WO2008111234A1 - Shaped plastic member with a metal film, a manufacturing method thereof and articles made therefrom - Google Patents

Shaped plastic member with a metal film, a manufacturing method thereof and articles made therefrom Download PDF

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Publication number
WO2008111234A1
WO2008111234A1 PCT/JP2007/055328 JP2007055328W WO2008111234A1 WO 2008111234 A1 WO2008111234 A1 WO 2008111234A1 JP 2007055328 W JP2007055328 W JP 2007055328W WO 2008111234 A1 WO2008111234 A1 WO 2008111234A1
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WO
WIPO (PCT)
Prior art keywords
metal film
plastic member
shaped plastic
manufacturing
film according
Prior art date
Application number
PCT/JP2007/055328
Other languages
French (fr)
Inventor
Kazufumi Ogawa
Satoshi Miyazawa
Original Assignee
Kazufumi Ogawa
Satoshi Miyazawa
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kazufumi Ogawa, Satoshi Miyazawa filed Critical Kazufumi Ogawa
Priority to PCT/JP2007/055328 priority Critical patent/WO2008111234A1/en
Publication of WO2008111234A1 publication Critical patent/WO2008111234A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
    • B05D1/185—Processes for applying liquids or other fluent materials performed by dipping applying monomolecular layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
    • B05D5/067—Metallic effect
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals

Definitions

  • This invention relates to a shaped plastic member, wherein a substrate surface of a shaped plastic member is covered with a metal film through a monomolecular film covalently bonded with the substrate surface, a manufacturing method thereof and articles using the shaped plastic members.
  • the articles here referred to include various kinds of ornaments and sundry articles, vehicles and their members as well as buildings and architectural materials.
  • plastic products requiring a shiny surface and peeling resistance, namely durability, such as automobile bumpers, architectural materials, reflectors for traffic signs, various types of toys and so on.
  • articles formed with a metal film on a substrate surface of a shaped plastic member are widely used for various kinds of ornaments and sundry articles, vehicles and buildings as well as special mirrors and reflectors and reflecting films.
  • a method was conventionally used that a surface of the shaped plastic member was subjected to a treatment with acid and alkali agents to make the surface irregular in order to improve adhesion utilizing a mechanical anchoring effect.
  • Patent Reference 1 discloses a method for improving adhesion using a technique different from the above description.
  • Patent Reference 1 Publication Number H9-59763
  • Patent Reference 1 a surface of a shaped plastic member is subjected to a coupling treatment using a silane coupling agent and then the surface of the shaped plastic member is formed with a metal film.
  • Patent Reference 1 describes that it is possible to improve the adhesion between the shaped plastic member and the metal film without providing irregularities to the surface of the shaped plastic member.
  • Patent Reference 1 There was a big problem, however, that a method of applying the silane coupling agent to the surface as shown in Patent Reference 1 allows a remaining silane coupling agent to be left over the substrate surface of the shaped plastic member and to obstruct proper improvement of adhesion. Moreover, in Patent Reference 1 , it was considered that one of causes of difficulty in improving adhesion is absence of any thickness adjustment of the silane coupling agent adhering on the substrate surface of the shaped plastic member.
  • this invention aims to provide a shaped plastic member with the improved adhesion between the shaped plastic member and the metal film, a manufacturing method thereof and articles using the shaped plastic members.
  • the outline of the invention is to provide a shaped plastic member, wherein a substrate surface of a shaped plastic member is covered with a metal film through a monomolecular film covalently bonded with the substrate surface using a process (a) for forming a monomolecular film on the substrate surface of the shaped plastic member and a process (b) for forming the metal film on the monomolecular film by applying plating, sputtering, vapor deposition, CVD or the like.
  • A is a functional group having a heterocyclic ring
  • n is an integer in the range from 1 to 30.
  • the anti-peeling strength between the metal film and the substrate surface of the shaped plastic member can be conveniently improved.
  • Formation of an intermediate film having the functional groups A formed between the monomolecular film and the metal film is convenient for further improving the anti-peeling strength between the metal film and the substrate surface of the shaped plastic member.
  • Bonding of the functional groups A contained in the monomolecular film and the intermediate film is convenient for furthermore improving the anti-peeling strength between the metal film and the substrate surface of the shaped plastic member.
  • Incorporation of a substance having the functional groups A into the metal film is convenient for improving the anti-peeling strength between the metal film and the substrate surface of the shaped plastic member.
  • the metal film containing at least one element selected from gold, silver, copper, aluminum, chromium, tin, lead, tantalum, tungsten, titanium, zinc or nickel makes it convenient to improve the anti-peeling strength between the metal film and the substrate surface of the shaped plastic member.
  • Molding of a plastic substrate with a synthetic resin containing a filler or a fiber reinforced plastic material makes it convenient to improve durability.
  • X 2 where A is a functional group having a heterocyclic ring, and n is an integer in the range from 1 to 30.
  • X1 through X3 are halogens or alcoxy groups with the number of carbons from one to four, respectively.
  • Insertion of a process (c) for forming an intermediate film having the functional groups A between the process (a) for forming a monomolecular film on the substrate surface of the shaped plastic member and the process (b) for forming the metal film on the monomolecular film by plating is convenient to improve anti-peeling strength.
  • formation of the intermediate film after immersing the shaped plastic member in a solution having the functional groups A is convenient for improving manufacturing efficiency in the process (c).
  • Insertion of a process (d) for making the shaped plastic member in contact with an oxidizing agent between the process (a) for forming a monomolecular film on the substrate surface of the shaped plastic member and the process (b) for forming the metal film on the monomolecular film by plating is convenient to further improve anti-peeling strength.
  • a salt containing at least one of iron, copper and aluminum or a halogen gas as the oxidizing agent is convenient to efficiently perform oxidization and polymerization at a lower cost.
  • formation of the metal film by plating while mixing substances having the functional groups A is convenient to further improve anti-peeling strength.
  • Formation of at least a part of the metal film by plating in an electroless plating method while mixing substances having the functional groups A in a catalyst solution or while mixing substances having the functional groups A in a plating solution is convenient to furthermore improve anti-peeling strength.
  • Formation of the metal film containing at least one of gold, silver, copper, aluminum, chromium or nickel by plating, sputtering, vapor deposition, CVD and so on is convenient for providing a plastic material with metallic decoration.
  • the invention enables improvement of the adhesion between the substrate of the shaped plastic member and the metal film far better than that of the conventional method without providing irregularities to a substrate surface of a shaped plastic member as in the conventional method, thus bringing an effect of widely enlarging the material selection range of the substrate of the shaped plastic member or the metal film. Therefore, the invention provides an effect of enabling wide application to plating for various kinds of ornaments, vehicles, buildings, sundry articles, reflectors and reflecting films that require durability.
  • Fig. 1 is a schematic sectional drawing showing a cross-section, cut in the direction vertical to a film surface, of a shaped plastic member with a metal film according to an embodiment of the invention.
  • the invention manufactures and provides a shaped plastic member, wherein a substrate surface of a shaped plastic member is covered with a metal film through a monomolecular film covalently bonded with the substrate surface using a process (a) for forming a monomolecular film on the substrate surface of the shaped plastic member and a process (b) for forming the metal film on the monomolecular film by plating.
  • the monomolecular film has a structure wherein the aforementioned compound (C1) is repetitively bonded.
  • the film having pyrrolyl groups as functional groups A is hereafter described.
  • Fig. 1 is a schematic sectional drawing showing a cross-section, cut in the direction vertical to a film surface, of a shaped plastic member with an outermost metal film according to the embodiment.
  • a monomolecular film 2 is formed on a substrate of a shaped plastic member 1 shown in Fig. 1.
  • the monomolecular film 2 consists of a large number of compounds (C3) shown below that are arranged on the substrate surface of the shaped plastic member.
  • a self-assembled monolayer (SAM) is formed by using a substance (C4) below as a start substance of the monomolecular film 2 because the substance has active reactive groups at the end of hydrocarbon chains. [C3] o —
  • the monomolecular film 2 is covalently bonded with the substrate surface of the shaped plastic member 1 strongly through the siloxane bonding (-Si-O-).
  • the substrate surface of the shaped plastic member 1 is subjected to a hydrophilic treatment in advance and the OH groups on the substrate surface of the shaped plastic member 1 are very strongly bonded with the substance shown by chemical formula 4 through a hydrochloric acid removing reaction.
  • An intermediate film 3 composed of a substance having pyrrolyl groups is formed on the monomolecular film 2.
  • the intermediate film 3 composed of a substance having pyrrolyl groups and the pyrrolyl groups of the monomolecular film are bonded with each other. Therefore, the monomolecular film 2 and the intermediate film 3 are strongly bonded.
  • a catalyst film 4 consisting of a catalyst for a plating reduction reaction is provided on the intermediate film 3 and a metal film 5 is formed by plating on the catalyst film 4 (Pd in Fig. 1) as shown in Fig. 1.
  • each of the aforementioned pyrrolyl groups has strong affinity with the metal film 5, the metal film 5 can be bonded on the monomolecular film 2.
  • the pyrrolyl groups of the monomolecular film 2 alone brings the aforementioned effect without providing the intermediate layer 3, the monomolecular film 2, if used independently, sometimes shows slightly lower density.
  • partial formation of a metal film not bonded with pyrrolyl groups causes a problem of low bonding strength over the whole metal film. Therefore, the intermediate film 3 having pyrrolyl groups is provided to increase the bonding strength.
  • ratio of the metal film 5 etc. adsorbed on the substrate surface etc. of the shaped plastic member 1 can be reduced to enable more effective improvement of the adhesion between the substrate of the shaped plastic member 1 and the metal film 5.
  • the adhesion between the substrate of the shaped plastic member 1 and the metal film 5 can be further improved.
  • Materials for the substrate of the shaped plastic member 1 include various types of plastics containing an inorganic filler and glass fiber reinforced plastics (FRP).
  • the metal film can be applied with a material containing at least one of gold, silver, copper, aluminum, chromium and nickel.
  • a substrate for a curved mirror was formed for surface preparation using a PPS (polyphenylene sulfide) resin mixed with glass fibers as a filler in advance and the surface was defatted and cleaned.
  • the substance (start substance) shown by the chemical formula (C4) was dissolved in a catalyst made by mixing chloroform and dimethyl silicone at a concentration of 0.05 mol/l to prepare an adsorption solution.
  • the substrate of the molded curved mirror was immersed in the adsorption material solution at room temperature for one hour (process for forming a monomolecular film). The substrate was taken out of the adsorption material solution, cleaned with chloroform and acetone to remove the start substances not yet reacted, washed with water and dried.
  • the substrate was immersed in a pyrrol solution made by dissolving pyrrol in a acetonitrile catalyst at a concentration of 0.2 mol/l at room temperature for five minutes, washed with water and dried (process for forming an intermediate film).
  • the substrate was then immersed in an aqueous solution containing 0.02 mo/I of ferric chloride at room temperature for five minutes, washed with water and dried (process for polymerizing pyrrolyl groups with each other).
  • the substrate was immersed in an acid aqueous solution containing a Pd-Sn colloid at 50 0 C for five minutes to adsorb the colloid on the surface of the shaped plastic member, immersed in a hydroborofluoric acid solution at room temperature for seven minutes to remove Sn from the adsorbed colloid and expose Pd over the substrate surface (process for forming a catalyst film).
  • the substrate was immersed in an electroless plating solution having main compositions of copper sulfide, sodium potassium tartrate, sodium hydroxide and formalin for 15 minutes to form a copper film with a film thickness of 0.3 ⁇ m on the substrate surface.
  • the substrate was subjected to plating in an electroplating solution mainly containing copper sulfide at a current density of 200 A/m 2 for one hour to grow the copper film to a total thickness of approximately 30 ⁇ m (process for forming a metal film).
  • an electroplating solution mainly containing copper sulfide at a current density of 200 A/m 2 for one hour to grow the copper film to a total thickness of approximately 30 ⁇ m (process for forming a metal film).
  • the outermost surface was provided with electroplating of chromium with a thickness of a few micrometers to successfully manufacture a curved mirror having a substrate made of FRP with high durability. (Embodiment 2)
  • the substrate was directly immersed in an acid aqueous solution containing a Pd-Sn colloid, and provided with a copper film by plating as in embodiment 1.
  • Samples of embodiments 1 through 4 and comparison example 1 were subjected to evaluation tests of the adhesion between the substrate and the copper film (metal film) in the 90-degree peeling method stipulated in JIS H8630.
  • bonding strength is 0.6 N/mm in embodiment 1 , 0.5 N/mm in embodiment 2, 0.5 N/mm in embodiment 3, and 0.3 N/mm in embodiment 4.
  • the bonding strength can be increased by immersing the substrate of the shaped plastic member (curved mirror) in a pyrrol solution or adding pyrrol to a plating solution etc. as shown in embodiments 1 through 3.
  • polymerization of pyrrolyl groups using an oxidizing agent contributed to further increase of the bonding strength.
  • Formation of a metal film on a substrate surface of a shaped plastic member according to this invention can be widely utilized in plating for various kinds of ornaments and sundry articles, plating for vehicle and building members (architectural materials), and plating for reflectors and reflecting films.
  • typical ornaments include mirrors made by depositing aluminum or silver on a surface of various formed resins and various types of metallic furniture deposited with chromium or nickel.
  • examples for application to vehicle parts include (1) ABS resin: lamp covers, instrument panels, interior parts and protectors for motor bicycles, (2) cellulose plastics: automobile marks and steering wheels, (3) FRP (fiber-reinforced plastic): outer bumpers and engine covers, (4) phenol resin: brakes, (5) polyacetal: wiper gears, gas valves and carburetor parts, (6) polyamide: radiator fans, (7) polyallylate: direction indication lenses, instrument panel lenses and relay housings, (8) polybuthylene terephthalate: rear ends and front fenders, (9) polyaminobismaleimide: engine parts, gear boxes, wheels and suspension drive systems, (10) metacryl resin: lamp cover lenses, instrument panel, instrument covers and center marks, (11) polypropylene: bumpers, (12) polyphenylene oxide: radiator grills and wheel caps, (13) polyurethane: bumpers, fenders, instrument panels and fans, and (14) unsaturated polyester resin: bodies, fuel tanks, heater housings and instrument panels.
  • ABS resin lamp covers, instrument panels, interior parts and
  • examples for application to buildings include materials for roof, external wall and interior.
  • examples for application to road signs include corner mirrors and various types of reflectors and reflecting films.
  • Applications to signboards, external ornaments for shops, bags, hats and clothes are also feasible.

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Abstract

In order to provide a shaped plastic member, wherein the adhesion between the substrate of the shaped plastic member and the metal film is improved, and an article using the shaped plastic member, the shaped plastic member is covered with the metal film through a monomolecular film covalently bonded with the substrate surface of the plastic member using a process (a) for forming the metal film on the substrate surface of the shaped plastic member and a process (b) for plating the metal film on the monomolecular film.

Description

DESCRIPTION
SHAPED PLASTIC MEMBER WITH A METAL FILM, A MANUFACTURING METHOD
THEREOF AND ARTICLES MADE THEREFROM
BACKGROUND OF THE INVENTION
Field of the Invention
. This invention relates to a shaped plastic member, wherein a substrate surface of a shaped plastic member is covered with a metal film through a monomolecular film covalently bonded with the substrate surface, a manufacturing method thereof and articles using the shaped plastic members.
The articles here referred to include various kinds of ornaments and sundry articles, vehicles and their members as well as buildings and architectural materials.
More specifically they include various kinds of plastic products requiring a shiny surface and peeling resistance, namely durability, such as automobile bumpers, architectural materials, reflectors for traffic signs, various types of toys and so on.
Description of Related Art
Conventionally, articles formed with a metal film on a substrate surface of a shaped plastic member are widely used for various kinds of ornaments and sundry articles, vehicles and buildings as well as special mirrors and reflectors and reflecting films.
Problems concerning these articles were adhesion between the substrate of the aforementioned shaped plastic member and the metal film.
For example, a method was conventionally used that a surface of the shaped plastic member was subjected to a treatment with acid and alkali agents to make the surface irregular in order to improve adhesion utilizing a mechanical anchoring effect.
In such a method, however, there was a big problem that irregularity provided to the surface of the shaped plastic member results in a loss of luster.
The following Patent Reference 1 discloses a method for improving adhesion using a technique different from the above description. [Patent Reference 1] Publication Number H9-59763
In Patent Reference 1 , a surface of a shaped plastic member is subjected to a coupling treatment using a silane coupling agent and then the surface of the shaped plastic member is formed with a metal film.
Thus Patent Reference 1 describes that it is possible to improve the adhesion between the shaped plastic member and the metal film without providing irregularities to the surface of the shaped plastic member.
There was a big problem, however, that a method of applying the silane coupling agent to the surface as shown in Patent Reference 1 allows a remaining silane coupling agent to be left over the substrate surface of the shaped plastic member and to obstruct proper improvement of adhesion. Moreover, in Patent Reference 1 , it was considered that one of causes of difficulty in improving adhesion is absence of any thickness adjustment of the silane coupling agent adhering on the substrate surface of the shaped plastic member.
On the other hand, this invention aims to provide a shaped plastic member with the improved adhesion between the shaped plastic member and the metal film, a manufacturing method thereof and articles using the shaped plastic members.
SUMMARY OF THE INVENTION
The outline of the invention is to provide a shaped plastic member, wherein a substrate surface of a shaped plastic member is covered with a metal film through a monomolecular film covalently bonded with the substrate surface using a process (a) for forming a monomolecular film on the substrate surface of the shaped plastic member and a process (b) for forming the metal film on the monomolecular film by applying plating, sputtering, vapor deposition, CVD or the like. Now, a method that the aforementioned monomolecular film is provided with a structure, wherein the following compound (C1) is repetitively bonded, and each compound is allowed to be covalently bonded on the substrate surface of a shaped plastic member through -SiO- bonding is convenient for providing a shaped plastic member with a metal film having high peeling resistance. [C1] O -
I
A- (C H 2) π - S .i - O-
I o~ where A is a functional group having a heterocyclic ring, and n is an integer in the range from 1 to 30.
When the aforementioned functional group A is selected from a pyrrolyl group, a thienyl group and a furyl group, the anti-peeling strength between the metal film and the substrate surface of the shaped plastic member can be conveniently improved.
Formation of an intermediate film having the functional groups A formed between the monomolecular film and the metal film is convenient for further improving the anti-peeling strength between the metal film and the substrate surface of the shaped plastic member.
Bonding of the functional groups A contained in the monomolecular film and the intermediate film is convenient for furthermore improving the anti-peeling strength between the metal film and the substrate surface of the shaped plastic member. Incorporation of a substance having the functional groups A into the metal film is convenient for improving the anti-peeling strength between the metal film and the substrate surface of the shaped plastic member.
Formation of the metal film containing at least one element selected from gold, silver, copper, aluminum, chromium, tin, lead, tantalum, tungsten, titanium, zinc or nickel makes it convenient to improve the anti-peeling strength between the metal film and the substrate surface of the shaped plastic member.
Molding of a plastic substrate with a synthetic resin containing a filler or a fiber reinforced plastic material makes it convenient to improve durability.
Manufacturing of various articles using the aforementioned shaped plastic members is convenient to improve durability.
Using a compound shown below (C2) as a start substance for forming a monomolecular film to make the compound covalently bonded with the substrate surface of the shaped plastic member through the SiO bonding generated by a reaction with the substrate surface of the shaped plastic member is convenient to improve the anti-peeling strength of the metal film. [C2]
X 1
I..
A- (C H 2) n-S i - X S
I
X 2 where A is a functional group having a heterocyclic ring, and n is an integer in the range from 1 to 30. X1 through X3 are halogens or alcoxy groups with the number of carbons from one to four, respectively.
Insertion of a process (c) for forming an intermediate film having the functional groups A between the process (a) for forming a monomolecular film on the substrate surface of the shaped plastic member and the process (b) for forming the metal film on the monomolecular film by plating is convenient to improve anti-peeling strength. In addition, formation of the intermediate film after immersing the shaped plastic member in a solution having the functional groups A is convenient for improving manufacturing efficiency in the process (c).
Insertion of a process (d) for making the shaped plastic member in contact with an oxidizing agent between the process (a) for forming a monomolecular film on the substrate surface of the shaped plastic member and the process (b) for forming the metal film on the monomolecular film by plating is convenient to further improve anti-peeling strength.
Using a salt containing at least one of iron, copper and aluminum or a halogen gas as the oxidizing agent is convenient to efficiently perform oxidization and polymerization at a lower cost.
In the process (b) for forming the metal film on the monomolecular film by plating, formation of the metal film by plating while mixing substances having the functional groups A is convenient to further improve anti-peeling strength. Formation of at least a part of the metal film by plating in an electroless plating method while mixing substances having the functional groups A in a catalyst solution or while mixing substances having the functional groups A in a plating solution is convenient to furthermore improve anti-peeling strength.
Formation of the metal film containing at least one of gold, silver, copper, aluminum, chromium or nickel by plating, sputtering, vapor deposition, CVD and so on is convenient for providing a plastic material with metallic decoration.
Using a member molded with a synthetic resin containing an inorganic filler or an inorganic fiber reinforced plastic as a substrate material for the shaped plastic member is convenient for forming a monomolecular film with higher bonding strength through the filler. [Effect of the Invention]
The invention enables improvement of the adhesion between the substrate of the shaped plastic member and the metal film far better than that of the conventional method without providing irregularities to a substrate surface of a shaped plastic member as in the conventional method, thus bringing an effect of widely enlarging the material selection range of the substrate of the shaped plastic member or the metal film. Therefore, the invention provides an effect of enabling wide application to plating for various kinds of ornaments, vehicles, buildings, sundry articles, reflectors and reflecting films that require durability.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 is a schematic sectional drawing showing a cross-section, cut in the direction vertical to a film surface, of a shaped plastic member with a metal film according to an embodiment of the invention.
DETAILED DESCRIPTION
The invention manufactures and provides a shaped plastic member, wherein a substrate surface of a shaped plastic member is covered with a metal film through a monomolecular film covalently bonded with the substrate surface using a process (a) for forming a monomolecular film on the substrate surface of the shaped plastic member and a process (b) for forming the metal film on the monomolecular film by plating.
The monomolecular film has a structure wherein the aforementioned compound (C1) is repetitively bonded. In this embodiment, the film having pyrrolyl groups as functional groups A is hereafter described.
Fig. 1 is a schematic sectional drawing showing a cross-section, cut in the direction vertical to a film surface, of a shaped plastic member with an outermost metal film according to the embodiment. A monomolecular film 2 is formed on a substrate of a shaped plastic member 1 shown in Fig. 1. The monomolecular film 2 consists of a large number of compounds (C3) shown below that are arranged on the substrate surface of the shaped plastic member. A self-assembled monolayer (SAM) is formed by using a substance (C4) below as a start substance of the monomolecular film 2 because the substance has active reactive groups at the end of hydrocarbon chains. [C3] o —
Figure imgf000008_0001
o-
[C4]
C I
Figure imgf000008_0002
C 1
Here, the monomolecular film 2 is covalently bonded with the substrate surface of the shaped plastic member 1 strongly through the siloxane bonding (-Si-O-). The substrate surface of the shaped plastic member 1 is subjected to a hydrophilic treatment in advance and the OH groups on the substrate surface of the shaped plastic member 1 are very strongly bonded with the substance shown by chemical formula 4 through a hydrochloric acid removing reaction.
An intermediate film 3 composed of a substance having pyrrolyl groups is formed on the monomolecular film 2. Here, the intermediate film 3 composed of a substance having pyrrolyl groups and the pyrrolyl groups of the monomolecular film are bonded with each other. Therefore, the monomolecular film 2 and the intermediate film 3 are strongly bonded.
A catalyst film 4 consisting of a catalyst for a plating reduction reaction is provided on the intermediate film 3 and a metal film 5 is formed by plating on the catalyst film 4 (Pd in Fig. 1) as shown in Fig. 1.
Since each of the aforementioned pyrrolyl groups has strong affinity with the metal film 5, the metal film 5 can be bonded on the monomolecular film 2. By the way, although the pyrrolyl groups of the monomolecular film 2 alone brings the aforementioned effect without providing the intermediate layer 3, the monomolecular film 2, if used independently, sometimes shows slightly lower density. In this case, partial formation of a metal film not bonded with pyrrolyl groups causes a problem of low bonding strength over the whole metal film. Therefore, the intermediate film 3 having pyrrolyl groups is provided to increase the bonding strength. Thus, ratio of the metal film 5 etc. adsorbed on the substrate surface etc. of the shaped plastic member 1 can be reduced to enable more effective improvement of the adhesion between the substrate of the shaped plastic member 1 and the metal film 5.
When the substance having pyrrolyl groups is contained in the catalyst film 4 or in the metal film 5, the adhesion between the substrate of the shaped plastic member 1 and the metal film 5 can be further improved.
According to this embodiment, excellent luster can be obtained because the substrate surface of the shaped plastic member 1 is not provided with irregularities that were conventionally provided.
Materials for the substrate of the shaped plastic member 1 include various types of plastics containing an inorganic filler and glass fiber reinforced plastics (FRP). The metal film can be applied with a material containing at least one of gold, silver, copper, aluminum, chromium and nickel.
The present invention will now be described in detail by way of the embodiments thereof, but it is to be understood that the scope of this invention is not limited by these embodiments. (Embodiment 1)
Firstly, a substrate for a curved mirror was formed for surface preparation using a PPS (polyphenylene sulfide) resin mixed with glass fibers as a filler in advance and the surface was defatted and cleaned. In parallel with this, the substance (start substance) shown by the chemical formula (C4) was dissolved in a catalyst made by mixing chloroform and dimethyl silicone at a concentration of 0.05 mol/l to prepare an adsorption solution. Then the substrate of the molded curved mirror was immersed in the adsorption material solution at room temperature for one hour (process for forming a monomolecular film). The substrate was taken out of the adsorption material solution, cleaned with chloroform and acetone to remove the start substances not yet reacted, washed with water and dried.
The substrate was immersed in a pyrrol solution made by dissolving pyrrol in a acetonitrile catalyst at a concentration of 0.2 mol/l at room temperature for five minutes, washed with water and dried (process for forming an intermediate film).
The substrate was then immersed in an aqueous solution containing 0.02 mo/I of ferric chloride at room temperature for five minutes, washed with water and dried (process for polymerizing pyrrolyl groups with each other).
The substrate was immersed in an acid aqueous solution containing a Pd-Sn colloid at 500C for five minutes to adsorb the colloid on the surface of the shaped plastic member, immersed in a hydroborofluoric acid solution at room temperature for seven minutes to remove Sn from the adsorbed colloid and expose Pd over the substrate surface (process for forming a catalyst film).
Then the substrate was immersed in an electroless plating solution having main compositions of copper sulfide, sodium potassium tartrate, sodium hydroxide and formalin for 15 minutes to form a copper film with a film thickness of 0.3 μm on the substrate surface.
Further the substrate was subjected to plating in an electroplating solution mainly containing copper sulfide at a current density of 200 A/m2 for one hour to grow the copper film to a total thickness of approximately 30 μm (process for forming a metal film). Finally, the outermost surface was provided with electroplating of chromium with a thickness of a few micrometers to successfully manufacture a curved mirror having a substrate made of FRP with high durability. (Embodiment 2)
The process for immersing the substrate in the aqueous solution of ferric chloride was only removed from the processes of the embodiment 1. (Embodiment 3)
The processes for immersing the substrate in the pyrrol solution and immersing the substrate in the aqueous solution of ferric chloride were only removed from the processes of the embodiment 1. Instead of this, the aqueous solution in the process for immersing the substrate in the acid aqueous solution containing a Pd-Sn colloid was added with pyrrol at a concentration of 0.2 mol/l. (Embodiment 4) The process for immersing the substrate in the pyrrol solution was only removed from the processes of the embodiment 1. (Comparison example 1)
By removing the processes from that for immersing the substrate in the adsorption material solution through that for immersing the substrate in the aqueous solution of ferric chloride, namely without forming a polymerized monomolecular film, the substrate was directly immersed in an acid aqueous solution containing a Pd-Sn colloid, and provided with a copper film by plating as in embodiment 1.
Samples of embodiments 1 through 4 and comparison example 1 were subjected to evaluation tests of the adhesion between the substrate and the copper film (metal film) in the 90-degree peeling method stipulated in JIS H8630.
As results, it was found that bonding strength is 0.6 N/mm in embodiment 1 , 0.5 N/mm in embodiment 2, 0.5 N/mm in embodiment 3, and 0.3 N/mm in embodiment 4.
On the other hand, in comparison example 1 , although a copper film was formed on the substrate by plating, bonding strength was too low to enable measurement.
It was identified that the bonding strength can be increased by immersing the substrate of the shaped plastic member (curved mirror) in a pyrrol solution or adding pyrrol to a plating solution etc. as shown in embodiments 1 through 3. Especially in embodiment 1 , polymerization of pyrrolyl groups using an oxidizing agent contributed to further increase of the bonding strength. [Industrial Applicability]
Formation of a metal film on a substrate surface of a shaped plastic member according to this invention can be widely utilized in plating for various kinds of ornaments and sundry articles, plating for vehicle and building members (architectural materials), and plating for reflectors and reflecting films.
For example, typical ornaments include mirrors made by depositing aluminum or silver on a surface of various formed resins and various types of metallic furniture deposited with chromium or nickel.
In addition, examples for application to vehicle parts include (1) ABS resin: lamp covers, instrument panels, interior parts and protectors for motor bicycles, (2) cellulose plastics: automobile marks and steering wheels, (3) FRP (fiber-reinforced plastic): outer bumpers and engine covers, (4) phenol resin: brakes, (5) polyacetal: wiper gears, gas valves and carburetor parts, (6) polyamide: radiator fans, (7) polyallylate: direction indication lenses, instrument panel lenses and relay housings, (8) polybuthylene terephthalate: rear ends and front fenders, (9) polyaminobismaleimide: engine parts, gear boxes, wheels and suspension drive systems, (10) metacryl resin: lamp cover lenses, instrument panel, instrument covers and center marks, (11) polypropylene: bumpers, (12) polyphenylene oxide: radiator grills and wheel caps, (13) polyurethane: bumpers, fenders, instrument panels and fans, and (14) unsaturated polyester resin: bodies, fuel tanks, heater housings and instrument panels.
Moreover, examples for application to buildings include materials for roof, external wall and interior. Examples for application to road signs include corner mirrors and various types of reflectors and reflecting films. Applications to signboards, external ornaments for shops, bags, hats and clothes are also feasible.

Claims

1. A shaped plastic member, wherein a substrate surface is covered with a metal film through a monomolecular film covalently bonded with a substrate surface.
2. A shaped plastic member with said metal film according to claim 1 , wherein said monomolecular film has a structure in which a compound shown below (C1) is repetitively bonded and each compound is covalently bonded on a substrate surface of a shaped plastic member through -SiO- bonding. [C1]
O-
!
A- (C H 2) π-S i - O-
I o ™ where A is a functional group having a heterocyclic ring, and n is an integer in the range from 1 to 30.
3. A shaped plastic member with said metal film according to claim 2, wherein said functional group A is selected from a pyrrolyl group, a thienyl group and a furyl group.
4. A shaped plastic member with said metal film according to claim 2, wherein an intermediate film having said functional groups A is formed between said monomolecular film and said metal film.
5. A shaped plastic member with said metal film according to claim 4, wherein said functional groups A contained in said monomolecular film and said intermediate film are bonded.
6. A shaped plastic member with said metal film according to claim 2, wherein a substance having said functional groups A is incorporated into said metal film.
7. A shaped plastic member with said metal film according to claim 1 , wherein said metal film is formed by containing at least one element selected from gold, silver, copper, aluminum, chromium, tin, lead, tantalum, tungsten, titanium or nickel.
8. A shaped plastic member with said metal film according to claim 1 , wherein a plastic substrate is formed with a synthetic resin containing a filler or a fiber reinforced plastic material.
9. An article, wherein said shaped plastic member according to claim 1 is used.
10. A method of manufacturing a shaped plastic member with a metal film, comprising a process (a) for forming a monomolecular film on a surface of said shaped plastic member and a process (b) for forming a metal film on said monomolecular film.
11. A method of manufacturing a shaped plastic member with a metal film according to claim 10, wherein a start substance for forming a monomolecular film contains a compound shown by a chemical formula 2 below and a plurality of said compounds are covalently bonded with said shaped plastic member through the SiO bonding by a desorption reaction. [C2]
X l
I
A- ( C H 2) n -S i - X S
I
X 2 where A is a functional group having a heterocyclic ring, and n is an integer in the range from 1 to 30. X1 through X3 are halogens or alcoxy groups with the number of carbons from one to four, respectively.
12. A method of manufacturing a shaped plastic member with said metal film according to claim 11, wherein said functional group A is selected from a pyrrolyl group, a thienyl group and a furyl group.
13. A method of manufacturing a shaped plastic member with said metal film according to claim 10, wherein a process (c) for forming an intermediate film having said functional groups A on said monomolecular film is included between said processes (a) and (b), and said metal film is formed on said intermediate film in said process (b).
14. A method of manufacturing a shaped plastic member with said metal film according to claim 13, wherein said intermediate film is formed by immersing said shaped plastic member in a solution having said functional groups A in said process
(C).
15. A method of manufacturing a shaped plastic member with said metal film according to claim 13, wherein a process (d) for making said shaped plastic member in contact with an oxidizing agent is included between said processes (c) and (b).
16. A method of manufacturing a shaped plastic member with said metal film according to claim 15, wherein a salt containing at least one of iron, copper and aluminum, or a halogen gas is used as said oxidizing agent.
17. A method of manufacturing a shaped plastic member with said metal film according to claim 10, wherein said metal film is formed by plating together with said substance having said functional groups A in said process (b).
18. A method of manufacturing a shaped plastic member with said metal film according to claim 17, wherein at least a part of said metal film is formed by plating in an electroless plating method while a substance having said functional groups A is added to a catalyst solution or a plating solution.
19. A method of manufacturing a shaped plastic member with said metal film according to claim 10, wherein said metal film is formed by plating by containing at least one element selected from gold, silver, copper, aluminum, tin, lead, tantalum, tungsten, titanium or nickel.
20. A method of manufacturing a shaped plastic member with said metal film according to claim 10, wherein a member made by molding a synthetic resin containing a filler or a fiber reinforced plastic material is used as a substrate of said shaped plastic member.
PCT/JP2007/055328 2007-03-12 2007-03-12 Shaped plastic member with a metal film, a manufacturing method thereof and articles made therefrom WO2008111234A1 (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0839728A (en) * 1994-07-27 1996-02-13 Sumitomo Metal Mining Co Ltd Production of metal-clad laminate substrate
JPH0959763A (en) * 1995-08-25 1997-03-04 Matsushita Electric Works Ltd Formation of metallic film on surface of organic substrate
WO2001081652A1 (en) * 2000-04-25 2001-11-01 Nikko Materials Co., Ltd. Pretreating agent for metal plating
JP2005213576A (en) * 2004-01-29 2005-08-11 Nikko Materials Co Ltd Electroless plating pretreatment agent, electroless plating method using the same, and electroless plated object
JP2006054357A (en) * 2004-08-13 2006-02-23 Nippon Steel Chem Co Ltd Laminate for flexible printed-wiring board, and its manufacturing method
JP2007076429A (en) * 2005-09-13 2007-03-29 Koito Mfg Co Ltd Head lamp system
JP2007076076A (en) * 2005-09-13 2007-03-29 Kagawa Univ Plastic molding having metallic film, its production method, and article using the molding and the method

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0839728A (en) * 1994-07-27 1996-02-13 Sumitomo Metal Mining Co Ltd Production of metal-clad laminate substrate
JPH0959763A (en) * 1995-08-25 1997-03-04 Matsushita Electric Works Ltd Formation of metallic film on surface of organic substrate
WO2001081652A1 (en) * 2000-04-25 2001-11-01 Nikko Materials Co., Ltd. Pretreating agent for metal plating
JP2005213576A (en) * 2004-01-29 2005-08-11 Nikko Materials Co Ltd Electroless plating pretreatment agent, electroless plating method using the same, and electroless plated object
JP2006054357A (en) * 2004-08-13 2006-02-23 Nippon Steel Chem Co Ltd Laminate for flexible printed-wiring board, and its manufacturing method
JP2007076429A (en) * 2005-09-13 2007-03-29 Koito Mfg Co Ltd Head lamp system
JP2007076076A (en) * 2005-09-13 2007-03-29 Kagawa Univ Plastic molding having metallic film, its production method, and article using the molding and the method

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