JP7167569B2 - Resin molded product with metal film - Google Patents

Description

TECHNICAL FIELD The present invention relates to a metal film-coated resin molded product in which a metal film is formed on the surface of a resin molded product made of a polycarbonate resin composition, and to a method for producing the metal film-coated resin molded product.
In the present invention, the term "metal film" refers not only to a film made of a single metal, but also to a wide range of metal films including alloy films made of two or more kinds of metals.

2. Description of the Related Art In recent years, with the rapid development of IT-oriented society, the speed of processing in electronic devices has increased, and the operating frequencies of ICs such as LSIs and microprocessors have increased. For example, in the field of communication, high-speed communication networks using optical fibers are used, 2 GHz in next-generation multimedia mobile communication; 5.8 GHz in ETS (Automatic Toll Collection System) in the field of ITS (Intelligent Transport System); An electromagnetic wave with a frequency of 76 GHz is used in an automobile-mounted radar of a driving support road system (AHS) for transmitting information to a driver, and it is expected that the range of use of high-frequency electromagnetic waves will further expand in the future. As the frequency of electromagnetic waves rises, it is easy to emit noise. On the other hand, malfunctions occur due to the deterioration of the noise environment inside electronic devices due to the miniaturization and high density of electronic devices. Adverse effects on the human body have also become a problem.

Conventionally, metal materials have been generally used as electromagnetic wave shielding materials (electromagnetic wave shielding materials) for preventing such electromagnetic waves, but in recent years, instead of metal materials with high specific gravity, A metal film formed by electroplating is widely used.

When forming a metal plating film on the surface of a resin molded product, electroless plating is performed prior to electroplating.
That is, since the resin is a non-conductive material, hexavalent chromic acid etching is performed as a pretreatment to form unevenness on the surface of the resin molded product, thereby enhancing the physical adhesion to the metal plating film and also seeding the resin. As a layer formation, a palladium catalyst is applied to activate the catalyst, followed by electroless plating.

However, hexavalent chromic acid, which is used in the etching process, has a large impact on the environment and is subject to regulation. Moreover, palladium used for the seed layer is a rare metal, which leads to an increase in cost.
Moreover, these processes require a large number of treatment tanks for water washing, neutralization, etc., and there are also problems such as the number of facilities and the treatment of waste liquids. I don't like it either. For this reason, it is desired to form a metal film as a base of an electrolytic plated film by a dry process instead of electroless plating.

Under such circumstances, the present applicant has proposed a method for forming a metal film with excellent adhesion on the surface of an insulating material such as resin by dry processing. A patent application has been filed for a method of forming a seed layer on the surface of a body and then electroplating (Japanese Patent Application No. 2018-97358).

On the other hand, polycarbonate resin is an engineering plastic that has been widely used in fields such as electrical equipment parts, mechanical parts, and automobile parts in recent years due to its excellent transparency, heat resistance, mechanical strength, and impact resistance. Therefore, in order to apply such a polycarbonate resin to an electromagnetic wave shielding material or the like, development of a method for forming a metal film by dry treatment on the surface of a polycarbonate resin molded product is desired. Furthermore, the development of a method for forming a metal film by dry treatment on the surface of a transparent polycarbonate resin molded product is desired.

Patent application 2018-97358

An object of the present invention is to provide a resin molded product with a metal film, in which a metal film with excellent adhesion is formed on the surface of a polycarbonate resin molded product by dry treatment instead of electroless plating, and a method for producing the same.

The metal film-coated resin molded article of the present invention is a metal film-coated resin molded article having a metal film on the surface of the molded article made of a polycarbonate resin composition containing a polycarbonate resin (A), wherein the polycarbonate resin (A) terminal hydroxyl group concentration is 50 ppm or more, and the metal film has a peel strength of 2.0 N / cm or more measured according to JIS H8630: 2006 Annex 1 (normative) adhesion test method .

The total amount of dihydroxy compounds represented by the following general formulas (1) to (5) measured after hydrolysis of the polycarbonate resin (A) used in the present invention is 100 ppm or more with respect to the entire polycarbonate resin (A). Preferably.

(R ¹ to R ⁶ each independently represent a hydrogen atom or a methyl group.)

Further, the total light transmittance of the polycarbonate resin composition according to the present invention measured at a thickness of 3 mm is preferably 50% or more.

In the method for producing a metal film-coated resin molded product of the present invention, the surface of a polycarbonate resin molded product is plasma-treated in a vacuum atmosphere, and then a metal film is formed on the plasma-treated surface by sputtering. It is characterized by manufacturing a resin molded product.

According to the present invention, it is possible to provide a metal-film-attached resin molded product in which a metal film having excellent adhesion is formed on the surface of a polycarbonate resin molded product by dry treatment instead of electroless plating.

BEST MODE FOR CARRYING OUT THE INVENTION Below, embodiments of the present invention will be described in detail.

[Resin molded product with metal film]
The metal film-coated resin molded article of the present invention is a metal film-coated resin molded article having a metal film on the surface of the molded article made of a polycarbonate resin composition containing a polycarbonate resin (A), wherein the polycarbonate resin (A) terminal hydroxyl group concentration is 50 ppm or more, and the metal film has a peel strength of 2.0 N / cm or more measured according to JIS H8630: 2006 Annex 1 (normative) adhesion test method .
Although the method for producing the metal film-coated resin molded article of the present invention is not limited, the present invention comprises plasma-treating the surface of a polycarbonate resin molded article in a vacuum atmosphere, and then forming a metal film on the plasma-treated surface by sputtering. It can be produced by the method for producing a resin molded product with a metal film according to the invention. Note that heat treatment may be performed prior to this plasma treatment.

Hereinafter, the polycarbonate resin composition used in the present invention may be referred to as the "polycarbonate resin composition of the present invention", and the molded article made of such a polycarbonate resin composition of the present invention may be referred to as the "molded article of the present invention". be. The component composition, manufacturing method and molding method of the polycarbonate resin composition of the present invention will be described later.

The metal film-coated resin molded product of the present invention will be described below according to the method for producing the metal film-coated resin molded product of the present invention.

[Heating process]
In the present invention, a heating step of heating the molded article of the present invention may be performed prior to the plasma step described later. By performing the heating step, moisture and gas volatilize from the molded article of the present invention in the plasma step. can be prevented, and a metal film having better adhesion can be formed.

The heating temperature in the heating step is lower than the softening temperature of the resin constituting the molded article of the present invention, and the moisture and gas are released in advance from the molded article of the present invention to prevent volatilization of these components in the plasma process. The temperature may be any temperature that allows the temperature to rise, and in the case of molded articles made of the polycarbonate resin composition of the present invention, it is usually 80 to 200°C, preferably 80 to 120°C. The heating time varies depending on the heating temperature, but if it is too short, the effect of the heating step cannot be sufficiently obtained, and if it is too long, the productivity will be impaired. About 3 hours is preferable.
_The atmosphere and pressure of the heating process are not particularly limited, and the ^heating process may be performed under atmospheric pressure. In some cases, the same effect as heating under normal pressure can be obtained by lowering the heating temperature and shortening the heating time.

After performing such a heating step, it is preferable to move to the next plasma step immediately, for example, within 0 to 30 minutes so that volatilized components such as moisture are not absorbed again by the molded article of the present invention.

[Plasma process]
The plasma process generates reactive functional groups on the surface of the molded product of the present invention, thereby enhancing bonding with metal atoms and improving adhesion with the metal film formed by subsequent sputtering. This is the activation treatment step.

This plasma process is preferably carried out under vacuum conditions using a hollow cathode electrode. In particular, the plasma process is preferably carried out by continuous treatment under vacuum conditions with the sputtering process, which will be described later, using the apparatus described in the aforementioned Japanese Patent Application No. 2018-97358.
Further, in order to more efficiently generate reactive functional groups on the surface of the molded article of the present invention by plasma treatment, as described later, the terminal hydroxyl group concentration of the polycarbonate resin (A) used in the polycarbonate resin composition of the present invention is , is preferably 50 ppm or more, and the total amount of dihydroxy compounds represented by the following general formulas (1) to (5) measured after hydrolysis of the polycarbonate resin (A) is the polycarbonate resin ( A) It is preferable that it is 100 ppm or more with respect to the whole.

Plasma processing using a hollow cathode electrode enables radical discharge with a high electron density (on the order of 10 ¹¹ cm ⁻³ ), so that it is possible to reduce temperature damage due to high temperatures on the object to be processed. In addition, plasma CVD using _O2 , which requires high energy for dissociation, becomes possible, stabilizing the discharge to enhance the _O2 treatment effect, and efficiently forming reactive functional groups on the surface of the molded article of the present invention. By forming it, the adhesion of the metal film formed by sputtering in the later stage can be further enhanced.
In particular, by continuously performing the plasma process and the later-described sputtering process under a vacuum atmosphere, the molded article of the present invention can be subjected to sputtering film formation without exposing it to the atmosphere after the plasma treatment. It is possible to stabilize the treated surface by preventing deterioration of the plasma-treated surface of the molded product.

Plasma CVD treatment is carried out by placing a plasma generation source, preferably a hollow cathode electrode and a counter electrode integrated with a gap therebetween, and the molded article of the present invention in a pressure chamber. The molded product of the present invention is placed at a position separated from the hollow cathode electrode so that the treated surface and the hollow cathode electrode face each other, the pressure in the chamber is reduced, and the hollow cathode electrode and the counter electrode of the plasma generation source are separated. It can be performed by supplying a reaction gas during and applying a voltage to the plasma generation source.

The reason why the temperature damage of the molded article of the present invention can be reduced by doing so is as follows.
That is, although the plasma is at a high temperature when it is emitted from the plasma source, it loses thermal energy during drift in the chamber due to collisions with the reaction gas present in the chamber. The temperature of the plasma is lowered when it reaches the molded article of the present invention, which is the arranged object to be processed.
In addition, part of the plasma changes from the plasma (charged state) to the activated state (radical state) due to the collision with the reaction gas or the like. Therefore, the molded article of the present invention is exposed not only to the plasma of the reactive gas but also to the reactive gas in an activated state (radical state). In this specification, the reactive gas in the plasma state and the reactive gas in the activated state (radical state) are referred to as highly reactive reactive gases. Activation of the surface of the molded article of the present invention, which is an object to be treated, with a plasma-state reaction gas and a radical-state reaction gas is called plasma treatment.

Thus, the effect that the temperature of the plasma decreases when reaching the molded article of the present invention, which is the object to be processed, and the reaction gas in a radical state also reaches the molded article of the present invention can be obtained from the hollow cathode electrode. This is because it is provided at a position away from the opposite electrode. In other words, in the plasma generation source, the molding of the present invention sandwiches the hollow cathode electrode such that the distance between the hollow cathode electrode and the molded product of the present invention is set longer than the distance between the hollow cathode electrode and the counter electrode. It is designed so that the article and the counter electrode are arranged.

As described above, the distance between the plasma generation source and the molded product of the present invention, which is the object to be processed, may reduce the concentration of the highly reactive reaction gas reaching the molded product of the present invention.
However, by reducing the pressure in the chamber in which the plasma generation source and the molded product of the present invention are provided to create a vacuum atmosphere, the plasma generated by the plasma generation source collides with gas molecules (reactant gas molecules) more than necessary. It is possible to prevent the concentration of the highly reactive reaction gas from decreasing.

In the present invention, the plasma treatment is preferably performed under the following procedures and conditions.

That is, first, a reaction gas having a first pressure P1 is supplied to the plasma generation source and electric power having a first output E1 is applied to form a first plasma state. A second plasma state is formed by supplying a reactive gas at a pressure P2 and applying a power of a second output E2 lower than the power of the first output E1. That is, when the pressure of the reaction gas in the plasma generation source is high at the start of the plasma processing, it is difficult to generate discharge between the hollow cathode electrode and the counter electrode, so plasma cannot be generated. Therefore, at the start of plasma processing, the pressure of the reaction gas in the plasma generation source is set to a relatively low first pressure P1 to generate discharge and generate plasma. After the plasma is generated, discharge is likely to continue due to charged plasma and electrons, so the pressure of the reaction gas in the plasma generation source is set to a second pressure P2 higher than the first pressure P1. As a result, high-concentration plasma can be generated from the plasma generation source, and the molded product of the present invention, which is the object to be processed, can be exposed to a larger amount of highly reactive reactive gas, further improving the processing capacity. can do.

The first pressure P1 is preferably, for example, 0.5 Pa or more and 3 Pa or less. If the first pressure P1 is lower than 0.5 Pa, the initial plasma concentration will be low, making it difficult to maintain a stable discharge. On the other hand, when the first pressure P1 is higher than 3 Pa, it becomes difficult to discharge.

Moreover, the second pressure P2 is preferably a pressure of 10 Pa or more and 50 Pa or less, for example. If the second pressure P2 is lower than 10 Pa, the plasma density will be low, making it difficult to exhibit high processing performance. On the other hand, when the second pressure P2 is higher than 50 Pa, it becomes difficult to maintain discharge.

The first output E1, which is the power applied to the hollow cathode electrode when the first plasma state is formed, is preferably 2 W/cm ² or more and 5 W/cm ² or less per unit area of the hollow cathode electrode. When the first output E1 is less than 2 W/cm ² , it becomes difficult to generate a discharge in the plasma generation source to form plasma. On the other hand, if the first output E1 is greater than 5 W/cm ² , abnormal discharge may occur within the plasma generation source.

Further, the second output E2, which is the power applied to the hollow cathode electrode when the second plasma state is formed, is preferably 0.5 W/cm ² or more and 2 W/cm ² or less per unit area of the hollow cathode electrode. . If the second power E2 is less than 0.5 W/cm ² , it becomes difficult to maintain the discharge and plasma formation within the plasma source. On the other hand, if the second output E2 is greater than 2 W/cm ² , abnormal discharge may occur within the plasma generation source.

Under the above processing conditions, the duration t1 of the first plasma state is preferably 0 to 5 seconds, the duration t2 of the second plasma state is 10 times or more the duration t1 of the first plasma state, For example, it is preferably 10 to 100 times. Since the second plasma state can generate a reactant gas with a higher concentration and higher reactivity than the first plasma state, as described above, by increasing the duration time t2 of the second plasma state, You can process more efficiently.

Under such plasma conditions, the distance from the hollow cathode electrode to the molded article of the present invention is preferably 100 mm or more and 250 mm or less. If this distance is shorter than 100 mm, the temperature of the molded product of the present invention may become high.

The plasma treatment in the present invention is preferably carried out by plasma treatment using not only a reactive gas in a plasma state but also a reactive gas in an activated state (radical state), and the reactive gas exhibits strong reactivity in a radical state. It is preferable to use the oxygen (O ₂ ) contained therein because the efficiency of plasma treatment can be further improved. Nitrogen can be used as the reaction gas, but it is preferable to use oxygen or a mixed gas of oxygen and an inert gas such as argon from the viewpoint of plasma processing efficiency. When a mixed gas of oxygen and an inert gas is used, the oxygen concentration in the mixed gas is preferably 99.9% or more.

[Sputtering process]
A metal film is then formed by sputtering on the plasma-treated surface of the molded article of the present invention whose surface has been activated by the plasma process described above.
As described above, it is important to perform this sputtering step without exposing the plasma-treated molded product of the present invention to the atmosphere in order to form a metal film with higher adhesion.

The sputtering process can be carried out by placing the plasma-treated molded product of the present invention in a decompression chamber so as to face a sputtering electrode composed of a target material and an electrode portion, and carrying out the sputtering process according to a conventional method. As mentioned above, it is preferable to use a high power of 30 kW or more in particular.
Generally, in the sputtering apparatus, the pressure inside the sputtering apparatus is reduced to about 0.1 Pa to increase the purity of the film to be deposited. If the pressure in the sputtering apparatus is higher than this, it is difficult to remove impurities such as water remaining in the sputtering apparatus or released from the object to be processed. This is because it decreases. However, especially when the object to be treated is a resin, the amount of impurities emitted from the object to be treated is large and continues to be emitted for a long period of time. It is difficult to form a film by reducing the pressure to such an extent.

Therefore, in the present invention, in order to form a high-performance film even if the amount of impurities emitted from the molded product of the present invention, which is the object to be processed, is large, the power source for sputtering is set at 10 kW for the sputtering electrode. It is preferable to use a device capable of applying power of 30 kW or more, more preferably 10 to 40 kW, and perform film formation under high power conditions.

When the power applied to the sputtering electrode is high, the amount of metal atoms such as copper emitted from the target material increases compared to when normal power is applied, and the kinetic energy of the metal atoms increases. also increases. As a result, the concentration of impurities in the processing system decreases relative to the concentration of metal atoms, thereby improving the purity of the film formed on the object to be processed. Furthermore, since the kinetic energy of the metal atoms colliding with the object to be processed is large, the molecules constituting the object to be processed and the metal atoms are stably bonded, so that a film with high adhesion to the object to be processed can be formed. be able to.

The metal atoms emitted from the target material travel straight through the chamber, but their direction of travel is diffused (scattered) by collision with the inert gas in the chamber. In conventional sputtering equipment, the kinetic energy of metal atoms is low, so the metal atoms that have lost their kinetic energy after colliding with the inert gas and being scattered cannot adhere to the object to be processed with sufficient strength. If the object has an uneven shape, only the metal atoms that have lost their kinetic energy due to scattering on the side surface of the uneven shape are irradiated. However, as described above, under high power conditions, the kinetic energy of the metal atoms emitted from the target material is large, so that the metal atoms have sufficient kinetic energy even after being scattered by the inert gas. Therefore, the object to be processed is irradiated with metal atoms that travel in various directions due to scattering and have a large kinetic energy, so that a uniform film can be formed even on the object to be processed that has an uneven shape. becomes possible.

In order to obtain the above effects, it is desirable that the pressure in the chamber during sputtering is about 0.5 Pa to 5 Pa. If the pressure in the chamber during sputtering is 0.5 Pa or more, metal atoms emitted from the target material can be sufficiently scattered, and if it is 5 Pa or less, the concentration of impurities in the chamber can be reduced. Film quality can be ensured.

In the present invention, the metal film formed by sputtering includes metals such as copper, aluminum, chromium, and nickel, and alloys containing two or more of these.
Moreover, the thickness of the metal film formed by sputtering is preferably about 100 to 500 nm. If this film thickness is equal to or greater than the above lower limit, the electric resistance can be lowered and the function as a seed layer can be sufficiently obtained. If this film thickness is equal to or less than the above upper limit, the manufacturing cost can be suppressed without lengthening the film formation time.

[Peel strength of metal film]
As described above, the metal film of the metal film-attached resin molded product of the present invention, which is formed by sputtering a metal film on the plasma-treated surface, was measured according to JIS H8630: 2006 Annex 1 (regulation) adhesion strength test method. It exhibits a high adhesion strength with a peel strength of 2.0 N/cm or more. This peel strength is preferably 3.0 N/cm or more, more preferably 5.0 N/cm or more.
The peel strength of the metal film is specifically measured by the method described in the section of Examples below.

[Polycarbonate resin composition]
The polycarbonate resin composition of the present invention is described below.

[Total light transmittance of polycarbonate resin composition]
The polycarbonate resin composition of the present invention preferably has a total light transmittance of 50% or more measured at a thickness of 3 mm. The total light transmittance is more preferably 70% or higher, more preferably 80% or higher, most preferably 85% or higher. A high total light transmittance increases the transparency of the molded article, and a molded article having good appearance and design can be obtained. If the total light transmittance is too low, the molded article may become opaque, failing to maintain good appearance and design.
The total light transmittance is measured according to JIS K7105. A specific measuring method is shown in the section of Examples below.

[Polycarbonate resin (A)]
The polycarbonate resin composition of the present invention contains polycarbonate resin (A) (hereinafter sometimes referred to as "polycarbonate resin (A) of the present invention") as a main component as a resin component. The term "main component" as used herein refers to a component that is contained in the largest amount in the resin component, and is usually a component that is contained in the polycarbonate resin composition in an amount of 50% by mass or more, preferably 60 to 100% by mass.

In the present invention, the polycarbonate resin (A) may be used alone or in combination of two or more.

Polycarbonate resins are thermoplastic polymers or copolymers obtained by reacting dihydroxy compounds with phosgene or carbonic acid diesters. The method for producing the polycarbonate resin is not particularly limited, and a conventionally known phosgene method (interfacial polymerization method) or a melting method (ester exchange method) can be used, but those produced by the melting method are more preferable.

A case of producing a polycarbonate resin by a melting method will be described.
Examples of the carbonic acid diester, which is one raw material of the polycarbonate resin, include diphenyl carbonate (hereinafter sometimes referred to as "DPC"), substituted diphenyl carbonate such as ditolyl carbonate, dimethyl carbonate, diethyl carbonate, di-t- Dialkyl carbonates such as butyl carbonate are included. These carbonic acid diesters can be used alone or in combination of two or more.

Carbonic acid diesters may be substituted with dicarboxylic acids or dicarboxylic acid esters in an amount of preferably 50 mol % or less, more preferably 30 mol % or less. Representative dicarboxylic acids or dicarboxylic acid esters include terephthalic acid, isophthalic acid, diphenyl terephthalate, diphenyl isophthalate, and the like. When substituted with such a dicarboxylic acid or dicarboxylic acid ester, a polyester carbonate is obtained.

The carbonic acid diester (including the above-mentioned substituted dicarboxylic acid or dicarboxylic acid ester; hereinafter the same) is used in an excess amount relative to the dihydroxy compound. That is, the carbonate diester is used in an amount (molar ratio) of 1.01 to 1.30 times, preferably 1.02 to 1.20 times (molar ratio), the amount of the dihydroxy compound. If this molar ratio is too small, the resulting polycarbonate resin will have too many terminal hydroxyl groups, and the thermal stability of the polycarbonate resin may deteriorate. On the other hand, if the molar ratio is too large, the number of terminal hydroxyl groups in the resulting polycarbonate resin may decrease, and the adhesion of the metal film may decrease.

The dihydroxy compound, which is another raw material for the polycarbonate resin, is a compound having two hydroxyl groups in the molecule. It is preferable to use an aromatic dihydroxy compound in which each hydroxyl group is bonded to an aromatic ring.

Specific examples of aromatic dihydroxy compounds include bis(4-hydroxydiphenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane , 2,2-bis(4-hydroxy-3-t-butylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3 ,5-dibromophenyl)propane, 4,4-bis(4-hydroxyphenyl)heptane, bisphenols such as 1,1-bis(4-hydroxyphenyl)cyclohexane; 4,4'-dihydroxybiphenyl, 3,3' , 5,5′-tetramethyl-4,4′-dihydroxybiphenyl and other biphenols; bis(4-hydroxyphenyl) sulfone, bis(4-hydroxyphenyl) sulfide, bis(4-hydroxyphenyl) ether, bis(4-hydroxyphenyl)ketone and the like. Among these, 2,2-bis(4-hydroxyphenyl)propane (that is, bisphenol A (hereinafter sometimes referred to as "BPA")) is preferred. These aromatic dihydroxy compounds can be used alone or in combination of two or more.

A transesterification catalyst is usually used when producing a polycarbonate resin by the melt exchange method. Any transesterification catalyst can be used. Among them, it is preferable to use, for example, an alkali metal compound and/or an alkaline earth metal compound. In addition, basic compounds such as basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds may be used in combination. In addition, 1 type may be used for an ester exchange catalyst and it may use 2 or more types together by arbitrary combinations and ratios. The amount of the transesterification catalyst to be used is generally 0.1 to 1.0 μmol, preferably 0.3 to 0.8 μmol, per 1 mol of the starting dihydroxy compound.

In the melt exchange method, the reaction temperature is usually 100-320°C. Moreover, the pressure during the reaction is usually carried out under a reduced pressure lower than normal pressure, and it is preferable that the reduced pressure state is adjusted according to the progress of the reaction, and the final condition is set to 0.1 kPa or less. As a specific operation, the melt polycondensation reaction may be carried out under the above conditions while removing by-products such as aromatic hydroxy compounds.

The melt polycondensation reaction can be carried out either batchwise or continuously. In the batch method, the order of mixing the reaction substrate, reaction medium, catalyst, additives, etc. is arbitrary as long as the desired aromatic polycarbonate resin can be obtained, and the appropriate order may be arbitrarily set. However, considering the stability of the polycarbonate resin, etc., it is preferable to carry out the melt polycondensation reaction in a continuous manner.

In the melt exchange method, a catalyst deactivator may be used, if desired. Any compound that neutralizes the transesterification catalyst can be used as the catalyst deactivator. Examples thereof include sulfur-containing acidic compounds and derivatives thereof. In addition, the catalyst deactivator may be used alone, or two or more thereof may be used in any combination and ratio.

The amount of the catalyst deactivator used is usually 0.5 equivalents or more, preferably 1 equivalent or more, and usually 10 equivalents or less, relative to the alkali metal or alkaline earth metal contained in the transesterification catalyst. It is preferably 5 equivalents or less. Furthermore, it is usually 1 ppm or more and usually 100 ppm or less, preferably 20 ppm or less, relative to the polycarbonate resin.

[Physical properties of polycarbonate resin (A)]
The terminal hydroxyl group concentration of the polycarbonate resin (A) of the present invention is preferably 50 ppm or more, more preferably 100 ppm or more, still more preferably 200 ppm or more, and most preferably 500 ppm or more. Also, it is preferably 2000 ppm or less, more preferably 1500 ppm or less, still more preferably 1300 ppm or less, and most preferably 1000 ppm or less. Plasma treatment is effective for obtaining a high plasma treatment effect, and the adhesion strength of the metal film tends to improve as the amount of terminal hydroxyl groups increases. However, if the amount of terminal hydroxyl groups is too large, deterioration of hue, transparency, and mechanical strength may not be sufficiently suppressed when used in a place exposed to ultraviolet rays or visible light for a long time.
The unit of concentration of terminal hydroxyl groups is ppm of the mass of terminal hydroxyl groups with respect to the mass of polycarbonate resin. The method for measuring the amount of terminal hydroxyl groups of the polycarbonate resin will be specifically described in the Examples section below.

The polycarbonate resin (A) of the present invention, when hydrolyzed, produces dihydroxy compounds represented by the following general formulas (1) to (5). That is, structural units derived from these dihydroxy compounds or these dihydroxy compounds are contained in the polycarbonate resin (A).

(R ¹ to R ⁶ each independently represent a hydrogen atom or a methyl group.)

The total content of these dihydroxy compounds produced by hydrolysis is preferably 100 ppm or more, more preferably 200 ppm or more, and even more preferably 400 ppm or more, relative to the entire polycarbonate resin (A). On the other hand, it is preferably 4000 ppm or less, more preferably 3000 ppm or less, still more preferably 1500 ppm or less, and most preferably 1000 ppm or less. These dihydroxy compounds are effective in obtaining a high plasma treatment effect from the plasma treatment described above, and there is a tendency that the greater the total amount of these dihydroxy compounds, the higher the adhesion strength of the metal film.
The content of these dihydroxy compounds can be measured by hydrolyzing the polycarbonate resin (A) of the present invention and then quantitatively analyzing it. A specific measuring method is shown in the section of Examples below.

The viscosity-average molecular weight of the polycarbonate resin (A) of the present invention is preferably 25,000 or less, more preferably 24,000 or less, even more preferably 23,000 or less. Also, the viscosity average molecular weight is preferably 12,000 or more, more preferably 14,000 or more. If the viscosity-average molecular weight is more than 25,000, the viscosity becomes too high, which may result in poor molding. Also, if the viscosity-average molecular weight is less than 12,000, the mechanical strength may decrease.
Here, the viscosity-average molecular weight is obtained by converting the viscosity of a solution measured at a temperature of 20° C. using methylene chloride as a solvent, and the specific measurement method thereof will be described in the Examples section below. Street.

[Other ingredients]
The polycarbonate resin composition of the present invention is not particularly limited as long as it contains the polycarbonate resin (A) of the present invention as a main component, but if necessary, additives and resins other than the polycarbonate resin (A) are blended. can also Additives include stabilizers, release agents, UV absorbers, flame retardants, anti-dripping agents, anti-static agents, anti-fogging agents, lubricants, anti-blocking agents, plasticizers, dispersants, fluidity improvers, and antibacterial agents. , coloring agents, and the like.

<Stabilizer>
It is preferable that the polycarbonate resin composition of the present invention contains a stabilizer because it has the effect of improving thermal stability and preventing deterioration of mechanical strength, transparency and hue. Phosphorus-based stabilizers and phenol-based stabilizers are preferred as stabilizers.

Phosphorus-based stabilizers include phosphorous acid, phosphoric acid, phosphites (phosphites), trivalent phosphates (phosphonites), pentavalent phosphates (phosphates) and the like, among which phosphites , phosphonites and phosphates are preferred.

Examples of phosphites include triphenyl phosphite, tris(nonylphenyl) phosphite, dilauryl hydrogen phosphite, triethyl phosphite, tridecyl phosphite, tris(2-ethylhexyl) phosphite, tris(tridecyl) phosphite. Phyto, tristearyl phosphite, diphenyl monodecyl phosphite, monophenyl didecyl phosphite, diphenyl mono (tridecyl) phosphite, tetraphenyl dipropylene glycol diphosphite, tetraphenyl tetra (tridecyl) pentaerythritol tetraphosphite, water Added bisphenol A phenol phosphite polymer, diphenyl hydrogen phosphite, 4,4′-butylidene-bis(3-methyl-6-tert-butylphenyl di(tridecyl)phosphite), tetra(tridecyl)4,4′- isopropylidene diphenyl diphosphite, bis (tridecyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, dilauryl pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tris(4-tert- butylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, hydrogenated bisphenol A pentaerythritol phosphite polymer, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite , bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, 2,2′-methylenebis(4,6-di-tert-butylphenyl)octylphosphite, bis(2, 4-dicumylphenyl)pentaerythritol diphosphite and the like.

Phosphonites include tetrakis(2,4-di-iso-propylphenyl)-4,4'-biphenylenediphosphonite, tetrakis(2,4-di-n-butylphenyl)-4,4'-biphenyl diphosphonite, tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylenediphosphonite, tetrakis(2,4-di-tert-butylphenyl)-4,3'-biphenylenediphosphonite night, tetrakis(2,4-di-tert-butylphenyl)-3,3'-biphenylenediphosphonite, tetrakis(2,6-di-iso-propylphenyl)-4,4'-biphenylenediphosphonite, Tetrakis (2,6-di-n-butylphenyl)-4,4'-biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, tetrakis ( 2,6-di-tert-butylphenyl)-4,3′-biphenylenediphosphonite, tetrakis(2,6-di-tert-butylphenyl)-3,3′-biphenylenediphosphonite, and the like. .

Examples of phosphates include methyl acid phosphate, ethyl acid phosphate, propyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, butoxyethyl acid phosphate, octyl acid phosphate, 2-ethylhexyl acid phosphate, decyl acid phosphate, and lauryl acid phosphate. , stearyl acid phosphate, oleyl acid phosphate, behenyl acid phosphate, phenyl acid phosphate, nonylphenyl acid phosphate, cyclohexyl acid phosphate, phenoxyethyl acid phosphate, alkoxypolyethylene glycol acid phosphate, bisphenol A acid phosphate, dimethyl acid phosphate, diethyl acid phosphate, Dipropyl acid phosphate, diisopropyl acid phosphate, dibutyl acid phosphate, dioctyl acid phosphate, di-2-ethylhexyl acid phosphate, dioctyl acid phosphate, dilauryl acid phosphate, distearyl acid phosphate, diphenyl acid phosphate, bisnonylphenyl acid phosphate, etc. mentioned.
As the phosphate, a mixture of monostearyl acid phosphate and distearyl acid phosphate can be preferably used.

One type of phosphorus stabilizer may be contained, or two or more types may be contained in any combination and ratio.

Specific examples of phenolic stabilizers include pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3-(3,5-di-tert-butyl- 4-hydroxyphenyl)propionate, thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexane-1,6-diylbis[3-(3, 5-di-tert-butyl-4-hydroxyphenyl)propionamide], 2,4-dimethyl-6-(1-methylpentadecyl)phenol, diethyl [[3,5-bis(1,1-dimethylethyl)- 4-hydroxyphenyl]methyl]phosphoate, 3,3′,3″,5,5′,5″-hexa-tert-butyl-a,a′,a″-(mesitylene-2,4,6 -triyl)tri-p-cresol, 4,6-bis(octylthiomethyl)-o-cresol, ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate ], hexamethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3, 5-triazin-2-ylamino)phenol and the like.

Among them, pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate preferable.

One type of phenol-based stabilizer may be contained, or two or more types may be contained in any combination and ratio.

When the polycarbonate resin composition of the present invention contains a stabilizer, its content is usually 0.001 parts by mass or more, preferably 0.005 parts by mass or more, relative to 100 parts by mass of the polycarbonate resin (A). It is preferably 0.01 parts by mass or more, and usually 1 part by mass or less, preferably 0.5 parts by mass or less, more preferably 0.3 parts by mass or less. If the content of the heat stabilizer is less than the lower limit of the range, the heat stabilizing effect may be insufficient, and if the content of the heat stabilizer exceeds the upper limit of the range, the effect will plateau. In addition, the long-term moist heat resistance may decrease.

<Release agent>
The polycarbonate resin composition of the present invention preferably also contains a release agent. Examples of release agents include aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15,000, and polysiloxane silicone oils.

Aliphatic carboxylic acids include, for example, saturated or unsaturated aliphatic monovalent, divalent or trivalent carboxylic acids. Here, the aliphatic carboxylic acid also includes alicyclic carboxylic acid. Among these, preferred aliphatic carboxylic acids are monovalent or divalent carboxylic acids having 6 to 36 carbon atoms, more preferably aliphatic saturated monovalent carboxylic acids having 6 to 36 carbon atoms. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, melissic acid, tetralyacontanoic acid, montanic acid, and adipine. acid, azelaic acid, and the like.

As the aliphatic carboxylic acid in the ester of aliphatic carboxylic acid and alcohol, for example, the same aliphatic carboxylic acid as mentioned above can be used. Alcohols, on the other hand, include, for example, saturated or unsaturated monohydric or polyhydric alcohols. These alcohols may have substituents such as fluorine atoms and aryl groups. Among these, monohydric or polyhydric saturated alcohols having 30 or less carbon atoms are preferable, and aliphatic saturated monohydric alcohols or saturated aliphatic polyhydric alcohols having 30 or less carbon atoms are more preferable. In addition, an alicyclic compound is also included with an aliphatic here.

Specific examples of such alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol, and the like. is mentioned.

The above esters may contain aliphatic carboxylic acids and/or alcohols as impurities. Further, the above ester may be a pure substance, or may be a mixture of multiple compounds. Furthermore, the aliphatic carboxylic acids and alcohols that form one ester by combining may be used alone, or two or more of them may be used in any combination and ratio.

Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture containing myricyl palmitate as a main component), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostea glycerin distearate, glycerin tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate and the like.

Examples of aliphatic hydrocarbons having a number average molecular weight of 200 to 15,000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomers having 3 to 12 carbon atoms. In addition, an alicyclic hydrocarbon is also contained as an aliphatic hydrocarbon here. Also, these hydrocarbons may be partially oxidized. Also, the number average molecular weight is preferably 5,000 or less. The aliphatic hydrocarbon may be a single substance, or a mixture of various constituents and molecular weights may be used as long as the main component is within the above range.

Among these, paraffin wax, polyethylene wax, or partial oxides of polyethylene wax are preferred, paraffin wax and polyethylene wax are more preferred, and polyethylene wax is particularly preferred.

One release agent may be contained, or two or more release agents may be contained in any combination and ratio.

When the polycarbonate resin composition of the present invention contains a release agent, the content thereof is usually 0.001 parts by mass or more, preferably 0.01 parts by mass or more, relative to 100 parts by mass of the polycarbonate resin (A). It is usually 2 parts by mass or less, preferably 1 part by mass or less. If the content of the release agent is less than the lower limit of the above range, the releasability effect may not be sufficient, and if the content of the release agent exceeds the upper limit of the above range, hydrolysis resistance may cause a decrease in the product, mold contamination during injection molding, and the like.

<Other resins>
The polycarbonate resin composition of the present invention may contain resins other than the polycarbonate resin (A) as resin components as long as the objects of the present invention are not impaired. Other resins that can be blended include, for example, polystyrene resins, high impact polystyrene resins, hydrogenated polystyrene resins, polyacrylic styrene resins, ABS resins, AS resins, AES resins, ASA resins, SMA resins, polyalkyl methacrylate resins, poly Methacrylic methacrylate resin, polyphenyl ether resin, polycarbonate resin other than polycarbonate resin (A), amorphous polyalkylene terephthalate resin, polyester resin, amorphous polyamide resin, poly-4-methylpentene-1, cyclic polyolefin resin, non Thermoplastic elastomers such as crystalline polyarylate resins, polyether sulfone, styrene thermoplastic elastomers, olefin thermoplastic elastomers, polyamide thermoplastic elastomers, polyester thermoplastic elastomers, and polyurethane thermoplastic elastomers can be used.

These may be used alone or in combination of two or more. In order to reliably obtain the effects of the present invention by using the polycarbonate resin (A), these other resins may be used. is contained, the content is preferably 100 parts by mass or less with respect to 100 parts by mass of the polycarbonate resin (A).

[Method for producing polycarbonate resin composition]
The method for producing the polycarbonate resin composition of the present invention is not limited, and a wide range of known methods for producing a polycarbonate resin composition can be employed. After premixing using various mixers such as a Henschel mixer, a method of melt-kneading with a mixer such as a Banbury mixer, a roll, a Brabender, a single-screw kneading extruder, a twin-screw kneading extruder, or a kneader can be used.

The melt-kneading temperature is not particularly limited, but is preferably in the range of 240 to 320°C, particularly preferably 240 to 300°C.

[Molding]
The polycarbonate resin composition (pellet) described above is molded by various molding methods to obtain the molded article of the present invention. The shape of the molded article of the present invention is not particularly limited, and can be appropriately selected according to the application and purpose. Circular, elliptical, polygonal, odd-shaped, hollow, frame-shaped, box-shaped, panel-shaped and the like can be mentioned.

The method for molding the molded article of the present invention is not particularly limited, and conventionally known molding methods can be employed, for example, injection molding, injection compression molding, extrusion molding, profile extrusion, transfer molding, hollow Molding method, gas-assisted blow molding method, blow molding method, extrusion blow molding, IMC (in-mold coating molding) molding method, rotational molding method, multi-layer molding method, two-color molding method, insert molding method, sandwich molding method, A foam molding method, a pressure molding method, and the like can be mentioned.

Among them, the molding is preferably performed by an injection molding method, and for example, injection molding is performed using a known injection molding machine such as an injection molding machine, a super high speed injection molding machine, an injection compression molding machine. The cylinder temperature of the injection molding machine during injection molding is preferably 240 to 320°C, more preferably 250 to 300°C, still more preferably 260 to 280°C. The injection speed during injection molding is preferably 10 to 1,000 mm/sec, more preferably 10 to 500 mm/sec.

As described above, the shape of the molded article of the present invention is not particularly limited, and is appropriately designed according to the application.
Moreover, the molding surface on which the metal film is formed according to the present invention may be flat or curved.

[Use]
The use of the metal film-attached resin molded product of the present invention is not particularly limited, but the metal film formed on the metal film-attached resin molded product of the present invention is used as a seed layer, and is further subjected to normal electroplating to a thickness of about 1 to 50 μm. It is effective for the purpose of forming a metal film and imparting various functions such as decoration, corrosion resistance, wear resistance, solderability, electrical conductivity, electromagnetic wave shielding, magnetic properties, and heat resistance to resin molded products. The plated products obtained can be used, for example, for portable electronic device parts, specifically, electronic notebooks, portable information terminals such as portable computers, pagers, mobile phones, internal structures such as PHS, and It is useful as a housing or the like.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention should not be construed as being limited to the following examples.
In the following description, "parts" means "parts by mass" based on mass unless otherwise specified.

The methods for measuring the viscosity average molecular weight, terminal hydroxyl group content, total amount of specific dihydroxy compounds produced by hydrolysis, and total light transmittance of the polycarbonate resins used in the following Examples and Comparative Examples are as follows.

[Viscosity average molecular weight (Mv)]
A methylene chloride solution of polycarbonate resin (concentration (C) is 0.6 g / dl) is prepared, and the specific viscosity (ηsp) of this solution at a temperature of 20 ° C. is measured using an Ubbelohde viscometer. Average molecular weight (Mv) was calculated.
ηsp/C=[η](1+0.28ηsp)
[η]=1.23×10 ⁻⁴ Mv ^0.83

[Concentration of terminal hydroxyl group]
0.1 g of polycarbonate resin was dissolved in 10 ml of methylene chloride, and 5 ml of a 5% methylene chloride solution of acetic acid (manufactured by Wako Pure Chemical Industries, special reagent grade) and titanium tetrachloride (manufactured by Wako Pure Chemical Industries, special reagent grade) were added. 10 ml of a 2.5% methylene chloride solution was added to develop color, and the absorbance at a wavelength of 546 nm was measured using a spectrophotometer (manufactured by Shimadzu Corporation, "UV160"). Separately, the absorption coefficient was obtained using the methylene chloride solution of dihydric phenol used in the production of the resin, and the terminal hydroxyl group concentration in the sample was quantified.

[Total amount of specific dihydroxy compound produced by hydrolysis]
After 0.5 g of polycarbonate resin was dissolved in 5 ml of methylene chloride, 45 ml of methanol and 5 ml of 25% by weight aqueous sodium hydroxide solution were added, and the mixture was stirred at 70° C. for 30 minutes for hydrolysis (methylene chloride solution). After that, 6 N hydrochloric acid was added to this methylene chloride solution to adjust the pH of the solution to about 2, and the volume was adjusted to 100 ml with pure water.
Next, 20 μl of the prepared methylene chloride solution was injected into the liquid chromatography, and the contents of the dihydroxy compounds represented by the general formulas (1), (2), (3), (4) and (5) (hereinafter , described as “the total amount of general formulas (1) to (5)”) was measured (unit: ppm).
The liquid chromatography and measurement conditions used are as follows.
Liquid chromatography: LC-10AD manufactured by Shimadzu Corporation
Column: YMC PACK ODS-AM M-307-3
4.6 mm ID x 75 mm L
Detector: UV280nm
Eluent: (a) 0.05% trifluoroacetic acid aqueous solution and (b) methanol Gradient conditions: 0 min ((b) is 40%), 25 min ((b) is 95%)
The total amount of general formulas (1) to (5) was calculated from each peak area based on a calibration curve prepared with bisphenol A.

[Total light transmittance]
For the polycarbonate resin molded product, according to JIS K7105, using an NDH-2000 type haze meter manufactured by Nippon Denshoku Industries Co., Ltd., D65 light source, 10 ° field of view, the total light transmittance (unit: %) was measured. .

[Production of polycarbonate resin (A1)]
It was manufactured using a continuous manufacturing apparatus having 3 vertical stirring reactors and 1 horizontal stirring reactor. The first vertical stirring reactor has a temperature of 220°C and a pressure of 13 kPa, the second vertical stirring reactor has a temperature of 260°C and a pressure of 4 kPa, and the third vertical stirring reactor has a temperature of 270°C and a pressure of 0.4 kPa. The stirred reactor was set at a temperature of 280° C. and a pressure of 0.07 kPa. Next, separately, in a raw material preparation step, BPA (manufactured by Mitsubishi Chemical Corporation) and DPC (manufactured by Mitsubishi Chemical Corporation) were mixed at a constant molar ratio (BPA/DPC = 1.025) under a nitrogen gas atmosphere, and the temperature was 155 ° C. to obtain a raw material mixture melt.

Subsequently, this raw material mixed melt was continuously fed into the first vertical stirring reactor controlled to the reaction liquid temperature and internal pressure described above through a raw material introduction pipe heated to 155°C. Simultaneously with the start of supply of the raw material mixture melt, an aqueous solution of cesium carbonate as a catalyst was continuously supplied into the first vertical stirring reactor at a rate of 0.5 μmol of cesium carbonate per 1 mol of dihydroxy compound.

The polymerization reaction liquid discharged from the bottom of the first vertical stirring reactor was continuously supplied to the second vertical stirring reactor, the third horizontal stirring reactor, and the fourth horizontal stirring reactor. .
The molten polycarbonate resin withdrawn from the fourth horizontal stirring reactor was transferred to the twin-screw extruder by means of a gear pump. The twin-screw extruder has three vent ports, devolatilizes from the vent ports using a vacuum pump, and has a catalyst deactivator addition port between the second and third vent ports to deactivate the catalyst. An active agent (butyl p-toluenesulfonate) was added to the polycarbonate resin so as to be 5 ppm. A gear pump and a polymer filter were installed on the discharge side of the twin-screw extruder, and molten polycarbonate resin was supplied.

The gear pump and polymer filter were followed by a die for stranding the resin. The discharged resin was water-cooled and solidified in the form of a strand, and then pelletized with a rotary cutter to obtain an aromatic polycarbonate resin A1.

Separately, a commercially available product shown in Table 1 below was used as the aromatic polycarbonate resin A2.
Table 1 shows the analysis results of polycarbonate resins A1 and A2 used in the following examples and comparative examples.

[Manufacturing of Polycarbonate Resin Molded Products]
After drying the pellets of the polycarbonate resins A1 and A2 shown in Table 1 at 120° C. for 5 hours, an injection molding machine ("J180AD" manufactured by Japan Steel Works, Ltd.) was used to set a cylinder temperature of 280° C. and a mold temperature of 280° C. Injection molding was carried out at 80° C. to obtain plate-shaped moldings each having a thickness of 100 mm×150 mm×3 mm.
The total light transmittance measured for the polycarbonate resin A1 molded article was 89.3%, and the total light transmittance measured for the polycarbonate resin A2 molded article was 89.4%.

[Examples 1 and 2]
The resulting polycarbonate resin A1 and A2 molded products were heated at 120° C. for 1 to 3 hours in an air/ _N2 /vacuum atmosphere under atmospheric pressure, _N2 : 133 Pa or less, vacuum: 10 ⁻¹ Pa or less. Immediately (within 0 to 30 minutes) after performing a heat treatment for 1 to 3 hours at a low temperature, a film formation apparatus that can perform plasma treatment using a hollow cathode electrode and sputtering treatment in a continuous process under vacuum conditions. A plasma CVD process and a sputtering process were continuously performed in an atmosphere without exposing the resin molded product being processed to the atmosphere to form a Cu film having a thickness of 200 nm or more. Plasma CVD conditions and sputtering conditions were as follows.

<Plasma CVD conditions>
The distance between the resin molded product and the hollow cathode electrode was set to 100 to 200 mm, and the preferred plasma CVD conditions described above were used.
As the reaction gas, an oxygen/argon mixed gas with an oxygen concentration of 99.9% or more was used.

<Sputtering conditions>
Power: 10-40kW
Pressure: 1.0-10Pa

[Comparative Example 1]
A Cu film was formed in the same manner as in Example 1, except that the resin molded product was directly subjected to the sputtering treatment without performing the plasma CVD treatment.

[Measurement of peel strength]
A Cu film having a thickness of 15 to 30 μm was formed on the metal film surface of the metal film-attached resin moldings obtained in Examples and Comparative Examples by electroplating according to a conventional method to prepare a test piece.
The peel strength of the Cu film of the obtained test piece was measured under the following conditions in accordance with JIS H8630:2006 Appendix 1 (regulation) adhesion test method.
・Test piece shape: 100 mm × 100 mm × 3 mm thick flat plate ・Sample preparation: Leave for 48 hours or more after plating ・Measuring machine: Universal testing machine “Tensilon RTF2350” manufactured by A&D Co., Ltd.

Table 2 shows the peel strength of each test piece.

From the results of Examples 1 and 2 and Comparative Example 1, when the plasma treatment is not performed, the metal film formed by sputtering shows almost no adhesion to the polycarbonate resin molded article (Comparative Example 1), but the film formation by sputtering It can be seen that a metal film having high adhesion can be formed by performing the plasma treatment prior to the formation (Examples 1 and 2).
Further, from the comparison between Example 1 and Example 2, it can be seen that when the amount of terminal hydroxyl groups of the polycarbonate resin is high and the total amount of general formulas (1) to (5) is large, the adhesion of the metal film can be further improved. I understand.

Claims (2)

A resin molded article with a metal film having a metal film on the surface of the molded article made of a polycarbonate resin composition containing a polycarbonate resin (A), wherein the polycarbonate resin (A) has a terminal hydroxyl group concentration of 200 ppm or more, The metal film has a peel strength of 2.0 N/cm or more as measured according to JIS H8630:2006 Annex 1 (normative) adhesion test method,
The total amount of dihydroxy compounds represented by the following general formulas (1) to (5) measured after hydrolysis of the polycarbonate resin (A) is 100 ppm or more with respect to the entire polycarbonate resin (A). A resin molded product with a metal film, characterized by:

(R ¹ to R ⁶ each independently represent a hydrogen atom or a methyl group.) 2. The resin molded product with a metal film according to claim 1, wherein the total light transmittance of the polycarbonate resin composition measured at a thickness of 3 mm is 50% or more.