[go: up one dir, main page]

WO2016039283A1 - Composition d'apprêt pour dépôt autocatalytique, élément d'apprêt pour dépôt autocatalytique et article plaqué - Google Patents

Composition d'apprêt pour dépôt autocatalytique, élément d'apprêt pour dépôt autocatalytique et article plaqué Download PDF

Info

Publication number
WO2016039283A1
WO2016039283A1 PCT/JP2015/075306 JP2015075306W WO2016039283A1 WO 2016039283 A1 WO2016039283 A1 WO 2016039283A1 JP 2015075306 W JP2015075306 W JP 2015075306W WO 2016039283 A1 WO2016039283 A1 WO 2016039283A1
Authority
WO
WIPO (PCT)
Prior art keywords
electroless plating
primer
primer composition
weight
plating according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2015/075306
Other languages
English (en)
Japanese (ja)
Inventor
秀国 安江
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nagase Chemtex Corp
Original Assignee
Nagase Chemtex Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nagase Chemtex Corp filed Critical Nagase Chemtex Corp
Priority to JP2016547427A priority Critical patent/JPWO2016039283A1/ja
Publication of WO2016039283A1 publication Critical patent/WO2016039283A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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 wave 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-dimensionally 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 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, (C) Inorganic filler having an average major axis of primary particles of 1 to 5 ⁇ m and an aspect ratio of 3 or more 45 to 75% by weight with respect to the total solid content, and (D) It contains an organic solvent.
  • the (C) inorganic filler is preferably calcium carbonate and / or talc.
  • the (C) inorganic filler is preferably a columnar or spindle type calcium carbonate.
  • the primer composition for electroless plating of the present invention preferably further contains (E) a dispersant, and (E) the dispersant is preferably a modified urea.
  • 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 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 preferably 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
  • PBT polymethylene phenyl polyisocyanate
  • 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, (C) Inorganic filler having an average major axis of primary particles of 1 to 5 ⁇ m and an aspect ratio of 3 or more 45 to 75% by weight with respect to the total solid content, and (D) 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. If the hydroxyl value is less than 2 mgKOH / g, curing may be insufficient, and the primer layer may have insufficient strength. If it exceeds 10 mgKOH / g, adhesion between the plated metal film and the primer layer may be poor. May be sufficient.
  • 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 primer composition for electroless plating of the present invention comprises (C) an inorganic filler having an average major axis of primary particles of 1 to 5 ⁇ m and an aspect ratio of 3 or more.
  • an inorganic filler having a specific average major axis and aspect ratio the heat cycle resistance is improved.
  • the inorganic filler is not particularly limited as long as the average major axis of primary particles is 1 to 5 ⁇ m and the aspect ratio is 3 or more, and examples thereof include calcium carbonate, talc, mica, and plate-like silica. These may be used alone or in combination of two or more. Among these, calcium carbonate and / or talc are preferable from the viewpoint of improving cost and heat cycle resistance. In general, when a large amount of an inorganic filler is added, the adhesion between the base material and the primer layer tends to decrease, but even when added in a large amount, the tendency for the adhesiveness to decrease is small. From the viewpoint of ensuring a wide degree of design freedom, columnar or spindle-type calcium carbonate is preferable.
  • the average major axis of the primary particles of the inorganic filler is 1 to 5 ⁇ m, preferably 2 to 5 ⁇ m. If the major axis is less than 1 ⁇ m, the heat cycle improvement effect may be insufficient, and if it exceeds 5 ⁇ m, the inorganic filler may break through the primer layer and be exposed, resulting in a decrease in plating deposition.
  • the aspect ratio of the inorganic filler is 3 or more, preferably 4 or more, and more preferably 5 or more. If the aspect ratio is less than 3, the heat cycle resistance improvement effect may be insufficient.
  • the content of the component (C) is 45 to 75% by weight, preferably 50 to 70% by weight, and 55 to 65% by weight based on the total solid content. More preferred. When the content is less than 45% by weight, the heat cycle improvement effect may be insufficient, and when it exceeds 75% by weight, the adhesion between the substrate and the primer layer may be lowered.
  • 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, (E) A dispersing agent, a leveling agent, a silane coupling agent, an inorganic and organic filler (except the above-mentioned (C) inorganic filler) etc. are mentioned.
  • the primer composition for electroless plating of the present invention further contains (E) a dispersant in order to prevent sedimentation of the (C) inorganic filler in the composition and aggregation of the (C) inorganic filler in the primer layer. It is preferable.
  • a dispersing agent A well-known dispersing agent can be used, and it may be used independently and may use 2 or more types together.
  • a modified urea is preferable from the point of not inhibiting electroless plating precipitation.
  • the content thereof is not particularly limited, but is 0.2 to 10% by weight with respect to the total solid content of the primer composition for electroless plating. % Is preferable, and 0.5 to 5% by weight is more preferable. When the content is less than 0.2% by weight, the effect of improving dispersibility may not be obtained. When the content exceeds 10% by weight, the adhesion between the plated metal film and the primer layer may be lowered.
  • 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 (D) 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 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
  • Curing agent / polymeric MDI (BASF INOAC Polyurethane Co., Ltd., Lupranate M5S)
  • Dispersant / modified urea (manufactured by Big Chemie Japan, BYK410, solid content 52%)
  • Organic solvent / aromatic hydrocarbon solvent (TonenGeneral Sekiyu KK, Solvesso 100) ⁇ 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 300 cycles (after the thermal cycle test), the process was repeated three times.
  • Examples 1 to 4 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.
  • the substrate adhesion was evaluated 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemically Coating (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention a pour objet une composition d'apprêt pour le dépôt autocatalytique, qui présente une excellente adhérence à une base en résine faiblement adhésive telle qu'un poly(téréphtalate de butylène) et un poly(sulfure de phénylène) et à un film de placage métallique qui est déposé par dépôt autocatalytique et qui permet la formation appropriée d'un film de placage métallique ayant un bon état de surface dans les cas où cette composition d'apprêt pour le dépôt autocatalytique est mise sous forme d'une couche d'apprêt. La composition d'apprêt pour le dépôt autocatalytique selon la présente invention est caractérisée en ce qu'elle contient : (A) 100 parties en poids d'un polyester ayant une température de transition vitreuse de 0 °C à 20 °C et un indice d'hydroxyle de 2 à 10 mg de KOH/g (exclusion faite des polyester-uréthanes) ; (B) 5 à 40 parties en poids d'un polyisocyanate de polyméthylènephényle ; (C) une charge inorganique ayant une longueur moyenne des particules primaires de 1 à 5 µm et un rapport de forme supérieur ou égale à 3 en une quantité de 45 à 75 % en poids par rapport à la teneur en matières solides totales ; et (D) un solvant organique.
PCT/JP2015/075306 2014-09-09 2015-09-07 Composition d'apprêt pour dépôt autocatalytique, élément d'apprêt pour dépôt autocatalytique et article plaqué Ceased WO2016039283A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2016547427A JPWO2016039283A1 (ja) 2014-09-09 2015-09-07 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

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2014183417 2014-09-09
JP2014-183417 2014-09-09

Publications (1)

Publication Number Publication Date
WO2016039283A1 true WO2016039283A1 (fr) 2016-03-17

Family

ID=55459031

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2015/075306 Ceased WO2016039283A1 (fr) 2014-09-09 2015-09-07 Composition d'apprêt pour dépôt autocatalytique, élément d'apprêt pour dépôt autocatalytique et article plaqué

Country Status (2)

Country Link
JP (1) JPWO2016039283A1 (fr)
WO (1) WO2016039283A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019039061A (ja) * 2017-08-29 2019-03-14 ユニチカ株式会社 ポリアミド樹脂めっき成形体
CN112654728A (zh) * 2018-09-11 2021-04-13 三菱工程塑料株式会社 带金属膜的树脂成型品及其制造方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007108351A1 (fr) * 2006-03-23 2007-09-27 Kimoto Co., Ltd. Materiau destine a etre plaque par placage anelectrolytique et procede de placage anelectrolytique de ce materiau
JP2012241208A (ja) * 2011-05-17 2012-12-10 Achilles Corp めっき下地塗膜層

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007108351A1 (fr) * 2006-03-23 2007-09-27 Kimoto Co., Ltd. Materiau destine a etre plaque par placage anelectrolytique et procede de placage anelectrolytique de ce materiau
JP2012241208A (ja) * 2011-05-17 2012-12-10 Achilles Corp めっき下地塗膜層

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019039061A (ja) * 2017-08-29 2019-03-14 ユニチカ株式会社 ポリアミド樹脂めっき成形体
CN112654728A (zh) * 2018-09-11 2021-04-13 三菱工程塑料株式会社 带金属膜的树脂成型品及其制造方法

Also Published As

Publication number Publication date
JPWO2016039283A1 (ja) 2017-06-15

Similar Documents

Publication Publication Date Title
US9228111B2 (en) Resin composition for surface treatment of steel sheet and surface-treated steel sheet using the same
Gupta et al. Polyaniline-lignosulfonate/epoxy coating for corrosion protection of AA2024-T3
EP2011838B1 (fr) Composition de revetement comprenant des nanofibres de carbone multicouches traités en surface
CN1175060C (zh) 氟树脂涂覆用水性底漆组合物
EP3315562B1 (fr) Composition liquide électroconductrice
CN110591483A (zh) 一种高导电性水性汽车保险杠底漆及其制备方法
TW201435150A (zh) 塗覆導電基板之方法及相關可電沉積組合物
CN103068936A (zh) 含有掺杂态聚苯胺和液体石蜡的防腐蜡组合物
JP2017145397A (ja) 電着液及び電着塗装体
WO2024158025A1 (fr) Collecteur de courant à couche mince pour batterie de stockage
WO2016039283A1 (fr) Composition d'apprêt pour dépôt autocatalytique, élément d'apprêt pour dépôt autocatalytique et article plaqué
CN1102460C (zh) 具有低接触电阻的表面处理钢板以及由此钢板制成的接线端子部件
KR100244650B1 (ko) 가공후 내흑화성이 우수한 수지처리 전기아연도금강판의 제조방 법
WO2016039282A1 (fr) Composition d'apprêt pour dépôt autocatalytique, élément d'apprêt pour dépôt autocatalytique, et article métallisé
US20120237775A1 (en) Powder coating method
JP2017125226A (ja) 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
JP2023111905A (ja) ドライフィルム、硬化物、該硬化物からなる層間絶縁層、および配線基板
US12110411B2 (en) Powder coating composition
US20120301714A1 (en) Multilayer structure, and a method for making the same
JP2012045470A (ja) 導電性塗膜の製造方法及び導電性塗膜
WO2017141885A1 (fr) Liquide d'électrodéposition et article revêtu par électrodéposition
WO2022141816A1 (fr) Composition de résine, film adhésif de résine, et application associée
JP6284536B2 (ja) 無電解めっき用塗料組成物
JP4922746B2 (ja) 樹脂被覆アルミニウム材、これを用いた電子機器用又は家電製品用の筐体、ならびに、この筐体を用いた電子機器又は家電製品
JP6515383B2 (ja) 黒色亜鉛合金めっき鋼板とその製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15839271

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2016547427

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15839271

Country of ref document: EP

Kind code of ref document: A1