WO2016092584A1

WO2016092584A1 - Resin product with plating film, and method for producing resin product and method for producing resin product with plating film

Info

Publication number: WO2016092584A1
Application number: PCT/JP2014/006113
Authority: WO
Inventors: 太輔岩下
Original assignee: キヤノン・コンポーネンツ株式会社
Priority date: 2014-12-08
Filing date: 2014-12-08
Publication date: 2016-06-16
Also published as: JP5856354B1; JPWO2016092584A1

Abstract

A method for modifying a resin product, on which a plating film is to be deposited, within a short period of time, said method comprising a first modification step for irradiating the resin product with ultraviolet rays having a main wavelength of less than 184 nm to thereby modify the surface, and a second modification step for further modifying the surface of the resin product having been irradiated with the ultraviolet rays as described above.

Description

Resin product with plating film, resin product, and method for producing resin product with plating film

The present invention relates to a resin product with a plating film, a resin product, and a method for producing a resin product with a plating film.

The resin product with a plating film provided with a functional film having a predetermined pattern provided on the resin product is particularly useful as a wiring board or a conductive film. Therefore, a method of providing a conductive wire having a predetermined pattern on a resin product has been studied. For example, Patent Document 1 describes a method for manufacturing a printed wiring board using surface modification by ultraviolet rays. Specifically, first, surface modification necessary for electroless plating is performed by irradiating the entire surface of the cycloolefin polymer material, which is a resin product, with ultraviolet rays from a low-pressure mercury lamp. And the plating film is formed by performing electroless plating on the surface of the modified resin product, and this is used as the material of the printed wiring board. By processing the obtained plating film so as to have a predetermined pattern using a photolithography process and an etching process, a conductive line having a predetermined pattern can be provided.

JP 2008-094923 A

In the method described in Patent Document 1, ultraviolet rays from a low-pressure mercury lamp are irradiated for 10 to 45 minutes in order to modify a resin product. For this reason, in order to improve production efficiency, a method capable of modifying a resin product in a shorter time has been demanded.

The object of the present invention is to modify the surface of a resin product in a short time so that a plating film is deposited.

In order to achieve the object of the present invention, for example, a method for producing a resin product of the present invention comprises the following arrangement. That is,
A method for producing a resin product modified so that a plating film is deposited on the surface by plating,
A first modification step of modifying the surface by irradiating the resin product with ultraviolet light having a dominant wavelength of less than 184 nm;
A second modification step of modifying the surface by further modifying the resin product irradiated with the ultraviolet rays;
It is characterized by having.

The surface of the resin product can be modified in a short time so that the plating film is deposited.

Other features and advantages of the present invention will become apparent from the following description with reference to the accompanying drawings. In the accompanying drawings, the same or similar components are denoted by the same reference numerals.

The accompanying drawings are included in the specification, constitute a part thereof, show an embodiment of the present invention, and are used to explain the principle of the present invention together with the description.
The figure explaining the manufacturing method of the resin product with a plating film which concerns on one Embodiment. The figure explaining the manufacturing method of the resin product with a plating film which concerns on one Embodiment. The figure explaining the manufacturing method of the resin product with a plating film which concerns on one Embodiment. The figure explaining the manufacturing method of the resin product with a plating film which concerns on one Embodiment. The flowchart of the manufacturing method of the resin product with a plating film which concerns on one Embodiment. The figure which shows an example of the irradiation method of the ultraviolet-ray in a 1st modification | reformation process. The figure which shows an example of the quartz chromium mask used at a 1st modification | reformation process.

The present inventor studied to irradiate ultraviolet rays with higher energy and shorter wavelengths instead of ultraviolet rays (main wavelength: 254 nm) from a low-pressure mercury lamp for the purpose of modifying the resin product in a short time. . However, it has been found that even when electroless plating is performed after irradiating a resin product with ultraviolet rays having a short wavelength, the plating film may not be sufficiently deposited.

As a result of various studies, the inventor irradiates a resin product with short-wavelength ultraviolet light, and then additionally irradiates longer-wavelength ultraviolet light in a shorter time than when using only long-wavelength ultraviolet light, The present inventors have found that resin products can be sufficiently modified. Based on such knowledge, the present inventor has completed the invention.

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 method for manufacturing a resin product with a plating film according to an embodiment of the present invention includes a first modification step, a second modification step, and a plating step. In particular, a resin product modified so that a plating film is deposited on the surface by electroless plating is produced by the first modification step and the second modification step. Hereinafter, each of these steps will be described with reference to FIGS. 1A to 1D and FIG.

(First modification step)
In the first modification step (S210), the surface is modified by irradiating the resin product with ultraviolet rays having a dominant wavelength of less than 184 nm. For example, by irradiating the resin product 110 shown in FIG. 1A with ultraviolet rays as shown in FIG. 1B, the modified portion 120 is formed in the portion irradiated with the ultraviolet rays.

In one embodiment, the resin product 110 is irradiated with ultraviolet rays in an atmosphere containing at least one of oxygen and 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 an ultraviolet ray having a specific wavelength or less capable of decomposing oxygen is irradiated in an atmosphere containing oxygen, the oxygen in the atmosphere is decomposed to generate ozone. Furthermore, active oxygen is generated in the process of decomposing ozone.

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)

Simultaneously, the bonds in the molecules constituting the resin on the resin surface are also broken by the short wavelength ultraviolet rays. At this time, the molecule constituting the resin reacts with active oxygen, and the resin surface is oxidized, that is, the resin surface has a C—O bond, a C═O bond, a C (═O) —O bond (the skeleton of the carboxyl group ) And the like are formed. Such a hydrophilic group increases the chemical adsorption between the resin product 110 and the plating film 140. In addition, since the portion embrittled by the oxidation of the surface of the resin product 110 is removed by, for example, alkali treatment or the like, a fine rough surface is formed. Will increase. Furthermore, catalyst ions can be selectively adsorbed in the modified portion when electroless plating is performed. Thus, it is considered that the plating film 140 by electroless plating is likely to be deposited on the surface of the resin product 110 modified by ultraviolet rays.

According to the method of modifying the surface of the resin product 110 using ultraviolet rays as in the present embodiment, fine irregularities on the order of nanometers are formed on the surface of the resin product 110. In one embodiment, the arithmetic average roughness Ra of the resin product surface is 10 nm or less. The unevenness formed in this way is much smaller than the unevenness of micrometer order obtained by, for example, irradiating the surface of a resin product with a higher-intensity visible laser, or formed by treatment with chromic acid or the like. It is expected. Thus, the plating film 140 deposited on a relatively smooth surface is considered to have a smooth surface as well. When such a smooth plating film 140 is used as a wiring, the loss of a high frequency signal can be suppressed. In this specification, the arithmetic average roughness Ra is defined by JIS B0601: 2001.

However, it is also possible to irradiate ultraviolet rays in other gas atmospheres such as an amine compound gas atmosphere such as ammonia or an amide compound gas atmosphere. By irradiation in an amine compound gas atmosphere or an amide compound gas atmosphere, the surface of the resin product 110 can be oxidized, that is, a bond containing nitrogen atoms can be generated on the surface of the resin product 110.

The resin product 110 used in the present embodiment is not particularly limited as long as it has a resin material that can be modified by ultraviolet rays on the surface. Examples of the resin material include cycloolefin polymers or polyolefins such as polystyrene, polyesters such as polyethylene terephthalate, polyvinyls such as polyvinyl chloride, and polycarbonates.

In this embodiment, it is assumed that the resin product 110 is a flat substrate. However, the resin product 110 may have an arbitrary three-dimensional shape. Moreover, it is not necessary that the resin product is composed only of resin. That is, in one embodiment, the resin product 110 is a composite material having a coating structure obtained by coating the surface of another material with a resin material. A specific example of the composite material includes a metal material whose surface is coated with a resin material. The shape of the metal material is not particularly limited, and may be a substrate shape or a more complicated three-dimensional shape. In one embodiment, the resin product 110 has a smooth surface. Since the resin product 110 has a smoother surface, a more uniform plating film 140 is formed by plating.

In one embodiment, the ultraviolet rays are applied to the entire surface of the resin product 110. However, in the present embodiment, as shown in FIG. 1B, ultraviolet rays are irradiated to a part of the surface of the resin product 110. In such an embodiment, the modified portion 120 is selectively formed on a part of the surface of the resin product 110. In a plating process described later, a plating film 140 is formed on the modified portion 120. That is, by selectively irradiating a part of the surface of the resin product 110 with ultraviolet rays, a plating film can be selectively deposited on a part of the surface of the resin product 110. According to such a configuration, the plating film 140 having a desired pattern can be formed without patterning the plating film by photolithography or the like.

On the other hand, as described later, it is not necessary to modify the resin product 110 so that the plating film 140 is deposited on the modified portion 120 only in the first modifying step. It is sufficient if the plating film 140 is deposited on the modified portion 120 after being modified in both the first modification step and the second modification step. For example, by using two or more appropriate reforming steps, it is possible to reduce the required reforming time and improve productivity compared to the case of using one reforming step.

The method used for selectively irradiating a part of the surface of the resin product 110 with ultraviolet rays is not particularly limited. In one embodiment, the irradiation range of ultraviolet rays is limited using a photomask. That is, by irradiating the resin product 110 with ultraviolet rays through a photomask having an ultraviolet transmissive portion and an ultraviolet non-transmissive portion, the modified portion 120 corresponding to the shape of the ultraviolet transmissive portion is formed.

In the present embodiment, ultraviolet light having a dominant wavelength of less than 184 nm is irradiated. Ultraviolet light having a dominant wavelength of less than 184 nm has higher energy than ultraviolet light having a larger dominant wavelength, such as ultraviolet light from a low-pressure mercury lamp. Therefore, the time required for the modification of the resin product 110 can be reduced. In one embodiment, ultraviolet light having a dominant wavelength of 172 nm or less is irradiated. 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 300 nm or less. Specifically, in the case of a low-pressure mercury lamp, the dominant wavelength is 254 nm.

In one embodiment, ultraviolet rays from an ultraviolet lamp or an ultraviolet LED are irradiated. An example of the ultraviolet lamp is an excimer lamp. For example, an Xe ₂ excimer lamp that emits ultraviolet light having a dominant wavelength of 172 nm is known. Quasi-monochromatic light is obtained from the excimer lamp, and visible light and infrared light are relatively small. For this reason, the use of an excimer lamp can suppress the heat generation of the substrate during irradiation. In addition, the excimer lamp has a characteristic that it can be turned on instantaneously as compared with, for example, a low-pressure mercury lamp. For this reason, when irradiating ultraviolet rays while conveying the resin product 110 on the belt conveyor, the ultraviolet rays are irradiated only when the resin product 110 reaches the irradiation position, and the ultraviolet rays are emitted while the resin product 110 is not at the irradiation position. It is possible to control the excimer lamp so as not to irradiate. In this way, it is possible to save energy and extend the life of the excimer lamp.

An example of an ultraviolet irradiation device will be described with reference to FIG. In the example of FIG. 3, ultraviolet light from the excimer lamp 310 is irradiated to the resin product 110 through the quartz chrome mask 320. The quartz chrome mask 320 is disposed so as to be in contact with the planar irradiation surface of the excimer lamp 310, and the resin product 110 is also disposed so as to be in contact with the quartz chrome mask 320. In the example of FIG. 3, the quartz chrome mask 320 and the resin product 110 are fixed using the holding glass 330. As described above, according to the configuration in which the photomask and the resin product 110 are brought into contact with the irradiation surface of the ultraviolet lamp or the ultraviolet LED, the irradiation is performed even when ultraviolet rays having a dominant wavelength of less than 184 nm are used. Can be carried out in the atmosphere. On the other hand, since the ultraviolet rays leaking from the resin product 110 are easily absorbed in the atmosphere, the influence on the human body can be suppressed. From this point of view, in one embodiment, quasi-monochromatic light such as ultraviolet light from an excimer lamp is used, in which most of the wavelengths that are easily absorbed in the atmosphere are used.

The ultraviolet irradiation time in the first modification step is not particularly limited as long as the resin product 110 can be modified so that the plating film 140 is deposited. For example, in one embodiment, the irradiation time of ultraviolet rays is 6 seconds or more. Moreover, in order to suppress the heat generation of the substrate, in one embodiment, the irradiation time of ultraviolet rays is 60 seconds or less. The irradiation amount of ultraviolet rays is not particularly limited as long as the resin product 110 can be modified so that the plating film 140 is deposited. For example, in one embodiment, the irradiation amount of ultraviolet rays is 100 mJ / cm ² or more. Moreover, in one Embodiment, the irradiation amount of an ultraviolet-ray is 2000 mJ / cm < ² > or less. The energy density of the irradiated ultraviolet rays is not particularly limited as long as the modification proceeds, and may be, for example, 1.0 × 10 ⁻³ W / cm ² or more, or 1.0 × 10 ² W / cm 2. ^It may be ² or less.

However, the deposition conditions for plating may vary depending on the type of plating solution, the type of substrate, the degree of contamination of the substrate surface, the concentration of the plating solution, temperature, pH, aging, fluctuations in the output of the ultraviolet lamp, and the like. In this case, the irradiation amount from the ultraviolet lamp may be appropriately determined so that the plating is selectively deposited on the modified portion 120 with reference to the above numerical values. The irradiation amount of ultraviolet rays can be controlled by changing the irradiation time. The amount of ultraviolet irradiation can also be controlled by changing the output, number, or irradiation distance of the ultraviolet lamp.

When the ultraviolet rays are irradiated for a long time, the temperature of the resin product 110 and the quartz chrome mask 320 may increase. For this reason, due to the difference in thermal expansion coefficient between the resin product 110 and the quartz chrome mask 320, the portion irradiated with the ultraviolet rays may be shifted during the irradiation of the ultraviolet rays. For example, when the ultraviolet ray from a low-pressure mercury lamp is irradiated for about 10 minutes as in the prior art, the temperature of the substrate rises from room temperature to about 50 ° C. In this case, it is conceivable that it is difficult to obtain a plating film 140 having a precise pattern. Therefore, in one embodiment, the irradiation time of the ultraviolet rays is selected so that the temperature rise of the resin product 110 and the quartz chrome mask 320 becomes sufficiently small. For example, the temperature rise of the resin product 110 due to ultraviolet irradiation is 10 ° C. or less in one embodiment, 5 ° C. or less in another embodiment, and 2 ° C. or less in a further embodiment. When irradiating ultraviolet rays with large energy as in this embodiment, the irradiation time of ultraviolet rays in the first modification step may be short, and for this reason, the temperature of the substrate can be increased without cooling the substrate. Can be suppressed.

(Second modification step)
As described above, the resin product 110 may not be sufficiently modified so that the plating film 140 is deposited by electroless plating only by irradiating ultraviolet rays having a dominant wavelength of less than 184 nm. Although the detailed reason is not clear, when the present inventor irradiates ultraviolet rays having a short wavelength (the main wavelength is less than 184 nm), the resin molecule breaks up smoothly, but the subsequent oxidation reaction does not proceed. It is estimated that one of the reasons is that it does not proceed smoothly. Actually, when the XPS spectrum of the surface of the resin product 110 after the modification by ultraviolet rays is compared, the resin product 110 is oxidized until there are many carboxyl groups on the surface of the resin product 110 in the irradiation of the low-pressure mercury lamp. It was confirmed. On the other hand, in the irradiation of the Xe ₂ excimer lamp, it was confirmed that many hydroxyl groups were generated on the surface of the resin product 110, but not so many carboxyl groups were generated. Furthermore, as this reason, it is also conceivable that the carboxyl group is decomposed by the high energy of the short wavelength ultraviolet rays. In any case, when the number of carboxy groups is small, it is conceivable that the catalyst ions selectively adsorbed on the carboxyl groups are difficult to be adsorbed.

Thus, in the present embodiment, the resin product 110 is subjected to the second modification step in addition to the first modification step. In the second modification step (S220), a modification process is performed on the resin product 110. That is, the second modification process is further performed on the resin product 110 irradiated with ultraviolet rays in the first modification step.

In the second reforming process according to the present embodiment, the reforming process is performed on a region including a portion irradiated with ultraviolet rays in the first reforming process. Thus, as shown in FIG. 1C, the modified portion 120 generated in the first modification step is sufficiently modified so that the plating film 140 is deposited in the plating step (S230). In one embodiment, the modification process is performed only on the portion irradiated with ultraviolet rays in the first modification step. However, in another embodiment, the reforming process is performed on a wider area including the portion irradiated with ultraviolet rays in the first reforming step. When such a configuration is used, it is not essential to limit the modification range using, for example, a mask or the like in the second modification process.

FIG. 1C shows an example in which the second reforming process is performed on the entire surface of the resin product 110. As shown in FIG. 1C, the reforming unit 120 is further reformed by the second reforming process, while the reforming unit 130 is also generated in a portion that has not been irradiated with ultraviolet rays in the first reforming process. However, the reforming unit 120 is reformed in the first reforming process and the second reforming process, whereas the reforming unit 130 is reformed only in the second reforming process. For this reason, by appropriately selecting the reforming conditions and the electroless plating conditions, the plating film 140 can be deposited only on the reforming part 120 without depositing the plating film 140 on the reforming part 130.

The modification treatment refers to treatment for modifying the surface of the resin product 110 so that a plating film is easily deposited by electroless plating, and specific examples include oxidation treatment. Specific examples of the oxidation treatment include photoexcitation ashing treatment, plasma ashing treatment, oxidation treatment using chemicals, and oxidation treatment by ultraviolet irradiation. Below, the method using the ultraviolet-ray which can be performed simply is demonstrated. Specifically, the resin product 110 is further modified by irradiating with ultraviolet rays in the same atmosphere as in the irradiation step. In one embodiment, irradiation with ultraviolet rays is performed in an atmosphere containing at least one of oxygen and ozone.

In the second modification step according to one embodiment, the surface of the resin product 110 is modified by irradiating with ultraviolet rays having a dominant wavelength of 184 nm or more. Irradiation with ultraviolet rays having a dominant wavelength of 184 nm or more further promotes modification of the resin product surface. Such ultraviolet rays can be irradiated using an ultraviolet lamp or an ultraviolet LED that continuously emits ultraviolet rays. Specific examples include a low-pressure mercury lamp and an excimer lamp. The low-pressure mercury lamp can irradiate ultraviolet rays having wavelengths of 185 nm and 254 nm. The KrBr excimer lamp can irradiate ultraviolet rays having a wavelength of 206 nm, and the KrCl excimer lamp can irradiate ultraviolet rays having a wavelength of 222 nm.

The energy density of the irradiated ultraviolet rays is not particularly limited as long as the modification proceeds, and may be, for example, 1.0 × 10 ⁻³ W / cm ² or more, or 1.0 × 10 ² W / cm 2. ^It may be ² or less.
It's okay.

The irradiation time and irradiation amount of ultraviolet rays in the second modification step can modify the resin product 110 so that the plating film 140 is deposited on the reforming part 120 and the plating film 140 is not deposited on the reforming part 130. If it is, it will not be restrict | limited in particular. For example, in one embodiment, the irradiation time of ultraviolet rays is 1 minute or longer. Moreover, in one Embodiment, the irradiation time of an ultraviolet-ray is 5 minutes or less. Moreover, in one Embodiment, the irradiation amount of an ultraviolet-ray is 100 mJ / cm < ² > or more. Moreover, in one Embodiment, the irradiation amount of an ultraviolet-ray is 1500 mJ / cm < ² > or less. The energy density of the irradiated ultraviolet rays is not particularly limited as long as the modification proceeds, and may be, for example, 1.0 × 10 ⁻³ W / cm ² or more, or 1.0 × 10 ² W / cm 2. ^It may be ² or less. However, as described above with respect to the first reforming step, the deposition conditions of the plating can change, so that the irradiation amount from the ultraviolet lamp is selected so that the plating is selectively deposited on the reforming portion 120 with reference to the above numerical values. Can be appropriately determined.

In the present embodiment, the reforming unit 120 has already been modified to some extent by using high-energy ultraviolet rays in the first reforming step. Therefore, the ultraviolet irradiation time in the second modification step may be shorter than the conventional case in which the first modification step is not used. In addition, since ultraviolet rays having high energy are used in the first modification step, the sum of the irradiation time of ultraviolet rays in the first modification step and the irradiation time of ultraviolet rays in the second modification step in the present embodiment. However, it can be made shorter than the conventional case in which the first reforming step is not used. When ultraviolet rays having a wavelength of less than 184 nm, for example, ultraviolet rays having a wavelength of 172 nm, are used in the first modification step, the surface is rapidly oxidized and modified in a short time by high energy due to ultraviolet rays having a short wavelength. Then, by performing the second reforming step, the surface is sufficiently reformed so that the catalyst ions are easily adsorbed. At this time, the time required for sufficient surface modification is shorter when the first modification step and the second modification step are combined than when the second modification step is used alone. be able to. From the viewpoint of shortening the irradiation time and improving production efficiency, the sum of the ultraviolet irradiation time in the first reforming step and the ultraviolet irradiation time in the second reforming step is 8 in one embodiment. Minutes or less, in another embodiment 5 minutes or less, and in further embodiments 3 minutes or less.

As described above, it is not essential to limit the modification range using, for example, a mask or the like in the second modification step. Therefore, the ultraviolet irradiation time in the second modification step is long, and even if the resin product 110 is heated, the shape of the obtained plating film 140 is not significantly affected. On the other hand, as described above, in the first modification step, the plating film 140 having a precise pattern can be obtained by limiting the irradiation time of ultraviolet rays. From such a viewpoint, in one embodiment, the ultraviolet irradiation time in the first modification step is shorter than the ultraviolet irradiation time in the second modification step.

(Plating process)
In the plating step (S230), as shown in FIG. 1D, electroless plating is performed on the resin product 110 whose surface has been modified in the first modification step and the second modification step. Specifically, the modified portion 120 irradiated with ultraviolet rays in the first modification step is modified so that the plating film 140 is deposited by the first modification step and the second modification step. . On the other hand, the modified portion 130 that has not been modified in the first reforming process has been reformed to such an extent that the plating film 140 is deposited, although the modification in the second reforming process has been performed. Not. Therefore, when electroless plating is performed on the resin product 110, the plating film 140 is deposited on the modified portion 120, but the plating film 140 is not deposited on the modified portion 130. Thus, for example, even when the entire resin product 110 is immersed in the electroless plating solution, the plating film 140 is selectively deposited on the desired modified portion 120.

Thus, in one embodiment, when plating is performed on the resin product 110 modified in the first modification step and the second modification step, a part of the surface of the resin product 110, for example, a modified portion. 120, a plating film 140 is deposited. On the other hand, the plating film 140 is not deposited in a region adjacent to this part, for example, the modified portion 130. Therefore, it is not essential to pattern the plating film 140 by a method such as photolithography and etching after the plating film 140 is formed.

The specific electroless plating method is not particularly limited. Examples of electroless plating methods that can be used include an electroless plating method using a formalin-based electroless plating bath and an electroless plating method using hypophosphorous acid as a reducing agent, which is slow in deposition but easy to handle. It is done. Further specific examples of the electroless plating method include electroless nickel plating, electroless copper plating, electroless copper nickel plating, and electroless zinc oxide plating. Thus, the plating film 140 formed by electroless plating can be a metal film. By modifying the resin product 110 as described above, the adhesion between the modified portion 120 and the deposited plating film 140 is improved.

In one embodiment, electroless plating can be performed by the following method.
1. (Alkali treatment) The resin product 110 is immersed in an alkali solution, degreased, and hydrophilicity is improved. Examples of the alkaline solution include an aqueous sodium hydroxide solution.
2. (Conditioner treatment) The resin product 110 is immersed in a solution containing a binder of the resin product 110 and catalyst ions. Examples of the binder include a cationic polymer.
3. (Activator treatment) The resin product 110 is immersed in a solution containing catalyst ions. Examples of the catalyst ion include a palladium complex such as an acidic palladium complex hydrochloride.
4). (Accelerator treatment) The resin product 110 is immersed in a solution containing a reducing agent to reduce and precipitate catalyst ions. Examples of the reducing agent include hydrogen gas, dimethylamine borane and sodium borohydride.
5. (Electroless plating treatment) A plating film 140 is deposited on the deposited catalyst.

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

In another embodiment, a palladium complex that easily adheres to the reforming unit 120 and has a positive charge at least partially is used as the catalyst ion. In an embodiment, a solution containing a palladium complex ion having a positive charge in the solution is used so that adhesion to the reforming unit 120 is improved. An example of a palladium complex having a positive charge at least partially includes a complex in which an amine-based ligand is coordinated. Another example of a palladium complex having a positive charge at least in part is a basic amino acid complex of palladium.

In this case, it is not essential to increase the affinity between the resin product 110 and the catalyst ions by performing a conditioner treatment on the resin product 110. 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.

Further, it is advantageous to use a palladium complex having a positive charge at least in part as the catalyst ion in that the plating film 140 is likely to be selectively deposited on the modified portion 120. It has been found that a palladium complex ion having a positive charge at least partially is particularly selectively adsorbed to a carboxyl group among hydroxyl groups, carbonyl groups and carboxyl groups, which are typical hydrophilic groups. That is, when such a catalyst is used, the plating film 140 is less likely to be deposited on a portion where the plating film 140 is not provided, for example, on the modified portion 130. On the other hand, if the carboxyl group is not sufficiently formed in the modification step, it is considered that palladium complex ions having a positive charge at least partially are not easily adsorbed on the surface, and the deposition of plating becomes insufficient. In addition, the use of a palladium complex having a positive charge at least in part as the catalyst ion is advantageous in that it can improve the productivity by omitting the conditioner treatment step.

Examples of the basic amino acid complex of palladium include those described in International Publication No. 2007/066460. Specific examples 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 methylene group, 1,2-ethanediyl group, 1,3-propanediyl group, and n-butane-1,4-diyl group. . In the above formula (I), 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.

Examples of the electroless plating kit using such a basic amino acid complex of palladium include ELFSEED (manufactured by JCU).

In another embodiment, the plating film 140 can be formed by a high-speed electroless plating method. According to the high speed electroless plating method, a thicker plating film can be formed. In a further embodiment, plating is further deposited on the plating film 140 formed by electroless plating using an electrolytic plating method. According to this method, a thicker plating film 140 can be formed. The specific method of electroplating is not specifically limited.

There is no particular limitation on the thickness of the plating film 140 to be obtained. A plating film 140 having an appropriate thickness is formed according to the intended use of the resin product 100 with a plating film. Further, the material of the plating film 140 is not particularly limited. An appropriate material is selected according to the use of the obtained resin product 100 with a plating film.

Thus, the resin product 100 with a plating film obtained in this way can be used for various uses, such as a wiring board or a electrically conductive film, for example. In particular, in an embodiment in which an ultraviolet lamp or an ultraviolet LED is used in the first modification step and the second modification step, the surface of the resin product 110 is considered to be relatively flat even after the modification. . Therefore, the resin product 100 with a plating film produced in this way is expected to be excellent in high-frequency characteristics since the interface between the resin product 110 and the plating film 140 is relatively flat.

[Example 1]
As the resin product 110, a cycloolefin polymer material (manufactured by Zeon Corporation, ZEONOR film ZF-16, film thickness 100 μm, surface roughness 1.01 nm) was used.

First, the surface of the resin product 110 was modified using an excimer lamp. As the excimer lamp, a Xe ₂ plane excimer lamp (manufactured by Quark Technology Co., Ltd., QEF160, wavelength 172 nm) was used. Specifically, as shown in FIG. 3, the resin product 110 is disposed on the planar irradiation surface of the excimer lamp 310 through the quartz chrome mask 320 in the atmosphere. The resin product 110 was fixed by the holding glass 330. In this state, the resin product 110 was irradiated with ultraviolet rays from the excimer lamp 310 through the quartz chrome mask 320 for 10 seconds. The intensity of the ultraviolet rays from the excimer lamp 310 measured through the quartz chrome mask 320 was 30 mW / cm ² . Moreover, when the change of the surface temperature of the resin product 110 before and after irradiating with ultraviolet rays for 10 seconds was measured three times, the average rise temperature was 0.5 ° C.

As shown in FIG. 4, the quartz chrome mask 320 had an ultraviolet opaque part 321 formed with a chromium film and an ultraviolet transparent part 322 where a chromium film was not formed. Therefore, a part of the surface of the resin product 110 was modified according to the shape of the ultraviolet transmitting part 322, and the modified part 120 corresponding to the shape of the ultraviolet transmitting part 322 was generated. Further, the quartz chrome mask 320 has a plurality of band-like ultraviolet transmitting portions 322, and each ultraviolet transmitting portion has a width of about 50 μm to 100 μm.

Next, the surface of the resin product 110 was further modified by an oxidation treatment using a low-pressure mercury lamp. Specifically, ultraviolet rays from a low-pressure mercury lamp (manufactured by Samco Corporation, UV-300, peak wavelengths of 185 nm and 254 nm) are applied to the entire surface of the resin product 110 on which the modified portion 120 is formed. Irradiated for 2 minutes 30 seconds. At this time, a mask for limiting the irradiation range of ultraviolet rays from the low-pressure mercury lamp was not used. The illuminance of the low-pressure mercury lamp at an irradiation distance of 3.5 cm was 5.40 mW / cm ² (254 nm) and 1.35 mW / cm ² (185 nm). Thus, the reforming part 120 was further reformed, and the reforming part 130 was also formed in the part not irradiated with the ultraviolet rays from the excimer lamp.

(Plating process)
Next, electroless plating was performed on the modified resin product 110. The electroless plating treatment included an alkali treatment step, an activator treatment step, an accelerator treatment step, and an electroless plating step.

In the alkali treatment step, the resin product 110 was treated with an alkali solution. Specifically, a treatment solution was prepared using EC-B and AISL-ATM contained in a plating solution set “AISL” manufactured by JCU, heated to 50 ° C., and the resin product 110 was immersed for 2 minutes. Thereafter, the resin product 110 was washed with water.

In the activator treatment step, the catalyst product was treated with a catalyst ion solution to give catalyst ions to the surface of the resin product 110. Specifically, a treatment solution was prepared using an activator solution ES-300 included in a plating solution set “ELFSEED” manufactured by JCU, and the resin product 110 was immersed for 5 minutes by heating to 50 ° C. Thereafter, the resin product 110 was washed with water.

In the accelerator treatment step, the catalyst product applied to the surface of the resin product 110 was reduced by treating the resin product 110 with a reducing agent. Thus, the catalyst was deposited on the surface of the resin product 110. Specifically, a treatment solution was prepared using an accelerator solution ES-400 included in a plating solution set “ELFSEED” manufactured by JCU, heated to 35 ° C., and immersed in the resin product 110 for 4 minutes. Thereafter, the resin product 110 was washed with water.

In the electroless plating step, the plating film 140 was deposited on the resin product 110 by immersing the resin product 110 in an electroless copper nickel plating solution. Specifically, an electroless copper nickel plating solution was prepared using a plating solution set “AISL” manufactured by JCU, and the resin product 110 was immersed for 5 minutes by heating to 60 ° C. Thereafter, the resin product 110 was washed with water. By this treatment, the resin product 100 with a plating film in which the plating film 140 is formed on the resin product 110 was obtained.

When the obtained resin product 110 was observed, the plating film 140 was uniformly deposited on the modified portion 120 irradiated with ultraviolet rays from the excimer lamp. That is, a strip-shaped plating film 140 having a width of about 50 μm to 100 μm was formed on the resin product 110. On the other hand, the plating film 140 was not deposited on the modified portion 130 that was not irradiated with ultraviolet rays from the excimer lamp.

[Example 2]
A resin product 100 with a plating film was produced in the same manner as in Example 1 except that the irradiation time of the ultraviolet rays from the excimer lamp was 15 seconds, 20 seconds, 25 seconds, 30 seconds, 35 seconds, and 40 seconds. In each case, the plating film 140 was uniformly deposited on the modified portion 120 irradiated with the ultraviolet rays from the excimer lamp. On the other hand, the plating film 140 was not deposited on the modified portion 130 that was not irradiated with ultraviolet rays from the excimer lamp.

[Example 3]
A resin product 100 with a plating film was produced in the same manner as in Example 1 except that the irradiation time of ultraviolet rays from the excimer lamp was set to 5 seconds. Although the plating film 140 was deposited on the modified portion 120 irradiated with ultraviolet rays from the excimer lamp, a portion with a small amount of deposition was also observed. On the other hand, the plating film 140 was not deposited on the modified portion 130 that was not irradiated with ultraviolet rays from the excimer lamp.

[Example 4]
A resin product 100 with a plating film was produced in the same manner as in Example 1 except that ultraviolet rays from a low-pressure mercury lamp were not irradiated. The plating film 140 was hardly deposited on the modified portion 120 irradiated with the ultraviolet rays from the excimer lamp.

[Example 5]
A resin product 100 with a plating film was produced in the same manner as in Example 1 except that the excimer lamp was not used and only the ultraviolet rays from the low-pressure mercury lamp were used for modification. At this time, in order to deposit the plating film 140, it was necessary to irradiate ultraviolet rays from a low-pressure mercury lamp for about 10 minutes.

The present invention is not limited to the above embodiment, and various changes and modifications can be made without departing from the spirit and scope of the present invention. Therefore, in order to make the scope of the present invention public, the following claims are attached.

DESCRIPTION OF SYMBOLS 100 Resin product with plating film 110 Resin product 140 Plating film S210 1st modification process S220 2nd modification process S230 Plating process 310 Excimer lamp

Claims

A method for producing a resin product modified so that a plating film is deposited on the surface by plating,
A first modification step of modifying the surface by irradiating the resin product with ultraviolet light having a dominant wavelength of less than 184 nm;
A second modification step of modifying the surface by further modifying the resin product irradiated with the ultraviolet rays;
A method for producing a resin product, comprising:
The method for producing a resin product according to claim 1, wherein in the first reforming step, ultraviolet rays are irradiated using an excimer lamp.
3. The method for producing a resin product according to claim 1, wherein in the second modification step, the surface of the resin product is modified by irradiating an ultraviolet ray having a dominant wavelength of 184 nm or more. 4. .
The method for producing a resin product according to claim 1 or 2, wherein, in the second modification step, the surface of the resin product is modified by irradiating with ultraviolet rays using a low-pressure mercury lamp.
The method for producing a resin product according to claim 3 or 4, wherein the ultraviolet irradiation time in the first modification step is shorter than the ultraviolet irradiation time in the second modification step.
6. The method according to claim 1, wherein the first reforming step and the second reforming step are performed in an atmosphere including at least one of oxygen and ozone. Manufacturing method of resin products.
The resin product production according to any one of claims 1 to 6, wherein in the first reforming step, the resin product is irradiated with ultraviolet rays so that an increase in temperature of the resin product is 10 ° C or less. Method.
In the first modification step, a part of the surface of the resin product is irradiated with ultraviolet rays,
8. The modification process according to claim 1, wherein in the second modification step, a modification process is performed on a region including a part of the surface of the resin product and wider than the part. Of resin products.
The plating film is deposited on a part of the surface of the resin product when the resin product is plated, and the plating film is not deposited on a region adjacent to the part. The manufacturing method of the resin product of any one of thru | or 8.
A modification step for producing a resin product modified according to the method for producing a resin product according to any one of claims 1 to 9,
A plating step of performing electroless plating on the resin product produced in the modification step;
The manufacturing method of the resin product with a plating film characterized by having.
The method for producing a resin product with a plating film according to claim 10, wherein in the plating step, a palladium complex having a positive charge at least partially is used as an electroless plating catalyst.
The method for producing a resin product with a plating film according to claim 10, wherein a basic amino acid complex of palladium is used as an electroless plating catalyst in the plating step.
A resin product with a plating film produced by the method according to any one of claims 10 to 12.
A resin product provided with a modified portion formed on the surface by irradiation with ultraviolet light having a dominant wavelength of less than 184 nm and further modification;
A plating film provided on the modified portion;
A resin product with a plating film, comprising: