inorganic substrate, a large plate-shaped slide glass (manufactured by Matsunami Glass Industry Co., Ltd., S9111, 76 mm×52 mm×thickness 0.8 to 1.0 mm) was prepared. The surface roughness (Ra) of the surface of the inorganic substrate was measured using a laser microscope (Keyence VK-9700). The surface roughness (Ra) was 0.015 μm. The surface roughness values of this sample and other samples described hereinafter are all values measured by the same measuring method.

A silane coupling agent (KBM-4803, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to a mixed solvent of ethanol:water=1:1. Acetic acid was added subsequently. After that, the mixture was stirred for 1 hour to prepare a silane coupling agent liquid. The inorganic substrate was immersed in the prepared silane coupling agent solution at room temperature for 5 seconds (dipping), and then dried in a dryer at 110° C. for 10 minutes. The silane coupling agent used is a silane coupling agent represented by formula (S).

(2) Formation of catalytic activity hindering layer A hyperbranched polymer layer (catalyst active blocking layer) was formed. A hyperbranched polymer represented by formula (5) was synthesized by the method disclosed in WO2018/131492.

The hyperbranched polymer represented by formula (5) is a polymer represented by formula (1), in which A ¹ is a group represented by formula ( ² ); a group represented by (3), wherein R ¹ is a single bond, R ² is hydrogen, and R ³ is an isopropyl group; and A ³ is a dithiocarbamate group represented by formula (4); and R ⁴ and R ⁵ are ethyl groups, and R ⁰ is a vinyl group or an ethyl group.

The molecular weight of the synthesized hyperbranched polymer was measured by GPC (gel permeation chromatography). The molecular weights were number average molecular weight (Mn) = 9,946 and weight average molecular weight (Mw) = 24,792. was value.

A polymer solution having a polymer concentration of 0.5% by weight was prepared by dissolving the synthesized polymer represented by the formula (5) in methyl ethyl ketone. The substrate was immersed in the room temperature polymer solution for 5 seconds and then dried in a 100° C. dryer for 10 minutes. This formed a catalytic activity impeding layer on the surface of the substrate. The thickness of the catalytically active impeding layer was 100 nm.

(3) Laser light irradiation Using a laser lithography device (manufactured by Keyence, MD-U1000C, YVO ₄ laser, wavelength 355 nm) on an inorganic substrate on which a catalytic activity hindering layer is formed, a laser intensity of 80% and a drawing speed of 300 mm / sec. , and a frequency of 40 kHz, laser drawing was performed by scanning once over a predetermined pattern. The patterns drawn by laser in this embodiment are the following three types of patterns. The surface roughness (Ra) of the laser drawn portion was 0.016 μm.

<Laser drawing pattern>
Pattern 1: 2 cm x 3 cm rectangular pattern. Laser drawing was performed so as to fill in straight lines with a pitch of 0.05 μm.
Pattern 2: A pattern consisting of a plurality of straight lines with a pitch of 100 μm, a line width of 50 μm, and a length of 4 cm (that is, the line and space (L/S) of the pattern is 50 μm/50 μm).
Pattern 3: A pattern consisting of a plurality of straight lines with a pitch of 400 μm, a line width of 200 μm, and a length of 4 cm (that is, the line and space (L/S) of the pattern is 200 μm/200 μm)

(4) Pretreatment for Catalyst Application As a pretreatment liquid, an aqueous solution of polyethyleneimine (PEI) (manufactured by Wako Pure Chemical Industries, Ltd.) having a weight average molecular weight of 70,000 was prepared (polyethyleneimine content (solid concentration): 30 g/ L). The inorganic substrate was immersed in the pretreatment liquid at room temperature for 5 minutes, and then thoroughly washed with water.

(5) Application of Electroless Plating Catalyst An inorganic substrate was immersed in a room temperature palladium chloride (PdCl ₂ ) aqueous solution (manufactured by Okuno Chemical Industry Co., Ltd., Activator) for 2 minutes, and then thoroughly washed with water.

(6) Electroless plating An inorganic substrate provided with an electroless plating catalyst is immersed in an electroless nickel phosphorous plating solution (manufactured by Okuno Chemical Industry Co., Ltd., Top Nicolon LTN) adjusted to 65°C for 15 minutes. An electroless nickel phosphorous plating film was grown to a thickness of 1 μm on the surface of the substrate. Sample 1 (plated component) was obtained by the manufacturing method described above.

[Sample 2] to [Sample 7]
Samples 2 to 7 were produced in the same manner as Sample 1, except that the laser beam irradiation conditions (laser drawing conditions) were changed as shown in Table 1. In the production of Samples 6 and 7, laser drawing was performed using a laser drawing apparatus (LP-300, manufactured by Panasonic Devices SUNX, wavelength: 10.6 μm).

[Evaluation 1 of electroless plating]
The plating film patterns formed on the surfaces of samples 1 to 7 were visually observed and evaluated according to the following evaluation criteria. Table 1 shows the evaluation results.

<Evaluation Criteria>
⊚: An electroless plating film was formed only in the laser drawing patterns 1 to 3, and no electroless plating film was deposited in the other regions.
◯: In addition to the laser-drawn patterns 1 to 3, the electroless plating film was partially deposited between and around the fine lines of the patterns 2 and 3.
△: In addition to the laser-drawn patterns 1 to 3, the electroless plated film is partially deposited between and around the fine lines of the patterns 2 and 3, and also partially in other non-laser-drawn parts (outliers 2) An electroless plating film was deposited.
x: A plating film was deposited on the entire surface of the inorganic substrate.

＊試料１～７に用いたシランカップリング剤：信越化学工業株式会社製、ＫＢＭ‐４８０３、グリシドキシオクチルトリメトキシシラン、式（Ｓ）において、Ｙがグリシドキシ基（エポキシ基を含む基）、Ｒが炭素数８個のアルキレン基

* Silane coupling agent used for samples 1 to 7: Shin-Etsu Chemical Co., Ltd., KBM-4803, glycidoxyoctyltrimethoxysilane, in formula (S), Y is a glycidoxy group (group containing an epoxy group), R is an alkylene group having 8 carbon atoms

[Sample 8] to [Sample 10]
Samples 8 to 10 were produced in the same manner as Sample 1, except that the type of silane coupling agent was changed to those shown in Table 2. The silane coupling agent used is a silane coupling agent represented by Formula (S). Electroless plating evaluation 1 was performed on the manufactured samples 8 to 10 in the same manner as sample 1. Table 2 shows the results.

＊試料８～１０のレーザー描画条件は、試料１と同様（レーザー光波長：３５５ｎｍ）
１）信越化学工業株式会社製、ｐ‐スチリルトリメトキシシラン
２）信越化学工業株式会社製、３‐メタクリロキシプロピルトリメトキシシラン
３）信越化学工業株式会社製、３‐グリシドキシプロピルトリエトキシシラン

* Laser drawing conditions for samples 8 to 10 are the same as for sample 1 (laser light wavelength: 355 nm)
1) p-styryltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd. 2) 3-methacryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd. 3) 3-glycidoxypropyltriethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.

[Sample 11] to [Sample 17]
As an inorganic substrate, an alumina ceramic plate (manufactured by Hirosugi Keiki Co., Ltd., CRP-0505-10) was used, and the laser light irradiation conditions (laser drawing conditions) were changed as shown in Table 3. Sample 1 and Samples 11-17 were produced in a similar manner. The surface roughness (Ra) of the surfaces of the inorganic substrates used for Samples 11 to 17 was 0.421 μm. Electroless plating evaluation 1 was performed on the manufactured samples 11 to 17 in the same manner as sample 1. Table 3 shows the results.

＊試料１１～１７に用いたシランカップリング剤：信越化学工業株式会社製、ＫＢＭ‐４８０３、グリシドキシオクチルトリメトキシシラン、式（Ｓ）において、Ｙがグリシドキシ基（エポキシ基を含む基）、Ｒが炭素数８個のアルキレン基

* Silane coupling agent used for samples 11 to 17: Shin-Etsu Chemical Co., Ltd., KBM-4803, glycidoxyoctyltrimethoxysilane, in formula (S), Y is a glycidoxy group (group containing an epoxy group), R is an alkylene group having 8 carbon atoms

[Sample 18] to [Sample 20]
As the inorganic substrate, an alumina ceramic plate (manufactured by Hirosugi Keiki Co., Ltd., CRP-0505-10) was used, and the type of silane coupling agent was changed to those shown in Table 4. The same method as in sample 1. Samples 18-20 were produced by. The silane coupling agent used is a silane coupling agent represented by Formula (S). Electroless plating evaluation 1 was performed on the manufactured samples 18 to 20 in the same manner as sample 1. Table 4 shows the results.

[Sample 21]
As an inorganic base material, an alumina ceramic plate (manufactured by Hirosugi Keiki Co., Ltd., CRP-0505-10) was used, and as a coupling agent, a titanate-based coupling agent (manufactured by Ajinomoto Fine-Techno, Plenact 338X) was used. , Sample 21 was prepared in the same manner as Sample 1.

(1) Application of Coupling Agent A titanate-based coupling agent was added to methyl ethyl ketone and stirred for 1 hour to prepare a coupling agent liquid. An inorganic substrate (alumina) was immersed in the prepared coupling agent solution at room temperature for 5 seconds (dipping), and then dried in a drier at 110° C. for 10 minutes.

(2) Then, in the same manner as in sample 1, formation of a catalytic activity hindering layer, laser light irradiation, pretreatment for catalyst application, electroless plating catalyst application, and electroless plating were performed to produce sample 21. Electroless plating evaluation 1 was performed on the manufactured sample 21 in the same manner as the sample 1. Table 4 shows the results.

＊試料１８～２１のレーザー描画条件は、試料１と同様（レーザー光波長：３５５ｎｍ）
１）信越化学工業株式会社製、ｐ‐スチリルトリメトキシシラン
２）信越化学工業株式会社製、３‐メタクリロキシプロピルトリメトキシシラン
３）信越化学工業株式会社製、３‐グリシドキシプロピルトリエトキシシラン
４）味の素ファインテクノ製、チタネート系カップリング剤

* Laser drawing conditions for samples 18 to 21 are the same as for sample 1 (laser light wavelength: 355 nm)
1) p-styryltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd. 2) 3-methacryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd. 3) 3-glycidoxypropyltriethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd. 4) Ajinomoto Fine-Techno Co., Ltd. Titanate Coupling Agent

[Sample 22]
Sample 22 was produced in the same manner as Sample 1, except that a borosilicate glass watch glass (manufactured by Schott, DURAN, diameter 80 mm) was used as the inorganic substrate, and the laser drawing pattern was changed. In sample 22, a plated film was formed on the three-dimensional surface of the inorganic substrate.

(1) By the same method as sample 1, a silane coupling agent was applied and a catalytic activity hindering layer was formed.

(2) Laser Light Irradiation In Sample 22, since laser drawing is performed on the three-dimensional surface of the inorganic base material, three-dimensional drawing data is created by combining the plan view of the drawing pattern with the three-dimensional figure data of the inorganic base material. bottom. Laser drawing was performed on the inorganic base material using the created three-dimensional drawing data. The device and laser drawing conditions used for laser drawing are the same as those for Sample 1. Also, the plan view of the drawing pattern used for the sample 22 is the same as the drawing pattern for the sample 1. FIG.

(3) After that, pretreatment for catalyst application, electroless plating catalyst application, and electroless plating were performed in the same manner as for sample 1, and sample 22 was manufactured. Electroless plating evaluation 1 was performed on the manufactured sample 22 in the same manner as the sample 1. Table 5 shows the results.

[Sample 23]
An inorganic base material was produced by providing a smooth layer on an original base material, and Sample 23 (plated part) was produced using the produced inorganic base material.

(1) Production of Inorganic Substrate An alumina plate (manufactured by AS ONE Corporation) was prepared as a raw substrate. The surface roughness (Ra) of the current substrate was 1.12 μm.

Next, a smooth layer was formed on the alumina plate by the sol-gel method described below. First, 25 g of tetraethyl orthosilicate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise to 37.6 mL of ethanol and stirred. Furthermore, while stirring, 23.8 g of water and 0.3 g of acetic acid were added dropwise in order. After that, the mixture was stirred for 3 hours to obtain a tetraethyl orthosilicate solution. The original substrate was dipped in the prepared solution at room temperature for 5 seconds and then dried in a 110° C. dryer for 30 minutes. As a result, a smooth layer (SiO ₂ ) was formed on the surface of the raw substrate (alumina). The surface roughness (Ra) of the smooth layer surface (smooth surface) was 0.326 μm.

(2) Thereafter, a silane coupling agent was applied and a catalytic activity hindering layer was formed in the same manner as in Sample 1.

(3) Laser light irradiation Using a laser drawing device (manufactured by Keyence, MD-U1000C, YVO ₄ laser, wavelength 355 nm) on an inorganic substrate formed with a catalytic activity hindering layer, the laser intensity is 80% and the drawing speed is 150 mm / sec. , and a frequency of 40 kHz, laser drawing was performed by scanning once over a predetermined pattern. The drawn pattern is the same as that of Sample 1.

(4) After that, pretreatment for applying a catalyst, applying an electroless plating catalyst, and electroless plating were performed in the same manner as for sample 1, and sample 23 was manufactured. Electroless plating evaluation 1 was performed on the manufactured sample 23 in the same manner as the sample 1. Table 5 shows the results.

５）信越化学工業株式会社製、グリシドキシオクチルトリメトキシシラン、式（Ｓ）において、Ｙがグリシドキシ基（エポキシ基を含む基）、Ｒが炭素数８個のアルキレン基

5) Glycidoxyoctyltrimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd. In formula (S), Y is a glycidoxy group (group containing an epoxy group), and R is an alkylene group having 8 carbon atoms.

[Sample 24] to [Sample 27]
Samples 24 to 27 were prepared in the same manner as Sample 1, except that an alumina plate (manufactured by AS ONE Corporation) was used as the inorganic substrate, and the laser light irradiation conditions (laser drawing conditions) were changed as shown in Table 6. manufactured. The surface roughness (Ra) of the surface of the inorganic base material used for Samples 24 to 27 was 1.12 μm. Electroless plating evaluation 1 was performed on the manufactured samples 24 to 27 in the same manner as sample 1. Table 6 shows the results.

＊試料２４～２７に用いたシランカップリング剤：信越化学工業株式会社製、ＫＢＭ‐４８０３、グリシドキシオクチルトリメトキシシラン、式（Ｓ）において、Ｙがグリシドキシ基（エポキシ基を含む基）、Ｒが炭素数８個のアルキレン基

* Silane coupling agent used for samples 24 to 27: Shin-Etsu Chemical Co., Ltd., KBM-4803, glycidoxyoctyltrimethoxysilane, in formula (S), Y is a glycidoxy group (group containing an epoxy group), R is an alkylene group having 8 carbon atoms

[Sample 28] to [Sample 30]
Samples 28 to 30 were produced in the same manner as Sample 1 except that an alumina plate (manufactured by AS ONE Corporation) was used as the inorganic substrate and the type of silane coupling agent was changed to those shown in Table 7. The surface roughness (Ra) of the surface of the inorganic base material used for Samples 28-30 was 1.12 μm. The silane coupling agent used for Samples 28 to 30 is a silane coupling agent represented by formula (S). Electroless plating evaluation 1 was performed on the manufactured samples 28 to 30 in the same manner as sample 1. Table 7 shows the results.

[Sample 31]
A sample was prepared in the same manner as in Sample 1, except that an alumina plate (manufactured by AS ONE Co., Ltd.) was used as the inorganic substrate and a titanate-based coupling agent (Plenact 338X, manufactured by Ajinomoto Fine-Techno Co., Ltd.) was used as the coupling agent. 31 was produced. The surface roughness (Ra) of the inorganic substrate used for Sample 31 was 1.12 μm.

(1) Application of Coupling Agent A titanate-based coupling agent was applied to the inorganic substrate in the same manner as in Sample 21.

(2) After that, in the same manner as for sample 1, formation of a catalytic activity hindering layer, laser light irradiation, pretreatment for catalyst application, electroless plating catalyst application, and electroless plating were performed to produce sample 31. Electroless plating evaluation 1 was performed on the manufactured sample 31 in the same manner as the sample 1. Table 7 shows the results.

＊試料２８～３１のレーザー描画条件は、試料１と同様（レーザー光波長：３５５ｎｍ）
１）信越化学工業株式会社製、ｐ‐スチリルトリメトキシシラン
２）信越化学工業株式会社製、３‐メタクリロキシプロピルトリメトキシシラン
３）信越化学工業株式会社製、３‐グリシドキシプロピルトリエトキシシラン
４）味の素ファインテクノ製、チタネート系カップリング剤

* Laser drawing conditions for samples 28 to 31 are the same as for sample 1 (laser light wavelength: 355 nm)
1) p-styryltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd. 2) 3-methacryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd. 3) 3-glycidoxypropyltriethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd. 4) Ajinomoto Fine-Techno Co., Ltd. Titanate Coupling Agent

[Sample 32]
Sample 32 was produced in the same manner as Sample 1, except that no catalytic activity hindering layer was provided. Electroless plating evaluation 1 was performed on the manufactured sample 32 in the same manner as the sample 1. The evaluation result was unsatisfactory (evaluation result: Δ).

[Discussion on Samples 1 to 32]
As shown in Tables 1 to 5, Samples 1 to 23, in which the smooth surface of the substrate had a surface roughness of 1 μm or less, gave good results in evaluation 1 of electroless plating. That is, in samples 1 to 23, deposition of the electroless plated film was suppressed in areas other than the predetermined area, and the electroless plated film could be formed only in the predetermined area. In samples 1 to 23, the catalytic activity hindering layer is formed on a smooth surface with a small surface roughness (Ra), so even with a thin catalytic activity hindering layer, the substrate surface can be uniformly covered. , it is presumed that the deposition of the electroless plating film could be sufficiently suppressed. On the other hand, as shown in Tables 6 and 7, in samples 24 to 31 in which the surface roughness of the substrate surface exceeds 1 μm, the evaluation result 1 of electroless plating is poor, and plating is deposited on the entire surface of the substrate. It's gone. In Samples 24 to 31, since the surface roughness of the inorganic base material was large, it is presumed that the catalyst activity hindering layer had a defect that exposed the base material surface, and the electroless plating film was deposited on the defect.

In addition, Sample 32, in which no catalytic activity hindering layer was provided, gave a poor result in evaluation 1 of electroless plating. The reason for this is presumed as follows. In Sample 32, the surface of the inorganic base material to which the silane coupling agent was applied is hydrophobic, so it is not compatible with water-based plating catalyst liquids and plating liquids. Therefore, no electroless plating film was formed on the entire surface of the inorganic substrate. However, with only the silane coupling agent, it is difficult to sufficiently suppress the deposition of the electroless plating film, and it is partially found between and around the fine lines of the patterns 2 and 3, and also in other non-laser drawing areas. It is presumed that an electroless plated film was deposited on the surface (in an enclave).

Samples 1 to 7 having different laser drawing conditions and the same other conditions are compared. Samples 1 to 7 use glass substrates. As shown in Table 1, Samples 1 to 5 with laser light wavelengths of 200 nm to 380 nm (ultraviolet light, 355 nm) had higher laser-drawn portions than Samples 6 and 7 with laser light wavelengths outside the above range. The surface roughness was small. The reason for this is presumed to be that the hyperbranched polymer represented by the formula (1) absorbs light (for example, ultraviolet light) having a wavelength in the above range, whereas glass hardly absorbs it. In samples 1 to 5, the hyperbranched polymer layer (catalytic activity hindering layer) could be removed without significantly roughening the glass substrate.

Samples 18 to 21 having different types of coupling agents and having the same other conditions are compared. Samples 18 to 20 using the silane coupling agent gave better results in evaluation 1 of electroless plating than sample 21 using the titanate coupling agent.

[Evaluation of electroless plating 2]
Samples 1 and 10 having different types of silane coupling agents and having the same other conditions were evaluated as follows. The silane coupling agents used for samples 1 and 10 are both silane coupling agents represented by formula (S). In the silane coupling agent used in sample 1, R in formula (S) is an alkylene group having 8 carbon atoms, and in the silane coupling agent used in sample 10, R in formula (S) is a carbon number 3 alkylene groups.

<Preparation of evaluation sample>
In the process of manufacturing Samples 1 and 10, the inorganic substrate was allowed to stand at room temperature for one week with the catalytic activity hindering layer formed thereon. After the standing, laser light irradiation, pretreatment for catalyst application, electroless plating catalyst application, and electroless plating were performed to produce evaluation samples corresponding to samples 1 and 10, respectively.

<Evaluation method>
The plating film pattern formed on the surface of the evaluation sample was visually observed and evaluated based on the same evaluation criteria as evaluation 1 of electroless plating. Table 8 shows the results of evaluation 2 of electroless plating together with the results of evaluation 1 of electroless plating.

５）信越化学工業株式会社製、グリシドキシオクチルトリメトキシシラン
３）信越化学工業株式会社製、３‐グリシドキシプロピルトリエトキシシラン

5) Glycidoxyoctyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd. 3) 3-Glycidoxypropyltriethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.

As shown in Table 8, sample 1 had good results in both evaluations 1 and 2 of electroless plating (evaluation result: ◯). The silane coupling agent used in Sample 1 has a relatively long hydrocarbon chain (R in the formula (S)) connecting the structure that reacts with the inorganic material and the structure that reacts with the organic material. It is presumed that the strength of adhesion to the catalytic activity hindrance layer was increased and that it could be maintained for a long period of time.

On the other hand, in sample 10, an electroless plating film was deposited partially (in an enclave) between and around the fine lines of patterns 2 and 3, and also on other non-laser-drawn portions (evaluation result: Δ). The silane coupling agent used in sample 10 has a shorter R in formula (S) than sample 1. For this reason, in sample 10, the adhesion strength between the inorganic substrate and the catalytic activity hindering layer was slightly weaker than in sample 1, and it is presumed that sufficient adhesion strength could not be maintained as time passed after the formation of the catalytic activity hindering layer. be done.

[Sample 33]
Sample 33 was produced by removing the catalytically active impeding layer from the produced plated part. First, a plated part was manufactured in the same manner as for Sample 1. The manufactured plated parts were immersed in methyl ethyl ketone (cleaning liquid) and cleaned by applying ultrasonic waves for 15 minutes. This gave sample 33 from which the catalytic activity hindering layer was removed.

[Sample 34]
Sample 34 was produced by removing the catalytically active impeding layer from the produced plated part. A sample 34 was produced in the same manner as the sample 33, except that propylene glycol monomethyl ether was used as a cleaning liquid for removing the catalytic activity inhibitor.

[Evaluation of Samples 33 and 34]
contained in the hyperbranched polymer represented by formula (1) in samples 33 and 34 before and after removing the catalytic activity hindering layer by scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDX) Sulfur element was detected. As a result, in Samples 33 and 34, elemental sulfur detected before cleaning was not detected after cleaning. This confirmed that the hyperbranched polymer (catalytic activity hindering layer) was removed by washing.

According to the method of manufacturing a plated component of the present invention, deposition of an electroless plated film on an inorganic base material such as glass or ceramics can be suppressed in areas other than a predetermined area, and an electroless plated film can be formed only in a predetermined area. Electronic parts having high insulation and heat dissipation properties can be produced by the method for producing plated parts of the present invention.

Claims (8)

A method for manufacturing a plated component,
forming a catalytic activity hindering layer containing a catalyst deactivator on the smooth surface of an inorganic substrate having a smooth surface with a surface roughness (Ra) of 1 μm or less;
irradiating a portion of the catalytic activity hindering layer on the substrate with a laser beam;
Applying an electroless plating catalyst to the surface of the inorganic substrate irradiated with the laser beam;
bringing an electroless plating solution into contact with the surface of the inorganic substrate to which the electroless plating catalyst has been applied to form an electroless plating film on the region irradiated with the laser light ;
and applying a coupling agent onto the smooth surface of the inorganic substrate prior to forming the catalytically active impeding layer. 2. The plating according to claim 1, further comprising, after forming the electroless plating film, contacting the surface of the inorganic substrate with a solvent to remove the catalytic activity hindering layer from the surface of the inorganic substrate. How the parts are made. 3. The method of manufacturing a plated component according to claim 1, wherein the inorganic substrate has a smooth layer forming the smooth surface on its surface. The method for producing a plated component according to any one of claims 1 to 3 , wherein the coupling agent is a silane coupling agent containing an epoxy group, an acryloxy group, a methacryloxy group, or a styryl group. The method for manufacturing a plated part according to any one of claims 1 to 4 , wherein the catalyst deactivator is a polymer having at least one selected from the group consisting of an amide group, an amino group and a dithiocarbamate group. . The method for producing a plated part according to any one of claims 1 to 5 , wherein the catalyst deactivator is a hyperbranched polymer represented by the following formula (1).

In formula (1), A ¹ is a group containing an aromatic ring, A ² is a group containing an amide group, A ³ is a group containing sulfur, R ⁰ is hydrogen or has 1 to 10 carbon atoms is a substituted or unsubstituted hydrocarbon group, m1 is 0.5-11, and n1 is 5-100. The method for manufacturing a plated component according to any one of claims 1 to 6 , wherein the laser beam has a wavelength of 200 to 380 nm. The method for manufacturing a plated component according to any one of claims 1 to 7 , wherein the electroless plating film forms an electric circuit or an antenna pattern on the inorganic substrate.

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