WO2012026225A1 - 加飾膜層と金属膜層を備えた樹脂シートの製造方法 - Google Patents
加飾膜層と金属膜層を備えた樹脂シートの製造方法 Download PDFInfo
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- WO2012026225A1 WO2012026225A1 PCT/JP2011/065687 JP2011065687W WO2012026225A1 WO 2012026225 A1 WO2012026225 A1 WO 2012026225A1 JP 2011065687 W JP2011065687 W JP 2011065687W WO 2012026225 A1 WO2012026225 A1 WO 2012026225A1
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- resin sheet
- film layer
- polymer fine
- fine particles
- decorative film
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
- B29C51/02—Combined thermoforming and manufacture of the preform
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
- B29C51/08—Deep drawing or matched-mould forming, i.e. using mechanical means only
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
- B29C51/14—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor using multilayered preforms or sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
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- 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
- C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
- C23C18/2073—Multistep pretreatment
- C23C18/2086—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
- H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
- H05K3/182—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method
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- 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
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2791/00—Shaping characteristics in general
- B29C2791/004—Shaping under special conditions
- B29C2791/006—Using vacuum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
- B29C51/10—Forming by pressure difference, e.g. vacuum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2009/00—Layered products
- B29L2009/003—Layered products comprising a metal layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2009/00—Layered products
- B29L2009/005—Layered products coated
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/34—Electrical apparatus, e.g. sparking plugs or parts thereof
- B29L2031/3456—Antennas, e.g. radomes
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/03—Conductive materials
- H05K2201/032—Materials
- H05K2201/0329—Intrinsically conductive polymer [ICP]; Semiconductive polymer
Definitions
- the present invention provides a method for producing a resin sheet provided with a decorative film layer and a metal film layer, and more specifically, a decorative film layer that constitutes a design surface, an antenna, and a circuit pattern
- the manufacturing method of the resin sheet provided with both the metal film layers which comprise is provided.
- a decorative film layer that forms the design surface is provided in advance on the resin sheet, and the resin sheet is arranged on the surface of the molded article substrate by an in-mold molding method.
- a resin sheet with a decorative film layer that forms the design surface is heated and softened, and is synthesized by vacuum forming or pressure forming to form the resin sheet along the mold using the differential pressure of air pressure.
- a method for producing a resin molded product is a method for producing a resin molded product.
- the present invention is a resin sheet as a precursor that can be used for the production of synthetic resin parts, and comprises a decorative film layer that constitutes a design surface, and an antenna and a circuit pattern. It is an object of the present invention to provide a method for producing a resin sheet having both of the metal film layers, which is a simple production process and at a low cost.
- a step of performing decorative printing that constitutes a decorative film layer on one side or both sides of a resin sheet (2) A step of applying the coating material containing conductive polymer fine particles to a predetermined region on one side or both sides of the resin sheet and without the decorative film layer or the decorative film layer; (3) immersing the resin sheet in a pre-treatment solution for dedoping in order to dedope the conductive polymer fine particles applied to the resin sheet; (4) a step of immersing the resin sheet in a catalyst solution in order to attach a plating catalyst metal to a coating region of the coating material containing the conductive polymer fine particles subjected to the dedope treatment; (5) a step of immersing the resin sheet in a plating solution in order to form a metal film layer by electroless plating in a coating region of the conductive polymer fine particle-containing paint to which the plating catalyst metal is attached;
- a step of performing decorative printing that constitutes a decorative film layer on one side or both sides of a resin sheet (2) A step of applying the reducing polymer fine particle-containing paint on one side or both sides of the resin sheet and in a region without the decorative film layer or a predetermined region on the decorative film layer; (3) a step of immersing the resin sheet in a catalyst solution in order to attach the plating catalyst metal to the coating region of the coating containing the reducing polymer fine particles; (4) a step of immersing the resin sheet in a plating solution in order to form a metal film layer by electroless plating in the coating region of the coating material containing the reducing polymer fine particles to which the plating catalyst metal is attached;
- the manufacturing method of the resin sheet provided with the decorating film layer and metal film layer which consist of was adopted.
- a resin sheet comprising a decorative film layer and a metal film layer, further comprising a step of drawing the resin sheet to form a three-dimensional solid shape on the resin sheet
- the manufacturing method was adopted.
- the resin sheet 3 is provided between the steps (2) and (3) of the invention according to the second aspect or between the steps (3) and (4).
- a method for producing a resin sheet provided with a decorative film layer and a metal film layer further provided with a step of drawing the resin sheet was adopted.
- the conductive polymer fine particle of the invention according to the first or third aspect is a conductive polypyrrole, the resin sheet comprising a decorative film layer and a metal film layer The manufacturing method was adopted.
- the reducing polymer fine particle of the invention according to the second or fourth aspect is a reducing polypyrrole, a resin sheet comprising a decorative film layer and a metal film layer The manufacturing method was adopted.
- a conductive polymer fine particle-containing paint is applied, and then the conductive polymer fine particles are dedoped or reduced.
- a coating material containing functional polymer fine particles it is possible to provide both a decorative film layer that forms a design surface on the surface of the resin sheet and a metal film layer that forms an antenna and a circuit pattern. It has become possible to realize a low cost with a simple manufacturing process.
- the resin sheet can be applied to an in-mold molding method, a vacuum molding method, a compressed air molding method, a hot press molding method, etc.
- synthetic resin parts having a wide variety of shapes, including both a decorative film layer that constitutes a metal film layer and a metal film layer that constitutes an antenna and a circuit pattern.
- FIG. 1 shows a flow of a resin sheet manufacturing process according to the first embodiment.
- FIG. 2 shows a flow of a resin sheet manufacturing process according to the second embodiment.
- FIG. 3 shows a flow of a resin sheet manufacturing process according to the third embodiment.
- FIG. 4 shows a flow of a resin sheet manufacturing process according to the fourth embodiment.
- FIG. 1 shows a manufacturing process of a resin sheet according to the first embodiment of the present invention.
- the manufacturing process of the resin sheet 101 according to the first embodiment is roughly divided into the following five processes.
- Step 12 of applying a coating material containing conductive polymer fine particles to the resin sheet 12
- Step 13 of immersing the resin sheet in a pretreatment solution for dedoping
- Step 14 of immersing the resin sheet in a catalyst solution containing a plating catalyst metal 14
- Step 15 of immersing the resin sheet in an electroless plating solution 15
- the material of the resin sheet 101 used in the present invention polypropylene resin, polyethylene resin, polyamide resin, polyester resin, acrylic resin, polyvinyl chloride resin, and the like can be used.
- the thickness of the resin sheet 101 is not particularly limited, and depends on the form in which the resin sheet 101 is finally used. For example, when the resin sheet 101 manufactured here is used as a skin layer in an in-mold molding method, it is desirable to use a resin sheet 101 having a thickness of about 0.1 mm to 2.0 mm. Further, the resin sheet 101 used here may be cut in a predetermined width and length, or may be in the form of a roll.
- step 11 decorative printing is performed to form a decorative film layer on the resin sheet 101.
- This decorative film layer constitutes the design surface of the final synthetic resin part, and is formed by printing a pattern, a pattern, a character, or the like.
- gradation is added to the color tone, printing to give a piano black background, printing with consideration for translucency for backlighting, etc. are performed .
- a printing method for forming the decorative film layer As a printing method for forming the decorative film layer, a commonly used printing method such as a screen printing method, a gravure printing method, an offset printing method, and an inkjet printing method can be employed. Also, a coating method such as a gravure coating method, a roll coating method, or a comma coating method can be employed. Which method is adopted is determined by the thickness of the decorative film layer, the texture of the design surface, whether it is multicolor printing or single color, or whether a special technique such as gradation is used. *
- Ink used for printing should be based on resins such as polyvinyl resin, polyamide resin, polyester resin, acrylic resin, polyurethane resin, etc., and ink containing the required pigments and dyes. Can do. Note that decorative printing can be performed on only one side or both sides of the resin sheet 101.
- a paint containing conductive polymer fine particles is applied to the resin sheet 101 on which decorative printing has been performed.
- the conductive polymer fine particle used in the present embodiment is a monomer having a ⁇ -conjugated double bond in an O / W type emulsion obtained by mixing and stirring an organic solvent, water, and an anionic surfactant. And the monomer is oxidatively polymerized.
- the monomer having a ⁇ -conjugated double bond is not particularly limited as long as it is a monomer used for producing a conductive polymer.
- pyrrole N-methylpyrrole, N-ethylpyrrole, N-phenyl Pyrrole, N-naphthylpyrrole, N-methyl-3-methylpyrrole, N-methyl-3-ethylpyrrole, N-phenyl-3-methylpyrrole, N-phenyl-3-ethylpyrrole, 3-methylpyrrole, 3- Ethyl pyrrole, 3-n-butyl pyrrole, 3-methoxy pyrrole, 3-ethoxy pyrrole, 3-n-propoxy pyrrole, 3-n-butoxy pyrrole, 3-phenyl pyrrole, 3-toluyl pyrrole, 3-naphthyl pyrrole, 3 -Phenoxypyrrole, 3-methylphenoxypyrrole, 3-amin
- anionic surfactants used in the production can be used, but those having a plurality of hydrophobic ends (for example, those having a branched structure in a hydrophobic group or those having a plurality of hydrophobic groups) are preferred. .
- an anionic surfactant having a plurality of hydrophobic ends stable micelles can be formed, and separation between the aqueous phase and the organic solvent phase is smooth after the polymerization. It is easy to obtain conductive polymer fine particles dispersed in.
- anionic surfactants having a plurality of hydrophobic ends di-2-ethylhexyl sodium sulfosuccinate (4 hydrophobic ends), di-2-ethyloctyl sodium sulfosuccinate (4 hydrophobic ends) and branched chain type Alkyl benzene sulfonate (two hydrophobic ends) can be preferably used.
- the amount of the anionic surfactant in the reaction system is preferably less than 0.2 mol, more preferably 0.05 mol to 0.15 mol, with respect to 1 mol of the monomer having a ⁇ -conjugated double bond. If the amount is less than 0.05 mol, the yield and dispersion stability decrease, while if the amount is 0.2 mol or more, the resulting conductive polymer fine particles may have a humidity dependency on the conductivity.
- the organic solvent forming the organic phase of the emulsion is preferably hydrophobic.
- toluene and xylene which are aromatic organic solvents, are preferable from the viewpoint of the stability of the O / W emulsion and the affinity with the monomer.
- the amphoteric solvent can polymerize a monomer having a ⁇ -conjugated double bond, it becomes difficult to separate the organic phase and the aqueous phase when the produced conductive polymer fine particles are recovered.
- the ratio of the organic phase to the aqueous phase in the emulsion is preferably 75% by volume or more in the aqueous phase. If the aqueous phase is 20% by volume or less, the amount of the monomer having a ⁇ -conjugated double bond is reduced, resulting in poor production efficiency.
- the oxidizing agent used in the production examples include those exemplified above, and a particularly preferable oxidizing agent is a persulfate such as ammonium persulfate.
- the amount of the oxidizing agent in the reaction system is preferably 0.1 mol or more and 0.8 mol or less, more preferably 0.2 to 0.6 mol with respect to 1 mol of the monomer having a ⁇ -conjugated double bond. is there. If the amount is less than 0.1 mol, the degree of polymerization of the monomer decreases, making it difficult to separate and collect the conductive polymer fine particles. On the other hand, if the amount is 0.8 mol or more, the particles are aggregated to increase the particle size of the conductive polymer fine particles. , Dispersion stability deteriorates.
- the method for producing the conductive polymer fine particles is performed, for example, in the following steps: (A) a step of preparing an emulsion by mixing and stirring an anionic surfactant, an organic solvent and water; (B) a step of dispersing a monomer having a ⁇ -conjugated double bond in an emulsion, (C) a step of oxidatively polymerizing the monomer and causing the anionic surfactant to contact and adsorb the polymer fine particles; (D) A step of separating the organic phase and collecting the conductive polymer fine particles.
- the mixing and stirring performed at the time of preparing the emulsion is not particularly limited.
- a magnetic stirrer, a stirrer, a homogenizer, or the like can be selected as appropriate.
- the polymerization temperature is 0 to 25 ° C., preferably 20 ° C. or less. If the polymerization temperature exceeds 25 ° C., side reactions occur, which is not preferable.
- the reaction system is divided into two phases, an organic phase and an aqueous phase. At this time, unreacted monomers, oxidizing agents and salts are dissolved and remain in the aqueous phase.
- organic phase is separated and recovered and washed several times with ion-exchanged water, conductive polymer fine particles dispersed in an organic solvent can be obtained.
- the conductive polymer fine particles obtained by the above production method are fine particles mainly composed of a monomer derivative having a ⁇ -conjugated double bond and containing an anionic surfactant. And the characteristic is that it can disperse
- the polymer fine particles are spherical fine particles, and the average particle size is preferably 10 to 100 nm.
- the conductive polymer fine particles dispersed in the organic solvent thus obtained can be used as the conductive polymer fine particle component of the coating as it is, after being concentrated or dried. Further, for example, commercially available conductive polymer fine particles can be used as a component of the paint, instead of the conductive polymer fine particles produced as described above.
- the region where the paint containing conductive polymer fine particles is applied is not only the region where the decorative film layer of the resin sheet 101 is not formed, but also the region where the decorative film layer is formed. You can also.
- the paint containing the conductive polymer fine particles used in the present embodiment may contain a binder in order to improve the adhesion with the resin film.
- a binder in order to improve the adhesion with the resin film.
- the binder to be added include polyvinyl chloride, polycarbonate, polystyrene, polymethyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, poly (N-vinylcarbazole), hydrocarbon resin, ketone resin, phenoxy resin, polyamide, and ethyl cellulose. , Vinyl acetate, ABS resin, polyurethane resin, melamine resin, unsaturated polyester resin, alkyd resin, epoxy resin, silicon resin and the like.
- the amount of the binder used is preferably 0.1 to 60 parts by mass with respect to 1 part by mass of the conductive polymer fine particles or conductive polymer fine particles.
- the binder exceeds 60 parts by mass, metal plating does not precipitate, and when the binder is less than 0.1 parts by mass, the adhesion to the resin film tends to be weak.
- the coating material used for this invention contains the organic solvent.
- the organic solvent to be used is not particularly limited as long as it does not damage the fine particles and can disperse the polymer fine particles. Preferred examples thereof include aromatic hydrocarbons such as benzene, toluene and xylene.
- the coating material used in the present invention can be added with a resin such as a dispersion stabilizer, a thickening agent, and an ink binder, depending on the application, application object, and the like.
- the screen printing method, the gravure printing method, the offset printing method, the ink jet printing method and the like are used as in the printing method for forming the decorative film layer. It can be applied using the printing techniques that have been developed. Moreover, it can also apply
- a metal film layer is formed by electroless plating in a region where a coating containing conductive polymer fine particles is applied. Since this metal film layer constitutes the antenna and circuit pattern, the area where the paint containing conductive polymer particles is applied is set according to the position, pattern, dimensions, etc. required for the antenna or circuit pattern. There is a need to.
- step 13 in order to dedope the conductive polymer fine particles of the resin sheet 101 coated with the conductive polymer fine particle-containing coating, the resin sheet 101 is immersed in a pretreatment liquid. This is because the conductive polymer fine particles contain a substance that acts as a dopant, and as a result, the fine particles exhibit conductivity. Therefore, in order to perform electroless plating using this, the dedoping treatment is performed. Because it becomes necessary.
- the pretreatment liquid for dedoping treatment is a reducing agent for dedoping by reduction, for example, borohydride compounds such as sodium borohydride and potassium borohydride, dimethylamine borane, diethylamine borane, trimethylamine borane, triethylamine.
- a solution containing an alkylamine borane such as borane and hydrazine or an alkaline solution can be used. It is preferable to use an alkaline solution from the viewpoints of operability and economy.
- Alkaline solutions include mild alkaline conditions such as 1M It can be treated with an aqueous sodium hydroxide solution or a solution having a pH of about 9 to 10.
- 1M Examples thereof include an aqueous sodium hydroxide solution, ATS Condicrine CIW-2 (Okuno Pharmaceutical Co., Ltd.)-10 mass% aqueous solution (pH 9 to 10), and the like.
- the treatment temperature is 20 to 70 ° C., preferably 30 to 60 ° C.
- the treatment time is 2 to 10 minutes, preferably 3 to 7 minutes.
- the amount of catalyst metal adsorbed on the surface of the coating layer is preferably 0.1 ⁇ g / cm 2 or more by the above dedoping treatment. When the adsorption amount is less than 0.1 ⁇ g / cm 2 , it is difficult to obtain a uniform metal plating film, or metal is difficult to deposit and it is difficult to form a plating film.
- step 14 the resin sheet 101 obtained by dedoping the conductive polymer fine particles is immersed in a catalyst solution containing a plating catalyst metal.
- This catalyst solution is a solution containing a noble metal (catalytic metal) having catalytic activity for electroless plating, and examples of the catalytic metal include palladium, gold, platinum, rhodium, etc. These metals may be simple substances or compounds, From the viewpoint of the stability of the solution containing the catalyst metal, a palladium compound is preferable, and palladium chloride is particularly preferable among them.
- a preferred specific catalyst solution is 0.02% palladium chloride-0.01% hydrochloric acid aqueous solution (pH 3).
- the treatment temperature is 20 to 50 ° C., preferably 30 to 40 ° C., and the treatment time is 0.1 to 10 minutes, preferably 1 to 5 minutes.
- the resin sheet 101 immersed in a catalyst solution containing a plating catalyst metal is immersed in an electroless plating solution.
- the electroless plating solution is not particularly limited as long as it is a plating solution usually used for electroless plating. That is, as the metal that can be used for electroless plating, copper, gold, silver, nickel, chromium, and the like can be applied, but copper is preferable.
- Specific examples of the electroless copper plating bath include, for example, an ATS add copper IW bath (Okuno Pharmaceutical Co., Ltd.).
- the treatment temperature is 20 to 50 ° C., preferably 30 to 40 ° C., and the treatment time is 1 to 30 minutes, preferably 5 to 15 minutes.
- the resin sheet 101 treated with the electroless plating solution may be only a metal film layer by electroless plating, or may be thickened by performing electroplating on the metal film layer by electroless plating. it can.
- the metal which can be used for the said electrolytic plating will not be specifically limited if it precipitates by electrolytic plating, For example, all, such as copper, gold
- a metal film layer is formed in the region of the resin sheet 101 treated with the electroless plating solution to which the paint containing the conductive polymer fine particles is applied.
- the resin sheet 101 including the decorative film layer and the metal film layer is manufactured at a low cost and at a low cost.
- the resin sheet 101 thus obtained is used as a precursor constituting the skin portion or the whole of a synthetic resin part produced by an in-mold molding method, a vacuum molding method, a pressure forming method, a hot press molding method, or the like.
- the resin sheet 101 obtained here is finally synthesized in the state of the resin sheet 101 without undergoing a molding process such as an in-mold molding method, a vacuum molding method, a pressure forming method, a hot press molding method, etc. Resin parts can also be configured.
- FIG. 2 shows a process for producing a resin sheet according to the second embodiment of the present invention.
- the manufacturing process of the resin sheet 101 according to the second embodiment is roughly divided into the following four processes.
- (1) Process 21 for performing decorative printing on resin sheets 21 (2) Step 22 of applying a coating material containing reducing polymer fine particles to the resin sheet 22 (3) Step 24 of immersing the resin sheet in a catalyst solution containing a plating catalyst metal 24 (4) Step of immersing the resin sheet in an electroless plating solution 25
- the second embodiment differs from the first embodiment in that a reducing polymer fine particle-containing paint is used in Step 22 instead of the conductive polymer fine particle-containing paint.
- the reducing polymer fine particles used in the present embodiment are ⁇ -conjugated in an O / W type emulsion obtained by mixing and stirring an organic solvent, water, an anionic surfactant and a nonionic surfactant. It is produced by adding a monomer having a double bond and subjecting the monomer to oxidative polymerization.
- Examples of the monomer having an ⁇ -conjugated double bond and an anionic surfactant include the same as those exemplified in the production of the conductive polymer fine particles, but preferably pyrrole, aniline, thiophene and 3 , 4-ethylenedioxythiophene and the like, more preferably pyrrole.
- the amount of the anionic surfactant in the reaction system is preferably less than 0.05 mol, more preferably 0.005 mol to 0.03 mol, with respect to 1 mol of the monomer having a ⁇ -conjugated double bond.
- the added anionic surfactant acts as a dopant, and the resulting fine particles exhibit conductivity. Therefore, in order to perform electroless plating using this, a dedoping step is required.
- Nonionic surfactants include, for example, polyoxyethylene alkyl ethers, alkyl glucosides, glycerin fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbidic fatty acid esters, polyoxyethylene fatty acid esters, fatty acid alkanolamides, poly Examples include oxyethylene alkylphenyl ethers. These may be used alone or in combination. In particular, those that stably form an O / W emulsion are preferred.
- the amount of the nonionic surfactant in the reaction system is preferably 0.2 mol or less, more preferably 0.2 mol or less with respect to 1 mol of the monomer having a ⁇ -conjugated double bond, plus the anionic surfactant. 05 to 0.15 mol. If the amount is less than 0.05 mol, the yield and dispersion stability are reduced. On the other hand, if the amount is 0.2 mol or more, it is difficult to separate the aqueous phase from the organic solvent phase after polymerization, and the reducing polymer fine particles in the organic solvent phase are present. It is not preferable because it becomes impossible to obtain.
- the organic solvent forming the organic phase of the emulsion is preferably hydrophobic.
- toluene and xylene which are aromatic organic solvents, are preferable from the viewpoint of the stability of the O / W emulsion and the affinity with the monomer having a ⁇ -conjugated double bond.
- the amphoteric solvent can polymerize a monomer having a ⁇ -conjugated double bond, it becomes difficult to separate the organic phase and the aqueous phase when the produced reducing polymer fine particles are recovered.
- the ratio of the organic phase to the aqueous phase in the emulsion is preferably 75% by volume or more in the aqueous phase. If the aqueous phase is 20% by volume or less, the amount of the monomer having a ⁇ -conjugated double bond is reduced, resulting in poor production efficiency.
- oxidizing agent used in the production examples include inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid and chlorosulfonic acid, organic acids such as alkylbenzenesulfonic acid and alkylnaphthalenesulfonic acid, potassium persulfate, ammonium persulfate and peroxidation.
- Peroxides such as hydrogen can be used. These may be used alone or in combination of two or more. Polymerization is also possible with a Lewis acid such as ferric chloride, but the produced particles may aggregate and cannot be finely dispersed.
- Particularly preferred oxidizing agents are persulfates such as ammonium persulfate.
- the amount of the oxidizing agent in the reaction system is preferably 0.1 mol or more and 0.8 mol or less, more preferably 0.2 to 0.6 mol with respect to 1 mol of the monomer having a ⁇ -conjugated double bond. is there. If the amount is less than 0.1 mol, the degree of polymerization of the monomer decreases, making it difficult to separate and recover the polymer fine particles. On the other hand, if the amount is 0.8 mol or more, the particles are aggregated to increase the particle size of the polymer fine particles, resulting in poor dispersion stability. To do.
- the polymer fine particle production method is performed, for example, in the following steps: (A) a step of preparing an emulsion by mixing and stirring an anionic surfactant, a nonionic surfactant, an organic solvent and water; (B) a step of dispersing a monomer having a ⁇ -conjugated double bond in an emulsion, (C) oxidative polymerization of the monomer, (D) A step of separating the organic phase and collecting the polymer fine particles.
- the mixing and stirring performed at the time of preparing the emulsion is not particularly limited.
- a magnetic stirrer, a stirrer, a homogenizer, or the like can be selected as appropriate.
- the polymerization temperature is 0 to 25 ° C., preferably 20 ° C. or less. If the polymerization temperature exceeds 25 ° C., side reactions occur, which is not preferable.
- the reaction system is divided into two phases, an organic phase and an aqueous phase. At this time, unreacted monomers, oxidizing agents and salts are dissolved and remain in the aqueous phase.
- the organic phase is separated and recovered and washed several times with ion-exchanged water, reducing polymer fine particles dispersed in an organic solvent can be obtained.
- the polymer fine particles obtained by the above production method are fine particles mainly composed of a polymer of a monomer derivative having a ⁇ -conjugated double bond and containing an anionic surfactant and a nonionic surfactant. And the characteristic is that it has a fine particle size and is dispersible in an organic solvent.
- the polymer fine particles are spherical fine particles, and the average particle size is preferably 10 to 100 nm. By using fine particles with a small average particle diameter as described above, the surface area of the fine particles becomes extremely large, and even with fine particles of the same mass, more palladium can be adsorbed, thereby enabling the coating layer to be thinned. It becomes.
- the conductivity of the obtained polymer fine particles is less than 0.01 S / cm, and preferably 0.005 S / cm or less.
- the reductive polymer fine particles dispersed in the organic solvent thus obtained can be used as the reductive polymer fine particle component of the coating as it is, after being concentrated or dried. Further, for example, commercially available reducing polymer fine particles may be used as a component of the coating material, instead of the reducing polymer fine particles produced as described above.
- the paint containing the reducing polymer fine particles used in the present embodiment can be prepared in the same manner as the paint containing the conductive polymer fine particles described in the first embodiment.
- Step 21, step 24, and step 25 in the second embodiment are the same as step 11, step 14, and step 15 in the first embodiment, respectively, and thus description thereof is omitted.
- the reducing polymer fine particle-containing paint is used.
- the step of immersing in the liquid is no longer necessary, and in the second embodiment, compared to the first embodiment, the resin sheet 101 including the decorative film layer and the metal film layer can be manufactured by a simpler process and at a lower cost. It becomes possible.
- FIG. 3 shows a resin sheet manufacturing process according to the third embodiment of the present invention.
- the manufacturing process of the resin sheet 101 according to the third embodiment is roughly divided into the following six processes.
- Process 31 for applying decorative printing to resin sheets 31 (2) Step 32 of applying a conductive polymer fine particle-containing coating to the resin sheet 32 (3) Step 33 of immersing the resin sheet in a pretreatment solution for dedoping (4) Step 34 of immersing the resin sheet in a catalyst solution containing a plating catalyst metal (5) Step 35 of immersing the resin sheet in an electroless plating solution (6)
- the resin sheet is drawn between steps (2) and (3), between steps (3) and (4), or between steps (4) and (5).
- the resin sheet 101 obtained in the first embodiment is used as a precursor constituting the skin portion or the whole of a synthetic resin part manufactured by an in-mold molding method, a vacuum molding method, a pressure molding method, a hot press molding method, or the like.
- the resin sheet 101 is deep drawn by these molding methods, the degree of bending or stretching of the resin sheet 101 becomes extremely large, and the resin sheet 101 formed by plating is used.
- the upper metal film layer may be broken.
- the third embodiment has been conceived to solve such a problem, and before forming the metal film layer by electroless plating on the resin sheet 101, that is, the above (2) and (3 ), Or between steps (3) and (4), or between steps (4) and (5), in-mold molding method, vacuum molding method, pressure molding method, hot press
- the resin sheet 101 is subjected to drawing processing.
- methods for drawing the resin sheet 101 in order to pre-shape the resin sheet 101 include a hot plate vacuum / pressure forming method and a hot press forming method, but are not limited thereto. It is not something. Therefore, in the third embodiment, after a predetermined three-dimensional shape is formed on the resin sheet 101, a metal film layer is formed by electroless plating.
- Step 31, step 32, step 33, step 34, and step 35 in the third embodiment are the same as step 11, step 12, step 13, step 14, and step 15 in the first embodiment, respectively. The description is omitted.
- FIG. 4 shows a resin sheet manufacturing process according to the fourth embodiment of the present invention.
- the manufacturing process of the resin sheet 101 according to the fourth embodiment is roughly divided into the following five processes.
- Step 42 of applying a coating material containing reducing polymer fine particles to the resin sheet 42
- Step 44 of immersing the resin sheet in a catalyst solution containing a plating catalyst metal
- Step 46 of drawing the resin sheet between the steps (2) and (3) or between the steps (3) and (4)
- the resin sheet 101 obtained in the second embodiment has been conceived in order to solve the same problem as described in the third embodiment. That is, before the metal film layer is formed on the resin sheet 101 by electroless plating, that is, between the steps (2) and (3) or between the steps (3) and (4).
- the resin sheet 101 Drawing is performed.
- the method for drawing the resin sheet 101 is the same as that described in the third embodiment. Therefore, in the fourth embodiment, as in the third embodiment, after a predetermined three-dimensional shape is formed on the resin sheet 101, a metal film layer is formed by electroless plating. Yes.
- step 41, step 42, step 44, and step 45 in the fourth embodiment are the same as step 21, step 22, step 24, and step 25 in the second embodiment, respectively, and thus description thereof is omitted.
Abstract
Description
意匠面を備えた合成樹脂部品にアンテナや回路パターンを一体的に設ける方法としては、アンテナパターンや回路パターンを金属膜層で構成するようにするために、無電解めっきによって合成樹脂部品に金属膜層を設ける方法がある。
従来、合成樹脂部品の表面に無電解めっきを施工する場合、樹脂基材とめっき膜の密着性を向上させるために、めっき処理前に樹脂基材の表面に微細孔を形成するためのエッチング処理を施すことが不可欠であった。
意匠面として加飾膜層を設けた合成樹脂部品に対してこのようなエッチング処理を行うと、加飾膜層が破壊されてしまい、意匠面を構成し得なくなってしまう。 また、合成樹脂部品にエッチング処理を行った後に、加飾膜層を設けようとしても、合成樹脂部品の表面には、微細孔が存在しているためにきれいな加飾膜層を設けることが困難になってしまう。
また、エッチング処理を行った後に無電解めっきを施工する場合には、合成樹脂部品の樹脂材料としてエッチング処理可能な樹脂材料に限定されるという問題もあった。
(1) 樹脂シートの片面または両面に加飾膜層を構成する加飾印刷を施工するステップと、
(2) 当該樹脂シートの片面または両面であって、加飾膜層のない領域あるいは加飾膜層の上の所定領域に、導電性高分子微粒子含有塗料を塗布するステップと、
(3) 当該樹脂シートに塗布された導電性高分子微粒子を脱ドープするために、当該樹脂シートを脱ドープ用前処理液に浸すステップと、
(4) 脱ドープ処理された導電性高分子微粒子含有塗料の塗布領域にめっき触媒金属を付着させるために、当該樹脂シートを触媒液に浸すステップと、
(5) めっき触媒金属を付着処理した導電性高分子微粒子含有塗料の塗布領域に無電解めっきによる金属膜層を形成するために、当該樹脂シートをめっき液に浸すステップと、
からなる加飾膜層と金属膜層を備えた樹脂シートの製造方法を採用した。
(1) 樹脂シートの片面または両面に加飾膜層を構成する加飾印刷を施工するステップと、
(2) 当該樹脂シートの片面または両面であって、加飾膜層のない領域あるいは加飾膜層の上の所定領域に、還元性高分子微粒子含有塗料を塗布するステップと、
(3) 還元性高分子微粒子含有塗料の塗布領域にめっき触媒金属を付着させるために、当該樹脂シートを触媒液に浸すステップと、
(4) めっき触媒金属を付着処理した還元性高分子微粒子含有塗料の塗布領域に無電解めっきによる金属膜層を形成するために、当該樹脂シートをめっき液に浸すステップと、
からなる加飾膜層と金属膜層を備えた樹脂シートの製造方法を採用した。
なお、係る樹脂シートは、インモールド成形法、真空成形法、圧空成形法、ホットプレス成形法等に適用することができ(すなわち、合成樹脂部品の前駆体として利用すること)、表面に意匠面を構成することとなる加飾膜層と、アンテナや回路パターンを構成することとなる金属膜層の両方を備えた、多種多様な形状を有する合成樹脂部品を形成することが可能となった。
図1は、本発明の第1の実施形態に係る樹脂シートの製造工程を示したものである。 第1の実施形態に係る樹脂シート101の製造工程は、大きく分けて以下の5つの工程から成り立っている。
(2) 当該樹脂シートに導電性高分子微粒子含有塗料を塗布する工程12
(3) 当該樹脂シートを脱ドープ用前処理液に浸す工程13
(4) 当該樹脂シートをめっき触媒金属を含有する触媒液に浸す工程14
(5) 当該樹脂シートを無電解めっき液に浸す工程15
なお、加飾印刷は樹脂シート101の片面だけ、あるいは両面に施工することができる。
本実施形態において使用される導電性高分子微粒子は、有機溶媒と水とアニオン系界面活性剤とを混合撹拌してなるO/W型の乳化液中に、π-共役二重結合を有するモノマーを添加し、該モノマーを酸化重合することにより製造される。
疎水性末端を複数有するアニオン系界面活性剤の中でも、スルホコハク酸ジ-2-エチルヘキシルナトリウム(疎水性末端4つ)、スルホコハク酸ジ-2-エチルオクチルナトリウム(疎水性末端4つ)および分岐鎖型アルキルベンゼンスルホン酸塩(疎水性末端2つ)が好適に使用できる。
反応系中での酸化剤の量は、π-共役二重結合を有するモノマー1molに対して0.1mol以上、0.8mol以下であることが好ましく、さらに好ましくは0.2~0.6molである。0.1mol未満ではモノマーの重合度が低下し、導電性高分子微粒子を分液回収することが困難になり、一方、0.8mol以上では凝集して導電性高分子微粒子の粒径が大きくなり、分散安定性が悪化する。
(a)アニオン系界面活性剤、有機溶媒および水を混合攪拌し乳化液を調製する工程、
(b)π-共役二重結合を有するモノマーを乳化液中に分散させる工程、
(c)モノマーを酸化重合しアニオン系界面活性剤にポリマー微粒子を接触吸着させる工程、
(d)有機相を分液し導電性高分子微粒子を回収する工程。
ポリマー微粒子は球形の微粒子となるが、その平均粒径は、10~100nmとするのが好ましい。
上記のように平均粒径の小さな微粒子にすることで、微粒子の表面積が極めて大きくなり、同一質量の微粒子でも、より多くの触媒金属を吸着できるようになり、それにより塗膜層の薄膜化が可能となる。
また、上記のようにして製造された導電性高分子微粒子でなくとも、例えば、市販で入手できる導電性高分子微粒子を塗料の成分として使用することもできる。
添加するバインダーとしては、例えば、ポリ塩化ビニル、ポリカーボネート、ポリスチレン、ポリメチルメタクリレート、ポリエステル、ポリスルホン、ポリフェニレンオキシド、ポリブタジエン、ポリ(N-ビニルカルバゾール)、炭化水素樹脂、ケトン樹脂、フェノキシ樹脂、ポリアミド、エチルセルロース、酢酸ビニル、ABS樹脂、ポリウレタン樹脂、メラミン樹脂、不飽和ポリエステル樹脂、アルキド樹脂、エポキシ樹脂、シリコン樹脂等が挙げられる。
バインダーを使用する場合の使用量は、好ましくは導電性高分子微粒子又は導電性高分子微粒子1質量部に対して0.1質量部ないし60質量部である。バインダーが60質量部を超えると金属めっきが析出せず、バインダーが0.1質量部未満であると、樹脂フィルムへの密着性が弱くなりやすい。
通常、バインダーを使用するのが好ましい。
更に、本発明に使用する塗料は用途や塗布対象物等の必要に応じて、分散安定剤、増粘剤、インキバインダ等の樹脂を加えることも可能である。
また、グラビアコート法、ロールコート法、コンマコート法等のコート法を採用して塗布することもできる。
導電性高分子微粒子を含有した塗料を塗布した領域には、後述するように無電解めっきによって金属膜層が形成される。 この金属膜層は、アンテナや回路パターンを構成することとなるため、導電性高分子微粒子を含有した塗料を塗布する領域は、アンテナや回路パターンとして必要な位置、パターン、寸法等に合わせて設定する必要がある。
これは、導電性高分子微粒子にはドーパントとして作用する物質が含まれており、その結果この微粒子は導電性を呈することになるため、これを用いて無電解めっきを行うためには脱ドープ処理が必要になるからである。
操作性及び経済性の観点からアルカリ性溶液を使用するのが好ましい。
アルカリ性溶液としては、緩和なアルカリ条件、例えば、1M
水酸化ナトリウム水溶液や、pH9ないし10程度の溶液で処理することができる。
具体的な溶液としては、1M
水酸化ナトリウム水溶液、ATSコンディクリンCIW-2(奥野製薬工業(株)社製)-10質量%水溶液(pH9~10)等が挙げられる。
処理温度は、20ないし70℃、好ましくは30ないし60℃であり、処理時間は、2ないし10分、好ましくは、3ないし7分である。
上記の脱ドープ処理により、塗膜層の表面上の触媒金属吸着量が0.1μg/cm2以上となるようにするのが好ましい。
上記吸着量が0.1μg/cm2未満であると、均一な金属めっき膜を得ることが困難であるか又は金属が析出しにくくめっき膜が形成されにくくなる。
この触媒液は、無電解めっきに対する触媒活性を有する貴金属(触媒金属)を含む溶液であり、触媒金属としては、パラジウム、金、白金、ロジウム等が挙げられ、これら金属は単体でも化合物でもよく、触媒金属を含む溶液の安定性の点からパラジウム化合物が好ましく、その中でも塩化パラジウムが特に好ましい。
好ましい、具体的な触媒液としては、0.02%塩化パラジウム-0.01%塩酸水溶液(pH3)が挙げられる。
処理温度は、20ないし50℃、好ましくは30ないし40℃であり、処理時間は、0.1ないし10分、好ましくは、1ないし5分である。
この無電解めっき液は、通常、無電解めっきに使用されるめっき液であれば、特に限定されない。
即ち、無電解めっきに使用できる金属は、銅、金、銀、ニッケル、クロム等、全て適用することができるが、銅が好ましい。
無電解銅めっき浴の具体例としては、例えば、ATSアドカッパーIW浴(奥野製薬工業(株)社製)等が挙げられる。
処理温度は、20ないし50℃、好ましくは30ないし40℃であり、処理時間は、1ないし30分、好ましくは、5ないし15分である。
以上説明したような工程を経ることにより、無電解めっき液により処理された樹脂シート101の導電性高分子微粒子を含有した塗料を塗布した領域には金属膜層が形成され、その結果、極めて簡単な工程で、かつ低コストで、加飾膜層と金属膜層を備えた樹脂シート101の製造が可能となる。
このようにして得られた樹脂シート101は、インモールド成形法、真空成形法、圧空成形法、ホットプレス成形法等によって製造される合成樹脂部品の表皮部分または全体を構成する前駆体として使用することができ、表面に意匠面を構成することとなる加飾膜層と、アンテナや回路パターンを構成することとなる金属膜層の両方を備えた、多種多様な形状を有する合成樹脂部品を形成することができる。
もちろん、ここで得られた樹脂シート101は、インモールド成形法、真空成形法、圧空成形法、ホットプレス成形法等の成形工程を経ることなく、樹脂シート101の状態のままで最終的な合成樹脂部品を構成することもできる。
図2は、本発明の第2の実施形態に係る樹脂シートの製造工程を示したものである。 第2の実施形態に係る樹脂シート101の製造工程は、大きく分けて以下の4つの工程から成り立っている。
(1) 樹脂シートに加飾印刷を施工する工程21
(2) 当該樹脂シートに還元性高分子微粒子含有塗料を塗布する工程22
(3) 当該樹脂シートをめっき触媒金属を含有する触媒液に浸す工程24
(4) 当該樹脂シートを無電解めっき液に浸す工程25
本実施形態において使用される還元性高分子微粒子は、有機溶媒と水とアニオン系界面活性剤及びノニオン系界面活性剤とを混合撹拌してなるO/W型の乳化液中に、π-共役二重結合を有するモノマーを添加し、該モノマーを酸化重合することにより製造される。
(a)アニオン系界面活性剤、ノニオン系界面活性剤、有機溶媒および水を混合攪拌し乳化液を調製する工程、
(b)π-共役二重結合を有するモノマーを乳化液中に分散させる工程、
(c)モノマーを酸化重合させる工程、
(d)有機相を分液しポリマー微粒子を回収する工程。
ポリマー微粒子は球形の微粒子となるが、その平均粒径は、10~100nmとするのが好ましい。
上記のように平均粒径の小さな微粒子にすることで、微粒子の表面積が極めて大きくなり、同一質量の微粒子でも、より多くのパラジウムを吸着できるようになり、それにより塗膜層の薄膜化が可能となる。
得られたポリマー微粒子の導電率は0.01S/cm未満であり、好ましくは、0.005S/cm以下である。
また、上記のようにして製造された還元性高分子微粒子でなくとも、例えば、市販で入手できる還元性高分子微粒子を塗料の成分として使用することもできる。
第2の実施形態における工程21、工程24、工程25は、第1の実施形態における工程11、工程14、工程15とそれぞれ同じであるため、説明は省略する。
図3は、本発明の第3の実施形態に係る樹脂シートの製造工程を示したものである。 第3の実施形態に係る樹脂シート101の製造工程は、大きく分けて以下の6つの工程から成り立っている。
(2) 当該樹脂シートに導電性高分子微粒子含有塗料を塗布する工程32
(3) 当該樹脂シートを脱ドープ用前処理液に浸す工程33
(4) 当該樹脂シートをめっき触媒金属を含有する触媒液に浸す工程34
(5) 当該樹脂シートを無電解めっき液に浸す工程35
(6) (2)と(3)の工程の間、あるいは(3)と(4)の工程の間、あるいは(4)と(5)の工程の間において、前記樹脂シートに絞り加工を施す工程36
第3の実施形態は、このような問題を解決するために考え出されたものであり、樹脂シート101上に無電解めっきによって金属膜層を形成する前、すなわち、前記(2)と(3)の工程の間、あるいは前記(3)と(4)の工程の間、あるいは前記(4)と(5)の工程の間において、インモールド成形法、真空成形法、圧空成形法、ホットプレス成形法等によって製造される最終的な合成樹脂部品の形状に合わせて、樹脂シート101を予め賦形しておくために、樹脂シート101に絞り加工を施すものである。
従って、第3の実施形態においては、樹脂シート101に所定の3次元的な形状を賦形した後に、無電解めっきによって金属膜層が形成されるようになっている。
図4は、本発明の第4の実施形態に係る樹脂シートの製造工程を示したものである。 第4の実施形態に係る樹脂シート101の製造工程は、大きく分けて以下の5つの工程から成り立っている。
(2) 当該樹脂シートに還元性高分子微粒子含有塗料を塗布する工程42
(3) 当該樹脂シートをめっき触媒金属を含有する触媒液に浸す工程44
(4) 当該樹脂シートを無電解めっき液に浸す工程45
(5) (2)と(3)の工程の間、あるいは(3)と(4)の工程の間において、前記樹脂シートに絞り加工を施す工程46
すなわち、樹脂シート101上に無電解めっきによって金属膜層を形成する前、すなわち、前記(2)と(3)の工程の間、あるいは前記(3)と(4)の工程の間において、インモールド成形法、真空成形法、圧空成形法、ホットプレス成形法等によって製造される最終的な合成樹脂部品の形状に合わせて、樹脂シート101を予め賦形しておくために、樹脂シート101に絞り加工を施すものである。
12, 22, 32, 42 導電性、または還元性高分子微粒子含有塗料塗布工程
13, 33 脱ドープ処理工程
14, 24, 34, 44 触媒処理工程
15, 25, 35, 45 無電解めっき処理工程
36, 46 絞り加工工程
Claims (6)
- 加飾膜層と金属膜層を備えた樹脂シートの製造方法であって、
(1) 樹脂シートの片面または両面に加飾膜層を構成する加飾印刷を施工するステップと、
(2) 当該樹脂シートの片面または両面であって、加飾膜層のない領域あるいは加飾膜層の上の所定領域に、導電性高分子微粒子含有塗料を塗布するステップと、
(3) 当該樹脂シートに塗布された導電性高分子微粒子を脱ドープするために、当該樹脂シートを脱ドープ用前処理液に浸すステップと、
(4) 脱ドープ処理された導電性高分子微粒子含有塗料の塗布領域にめっき触媒金属を付着させるために、当該樹脂シートを触媒液に浸すステップと、
(5) めっき触媒金属を付着処理した導電性高分子微粒子含有塗料の塗布領域に無電解めっきによる金属膜層を形成するために、当該樹脂シートをめっき液に浸すステップと、
からなる樹脂シートの製造方法。 - 加飾膜層と金属膜層を備えた樹脂シートの製造方法であって、
(1) 樹脂シートの片面または両面に加飾膜層を構成する加飾印刷を施工するステップと、
(2) 当該樹脂シートの片面または両面であって、加飾膜層のない領域あるいは加飾膜層の上の所定領域に、還元性高分子微粒子含有塗料を塗布するステップと、
(3) 還元性高分子微粒子含有塗料の塗布領域にめっき触媒金属を付着させるために、当該樹脂シートを触媒液に浸すステップと、
(4) めっき触媒金属を付着処理した還元性高分子微粒子含有塗料の塗布領域に無電解めっきによる金属膜層を形成するために、当該樹脂シートをめっき液に浸すステップと、
からなる樹脂シートの製造方法。 - 請求項1に記載の加飾膜層と金属膜層を備えた樹脂シートの製造方法であって、
前記(2)と(3)のステップの間、あるいは前記(3)と(4)のステップの間、あるいは前記(4)と(5)のステップの間において、
前記樹脂シートに3次元的な立体形状を賦形するために、前記樹脂シートに絞り加工を施すステップを更に備えることを特徴とする樹脂シートの製造方法。 - 請求項2に記載の加飾膜層と金属膜層を備えた樹脂シートの製造方法であって、
前記(2)と(3)のステップの間、あるいは前記(3)と(4)のステップの間において、
前記樹脂シートに3次元的な立体形状を賦形するために、前記樹脂シートに絞り加工を施すステップを更に備えることを特徴とする樹脂シートの製造方法。 - 請求項1又は3に記載の加飾膜層と金属膜層を備えた樹脂シートの製造方法であって、前記導電性高分子微粒子が導電性のポリピロールであることを特徴とする樹脂シートの製造方法。
- 請求項2又は4に記載の加飾膜層と金属膜層を備えた樹脂シートの製造方法であって、前記還元性高分子微粒子が還元性のポリピロールであることを特徴とする樹脂シートの製造方法。
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EP3296845A4 (en) * | 2015-05-11 | 2018-07-25 | FUJIFILM Corporation | Conductive laminate manufacturing method, conductive laminate, substrate with plate-layer precursor layer, substrate with plate layer, and touch sensor |
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