WO2016039282A1 - Primer composition for electroless plating, primer member for electroless plating, and plated article - Google Patents

Primer composition for electroless plating, primer member for electroless plating, and plated article Download PDF

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Publication number
WO2016039282A1
WO2016039282A1 PCT/JP2015/075303 JP2015075303W WO2016039282A1 WO 2016039282 A1 WO2016039282 A1 WO 2016039282A1 JP 2015075303 W JP2015075303 W JP 2015075303W WO 2016039282 A1 WO2016039282 A1 WO 2016039282A1
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Prior art keywords
electroless plating
primer
primer composition
weight
polyester
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PCT/JP2015/075303
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French (fr)
Japanese (ja)
Inventor
秀国 安江
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ナガセケムテックス株式会社
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Priority to JP2016547426A priority Critical patent/JPWO2016039282A1/en
Publication of WO2016039282A1 publication Critical patent/WO2016039282A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters
    • 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
    • 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
    • H05K9/00—Screening of apparatus or components against electric or magnetic fields

Definitions

  • the present invention relates to a primer composition for electroless plating, a primer member for electroless plating, and a plated product. Specifically, the present invention relates to a primer composition for electroless plating on a hardly-adhesive resin base material such as polybutylene terephthalate (PBT) and polyphenylene sulfide (PPS) which are preferably used for the production of electromagnetic shielding members, circuit components and the like.
  • PBT polybutylene terephthalate
  • PPS polyphenylene sulfide
  • an electromagnetic shielding member, a circuit component, etc. are manufactured by forming a metal film on the surface of a resin substrate which is excellent in heat resistance, such as polybutylene terephthalate (PBT) and polyphenylene sulfide (PPS), but is hardly adhesive.
  • a resin substrate which is excellent in heat resistance
  • PBT polybutylene terephthalate
  • PPS polyphenylene sulfide
  • the metal film In order to improve electromagnetic shielding properties and reduce circuit wiring resistance, the metal film must have a uniform film thickness, no defects such as cracks, and a thick film (for example, a film thickness of 1 ⁇ m or more). Is required.
  • Known techniques for forming a metal film on the surface of a substrate include metal vapor deposition, metal sputtering, and plating.
  • the plating method can also be applied when the substrate is a three-dimensional formed product, and an electroplating method is applied to a conductive substrate, and an electroless plating method is applied to a non-conductive substrate such as PBT.
  • the electroless plating method has a lower deposition rate than the electroplating method, and it is difficult to form a thick film. If necessary, a metal thin film is formed on a non-conductive substrate by the electroless plating method. After that, a thick metal film may be formed by an electrolytic plating method using a metal thin film as a conductor.
  • the plating metal does not deposit or deposits non-uniformly, and even if the plated metal film is formed, the adhesion to the resin substrate is insufficient. There is a problem that. Therefore, in order to improve the adhesion between the plated metal film and the substrate, the substrate surface is subjected to a wet treatment with a strong oxidizing chemical such as chromic acid or a dry treatment such as corona or sandblasting on the substrate.
  • a strong oxidizing chemical such as chromic acid or a dry treatment such as corona or sandblasting on the substrate.
  • chromic acid is a harmful substance, which has an adverse effect on the work environment.
  • Patent Document 1 discloses a resin composition for electroless plating having a combination of a chemical structure having a nitrogen / hydrogen bond such as an amino group and a salt-forming functional group such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group. It has been reported. However, since the composition contains a large number of highly hydrophilic salt-forming functional groups, there is a problem that it is inferior in heat and moisture resistance.
  • Patent Document 2 describes that a synthetic resin composition containing a silane coupling agent having at least one amino group or ureido group is used as a primer composition for electroless plating.
  • Patent Document 3 describes an easy-plating resin composition containing a polyester resin and / or a polyurethane resin.
  • these compositions have problems of insufficient adhesion to difficult-to-adhere resin base materials such as PBT and PPS, and insufficient plating metal deposition by electroless plating.
  • the present invention is a plated metal film having excellent adhesion to a hard-to-adhesive resin substrate such as PBT and PPS, and a plated metal film deposited by electroless plating, and having a good surface state when used as a primer layer. It aims at providing the primer composition for electroless plating which can form suitably.
  • the inventor of the present invention has a composition containing a specific glass transition temperature (Tg), a polyester having a specific hydroxyl value, and a polymethylene phenyl polyisocyanate in a specific ratio.
  • Tg glass transition temperature
  • the inventors have found that the above-described problems can be solved.
  • the primer composition for electroless plating of the present invention is (A) 100 parts by weight of a polyester having a glass transition temperature of 0 to 20 ° C. and a hydroxyl value of 2 to 10 mg KOH / g (excluding polyester urethane), (B) 5 to 40 parts by weight of polymethylene phenyl polyisocyanate, and (C) It contains an organic solvent.
  • the acid value of (A) polyester is preferably less than 2 mgKOH / g.
  • the total amount of the total solid content is preferably 2 to 25% by weight.
  • the primer composition for electroless plating of the present invention preferably further contains (D) hydrophobic fumed silica in an amount of 5 to 25% by weight based on the total solid content.
  • the primer member for electroless plating of the present invention is obtained by applying a primer composition for electroless plating of the present invention on a substrate to form a primer layer.
  • the substrate is not subjected to surface roughening treatment.
  • the plated product of the present invention is obtained using the primer member for electroless plating of the present invention.
  • the primer composition for electroless plating according to the present invention contains polyester having a specific glass transition temperature (Tg) and a specific hydroxyl value and polymethylene phenyl polyisocyanate in a specific ratio, PBT, PPS, etc.
  • Tg glass transition temperature
  • PBT polymethylene phenyl polyisocyanate
  • the primer member for electroless plating of the present invention is obtained by applying the primer composition for electroless plating of the present invention to form a primer layer, the substrate is not subjected to surface roughening treatment. Even when is used, the adhesion between the substrate and the primer layer is excellent. Moreover, it is suitably used for forming a plated metal film having a good surface state by an electroless plating method. Furthermore, since the plated product of the present invention was obtained using the primer member for electroless plating of the present invention, the adhesion between the substrate and the primer layer, and the adhesion between the primer layer and the plated metal film are excellent. In addition, a plated metal film having a good surface state is provided.
  • the primer composition for electroless plating of the present invention is (A) 100 parts by weight of a polyester having a glass transition temperature of 0 to 20 ° C. and a hydroxyl value of 2 to 10 mg KOH / g (excluding polyester urethane), (B) 5 to 40 parts by weight of polymethylene phenyl polyisocyanate, and (C) It contains an organic solvent.
  • the primer composition for electroless plating of the present invention contains (A) a polyester having a glass transition temperature of 0 to 20 ° C. and a hydroxyl value of 2 to 10 mg KOH / g (excluding polyester urethane) as a binder. To do.
  • Polyester is a polymer compound obtained by polycondensation of a compound having two or more carboxyl groups in the molecule and a compound having two or more hydroxyl groups in the molecule, and is made of glass. There is no particular limitation as long as it has a transition temperature of 0 to 20 ° C. and a hydroxyl value of 2 to 10 mgKOH / g.
  • As polyester a specific kind may be used independently and 2 or more types may be used together. However, since the adhesion between the deposited plated metal film and the primer layer may not be obtained, polyester urethane cannot be used as the (A) polyester in the primer composition for electroless plating of the present invention.
  • the glass transition temperature (Tg) of the polyester is 0 to 20 ° C., preferably 5 to 15 ° C.
  • Tg glass transition temperature
  • the plating deposition property may be insufficient
  • it exceeds 20 ° C. the adhesion between the plated metal film and the primer layer may be insufficient.
  • the hydroxyl value of the polyester is 2 to 10 mgKOH / g, preferably 4 to 8 mgKOH / g.
  • the hydroxyl value is less than 2 mgKOH / g, curing is insufficient, and the strength of the primer layer may be insufficient.
  • it exceeds 10 mgKOH / g the adhesion between the plated metal film and the primer layer is insufficient. It may become.
  • the acid value of polyester is not specifically limited, Less than 2 mgKOH / g is preferable. When the acid value is 2 mgKOH / g or more, the heat and moisture resistance may be insufficient.
  • the acid value of polyester can be adjusted to less than 2 mgKOH / g by reacting with a substance having a reactive group that reacts with an acidic site.
  • the molecular weight of the polyester is not particularly limited, but is preferably 5,000 to 100,000, more preferably 10,000 to 50,000. When the molecular weight is less than 5,000, the primer layer may have insufficient strength, and when it exceeds 100,000, a uniform primer layer may not be obtained due to a decrease in coating properties.
  • Byron 630 manufactured by Toyobo Co., Ltd., glass transition temperature 7 ° C., hydroxyl value 5 mgKOH / g, acid value ⁇ 2 mgKOH / g
  • Byron GK340 manufactured by Toyobo Co., Ltd., Glass transition temperature 0 ° C., hydroxyl value 7 mgKOH / g, acid value 5 mgKOH / g
  • the primer composition for electroless plating of the present invention contains (B) polymethylene phenyl polyisocyanate as a curing agent.
  • (B) Polymethylene phenyl polyisocyanate is also called polymeric MDI or crude MDI. These may be used alone or in combination of two or more.
  • the content of the component (B) is 5 to 40 parts by weight with respect to 100 parts by weight of the component (A), preferably 10 to 30 parts by weight. 20 parts by weight is more preferable.
  • the content is less than 5 parts by weight, the plating deposition property may be insufficient, and when it exceeds 40 parts by weight, the adhesion between the plated metal film and the primer layer may be insufficient.
  • Examples of commercially available products that can be used as the component (B) include Lupranate M5S (BASF INOAC, polyurethane), Cosmonate M-200 (Mitsui Chemicals), and the like.
  • the organic solvent is not particularly limited, and examples thereof include aromatic hydrocarbons such as toluene, 1,3,5-trimethylbenzene, 1,2,4-trimethylbenzene, naphthalene, xylene, solvent naphtha, and methyl ethyl ketone.
  • aromatic hydrocarbons such as toluene, 1,3,5-trimethylbenzene, 1,2,4-trimethylbenzene, naphthalene, xylene, solvent naphtha, and methyl ethyl ketone.
  • MEK methyl isobutyl ketone
  • ketones such as acetone and cyclohexanone, ethyl acetate, butyl acetate, methylcyclohexane, N-methylpyrrolidone and the like. These may be used alone or in combination of two or more.
  • the primer composition for electroless plating of the present invention may optionally contain other components as long as the object of the present invention is not impaired.
  • other components for example, (D) Hydrophobic fumed silica, a dispersing agent, a leveling agent, a silane coupling agent, an inorganic and organic filler (except for (D) hydrophobic fumed silica mentioned later) ).
  • Adhesion of the primer layer formed using the primer composition for electroless plating of the present invention to the plated metal film by blending (D) hydrophobic fumed silica with the primer composition for electroless plating of the present invention Can be improved.
  • the content is not particularly limited, but it is 5 to 25% by weight based on the total solid content of the primer composition for electroless plating. Preferably, 10 to 20% by weight is more preferable. When the content is less than 5% by weight, the effect of improving the adhesiveness may not be obtained, and when it exceeds 25% by weight, the adhesion between the primer layer and the substrate may be insufficient.
  • the total amount of the total solid content is not particularly limited, but is preferably 2 to 25% by weight, more preferably 5 to 20% by weight.
  • the total amount of the total solids is less than 2% by weight, it is uneconomical to apply a large amount of the electroless plating primer composition to obtain a predetermined film thickness, and the electroless plating primer.
  • a uniform primer layer may not be obtained due to a decrease in coating properties of the composition.
  • it exceeds 25% by weight a uniform primer layer may not be obtained due to a decrease in the coating property of the primer composition for electroless plating.
  • the primer composition for electroless plating of the present invention may be mixed with a compound having a thiol group due to the addition of a silane coupling agent containing a thiol group.
  • content of the compound which has a thiol group is not specifically limited, It is preferable that it is 2 weight% or less with respect to the total solid, and it is more preferable that it is 1 weight% or less. If the content exceeds 2% by weight, abnormalities such as cracks occur in the plated metal film, and the adhesion between the plated metal film and the primer layer, particularly the adhesion after the wet heat resistance test may be lowered.
  • the content of the compound having a thiol group can be calculated from the content of the compound having a thiol group contained in the additive used.
  • a component insoluble in the organic solvent is uniformly dispersed. good.
  • treatment using means usually used in the art may be performed, and examples thereof include treatment using means such as a disper, a homogenizer, an ultrasonic homogenizer, and a bead mill. In these, since it can be set as favorable dispersion
  • Primer member for electroless plating is obtained by applying a primer composition for electroless plating of the present invention on a substrate to form a primer layer.
  • a primer composition for electroless plating of the present invention even when the surface of the substrate is not roughened before the application of the primer composition for electroless plating, the adhesion between the substrate and the primer layer is improved.
  • An excellent primer member for electroless plating of the present invention can be obtained.
  • Base material Although it does not specifically limit as a base material, the base material which consists of materials, such as PBT, PPS, a polyethylene terephthalate (PET), polyamide (PA), a polyamideimide (PAI), is mentioned. These may be used alone or in combination of two or more.
  • PBT polyethylene terephthalate
  • PA polyamide
  • PAI polyamideimide
  • the surface roughening treatment may be performed on the substrate in advance according to a conventional method, but the primer composition for electroless plating of the present invention
  • the adhesiveness between the base material and the primer layer is improved without performing the surface roughening treatment, and thus the surface roughening treatment may not be performed.
  • the substrate is not subjected to surface roughening treatment from the viewpoint of simplifying the work by omitting the trouble of surface roughening the substrate.
  • it is not excluded to roughen the surface of the base material in order to further strengthen the adhesion between the base material and the primer layer.
  • a method for forming a primer layer using the primer composition for electroless plating of the present invention is not particularly limited, but after applying the primer composition for electroless plating on a substrate, heat treatment, light irradiation treatment, etc. And the like.
  • the method for applying the primer composition for electroless plating on the substrate is not particularly limited.
  • a coating method, a doctor coating method, or the like can be used.
  • the spray coating method is particularly preferable.
  • the primer layer can be formed on the substrate by subjecting the primer composition for electroless plating applied on the substrate to heat treatment, light irradiation treatment, or the like.
  • the heat treatment is not particularly limited and may be performed by a known method.
  • the heat treatment may be performed using a blow oven, an infrared oven, a vacuum oven, or the like.
  • the (C) organic solvent which the primer composition for electroless plating contains is removed by heat processing.
  • heat processing is not specifically limited, It is preferable to perform on 150 degreeC or less temperature conditions.
  • the temperature of the heat treatment exceeds 150 ° C.
  • the material of the base material to be used is limited, and for example, a base material made of a material such as polyethylene terephthalate (PET), polycarbonate (PC), or acrylic resin cannot be used.
  • the temperature of the heat treatment is preferably 60 to 140 ° C., more preferably 80 to 130 ° C.
  • the treatment time for the heat treatment is not particularly limited, but is preferably 0.1 to 60 minutes, more preferably 0.5 to 30 minutes.
  • the light irradiation treatment is not particularly limited, but mainly ultraviolet rays, visible light, electron beams, ionizing radiation, etc. are used.
  • ultraviolet rays emitted from a light source such as an ultra-high pressure mercury lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, a xenon arc, or a metal halide lamp can be used.
  • the irradiation amount of the energy ray source is about 50 to 5000 mJ / cm 2 as an integrated exposure amount at an ultraviolet wavelength of 365 nm.
  • the surface roughness (Ra) of the primer layer is preferably 1000 nm or more, and more preferably 2000 nm or more. If the surface roughness is less than 1000 nm, the adhesion to the plated metal film may be insufficient.
  • the surface roughness of the primer layer can be adjusted to 1000 nm or more by adjusting the amount of (D) hydrophobic fumed silica added.
  • the thickness of the primer layer is not particularly limited, but is preferably 2 to 50 ⁇ m, more preferably 5 to 20 ⁇ m. If the thickness is less than 2 ⁇ m, the adhesion between the plated metal film and the primer layer may be insufficient, and if it exceeds 50 ⁇ m, it is uneconomical.
  • Plating product is obtained using the primer member for electroless plating of the present invention.
  • an electroless plating method is performed on the primer member for electroless plating, and the deposited metal film is further electroplated as a conductor.
  • the method of performing a law etc. are mentioned.
  • the electroless plating method and the electrolytic plating method may be performed by known methods.
  • the thickness of the plated metal film is not particularly limited, but is preferably 1 ⁇ m or more, and more preferably 20 ⁇ m or more. If the film thickness is less than 1 ⁇ m, problems such as insufficient electromagnetic shielding characteristics and high wiring resistance may occur.
  • the use of the plated product of the present invention is not particularly limited as long as conductivity is required, and examples thereof include an electromagnetic wave shielding member and a circuit component.
  • Binder polyester by Toyobo Co., Ltd., Byron 630, glass transition temperature 7 ° C., hydroxyl value 5 mgKOH / g, acid value ⁇ 2 mgKOH / g) Polyester (Toyobo Co., Ltd., Byron GK340, glass transition temperature 0 ° C., hydroxyl value 7 mgKOH / g, acid value 5 mgKOH / g) Polyester (by Toyobo Co., Ltd., Byron BX1001, glass transition temperature -18 ° C., hydroxyl value 8 mgKOH / g, acid value ⁇ 2 mgKOH / g) Polyester (Toyobo Co., Ltd., Byron 600, glass transition temperature 47 ° C., hydroxyl value 7 mg KOH / g, acid value ⁇ 2 mg KOH / g) Polyester (by Toyobo Co., Ltd., Byron 670, glass transition temperature 7 ° C., hydroxyl value
  • Organic solvent / aromatic hydrocarbon solvent (TonenGeneral Sekiyu KK, Solvesso 100) ⁇ Aromatic hydrocarbon solvent (manufactured by TonenGeneral Sekiyu KK, Solvesso 150) ⁇ Toluene methyl ethyl ketone (MEK)
  • Evaluation method 2-1 A cellophane tape was applied to the primer layer formed on the substrate adhesive substrate and peeled off at once. Then, the peeled state of the primer layer was visually observed and evaluated according to the following criteria. ⁇ : No peeling is observed. ⁇ : Peeling is observed in part. X: Peeling is observed throughout.
  • the ratio (precipitation rate) of the portion where the plating metal was deposited by the electroless plating method with respect to the entire surface of the plating metal precipitation primer layer was estimated by visual observation, and evaluated according to the following criteria.
  • Plating metal film Adhesive cuts with a width of 10 mm and a length of 30 mm were made in the plated metal film (and primer layer) obtained by the electrolytic plating method. Using a handy digital force gauge (manufactured by Japan Measuring System Co., Ltd., Force Gauge HF-10) and an automatic vertical servo stand (manufactured by Japan Measuring System Co., Ltd., servo stand JSV-H1000), pulling 10 mm wide and 25 mm long The peel strength was measured and evaluated according to the following criteria. A: Peel strength is 10 N / cm or more. ⁇ : Peel strength is 5 N / cm or more and less than 10 N / cm.
  • Peel strength is 3 N / cm or more and less than 5 N / cm.
  • X Peel strength is less than 3 N / cm. Peeling: A part or all of the plated metal film has already peeled from the primer layer before the peel strength measurement.
  • Peel strength was measured immediately after the electroplating method (initial), after storage for 96 hours under conditions of a temperature of 85 ° C. and a humidity of 85% (after a moist heat test), and after storage at ⁇ 40 ° C. for 30 minutes.
  • the process of storing at 125 ° C. for 30 minutes was defined as one cycle, and after 100 cycles (after the thermal cycle test), the test was performed three times.
  • Examples 1 to 8, Comparative Examples 1 to 6 Processed by mixing each component in the weight ratio shown in Table 1 using an ultrasonic homogenizer (Branson, SONIFIER 450) (10 minutes under OUTPUT 40 conditions while cooling in an ice bath) for electroless plating
  • a primer composition was prepared.
  • the surface of a PBT base material (80 ⁇ 50 ⁇ 2 mm) containing 30% glass fiber prepared according to a conventional method was degreased using a waste impregnated with isopropyl alcohol (IPA).
  • the prepared primer composition for electroless plating is filled in a hand gun (CREAMY K3, manufactured by Kinki Seisakusho Co., Ltd., nozzle diameter: 0.5 mm), and is reciprocated 8 times while spraying onto the base material.
  • the product was applied to the substrate. Then, after leaving still at normal temperature for 5 minutes, the primer composition for electroless plating was dried by heat-processing at 100 degreeC for 30 minute (s) in oven (made by Tokyo Rika Kikai Co., Ltd.), and a primer layer was formed. A primer member for electroless plating was obtained.
  • the above 2-5 In addition to evaluating the substrate adhesion by the method described in 2), the above 2-5. The surface roughness (Ra) of the primer layer was measured by the method described in 1).
  • the electroless plating method was performed by the following method.
  • a series of chemicals for electroless plating used chemicals from Atotech Japan.
  • the primer member for electroless plating was immersed for 1 minute at room temperature using a pre-dip Neogant B diluent.
  • an activator 834 adjusting solution as a catalyst solution, it was immersed at 40 ° C. for 5 minutes, and then washed with water.
  • the reducer Neogant WA801 adjusting solution was used as a reducing solution, and after immersion treatment at room temperature for 5 minutes, it was washed with water.
  • using a print Gantt V adjustment solution as an electroless plating solution, it was immersed in air bubbling at 34 ° C. for 5 minutes, and then washed with water.
  • after draining with an air gun it was naturally dried at room temperature for 12 hours or more.
  • the plating metal depositability and the plating metal film appearance were evaluated by the methods described in 1).
  • the electrolytic plating method was performed by the following method.
  • CUPLEX 330 adjustment solution of Atotech Japan Co., Ltd. is used as a chemical solution for electrolytic plating
  • Hull cell anode plate containing phosphorous copper manufactured by Yamamoto Kakin Tester Co., Ltd.
  • HKD-1530F manufactured by Sansha Electric Co., Ltd.
  • An object to be plated was set in a plating bath containing a chemical solution for electrolytic plating, a power source was connected, and electrolytic plating was performed at 1.8 ampere at room temperature for 24 minutes. After electrolytic plating, washing with water was performed, and finally, drying was performed in an oven at 80 ° C. for 60 minutes.
  • the plating metal film adhesiveness was evaluated by the method described in 1). The above evaluation results are shown in Table 2.

Abstract

The purpose of the present invention is to provide a primer composition for electroless plating, which exhibits superior adhesiveness to a resin base material with poor adhesiveness such as polybutylene terephthalate or polyphenylene sulfide, as well as to a plated metal film deposited by electroless plating, and, when used as a primer layer, can appropriately form a plated metal film having a good surface state. The primer composition for electroless plating is characterized by comprising (A) 100 parts by weight of polyester (excluding polyester urethane) that has a glass transition temperature of 0 to 20°C and a hydroxyl value of 2 to 10 mg KOH/g, (B) 5 to 40 parts by weight of polymethylene phenyl polyisocyanate, and (C) an organic solvent.

Description

無電解めっき用プライマー組成物、無電解めっき用プライマー部材及びめっき物Electroless plating primer composition, electroless plating primer member and plated product
本発明は、無電解めっき用プライマー組成物、無電解めっき用プライマー部材及びめっき物に関する。詳細には、電磁波シールド部材、回路部品等の製造に好適に使用されるポリブチレンテレフタレート（ＰＢＴ）、ポリフェニレンスルフィド（ＰＰＳ）等の難接着性樹脂基材に対する無電解めっき用プライマー組成物等に関する。 The present invention relates to a primer composition for electroless plating, a primer member for electroless plating, and a plated product. Specifically, the present invention relates to a primer composition for electroless plating on a hardly-adhesive resin base material such as polybutylene terephthalate (PBT) and polyphenylene sulfide (PPS) which are preferably used for the production of electromagnetic shielding members, circuit components and the like.
近年、ポリブチレンテレフタレート（ＰＢＴ）、ポリフェニレンスルフィド（ＰＰＳ）等の耐熱性に優れるものの難接着性である樹脂基材の表面に金属膜を形成することにより、電磁波シールド部材、回路部品等を製造するという要望が高まっている。電磁波シールド性の向上や回路の配線抵抗軽減のため、金属膜には、膜厚が均一であること、クラック等の欠損がないこと、及び、厚膜（例えば、膜厚が１μｍ以上）であることが要求される。基材の表面に金属膜を形成する技術としては、金属蒸着法、金属スパッタ法、めっき法等が知られている。金属蒸着法及び金属スパッタ法は、基材が非導電性であっても成膜可能ではあるものの、成膜速度が小さいために金属厚膜の形成が困難であり、基本的に水平面にしか成膜できないという問題がある。めっき法は基材が三次元形成品である場合にも適用可能であり導電体基材には電解めっき法が、ＰＢＴ等の非導電体基材には無電解めっき法が適用される。無電解めっき法は、電解めっき法と比較して成膜速度が小さく、また、厚膜形成が困難なため、必要に応じて、無電解めっき法により非導電性基材上に金属薄膜を形成した後に、金属薄膜を導電体とした電解めっき法により金属厚膜が形成されることがある。 In recent years, an electromagnetic shielding member, a circuit component, etc. are manufactured by forming a metal film on the surface of a resin substrate which is excellent in heat resistance, such as polybutylene terephthalate (PBT) and polyphenylene sulfide (PPS), but is hardly adhesive. There is a growing demand. In order to improve electromagnetic shielding properties and reduce circuit wiring resistance, the metal film must have a uniform film thickness, no defects such as cracks, and a thick film (for example, a film thickness of 1 μm or more). Is required. Known techniques for forming a metal film on the surface of a substrate include metal vapor deposition, metal sputtering, and plating. Although the metal vapor deposition method and the metal sputtering method can form a film even if the base material is non-conductive, it is difficult to form a thick metal film because the film formation rate is low. There is a problem that the film cannot be formed. The plating method can also be applied when the substrate is a three-dimensional formed product, and an electroplating method is applied to a conductive substrate, and an electroless plating method is applied to a non-conductive substrate such as PBT. The electroless plating method has a lower deposition rate than the electroplating method, and it is difficult to form a thick film. If necessary, a metal thin film is formed on a non-conductive substrate by the electroless plating method. After that, a thick metal film may be formed by an electrolytic plating method using a metal thin film as a conductor.
一般的な樹脂基材に無電解めっき法を行うと、めっき金属が析出しない又は不均一に析出し、めっき金属膜が形成された部分であっても、樹脂基材との接着性が不十分であるという問題がある。そこで、めっき金属膜と基材との接着性を向上させるため、基材に対してクロム酸等の強酸化性薬液によるウェット処理、又は、コロナやサンドブラスト等のドライ処理を行うことにより基材表面を粗化する手法が知られている。しかし、ウェット処理は、粗化のための添加剤が添加されためっき専用グレードの樹脂からなる基材にしか適用することができず、また、クロム酸が有害物質であるため作業環境に対する悪影響が大きいという問題がある。ドライ処理は、基材の材質（樹脂の種類）に対する制限は少ないものの、突起物周りや孔の側壁など、影になる部分を処理できないため、複雑な形状の三次元形成品の表面全体を均一に処理することが困難であるという問題がある。また、基材表面の粗化のみでは、基材とめっき金属膜との接着性を向上することはできても、めっき金属の析出性を改善することは困難である。 When electroless plating is performed on a general resin substrate, the plating metal does not deposit or deposits non-uniformly, and even if the plated metal film is formed, the adhesion to the resin substrate is insufficient. There is a problem that. Therefore, in order to improve the adhesion between the plated metal film and the substrate, the substrate surface is subjected to a wet treatment with a strong oxidizing chemical such as chromic acid or a dry treatment such as corona or sandblasting on the substrate. There are known methods for roughening. However, the wet treatment can only be applied to substrates made of plating-grade resin to which additives for roughening have been added, and chromic acid is a harmful substance, which has an adverse effect on the work environment. There is a problem of being big. Although there are few restrictions on the base material (type of resin), the dry treatment cannot process shadowed parts such as the periphery of protrusions and the side walls of holes, so the entire surface of a three-dimensionally formed product with a complex shape is uniform. There is a problem that it is difficult to process. Further, only by roughening the surface of the base material, it is difficult to improve the depositing property of the plated metal even though the adhesion between the base material and the plated metal film can be improved.
一方、無電解めっき用プライマー組成物を基材に塗布してプライマー層（以下、無電解めっき用プライマー組成物を塗布して得られた塗膜のことを単にプライマー層という場合がある）を形成した後、無電解めっきを行う方法も知られている。特許文献１には、アミノ基等の窒素・水素結合を有する化学構造と、カルボキシル基、スルフォン酸基及びリン酸基等の造塩性官能基とを組み合わせて有する無電解めっき用樹脂組成物が報告されている。しかし、該組成物は親水性の高い造塩性官能基を多数含有するため、耐湿熱性に劣るという問題がある。 On the other hand, the primer layer for electroless plating is applied to a substrate to form a primer layer (hereinafter, the coating obtained by applying the primer composition for electroless plating may be simply referred to as a primer layer). Then, a method of performing electroless plating is also known. Patent Document 1 discloses a resin composition for electroless plating having a combination of a chemical structure having a nitrogen / hydrogen bond such as an amino group and a salt-forming functional group such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group. It has been reported. However, since the composition contains a large number of highly hydrophilic salt-forming functional groups, there is a problem that it is inferior in heat and moisture resistance.
特許文献２には、少なくとも１個のアミノ基又はウレイド基を有するシランカップリング剤を含む合成樹脂組成物を、無電解めっき用プライマー組成物として用いることが記載されている。また、特許文献３には、ポリエステル樹脂及び／又はポリウレタン樹脂を含む易めっき性樹脂組成物が記載されている。しかし、これらの組成物はＰＢＴ、ＰＰＳ等の難接着性樹脂基材に対する接着性が不十分であり、また、無電解めっき法によるめっき金属の析出性が不十分であるという問題がある。 Patent Document 2 describes that a synthetic resin composition containing a silane coupling agent having at least one amino group or ureido group is used as a primer composition for electroless plating. Patent Document 3 describes an easy-plating resin composition containing a polyester resin and / or a polyurethane resin. However, these compositions have problems of insufficient adhesion to difficult-to-adhere resin base materials such as PBT and PPS, and insufficient plating metal deposition by electroless plating.
特開平１０－１８３３５８号公報Japanese Patent Laid-Open No. 10-183358 特開２０１１－８６７８６号公報JP 2011-86786 A 特開２０１１－３５２２０号公報JP 2011-35220 A
本発明は、ＰＢＴ、ＰＰＳ等の難接着性樹脂基材、及び、無電解めっきにより析出しためっき金属膜に対する接着性に優れ、かつ、プライマー層とした場合に、表面状態が良好なめっき金属膜を好適に形成することができる無電解めっき用プライマー組成物を提供することを目的とする。 The present invention is a plated metal film having excellent adhesion to a hard-to-adhesive resin substrate such as PBT and PPS, and a plated metal film deposited by electroless plating, and having a good surface state when used as a primer layer. It aims at providing the primer composition for electroless plating which can form suitably.
本発明者は、上記課題を解決するため鋭意検討した結果、特定のガラス転移温度（Ｔｇ）及び特定の水酸基価を有するポリエステルと、ポリメチレンフェニルポリイソシアネートとを特定の割合で含有する組成物により、上述の課題を解決することができることを見出した。 As a result of intensive studies to solve the above problems, the inventor of the present invention has a composition containing a specific glass transition temperature (Tg), a polyester having a specific hydroxyl value, and a polymethylene phenyl polyisocyanate in a specific ratio. The inventors have found that the above-described problems can be solved.
すなわち、本発明の無電解めっき用プライマー組成物は、
（Ａ）ガラス転移温度が０～２０℃、かつ、水酸基価が２～１０ｍｇＫＯＨ／ｇであるポリエステル（但し、ポリエステルウレタンを除く）　１００重量部、
（Ｂ）ポリメチレンフェニルポリイソシアネート　５～４０重量部、及び、
（Ｃ）有機溶剤
を含有することを特徴とする。 That is, the primer composition for electroless plating of the present invention is
(A) 100 parts by weight of a polyester having a glass transition temperature of 0 to 20 ° C. and a hydroxyl value of 2 to 10 mg KOH / g (excluding polyester urethane),
(B) 5 to 40 parts by weight of polymethylene phenyl polyisocyanate, and
(C) It contains an organic solvent.
本発明の無電解めっき用プライマー組成物において、（Ａ）ポリエステルの酸価は２ｍｇＫＯＨ／ｇ未満であることが好ましい。 In the primer composition for electroless plating of the present invention, the acid value of (A) polyester is preferably less than 2 mgKOH / g.
本発明の無電解めっき用プライマー組成物において、全固形分の合計量は２～２５重量％であることが好ましい。 In the primer composition for electroless plating of the present invention, the total amount of the total solid content is preferably 2 to 25% by weight.
本発明の無電解めっき用プライマー組成物は、さらに、（Ｄ）疎水性フュームドシリカを全固形分に対して５～２５重量％含むことが好ましい。 The primer composition for electroless plating of the present invention preferably further contains (D) hydrophobic fumed silica in an amount of 5 to 25% by weight based on the total solid content.
本発明の無電解めっき用プライマー部材は、基材上に、本発明の無電解めっき用プライマー組成物を塗布してプライマー層を形成して得られたことを特徴とする。 The primer member for electroless plating of the present invention is obtained by applying a primer composition for electroless plating of the present invention on a substrate to form a primer layer.
本発明の無電解めっき用プライマー部材において、基材が表面粗化処理されていないものであることが好ましい。 In the primer member for electroless plating of the present invention, it is preferable that the substrate is not subjected to surface roughening treatment.
本発明のめっき物は、本発明の無電解めっき用プライマー部材を用いて得られたことを特徴とする。 The plated product of the present invention is obtained using the primer member for electroless plating of the present invention.
本発明の無電解めっき用プライマー組成物は、特定のガラス転移温度（Ｔｇ）及び特定の水酸基価を有するポリエステルと、ポリメチレンフェニルポリイソシアネートとを特定の割合で含有するため、ＰＢＴ、ＰＰＳ等の難接着性樹脂基材、及び、無電解めっきにより析出しためっき金属膜に対する接着性に優れ、かつ、プライマー層とした場合に、表面状態が良好なめっき金属膜を好適に形成することができる。また、耐湿熱試験、熱サイクル試験等を行った後でも良好な接着性を維持することができる。 Since the primer composition for electroless plating according to the present invention contains polyester having a specific glass transition temperature (Tg) and a specific hydroxyl value and polymethylene phenyl polyisocyanate in a specific ratio, PBT, PPS, etc. When the primer layer is excellent in adhesion to a hardly adhesive resin substrate and a plated metal film deposited by electroless plating, a plated metal film having a good surface state can be suitably formed. Moreover, good adhesiveness can be maintained even after performing a heat and humidity resistance test, a heat cycle test, and the like.
また、本発明の無電解めっき用プライマー部材は、本発明の無電解めっき用プライマー組成物を塗布してプライマー層を形成して得られたものであるため、表面粗化処理されていない基材を用いた場合でもなお、基材とプライマー層との接着性に優れる。また、無電解めっき法により、表面状態が良好なめっき金属膜を形成するのに好適に用いられる。さらに、本発明のめっき物は、本発明の無電解めっき用プライマー部材を用いて得られたため、基材とプライマー層との接着性、及び、プライマー層とめっき金属膜との接着性に優れ、また、表面状態が良好なめっき金属膜を備える。 Moreover, since the primer member for electroless plating of the present invention is obtained by applying the primer composition for electroless plating of the present invention to form a primer layer, the substrate is not subjected to surface roughening treatment. Even when is used, the adhesion between the substrate and the primer layer is excellent. Moreover, it is suitably used for forming a plated metal film having a good surface state by an electroless plating method. Furthermore, since the plated product of the present invention was obtained using the primer member for electroless plating of the present invention, the adhesion between the substrate and the primer layer, and the adhesion between the primer layer and the plated metal film are excellent. In addition, a plated metal film having a good surface state is provided.
＜＜無電解めっき用プライマー組成物＞＞
本発明の無電解めっき用プライマー組成物は、
（Ａ）ガラス転移温度が０～２０℃、かつ、水酸基価が２～１０ｍｇＫＯＨ／ｇであるポリエステル（但し、ポリエステルウレタンを除く）　１００重量部、
（Ｂ）ポリメチレンフェニルポリイソシアネート　５～４０重量部、及び、
（Ｃ）有機溶剤
を含有することを特徴とする。 << Primer composition for electroless plating >>
The primer composition for electroless plating of the present invention is
(A) 100 parts by weight of a polyester having a glass transition temperature of 0 to 20 ° C. and a hydroxyl value of 2 to 10 mg KOH / g (excluding polyester urethane),
(B) 5 to 40 parts by weight of polymethylene phenyl polyisocyanate, and
(C) It contains an organic solvent.
＜（Ａ）ポリエステル＞
本発明の無電解めっき用プライマー組成物は、バインダーとして、（Ａ）ガラス転移温度が０～２０℃、かつ、水酸基価が２～１０ｍｇＫＯＨ／ｇであるポリエステル（但し、ポリエステルウレタンを除く）を含有する。 <(A) Polyester>
The primer composition for electroless plating of the present invention contains (A) a polyester having a glass transition temperature of 0 to 20 ° C. and a hydroxyl value of 2 to 10 mg KOH / g (excluding polyester urethane) as a binder. To do.
（Ａ）ポリエステルとしては、分子内に２つ以上のカルボキシル基を有する化合物と、分子内に２つ以上のヒドロキシル基を有する化合物とを重縮合して得られた高分子化合物であって、ガラス転移温度が０～２０℃、かつ、水酸基価が２～１０ｍｇＫＯＨ／ｇであるものであれば特に限定されない。（Ａ）ポリエステルとしては、特定の種類のものを単独で用いても良いし、２種以上を併用しても良い。但し、析出しためっき金属膜とプライマー層との接着性が得られないことがあるため、本発明の無電解めっき用プライマー組成物において、ポリエステルウレタンを（Ａ）ポリエステルとして用いることはできない。 (A) Polyester is a polymer compound obtained by polycondensation of a compound having two or more carboxyl groups in the molecule and a compound having two or more hydroxyl groups in the molecule, and is made of glass. There is no particular limitation as long as it has a transition temperature of 0 to 20 ° C. and a hydroxyl value of 2 to 10 mgKOH / g. (A) As polyester, a specific kind may be used independently and 2 or more types may be used together. However, since the adhesion between the deposited plated metal film and the primer layer may not be obtained, polyester urethane cannot be used as the (A) polyester in the primer composition for electroless plating of the present invention.
（Ａ）ポリエステルのガラス転移温度（Ｔｇ）は、０～２０℃であるが、５～１５℃が好ましい。ガラス転移温度が０℃未満であると、めっき析出性が不十分となることがあり、２０℃を超えると、めっき金属膜とプライマー層との接着性が不十分となることがある。 (A) The glass transition temperature (Tg) of the polyester is 0 to 20 ° C., preferably 5 to 15 ° C. When the glass transition temperature is less than 0 ° C., the plating deposition property may be insufficient, and when it exceeds 20 ° C., the adhesion between the plated metal film and the primer layer may be insufficient.
（Ａ）ポリエステルの水酸基価は、２～１０ｍｇＫＯＨ／ｇであるが、４～８ｍｇＫＯＨ／ｇが好ましい。水酸基価が２ｍｇＫＯＨ／ｇ未満であると、硬化が不十分となり、プライマー層の強度が不十分となることがあり、１０ｍｇＫＯＨ／ｇを超えると、めっき金属膜とプライマー層との接着性が不十分となることがある。 (A) The hydroxyl value of the polyester is 2 to 10 mgKOH / g, preferably 4 to 8 mgKOH / g. When the hydroxyl value is less than 2 mgKOH / g, curing is insufficient, and the strength of the primer layer may be insufficient. When it exceeds 10 mgKOH / g, the adhesion between the plated metal film and the primer layer is insufficient. It may become.
（Ａ）ポリエステルの酸価は、特に限定されないが、２ｍｇＫＯＨ／ｇ未満が好ましい。酸価が２ｍｇＫＯＨ／ｇ以上であると、耐湿熱性が不十分となることがある。（Ａ）ポリエステルの酸価は、酸性部位と反応する反応基を有する物質と反応させることにより、２ｍｇＫＯＨ／ｇ未満に調節することができる。 (A) Although the acid value of polyester is not specifically limited, Less than 2 mgKOH / g is preferable. When the acid value is 2 mgKOH / g or more, the heat and moisture resistance may be insufficient. (A) The acid value of polyester can be adjusted to less than 2 mgKOH / g by reacting with a substance having a reactive group that reacts with an acidic site.
（Ａ）ポリエステルの分子量は、特に限定されないが、５，０００～１００，０００が好ましく、１０，０００～５０，０００がより好ましい。分子量が５，０００未満であると、プライマー層の強度が不十分となることがあり、１００，０００を超えると、塗布性の低下により均一なプライマー層が得られないことがある。 (A) The molecular weight of the polyester is not particularly limited, but is preferably 5,000 to 100,000, more preferably 10,000 to 50,000. When the molecular weight is less than 5,000, the primer layer may have insufficient strength, and when it exceeds 100,000, a uniform primer layer may not be obtained due to a decrease in coating properties.
（Ａ）ポリエステルとして使用できる市販品としては、例えば、バイロン６３０（東洋紡株式会社製、ガラス転移温度７℃、水酸基価５ｍｇＫＯＨ／ｇ、酸価＜２ｍｇＫＯＨ／ｇ）、バイロンＧＫ３４０（東洋紡株式会社製、ガラス転移温度０℃、水酸基価７ｍｇＫＯＨ／ｇ、酸価５ｍｇＫＯＨ／ｇ）等が挙げられる。 (A) As a commercial item which can be used as polyester, for example, Byron 630 (manufactured by Toyobo Co., Ltd., glass transition temperature 7 ° C., hydroxyl value 5 mgKOH / g, acid value <2 mgKOH / g), Byron GK340 (manufactured by Toyobo Co., Ltd., Glass transition temperature 0 ° C., hydroxyl value 7 mgKOH / g, acid value 5 mgKOH / g) and the like.
＜（Ｂ）ポリメチレンフェニルポリイソシアネート＞
本発明の無電解めっき用プライマー組成物は、硬化剤として、（Ｂ）ポリメチレンフェニルポリイソシアネートを含有する。（Ｂ）ポリメチレンフェニルポリイソシアネートは、ポリメリックＭＤＩ又はクルードＭＤＩとも呼称される。これらは単独で用いても良いし、２種以上を併用しても良い。 <(B) Polymethylene phenyl polyisocyanate>
The primer composition for electroless plating of the present invention contains (B) polymethylene phenyl polyisocyanate as a curing agent. (B) Polymethylene phenyl polyisocyanate is also called polymeric MDI or crude MDI. These may be used alone or in combination of two or more.
本発明の無電解めっき用プライマー組成物において、（Ｂ）成分の含有量は、（Ａ）成分１００重量部に対して５～４０重量部であるが、１０～３０重量部が好ましく、１０～２０重量部がより好ましい。含有量が５重量部未満であると、めっき析出性が不十分となることがあり、４０重量部を超えると、めっき金属膜とプライマー層との接着性が不十分となることがある。 In the primer composition for electroless plating of the present invention, the content of the component (B) is 5 to 40 parts by weight with respect to 100 parts by weight of the component (A), preferably 10 to 30 parts by weight. 20 parts by weight is more preferable. When the content is less than 5 parts by weight, the plating deposition property may be insufficient, and when it exceeds 40 parts by weight, the adhesion between the plated metal film and the primer layer may be insufficient.
（Ｂ）成分として使用できる市販品としては、例えば、ルプラネートＭ５Ｓ（ＢＡＳＦ　ＩＮＯＡＣ　ポリウレタン株式会社製）、コスモネートＭ－２００（三井化学株式会社製）等が挙げられる。 Examples of commercially available products that can be used as the component (B) include Lupranate M5S (BASF INOAC, polyurethane), Cosmonate M-200 (Mitsui Chemicals), and the like.
＜（Ｃ）有機溶剤＞
（Ｃ）有機溶剤としては、特に限定されないが、例えば、トルエン、１，３，５－トリメチルベンゼン、１，２，４－トリメチルベンゼン、ナフタレン、キシレン、ソルベントナフサ等の芳香族系炭化水素、メチルエチルケトン（ＭＥＫ）、メチルイソブチルケトン（ＭＩＢＫ）、アセトン、シクロヘキサノン等のケトン類、酢酸エチル、酢酸ブチル、メチルシクロヘキサン、Ｎ－メチルピロリドン等が挙げられる。これらは単独で用いても良いし、２種以上を併用しても良い。 <(C) Organic solvent>
(C) The organic solvent is not particularly limited, and examples thereof include aromatic hydrocarbons such as toluene, 1,3,5-trimethylbenzene, 1,2,4-trimethylbenzene, naphthalene, xylene, solvent naphtha, and methyl ethyl ketone. (MEK), methyl isobutyl ketone (MIBK), ketones such as acetone and cyclohexanone, ethyl acetate, butyl acetate, methylcyclohexane, N-methylpyrrolidone and the like. These may be used alone or in combination of two or more.
本発明の無電解めっき用プライマー組成物は、前記成分に加えて、本発明の目的を損なわない範囲内で、任意に他の成分を含有していても良い。他の成分としては、特に限定されないが、例えば、（Ｄ）疎水性ヒュームドシリカ、分散剤、レベリング剤、シランカップリング剤、無機及び有機フィラー（後述の（Ｄ）疎水性ヒュームドシリカを除く）が挙げられる。 In addition to the above components, the primer composition for electroless plating of the present invention may optionally contain other components as long as the object of the present invention is not impaired. Although it does not specifically limit as another component, For example, (D) Hydrophobic fumed silica, a dispersing agent, a leveling agent, a silane coupling agent, an inorganic and organic filler (except for (D) hydrophobic fumed silica mentioned later) ).
＜（Ｄ）疎水性ヒュームドシリカ＞
本発明の無電解めっき用プライマー組成物に（Ｄ）疎水性ヒュームドシリカを配合することにより、本発明の無電解めっき用プライマー組成物を用いて形成したプライマー層の、めっき金属膜に対する接着性を向上させることができる。 <(D) Hydrophobic fumed silica>
Adhesion of the primer layer formed using the primer composition for electroless plating of the present invention to the plated metal film by blending (D) hydrophobic fumed silica with the primer composition for electroless plating of the present invention Can be improved.
本発明の無電解めっき用プライマー組成物が（Ｄ）成分を含有する場合、その含有量は、特に限定されないが、無電解めっき用プライマー組成物の全固形分に対して５～２５重量％が好ましく、１０～２０重量％がより好ましい。含有量が５重量％未満であると、接着性向上効果が得られないことがあり、２５重量％を超えると、プライマー層と基材との接着性が不十分となることがある。 When the primer composition for electroless plating of the present invention contains the component (D), the content is not particularly limited, but it is 5 to 25% by weight based on the total solid content of the primer composition for electroless plating. Preferably, 10 to 20% by weight is more preferable. When the content is less than 5% by weight, the effect of improving the adhesiveness may not be obtained, and when it exceeds 25% by weight, the adhesion between the primer layer and the substrate may be insufficient.
本発明の無電解めっき用プライマー組成物において、全固形分の合計量は、特に限定されないが、２～２５重量％が好ましく、５～２０重量％がより好ましい。全固形分の合計量が２重量％未満であると、所定の膜厚を得るために大量の無電解めっき用プライマー組成物を塗布することになり不経済であり、また、無電解めっき用プライマー組成物の塗布性低下により均一なプライマー層が得られないことがある。一方、２５重量％を超えると、無電解めっき用プライマー組成物の塗布性低下により均一なプライマー層が得られないことがある。 In the primer composition for electroless plating of the present invention, the total amount of the total solid content is not particularly limited, but is preferably 2 to 25% by weight, more preferably 5 to 20% by weight. When the total amount of the total solids is less than 2% by weight, it is uneconomical to apply a large amount of the electroless plating primer composition to obtain a predetermined film thickness, and the electroless plating primer. A uniform primer layer may not be obtained due to a decrease in coating properties of the composition. On the other hand, if it exceeds 25% by weight, a uniform primer layer may not be obtained due to a decrease in the coating property of the primer composition for electroless plating.
本発明の無電解めっき用プライマー組成物には、チオール基を含有するシランカップリング剤の添加等により、チオール基を有する化合物が混入することがある。チオール基を有する化合物の含有量は、特に限定されないが、全固形分に対して２重量％以下であることが好ましく、１重量％以下であることがより好ましい。含有量が２重量％を超えると、めっき金属膜にクラック等の異常が発生し、めっき金属膜とプライマー層との接着性、特に耐湿熱試験後の接着性が低下することがある。チオール基を有する化合物の含有量は、使用する添加剤に含まれるチオール基を有する化合物の含有量等から算出することができる。 The primer composition for electroless plating of the present invention may be mixed with a compound having a thiol group due to the addition of a silane coupling agent containing a thiol group. Although content of the compound which has a thiol group is not specifically limited, It is preferable that it is 2 weight% or less with respect to the total solid, and it is more preferable that it is 1 weight% or less. If the content exceeds 2% by weight, abnormalities such as cracks occur in the plated metal film, and the adhesion between the plated metal film and the primer layer, particularly the adhesion after the wet heat resistance test may be lowered. The content of the compound having a thiol group can be calculated from the content of the compound having a thiol group contained in the additive used.
本発明の無電解めっき用プライマー組成物を得る際には、前記成分を配合した後で、（Ｃ）有機溶剤に不溶な成分を均一に分散させるため、必要に応じて分散処理を行っても良い。分散処理としては、当該分野で通常用いられる手段を用いた処理を行えば良く、例えば、ディスパー、ホモジナイザー、超音波ホモジナイザー、ビーズミル等の手段を用いた処理が挙げられる。これらの中では、簡便な処理で良好な分散とすることが出来ることから、超音波ホモジナイザーを用いた処理が好ましい。 When obtaining the primer composition for electroless plating according to the present invention, after blending the components, (C) a component insoluble in the organic solvent is uniformly dispersed. good. As the dispersion treatment, treatment using means usually used in the art may be performed, and examples thereof include treatment using means such as a disper, a homogenizer, an ultrasonic homogenizer, and a bead mill. In these, since it can be set as favorable dispersion | distribution by a simple process, the process using an ultrasonic homogenizer is preferable.
＜＜無電解めっき用プライマー部材＞＞
本発明の無電解めっき用プライマー部材は、基材上に、本発明の無電解めっき用プライマー組成物を塗布してプライマー層を形成して得られることを特徴とする。本発明の無電解めっき用プライマー組成物を用いることで、無電解めっき用プライマー組成物の塗布前に基材を表面粗化処理しない場合であっても、基材とプライマー層との接着性に優れた本発明の無電解めっき用プライマー部材を得ることができる。 << Primer member for electroless plating >>
The primer member for electroless plating of the present invention is obtained by applying a primer composition for electroless plating of the present invention on a substrate to form a primer layer. By using the primer composition for electroless plating of the present invention, even when the surface of the substrate is not roughened before the application of the primer composition for electroless plating, the adhesion between the substrate and the primer layer is improved. An excellent primer member for electroless plating of the present invention can be obtained.
＜基材＞
基材としては、特に限定されないが、例えば、ＰＢＴ、ＰＰＳ、ポリエチレンテレフタレート（ＰＥＴ）、ポリアミド（ＰＡ）、ポリアミドイミド（ＰＡＩ）等の材質からなる基材が挙げられる。これらは単独で用いても良いし、２種以上を併用しても良い。 <Base material>
Although it does not specifically limit as a base material, For example, the base material which consists of materials, such as PBT, PPS, a polyethylene terephthalate (PET), polyamide (PA), a polyamideimide (PAI), is mentioned. These may be used alone or in combination of two or more.
本発明の無電解めっき用プライマー組成物を用いてプライマー層を形成する際、常法に従い、基材に対して予め表面粗化処理を行っても良いが、本発明の無電解めっき用プライマー組成物を用いた場合、表面粗化処理をせずとも基材とプライマー層との接着性が良好となるため、表面粗化処理を行わなくても良い。
本発明の無電解めっき用プライマー部材において、基材を表面粗化処理する手間を省き、作業を簡略化する観点からは、基材は表面粗化処理されていないものであることが好ましいが、本発明では、基材とプライマー層との接着性をさらに強固なものとするために基材を表面粗化処理することが排除されるわけではない。 When a primer layer is formed using the primer composition for electroless plating of the present invention, the surface roughening treatment may be performed on the substrate in advance according to a conventional method, but the primer composition for electroless plating of the present invention When an object is used, the adhesiveness between the base material and the primer layer is improved without performing the surface roughening treatment, and thus the surface roughening treatment may not be performed.
In the primer member for electroless plating of the present invention, it is preferable that the substrate is not subjected to surface roughening treatment from the viewpoint of simplifying the work by omitting the trouble of surface roughening the substrate. In the present invention, it is not excluded to roughen the surface of the base material in order to further strengthen the adhesion between the base material and the primer layer.
本発明の無電解めっき用プライマー組成物を用いてプライマー層を形成する方法としては、特に限定されないが、無電解めっき用プライマー組成物を基材上に塗布した後、加熱処理、光照射処理等する方法等が挙げられる。無電解めっき用プライマー組成物を基材上に塗布する方法としては、特に限定されないが、例えば、ロールコート法、バーコート法、ディップコーティング法、スピンコーティング法、ブレードコート法、カーテンコート法、スプレーコート法、ドクターコート法等を用いることができる。これらの中では、特にスプレーコート法が好ましい。 A method for forming a primer layer using the primer composition for electroless plating of the present invention is not particularly limited, but after applying the primer composition for electroless plating on a substrate, heat treatment, light irradiation treatment, etc. And the like. The method for applying the primer composition for electroless plating on the substrate is not particularly limited. For example, a roll coating method, a bar coating method, a dip coating method, a spin coating method, a blade coating method, a curtain coating method, a spraying method. A coating method, a doctor coating method, or the like can be used. Among these, the spray coating method is particularly preferable.
基材上に塗布された無電解めっき用プライマー組成物を加熱処理、光照射処理等することにより、基材上にプライマー層を形成することができる。加熱処理は、特に限定されず公知の方法により行えば良く、例えば、送風オーブン、赤外線オーブン、真空オーブン等を用いて行えば良い。なお、無電解めっき用プライマー組成物が含有する（Ｃ）有機溶剤は、加熱処理により除去される。 The primer layer can be formed on the substrate by subjecting the primer composition for electroless plating applied on the substrate to heat treatment, light irradiation treatment, or the like. The heat treatment is not particularly limited and may be performed by a known method. For example, the heat treatment may be performed using a blow oven, an infrared oven, a vacuum oven, or the like. In addition, the (C) organic solvent which the primer composition for electroless plating contains is removed by heat processing.
加熱処理は、特に限定されないが、１５０℃以下の温度条件で行うことが好ましい。加熱処理の温度が１５０℃を超えると、用いる基材の材質が限定され、例えば、ポリエチレンテレフタレート（ＰＥＴ）、ポリカーボネート（ＰＣ）、アクリル樹脂等の材質からなる基材を用いることが出来なくなる。 Although heat processing is not specifically limited, It is preferable to perform on 150 degreeC or less temperature conditions. When the temperature of the heat treatment exceeds 150 ° C., the material of the base material to be used is limited, and for example, a base material made of a material such as polyethylene terephthalate (PET), polycarbonate (PC), or acrylic resin cannot be used.
加熱処理の温度は、６０～１４０℃であることが好ましく、８０～１３０℃であることがより好ましい。加熱処理の処理時間は、特に限定されないが、０．１～６０分間であることが好ましく、０．５～３０分間であることがより好ましい。 The temperature of the heat treatment is preferably 60 to 140 ° C., more preferably 80 to 130 ° C. The treatment time for the heat treatment is not particularly limited, but is preferably 0.1 to 60 minutes, more preferably 0.5 to 30 minutes.
光照射処理には、特に限定されないが、主に、紫外線、可視光、電子線、電離放射線等を使用する。紫外線硬化の場合には、超高圧水銀灯、高圧水銀灯、低圧水銀灯、カーボンアーク、キセノンアーク、メタルハライドランプ等の光源から発する紫外線等を使用することができる。ここで、エネルギー線源の照射量は、紫外線波長３６５ｎｍでの積算露光量として、５０～５０００ｍＪ／ｃｍ２程度である。 The light irradiation treatment is not particularly limited, but mainly ultraviolet rays, visible light, electron beams, ionizing radiation, etc. are used. In the case of ultraviolet curing, ultraviolet rays emitted from a light source such as an ultra-high pressure mercury lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, a xenon arc, or a metal halide lamp can be used. Here, the irradiation amount of the energy ray source is about 50 to 5000 mJ / cm 2 as an integrated exposure amount at an ultraviolet wavelength of 365 nm.
プライマー層の表面粗さ（Ｒａ）は、１０００ｎｍ以上が好ましく、２０００ｎｍ以上がより好ましい。表面粗さが１０００ｎｍ未満であると、めっき金属膜との接着性が不十分となることがある。プライマー層の表面粗さは、（Ｄ）疎水性フュームドシリカの添加量を調整することにより、１０００ｎｍ以上に調節することができる。 The surface roughness (Ra) of the primer layer is preferably 1000 nm or more, and more preferably 2000 nm or more. If the surface roughness is less than 1000 nm, the adhesion to the plated metal film may be insufficient. The surface roughness of the primer layer can be adjusted to 1000 nm or more by adjusting the amount of (D) hydrophobic fumed silica added.
プライマー層の厚さは、特に限定されないが、２～５０μｍが好ましく、５～２０μｍがより好ましい。厚さが２μｍ未満であると、めっき金属膜とプライマー層との接着性が不十分となることがあり、５０μｍを超えると、不経済である。 The thickness of the primer layer is not particularly limited, but is preferably 2 to 50 μm, more preferably 5 to 20 μm. If the thickness is less than 2 μm, the adhesion between the plated metal film and the primer layer may be insufficient, and if it exceeds 50 μm, it is uneconomical.
＜＜めっき物＞＞
本発明のめっき物は、本発明の無電解めっき用プライマー部材を用いて得られたことを特徴とする。 << Plating product >>
The plated product of the present invention is obtained using the primer member for electroless plating of the present invention.
本発明の無電解めっき用プライマー部材を用いてめっき物を得る方法としては、例えば、無電解めっき用プライマー部材に対して無電解めっき法を行い、析出しためっき金属膜を導電体としてさらに電解めっき法を行う方法等が挙げられる。無電解めっき法、電解めっき法は、それぞれ公知の方法により行えば良い。 As a method for obtaining a plated product using the primer member for electroless plating according to the present invention, for example, an electroless plating method is performed on the primer member for electroless plating, and the deposited metal film is further electroplated as a conductor. The method of performing a law etc. are mentioned. The electroless plating method and the electrolytic plating method may be performed by known methods.
本発明のめっき物において、めっき金属膜の膜厚は、特に限定されないが、１μｍ以上が好ましく、２０μｍ以上がより好ましい。膜厚が１μｍ未満であると、電磁波シールド特性が不十分であったり、配線抵抗が大きい等の不具合が発生することがある。 In the plated product of the present invention, the thickness of the plated metal film is not particularly limited, but is preferably 1 μm or more, and more preferably 20 μm or more. If the film thickness is less than 1 μm, problems such as insufficient electromagnetic shielding characteristics and high wiring resistance may occur.
本発明のめっき物の用途は、導電性が要求される用途であれば特に限定されないが、例えば、電磁波シールド部材、回路部品等が挙げられる。 The use of the plated product of the present invention is not particularly limited as long as conductivity is required, and examples thereof include an electromagnetic wave shielding member and a circuit component.
以下、実施例を挙げて本発明を説明するが、本発明は以下の実施例に限定されない。以下、「部」又は「％」は特記ない限り、それぞれ「重量部」又は「重量％」を意味する。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated, this invention is not limited to a following example. Hereinafter, “part” or “%” means “part by weight” or “% by weight”, respectively, unless otherwise specified.
１．使用材料
１－１．バインダー
・ポリエステル（東洋紡株式会社製、バイロン６３０、ガラス転移温度７℃、水酸基価５ｍｇＫＯＨ／ｇ、酸価＜２ｍｇＫＯＨ／ｇ）
・ポリエステル（東洋紡株式会社製、バイロンＧＫ３４０、ガラス転移温度０℃、水酸基価７ｍｇＫＯＨ／ｇ、酸価５ｍｇＫＯＨ／ｇ）
・ポリエステル（東洋紡株式会社製、バイロンＢＸ１００１、ガラス転移温度－１８℃、水酸基価８ｍｇＫＯＨ／ｇ、酸価＜２ｍｇＫＯＨ／ｇ）
・ポリエステル（東洋紡株式会社製、バイロン６００、ガラス転移温度４７℃、水酸基価７ｍｇＫＯＨ／ｇ、酸価＜２ｍｇＫＯＨ／ｇ）
・ポリエステル（東洋紡株式会社製、バイロン６７０、ガラス転移温度７℃、水酸基価２ｍｇＫＯＨ／ｇ未満、酸価２ｍｇＫＯＨ／ｇ） 1. Materials used 1-1. Binder polyester (by Toyobo Co., Ltd., Byron 630, glass transition temperature 7 ° C., hydroxyl value 5 mgKOH / g, acid value <2 mgKOH / g)
Polyester (Toyobo Co., Ltd., Byron GK340, glass transition temperature 0 ° C., hydroxyl value 7 mgKOH / g, acid value 5 mgKOH / g)
Polyester (by Toyobo Co., Ltd., Byron BX1001, glass transition temperature -18 ° C., hydroxyl value 8 mgKOH / g, acid value <2 mgKOH / g)
Polyester (Toyobo Co., Ltd., Byron 600, glass transition temperature 47 ° C., hydroxyl value 7 mg KOH / g, acid value <2 mg KOH / g)
Polyester (by Toyobo Co., Ltd., Byron 670, glass transition temperature 7 ° C., hydroxyl value less than 2 mgKOH / g, acid value 2 mgKOH / g)
１－２．硬化剤
・ポリメリックＭＤＩ（ＢＡＳＦ　ＩＮＯＡＣ　ポリウレタン株式会社製、ルプラネートＭ５Ｓ）
・ポリメリックＭＤＩ（三井化学株式会社製、コスモネートＭ－２００）
・ＭＤＩモノマー（三井化学株式会社製、コスモネートＰＨ） 1-2. Curing agent / polymeric MDI (BASF INOAC Polyurethane Co., Ltd., Lupranate M5S)
・ Polymeric MDI (Mitsui Chemicals Cosmonate M-200)
・ MDI monomer (Mitsui Chemicals, Cosmonate PH)
１－３．フィラー
・疎水性ヒュームドシリカ（日本アエロジル株式会社製、アエロジルＲＹ－２００Ｓ） 1-3. Filler / hydrophobic fumed silica (Aerosil RY-200S, manufactured by Nippon Aerosil Co., Ltd.)
１－４．有機溶剤
・芳香族系炭化水素溶剤（東燃ゼネラル石油株式会社製、ソルベッソ１００）
・芳香族系炭化水素溶剤（東燃ゼネラル石油株式会社製、ソルベッソ１５０）
・トルエン
・メチルエチルケトン（ＭＥＫ） 1-4. Organic solvent / aromatic hydrocarbon solvent (TonenGeneral Sekiyu KK, Solvesso 100)
・ Aromatic hydrocarbon solvent (manufactured by TonenGeneral Sekiyu KK, Solvesso 150)
・ Toluene methyl ethyl ketone (MEK)
２．評価方法
２－１．基材接着性
基材上に形成したプライマー層にセロハンテープを張り付け、一気に剥がした後、プライマー層の剥離状態を目視で観察し、下記の基準で評価した。
○：剥離は観察されない。
△：一部に剥離が観察される。
×：全体に剥離が観察される。 2. Evaluation method 2-1. A cellophane tape was applied to the primer layer formed on the substrate adhesive substrate and peeled off at once. Then, the peeled state of the primer layer was visually observed and evaluated according to the following criteria.
○: No peeling is observed.
Δ: Peeling is observed in part.
X: Peeling is observed throughout.
２－２．めっき金属析出性
プライマー層の表面全体に対する、無電解めっき法によりめっき金属が析出した部分の割合（析出率）を目視により概算し、下記の基準で評価した。
○：析出率は９５％以上である。
△：析出率は９０％以上９５％未満である。
×：析出率は９０％未満である。 2-2. The ratio (precipitation rate) of the portion where the plating metal was deposited by the electroless plating method with respect to the entire surface of the plating metal precipitation primer layer was estimated by visual observation, and evaluated according to the following criteria.
(Circle): A precipitation rate is 95% or more.
Δ: The precipitation rate is 90% or more and less than 95%.
X: The precipitation rate is less than 90%.
２－３．めっき金属膜外観
無電解めっき法により得られためっき金属膜の表面状態を、目視及び光学顕微鏡で観察し、外観異常（クラック、孔、しわ等）の有無を評価した。 2-3. The surface state of the plated metal film obtained by the electroless plating method of the plated metal film appearance was observed visually and with an optical microscope to evaluate the presence or absence of abnormal appearance (cracks, holes, wrinkles, etc.).
２－４．めっき金属膜接着性
電解めっき法により得られためっき金属膜（及びプライマー層）に、幅１０ｍｍ、長さ３０ｍｍの切り込みを入れた。ハンディデジタルフォースゲージ（日本計測システム株式会社製、フォースゲージＨＦ－１０）及び自動縦型サーボスタンド（日本計測システム株式会社製、サーボスタンドＪＳＶ－Ｈ１０００）を用いて、幅１０ｍｍ、長さ２５ｍｍの引き剥がし（ピール）強度を測定し、下記の基準で評価した。
◎：ピール強度が１０Ｎ／ｃｍ以上である。
○：ピール強度が５Ｎ／ｃｍ以上１０Ｎ／ｃｍ未満である。
△：ピール強度が３Ｎ／ｃｍ以上５Ｎ／ｃｍ未満である。
×：ピール強度が３Ｎ／ｃｍ未満である。
剥離：ピール強度測定前にめっき金属膜の一部又は全てがプライマー層から既に剥離している。 2-4. Plating metal film Adhesive cuts with a width of 10 mm and a length of 30 mm were made in the plated metal film (and primer layer) obtained by the electrolytic plating method. Using a handy digital force gauge (manufactured by Japan Measuring System Co., Ltd., Force Gauge HF-10) and an automatic vertical servo stand (manufactured by Japan Measuring System Co., Ltd., servo stand JSV-H1000), pulling 10 mm wide and 25 mm long The peel strength was measured and evaluated according to the following criteria.
A: Peel strength is 10 N / cm or more.
○: Peel strength is 5 N / cm or more and less than 10 N / cm.
Δ: Peel strength is 3 N / cm or more and less than 5 N / cm.
X: Peel strength is less than 3 N / cm.
Peeling: A part or all of the plated metal film has already peeled from the primer layer before the peel strength measurement.
ピール強度の測定は、電解めっき法を行った直後（初期）、温度８５℃、湿度８５％の条件下で９６時間保管後（耐湿熱試験後）、及び、－４０℃で３０分間保管後、１２５℃で３０分間保管する工程を１サイクルとして、１００サイクル経た後（熱サイクル試験後）、の３回ずつ行った。 Peel strength was measured immediately after the electroplating method (initial), after storage for 96 hours under conditions of a temperature of 85 ° C. and a humidity of 85% (after a moist heat test), and after storage at −40 ° C. for 30 minutes. The process of storing at 125 ° C. for 30 minutes was defined as one cycle, and after 100 cycles (after the thermal cycle test), the test was performed three times.
２－５．プライマー層の表面粗さ（Ｒａ）
表面粗さＲａは、触針式表面形状測定装置Ｄｅｋｔａｋ　６Ｍ（Ｂｒｕｋｅｒ　Ｎａｎｏ社製）を用いて測定した。 2-5. Surface roughness of primer layer (Ra)
The surface roughness Ra was measured using a stylus type surface shape measuring device Dektak 6M (manufactured by Bruker Nano).
（実施例１～８、比較例１～６）
表１に記載した重量比で各成分を混合したものを超音波ホモジナイザー（ブランソン社製、ＳＯＮＩＦＩＥＲ４５０）を用いて処理し（アイスバスで冷却しながらＯＵＴＰＵＴ　４０の条件で１０分間）、無電解めっき用プライマー組成物を作製した。常法に従い作製したグラスファイバー３０％含有ＰＢＴ製の基材（８０×５０×２ｍｍ）の表面を、イソプロピルアルコール（ＩＰＡ）を浸み込ませたウェスを用いて脱脂した。作製した無電解めっき用プライマー組成物をハンドガン（株式会社近畿製作所製、ＣＲＥＡＭＹ　Ｋ３、ノズル口径０．５ｍｍ）に充填し、基材にスプレー噴射しながら８往復することで、無電解めっき用プライマー組成物を基材に塗布した。その後、常温で５分間静置した後、オーブン（東京理化器械株式会社製）にて１００℃で３０分間加熱処理することにより、無電解めっき用プライマー組成物を乾燥させ、プライマー層を形成して無電解めっき用プライマー部材を得た。ここで、上記２－１．に記載した方法により基材接着性を評価するとともに、上記２－５．に記載した方法によりプライマー層の表面粗さ（Ｒａ）を測定した。 (Examples 1 to 8, Comparative Examples 1 to 6)
Processed by mixing each component in the weight ratio shown in Table 1 using an ultrasonic homogenizer (Branson, SONIFIER 450) (10 minutes under OUTPUT 40 conditions while cooling in an ice bath) for electroless plating A primer composition was prepared. The surface of a PBT base material (80 × 50 × 2 mm) containing 30% glass fiber prepared according to a conventional method was degreased using a waste impregnated with isopropyl alcohol (IPA). The prepared primer composition for electroless plating is filled in a hand gun (CREAMY K3, manufactured by Kinki Seisakusho Co., Ltd., nozzle diameter: 0.5 mm), and is reciprocated 8 times while spraying onto the base material. The product was applied to the substrate. Then, after leaving still at normal temperature for 5 minutes, the primer composition for electroless plating was dried by heat-processing at 100 degreeC for 30 minute (s) in oven (made by Tokyo Rika Kikai Co., Ltd.), and a primer layer was formed. A primer member for electroless plating was obtained. Here, in 2-1. In addition to evaluating the substrate adhesion by the method described in 2), the above 2-5. The surface roughness (Ra) of the primer layer was measured by the method described in 1).
以下の方法により無電解めっき法を行った。
一連の無電解めっき用薬液はアトテックジャパン株式会社の薬液を使用した。まず無電解めっき用プライマー部材をプリディップネオガントＢ希釈液を用いて常温で１分間浸漬処理した。次に触媒液としてアクチベーター８３４調整液を用いて４０℃で５分間浸漬した後、水洗を行った。次に還元液としてリデューサーネオガントＷＡ８０１調整液を用いて常温で５分間浸漬処理した後、水洗を行った。次に無電解めっき液としてプリントガントＶ調整液を用いて３４℃で５分間、エアバブリングしながら浸漬処理した後、水洗を行った。最後にエアガンで水切りしたのち、常温で１２時間以上自然乾燥を行った。
ここで、上記２－２．～２－３．に記載した方法により、めっき金属析出性及びめっき金属膜外観を評価した。 The electroless plating method was performed by the following method.
A series of chemicals for electroless plating used chemicals from Atotech Japan. First, the primer member for electroless plating was immersed for 1 minute at room temperature using a pre-dip Neogant B diluent. Next, using an activator 834 adjusting solution as a catalyst solution, it was immersed at 40 ° C. for 5 minutes, and then washed with water. Next, the reducer Neogant WA801 adjusting solution was used as a reducing solution, and after immersion treatment at room temperature for 5 minutes, it was washed with water. Next, using a print Gantt V adjustment solution as an electroless plating solution, it was immersed in air bubbling at 34 ° C. for 5 minutes, and then washed with water. Finally, after draining with an air gun, it was naturally dried at room temperature for 12 hours or more.
Here, 2-2. 2-3. The plating metal depositability and the plating metal film appearance were evaluated by the methods described in 1).
以下の方法により電解めっき法を行った。
電解めっき用薬液としてアトテックジャパン株式会社のＣＵＰＬＥＸ３３０調整液、アノードとしてハルセル陽極板　含燐銅（株式会社山本鍍金試験機社製）、電源としてＨＫＤ－１５３０Ｆ（株式会社三社電機作成所製）を使用した。電解めっき用薬液を入れためっき浴にめっき対象物をセットして電源を接続し、１．８アンペアで常温、２４分間の条件で電解めっきを行った。電解めっき後に水洗を行い、最後に８０℃のオーブンで６０分間乾燥した。
ここで、上記２－４．に記載した方法により、めっき金属膜接着性を評価した。以上の評価結果を表２に示す。 The electrolytic plating method was performed by the following method.
CUPLEX 330 adjustment solution of Atotech Japan Co., Ltd. is used as a chemical solution for electrolytic plating, Hull cell anode plate containing phosphorous copper (manufactured by Yamamoto Kakin Tester Co., Ltd.) as anode, and HKD-1530F (manufactured by Sansha Electric Co., Ltd.) as power did. An object to be plated was set in a plating bath containing a chemical solution for electrolytic plating, a power source was connected, and electrolytic plating was performed at 1.8 ampere at room temperature for 24 minutes. After electrolytic plating, washing with water was performed, and finally, drying was performed in an oven at 80 ° C. for 60 minutes.
Here, the above 2-4. The plating metal film adhesiveness was evaluated by the method described in 1). The above evaluation results are shown in Table 2.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002

Claims (7)

  1. （Ａ）ガラス転移温度が０～２０℃、かつ、水酸基価が２～１０ｍｇＫＯＨ／ｇであるポリエステル（但し、ポリエステルウレタンを除く）　１００重量部、
    （Ｂ）ポリメチレンフェニルポリイソシアネート　５～４０重量部、及び、
    （Ｃ）有機溶剤
    を含有することを特徴とする無電解めっき用プライマー組成物。     (A) 100 parts by weight of a polyester having a glass transition temperature of 0 to 20 ° C. and a hydroxyl value of 2 to 10 mg KOH / g (excluding polyester urethane),
    (B) 5 to 40 parts by weight of polymethylene phenyl polyisocyanate, and
    (C) A primer composition for electroless plating containing an organic solvent.
  2. （Ａ）ポリエステルの酸価が２ｍｇＫＯＨ／ｇ未満である、請求項１に記載の無電解めっき用プライマー組成物。 (A) The primer composition for electroless plating according to claim 1, wherein the acid value of the polyester is less than 2 mgKOH / g.
  3. 全固形分の合計量が２～２５重量％である、請求項１又は２に記載の無電解めっき用プライマー組成物。 The primer composition for electroless plating according to claim 1 or 2, wherein the total amount of the total solids is 2 to 25% by weight.
  4. さらに、（Ｄ）疎水性フュームドシリカを全固形分に対して５～２５重量％含む、請求項１～３のいずれか１項に記載の無電解めっき用プライマー組成物。 The primer composition for electroless plating according to any one of claims 1 to 3, further comprising (D) 5 to 25% by weight of hydrophobic fumed silica based on the total solid content.
  5. 基材上に、請求項１～４のいずれか１項に記載の無電解めっき用プライマー組成物を塗布してプライマー層を形成して得られたことを特徴とする無電解めっき用プライマー部材。 An electroless plating primer member obtained by applying the primer composition for electroless plating according to any one of claims 1 to 4 to form a primer layer on a substrate.
  6. 基材が表面粗化処理されていないものである、請求項５に記載の無電解めっき用プライマー部材。 The primer member for electroless plating according to claim 5, wherein the base material is not subjected to surface roughening treatment.
  7. 請求項５又は６に記載の無電解めっき用プライマー部材を用いて得られたことを特徴とするめっき物。 A plated article obtained using the primer member for electroless plating according to claim 5 or 6.
PCT/JP2015/075303 2014-09-09 2015-09-07 Primer composition for electroless plating, primer member for electroless plating, and plated article WO2016039282A1 (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007108351A1 (en) * 2006-03-23 2007-09-27 Kimoto Co., Ltd. Material to be plated by electroless plating and method of electroless plating on the same
JP2012241208A (en) * 2011-05-17 2012-12-10 Achilles Corp Plating undercoat layer

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007108351A1 (en) * 2006-03-23 2007-09-27 Kimoto Co., Ltd. Material to be plated by electroless plating and method of electroless plating on the same
JP2012241208A (en) * 2011-05-17 2012-12-10 Achilles Corp Plating undercoat layer

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