JP6130332B2 - Manufacturing method of resin product with metal film - Google Patents

Description

  The present invention relates to a resin product with a metal film and a method for producing the same.

  A resin product provided with a metal film having a predetermined pattern is useful as, for example, a wiring board or a conductive film. As a method for producing such a resin product with a metal film, a method using electroless plating is known.

  For example, Patent Document 1 discloses a method for manufacturing a wiring board using surface modification by ultraviolet rays. Specifically, first, the surface of the cycloolefin polymer material is modified by irradiating the entire surface of the cycloolefin polymer material with ultraviolet rays from an ultraviolet lamp. An electroless plating film is likely to be deposited on the modified portion. Thereafter, a metal film is formed on the entire surface of the cycloolefin polymer material modified by performing electroless plating. Finally, photolithography and etching are performed to pattern the metal film so as to have a desired pattern.

  Patent Document 2 discloses a method of forming a metal thin film pattern on the surface of a polyimide resin substrate. Specifically, a resist pattern is formed on the surface of the polyimide resin substrate, and by performing alkali modification, addition of fine metal particles, and electroless plating on the exposed portion of the resist pattern opening, A metal thin film is formed in the opening of the resist pattern.

JP 2008-094923 A JP 2009-007613 A

  In order to form a metal film having a desired pattern by the method described in Patent Document 1, photolithography and etching are required. Also in the method described in Patent Document 2, it is necessary to form a resist pattern by photolithography. For this reason, the methods described in Patent Documents 1 and 2 are costly and have a problem of high environmental load due to the generation of a large amount of waste liquid.

  An object of the present invention is to form a metal film having a desired pattern on a resin product at low cost.

In order to achieve the object of the present invention, for example, the method for producing a resin product with a metal film of the present invention comprises the following constitution. That is,
An irradiation step for selectively irradiating a portion of the surface of the resin product having a resin having an ester bond, an amide bond, or an imide bond with which the metal film is not deposited on the surface , and modifying the surface.
By treating both the portion that does not deposit the modified metal film irradiated with the ultraviolet light and the portion that deposits the metal film not irradiated with ultraviolet light on the surface of the resin product with an alkaline solution. , A treatment step of modifying the portion on which the metal film is deposited while dropping off the modified portion irradiated with the ultraviolet rays ,
The metal modified in the treatment step in the surface of the resin product treated with the alkali solution by performing a catalyst application treatment on both the portion where the metal coating is deposited and the portion where the metal coating is not deposited. An application step of directly attaching an electroless plating catalyst to a portion where a film is deposited ;
A plating step of depositing a metal film on a portion of the surface of the resin product that is not selectively irradiated with ultraviolet rays by immersing the resin product provided with the electroless plating catalyst in an electroless plating solution;
It is characterized by including.

  A metal film having a desired pattern can be formed on a resin product at low cost.

The figure explaining the manufacturing method of the resin product with a metal film which concerns on one Embodiment. The flowchart of the manufacturing method of the resin product with a metal film which concerns on one Embodiment.

  The present inventor applies a technique described in Patent Document 1 to irradiate ultraviolet rays from an ultraviolet lamp only on a portion on which a metal film is to be formed on a resin product, so that a part of the surface of the resin product is obtained. Knew the technology to selectively reform. According to this technique, a metal film is selectively deposited on the portion irradiated with ultraviolet rays by electroless plating. Therefore, it is possible to form a metal film having a desired pattern at low cost without using photolithography or etching. However, the present inventor has found that when such a technique is used, an unnecessary metal film may be deposited on a portion not irradiated with ultraviolet rays depending on conditions such as the type of resin product to be used. It was.

  As a result of the study, the inventors surprisingly did not irradiate ultraviolet rays when applying an electroless plating catalyst and performing electroless plating after performing an alkali treatment on a resin product irradiated with ultraviolet rays. It has been found that a metal film is selectively deposited on the portion. On the other hand, no metal film was deposited on the portion irradiated with ultraviolet rays. In this way, it has become possible to form a metal film having a desired pattern at a low cost without using a photolithography process, an etching process, and the like.

  Hereinafter, embodiments to which the present invention can be applied will be described with reference to the drawings. However, the scope of the present invention is not limited to the following embodiments. The manufacturing method of the resin product 100 with a metal film which concerns on one Embodiment of this invention includes an irradiation process, a process process, an provision process, and a plating process. Hereinafter, each of these steps will be described with reference to FIGS.

(Irradiation process)
In the irradiation step (S210), ultraviolet rays are selectively irradiated to a portion 120 of the surface of the resin product 110. FIG. 1A shows a surface of the resin product 110, a portion 120 irradiated with ultraviolet rays, and a portion 140 not irradiated with ultraviolet rays. The portion 120 irradiated with ultraviolet rays is modified by the irradiation with ultraviolet rays.

  In one embodiment, the resin product 110 is irradiated with ultraviolet rays in an atmosphere containing oxygen or ozone. As a specific example, irradiation of the resin product 110 with ultraviolet rays can be performed in the atmosphere. In another embodiment, irradiation is performed in an atmosphere containing ozone in order to further promote the modification.

  For example, when ultraviolet rays are irradiated in an atmosphere containing oxygen, oxygen in the atmosphere is decomposed to generate ozone. Furthermore, active oxygen is generated in the process of decomposing ozone. Further, the bonds in the molecules constituting the resin are also broken on the resin surface. At this time, the molecule constituting the resin reacts with the active oxygen, and the resin surface is oxidized, that is, the C—O bond, the C═O bond, the C (═O) —O bond (the skeleton of the carboxyl group) on the resin surface. ) And the like are formed. In addition, with such oxidation, a fine rough surface is formed in the portion 120 irradiated with ultraviolet rays.

The energy of a photon with a specific wavelength can be expressed by the following equation.
E = Nhc / λ (KJ · mol ⁻¹ )
N = 6.022 × 10 ²³ mol ⁻¹ (Avocado number)
h = 6.626 × 10 ⁻³⁷ KJ · s (Planck constant)
c = 2.88 × 10 ⁸ m · s ⁻¹ (speed of light)
λ = wavelength of light (nm)

Here, the binding energy of the oxygen molecule is 490.4 KJ · mol ⁻¹ . From the photon energy formula, this binding energy is converted to the wavelength of light, which is about 243 nm. This indicates that oxygen molecules in the atmosphere absorb and decompose ultraviolet rays having a wavelength of 243 nm or less. As a result, ozone O ₃ is generated. Furthermore, active oxygen is generated in the process of decomposing ozone. At this time, if ultraviolet rays having a wavelength of 310 nm or less are present, ozone is efficiently decomposed and active oxygen is generated. Furthermore, ultraviolet light having a wavelength of 254 nm decomposes ozone most efficiently.
O ₂ + hν (243 nm or less) → O (3P) + O (3P)
O ₂ + O (3P) → O ₃ (ozone)
O ₃ + hν (310 nm or less) → O ₂ + O (1D) (active oxygen)
O (3P): Ground state oxygen atom O (1D): Excited oxygen atom (active oxygen)

  The ultraviolet irradiation method is not particularly limited, and for example, an ultraviolet lamp, an ultraviolet LED, or an ultraviolet laser can be used. In one embodiment, the resin product 110 is irradiated with ultraviolet rays from an ultraviolet lamp or the like through a quartz chrome mask or a metal mask on which a desired pattern is formed. In another embodiment, the portion 120 irradiated with ultraviolet rays is scanned using ultraviolet rays from an ultraviolet laser or the like.

  The wavelength of the ultraviolet light is not particularly limited, and one that promotes the modification of the surface of the resin product 110 is selected. In one embodiment, the wavelength of the ultraviolet light is 243 nm or less. When the wavelength is 243 nm or less, the modification of the surface of the resin product 110 is further promoted. Moreover, when the wavelength of ultraviolet rays is shorter than 243 nm, the surface of the resin product 110 can be modified according to a finer pattern.

The irradiation amount of ultraviolet rays is not particularly limited, and can be appropriately selected so that plating is selectively deposited on the portion 140 where ultraviolet rays are not irradiated. In one embodiment, integrated irradiation dose of ultraviolet rays of the main wavelength is at 400 mJ / cm ² or more, preferably 600 mJ / cm ² or more. Moreover, in one Embodiment, the integrated irradiation amount about a dominant wavelength is 2000 mJ / cm < ² > or less. In this specification, unless otherwise specified, the irradiation amount and irradiation intensity of ultraviolet rays refer to values at the dominant wavelength. In this specification, the dominant wavelength refers to a wavelength having the highest intensity in a region of 243 nm or less. Specifically, in the case of a low-pressure mercury lamp, the dominant wavelength is 185 nm.

  However, the plating deposition conditions depend on the type of plating solution, the type of resin product 110, the degree of contamination of the surface of the resin product 110, the concentration of the plating solution, temperature, pH, aging, and fluctuations in the output of an ultraviolet lamp, etc. It can change. In this case, the irradiation amount of ultraviolet rays may be appropriately determined with reference to the above-described numerical values.

  In the present embodiment, the surface of the resin product 110 includes a portion 120 that is irradiated with ultraviolet rays and a portion 140 that is not irradiated with ultraviolet rays. However, in one embodiment, the surface of the resin product 110 includes a portion irradiated with a certain amount or more of ultraviolet rays and a portion irradiated with less than a certain amount of ultraviolet rays or not irradiated with ultraviolet rays. In this embodiment, the portion irradiated with a certain amount or more of ultraviolet rays corresponds to the portion selectively irradiated with ultraviolet rays, and the portion irradiated with less than a certain amount of ultraviolet rays or not irradiated with ultraviolet rays is selectively selected. This corresponds to a portion not irradiated with ultraviolet rays. More ultraviolet rays are irradiated to the portion irradiated with a certain amount or more of ultraviolet rays so that the metal film 130 is not deposited in the plating step (S240) described later. On the other hand, only a smaller amount of ultraviolet rays is irradiated on the portion irradiated with less than a certain amount of ultraviolet rays so that the metal film 130 is deposited in the plating step (S240) described later. It is advantageous to irradiate the portion on which the metal film 130 is deposited with ultraviolet rays in that fine unevenness is generated on the surface of the resin product 110 and the adhesive force between the resin product 110 and the metal film 130 can be improved.

  The resin product 110 is not particularly limited as long as it has a resin material on the surface that can be selectively modified by a combination of the irradiation step (S210) and the treatment step (S220). In one embodiment, the resin product 110 has a resin material with low alkali resistance. The resin material having low alkali resistance refers to a resin material whose surface is modified by alkali treatment, that is, a bond between atoms is broken on the surface by alkali treatment. Examples of the resin material that is easily modified by alkali treatment include polyimide resin, polyamide resin, polycarbonate resin, acrylic resin, and polyester resin. In one embodiment, a resin material that generates a carboxyl group by hydrolysis, such as an ester bond, an amide bond, or an imide bond, is used. For example, when a polyimide resin is used as the resin material, when an alkali treatment is performed on the resin product 110, imide ring opening occurs, and a carboxyl group or a carboxyl ion may be generated on the surface of the resin product 110.

  The manufacturing method of this embodiment is particularly preferably used for the resin product 110 having a polyimide resin or a polyamide resin on the surface. Above all, polyimide resin is excellent in heat resistance and strength, so it can be soldered (including reflow) to the wiring board obtained by forming a metal film pattern on the polyimide resin substrate. It becomes.

  The shape of the resin product 110 is not particularly limited, and may be, for example, a substrate shape or a film shape. The resin product 110 may be composed of a plurality of resin materials, may have a laminated structure of a plurality of resin materials, or is obtained by coating the surface of another material with a resin material. It may be a composite material having a covering structure.

(Processing process)
In the treatment step (S220), the resin product 110 irradiated with ultraviolet rays is treated with an alkaline solution. The treatment method is not particularly limited, and examples thereof include a method of immersing the resin product 110 in an alkali treatment liquid, a method of applying the alkali treatment liquid to the resin product 110, and the like.

  In one embodiment, the alkali treatment is performed by immersing the resin product 110 in an alkali treatment liquid. As the alkali treatment liquid, for example, an aqueous solution of alkali metal hydroxide or alkaline earth metal hydroxide can be used. Specific examples of the alkali treatment liquid include an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution. After the alkali treatment, the resin product 110 may be washed with water or the like.

  As a result of the alkali treatment, the portion 120 of the resin product 110 that has been irradiated with ultraviolet rays is modified so that the metal film is not deposited in the plating step (S240). The reason is not clear, but it is considered that one of the reasons is that the portion 120 irradiated with ultraviolet rays is altered by alkali treatment. For example, since the surface of the portion 120 irradiated with ultraviolet rays is fragile due to the irradiation of ultraviolet rays, there is a possibility that the portion modified by the alkali treatment falls off. For this reason, it is considered that catalyst ions are less likely to adhere to the portion 120 irradiated with ultraviolet rays in the applying step (S230) described later. This is considered to be the reason why the metal film does not deposit on the portion 120 irradiated with ultraviolet rays.

  Further, the portion 140 of the resin product 110 that is not irradiated with ultraviolet rays is modified so that a metal film is deposited in the plating step (S240). This is thought to be because, due to the alkali treatment, a hydrophilic group is formed in the portion 140 that is not irradiated with ultraviolet rays, so that catalyst ions are likely to adhere to the portion 140 that is not irradiated with ultraviolet rays in the applying step (S230) described later. .

  The strength of the alkali treatment for the resin product 110 can be selected as appropriate so that the metal film does not deposit on the portion 120 irradiated with ultraviolet rays and the metal film precipitates on the portion 140 not irradiated with ultraviolet rays. Generally, in the portion 120 irradiated with ultraviolet rays, the stronger the alkali treatment, for example, the higher the concentration of the alkali treatment liquid and the longer the immersion time, the more difficult the metal film is to be deposited. In addition, the portion 140 that is not irradiated with ultraviolet rays also tends to be less liable to deposit a metal film as the alkali treatment becomes stronger. However, in order not to deposit the metal film, the portion 140 not irradiated with ultraviolet rays tends to require stronger alkali treatment than the portion 120 irradiated with ultraviolet rays.

  For example, when alkali treatment is performed on polyimide, a carboxyl group or a carboxyl ion is generated by hydrolysis. On the other hand, when the imide ring is completely hydrolyzed, the polymer chain is broken at that portion and the molecule is dropped. That is, it dissolves. That is, it is considered that both the generation of carboxyl groups or carboxyl ions and the disappearance of the carboxyl groups or carboxyl ions due to dropping occur during the alkali treatment. If the alkali treatment is strong, the drop-off speed is considered to be particularly fast.

  In one embodiment, the immersion time of the resin product 110 in the alkaline treatment liquid is 1 second or longer, preferably 5 seconds or longer, more preferably 20 seconds or longer. Moreover, in one Embodiment, immersion time is 300 second or less, Preferably it is 100 second or less, More preferably, it is 60 second or less.

  In one embodiment, the concentration of the alkali metal hydroxide contained in the alkali treatment liquid is 0.010 mol / L or more, preferably 0.10 mol / L or more, more preferably 0.30 mol / L or more. It is. Moreover, in one Embodiment, the density | concentration of the alkali metal hydroxide which an alkali treatment liquid contains is 10 mol / L or less, More preferably, it is 3.0 mol / L or less. Furthermore, in another embodiment, the pH of the alkaline treatment liquid is 12.0 or more, preferably 13.0 or more, and more preferably 13.5 or more.

(Granting process)
In the application step (S230), an electroless plating catalyst is applied to the surface of the resin product 110 treated with the alkaline solution. The application of the electroless plating catalyst can be performed according to a conventionally known method.

For example, an electroless plating catalyst can be provided by using the following two steps.
(Step 1) The resin product 110 is immersed in a solution containing catalyst ions. In one embodiment, electroless plating catalyst ions having a positive charge are used as the catalyst ions. The electroless plating catalyst ions having a positive charge are considered to be easily adsorbed on the surface of the resin product 110 when, for example, a carboxyl group or the like is formed on the surface of the resin product 110 by alkali treatment. As described above, when the resin product 110 is immersed in a solution containing catalyst ions, the catalyst ions are less likely to adhere to the portion 120 of the resin product 110 that has been irradiated with ultraviolet rays, and the portion 140 that is not irradiated with ultraviolet rays has catalytic ions. It is thought that is likely to adhere.

(Step 2) The catalyst ions are reduced by immersing the resin product in a solution containing a reducing agent. Thus, the catalyst is precipitated. Since catalyst ions easily adhere to the portion 140 of the resin product 110 that is not irradiated with ultraviolet rays, as a result of the reduction, the portion 140 that is not irradiated with ultraviolet rays is given more catalyst than the portion 120 that is irradiated with ultraviolet rays. It is thought that. As the reducing agent, those conventionally used can be employed, and for example, hydrogen gas, dimethylamine borane, sodium borohydride, and the like can be used as listed in International Publication No. 2007/066460. .

  As an example of the electroless plating catalyst ion having a positive charge, a metal complex having an amine-based ligand, particularly a metal complex having a basic amino acid as a ligand can be used. An example is a basic amino acid complex of palladium. The basic amino acid complex of palladium is a complex of palladium ion and basic amino acid. The palladium ion is not limited, but divalent palladium ions are often used. The basic amino acid may be a natural amino acid or an artificial amino acid. In one embodiment, the amino acid is an α-amino acid. Examples of basic amino acids include amino acids having a basic substituent such as an amino group or a guanidyl group in the side chain. Examples of basic amino acids include lysine, arginine, ornithine and the like.

As examples of the basic amino acid complex of palladium, those listed in International Publication No. 2007/066460 can be used. Specific examples of the basic amino acid complex of palladium include those represented by the following formula (I).

In the above formula (I), L ₁ and L ₂ each independently represent an alkylene group having 1 to 10 carbon atoms, and R ₃ and R ₄ each independently represent an amino group or a guanidyl group. Examples of the alkylene group having 1 to 10 carbon atoms include linear alkylene groups such as a methylene group, 1,2-ethanediyl group, 1,3-propanediyl group, and n-butane-1,4-diyl group. . In the above formula (II), the two amino groups are coordinated at the trans position, but the two amino groups may be coordinated at the cis position. The basic amino acid complex of palladium may be a mixture of a cis isomer and a trans isomer. Also, other metal atoms that act as an electroless plating catalyst may be used instead of palladium.

(Plating process)
In the plating step (S240), the resin product 110 provided with the electroless plating catalyst is immersed in the electroless plating solution. As a result, as shown in FIG. 1B, the metal film 130 is deposited on the portion 140 of the surface of the resin product 110 that is not irradiated with ultraviolet rays. As described above, it is considered that more catalyst is applied to the portion 140 that is not irradiated with ultraviolet light compared to the portion 120 that is irradiated with ultraviolet light. For this reason, it is considered that the metal film 130 is selectively deposited on the portion 140 not irradiated with ultraviolet rays. Further, as described above, the metal film 130 can be prevented from being deposited on the portion 120 irradiated with ultraviolet rays by appropriately performing the irradiation step (S210), the processing step (S220), and the applying step (S230).

  The specific method of electroless plating is not particularly limited. Examples of electroless plating that can be used include electroless plating using a formalin-based electroless plating bath, and electroless plating using hypophosphorous acid, which does not require formalin and has a slow deposition rate, as a reducing agent. It is done. Further, in order to form a thicker plating film, the metal film 130 may be formed by a high-speed electroless plating method. Further specific examples of electroless plating include electroless nickel plating, electroless copper plating, and electroless copper nickel plating.

  Electroless plating according to such a method can be performed using an electroless plating solution set such as a Cu-Ni plating solution set “AISL” manufactured by JCU.

  Since the metal film formed by electroless plating in this way is often thin, the thickness of the metal film may be increased by further performing electroplating. The material of the metal layer provided by electrolytic plating is not limited, but examples include copper, nickel, copper-nickel alloy, zinc oxide, zinc, silver, cadmium, iron, cobalt, chromium, nickel- Examples thereof include a chromium alloy, tin, tin-lead alloy, tin-silver alloy, tin-bismuth alloy, tin-copper alloy, gold, platinum, rhodium, palladium, or palladium-nickel alloy. Further, silver or the like may be deposited on the metal film 130 by displacement plating.

  According to the method of the present embodiment, by selectively irradiating the portion of the resin product 110 where the metal film is not formed with ultraviolet rays, the resin product with a metal film 100 on which the metal film is selectively formed is obtained. be able to. According to this embodiment, since a metal film having a desired pattern can be formed without using photolithography and etching, the number of steps necessary for producing the resin product 100 with a metal film can be reduced. That is, the cost can be reduced.

[Example 1-1]
As the resin product 110, a polyimide plate (manufactured by Toray DuPont, Kapton EN200, thickness 50 μm) was used.

First, the portion 120 on the resin product 110 where the metal film was not formed was irradiated with ultraviolet rays through a photomask in the atmosphere. The ultraviolet irradiation conditions were as follows.
Low-pressure mercury lamp: Samco UV-300 (main wavelength: 185 nm, 254 nm)
Irradiation distance: 3.5cm
Illuminance at an irradiation distance of 3.5 cm: 5.40 mW / cm ² (254 nm)
1.35 mW / cm ² (185 nm)
Irradiation time: 10 minutes

  Next, the alkali treatment was performed on the resin product 110 irradiated with ultraviolet rays. Specifically, the resin product 110 was immersed for 5 seconds by heating to 50 ° C. using an alkali treatment solution (pH 13.58: measured value) used in a Cu—Ni plating solution set “AISL” manufactured by JCU. Then, the resin product 110 was stirred and washed in pure water at 50 ° C. for 1 minute.

  Next, a catalyst ion application treatment was performed on the resin product 110 after the alkali treatment. Specifically, the resin product 110 was immersed for 2 minutes at 50 ° C. using an activator solution containing a palladium (II) basic amino acid complex (manufactured by JCU Corporation, product name ELFSEED ES-300). Thereafter, the resin product 110 was washed by reciprocating three times in 25 ° C. pure water.

  Next, the reduction treatment was performed on the resin product 110 after the alkali cleaning. Specifically, the resin product 110 was immersed for 2 minutes at 35 ° C. using an accelerator liquid (manufactured by JCU Corporation, product name ELFSEED ES-400). Thereafter, the resin product 110 was washed by reciprocating three times in pure water at 25 ° C., and the resin product 110 was dried using a dryer.

  Next, electroless copper nickel plating was performed on the resin product 110 after the reduction treatment. Specifically, the electroless Cu—Ni plating solution used in the Cu—Ni plating solution set “AISL” manufactured by JCU was used, and the resin product 110 was immersed for 5 minutes by heating to 60 ° C. Thereafter, the resin product 110 was washed by reciprocating three times in 25 ° C. pure water. Thus, the resin product 100 with a metal film was produced.

  In the obtained resin product 100 with a metal coating, the metal coating was not deposited on the portion 120 irradiated with ultraviolet rays, while the metal coating was deposited on the portion 140 not irradiated with ultraviolet rays.

[Example 1-2]
In the alkali treatment, a resin product 100 with a metal film was produced in the same manner as in Example 1-1 except that the resin product 110 was immersed in an alkali treatment solution for 10 seconds. In the obtained resin product 100 with a metal coating, the metal coating was not deposited on the portion 120 irradiated with ultraviolet rays, while the metal coating was deposited on the portion 140 not irradiated with ultraviolet rays.

[Example 1-3]
In the alkali treatment, a resin product 100 with a metal film was produced in the same manner as in Example 1-1 except that the resin product 110 was immersed in an alkali treatment solution for 20 seconds. In the obtained resin product 100 with a metal coating, the metal coating was not deposited on the portion 120 irradiated with ultraviolet rays, while the metal coating was deposited on the portion 140 not irradiated with ultraviolet rays.

[Example 1-4]
In the alkali treatment, a resin product 100 with a metal film was produced in the same manner as in Example 1-1 except that the resin product 110 was immersed in an alkali treatment solution for 60 seconds. In the obtained resin product 100 with a metal coating, the metal coating was not deposited on the portion 120 irradiated with ultraviolet rays. About the part 140 which was not irradiated with an ultraviolet-ray, although the metal membrane | film | coat precipitated mostly, the part which the metal membrane | film | coat did not precipitate was seen in part.

[Example 1-5]
In the alkali treatment, a resin product 100 with a metal film was produced in the same manner as in Example 1-1 except that the resin product 110 was immersed in an alkali treatment solution for 120 seconds. In the obtained resin product 100 with a metal coating, the metal coating was not deposited on the portion 120 irradiated with ultraviolet rays. About the part 140 which was not irradiated with an ultraviolet-ray, although the metal membrane | film | coat precipitated mostly, the part which the metal membrane | film | coat did not precipitate was seen in part. The part where the metal film was not deposited was larger than Example 1-4.

[Example 1-6]
A resin product 100 with a metal film was produced in the same manner as in Example 1-1 except that the alkali treatment was not performed. In the obtained resin product 100 with a metal film, although the metal film was sparsely deposited on the portion 120 irradiated with ultraviolet rays, the surface of the resin product 110 was exposed in most parts.

[Example 2-1]
Except for the following points, a resin product 100 with a metal film was produced in the same manner as in Example 1-1. That is, in the catalyst ion application treatment, an activator solution having a concentration three times that of Example 1-1 was used. Further, in the catalyst ion application treatment, the resin product 110 was immersed in an activator solution for 5 minutes. In the reduction treatment, the resin product 110 was immersed in the accelerator liquid for 4 minutes. Thus, it experimented on the conditions with which an electroless-plating catalyst is easy to be provided on the resin product 110 rather than Example 1-1.

  In the obtained resin product 100 with a metal coating, the metal coating was deposited on most of the portion 120 irradiated with ultraviolet rays. Moreover, the metal film was deposited also in the part 140 where the ultraviolet rays were not irradiated.

[Example 2-2]
In the alkali treatment, a resin product 100 with a metal film was produced in the same manner as in Example 2-1, except that the resin product 110 was immersed in an alkali treatment solution for 10 seconds. In the obtained resin product 100 with a metal coating, the metal coating was deposited on most of the portion 120 irradiated with ultraviolet rays. Further, a metal film was deposited on the portion 140 not irradiated with ultraviolet rays.

[Example 2-3]
In the alkali treatment, a resin product 100 with a metal film was produced in the same manner as in Example 2-1, except that the resin product 110 was immersed in an alkali treatment solution for 20 seconds. In the obtained resin product 100 with a metal film, almost no metal film was deposited on the portion 120 irradiated with ultraviolet rays, while a metal film was deposited on the portion 140 not irradiated with ultraviolet rays.

[Example 2-4]
In the alkali treatment, a resin product 100 with a metal film was produced in the same manner as in Example 2-1, except that the resin product 110 was immersed in an alkali treatment solution for 60 seconds. In the obtained resin product 100 with a metal coating, the metal coating was not deposited on the portion 120 irradiated with ultraviolet rays, while the metal coating was deposited on the portion 140 not irradiated with ultraviolet rays.

[Example 2-5]
In the alkali treatment, a resin product 100 with a metal film was produced in the same manner as in Example 2-1, except that the resin product 110 was immersed in an alkali treatment solution for 120 seconds. In the obtained resin product 100 with a metal coating, the metal coating was not deposited on the portion 120 irradiated with ultraviolet rays. On the other hand, about the part 140 which was not irradiated with the ultraviolet ray, the metal film was mostly deposited, but the part where the metal film was not partially deposited was seen.

[Example 2-6]
In the alkali treatment, a resin product 100 with a metal film was produced in the same manner as in Example 2-1, except that the resin product 110 was immersed in an alkali treatment solution for 180 seconds. In the obtained resin product 100 with a metal coating, the metal coating was not deposited on the portion 120 irradiated with ultraviolet rays. On the other hand, about the part 140 which was not irradiated with the ultraviolet ray, the metal film was mostly deposited, but the part where the metal film was not partially deposited was seen. The portion where the metal film was not deposited was larger than Example 2-5.

[Example 2-7]
In the alkali treatment, a resin product 100 with a metal film was produced in the same manner as in Example 2-1, except that the resin product 110 was immersed in an alkali treatment solution for 240 seconds. In the obtained resin product 100 with a metal coating, the metal coating was not deposited on the portion 120 irradiated with ultraviolet rays. On the other hand, as for the portion 140 not irradiated with ultraviolet rays, a portion where a metal film was deposited and a portion where no metal film was deposited were observed. The portion where the metal film was not deposited was larger than Example 2-6.

[Example 2-8]
A resin product 100 with a metal film was produced in the same manner as in Example 2-1, except that the alkali treatment was not performed. In the obtained resin product 100 with a metal film, although the metal film was sparsely deposited on the portion 120 irradiated with ultraviolet rays, the surface of the resin product 110 was exposed in most parts.

  As described above, it was found that by performing alkali treatment after ultraviolet irradiation, electroless plating can be performed so that the metal film is deposited on the portion 140 not irradiated with ultraviolet light. On the other hand, it was found that electroless plating can be performed so that a metal film does not deposit on the portion 120 irradiated with ultraviolet rays by performing an alkali treatment under appropriate conditions.

  In addition, if the alkali treatment time is short, the metal film tends to be deposited on the portion 120 irradiated with ultraviolet rays, and if the alkali treatment time is long, the metal film tends to be difficult to deposit on the portion 140 not irradiated with ultraviolet rays. I understood. Furthermore, it was found that the ease of deposition of the metal film also depends on the conditions of the catalyst ion application treatment and the reduction treatment. However, referring to the above results, by appropriately adjusting the strength of the alkali treatment (for example, the treatment time or the concentration of the alkali solution), the portion 140 that has not been irradiated with ultraviolet rays under any conditions is selectively used. It is considered possible to deposit a metal film.

DESCRIPTION OF SYMBOLS 100 Resin product with metal coating 110 Resin product 120 Part 130 irradiated with ultraviolet rays Metal coating 140 Part not irradiated with ultraviolet rays S210 Irradiation step S220 Processing step S230 Application step S240 Plating step

Claims (8)

An irradiation step for selectively irradiating a portion of the surface of the resin product having a resin having an ester bond, an amide bond, or an imide bond with which the metal film is not deposited on the surface , and modifying the surface.
By treating both the portion that does not deposit the modified metal film irradiated with the ultraviolet light and the portion that deposits the metal film not irradiated with ultraviolet light on the surface of the resin product with an alkaline solution. , A treatment step of modifying the portion on which the metal film is deposited while dropping off the modified portion irradiated with the ultraviolet rays ,
The metal modified in the treatment step in the surface of the resin product treated with the alkali solution by performing a catalyst application treatment on both the portion where the metal coating is deposited and the portion where the metal coating is not deposited. An application step of directly attaching an electroless plating catalyst to a portion where a film is deposited ;
A plating step of depositing a metal film on a portion of the surface of the resin product that is not selectively irradiated with ultraviolet rays by immersing the resin product provided with the electroless plating catalyst in an electroless plating solution;
A method for producing a resin product with a metal film, comprising: The method for producing a resin product with a metal film according to claim 1 , wherein in the irradiation step, the ultraviolet ray is irradiated in the atmosphere. Wherein in the irradiation process, characterized by oxidizing a portion of the surface by oxygen, producing method of metallic coating with a resin product according to claim 1 or 2. In the said provision process, the said resin product is processed with the solution of the electroless-plating catalyst ion which has a positive charge, The manufacture of the resin product with a metal film of any one of the Claims 1 thru | or 3 characterized by the above-mentioned. Method. The method for producing a resin product with a metal film according to any one of claims 1 to 4 , wherein the pH of the alkaline solution is 12.0 or more. The method for producing a resin product with a metal film according to any one of claims 1 to 5 , wherein the alkali solution is an alkali metal hydroxide solution. The method for producing a resin product with a metal film according to any one of claims 1 to 6 , wherein in the treatment step, the resin product is immersed in the alkaline solution for 1 second or more and 100 seconds or less. . The method for producing a resin product with a metal film according to any one of claims 1 to 7 , wherein the surface of the resin product contains a polyimide resin or a polyamide resin.

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