WO2020090868A1 - Topcoating composition for discontinuous metallic thin film, and undercoating composition for discontinuous metallic thin film - Google Patents

Topcoating composition for discontinuous metallic thin film, and undercoating composition for discontinuous metallic thin film Download PDF

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Publication number
WO2020090868A1
WO2020090868A1 PCT/JP2019/042521 JP2019042521W WO2020090868A1 WO 2020090868 A1 WO2020090868 A1 WO 2020090868A1 JP 2019042521 W JP2019042521 W JP 2019042521W WO 2020090868 A1 WO2020090868 A1 WO 2020090868A1
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Prior art keywords
thin film
metal thin
discontinuous metal
coating composition
group
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PCT/JP2019/042521
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French (fr)
Japanese (ja)
Inventor
英明 奥田
水口　克美
晋之介 河野
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日本ペイント・オートモーティブコーティングス株式会社
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Publication of WO2020090868A1 publication Critical patent/WO2020090868A1/en

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    • 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
    • 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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; 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
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09D201/06—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic

Definitions

  • the present invention relates to a coating composition for a discontinuous metal thin film topcoat and a coating composition for a discontinuous metal thin film undercoat.
  • the discontinuous metal thin film has luster and has a metallic luster appearance, while also having electromagnetic wave transmission performance.
  • a discontinuous metal thin film for example, can bring a glittering or metallic luster appearance to a member of a system that performs mutual authentication by transmitting and receiving electromagnetic waves or a system that performs electronic control, and thus enhances designability. This has the advantage that the design selection possibilities can be expanded.
  • Such a discontinuous metal thin film is used in, for example, a front part of an automobile, a door handle of an automobile, a communication device mounted on a car, a mobile phone, a portable information terminal device, various home electric appliances having an electromagnetic wave transmission / reception system, and housing equipment. Or is being considered for use.
  • Patent Document 1 describes a tin thin film or an indium thin film formed on a substrate, and an undercoat layer and an overcoat layer formed adjacent to the tin thin film or the indium thin film.
  • the undercoat layer and / or the overcoat layer is formed from a tin thin film or indium thin film coating composition containing a coating film forming component and a metal soap. It is described (Claims 1 and 2). It is described that this composite coating film has a texture unique to metal and is excellent in design.
  • Patent Document 2 discloses a door handle for opening and closing a door provided on a vehicle door, an electrode arranged on the door handle, and a human body part approaching or approaching the door handle.
  • a detection circuit that outputs a lock or unlock operation signal by detecting a change in capacitance that occurs in the vicinity of the electrode due to a contact; a device that locks or unlocks the door by the operation signal;
  • a transmitting / receiving antenna for transmitting / receiving to / from a portable device corresponding to the above, and the door handle has a base made of an insulator, and SiO 2 and Al 2 O 3 are provided on at least a vehicle outer surface of the base.
  • a door opening and closing device is described in which a metal thin film layer deposited on the surface of the film layer is provided (Claim 1). It is described that this door opening / closing device has an excellent metallic luster and is less likely to cause malfunction or non-operation.
  • a vehicle door handle component as described in Patent Document 2 is a component provided on the outside of the vehicle, and therefore it is required to have excellent weather resistance (UV resistance, water resistance, etc.). Since the vehicle door handle component is a component that is frequently touched by the occupant of the vehicle, durability against sweat, moisture and grease adhered to the occupant's hand and scratch resistance are also required. Further, since a vehicle door handle component is a component that can be seen by a passenger of the vehicle when getting on the vehicle, it is also required to have a performance of maintaining a high design property for a long time.
  • weather resistance UV resistance, water resistance, etc.
  • the present invention is to solve the above-mentioned conventional problems, and the purpose thereof is to provide a discontinuous metal thin film-containing multilayer coating film excellent in various durability, a coating composition for a top coat, and An object of the present invention is to provide a coating composition for undercoat.
  • a coating composition for a discontinuous metal thin film top coat comprising:
  • the polyisocyanate compound (B-1) contains a nurate of an aliphatic diisocyanate having 4 to 5 carbon atoms, A coating composition for a discontinuous metal thin film top coat.
  • the equivalent ratio E1 (NCO group / OH group) of the hydroxyl group of the hydroxyl group-containing resin (A-1) and the isocyanate group of the polyisocyanate compound (B-1) is in the range of 1.0 to 3.0, A coating composition for a discontinuous metal thin film top coat.
  • the Tg of the cured coating film of the discontinuous metal thin film topcoat coating composition is in the range of 80 to 130 ° C., A coating composition for a discontinuous metal thin film top coat.
  • the silane coupling agent (C-1) is a coupling agent selected from the group consisting of an amino group-containing silane coupling agent, an epoxy group-containing silane coupling agent and an isocyanate group-containing silane coupling agent, A coating composition for a discontinuous metal thin film top coat.
  • a coating composition for a discontinuous metal thin film undercoat comprising: Tg of the cured coating film of the discontinuous metal thin film undercoat coating composition is less than 80 ° C., A coating composition for a discontinuous metal thin film undercoat.
  • the equivalent ratio E2 (NCO group / OH group) of the hydroxyl group of the hydroxyl group-containing resin (A-2) and the isocyanate group of the polyisocyanate compound (B-2) is in the range of 0.3 to 0.95.
  • a coating composition for a discontinuous metal thin film undercoat is in the equivalent ratio E2 (NCO group / OH group) of the hydroxyl group of the hydroxyl group-containing resin (A-2) and the isocyanate group of the polyisocyanate compound (B-2) is in the range of 0.3 to 0.95.
  • the silane coupling agent (C-2) is a coupling agent selected from the group consisting of an amino group-containing silane coupling agent, an epoxy group-containing silane coupling agent and an isocyanate group-containing silane coupling agent.
  • a coating composition for a discontinuous metal thin film undercoat is a coating set for forming a discontinuous metal thin film-containing multi-layer coating film, containing the coating composition for a discontinuous metal thin film topcoat and the coating composition for a discontinuous metal thin film undercoat.
  • the equivalent ratio E1 (NCO groups / OH groups) in the coating composition for a discontinuous metal thin film topcoat and the equivalent ratio E2 (NCO groups / OH group) in the coating composition for a discontinuous metal thin film undercoat are as follows.
  • Formula E1 / E2 1.3-4 A coating set for forming a multilayer coating film containing a discontinuous metal thin film that satisfies the above conditions.
  • An article to be coated is provided with an undercoat layer by coating the discontinuous metal thin film undercoat coating composition, an undercoat layer forming step, Providing a discontinuous metal thin film on the undercoat layer, a discontinuous metal thin film forming step, On the discontinuous metal thin film, the coating composition for the discontinuous metal thin film topcoat is applied to provide a topcoat layer, a topcoat layer forming step, and the undercoat layer and the topcoat layer are cured.
  • Curing process A method of forming a discontinuous metal thin film-containing multilayer coating film, comprising: The discontinuous metal thin film contains indium, tin, chromium or alloys thereof, A method for forming a multilayer coating film containing a discontinuous metal thin film.
  • a multilayer coating film formed by using the undercoat coating composition and the discontinuous metal thin film topcoat coating composition has excellent weather resistance (UV resistance, water resistance, etc.), durability, and scratch resistance. It has the advantage of being excellent.
  • This multi-layer coating film can be suitably used in various members having an electromagnetic wave transmitting / receiving system.
  • the present disclosure discloses a coating composition for a discontinuous metal thin film topcoat, a coating composition for a discontinuous metal thin film undercoat, and a coating set for forming a discontinuous metal thin film-containing multilayer coating film containing these coating compositions. To do.
  • the coating composition for the discontinuous metal thin film topcoat and the coating composition for the discontinuous metal thin film undercoat are subjected to the following steps: An article to be coated is provided with an undercoat layer by coating the discontinuous metal thin film undercoat coating composition, an undercoat layer forming step, Providing a discontinuous metal thin film on the undercoat layer, a discontinuous metal thin film forming step, The coating composition for a discontinuous metal thin film top coat is applied onto the discontinuous metal thin film to form a top coat layer, a top coat layer forming step, and the obtained undercoat layer and top coat layer are cured. , Curing process, When used in, a discontinuous metal thin film-containing multilayer coating film can be formed.
  • each coating composition will be described.
  • Coating composition for discontinuous metal thin film topcoat The coating composition for discontinuous metal thin film topcoat, Hydroxyl group-containing resin (A-1), A polyisocyanate compound (B-1), and a silane coupling agent (C-1), including.
  • the hydroxyl group-containing resin (A-1) contained in the coating composition for a discontinuous metal thin film top coat is a resin that functions as a coating film forming resin that reacts with a polyisocyanate compound to form a coating film.
  • the hydroxyl group-containing resin (A-1) is not particularly limited as long as it is a coating film forming resin which has a hydroxyl group and reacts with a polyisocyanate compound to form a coating film, but a hydroxyl group containing acrylic resin and / or a hydroxyl group containing polyester.
  • a resin is preferable because it is easy to manufacture and obtain. From the viewpoint of adjusting the physical properties of the coating film, it is more preferable to use a hydroxyl group-containing acrylic resin as the hydroxyl group-containing resin (A-1).
  • the hydroxyl group-containing acrylic resin is obtained by polymerizing a monomer mixture containing an ⁇ , ⁇ -ethylenically unsaturated monomer having a hydroxyl group and another ⁇ , ⁇ -ethylenically unsaturated monomer by a known method. It can be prepared.
  • the ⁇ , ⁇ -ethylenically unsaturated monomer having a hydroxyl group is not particularly limited, and examples of the ⁇ , ⁇ -ethylenically unsaturated monomer having a primary hydroxyl group include 2-hydroxyethyl (meth) Acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-1-methyl (meth) acrylate, Praxel FM1 ( ⁇ -caprolactone modified hydroxyethyl methacrylate, manufactured by Daicel Chemical Industries), polyethylene Examples thereof include glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate.
  • Examples of the ⁇ , ⁇ -ethylenically unsaturated monomer having a secondary hydroxyl group include 2-hydroxypropyl (meth) acrylate and 2-hydroxybutyl acrylate.
  • (meth) acrylate means an acrylate and / or a methacrylate.
  • Examples of the other unsaturated monomers include acid group-containing ⁇ , ⁇ -ethylenically unsaturated monomers.
  • Examples of the acid group-containing ⁇ , ⁇ -ethylenically unsaturated monomer include, for example, acrylic acid, methacrylic acid, acrylic acid dimer, crotonic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl succinic acid. , ⁇ -carboxy-polycaprolactone mono (meth) acrylate, maleic acid, fumaric acid, itaconic acid and the like. Of these, preferred are acrylic acid and methacrylic acid.
  • the ⁇ , ⁇ -ethylenically unsaturated monomer other than the hydroxyl group-containing ⁇ , ⁇ -ethylenically unsaturated monomer and the acid group-containing ⁇ , ⁇ -ethylenically unsaturated monomer is not particularly limited.
  • (Meth) acrylic acid ester monomers such as methyl (meth) acrylate, ethyl, propyl, butyl, hexyl, ethylhexyl, lauryl, phenyl, isobornyl, cyclohexyl;
  • a vinyl alcohol ester monomer which is an esterified product of vinyl alcohol and a carboxylic acid such as acetic acid or propionic acid;
  • Polymerizable unsaturated hydrocarbon monomers such as styrene, ⁇ -methylstyrene, vinylnaphthalene, butadiene and isoprene;
  • Polymerizable nitrile monomer such as acrylonitrile and methacrylonitrile;
  • Acrylamide monomers such as acrylamide, methacrylamide, N-methylol acrylamide, N, N-dimethyl acrylamide, diacetone acrylamide; And so on.
  • the hydroxyl group-containing acrylic resin is preferably prepared by solution polymerization.
  • the solution polymerization is generally carried out by stirring a mixture of ⁇ , ⁇ -ethylenically unsaturated monomers used as a raw material under heating with a polymerization initiator while dropping the mixture in a solvent.
  • the conditions for solution polymerization are, for example, a polymerization temperature of 60 to 160 ° C. and a dropping time of 0.5 to 10 hours.
  • the ⁇ , ⁇ -ethylenically unsaturated monomer used as the starting material can be polymerized in two stages. In this case, the ⁇ , ⁇ -ethylenically unsaturated monomer used as a raw material as a whole may satisfy the requirements for the hydroxyl group.
  • the polymerization initiator is not particularly limited as long as it can be used in ordinary polymerization, and examples thereof include azo compounds and peroxides. Generally, the amount of the polymerization initiator is 0.1 to 18 parts by mass, preferably 0.3 to 12 parts by mass, based on 100 parts by mass of the monomer mixture.
  • the solvent used here is not particularly limited as long as it does not adversely affect the reaction, and examples thereof include alcohols, ketones, ethers and hydrocarbon solvents. Further, in order to control the molecular weight, a mercaptan such as lauryl mercaptan and a chain transfer agent such as ⁇ -methylstyrene dimer can be optionally used.
  • the hydroxyl group in the hydroxyl group-containing resin (A-1) contains primary and secondary hydroxyl groups, and the content ratio (primary hydroxyl group / secondary hydroxyl group) is 10/90 to 80/20 based on the hydroxyl value. It is preferably from 30/70 to 50/50. Since the primary hydroxyl group has high reactivity with the polyisocyanate compound, the curing reaction proceeds well with the polyisocyanate compound in the top coat layer. However, when the reaction in the topcoat layer proceeds favorably, the polyisocyanate compound (B-1) in the topcoat layer and the hydroxyl group-containing resin (A-2) in the undercoat layer, which are between the layers, are crossed. There is also a possibility of inhibiting the curing reaction of.
  • the secondary hydroxyl group has low reactivity with the polyisocyanate compound (B-1). Therefore, it has the property of promoting the curing reaction between the polyisocyanate compound (B-1) in the topcoat layer and the hydroxyl group-containing resin (A-2) in the undercoat layer beyond the interlayer. Therefore, when the content ratio of the hydroxyl groups in the hydroxyl group-containing resin (A-1) (primary hydroxyl group / secondary hydroxyl group) is 10/90 to 80/20 based on the hydroxyl group value, the top coat which exceeds the interlayer is obtained.
  • a curing reaction between the polyisocyanate compound (B-1) in the layer and the hydroxyl group-containing resin (A-2) in the undercoat layer can be ensured, and the resistance of the multilayer coating film containing a discontinuous metal thin film in between can be secured.
  • the chemical resistance, solvent resistance, and weather resistance can be improved, and the curing reactivity of the hydroxyl group-containing resin (A-1) and polyisocyanate compound (B-1) in the topcoat layer can be secured.
  • the weight average molecular weight (Mw) of the hydroxyl group-containing resin (A-1) is preferably 5,000 or more and 20,000 or less, more preferably 5,500 or more and 15,000 or less.
  • Mw weight average molecular weight
  • the number average molecular weight of the hydroxyl group-containing resin can be measured by gel permeation chromatography (GPC) using a polystyrene standard sample standard.
  • the hydroxyl value of the hydroxyl group-containing resin (A-1) is preferably 80 to 220 mgKOH / g, and more preferably 120 to 190 mgKOH / g.
  • the hydroxyl value is less than 80 mgKOH / g, the crosslink density of the topcoat layer becomes insufficient, and the chemical resistance, solvent resistance, and weather resistance of the multilayer film may deteriorate. If the hydroxyl value exceeds 220 mgKOH / g, a large amount of polyisocyanate compound may be required.
  • the acid value of the hydroxyl group-containing resin (A-1) is preferably 0 to 30 mgKOH / g, more preferably 0.5 to 7 mgKOH / g.
  • the acid value of the hydroxyl group-containing resin (A-1) is in the above range, there is an advantage that the curability and the curing speed of the topcoat coating composition can be designed in an appropriate range.
  • the glass transition temperature (Tg) of the hydroxyl group-containing resin (A-1) is preferably 0 to 100 ° C. When the glass transition temperature (Tg) of the hydroxyl group-containing resin (A-1) is less than 0 ° C, good durability against various chemicals and scratch resistance may not be obtained. When the glass transition temperature (Tg) of the hydroxyl group-containing resin (A-1) exceeds 100 ° C., the appearance and the like may be deteriorated.
  • the glass transition point of the hydroxyl group-containing resin can be calculated from the type and amount of the monomer used for the preparation. Further, the glass transition point of the hydroxyl group-containing resin may be measured by a differential scanning calorimeter (DSC).
  • hydroxyl group-containing resin (A-1) other resins than the above may be used in combination.
  • other resins include hydroxyl group-containing polycarbonate resin, hydroxyl group-containing urethane resin, hydroxyl group-containing polyester resin and the like.
  • Polyisocyanate compound (B-1) The polyisocyanate compound (B-1) contained in the coating composition for a discontinuous metal thin film top coat is a component that reacts with a hydroxyl group-containing resin to form a coating film.
  • the polyisocyanate compound (B-1) contains a nurate of an aliphatic diisocyanate having 4 to 5 carbon atoms.
  • the polyisocyanate compound (B-1) contained in the coating composition for a discontinuous metal thin film top coat contains a nurate of an aliphatic diisocyanate having 4 to 5 carbon atoms, whereby a coating composition for a discontinuous metal thin film top coat is obtained. Good curing reactivity with the hydroxyl group-containing resin (A-1) contained in can be secured. Furthermore, since the polyisocyanate compound (B-1) contains a nurate of an aliphatic diisocyanate having 4 to 5 carbon atoms, the cohesive force of the isocyanate group is increased, and the durability and scratch resistance to various chemical agents are excellent. Etc. can be secured.
  • aliphatic diisocyanate having 4 to 5 carbon atoms in the present specification means a diisocyanate having an aliphatic group having 4 to 5 carbon atoms.
  • Specific examples of the aliphatic diisocyanate having 4 to 5 carbon atoms include tetramethylene-1,4-diisocyanate and pentamethylene-1,5-diisocyanate.
  • the nurate of an aliphatic diisocyanate having 4 to 5 carbon atoms can be obtained by using the aliphatic diisocyanate having 4 to 5 carbon atoms as a catalyst (such as (2-hydroxypropyl) trimethylammonium para tert-butyl benzoate) as necessary. It can be prepared by carrying out a cyclization reaction in the presence.
  • a catalyst such as (2-hydroxypropyl) trimethylammonium para tert-butyl benzoate
  • a commercial product may be used as a nurate of an aliphatic diisocyanate having 4 to 5 carbon atoms.
  • Examples of commercially available products include Stabio (registered trademark) D370N, D376N, and XD3725N manufactured by Mitsui Chemicals, Inc.
  • the polyisocyanate compound (B-1) may contain an isocyanate compound other than the nurate of an aliphatic diisocyanate having 4 to 5 carbon atoms.
  • polyisocyanate compounds include aliphatic or alicyclic polyisocyanate compounds.
  • the aliphatic or alicyclic polyisocyanate compound include, for example, hexamethylene diisocyanate, isophorone diisocyanate, methylenebiscyclohexyl isocyanate, and the like, isocyanurate compounds derived from these, uretdione compounds, urethane compounds, and allophanate. Examples thereof include compounds, buret compounds, and adducts with trimethylolpropane.
  • the content of the nurate of the aliphatic diisocyanate having 4 to 5 carbon atoms contained in the polyisocyanate compound (B-1) is preferably in the range of 40 to 100% by mass, and 80 to 100% by mass. It is more preferable that it is within the range.
  • the average number of isocyanate groups per molecule of the polyisocyanate compound (B-1) is preferably 3.0 to 3.5, and more preferably 3.1 to 3.3.
  • the average number of isocyanate groups is within the above range, there are advantages such as improvement in solvent resistance, weather resistance and water resistance of the resulting multilayer coating film.
  • the equivalent ratio E1 (NCO group / OH group) of the isocyanate group in the polyisocyanate compound (B-1) and the hydroxyl group in the hydroxyl group-containing resin (A-1) is in the range of 1.0 to 3.0. Is preferable, and more preferably within the range of 1.1 to 1.8.
  • E1 is 1.0 or more
  • the equivalent ratio E1 is 3 or less, the crosslinking density of the top coat layer can be secured, and the solvent resistance and weather resistance of the obtained multilayer coating film can be improved. ..
  • Silane coupling agent (C-1) The discontinuous metal thin film top coat coating composition contains a silane coupling agent (C-1). The inclusion of the silane coupling agent (C-1) has the advantage of improving the adhesion of the resulting topcoat layer to the discontinuous metal thin film.
  • silane coupling agent (C-1) examples include amino group-containing silane coupling agents, epoxy group-containing silane coupling agents, and isocyanate group-containing silane coupling agents.
  • the amino group-containing silane coupling agent is a silane coupling agent having at least one amino group in one molecule.
  • Specific examples of the amino group-containing silane coupling agent include N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, and N- (2 -Aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N Examples thereof include -phenyl-3-aminopropyltrimethoxysilane, and N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxys
  • amino group-containing silane coupling agents "KBM-602", “KBM-603”, “KBE-603”, “KBM-903”, “KBE-903”, “KBE-9103”, and “KBE-9103”. It is also possible to use "KBM-573", “KBP-90” (all trade names, manufactured by Shin-Etsu Chemical Co., Ltd.), "XS1003” (trade name, manufactured by Chisso Corporation), and the like.
  • amino group-containing silane coupling agent a hydrolysis-condensation product of aminosilane can also be used.
  • the epoxy group-containing silane coupling agent is a silane coupling agent having at least one epoxy group in one molecule.
  • Specific examples of the epoxy group-containing silane coupling agent include, for example, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3 -Glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane and the like can be mentioned.
  • Commercially available epoxy group-containing silane coupling agents such as "KBM-403", “KBE-403", and "KBM-4803" (all trade names, manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used.
  • the isocyanate group-containing silane coupling agent is a silane coupling agent having at least one isocyanate group in one molecule.
  • Specific examples of the isocyanate group-containing silane coupling agent include 3-isocyanatopropyltriethoxysilane.
  • silane coupling agent (C-1) a silane coupling agent other than the above can be used.
  • Vinyl group-containing silane coupling agents such as vinyltrimethoxysilane and vinyltriethoxysilane
  • a styryl group-containing silane coupling agent such as p-styryltrimethoxysilane
  • (Meth) such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane
  • Acrylic group-containing silane coupling agent Ureido group-containing silane coupling agent such as 3-ureidopropyltriethoxysilane; And so on.
  • the silane coupling agent (C-1) is preferably a coupling agent selected from the group consisting of an amino group-containing silane coupling agent, an epoxy group-containing silane coupling agent and an isocyanate group-containing silane coupling agent. ..
  • the amount of the silane coupling agent (C-1) contained in the coating composition for a discontinuous metal thin film top coat is such that the total solid content of the hydroxyl group-containing resin (A-1) and the polyisocyanate compound (B-1) is 100.
  • the amount is preferably 0.5 to 25 parts by mass, more preferably 1 to 20 parts by mass, relative to the parts by mass.
  • the coating composition for discontinuous metal thin film topcoat in addition to the above components, other resin components, pigments, organic or inorganic It may contain fine particles, a curing catalyst, a surface modifier, a defoaming agent, a pigment dispersant, a plasticizer, a film-forming aid, an ultraviolet absorber, an antioxidant and the like.
  • the discontinuous metal thin film top coat coating composition can be prepared by mixing the above-mentioned components (A-1) to (C-1) and any necessary components by a commonly used means. it can.
  • the discontinuous metal thin film top coat coating composition may include an organic solvent, if necessary.
  • an organic solvent such as propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether: Ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone: Ethyl acetate, 2-methoxy-1-methylethyl acetate, amyl acetate, isoamyl acetate, isobutyl acetate, Isopropyl acetate, octyl acetate, n-butyl acetate, sec-butyl acetate, tert-butyl acetate, Ester solvents such as propyl a
  • the resin solid content concentration of the coating composition for a discontinuous metal thin film top coat varies depending on the coating conditions, but is generally preferably set to 15 to 60% by mass, and is set to 40 to 50% by mass. More preferable.
  • the Tg of the cured coating film of the coating composition for a discontinuous metal thin film top coat is preferably in the range of 80 to 130 ° C.
  • the Tg of the cured coating film is within the above range, good physical properties as the topcoat layer can be secured, and the resulting multilayer coating film has advantages such as improved weather resistance and scratch resistance. is there.
  • the Tg of the cured coating film is the Tg measured using a cured coating film obtained by coating the coating composition so as to have a dry film thickness of 30 ⁇ m and then heat curing at 80 ° C. for 30 minutes.
  • the Tg of the cured coating film can be measured using a dynamic viscoelasticity measuring device. Specifically, using a dynamic viscoelasticity measuring device DVE-V4FT Spectra (manufactured by Rheology), the film prepared above was cut into 20 nm ⁇ 5 mm, and a basic sinusoidal strain of 11 Hz was applied in a temperature-dependent mode. The temperature at which the loss tangent tan ⁇ obtained by measurement is increased from 30 ° C. to 150 ° C. by 3 ° C. per minute can be measured as Tg.
  • DVE-V4FT Spectra manufactured by Rheology
  • Coating composition for discontinuous metal thin film undercoat The coating composition for discontinuous metal thin film undercoat, Hydroxyl group-containing resin (A-2), A polyisocyanate compound (B-2), and a silane coupling agent (C-2), It is a coating composition containing.
  • the Tg of the cured coating film of the discontinuous metal thin film undercoat coating composition is set to be less than 80 ° C.
  • the hydroxyl group-containing resin (A-2) contained in the discontinuous metal thin film undercoat coating composition is a resin that functions as a coating film forming resin that reacts with a polyisocyanate compound to form a coating film.
  • the hydroxyl group-containing resin (A-2) is not particularly limited as long as it is a coating film-forming resin that has a hydroxyl group and reacts with a polyisocyanate compound to form a coating film.
  • a hydroxyl group-containing acrylic resin and / or a hydroxyl group-containing polyester A resin is preferable because it is easy to manufacture and obtain.
  • the hydroxyl group-containing acrylic resin can be prepared by the same procedure as the above hydroxyl group-containing acrylic resin.
  • the hydroxyl group in the hydroxyl group-containing resin (A-2) is particularly preferably a primary hydroxyl group. Since the primary hydroxyl group has high reactivity with polyisocyanate, a large amount of primary hydroxyl group is contained as the hydroxyl group in the hydroxyl group-containing resin (A-2), so that the polyisocyanate compound (B-2) and the discontinuous metal There is an advantage that the curing reaction proceeds well with the polyisocyanate compound (B-1) contained in the coating composition for a thin film top coat, and the weather resistance of the resulting multilayer coating film is improved.
  • the weight average molecular weight (Mw) of the hydroxyl group-containing resin (A-2) is preferably 1,000 or more and 20,000 or less, more preferably 1500 or more and 15,000 or less.
  • Mw weight average molecular weight
  • the hydroxyl value of the hydroxyl group-containing resin (A-2) is preferably 20 to 170 mgKOH / g, and more preferably 40 to 150 mgKOH / g.
  • the hydroxyl value is within the above range, there is an advantage that the physical properties of the obtained multilayer coating film can be designed in a favorable range.
  • the acid value of the hydroxyl group-containing resin (A-2) is preferably 0 to 20 mgKOH / g, more preferably 0.5 to 5 mgKOH / g.
  • the acid value of the hydroxyl group-containing resin (A-2) is within the above range, there is an advantage that the curability and the curing speed of the undercoat coating composition can be designed in an appropriate range.
  • the glass transition temperature (Tg) of the hydroxyl group-containing resin (A-2) is preferably 0 ° C to 60 ° C.
  • Tg glass transition temperature of the hydroxyl group-containing resin
  • the glass transition point of the hydroxyl group-containing resin can be determined in the same manner as the above ((A-1 resin)).
  • hydroxyl group-containing resin (A-2) resins other than the above may be used in combination.
  • other resins include hydroxyl group-containing polycarbonate resin, hydroxyl group-containing urethane resin, hydroxyl group-containing polyester resin and the like.
  • Polyisocyanate compound (B-2) The polyisocyanate compound (B-2) contained in the discontinuous metal thin film undercoat coating composition is a component that reacts with a hydroxyl group-containing resin to form a coating film.
  • the polyisocyanate compound (B-2) may or may not contain the nurate of the above aliphatic diisocyanate having 4 to 5 carbon atoms.
  • polyisocyanate compound (B-2) examples include an aliphatic diisocyanate, an alicyclic diisocyanate, an aromatic diisocyanate, and an isocyanurate compound, a uretdione compound, a urethane compound, an allophanate compound, a buret compound, and trimethylolpropane derived from these compounds. And the like.
  • polyisocyanate compound (B-2) examples include, for example, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexane diisocyanate, undecane diisocyanate- (1,11), lysine ester diisocyanate.
  • Cyclohexane-1,3- and 1,4-diisocyanate 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane (IPDI), 4,4′-diisocyanatodicyclodicyclomethane, ⁇ , ⁇ '-dipropyl ether diisocyanate, thiodipropyl diisocyanate, cyclohexyl-1,4-diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,5-dimethyl-2,4 -Bis (isocyanatomethyl) benzene, 1,5-trimethyl-2,4-bis ( ⁇ -isocyanatoethyl) -benzene, 1,3,5-trimethyl-2,4-bis (isocyanatomethyl) benzene, 1,3,5-Triethyl-2,4-bis (isocyanatomethyl) benzene,
  • a commercially available product may be used as the polyisocyanate compound (B-2).
  • Examples of commercially available products include Asahi Kasei's Duranate TPA100, TKA100, 24A-100, P301-75E, Covestro's Dismodule N3300, N3900, N3200, N3400, ecoN7380, xP2860, Tosoh's Coronate HX, and the like.
  • the average number of isocyanate groups per molecule of the polyisocyanate compound (B-2) is preferably 2.5 to 3.4, and more preferably 2.6 to 3.2.
  • the average number of isocyanate groups is within the above range, there are advantages such as improvement in physical performance of the obtained multilayer coating film.
  • the equivalent ratio E2 (NCO group / OH group) of the isocyanate group in the polyisocyanate compound (B-2) and the hydroxyl group in the hydroxyl group-containing resin (A-2) is in the range of 0.3 to 0.95. Is preferable, and more preferably within the range of 0.5 to 0.8.
  • E2 is 0.95 or less, the polyisocyanate compound (B-1) in the subsequently formed topcoat layer and the hydroxyl group-containing resin (A-2) in the undercoat layer exceed the interlayer. There is an advantage that the curing reaction can be secured and the durability of the obtained multilayer coating film can be improved.
  • Silane coupling agent (C-2) The discontinuous metal thin film undercoat coating composition contains a silane coupling agent (C-2).
  • the inclusion of the silane coupling agent (C-2) has the advantage of improving the adhesion of the obtained undercoat layer to the discontinuous metal thin film.
  • silane coupling agent (C-2) examples include amino group-containing silane coupling agents, epoxy group-containing silane coupling agents, and isocyanate group-containing silane coupling agents.
  • silane coupling agent the same silane coupling agent as the above silane coupling agent (C-1) can be used.
  • the silane coupling agent (C-2) contained in the coating composition for a discontinuous metal thin film undercoat is the same as the silane coupling agent (C-1) contained in the coating composition for a discontinuous metal thin film topcoat. It is preferably of the type: For example, when the silane coupling agent (C-1) contains an amino group-containing silane coupling agent, it is preferable that the silane coupling agent (C-2) contains an amino group-containing silane coupling agent.
  • the amount of the silane coupling agent (C-2) contained in the discontinuous metal thin film undercoat coating composition is such that the total solid content of the hydroxyl group-containing resin (A-2) and the polyisocyanate compound (B-2) is 100.
  • the amount is preferably 0.5 to 25 parts by mass, more preferably 1 to 20 parts by mass, relative to the parts by mass.
  • the above-mentioned discontinuous metal thin film undercoat coating composition in addition to the above components, other resin components, pigments, curing catalysts, surfaces, if necessary. It may contain a regulator, an antifoaming agent, a pigment dispersant, a plasticizer, a film-forming aid, an ultraviolet absorber, an antioxidant, and the like.
  • the coating composition for a discontinuous metal thin film undercoat can be prepared by mixing the above-mentioned components (A-2) to (C-2) and, if necessary, each component by a commonly used means. it can.
  • the discontinuous metal thin film undercoat coating composition may optionally contain an organic solvent.
  • the organic solvent described above can be used as the organic solvent.
  • the resin solid content concentration of the coating composition for a discontinuous metal thin film undercoat varies depending on the coating conditions, but generally it is preferably set to 15 to 60% by mass, and set to 35 to 50% by mass. More preferable.
  • the Tg of the cured coating film of the above discontinuous metal thin film undercoat coating composition must be less than 80 ° C.
  • the Tg of the cured coating film of the coating composition for a discontinuous metal thin film undercoat is 80 ° C. or higher, the smoothness of the undercoat layer becomes poor, and the appearance of the discontinuous metal thin film formed thereafter deteriorates. The appearance of the resulting multilayer coating film may deteriorate.
  • the Tg of the cured coating film of the coating composition for a discontinuous metal thin film undercoat is preferably 30 ° C. or higher and lower than 80 ° C., and more preferably 50 ° C. or higher and lower than 80 ° C.
  • a coating set for forming a multi-layer coating film containing a discontinuous metal thin film includes a coating composition for a discontinuous metal thin film top coat and a coating composition for a discontinuous metal thin film undercoat, containing a discontinuous metal thin film-containing coating composition.
  • Disclosed is a paint set for forming a layer coating film.
  • E1 / E2 satisfies the above range, a large amount of OH groups are present in the undercoat layer, while a large amount of NCO groups are present in the topcoat layer.
  • the silane coupling agent (C-2) contained in the coating composition for a discontinuous metal thin film undercoat is a coating composition for a discontinuous metal thin film topcoat. It is preferably the same type as the silane coupling agent (C-1) contained in the product. Since the silane coupling agent (C-2) and the silane coupling agent (C-1) are of the same type, the discontinuous metal thin film can be better fixed, and the weather resistance of the obtained multilayer coating film can be improved. And there is an advantage that the chemical resistance can be improved.
  • Method for forming a discontinuous metal thin film-containing multilayer coating film The present specification further comprises An article to be coated is provided with an undercoat layer by coating the discontinuous metal thin film undercoat coating composition, an undercoat layer forming step, Providing a discontinuous metal thin film on the undercoat layer, a discontinuous metal thin film forming step, The coating composition for a discontinuous metal thin film top coat is applied onto the discontinuous metal thin film to form a top coat layer, a top coat layer forming step, and the obtained undercoat layer and top coat layer are cured.
  • a method of forming a discontinuous metal thin film-containing multilayer coating film comprising: The discontinuous metal thin film contains indium, tin, chromium or alloys thereof, A method for forming a multi-layer coating film containing a discontinuous metal thin film is disclosed.
  • the base material examples include polyethylene resin, EVA resin, polyolefin resin (polyethylene resin, polypropylene resin, etc.), vinyl chloride resin, styrene resin, polyester resin (including PET resin, PBT resin, etc.), polycarbonate resin, acrylic resin, acrylonitrile.
  • Resins such as butadiene styrene (ABS) resin, acrylonitrile styrene (AS) resin, polyamide resin, acetal resin, phenol resin, fluororesin, melamine resin, urethane resin, epoxy resin, polyphenylene oxide (PPO); Examples thereof include composite materials, hybrid materials of the above resins, and organic-inorganic hybrid materials. These may be in a molded state.
  • the above resin may be washed with steam using an organic solvent, or may be washed with a neutral detergent, if necessary. Furthermore, a primer coating may be applied if necessary.
  • the above coating composition for a discontinuous metal thin film undercoat is applied to an object to be coated to form an undercoat layer (undercoat layer forming step).
  • the coating composition for a discontinuous metal thin film undercoat can be coated by a commonly used coating method.
  • the coating method include spray coating, brush coating, roll coating, and flow coating.
  • Spray coating is preferably used as the coating method, and in particular, multistage coating method by air spray coating (preferably two stage coating) or air electrostatic spray coating, commonly known as “ ⁇ (micro micro) bell” and “ ⁇ ( It is also possible to use a coating method in combination with a rotary atomization type coating machine called "micro) bell” or "metabell”.
  • the thickness of the coating film of the discontinuous metal thin film undercoat coating composition can be appropriately selected according to the desired application.
  • the film thickness is, for example, preferably 15 to 35 ⁇ m, more preferably 15 to 30 ⁇ m.
  • the drying conditions are not particularly limited, and examples thereof include a method of drying for 20 to 60 minutes under the temperature condition of 60 ° C to 90 ° C.
  • discontinuous metal thin film forming step a discontinuous metal thin film layer is provided on the undercoat layer (discontinuous metal thin film forming step).
  • the discontinuous metal thin film can be formed by providing a thin film of metal particles in an island-shaped discontinuous state (dispersed state) on the undercoat layer.
  • the metal forming the discontinuous metal thin film include indium, tin, chromium or alloys thereof.
  • a discontinuous metal thin film can be formed by forming a metal thin film having a film thickness of 70 nm or less from indium, tin, chromium or an alloy thereof by a vapor deposition method or a sputtering method.
  • the film thickness is preferably 60 nm or less, and more preferably 50 nm or less.
  • the vapor deposition method and the sputtering method can be performed by methods known to those skilled in the art.
  • the vapor deposition method is preferably a vacuum vaporization method in which a metal is vaporized (vaporized) in a vacuum container whose pressure is reduced to, for example, 10 ⁇ 3 to 10 ⁇ 2 Pa.
  • the coating composition for a discontinuous metal thin film top coat can be applied in the same manner as the above-mentioned coating composition for an undercoat.
  • the film thickness of the coating composition of the discontinuous metal thin film topcoat coating composition can be appropriately selected according to the desired application.
  • the film thickness is, for example, preferably 15 to 35 ⁇ m, more preferably 15 to 30 ⁇ m.
  • the above curing can be suitably performed by heat curing.
  • the heating and curing temperature and the heating time can be appropriately selected depending on the type of the substrate that is the object to be coated, the type of metal that constitutes the discontinuous metal thin film, and the type of coating composition.
  • the heat curing temperature is, for example, preferably in the range of 50 to 120 ° C, more preferably in the range of 60 to 120 ° C.
  • the heating time is generally 10 to 120 minutes, preferably 20 to 60 minutes.
  • a heating device usually used by those skilled in the art can be used, and for example, a drying oven using a heating source such as hot air, electricity, gas, infrared rays, or the like can be used.
  • a multilayer coating film having a discontinuous metal thin film can be formed.
  • the multilayer coating film formed by using the above coating composition for undercoat and coating composition for discontinuous metal thin film topcoat has weather resistance (UV resistance, water resistance, etc.), durability, scratch resistance. Has the advantage of being excellent.
  • This multi-layer coating film is used for automobile front parts, automobile door handles, vehicle-mounted communication devices, mobile phones, personal digital assistants (tablets, mobile devices, electronic notebooks, etc.), and various home appliances with electromagnetic wave transmission / reception systems. It can be suitably used in products and housing equipment.
  • Production Example 1 Production of hydroxyl group-containing resin (A-1) (1) for coating composition for discontinuous metal thin film top coat , equipped with stirring blade, thermometer, dropping device, temperature control device, nitrogen gas inlet and cooling pipe 140 parts of butyl acetate as an organic solvent was charged into the reaction apparatus, and the temperature was raised to 125 ° C. with stirring while introducing nitrogen gas. Next, as a monomer mixture, 58.5 parts of 2-hydroxyethyl methacrylate, 97.2 parts of 2-hydroxypropyl methacrylate, 45 parts of styrene, 112.9 parts of t-butyl methacrylate and 133.2 parts of n-butyl acrylate.
  • Production Examples 5 to 7 Monomer mixtures used in the production of the hydroxyl group-containing resins (A-2) (1) to (3) for the coating composition for discontinuous metal thin film undercoat are the monomers shown in the following table.
  • a hydroxyl group-containing acrylic resin was prepared by the same procedure as in Production Example 1 except that a monomer mixture containing was used.
  • Various characteristic values of the obtained hydroxyl group-containing acrylic resin are shown in the following table.
  • Viketol Special manufactured by Big Chemie Japan
  • DBTDL dibutyltin dilaurate
  • Tinuvin 292 manufactured by Ciba Specialty Chemicals Co., Ltd.
  • 0.8 parts of TINUVIN 384-2 manufactured by Ciba Specialty Chemicals Co., Ltd.
  • 18 parts of butyl acetate, and 13 parts of methyl ethyl ketone (MEK) were sequentially charged into a container and uniformly stirred, and the top coat coating composition (1-1 ) As the main ingredient.
  • KBM-403 manufactured by Shin-Etsu Chemical Co.
  • 4 parts of carbitol acetate , 2.4 parts of methyl ethyl ketone (MEK) were sequentially charged and uniformly stirred to obtain a curing agent for the top coat coating composition (1-1).
  • the main component and curing agent were mixed to form a coating composition.
  • the nonvolatile content of the coating composition was 51.2%.
  • Topcoat Coating Compositions (1-2) to (1-8) By mixing the components shown in the following table in the amounts described in the table, the main component of the topcoat coating composition and curing The agent was prepared. Next, the obtained base material and curing agent were mixed to prepare coating compositions (1-2) to (1-8) for top coat.
  • coating composition for undercoat (2-1) Same as the above coating composition for topcoat (1-1), except that the components shown in the following table were used in the amounts described in the table and mixed.
  • the main component (, the curing agent of the undercoat coating composition was prepared.
  • the obtained main component and the curing agent were mixed to prepare the undercoat coating composition (2-1).
  • N3300 Dismodur N3300 manufactured by Covestro, a nurate of hexamethylene diisocyanate.
  • Example 1 On a polycarbonate PBT substrate (composite substrate of polycarbonate resin / PBT resin, manufactured by Mitsubishi Engineering Plastics Co., Ltd.) washed with isopropyl alcohol (IPA), a coating composition for undercoat (2-1 ) was diluted to 30% with diluted thinner T-501CM (manufactured by Nippon Paint Automotive Coatings) and spray coated. Then, after leaving at room temperature for 2 minutes, it was dried at 80 ° C. for 40 minutes. After being left to cool to room temperature, an indium layer (discontinuous metal thin film) having a thickness of 50 nm was formed by vapor deposition under a voltage condition of 4 V under 1.0 ⁇ 10 ⁇ 2 Pa using a vacuum vapor deposition apparatus.
  • IPA isopropyl alcohol
  • the coating composition for a top coat (1-1) was diluted to 30% with diluted thinner T-505HL (manufactured by Nippon Paint Automotive Coatings Co., Ltd.) to obtain a dry film thickness. It was spray-coated so as to have a thickness of 25 ⁇ m and left at room temperature for 5 minutes. Next, the formed undercoat layer and topcoat layer were heat-cured at 80 ° C. for 40 minutes to obtain a discontinuous metal thin film-containing multilayer coating film.
  • Examples 2-10 and Comparative Examples 1-6 A multilayer coating film was formed in the same manner as in Example 1 except that the coating composition for undercoat and the coating composition for topcoat described in the following table were used.
  • Tg of cured coating The Tg of the cured coating film was measured by the following procedure. Each coating composition was coated on a polypropylene sheet so that the dry film thickness was 30 ⁇ m, and then heat-cured at 80 ° C. for 40 minutes to obtain a cured coating film.
  • the cured coating film (film) prepared above was cut into 20 nm ⁇ 5 mm, and using a dynamic viscoelasticity measuring device DVE-V4FT Spectra (Rheology), in a temperature-dependent mode with a fundamental sine wave distortion of 11 Hz. The temperature at which the loss tangent tan ⁇ obtained by measuring was increased from 30 ° C. to 150 ° C. by 3 ° C. per minute was defined as Tg.
  • the multi-layer coating film was immersed in 40 ° C. warm water for 240 hours, dried at room temperature for one day, and visually evaluated for blisters (swelling of the coating film due to water permeation) according to ASTM D714.
  • a tape peel test was conducted. Compared to before the test, the case where blister was generated in the appearance was evaluated as ⁇ , the case of occurrence of swelling due to swelling was evaluated as ⁇ , and the case where there was no abnormality was evaluated as ⁇ .
  • x when peeling occurred, x was given, when a slight peeling occurred, it was given, and when there was no peeling, it was given as o.
  • Sebum-resistant oleic acid was uniformly applied in an amount of 0.05 g per 100 cm 2 of the coating film, covered with gauze, and kept in an oven at 80 ° C. for 24 hours. Then, it was taken out and washed with water, and the following evaluation was performed. The coating film after the appearance evaluation test was visually evaluated. The case where there was blistering or coating film floating was rated as X, the case where there was a mark due to swelling was rated as ⁇ , and the case where there was no abnormality was rated as ⁇ .
  • the coating film after the adhesion evaluation test was cross-cut, and cellophane tape (trademark) was attached and peeled off to evaluate the adhesion. Peeling of 5 mm 2 or more was rated as ⁇ , peeling with a slight chipping was rated as ⁇ , and no peeling was rated as ⁇ .
  • Scratch resistance evaluation A surface of the multilayer coating film was subjected to a scratch resistance test by adhering glass beads having an average of 300 ⁇ m to a friction element with a double-sided tape at a load of 21.6 N per 4 cm 2 and reciprocating 50 times. Then, the gloss retention at 20 ° C. was measured, and 95% or more was marked with ⁇ , 80% or more was marked with ⁇ , 60% or more was marked with ⁇ , and less than 60% was marked with x.
  • a xenon weather meter (xenon, manufactured by Suga Test Instruments Co., Ltd.) was used as an accelerated weather resistance test.
  • the gloss retention rate is 85% or more and the color difference ( ⁇ E) is 3 or less, and the case where the above conditions are not satisfied due to contamination is marked as x.
  • Comparative Example 1 is an example in which the polyisocyanate compound contained in the coating composition for a top coat is not a nurate of an aliphatic diisocyanate having 4 to 5 carbon atoms. In this example, it was confirmed that the chemical resistance (adhesion) was inferior.
  • Comparative Example 2 is an example in which the topcoat coating composition does not contain a silane coupling agent. In this example, it was confirmed that the chemical resistance (adhesion) was inferior.
  • Comparative Example 3 is an example in which the cured coating film of the undercoat coating composition has a Tg of 80 ° C. or higher.
  • Comparative Example 4 is an example in which the undercoat coating composition does not contain a silane coupling agent. In this example, it was confirmed that the chemical resistance (adhesion) was inferior.
  • Comparative Example 5 is an example in which neither the coating composition for top coat nor the coating composition for undercoat contains a silane coupling agent. In this example, it was confirmed that the coating film appearance, water resistance and chemical resistance were poor.
  • Comparative Example 6 is an example in which the topcoat coating composition was used as the undercoat coating composition, and the undercoat coating composition was used as the topcoat coating composition. In this example, it was confirmed that the chemical resistance and weather resistance were poor.
  • a multilayer coating film formed by using the above coating composition for undercoat and coating composition for discontinuous metal thin film topcoat has chemical resistance (hand cream resistance, juice resistance, etc.), weather resistance (contamination durability). Properties, water resistance, etc.), durability, and scratch resistance.
  • This multi-layer coating film is used for automobile front parts, automobile door handles, vehicle-mounted communication devices, mobile phones, personal digital assistants (tablets, mobile devices, electronic notebooks, etc.), and various home appliances with electromagnetic wave transmission / reception systems. It can be suitably used in products and housing equipment.

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Abstract

A topcoating composition and an undercoating composition are provided with which it is possible to provide a multilaylered coating film including a discontinuous metallic thin film and having excellent durability of various kinds. The topcoating composition for discontinuous metallic thin films comprises a hydroxylated resin (A-1), a polyisocyanate compound (B-1), and a silane coupling agent (C-1), wherein the polyisocyanate compound (B-1) includes a nurate of an aliphatic diisocyanate having 4 or 5 carbon atoms. The undercoating composition for discontinuous metallic thin films comprises a hydroxylated resin (A-2), a polyisocyanate compound (B-2), and a silane coupling agent (C-2) and gives a cured coating film having a Tg lower than 80°C.

Description

不連続金属薄膜トップコート用塗料組成物および不連続金属薄膜アンダーコート用塗料組成物Coating composition for discontinuous metal thin film topcoat and coating composition for discontinuous metal thin film undercoat
　本発明は、不連続金属薄膜トップコート用塗料組成物および不連続金属薄膜アンダーコート用塗料組成物に関する。 The present invention relates to a coating composition for a discontinuous metal thin film topcoat and a coating composition for a discontinuous metal thin film undercoat.
　不連続金属薄膜は、光輝性を有しており金属光沢外観を呈する一方で、電磁波透過性能も有している。このような不連続金属薄膜は、例えば、電磁波の受発信により相互認証を行うシステムまたは電子制御を行うシステムの部材に対して、光輝性または金属光沢外観をもたらすことができるため、意匠性を高めることができ、意匠選択可能性を広げることができる利点がある。このような不連続金属薄膜は、例えば、自動車のフロント部、自動車のドアハンドル、車搭載通信機器、携帯電話、携帯情報端末機器、電磁波の受発信システムを有する各種家電製品および住宅設備などにおいて用いられているか、あるいは使用の検討が行われつつある。 ∙ The discontinuous metal thin film has luster and has a metallic luster appearance, while also having electromagnetic wave transmission performance. Such a discontinuous metal thin film, for example, can bring a glittering or metallic luster appearance to a member of a system that performs mutual authentication by transmitting and receiving electromagnetic waves or a system that performs electronic control, and thus enhances designability. This has the advantage that the design selection possibilities can be expanded. Such a discontinuous metal thin film is used in, for example, a front part of an automobile, a door handle of an automobile, a communication device mounted on a car, a mobile phone, a portable information terminal device, various home electric appliances having an electromagnetic wave transmission / reception system, and housing equipment. Or is being considered for use.
　例えば特開２０１１－１７８８８７号公報（特許文献１）には、基材上に形成されたスズ薄膜またはインジウム薄膜と、該スズ薄膜またはインジウム薄膜に隣接して形成された下塗り層および上塗り層とを備えた複合塗膜において、前記下塗り層および／または上塗り層が、塗膜形成成分と金属石ケンとを含むスズ薄膜またはインジウム薄膜用塗料組成物より形成されたことを特徴とする複合塗膜について記載される（請求項１、２）。この複合塗膜は、金属独特の風合いを有し、意匠性に優れると記載される。 For example, Japanese Patent Laid-Open No. 2011-178887 (Patent Document 1) describes a tin thin film or an indium thin film formed on a substrate, and an undercoat layer and an overcoat layer formed adjacent to the tin thin film or the indium thin film. In a composite coating film provided, the undercoat layer and / or the overcoat layer is formed from a tin thin film or indium thin film coating composition containing a coating film forming component and a metal soap. It is described (Claims 1 and 2). It is described that this composite coating film has a texture unique to metal and is excellent in design.
　特開２０１２－２２５０４１号公報（特許文献２）には、車両のドアに設けられたドア開閉用のドアハンドルと、このドアハンドルに配置された電極と、人体部分の前記ドアハンドルへの接近または接触によって前記電極の付近に生じる静電容量の変化を検出してロックまたはアンロックの操作信号を出力する検出回路と、前記操作信号によって前記ドアのロックまたはアンロックを実行する装置と、前記車両に対応する携帯機との間で送受信を行うための送受信アンテナとを備え、前記ドアハンドルが絶縁体からなる基体を有し、前記基体の少なくとも車両外側面には、ＳｉＯ２及びＡｌ２Ｏ３の少なくともいずれかで構成され、前記基体の表面に被着された無機薄膜層と、互いに分離された島状の金属粒子の集合からなり、前記無機薄膜層の表面に被着された金属薄膜層とが設けられているドア開閉装置について記載される（請求項１）。このドア開閉装置は、優れた金属光沢を有しており、かつ、誤作動または不作動が生じ難い利点があると記載される。 Japanese Unexamined Patent Application Publication No. 2012-225041 (Patent Document 2) discloses a door handle for opening and closing a door provided on a vehicle door, an electrode arranged on the door handle, and a human body part approaching or approaching the door handle. A detection circuit that outputs a lock or unlock operation signal by detecting a change in capacitance that occurs in the vicinity of the electrode due to a contact; a device that locks or unlocks the door by the operation signal; And a transmitting / receiving antenna for transmitting / receiving to / from a portable device corresponding to the above, and the door handle has a base made of an insulator, and SiO 2 and Al 2 O 3 are provided on at least a vehicle outer surface of the base. Which is composed of at least one of the following: an inorganic thin film layer deposited on the surface of the substrate; and a group of island-shaped metal particles separated from each other. A door opening and closing device is described in which a metal thin film layer deposited on the surface of the film layer is provided (Claim 1). It is described that this door opening / closing device has an excellent metallic luster and is less likely to cause malfunction or non-operation.
特開２０１１－１７８８８７号公報JP, 2011-178887, A 特開２０１２－２２５０４１号公報JP 2012-225041 A
　例えば上記特許文献２に記載されるような車両のドアハンドル部品は、車両の外側に設けられる部品であるため、耐候性（耐紫外線耐久性、耐水性など）に優れることが必要とされる。車両のドアハンドル部品はさらに、車両の搭乗者が頻繁に触れる部品であることから、搭乗者の手に付着する汗、水分および油脂に対する耐久性、さらには耐擦傷性もまた必要とされる。車両のドアハンドル部品はさらに、車両の搭乗者が乗車する際に視界に入る部品であることから、高意匠性を長期間維持する性能もまた求められる。 For example, a vehicle door handle component as described in Patent Document 2 is a component provided on the outside of the vehicle, and therefore it is required to have excellent weather resistance (UV resistance, water resistance, etc.). Since the vehicle door handle component is a component that is frequently touched by the occupant of the vehicle, durability against sweat, moisture and grease adhered to the occupant's hand and scratch resistance are also required. Further, since a vehicle door handle component is a component that can be seen by a passenger of the vehicle when getting on the vehicle, it is also required to have a performance of maintaining a high design property for a long time.
　本発明は上記従来の課題を解決するものであり、その目的とするところは、各種耐久性に優れた不連続金属薄膜含有複層塗膜を提供することができる、トップコート用塗料組成物およびアンダーコート用塗料組成物を提供することにある。 The present invention is to solve the above-mentioned conventional problems, and the purpose thereof is to provide a discontinuous metal thin film-containing multilayer coating film excellent in various durability, a coating composition for a top coat, and An object of the present invention is to provide a coating composition for undercoat.
　上記課題を解決するため、本発明は下記態様を提供する。
［１］
　水酸基含有樹脂（Ａ－１）、
ポリイソシアネート化合物（Ｂ－１）、および
シランカップリング剤（Ｃ－１）、
を含む、不連続金属薄膜トップコート用塗料組成物であって、
　上記ポリイソシアネート化合物（Ｂ－１）は、炭素数４～５の脂肪族ジイソシアネートのヌレート体を含む、
不連続金属薄膜トップコート用塗料組成物。
［２］
　上記水酸基含有樹脂（Ａ－１）の水酸基および上記ポリイソシアネート化合物（Ｂ－１）のイソシアネート基の当量比Ｅ１（ＮＣＯ基／ＯＨ基）は、１．０～３．０の範囲内である、
不連続金属薄膜トップコート用塗料組成物。
［３］
　上記水酸基含有樹脂（Ａ－１）は、１級水酸基および２級水酸基の両方を有し、上記水酸基の比率は、１級水酸基／２級水酸基＝１０／９０～８０／２０の範囲内である、
不連続金属薄膜トップコート用塗料組成物。
［４］
　上記不連続金属薄膜トップコート用塗料組成物の硬化塗膜のＴｇは、８０～１３０℃の範囲内である、
不連続金属薄膜トップコート用塗料組成物。
［５］
　上記シランカップリング剤（Ｃ－１）は、アミノ基含有シランカップリング剤、エポキシ基含有シランカップリング剤およびイソシアネート基含有シランカップリング剤からなる群から選択されるカップリング剤である、
不連続金属薄膜トップコート用塗料組成物。
［６］
　水酸基含有樹脂（Ａ－２）、
ポリイソシアネート化合物（Ｂ－２）、および
シランカップリング剤（Ｃ－２）、
を含む、不連続金属薄膜アンダーコート用塗料組成物であって、
　上記不連続金属薄膜アンダーコート用塗料組成物の硬化塗膜のＴｇは、８０℃未満である、
不連続金属薄膜アンダーコート用塗料組成物。
［７］
　上記水酸基含有樹脂（Ａ－２）の水酸基および上記ポリイソシアネート化合物（Ｂ－２）のイソシアネート基の当量比Ｅ２（ＮＣＯ基／ＯＨ基）は、０．３～０．９５の範囲内である、
不連続金属薄膜アンダーコート用塗料組成物。
［８］
　上記シランカップリング剤（Ｃ－２）は、アミノ基含有シランカップリング剤、エポキシ基含有シランカップリング剤およびイソシアネート基含有シランカップリング剤からなる群から選択されるカップリング剤である、
不連続金属薄膜アンダーコート用塗料組成物。
［９］
　上記不連続金属薄膜トップコート用塗料組成物、および、上記不連続金属薄膜アンダーコート用塗料組成物を含む、不連続金属薄膜含有複層塗膜形成用塗料セット。
［１０］
　上記不連続金属薄膜トップコート用塗料組成物における上記当量比Ｅ１（ＮＣＯ基／ＯＨ基）および上記不連続金属薄膜アンダーコート用塗料組成物における上記当量比Ｅ２（ＮＣＯ基／ＯＨ基）が、下記式
Ｅ１／Ｅ２＝１．３～４
を満たす、不連続金属薄膜含有複層塗膜形成用塗料セット。
［１１］
　被塗物に、上記不連続金属薄膜アンダーコート用塗料組成物を塗装してアンダーコート層を設ける、アンダーコート層形成工程、
　上記アンダーコート層の上に不連続金属薄膜を設ける、不連続金属薄膜形成工程、
　上記不連続金属薄膜の上に、上記不連続金属薄膜トップコート用塗料組成物を塗装して、トップコート層を設ける、トップコート層形成工程、および
上記アンダーコート層およびトップコート層を硬化させる、硬化工程、
を包含する、不連続金属薄膜含有複層塗膜の形成方法であって、
　上記不連続金属薄膜は、インジウム、スズ、クロムまたはこれらの合金を含む、
不連続金属薄膜含有複層塗膜の形成方法。
［１２］
　上記不連続金属薄膜トップコート用塗料組成物における当量比Ｅ１（ＮＣＯ基／ＯＨ基）および上記不連続金属薄膜アンダーコート用塗料組成物における当量比Ｅ２（ＮＣＯ基／ＯＨ基）が、下記式
Ｅ１／Ｅ２＝１．３～４
を満たす、上記形成方法。 In order to solve the above problems, the present invention provides the following aspects.
[1]
Hydroxyl group-containing resin (A-1),
A polyisocyanate compound (B-1), and a silane coupling agent (C-1),
A coating composition for a discontinuous metal thin film top coat, comprising:
The polyisocyanate compound (B-1) contains a nurate of an aliphatic diisocyanate having 4 to 5 carbon atoms,
A coating composition for a discontinuous metal thin film top coat.
[2]
The equivalent ratio E1 (NCO group / OH group) of the hydroxyl group of the hydroxyl group-containing resin (A-1) and the isocyanate group of the polyisocyanate compound (B-1) is in the range of 1.0 to 3.0,
A coating composition for a discontinuous metal thin film top coat.
[3]
The above hydroxyl group-containing resin (A-1) has both primary hydroxyl groups and secondary hydroxyl groups, and the ratio of the above hydroxyl groups is within the range of primary hydroxyl group / secondary hydroxyl group = 10/90 to 80/20. ,
A coating composition for a discontinuous metal thin film top coat.
[4]
The Tg of the cured coating film of the discontinuous metal thin film topcoat coating composition is in the range of 80 to 130 ° C.,
A coating composition for a discontinuous metal thin film top coat.
[5]
The silane coupling agent (C-1) is a coupling agent selected from the group consisting of an amino group-containing silane coupling agent, an epoxy group-containing silane coupling agent and an isocyanate group-containing silane coupling agent,
A coating composition for a discontinuous metal thin film top coat.
[6]
Hydroxyl group-containing resin (A-2),
A polyisocyanate compound (B-2), and a silane coupling agent (C-2),
A coating composition for a discontinuous metal thin film undercoat, comprising:
Tg of the cured coating film of the discontinuous metal thin film undercoat coating composition is less than 80 ° C.,
A coating composition for a discontinuous metal thin film undercoat.
[7]
The equivalent ratio E2 (NCO group / OH group) of the hydroxyl group of the hydroxyl group-containing resin (A-2) and the isocyanate group of the polyisocyanate compound (B-2) is in the range of 0.3 to 0.95.
A coating composition for a discontinuous metal thin film undercoat.
[8]
The silane coupling agent (C-2) is a coupling agent selected from the group consisting of an amino group-containing silane coupling agent, an epoxy group-containing silane coupling agent and an isocyanate group-containing silane coupling agent.
A coating composition for a discontinuous metal thin film undercoat.
[9]
A coating set for forming a discontinuous metal thin film-containing multi-layer coating film, containing the coating composition for a discontinuous metal thin film topcoat and the coating composition for a discontinuous metal thin film undercoat.
[10]
The equivalent ratio E1 (NCO groups / OH groups) in the coating composition for a discontinuous metal thin film topcoat and the equivalent ratio E2 (NCO groups / OH group) in the coating composition for a discontinuous metal thin film undercoat are as follows. Formula E1 / E2 = 1.3-4
A coating set for forming a multilayer coating film containing a discontinuous metal thin film that satisfies the above conditions.
[11]
An article to be coated is provided with an undercoat layer by coating the discontinuous metal thin film undercoat coating composition, an undercoat layer forming step,
Providing a discontinuous metal thin film on the undercoat layer, a discontinuous metal thin film forming step,
On the discontinuous metal thin film, the coating composition for the discontinuous metal thin film topcoat is applied to provide a topcoat layer, a topcoat layer forming step, and the undercoat layer and the topcoat layer are cured. Curing process,
A method of forming a discontinuous metal thin film-containing multilayer coating film, comprising:
The discontinuous metal thin film contains indium, tin, chromium or alloys thereof,
A method for forming a multilayer coating film containing a discontinuous metal thin film.
[12]
The equivalent ratio E1 (NCO group / OH group) in the coating composition for a discontinuous metal thin film topcoat and the equivalent ratio E2 (NCO group / OH group) in the coating composition for a discontinuous metal thin film undercoat are represented by the following formula E1. /E2=1.3-4
The above-mentioned forming method, wherein
　上記アンダーコート用塗料組成物および不連続金属薄膜トップコート用塗料組成物を用いて形成される複層塗膜は、耐候性（耐紫外線耐久性、耐水性など）、耐久性、耐擦傷性に優れるという利点がある。この複層塗膜を部材に形成することによって、不連続金属薄膜による金属調加飾を施すことができる。この複層塗膜は、電磁波の受発信システムを有する各種部材において好適に用いることができる。 A multilayer coating film formed by using the undercoat coating composition and the discontinuous metal thin film topcoat coating composition has excellent weather resistance (UV resistance, water resistance, etc.), durability, and scratch resistance. It has the advantage of being excellent. By forming this multi-layer coating film on the member, it is possible to apply a metal tone decoration with the discontinuous metal thin film. This multilayer coating film can be suitably used in various members having an electromagnetic wave transmitting / receiving system.
　本明細書は、不連続金属薄膜トップコート用塗料組成物、不連続金属薄膜アンダーコート用塗料組成物、そしてこれらの塗料組成物を含む不連続金属薄膜含有複層塗膜形成用塗料セットについて開示する。そして上記不連続金属薄膜トップコート用塗料組成物および不連続金属薄膜アンダーコート用塗料組成物を、下記工程：
被塗物に、上記不連続金属薄膜アンダーコート用塗料組成物を塗装してアンダーコート層を設ける、アンダーコート層形成工程、
アンダーコート層の上に不連続金属薄膜を設ける、不連続金属薄膜形成工程、
不連続金属薄膜の上に、上記不連続金属薄膜トップコート用塗料組成物を塗装して、トップコート層を設ける、トップコート層形成工程、および
得られたアンダーコート層およびトップコート層を硬化させる、硬化工程、
において用いることによって、不連続金属薄膜含有複層塗膜を形成することができる。
　以下、各塗料組成物について記載する。 The present disclosure discloses a coating composition for a discontinuous metal thin film topcoat, a coating composition for a discontinuous metal thin film undercoat, and a coating set for forming a discontinuous metal thin film-containing multilayer coating film containing these coating compositions. To do. Then, the coating composition for the discontinuous metal thin film topcoat and the coating composition for the discontinuous metal thin film undercoat are subjected to the following steps:
An article to be coated is provided with an undercoat layer by coating the discontinuous metal thin film undercoat coating composition, an undercoat layer forming step,
Providing a discontinuous metal thin film on the undercoat layer, a discontinuous metal thin film forming step,
The coating composition for a discontinuous metal thin film top coat is applied onto the discontinuous metal thin film to form a top coat layer, a top coat layer forming step, and the obtained undercoat layer and top coat layer are cured. , Curing process,
When used in, a discontinuous metal thin film-containing multilayer coating film can be formed.
Hereinafter, each coating composition will be described.
不連続金属薄膜トップコート用塗料組成物
　上記不連続金属薄膜トップコート用塗料組成物は、
水酸基含有樹脂（Ａ－１）、
ポリイソシアネート化合物（Ｂ－１）、および
シランカップリング剤（Ｃ－１）、
を含む。 Coating composition for discontinuous metal thin film topcoat The coating composition for discontinuous metal thin film topcoat,
Hydroxyl group-containing resin (A-1),
A polyisocyanate compound (B-1), and a silane coupling agent (C-1),
including.
　　水酸基含有樹脂（Ａ－１）
　上記不連続金属薄膜トップコート用塗料組成物に含まれる水酸基含有樹脂（Ａ－１）は、ポリイソシアネート化合物と反応して塗膜を形成する塗膜形成樹脂として機能する樹脂である。 Hydroxyl group-containing resin (A-1)
The hydroxyl group-containing resin (A-1) contained in the coating composition for a discontinuous metal thin film top coat is a resin that functions as a coating film forming resin that reacts with a polyisocyanate compound to form a coating film.
　水酸基含有樹脂（Ａ－１）は、水酸基を有しておりポリイソシアネート化合物と反応して塗膜を形成する塗膜形成樹脂であれば特に限定されないが、水酸基含有アクリル樹脂および／または水酸基含有ポリエステル樹脂であることが、製造および入手が容易なことから好ましい。塗膜物性の調整の観点から、上記水酸基含有樹脂（Ａ－１）として、水酸基含有アクリル樹脂を用いるのがより好ましい。 The hydroxyl group-containing resin (A-1) is not particularly limited as long as it is a coating film forming resin which has a hydroxyl group and reacts with a polyisocyanate compound to form a coating film, but a hydroxyl group containing acrylic resin and / or a hydroxyl group containing polyester. A resin is preferable because it is easy to manufacture and obtain. From the viewpoint of adjusting the physical properties of the coating film, it is more preferable to use a hydroxyl group-containing acrylic resin as the hydroxyl group-containing resin (A-1).
　水酸基含有アクリル樹脂は、水酸基を有するα，β－エチレン性不飽和単量体および他のα，β－エチレン性不飽和単量体を含む単量体混合物を、公知の方法で重合させることによって調製することができる。 The hydroxyl group-containing acrylic resin is obtained by polymerizing a monomer mixture containing an α, β-ethylenically unsaturated monomer having a hydroxyl group and another α, β-ethylenically unsaturated monomer by a known method. It can be prepared.
　水酸基を有するα，β－エチレン性不飽和単量体としては、特に限定されず、例えば、１級水酸基含有α，β－エチレン性不飽和単量体として、例えば、２－ヒドロキシエチル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、２－ヒドロキシ－１－メチル（メタ）アクリレート、プラクセルＦＭ１（εーカプロラクトン変性ヒドロキシエチルメタクリレート、ダイセル化学社製）、ポリエチレングリコールモノ（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレートなどが挙げられる。２級水酸基含有α，β－エチレン性不飽和単量体としては、例えば、２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチルアクリレートなどが挙げられる。
　なお本明細書において（メタ）アクリレートとは、アクリレートおよび／またはメタクリレートを意味する。 The α, β-ethylenically unsaturated monomer having a hydroxyl group is not particularly limited, and examples of the α, β-ethylenically unsaturated monomer having a primary hydroxyl group include 2-hydroxyethyl (meth) Acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-1-methyl (meth) acrylate, Praxel FM1 (ε-caprolactone modified hydroxyethyl methacrylate, manufactured by Daicel Chemical Industries), polyethylene Examples thereof include glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate. Examples of the α, β-ethylenically unsaturated monomer having a secondary hydroxyl group include 2-hydroxypropyl (meth) acrylate and 2-hydroxybutyl acrylate.
In addition, in this specification, (meth) acrylate means an acrylate and / or a methacrylate.
　上記他の不飽和単量体として、例えば、酸基含有α，β－エチレン性不飽和単量体が挙げられる。酸基含有α，β－エチレン性不飽和単量体の例として、例えば、アクリル酸、メタクリル酸、アクリル酸二量体、クロトン酸、２－アクリロイルオキシエチルフタル酸、２－アクリロイルオキシエチルコハク酸、ω－カルボキシ－ポリカプロラクトンモノ（メタ）アクリレート、マレイン酸、フマル酸、イタコン酸などを挙げることができる。これらの中で好ましいものは、アクリル酸、メタクリル酸である。 Examples of the other unsaturated monomers include acid group-containing α, β-ethylenically unsaturated monomers. Examples of the acid group-containing α, β-ethylenically unsaturated monomer include, for example, acrylic acid, methacrylic acid, acrylic acid dimer, crotonic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl succinic acid. , Ω-carboxy-polycaprolactone mono (meth) acrylate, maleic acid, fumaric acid, itaconic acid and the like. Of these, preferred are acrylic acid and methacrylic acid.
　水酸基含有α，β－エチレン性不飽和単量体、酸基含有α，β－エチレン性不飽和単量体以外のα，β－エチレン性不飽和単量体としては、特に限定されず、例えば、
（メタ）アクリル酸メチル、エチル、プロピル、ブチル、ヘキシル、エチルヘキシル、ラウリル、フェニル、イソボルニル、シクロヘキシルなどの、（メタ）アクリル酸エステル単量体；
ビニルアルコールと、酢酸、プロピオン酸などのカルボン酸とのエステル化物である、ビニルアルコールエステル単量体；
スチレン、α－メチルスチレン、ビニルナフタレン、ブタジエン、イソプレンなどの重合性不飽和炭化水素単量体；
アクリロニトリル、メタクリロニトリルなどの重合性ニトリル単量体；
アクリルアミド、メタクリルアミド、Ｎ－メチロールアクリルアミド、Ｎ，Ｎ－ジメチルアクリルアミド、ジアセトンアクリルアミドなどのアクリルアミド単量体；
などが挙げられる。 The α, β-ethylenically unsaturated monomer other than the hydroxyl group-containing α, β-ethylenically unsaturated monomer and the acid group-containing α, β-ethylenically unsaturated monomer is not particularly limited. ,
(Meth) acrylic acid ester monomers such as methyl (meth) acrylate, ethyl, propyl, butyl, hexyl, ethylhexyl, lauryl, phenyl, isobornyl, cyclohexyl;
A vinyl alcohol ester monomer which is an esterified product of vinyl alcohol and a carboxylic acid such as acetic acid or propionic acid;
Polymerizable unsaturated hydrocarbon monomers such as styrene, α-methylstyrene, vinylnaphthalene, butadiene and isoprene;
Polymerizable nitrile monomer such as acrylonitrile and methacrylonitrile;
Acrylamide monomers such as acrylamide, methacrylamide, N-methylol acrylamide, N, N-dimethyl acrylamide, diacetone acrylamide;
And so on.
　水酸基含有アクリル樹脂は、溶液重合により調製するのが好ましい。溶液重合は、加熱条件下において、原料として使用するα，β－エチレン性不飽和単量体を混合したものを重合開始剤と共に溶媒中へ滴下しながら撹拌する方法が一般的である。溶液重合する際の条件は、例えば、重合温度が６０～１６０℃、滴下時間が０．５～１０時間である。上記原料として使用するα，β－エチレン性不飽和単量体は、２段階に分けて重合することも可能である。この場合、原料として使用するα，β－エチレン性不飽和単量体全体として、上記水酸基についての要件を満たしていればよい。 The hydroxyl group-containing acrylic resin is preferably prepared by solution polymerization. The solution polymerization is generally carried out by stirring a mixture of α, β-ethylenically unsaturated monomers used as a raw material under heating with a polymerization initiator while dropping the mixture in a solvent. The conditions for solution polymerization are, for example, a polymerization temperature of 60 to 160 ° C. and a dropping time of 0.5 to 10 hours. The α, β-ethylenically unsaturated monomer used as the starting material can be polymerized in two stages. In this case, the α, β-ethylenically unsaturated monomer used as a raw material as a whole may satisfy the requirements for the hydroxyl group.
　上記重合開始剤は、通常の重合に用いられるものであれば特に限定されず、例えば、アゾ系化合物または過酸化物が挙げられる。一般に、単量体混合物１００質量部に対する重合開始剤の量は０．１～１８質量部であり、好ましくは０．３～１２質量部である。 The polymerization initiator is not particularly limited as long as it can be used in ordinary polymerization, and examples thereof include azo compounds and peroxides. Generally, the amount of the polymerization initiator is 0.1 to 18 parts by mass, preferably 0.3 to 12 parts by mass, based on 100 parts by mass of the monomer mixture.
　また、ここで用い得る溶媒は反応に悪影響を与えないものであれば特に限定されず、例えば、アルコール、ケトン、エーテルおよび炭化水素系溶媒などが挙げられる。さらに、分子量を調節するために、ラウリルメルカプタンのようなメルカプタン、および、α－メチルスチレンダイマーなどの連鎖移動剤を必要に応じて用いることができる。 The solvent used here is not particularly limited as long as it does not adversely affect the reaction, and examples thereof include alcohols, ketones, ethers and hydrocarbon solvents. Further, in order to control the molecular weight, a mercaptan such as lauryl mercaptan and a chain transfer agent such as α-methylstyrene dimer can be optionally used.
　上記水酸基含有樹脂（Ａ－１）中の水酸基は、１級および２級の水酸基を含み、その含有比率（１級水酸基／２級水酸基）が水酸基価を基準として１０／９０～８０／２０であるのが好ましく、３０／７０～５０／５０であるのがより好ましい。１級水酸基はポリイソシアネート化合物との反応性が高いため、トップコート層内でポリイソシアネート化合物と良好に硬化反応が進行する。しかしながら、トップコート層内での反応が良好に進行する場合は、層間を超えた、トップコート層内のポリイソシアネート化合物（Ｂ－１）とアンダーコート層内の水酸基含有樹脂（Ａ－２）との硬化反応を阻害する可能性もある。
一方で、２級水酸基はポリイソシアネート化合物（Ｂ－１）との反応性が低い。そのため、層間を超えた、トップコート層内のポリイソシアネート化合物（Ｂ－１）とアンダーコート層内の水酸基含有樹脂（Ａ－２）との硬化反応を促進する特性がある。
　従って、水酸基含有樹脂（Ａ－１）中の水酸基における含有比率（１級水酸基／２級水酸基）が水酸基価を基準として１０／９０～８０／２０であることによって、層間を超えた、トップコート層内のポリイソシアネート化合物（Ｂ－１）とアンダーコート層内の水酸基含有樹脂（Ａ－２）との硬化反応を確保することができ、不連続金属薄膜を間に含む複層塗膜の耐薬品性、耐溶剤性、耐候性を向上させることができ、さらに、トップコート層内における水酸基含有樹脂（Ａ－１）およびポリイソシアネート化合物（Ｂ－１）の硬化反応性も確保することができる利点がある。 The hydroxyl group in the hydroxyl group-containing resin (A-1) contains primary and secondary hydroxyl groups, and the content ratio (primary hydroxyl group / secondary hydroxyl group) is 10/90 to 80/20 based on the hydroxyl value. It is preferably from 30/70 to 50/50. Since the primary hydroxyl group has high reactivity with the polyisocyanate compound, the curing reaction proceeds well with the polyisocyanate compound in the top coat layer. However, when the reaction in the topcoat layer proceeds favorably, the polyisocyanate compound (B-1) in the topcoat layer and the hydroxyl group-containing resin (A-2) in the undercoat layer, which are between the layers, are crossed. There is also a possibility of inhibiting the curing reaction of.
On the other hand, the secondary hydroxyl group has low reactivity with the polyisocyanate compound (B-1). Therefore, it has the property of promoting the curing reaction between the polyisocyanate compound (B-1) in the topcoat layer and the hydroxyl group-containing resin (A-2) in the undercoat layer beyond the interlayer.
Therefore, when the content ratio of the hydroxyl groups in the hydroxyl group-containing resin (A-1) (primary hydroxyl group / secondary hydroxyl group) is 10/90 to 80/20 based on the hydroxyl group value, the top coat which exceeds the interlayer is obtained. A curing reaction between the polyisocyanate compound (B-1) in the layer and the hydroxyl group-containing resin (A-2) in the undercoat layer can be ensured, and the resistance of the multilayer coating film containing a discontinuous metal thin film in between can be secured. The chemical resistance, solvent resistance, and weather resistance can be improved, and the curing reactivity of the hydroxyl group-containing resin (A-1) and polyisocyanate compound (B-1) in the topcoat layer can be secured. There are advantages.
　上記水酸基含有樹脂（Ａ－１）の重量平均分子量（Ｍｗ）は、５０００以上２００００以下であるのが好ましく、５５００以上１５０００以下であるのがより好ましい。重量平均分子量（Ｍｗ）が上記範囲内であることによって、耐薬品性、耐候性などがより向上するなどの利点がある。本明細書において、水酸基含有樹脂の数平均分子量は、ポリスチレン標準サンプル基準を用いたゲルパーミエーションクロマトグラフィ（ＧＰＣ）で測定することができる。 The weight average molecular weight (Mw) of the hydroxyl group-containing resin (A-1) is preferably 5,000 or more and 20,000 or less, more preferably 5,500 or more and 15,000 or less. When the weight average molecular weight (Mw) is within the above range, there are advantages such as further improved chemical resistance and weather resistance. In the present specification, the number average molecular weight of the hydroxyl group-containing resin can be measured by gel permeation chromatography (GPC) using a polystyrene standard sample standard.
　上記水酸基含有樹脂（Ａ－１）の水酸基価は８０～２２０ｍｇＫＯＨ／ｇであるのが好ましく、１２０～１９０ｍｇＫＯＨ／ｇであるのがより好ましい。水酸基価が８０ｍｇＫＯＨ／ｇ未満である場合は、トップコート層の架橋密度が不十分となり、複層膜の耐薬品性、耐溶剤性、耐候性が低下するおそれがある。水酸基価が２２０ｍｇＫＯＨ／ｇを超える場合は、多量のポリイソシアネート化合物が必要となるおそれがある。 The hydroxyl value of the hydroxyl group-containing resin (A-1) is preferably 80 to 220 mgKOH / g, and more preferably 120 to 190 mgKOH / g. When the hydroxyl value is less than 80 mgKOH / g, the crosslink density of the topcoat layer becomes insufficient, and the chemical resistance, solvent resistance, and weather resistance of the multilayer film may deteriorate. If the hydroxyl value exceeds 220 mgKOH / g, a large amount of polyisocyanate compound may be required.
　また、水酸基含有樹脂（Ａ－１）の酸価が０～３０ｍｇＫＯＨ／ｇであることが好ましく、０．５～７ｍｇＫＯＨ／ｇであるのがより好ましい。水酸基含有樹脂（Ａ－１）の酸価が上記範囲内であることによって、トップコート用塗料組成物の硬化性および硬化速度を適切な範囲に設計することができる利点がある。 The acid value of the hydroxyl group-containing resin (A-1) is preferably 0 to 30 mgKOH / g, more preferably 0.5 to 7 mgKOH / g. When the acid value of the hydroxyl group-containing resin (A-1) is in the above range, there is an advantage that the curability and the curing speed of the topcoat coating composition can be designed in an appropriate range.
　上記水酸基含有樹脂（Ａ－１）のガラス転移温度（Ｔｇ）は０～１００℃であることが好ましい。上記水酸基含有樹脂（Ａ－１）のガラス転移温度（Ｔｇ）が０℃未満であると、良好な種々の薬品に対する耐久性や耐擦傷性が得られないおそれがある。上記水酸基含有樹脂（Ａ－１）のガラス転移温度（Ｔｇ）が１００℃を超えると、外観などが低下するおそれがある。水酸基含有樹脂のガラス転移点は、調製に用いた単量体の種類および量から計算によって求めることができる。また、水酸基含有樹脂のガラス転移点を、示差走査型熱量計（ＤＳＣ）によって測定してもよい。 The glass transition temperature (Tg) of the hydroxyl group-containing resin (A-1) is preferably 0 to 100 ° C. When the glass transition temperature (Tg) of the hydroxyl group-containing resin (A-1) is less than 0 ° C, good durability against various chemicals and scratch resistance may not be obtained. When the glass transition temperature (Tg) of the hydroxyl group-containing resin (A-1) exceeds 100 ° C., the appearance and the like may be deteriorated. The glass transition point of the hydroxyl group-containing resin can be calculated from the type and amount of the monomer used for the preparation. Further, the glass transition point of the hydroxyl group-containing resin may be measured by a differential scanning calorimeter (DSC).
　水酸基含有樹脂（Ａ－１）として、上記以外の他の樹脂を併用してもよい。他の樹脂として、例えば、水酸基含有ポリカーボネート樹脂、水酸基含有ウレタン樹脂、水酸基含有ポリエステル樹脂などが挙げられる。 As the hydroxyl group-containing resin (A-1), other resins than the above may be used in combination. Examples of other resins include hydroxyl group-containing polycarbonate resin, hydroxyl group-containing urethane resin, hydroxyl group-containing polyester resin and the like.
　　ポリイソシアネート化合物（Ｂ－１）
　上記不連続金属薄膜トップコート用塗料組成物に含まれるポリイソシアネート化合物（Ｂ－１）は、水酸基含有樹脂と反応して塗膜を形成する成分である。そして上記ポリイソシアネート化合物（Ｂ－１）は、炭素数４～５の脂肪族ジイソシアネートのヌレート体を含む。 Polyisocyanate compound (B-1)
The polyisocyanate compound (B-1) contained in the coating composition for a discontinuous metal thin film top coat is a component that reacts with a hydroxyl group-containing resin to form a coating film. The polyisocyanate compound (B-1) contains a nurate of an aliphatic diisocyanate having 4 to 5 carbon atoms.
　不連続金属薄膜トップコート用塗料組成物に含まれるポリイソシアネート化合物（Ｂ－１）が、炭素数４～５の脂肪族ジイソシアネートのヌレート体を含むことによって、不連続金属薄膜トップコート用塗料組成物に含まれる水酸基含有樹脂（Ａ－１）との良好な硬化反応性を確保することができる。さらに、ポリイソシアネート化合物（Ｂ－１）が、炭素数４～５の脂肪族ジイソシアネートのヌレート体を含むことによって、イソシアネート基の凝集力が高くなり、良好な種々の薬品に対する耐久性や耐擦傷性などを確保することができる利点がある。 The polyisocyanate compound (B-1) contained in the coating composition for a discontinuous metal thin film top coat contains a nurate of an aliphatic diisocyanate having 4 to 5 carbon atoms, whereby a coating composition for a discontinuous metal thin film top coat is obtained. Good curing reactivity with the hydroxyl group-containing resin (A-1) contained in can be secured. Furthermore, since the polyisocyanate compound (B-1) contains a nurate of an aliphatic diisocyanate having 4 to 5 carbon atoms, the cohesive force of the isocyanate group is increased, and the durability and scratch resistance to various chemical agents are excellent. Etc. can be secured.
　本明細書における「炭素数４～５の脂肪族ジイソシアネート」は、炭素数４～５の脂肪族基を有するジイソシアネートを意味する。炭素数４～５の脂肪族ジイソシアネートの具体例として、例えば、テトラメチレン－１，４－ジイソシアネート、ペンタメチレン－１，５－ジイソシアネートなどが挙げられる。 The “aliphatic diisocyanate having 4 to 5 carbon atoms” in the present specification means a diisocyanate having an aliphatic group having 4 to 5 carbon atoms. Specific examples of the aliphatic diisocyanate having 4 to 5 carbon atoms include tetramethylene-1,4-diisocyanate and pentamethylene-1,5-diisocyanate.
　炭素数４～５の脂肪族ジイソシアネートのヌレート体は、上記炭素数４～５の脂肪族ジイソシアネートを、必要に応じた触媒（例えば（２－ヒドロキシプロピル）トリメチルアンモニウムパラ第三級ブチルベンゾエートなど）の存在下で環化反応させることによって調製することができる。 The nurate of an aliphatic diisocyanate having 4 to 5 carbon atoms can be obtained by using the aliphatic diisocyanate having 4 to 5 carbon atoms as a catalyst (such as (2-hydroxypropyl) trimethylammonium para tert-butyl benzoate) as necessary. It can be prepared by carrying out a cyclization reaction in the presence.
　炭素数４～５の脂肪族ジイソシアネートのヌレート体として市販品を用いてもよい。市販品として、例えば、三井化学社製、スタビオ（登録商標）Ｄ３７０Ｎ、Ｄ３７６Ｎ、ＸＤ３７２５Ｎなどが挙げられる。 A commercial product may be used as a nurate of an aliphatic diisocyanate having 4 to 5 carbon atoms. Examples of commercially available products include Stabio (registered trademark) D370N, D376N, and XD3725N manufactured by Mitsui Chemicals, Inc.
　ポリイソシアネート化合物（Ｂ－１）は、炭素数４～５の脂肪族ジイソシアネートのヌレート体以外のイソシアネート化合物を含んでもよい。このようなポリイソシアネート化合物として、例えば、脂肪族または脂環族系のポリイソシアネート化合物が挙げられる。
　脂肪族または脂環族系のポリイソシアネート化合物としては、例えば、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、メチレンビスシクロヘキシルイソシアネートなどが挙げられ、また、これらから誘導されるイソシアヌレート化合物、ウレトジオン化合物、ウレタン化合物、アロファナート化合物、ビュレット化合物、トリメチロールプロパンとの付加物などが挙げられる。 The polyisocyanate compound (B-1) may contain an isocyanate compound other than the nurate of an aliphatic diisocyanate having 4 to 5 carbon atoms. Examples of such polyisocyanate compounds include aliphatic or alicyclic polyisocyanate compounds.
Examples of the aliphatic or alicyclic polyisocyanate compound include, for example, hexamethylene diisocyanate, isophorone diisocyanate, methylenebiscyclohexyl isocyanate, and the like, isocyanurate compounds derived from these, uretdione compounds, urethane compounds, and allophanate. Examples thereof include compounds, buret compounds, and adducts with trimethylolpropane.
　ポリイソシアネート化合物（Ｂ－１）中に含まれる、上記炭素数４～５の脂肪族ジイソシアネートのヌレート体の含有量は、４０～１００質量％の範囲内であるのが好ましく、８０～１００質量％の範囲内であるのがより好ましい。 The content of the nurate of the aliphatic diisocyanate having 4 to 5 carbon atoms contained in the polyisocyanate compound (B-1) is preferably in the range of 40 to 100% by mass, and 80 to 100% by mass. It is more preferable that it is within the range.
　ポリイソシアネート化合物（Ｂ－１）の一分子あたりの平均イソシアネート基数は、３．０～３．５であるのが好ましく、３．１～３．３であるのがより好ましい。平均イソシアネート基数が上記範囲内であることによって、得られる複層塗膜の耐溶剤性、耐候性、耐水性などの性能が向上するなどの利点がある。 The average number of isocyanate groups per molecule of the polyisocyanate compound (B-1) is preferably 3.0 to 3.5, and more preferably 3.1 to 3.3. When the average number of isocyanate groups is within the above range, there are advantages such as improvement in solvent resistance, weather resistance and water resistance of the resulting multilayer coating film.
　上記ポリイソシアネート化合物（Ｂ－１）中のイソシアネート基と上記水酸基含有樹脂（Ａ－１）中の水酸基との当量比Ｅ１（ＮＣＯ基／ＯＨ基）は、１．０～３．０の範囲内であるのが好ましく、１．１～１．８の範囲内であるのがより好ましい。当量比Ｅ１が１．０以上であることによって、層間を超えた、トップコート層内のポリイソシアネート化合物（Ｂ－１）とアンダーコート層内の水酸基含有樹脂（Ａ－２）との硬化反応を確保することができ、得られる複層塗膜の耐久性を向上させることができる利点がある。また、上記当量比Ｅ１が３以下であることによって、トップコート層の架橋密度を確保することができ、得られる複層塗膜の耐溶剤性、耐候性などを向上させることができる利点がある。 The equivalent ratio E1 (NCO group / OH group) of the isocyanate group in the polyisocyanate compound (B-1) and the hydroxyl group in the hydroxyl group-containing resin (A-1) is in the range of 1.0 to 3.0. Is preferable, and more preferably within the range of 1.1 to 1.8. When the equivalent ratio E1 is 1.0 or more, the curing reaction between the polyisocyanate compound (B-1) in the topcoat layer and the hydroxyl group-containing resin (A-2) in the undercoat layer, which exceeds the interlayer, is caused. There is an advantage that it can be secured and the durability of the obtained multilayer coating film can be improved. Further, when the equivalent ratio E1 is 3 or less, the crosslinking density of the top coat layer can be secured, and the solvent resistance and weather resistance of the obtained multilayer coating film can be improved. ..
　　シランカップリング剤（Ｃ－１）
　上記不連続金属薄膜トップコート用塗料組成物は、シランカップリング剤（Ｃ－１）を含む。シランカップリング剤（Ｃ－１）が含まれることによって、得られるトップコート層の、不連続金属薄膜に対する密着性が向上する利点がある。 Silane coupling agent (C-1)
The discontinuous metal thin film top coat coating composition contains a silane coupling agent (C-1). The inclusion of the silane coupling agent (C-1) has the advantage of improving the adhesion of the resulting topcoat layer to the discontinuous metal thin film.
　シランカップリング剤（Ｃ－１）として、例えば、アミノ基含有シランカップリング剤、エポキシ基含有シランカップリング剤およびイソシアネート基含有シランカップリング剤などが挙げられる。 Examples of the silane coupling agent (C-1) include amino group-containing silane coupling agents, epoxy group-containing silane coupling agents, and isocyanate group-containing silane coupling agents.
　アミノ基含有シランカップリング剤は、１分子中に少なくとも１つのアミノ基を有するシランカップリング剤である。アミノ基含有シランカップリング剤の具体例として、Ｎ－（２－アミノエチル）－３－アミノプロピルメチルジメトキシシラン、Ｎ－（２－アミノエチル）－３－アミノプロピルトリメトキシシラン、Ｎ－（２－アミノエチル）－３－アミノプロピルトリエトキシシラン、３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリエトキシシラン、３－トリエトキシシリル－Ｎ－（１，３－ジメチル－ブチリデン）プロピルアミン、Ｎ－フェニル－３－アミノプロピルトリメトキシシラン、およびＮ－（ビニルベンジル）－２－アミノエチル－３－アミノプロピルトリメトキシシランの塩酸塩などを挙げることができる。市販されているアミノ基含有シランカップリング剤である「ＫＢＭ－６０２」、「ＫＢＭ－６０３」、「ＫＢＥ－６０３」、「ＫＢＭ－９０３」、「ＫＢＥ－９０３」、「ＫＢＥ－９１０３」、「ＫＢＭ－５７３」、「ＫＢＰ－９０」（いずれも商品名、信越化学工業社製）、および「ＸＳ１００３」（商品名、チッソ社製）などを使用することもできる。アミノ基含有シランカップリング剤として、アミノシランの加水分解縮合物を用いることもできる。 The amino group-containing silane coupling agent is a silane coupling agent having at least one amino group in one molecule. Specific examples of the amino group-containing silane coupling agent include N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, and N- (2 -Aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N Examples thereof include -phenyl-3-aminopropyltrimethoxysilane, and N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride. Commercially available amino group-containing silane coupling agents "KBM-602", "KBM-603", "KBE-603", "KBM-903", "KBE-903", "KBE-9103", and "KBE-9103". It is also possible to use "KBM-573", "KBP-90" (all trade names, manufactured by Shin-Etsu Chemical Co., Ltd.), "XS1003" (trade name, manufactured by Chisso Corporation), and the like. As the amino group-containing silane coupling agent, a hydrolysis-condensation product of aminosilane can also be used.
　エポキシ基含有シランカップリング剤は、１分子中に少なくとも１つのエポキシ基を有するシランカップリング剤である。エポキシ基含有シランカップリング剤の具体例として、例えば、２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、３－グリシドキシプロピルメチルジメトキシシラン、３－グリシドキシプロピルトリメトキシシラン、３－グリシドキシプロピルメチルジエトキシシラン、３－グリシドキシプロピルトリエトキシシランなどが挙げられる。市販されているエポキシ基含有シランカップリング剤である「ＫＢＭ－４０３」、「ＫＢＥ－４０３」、「ＫＢＭ－４８０３」（いずれも商品名、信越化学工業社製）などを使用することもできる。 The epoxy group-containing silane coupling agent is a silane coupling agent having at least one epoxy group in one molecule. Specific examples of the epoxy group-containing silane coupling agent include, for example, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3 -Glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane and the like can be mentioned. Commercially available epoxy group-containing silane coupling agents such as "KBM-403", "KBE-403", and "KBM-4803" (all trade names, manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used.
　イソシアネート基含有シランカップリング剤は、１分子中に少なくとも１つのイソシアネート基を有するシランカップリング剤である。イソシアネート基含有シランカップリング剤の具体例として、例えば、３－イソシアネートプロピルトリエトキシシランなどが挙げられる。 The isocyanate group-containing silane coupling agent is a silane coupling agent having at least one isocyanate group in one molecule. Specific examples of the isocyanate group-containing silane coupling agent include 3-isocyanatopropyltriethoxysilane.
　シランカップリング剤（Ｃ－１）として、上記以外のシランカップリング剤を用いることもできる。例えば、
ビニルトリメトキシシラン、ビニルトリエトキシシランなどのビニル基含有シランカップリング剤；
ｐ－スチリルトリメトキシシランなどのスチリル基含有シランカップリング剤；
３－メタクリロキシプロピルメチルジメトキシシラン、３－メタクリロキシプロピルトリメトキシシラン、３－メタクリロキシプロピルメチルジエトキシシラン、３－メタクリロキシプロピルトリエトキシシラン、３－アクリロキシプロピルトリメトキシシランなどの（メタ）アクリル基含有シランカップリング剤；
３－ウレイドプロピルトリエトキシシランなどのウレイド基含有シランカップリング剤；
などが挙げられる。 As the silane coupling agent (C-1), a silane coupling agent other than the above can be used. For example,
Vinyl group-containing silane coupling agents such as vinyltrimethoxysilane and vinyltriethoxysilane;
a styryl group-containing silane coupling agent such as p-styryltrimethoxysilane;
(Meth) such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane Acrylic group-containing silane coupling agent;
Ureido group-containing silane coupling agent such as 3-ureidopropyltriethoxysilane;
And so on.
　上記シランカップリング剤（Ｃ－１）は、アミノ基含有シランカップリング剤、エポキシ基含有シランカップリング剤およびイソシアネート基含有シランカップリング剤からなる群から選択されるカップリング剤であるのが好ましい。 The silane coupling agent (C-1) is preferably a coupling agent selected from the group consisting of an amino group-containing silane coupling agent, an epoxy group-containing silane coupling agent and an isocyanate group-containing silane coupling agent. ..
　上記不連続金属薄膜トップコート用塗料組成物に含まれるシランカップリング剤（Ｃ－１）の量は、上記水酸基含有樹脂（Ａ－１）およびポリイソシアネート化合物（Ｂ－１）の合計固形分量１００質量部に対して０．５～２５質量部であるのが好ましく、１～２０質量部であるのがより好ましい。シランカップリング剤の含有量が上記範囲内であることによって、得られるトップコート層の塗膜物性を確保しつつ、不連続金属薄膜に対する密着性を向上させることができる利点がある。 The amount of the silane coupling agent (C-1) contained in the coating composition for a discontinuous metal thin film top coat is such that the total solid content of the hydroxyl group-containing resin (A-1) and the polyisocyanate compound (B-1) is 100. The amount is preferably 0.5 to 25 parts by mass, more preferably 1 to 20 parts by mass, relative to the parts by mass. When the content of the silane coupling agent is within the above range, there is an advantage that the adhesiveness to the discontinuous metal thin film can be improved while securing the coating film physical properties of the obtained top coat layer.
　　他の成分および不連続金属薄膜トップコート用塗料組成物の調製
　上記不連続金属薄膜トップコート用塗料組成物は、上記成分以外に、必要に応じて、他の樹脂成分、顔料、有機または無機の微粒子、硬化触媒、表面調整剤、消泡剤、顔料分散剤、可塑剤、造膜助剤、紫外線吸収剤、酸化防止剤などを含んでもよい。 Preparation of other components and coating composition for discontinuous metal thin film topcoat The coating composition for discontinuous metal thin film topcoat, in addition to the above components, other resin components, pigments, organic or inorganic It may contain fine particles, a curing catalyst, a surface modifier, a defoaming agent, a pigment dispersant, a plasticizer, a film-forming aid, an ultraviolet absorber, an antioxidant and the like.
　上記不連続金属薄膜トップコート用塗料組成物は、上記各成分（Ａ－１）～（Ｃ－１）および必要に応じた各成分を、通常用いられる手段によって混合することによって、調製することができる。 The discontinuous metal thin film top coat coating composition can be prepared by mixing the above-mentioned components (A-1) to (C-1) and any necessary components by a commonly used means. it can.
　上記不連続金属薄膜トップコート用塗料組成物は、必要に応じて有機溶媒を含んでもよい。有機溶媒を用いる場合は、上記成分（例えばイソシアネート基など）に対して不活性である有機溶媒を用いるのが好ましい。好ましい有機溶媒として、例えば、
プロピレングリコールジメチルエーテル、ジプロピレングリコールジメチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテルなどのエーテル系溶媒：
メチルエチルケトン、メチルイソブチルケトンなどのケトン系溶媒：
酢酸エチル、酢酸２－メトキシ－１－メチルエチル、酢酸アミル、酢酸イソアミル、酢酸イソブチル、
酢酸イソプロピル、酢酸オクチル、酢酸ｎ－ブチル、酢酸ｓｅｃ－ブチル、酢酸ｔｅｒｔ－ブチル、
酢酸プロピル、酢酸ヘプチルなどのエステル系溶媒：
などが挙げられる。 The discontinuous metal thin film top coat coating composition may include an organic solvent, if necessary. When an organic solvent is used, it is preferable to use an organic solvent which is inactive with respect to the above-mentioned components (for example, isocyanate group). As a preferred organic solvent, for example,
Ether solvents such as propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether:
Ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone:
Ethyl acetate, 2-methoxy-1-methylethyl acetate, amyl acetate, isoamyl acetate, isobutyl acetate,
Isopropyl acetate, octyl acetate, n-butyl acetate, sec-butyl acetate, tert-butyl acetate,
Ester solvents such as propyl acetate and heptyl acetate:
And so on.
　上記不連続金属薄膜トップコート用塗料組成物の樹脂固形分濃度は、塗装条件によって異なるが、一般的には１５～６０質量％に設定することが好ましく、４０～５０質量％に設定することがより好ましい。 The resin solid content concentration of the coating composition for a discontinuous metal thin film top coat varies depending on the coating conditions, but is generally preferably set to 15 to 60% by mass, and is set to 40 to 50% by mass. More preferable.
　上記不連続金属薄膜トップコート用塗料組成物の硬化塗膜のＴｇは、８０～１３０℃の範囲内であるのが好ましい。硬化塗膜のＴｇが上記範囲内であることによって、トップコート層としての良好な物性を確保することができ、得られる複層塗膜の耐候性および耐擦傷性などが向上するなどの利点がある。 The Tg of the cured coating film of the coating composition for a discontinuous metal thin film top coat is preferably in the range of 80 to 130 ° C. When the Tg of the cured coating film is within the above range, good physical properties as the topcoat layer can be secured, and the resulting multilayer coating film has advantages such as improved weather resistance and scratch resistance. is there.
　本明細書において、硬化塗膜のＴｇは、塗料組成物を乾燥膜厚３０μｍとなるように塗装し、次いで８０℃で３０分間加熱硬化させて得られた硬化塗膜を用いて測定したＴｇをいう。 In the present specification, the Tg of the cured coating film is the Tg measured using a cured coating film obtained by coating the coating composition so as to have a dry film thickness of 30 μm and then heat curing at 80 ° C. for 30 minutes. Say.
　また本明細書において硬化塗膜のＴｇは、動的粘弾性測定装置を用いて測定することができる。具体的には、動的粘弾性測定装置ＤＶＥ－Ｖ４ＦＴスペクトラー（レオロジ－社製）を用いて、上記で調整したフィルムを２０ｎｍ×５ｍｍにカットし、温度依存モードにて１１Ｈｚの基本正弦波歪で３０℃から１５０℃まで毎分３℃上昇させ、測定して得られる損失正接ｔａｎδの最大となる温度をＴｇとして測定することができる。 In the present specification, the Tg of the cured coating film can be measured using a dynamic viscoelasticity measuring device. Specifically, using a dynamic viscoelasticity measuring device DVE-V4FT Spectra (manufactured by Rheology), the film prepared above was cut into 20 nm × 5 mm, and a basic sinusoidal strain of 11 Hz was applied in a temperature-dependent mode. The temperature at which the loss tangent tan δ obtained by measurement is increased from 30 ° C. to 150 ° C. by 3 ° C. per minute can be measured as Tg.
不連続金属薄膜アンダーコート用塗料組成物
　上記不連続金属薄膜アンダーコート用塗料組成物は、
水酸基含有樹脂（Ａ－２）、
ポリイソシアネート化合物（Ｂ－２）、および
シランカップリング剤（Ｃ－２）、
を含む塗料組成物である。そして、上記不連続金属薄膜アンダーコート用塗料組成物の硬化塗膜のＴｇは、８０℃未満であることを条件とする。 Coating composition for discontinuous metal thin film undercoat The coating composition for discontinuous metal thin film undercoat,
Hydroxyl group-containing resin (A-2),
A polyisocyanate compound (B-2), and a silane coupling agent (C-2),
It is a coating composition containing. The Tg of the cured coating film of the discontinuous metal thin film undercoat coating composition is set to be less than 80 ° C.
　　水酸基含有樹脂（Ａ－２）
　上記不連続金属薄膜アンダーコート用塗料組成物に含まれる水酸基含有樹脂（Ａ－２）は、ポリイソシアネート化合物と反応して塗膜を形成する塗膜形成樹脂として機能する樹脂である。水酸基含有樹脂（Ａ－２）として、水酸基を有しておりポリイソシアネート化合物と反応して塗膜を形成する塗膜形成樹脂であれば特に限定されないが、水酸基含有アクリル樹脂および／または水酸基含有ポリエステル樹脂であることが、製造および入手が容易なことから好ましい。 Hydroxyl group-containing resin (A-2)
The hydroxyl group-containing resin (A-2) contained in the discontinuous metal thin film undercoat coating composition is a resin that functions as a coating film forming resin that reacts with a polyisocyanate compound to form a coating film. The hydroxyl group-containing resin (A-2) is not particularly limited as long as it is a coating film-forming resin that has a hydroxyl group and reacts with a polyisocyanate compound to form a coating film. However, a hydroxyl group-containing acrylic resin and / or a hydroxyl group-containing polyester A resin is preferable because it is easy to manufacture and obtain.
　水酸基含有アクリル樹脂は、上記水酸基含有アクリル樹脂の調製と同様の手順により調製することができる。 The hydroxyl group-containing acrylic resin can be prepared by the same procedure as the above hydroxyl group-containing acrylic resin.
　水酸基含有樹脂（Ａ－２）中の水酸基は１級水酸基であるのが特に好ましい。１級水酸基はポリイソシアネートとの反応性が高いため、水酸基含有樹脂（Ａ－２）中の水酸基として１級水酸基が多く含まれることによって、ポリイソシアネート化合物（Ｂ－２）、そして、不連続金属薄膜トップコート用塗料組成物中に含まれるポリイソシアネート化合物（Ｂ－１）と、良好に硬化反応が進行し、得られる複層塗膜の耐候性などが向上する利点がある。 The hydroxyl group in the hydroxyl group-containing resin (A-2) is particularly preferably a primary hydroxyl group. Since the primary hydroxyl group has high reactivity with polyisocyanate, a large amount of primary hydroxyl group is contained as the hydroxyl group in the hydroxyl group-containing resin (A-2), so that the polyisocyanate compound (B-2) and the discontinuous metal There is an advantage that the curing reaction proceeds well with the polyisocyanate compound (B-1) contained in the coating composition for a thin film top coat, and the weather resistance of the resulting multilayer coating film is improved.
　上記水酸基含有樹脂（Ａ－２）の重量平均分子量（Ｍｗ）は、１０００以上２００００以下であるのが好ましく、１５００以上１５０００以下であるのがより好ましい。重量平均分子量（Ｍｗ）が上記範囲内であることによって、アンダーコート層の塗膜平滑性を向上させることができ、そして得られる複層塗膜の塗膜外観を良好なものとすることができる利点がある。 The weight average molecular weight (Mw) of the hydroxyl group-containing resin (A-2) is preferably 1,000 or more and 20,000 or less, more preferably 1500 or more and 15,000 or less. When the weight average molecular weight (Mw) is within the above range, the coating film smoothness of the undercoat layer can be improved, and the coating film appearance of the obtained multilayer coating film can be improved. There are advantages.
　上記水酸基含有樹脂（Ａ－２）の水酸基価は２０～１７０ｍｇＫＯＨ／ｇであるのが好ましく、４０～１５０ｍｇＫＯＨ／ｇであるのがより好ましい。水酸基価が上記範囲内であることによって、得られる複層塗膜の物性を良好な範囲に設計することができる利点がある。 The hydroxyl value of the hydroxyl group-containing resin (A-2) is preferably 20 to 170 mgKOH / g, and more preferably 40 to 150 mgKOH / g. When the hydroxyl value is within the above range, there is an advantage that the physical properties of the obtained multilayer coating film can be designed in a favorable range.
　また、水酸基含有樹脂（Ａ－２）の酸価は、０～２０ｍｇＫＯＨ／ｇであることが好ましく、０．５～５ｍｇＫＯＨ／ｇであるのがより好ましい。水酸基含有樹脂（Ａ－２）の酸価が上記範囲内であることによって、アンダーコート用塗料組成物の硬化性および硬化速度を適切な範囲に設計することができる利点がある。 The acid value of the hydroxyl group-containing resin (A-2) is preferably 0 to 20 mgKOH / g, more preferably 0.5 to 5 mgKOH / g. When the acid value of the hydroxyl group-containing resin (A-2) is within the above range, there is an advantage that the curability and the curing speed of the undercoat coating composition can be designed in an appropriate range.
　上記水酸基含有樹脂（Ａ－２）のガラス転移温度（Ｔｇ）は０℃～６０℃であることが好ましい。上記水酸基含有樹脂（Ａ－２）のガラス転移温度（Ｔｇ）が上記範囲内であることによって、複層塗膜の塗膜外観を向上させることができる利点がある。水酸基含有樹脂のガラス転移点は、上記（前記（Ａ－１樹脂））と同様にして求めることができる。 The glass transition temperature (Tg) of the hydroxyl group-containing resin (A-2) is preferably 0 ° C to 60 ° C. When the glass transition temperature (Tg) of the hydroxyl group-containing resin (A-2) is within the above range, there is an advantage that the coating film appearance of the multilayer coating film can be improved. The glass transition point of the hydroxyl group-containing resin can be determined in the same manner as the above ((A-1 resin)).
　水酸基含有樹脂（Ａ－２）として、上記以外の他の樹脂を併用してもよい。他の樹脂として、例えば、水酸基含有ポリカーボネート樹脂、水酸基含有ウレタン樹脂、水酸基含有ポリエステル樹脂などが挙げられる。 As the hydroxyl group-containing resin (A-2), resins other than the above may be used in combination. Examples of other resins include hydroxyl group-containing polycarbonate resin, hydroxyl group-containing urethane resin, hydroxyl group-containing polyester resin and the like.
　　ポリイソシアネート化合物（Ｂ－２）
　上記不連続金属薄膜アンダーコート用塗料組成物に含まれるポリイソシアネート化合物（Ｂ－２）は、水酸基含有樹脂と反応して塗膜を形成する成分である。なお、ポリイソシアネート化合物（Ｂ－２）は、上記炭素数４～５の脂肪族ジイソシアネートのヌレート体を含んでもよく、含まなくてもよい。 Polyisocyanate compound (B-2)
The polyisocyanate compound (B-2) contained in the discontinuous metal thin film undercoat coating composition is a component that reacts with a hydroxyl group-containing resin to form a coating film. The polyisocyanate compound (B-2) may or may not contain the nurate of the above aliphatic diisocyanate having 4 to 5 carbon atoms.
　ポリイソシアネート化合物（Ｂ－２）として、脂肪族ジイソシアネート、脂環式ジイソシアネート、芳香族ジイソシアネート、および、これらから誘導されるイソシアヌレート化合物、ウレトジオン化合物、ウレタン化合物、アロファナート化合物、ビュレット化合物、トリメチロールプロパンとの付加物などが挙げられる。 Examples of the polyisocyanate compound (B-2) include an aliphatic diisocyanate, an alicyclic diisocyanate, an aromatic diisocyanate, and an isocyanurate compound, a uretdione compound, a urethane compound, an allophanate compound, a buret compound, and trimethylolpropane derived from these compounds. And the like.
　ポリイソシアネート化合物（Ｂ－２）の具体例として、例えば、トリメチレンジイソシアネート、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート、２，２，４－トリメチルへキサンジイソシアネート、ウンデカンジイソシアネート－（１，１１）、リジンエステルジイソシアネート、シクロヘキサン－１，３－および１，４－ジイソシアネート、１－イソシアナト－３－イソシアナトメチル－３，５，５－トリメチルシクロヘキサン（ＩＰＤＩ）、４，４’－ジイソシアナトジシクロジシクロメタン、ω，ω’－ジプロピルエーテルジイソシアネート、チオジプロピルジイソシアネート、シクロヘキシル－１，４－ジイソシアネート、ジシクロヘキシルメタン－４，４’－ジイソシアネート、１，５－ジメチル－２，４－ビス（イソシアナトメチル）ベンゼン、１，５－トリメチル－２，４－ビス（ω－イソシアナトエチル）－ベンゼン、１，３，５－トリメチル－２，４－ビス（イソシアナトメチル）ベンゼン、１，３，５－トリエチル‐２，４－ビス（イソシアナトメチル）ベンゼン、ジシクロヘキシルジメチルメタン－４，４’－ジイソシアネート、２，４－トルエンジイソシアネート、２，６－トルエンジイソシアネートおよびジフェニルメタン－４，４’－ジイソシアネート、２，４－ジイソシアナトトルエンおよび／または２，６－ジイソシアナトトルエン、４，４’－ジイソシアナトジフェニルメタンおよび１，４－ジイソシアナトイソプロピルベンゼン、シクロヘキシル－１，４－ジイソシアネート、トルエンジイソシアネートおよびヘキサメチレンジイソシアネートなどが挙げられる。これらは１種のみを単独で用いてもよく、２種またはそれ以上を併用してもよい。 Specific examples of the polyisocyanate compound (B-2) include, for example, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexane diisocyanate, undecane diisocyanate- (1,11), lysine ester diisocyanate. , Cyclohexane-1,3- and 1,4-diisocyanate, 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane (IPDI), 4,4′-diisocyanatodicyclodicyclomethane, ω , Ω'-dipropyl ether diisocyanate, thiodipropyl diisocyanate, cyclohexyl-1,4-diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,5-dimethyl-2,4 -Bis (isocyanatomethyl) benzene, 1,5-trimethyl-2,4-bis (ω-isocyanatoethyl) -benzene, 1,3,5-trimethyl-2,4-bis (isocyanatomethyl) benzene, 1,3,5-Triethyl-2,4-bis (isocyanatomethyl) benzene, dicyclohexyldimethylmethane-4,4'-diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate and diphenylmethane-4,4 '-Diisocyanate, 2,4-diisocyanatotoluene and / or 2,6-diisocyanatotoluene, 4,4'-diisocyanatodiphenylmethane and 1,4-diisocyanatoisopropylbenzene, cyclohexyl-1,4- Diisocyanate, toluene diisocyanate and hexa Such as Chi diisocyanate and the like. These may be used alone or in combination of two or more.
　上記ポリイソシアネート化合物（Ｂ－２）として市販品を用いてもよい。市販品として、例えば、旭化成社製デュラネートＴＰＡ１００、ＴＫＡ１００、２４Ａ－１００、Ｐ３０１－７５Ｅ、コベストロ社製ディスモジュールＮ３３００、Ｎ３９００、Ｎ３２００、Ｎ３４００、ｅｃｏＮ７３８０、ｘＰ２８６０、東ソー社製コロネートＨＸなどが挙げられる。 A commercially available product may be used as the polyisocyanate compound (B-2). Examples of commercially available products include Asahi Kasei's Duranate TPA100, TKA100, 24A-100, P301-75E, Covestro's Dismodule N3300, N3900, N3200, N3400, ecoN7380, xP2860, Tosoh's Coronate HX, and the like.
　ポリイソシアネート化合物（Ｂ－２）の一分子あたりの平均イソシアネート基数は、２．５～３．４であるのが好ましく、２．６～３．２であるのがより好ましい。平均イソシアネート基数が上記範囲内であることによって、得られる複層塗膜の物理的性能が向上するなどの利点がある。 The average number of isocyanate groups per molecule of the polyisocyanate compound (B-2) is preferably 2.5 to 3.4, and more preferably 2.6 to 3.2. When the average number of isocyanate groups is within the above range, there are advantages such as improvement in physical performance of the obtained multilayer coating film.
　上記ポリイソシアネート化合物（Ｂ－２）中のイソシアネート基と上記水酸基含有樹脂（Ａ－２）中の水酸基との当量比Ｅ２（ＮＣＯ基／ＯＨ基）は、０．３～０．９５の範囲内であるのが好ましく、０．５～０．８の範囲内であるのがより好ましい。当量比Ｅ２が０．９５以下であることによって、後に形成されるトップコート層内のポリイソシアネート化合物（Ｂ－１）とアンダーコート層内の水酸基含有樹脂（Ａ－２）との、層間を超えた硬化反応を確保することができ、得られる複層塗膜の耐久性を向上させることができる利点がある。 The equivalent ratio E2 (NCO group / OH group) of the isocyanate group in the polyisocyanate compound (B-2) and the hydroxyl group in the hydroxyl group-containing resin (A-2) is in the range of 0.3 to 0.95. Is preferable, and more preferably within the range of 0.5 to 0.8. When the equivalent ratio E2 is 0.95 or less, the polyisocyanate compound (B-1) in the subsequently formed topcoat layer and the hydroxyl group-containing resin (A-2) in the undercoat layer exceed the interlayer. There is an advantage that the curing reaction can be secured and the durability of the obtained multilayer coating film can be improved.
　　シランカップリング剤（Ｃ－２）
　上記不連続金属薄膜アンダーコート用塗料組成物は、シランカップリング剤（Ｃ－２）を含む。シランカップリング剤（Ｃ－２）が含まれることによって、得られるアンダーコート層の、不連続金属薄膜に対する密着性が向上する利点がある。 Silane coupling agent (C-2)
The discontinuous metal thin film undercoat coating composition contains a silane coupling agent (C-2). The inclusion of the silane coupling agent (C-2) has the advantage of improving the adhesion of the obtained undercoat layer to the discontinuous metal thin film.
　シランカップリング剤（Ｃ－２）として、例えば、アミノ基含有シランカップリング剤、エポキシ基含有シランカップリング剤およびイソシアネート基含有シランカップリング剤などが挙げられる。このようなシランカップリング剤として、上記シランカップリング剤（Ｃ－１）と同様のシランカップリング剤を用いることができる。 Examples of the silane coupling agent (C-2) include amino group-containing silane coupling agents, epoxy group-containing silane coupling agents, and isocyanate group-containing silane coupling agents. As such a silane coupling agent, the same silane coupling agent as the above silane coupling agent (C-1) can be used.
　上記不連続金属薄膜アンダーコート用塗料組成物に含まれるシランカップリング剤（Ｃ－２）は、上記不連続金属薄膜トップコート用塗料組成物に含まれるシランカップリング剤（Ｃ－１）と同種類のものであるのが好ましい。例えば、シランカップリング剤（Ｃ－１）がアミノ基含有シランカップリング剤を含む場合は、シランカップリング剤（Ｃ－２）がアミノ基含有シランカップリング剤を含むのが好ましい。 The silane coupling agent (C-2) contained in the coating composition for a discontinuous metal thin film undercoat is the same as the silane coupling agent (C-1) contained in the coating composition for a discontinuous metal thin film topcoat. It is preferably of the type: For example, when the silane coupling agent (C-1) contains an amino group-containing silane coupling agent, it is preferable that the silane coupling agent (C-2) contains an amino group-containing silane coupling agent.
　上記不連続金属薄膜アンダーコート用塗料組成物に含まれるシランカップリング剤（Ｃ－２）の量は、上記水酸基含有樹脂（Ａ－２）およびポリイソシアネート化合物（Ｂ－２）の合計固形分量１００質量部に対して０．５～２５質量部であるのが好ましく、１～２０質量部であるのがより好ましい。シランカップリング剤の含有量が上記範囲内であることによって、得られるアンダーコート層の塗膜物性を確保しつつ、不連続金属薄膜に対する密着性を向上させることができる利点がある。 The amount of the silane coupling agent (C-2) contained in the discontinuous metal thin film undercoat coating composition is such that the total solid content of the hydroxyl group-containing resin (A-2) and the polyisocyanate compound (B-2) is 100. The amount is preferably 0.5 to 25 parts by mass, more preferably 1 to 20 parts by mass, relative to the parts by mass. When the content of the silane coupling agent is within the above range, there is an advantage that the adhesiveness to the discontinuous metal thin film can be improved while securing the coating film physical properties of the obtained undercoat layer.
　　他の成分および不連続金属薄膜アンダーコート用塗料組成物の調製
　上記不連続金属薄膜アンダーコート用塗料組成物は、上記成分以外に、必要に応じて、他の樹脂成分、顔料、硬化触媒、表面調整剤、消泡剤、顔料分散剤、可塑剤、造膜助剤、紫外線吸収剤、酸化防止剤などを含んでもよい。 Preparation of coating composition for other components and discontinuous metal thin film undercoat The above-mentioned discontinuous metal thin film undercoat coating composition, in addition to the above components, other resin components, pigments, curing catalysts, surfaces, if necessary. It may contain a regulator, an antifoaming agent, a pigment dispersant, a plasticizer, a film-forming aid, an ultraviolet absorber, an antioxidant, and the like.
　上記不連続金属薄膜アンダーコート用塗料組成物は、上記各成分（Ａ－２）～（Ｃ－２）および必要に応じた各成分を、通常用いられる手段によって混合することによって、調製することができる。上記不連続金属薄膜アンダーコート用塗料組成物は、必要に応じて有機溶媒を含んでもよい。有機溶媒として、上述の有機溶媒を用いることができる。 The coating composition for a discontinuous metal thin film undercoat can be prepared by mixing the above-mentioned components (A-2) to (C-2) and, if necessary, each component by a commonly used means. it can. The discontinuous metal thin film undercoat coating composition may optionally contain an organic solvent. The organic solvent described above can be used as the organic solvent.
　上記不連続金属薄膜アンダーコート用塗料組成物の樹脂固形分濃度は、塗装条件によって異なるが、一般的には１５～６０質量％に設定することが好ましく、３５～５０質量％に設定することがより好ましい。 The resin solid content concentration of the coating composition for a discontinuous metal thin film undercoat varies depending on the coating conditions, but generally it is preferably set to 15 to 60% by mass, and set to 35 to 50% by mass. More preferable.
　上記不連続金属薄膜アンダーコート用塗料組成物の硬化塗膜のＴｇは、８０℃未満であることを条件とする。不連続金属薄膜アンダーコート用塗料組成物の硬化塗膜のＴｇが８０℃以上である場合は、アンダーコート層の平滑性が劣ることとなり、その後に形成される不連続金属薄膜の外観が低下し、得られる複層塗膜の塗膜外観が低下するおそれがある。上記不連続金属薄膜アンダーコート用塗料組成物の硬化塗膜のＴｇは３０℃以上８０℃未満であるのが好ましく、５０℃以上８０℃未満であるのがより好ましい。 The Tg of the cured coating film of the above discontinuous metal thin film undercoat coating composition must be less than 80 ° C. When the Tg of the cured coating film of the coating composition for a discontinuous metal thin film undercoat is 80 ° C. or higher, the smoothness of the undercoat layer becomes poor, and the appearance of the discontinuous metal thin film formed thereafter deteriorates. The appearance of the resulting multilayer coating film may deteriorate. The Tg of the cured coating film of the coating composition for a discontinuous metal thin film undercoat is preferably 30 ° C. or higher and lower than 80 ° C., and more preferably 50 ° C. or higher and lower than 80 ° C.
不連続金属薄膜含有複層塗膜形成用塗料セット
　本明細書は、上記不連続金属薄膜トップコート用塗料組成物および上記不連続金属薄膜アンダーコート用塗料組成物を含む、不連続金属薄膜含有複層塗膜形成用塗料セットを開示する。
　上記不連続金属薄膜含有複層塗膜形成用塗料セットにおいて、不連続金属薄膜トップコート用塗料組成物における上記当量比Ｅ１（ＮＣＯ基／ＯＨ基）および不連続金属薄膜アンダーコート用塗料組成物における上記当量比Ｅ２（ＮＣＯ基／ＯＨ基）が、下記式
Ｅ１／Ｅ２＝１．３～４
を満たすのが好ましい。
　Ｅ１／Ｅ２の値が上記範囲を満たす場合は、アンダーコート層内にＯＨ基が多量に存在し、一方でトップコート層内にはＮＣＯ基が多量に存在する状態となる。これにより、トップコート層内のポリイソシアネート化合物（Ｂ－１）とアンダーコート層内の水酸基含有樹脂（Ａ－２）との、層間を超えた硬化反応を確保することができ、これにより、得られる複層塗膜において不連続金属薄膜を良好に固定することができる利点がある。 A coating set for forming a multi-layer coating film containing a discontinuous metal thin film The present specification includes a coating composition for a discontinuous metal thin film top coat and a coating composition for a discontinuous metal thin film undercoat, containing a discontinuous metal thin film-containing coating composition. Disclosed is a paint set for forming a layer coating film.
In the coating set for forming a multilayer coating film containing a discontinuous metal thin film, the equivalent ratio E1 (NCO group / OH group) in the coating composition for a discontinuous metal thin film top coat and the coating composition for a discontinuous metal thin film undercoat in the coating composition The equivalent ratio E2 (NCO group / OH group) is calculated by the following formula E1 / E2 = 1.3 to 4
It is preferable to satisfy.
When the value of E1 / E2 satisfies the above range, a large amount of OH groups are present in the undercoat layer, while a large amount of NCO groups are present in the topcoat layer. This makes it possible to secure a curing reaction between the polyisocyanate compound (B-1) in the topcoat layer and the hydroxyl group-containing resin (A-2) in the undercoat layer that exceeds the inter-layers. There is an advantage that the discontinuous metal thin film can be satisfactorily fixed in the obtained multilayer coating film.
　また、不連続金属薄膜含有複層塗膜形成用塗料セットにおいて、不連続金属薄膜アンダーコート用塗料組成物に含まれるシランカップリング剤（Ｃ－２）は、不連続金属薄膜トップコート用塗料組成物に含まれるシランカップリング剤（Ｃ－１）と同種類のものであるのが好ましい。シランカップリング剤（Ｃ－２）およびシランカップリング剤（Ｃ－１）が同種類であることによって、不連続金属薄膜をより良好に固定することができ、得られる複層塗膜の耐候性および耐薬品性を向上させることができる利点がある。 In the coating set for forming a multi-layer coating film containing a discontinuous metal thin film, the silane coupling agent (C-2) contained in the coating composition for a discontinuous metal thin film undercoat is a coating composition for a discontinuous metal thin film topcoat. It is preferably the same type as the silane coupling agent (C-1) contained in the product. Since the silane coupling agent (C-2) and the silane coupling agent (C-1) are of the same type, the discontinuous metal thin film can be better fixed, and the weather resistance of the obtained multilayer coating film can be improved. And there is an advantage that the chemical resistance can be improved.
不連続金属薄膜含有複層塗膜の形成方法
　本明細書はさらに、
被塗物に、上記不連続金属薄膜アンダーコート用塗料組成物を塗装してアンダーコート層を設ける、アンダーコート層形成工程、
アンダーコート層の上に不連続金属薄膜を設ける、不連続金属薄膜形成工程、
不連続金属薄膜の上に、上記不連続金属薄膜トップコート用塗料組成物を塗装して、トップコート層を設ける、トップコート層形成工程、および
得られたアンダーコート層およびトップコート層を硬化させる、硬化工程、
を包含する、不連続金属薄膜含有複層塗膜の形成方法であって、
上記不連続金属薄膜は、インジウム、スズ、クロムまたはこれらの合金を含む、
不連続金属薄膜含有複層塗膜の形成方法、を開示する。 Method for forming a discontinuous metal thin film-containing multilayer coating film The present specification further comprises
An article to be coated is provided with an undercoat layer by coating the discontinuous metal thin film undercoat coating composition, an undercoat layer forming step,
Providing a discontinuous metal thin film on the undercoat layer, a discontinuous metal thin film forming step,
The coating composition for a discontinuous metal thin film top coat is applied onto the discontinuous metal thin film to form a top coat layer, a top coat layer forming step, and the obtained undercoat layer and top coat layer are cured. , Curing process,
A method of forming a discontinuous metal thin film-containing multilayer coating film, comprising:
The discontinuous metal thin film contains indium, tin, chromium or alloys thereof,
A method for forming a multi-layer coating film containing a discontinuous metal thin film is disclosed.
　被塗物として、不連続金属薄膜による金属調加飾を施す対象である各種基材が挙げられる。基材として、例えば、ポリエチレン樹脂、ＥＶＡ樹脂、ポリオレフィン樹脂（ポリエチレン樹脂、ポリプロピレン樹脂など）、塩化ビニル樹脂、スチロール樹脂、ポリエステル樹脂（ＰＥＴ樹脂、ＰＢＴ樹脂などを含む）、ポリカーボネート樹脂、アクリル樹脂、アクリロニトリルブタジエンスチレン（ＡＢＳ）樹脂、アクリロニトリルスチレン（ＡＳ）樹脂、ポリアミド樹脂、アセタール樹脂、フェノール樹脂、フッ素樹脂、メラミン樹脂、ウレタン樹脂、エポキシ樹脂、ポリフェニレンオキサイド（ＰＰＯ）などの樹脂；および、上記の樹脂のコンポジット材、上記の樹脂のハイブリッド材、さらに有機－無機ハイブリッド材などが挙げられる。これらは成形された状態であってもよい。 As the article to be coated, various base materials to which metal-like decoration is applied by the discontinuous metal thin film are listed. Examples of the base material include polyethylene resin, EVA resin, polyolefin resin (polyethylene resin, polypropylene resin, etc.), vinyl chloride resin, styrene resin, polyester resin (including PET resin, PBT resin, etc.), polycarbonate resin, acrylic resin, acrylonitrile. Resins such as butadiene styrene (ABS) resin, acrylonitrile styrene (AS) resin, polyamide resin, acetal resin, phenol resin, fluororesin, melamine resin, urethane resin, epoxy resin, polyphenylene oxide (PPO); Examples thereof include composite materials, hybrid materials of the above resins, and organic-inorganic hybrid materials. These may be in a molded state.
　上記樹脂は、必要に応じて、有機溶媒を用いた蒸気洗浄が行われていてもよく、または中性洗剤を用いた洗浄が行われていてもよい。さらに、必要に応じたプライマー塗装が施されていてもよい。 The above resin may be washed with steam using an organic solvent, or may be washed with a neutral detergent, if necessary. Furthermore, a primer coating may be applied if necessary.
　被塗物に、上記不連続金属薄膜アンダーコート用塗料組成物を塗装してアンダーコート層を設ける（アンダーコート層形成工程）。不連続金属薄膜アンダーコート用塗料組成物の塗装は、通常用いられる塗装方法によって塗装することができる。塗装方法として、例えば、スプレー塗装、刷毛塗り、ロール塗り、流し塗りなどが挙げられる。塗装方法としてスプレー塗装が好ましく用いられ、特に、エアースプレー塗装による多ステージ塗装方法（好ましくは２ステージ塗装）、または、エアー静電スプレー塗装と、通称「μμ（マイクロマイクロ）ベル」、「μ（マイクロ）ベル」あるいは「メタベル」等と言われる回転霧化式の塗装機とを組み合わせた塗装方法などを用いることもできる。 ③ The above coating composition for a discontinuous metal thin film undercoat is applied to an object to be coated to form an undercoat layer (undercoat layer forming step). The coating composition for a discontinuous metal thin film undercoat can be coated by a commonly used coating method. Examples of the coating method include spray coating, brush coating, roll coating, and flow coating. Spray coating is preferably used as the coating method, and in particular, multistage coating method by air spray coating (preferably two stage coating) or air electrostatic spray coating, commonly known as “μμ (micro micro) bell” and “μ ( It is also possible to use a coating method in combination with a rotary atomization type coating machine called "micro) bell" or "metabell".
　不連続金属薄膜アンダーコート用塗料組成物の塗膜の膜厚は、所望の用途などに応じて適宜選択することができる。膜厚は、例えば１５～３５μｍであるのが好ましく、１５～３０μｍであるのがさらに好ましい。 The thickness of the coating film of the discontinuous metal thin film undercoat coating composition can be appropriately selected according to the desired application. The film thickness is, for example, preferably 15 to 35 μm, more preferably 15 to 30 μm.
　不連続金属薄膜アンダーコート用塗料組成物を塗装した後、不連続金属薄膜を設ける前に、乾燥処理を行い、硬化塗膜を作製するのが好ましい。乾燥条件は特に限定されないが、例えば、６０℃～９０℃の温度条件下で２０～６０分間乾燥する方法などが挙げられる。不連続金属薄膜を設ける前に乾燥処理を行うことによって、塗膜の平滑性を確保し、これにより良好な鏡面性を有する不連続金属薄膜を設けることができる利点がある。 After coating the coating composition for the discontinuous metal thin film undercoat, and before providing the discontinuous metal thin film, it is preferable to perform a drying treatment to prepare a cured coating film. The drying conditions are not particularly limited, and examples thereof include a method of drying for 20 to 60 minutes under the temperature condition of 60 ° C to 90 ° C. By performing a drying treatment before providing the discontinuous metal thin film, there is an advantage that the smoothness of the coating film can be ensured and thus the discontinuous metal thin film having good specularity can be provided.
　次いで、アンダーコート層の上に不連続金属薄膜層を設ける（不連続金属薄膜形成工程）。不連続金属薄膜は、金属粒子の薄膜を、島状の不連続状態（分散状態）でアンダーコート層の上に設けることによって、形成することができる。不連続金属薄膜を形成する金属として、例えば、インジウム、スズ、クロムまたはこれらの合金が挙げられる。 Next, a discontinuous metal thin film layer is provided on the undercoat layer (discontinuous metal thin film forming step). The discontinuous metal thin film can be formed by providing a thin film of metal particles in an island-shaped discontinuous state (dispersed state) on the undercoat layer. Examples of the metal forming the discontinuous metal thin film include indium, tin, chromium or alloys thereof.
　不連続金属薄膜を形成する金属として、インジウム、スズ、クロムまたはこれらの合金が好適に用いられる。例えばインジウム、スズ、クロムまたはこれらの合金を、蒸着法またはスパッタリング法などによって、膜厚７０ｎｍ以下の金属薄膜を形成することによって、不連続金属薄膜を形成することができる。上記膜厚は、６０ｎｍ以下であるのが好ましく、５０ｎｍ以下であるのがより好ましい。金属薄膜の膜厚を調節することによって、金属粒子の不連続状態を調整することができる。上記蒸着法およびスパッタリング法は、当業者に知られた方法によって行うことができる。例えば蒸着法においては、たとえば１０－３～１０－２Ｐａ程に減圧した真空容器内で金属を蒸発（気化）させる真空蒸発法で行うのが好ましい。 Indium, tin, chromium or alloys thereof are preferably used as the metal forming the discontinuous metal thin film. For example, a discontinuous metal thin film can be formed by forming a metal thin film having a film thickness of 70 nm or less from indium, tin, chromium or an alloy thereof by a vapor deposition method or a sputtering method. The film thickness is preferably 60 nm or less, and more preferably 50 nm or less. By adjusting the film thickness of the metal thin film, the discontinuous state of the metal particles can be adjusted. The vapor deposition method and the sputtering method can be performed by methods known to those skilled in the art. For example, the vapor deposition method is preferably a vacuum vaporization method in which a metal is vaporized (vaporized) in a vacuum container whose pressure is reduced to, for example, 10 −3 to 10 −2 Pa.
　次いで、得られた不連続金属薄膜の上に、上記不連続金属薄膜トップコート用塗料組成物を塗装して、トップコート層を設ける（トップコート層形成工程）。不連続金属薄膜トップコート用塗料組成物の塗装は、上記アンダーコート用塗料組成物の塗装と同様にして行うことができる。不連続金属薄膜トップコート用塗料組成物の塗膜の膜厚は、所望の用途などに応じて適宜選択することができる。膜厚は、例えば１５～３５μｍであるのが好ましく、１５～３０μｍであるのがさらに好ましい。 Next, the above discontinuous metal thin film topcoat coating composition is applied onto the obtained discontinuous metal thin film to form a topcoat layer (topcoat layer forming step). The coating composition for a discontinuous metal thin film top coat can be applied in the same manner as the above-mentioned coating composition for an undercoat. The film thickness of the coating composition of the discontinuous metal thin film topcoat coating composition can be appropriately selected according to the desired application. The film thickness is, for example, preferably 15 to 35 μm, more preferably 15 to 30 μm.
　次いで、上記より形成されたアンダーコート層およびトップコート層を硬化させる（硬化工程）。上記硬化は、加熱硬化によって好適に行うことができる。加熱硬化温度および加熱時間は、被塗物である基材の種類、不連続金属薄膜を構成する金属の種類そして塗料組成物の種類に応じて、適宜選択することができる。加熱硬化温度は、例えば５０～１２０℃の範囲内であるのが好ましく、６０～１２０℃の範囲内であるのがより好ましい。加熱時間は一般に１０～１２０分間であり、２０～６０分間であるのが好ましい。加熱装置は、当業者に通常用いられる装置を用いることができ、例えば、熱風、電気、ガス、赤外線等の加熱源を利用した乾燥炉などを用いることができる。 Next, the undercoat layer and topcoat layer formed as described above are cured (curing step). The above curing can be suitably performed by heat curing. The heating and curing temperature and the heating time can be appropriately selected depending on the type of the substrate that is the object to be coated, the type of metal that constitutes the discontinuous metal thin film, and the type of coating composition. The heat curing temperature is, for example, preferably in the range of 50 to 120 ° C, more preferably in the range of 60 to 120 ° C. The heating time is generally 10 to 120 minutes, preferably 20 to 60 minutes. As the heating device, a device usually used by those skilled in the art can be used, and for example, a drying oven using a heating source such as hot air, electricity, gas, infrared rays, or the like can be used.
　上記工程により、不連続金属薄膜を有する複層塗膜を形成することができる。そして上記アンダーコート用塗料組成物および不連続金属薄膜トップコート用塗料組成物を用いて形成される複層塗膜は、耐候性（耐紫外線耐久性、耐水性など）、耐久性、耐擦傷性に優れるという利点がある。この複層塗膜は、自動車のフロント部、自動車のドアハンドル、車搭載通信機器、携帯電話、携帯情報端末機器（タブレットパソコン、モバイル機器および電子手帳など）、電磁波の受発信システムを有する各種家電製品および住宅設備などにおいて好適に用いることができる。 By the above process, a multilayer coating film having a discontinuous metal thin film can be formed. The multilayer coating film formed by using the above coating composition for undercoat and coating composition for discontinuous metal thin film topcoat has weather resistance (UV resistance, water resistance, etc.), durability, scratch resistance. Has the advantage of being excellent. This multi-layer coating film is used for automobile front parts, automobile door handles, vehicle-mounted communication devices, mobile phones, personal digital assistants (tablets, mobile devices, electronic notebooks, etc.), and various home appliances with electromagnetic wave transmission / reception systems. It can be suitably used in products and housing equipment.
　以下の実施例により本発明をさらに具体的に説明するが、本発明はこれらに限定されない。実施例中、「部」および「％」は、ことわりのない限り、質量基準による。 The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. In the examples, "parts" and "%" are based on mass unless otherwise specified.
製造例１　不連続金属薄膜トップコート用塗料組成物用の水酸基含有樹脂（Ａ－１）（１）の製造
　攪拌羽根、温度計、滴下装置、温度制御装置、窒素ガス導入口および冷却管を備えた反応装置に、有機溶媒として酢酸ブチル１４０部を仕込み、窒素ガスを導入しつつ、攪拌下１２５℃まで昇温した。
　次に、単量体混合物として、２－ヒドロキシエチルメタクリレート５８．５部、２－ヒドロキシプロピルメタクリレート９７．２部、スチレン４５部、ｔ－ブチルメタクリレート１１２．９部、ｎ－ブチルアクリレート１３３．２部、メタクリル酸３．５部の混合物、および、重合開始剤（１）として、カヤエステルＯ（ｔ－ブチルパーオキシ－２－エチルヘキサナート、化薬アクゾ社製）４５部を酢酸ブチル９０部に溶解した溶液を反応装置中に３時間かけて滴下した。 Production Example 1 Production of hydroxyl group-containing resin (A-1) (1) for coating composition for discontinuous metal thin film top coat , equipped with stirring blade, thermometer, dropping device, temperature control device, nitrogen gas inlet and cooling pipe 140 parts of butyl acetate as an organic solvent was charged into the reaction apparatus, and the temperature was raised to 125 ° C. with stirring while introducing nitrogen gas.
Next, as a monomer mixture, 58.5 parts of 2-hydroxyethyl methacrylate, 97.2 parts of 2-hydroxypropyl methacrylate, 45 parts of styrene, 112.9 parts of t-butyl methacrylate and 133.2 parts of n-butyl acrylate. A mixture of 3.5 parts of methacrylic acid and 45 parts of Kayaester O (t-butylperoxy-2-ethylhexanate, manufactured by Kayaku Akzo Co., Ltd.) as a polymerization initiator (1) in 90 parts of butyl acetate. The dissolved solution was dropped into the reactor over 3 hours.
　滴下終了後１時間熟成させ、さらに、重合開始剤（２）としてカヤエステルＯ（ｔ－ブチルパーオキシ－２－エチルヘキサナート）０．９部を酢酸ブチル１０部に溶解して、１時間かけて反応装置中に滴下した。その後１２５℃を保ったまま２時間熟成させて冷却し、反応を終了して、水酸基含有アクリル樹脂を得た。
　得られた水酸基含有アクリル樹脂の重量平均分子量を、ＧＰＣを用いて測定したところ、７０００であった。また不揮発分は６５％であった。
　得られた水酸基含有アクリル樹脂の各種特数値を、下記表に示す。 After completion of the dropping, the mixture was aged for 1 hour, and 0.9 part of Kayaester O (t-butylperoxy-2-ethylhexanate) as a polymerization initiator (2) was dissolved in 10 parts of butyl acetate, followed by 1 hour. And dropped into the reactor. Thereafter, while maintaining the temperature at 125 ° C., the mixture was aged for 2 hours and cooled, and the reaction was terminated to obtain a hydroxyl group-containing acrylic resin.
The weight average molecular weight of the obtained hydroxyl group-containing acrylic resin was measured by GPC and found to be 7,000. The nonvolatile content was 65%.
Various characteristic values of the obtained hydroxyl group-containing acrylic resin are shown in the following table.
製造例２～４　水酸基含有樹脂（Ａ－１）（２）～（４）の製造
　用いた単量体混合物が、下記表に示される単量体を含む単量体混合物を用いたこと以外は、製造例１と同様の手順により、水酸基含有アクリル樹脂を調製した。
　得られた水酸基含有アクリル樹脂の各種特数値を、下記表に示す。 Production Examples 2 to 4 Except that the monomer mixture used for producing the hydroxyl group-containing resins (A-1) (2) to (4) was a monomer mixture containing the monomers shown in the following table. A hydroxyl group-containing acrylic resin was prepared in the same procedure as in Production Example 1.
Various characteristic values of the obtained hydroxyl group-containing acrylic resin are shown in the following table.
製造例５～７　不連続金属薄膜アンダーコート用塗料組成物用の水酸基含有樹脂（Ａ－２）（１）～（３）の製造
　用いた単量体混合物が、下記表に示される単量体を含む単量体混合物を用いたこと以外は、製造例１と同様の手順により、水酸基含有アクリル樹脂を調製した。
　得られた水酸基含有アクリル樹脂の各種特数値を、下記表に示す。 Production Examples 5 to 7 Monomer mixtures used in the production of the hydroxyl group-containing resins (A-2) (1) to (3) for the coating composition for discontinuous metal thin film undercoat are the monomers shown in the following table. A hydroxyl group-containing acrylic resin was prepared by the same procedure as in Production Example 1 except that a monomer mixture containing was used.
Various characteristic values of the obtained hydroxyl group-containing acrylic resin are shown in the following table.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
トップコート用塗料組成物（１－１）の調製
　容器に、調製した水酸基含有樹脂（Ａ－１）を５９．３部仕込み、攪拌しながら、ＢＹＫ－３１０（ビッグケミー・ジャパン社製）０．３部、ビケトールスペシャル（ビッグケミー・ジャパン社製）０．３部、１％ジブチルスズジラウレート（ＤＢＴＤＬ）の酢酸ブチル溶液０．４部、チヌビン２９２（チバ・スペシャリティ・ケミカルズ株式会社製）０．４部、チヌビン３８４－２（チバ・スペシャリティ・ケミカルズ株式会社製）０．８部、酢酸ブチル１８部、メチルエチルケトン（ＭＥＫ）１３部を順次容器に仕込み均一に攪拌し、トップコート用塗料組成物（１－１）の主剤とした。 59.3 parts of the prepared hydroxyl group-containing resin (A-1) was placed in a container for preparation of the coating composition for top coat (1-1) , and BYK-310 (manufactured by Big Chemie Japan Co., Ltd.) 0.3 with stirring. Part, Viketol Special (manufactured by Big Chemie Japan) 0.3 part, 1% dibutyltin dilaurate (DBTDL) solution in butyl acetate 0.4 part, Tinuvin 292 (manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.4 part, 0.8 parts of TINUVIN 384-2 (manufactured by Ciba Specialty Chemicals Co., Ltd.), 18 parts of butyl acetate, and 13 parts of methyl ethyl ketone (MEK) were sequentially charged into a container and uniformly stirred, and the top coat coating composition (1-1 ) As the main ingredient.
　また別の容器に、信越化学工業社製ＫＢＭ－４０３を３．９部、三井化学社製スタビオ（登録商標）Ｄ３７０Ｎ（炭素数５の脂肪族ジイソシアネートのヌレート体）を１９部、酢酸カービトール４部、メチルエチルケトン（ＭＥＫ）２．４部を順次仕込み均一に攪拌し、トップコート用塗料組成物（１－１）の硬化剤とした。 In another container, 3.9 parts of KBM-403 manufactured by Shin-Etsu Chemical Co., 19 parts of Stabio (registered trademark) D370N (a nurate of an aliphatic diisocyanate having 5 carbon atoms ) manufactured by Mitsui Chemicals, and 4 parts of carbitol acetate , 2.4 parts of methyl ethyl ketone (MEK) were sequentially charged and uniformly stirred to obtain a curing agent for the top coat coating composition (1-1).
　主剤と硬化剤は上記を混合して塗料組成物とした。塗料組成物の不揮発分は５１．２％であった。 The main component and curing agent were mixed to form a coating composition. The nonvolatile content of the coating composition was 51.2%.
トップコート用塗料組成物（１－２）～（１－８）の調製
　下記表に示す成分を表中に記載される量で用いて混合することによって、トップコート用塗料組成物の主剤、硬化剤を調製した。次いで得られた主剤および硬化剤を混合することによって、トップコート用塗料組成物（１－２）～（１－８）を調製した。 Preparation of Topcoat Coating Compositions (1-2) to (1-8) By mixing the components shown in the following table in the amounts described in the table, the main component of the topcoat coating composition and curing The agent was prepared. Next, the obtained base material and curing agent were mixed to prepare coating compositions (1-2) to (1-8) for top coat.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
アンダーコート用塗料組成物（２－１）の調製
　下記表に示す成分を表中に記載される量で用いて混合すること以外は、上記トップコート用塗料組成物（１－１）と同様の手順によって、アンダーコート用塗料組成物の主剤（、硬化剤を調製した。次いで得られた主剤および硬化剤を混合することによって、アンダーコート用塗料組成物（２－１）を調製した。 Preparation of coating composition for undercoat (2-1) Same as the above coating composition for topcoat (1-1), except that the components shown in the following table were used in the amounts described in the table and mixed. By the procedure, the main component (, the curing agent of the undercoat coating composition was prepared. Then, the obtained main component and the curing agent were mixed to prepare the undercoat coating composition (2-1).
アンダーコート用塗料組成物（２－２）～（２－５）の調製
　下記表に示す成分を表中に記載される量で用いて混合することによって、アンダーコート用塗料組成物の主剤、硬化剤を調製した。次いで得られた主剤および硬化剤を混合することによって、アンダーコート用塗料組成物（２－２）～（２－５）を調製した。 Preparation of Coating Compositions for Undercoat (2-2) to (2-5) By mixing the components shown in the table below in the amounts described in the table, the main component of the coating composition for undercoat and curing The agent was prepared. Then, the obtained base material and curing agent were mixed to prepare undercoating coating compositions (2-2) to (2-5).
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　上記表中、
Ｎ３３００：コベストロ社製、ディスモジュールＮ３３００、ヘキサメチレンジイソシアナートのヌレート体である。 In the above table,
N3300: Dismodur N3300 manufactured by Covestro, a nurate of hexamethylene diisocyanate.
実施例１
　イソプロピルアルコール（ＩＰＡ）で洗浄したポリカＰＢＴ基材（ポリカーボネート樹脂／ＰＢＴ樹脂の複合基材、三菱エンジニアリングプラスチック社製）に、乾燥膜厚２５μｍとなるように、アンダーコート用塗料組成物（２－１）を希釈シンナーＴ－５０１ＣＭ（日本ペイント・オートモーティブコーティングス社製）で３０％に希釈してスプレー塗装した。その後、室温にて２分間放置後、８０℃で４０分間乾燥した。
　室温まで放置冷却した後、真空蒸着装置を用いて、１．０×１０－２Ｐａ下、４Ｖの電圧条件下で、厚さ５０ｎｍのインジウム層（不連続金属薄膜）を蒸着により形成した。
　得られた不連続金属薄膜の上に、トップコート用塗料組成物（１－１）を、希釈シンナーＴ－５０５ＨＬ（日本ペイント・オートモーティブコーティングス社製）で３０％に希釈して、乾燥膜厚２５μｍとなるようにスプレー塗装し、室温で５分放置した。
　次いで、形成したアンダーコート層およびトップコート層を、８０℃で４０分間加熱硬化して、不連続金属薄膜含有複層塗膜を得た。 Example 1
On a polycarbonate PBT substrate (composite substrate of polycarbonate resin / PBT resin, manufactured by Mitsubishi Engineering Plastics Co., Ltd.) washed with isopropyl alcohol (IPA), a coating composition for undercoat (2-1 ) Was diluted to 30% with diluted thinner T-501CM (manufactured by Nippon Paint Automotive Coatings) and spray coated. Then, after leaving at room temperature for 2 minutes, it was dried at 80 ° C. for 40 minutes.
After being left to cool to room temperature, an indium layer (discontinuous metal thin film) having a thickness of 50 nm was formed by vapor deposition under a voltage condition of 4 V under 1.0 × 10 −2 Pa using a vacuum vapor deposition apparatus.
On the obtained discontinuous metal thin film, the coating composition for a top coat (1-1) was diluted to 30% with diluted thinner T-505HL (manufactured by Nippon Paint Automotive Coatings Co., Ltd.) to obtain a dry film thickness. It was spray-coated so as to have a thickness of 25 μm and left at room temperature for 5 minutes.
Next, the formed undercoat layer and topcoat layer were heat-cured at 80 ° C. for 40 minutes to obtain a discontinuous metal thin film-containing multilayer coating film.
実施例２～１０および比較例１～６
　下記表に記載されるアンダーコート用塗料組成物およびトップコート用塗料組成物を用いたこと以外は、実施例１と同様にして、複層塗膜を形成した。 Examples 2-10 and Comparative Examples 1-6
A multilayer coating film was formed in the same manner as in Example 1 except that the coating composition for undercoat and the coating composition for topcoat described in the following table were used.
　上記実施例および比較例で用いた塗料組成物および得られた複層塗膜を用いて、下記評価を行った。評価結果を下記表に示す。 The following evaluations were performed using the coating compositions used in the above Examples and Comparative Examples and the obtained multilayer coating films. The evaluation results are shown in the table below.
硬化塗膜のＴｇ
　硬化塗膜のＴｇは、以下の手順により測定した。
　ポリプロピレンシートに、各塗料組成物を乾燥膜厚３０μｍとなるように塗装し、次いで８０℃で４０分間加熱硬化させて、硬化塗膜を得た。
　上記で調製した硬化塗膜（フィルム）を２０ｎｍ×５ｍｍにカットし、動的粘弾性測定装置ＤＶＥ－Ｖ４ＦＴスペクトラー（レオロジ－社製）を用いて、温度依存モードにて１１Ｈｚの基本正弦波歪で３０℃から１５０℃まで毎分３℃上昇させ、測定して得られた損失正接ｔａｎδの最大となる温度をＴｇとした。 Tg of cured coating
The Tg of the cured coating film was measured by the following procedure.
Each coating composition was coated on a polypropylene sheet so that the dry film thickness was 30 μm, and then heat-cured at 80 ° C. for 40 minutes to obtain a cured coating film.
The cured coating film (film) prepared above was cut into 20 nm × 5 mm, and using a dynamic viscoelasticity measuring device DVE-V4FT Spectra (Rheology), in a temperature-dependent mode with a fundamental sine wave distortion of 11 Hz. The temperature at which the loss tangent tan δ obtained by measuring was increased from 30 ° C. to 150 ° C. by 3 ° C. per minute was defined as Tg.
耐水性評価
　複層塗膜を４０℃の温水に２４０時間浸漬した後、一日室温乾燥してブリスター（水浸透による塗膜の膨れ）をＡＳＴＭ  Ｄ７１４に基づき目視評価するとともに、ＪＩＳ  Ｋ５６００の碁盤目テープ剥離試験を行った。
　試験前と比較して外観にブリスターが発生した場合×、膨潤によるチヂミが発生した場合△、異常が無かった場合○とした。また、剥離が発生した場合×、かけ程度の剥離が発生した場合△、剥離が無かった場合○とした。 Water resistance evaluation The multi-layer coating film was immersed in 40 ° C. warm water for 240 hours, dried at room temperature for one day, and visually evaluated for blisters (swelling of the coating film due to water permeation) according to ASTM D714. A tape peel test was conducted.
Compared to before the test, the case where blister was generated in the appearance was evaluated as ×, the case of occurrence of swelling due to swelling was evaluated as Δ, and the case where there was no abnormality was evaluated as ○. In addition, when peeling occurred, x was given, when a slight peeling occurred, it was given, and when there was no peeling, it was given as o.
耐薬品性評価
（１）耐ハンドクリーム性
　アトリックス社製ハンドクリームを、塗膜１００ｃｍ２当たり２ｇの量で均一に塗布し、ガーゼで覆い８０℃にしたオーブンで１週間保持した。その後、取り出して水洗いし、下記評価を行った。

　　外観評価
　試験後の塗膜を目視評価した。ブリスターや塗膜浮きがある場合を×、膨潤による跡がある場合を△、異常がない場合を○とした。

　　密着性評価
　試験後の塗膜にクロスカットを施し、セロハンテープ（商標）を貼り付けてはがすことにより、密着性を評価した。
　５ｍｍ２以上の剥離で×、僅かな欠け程度の剥離で△、剥離無しで○とした。

（２）耐皮脂性
　オレイン酸を、塗膜１００ｃｍ２当たり０．０５ｇの量で均一に塗布し、ガーゼで覆い、８０℃にしたオーブンで２４時間保持した。その後、取り出して水洗いし、下記評価を行った。

　　外観評価
　試験後の塗膜を目視評価した。ブリスターや塗膜浮きがある場合を×、膨潤による跡がある場合を△、異常がない場合を○とした。

　　密着性評価
　試験後の塗膜にクロスカットを施し、セロハンテープ（商標）を貼り付けてはがすことにより、密着性を評価した。
　５ｍｍ２以上の剥離で×、僅かな欠け程度の剥離で△、剥離無しで○とした。 Chemical resistance evaluation
(1) Hand cream resistance A hand cream manufactured by ATRIX Co., Ltd. was uniformly applied in an amount of 2 g per 100 cm 2 of the coating film, covered with gauze, and kept in an oven at 80 ° C. for 1 week. Then, it was taken out and washed with water, and the following evaluation was performed.

The coating film after the appearance evaluation test was visually evaluated. The case where there was blistering or coating film floating was rated as X, the case where there was a mark due to swelling was rated as Δ, and the case where there was no abnormality was rated as ○.

The coating film after the adhesion evaluation test was cross-cut, and cellophane tape (trademark) was attached and peeled off to evaluate the adhesion.
Peeling of 5 mm 2 or more was rated as ×, peeling with a slight chipping was rated as Δ, and no peeling was rated as ◯.

(2) Sebum-resistant oleic acid was uniformly applied in an amount of 0.05 g per 100 cm 2 of the coating film, covered with gauze, and kept in an oven at 80 ° C. for 24 hours. Then, it was taken out and washed with water, and the following evaluation was performed.

The coating film after the appearance evaluation test was visually evaluated. The case where there was blistering or coating film floating was rated as X, the case where there was a mark due to swelling was rated as Δ, and the case where there was no abnormality was rated as ○.

The coating film after the adhesion evaluation test was cross-cut, and cellophane tape (trademark) was attached and peeled off to evaluate the adhesion.
Peeling of 5 mm 2 or more was rated as ×, peeling with a slight chipping was rated as Δ, and no peeling was rated as ◯.
耐擦傷性評価
　複層塗膜の表面を、４ｃｍ２当たり２１．６Ｎの荷重にて、平均３００μｍのガラスビーズを両面テープで摩擦子に貼りつけ５０往復させ、耐擦傷試験を行った。その後２０℃の光沢保持率を測定し、９５％以上を◎、８０％以上を○、６０％以上を△、６０％未満を×とした。 Scratch resistance evaluation A surface of the multilayer coating film was subjected to a scratch resistance test by adhering glass beads having an average of 300 μm to a friction element with a double-sided tape at a load of 21.6 N per 4 cm 2 and reciprocating 50 times. Then, the gloss retention at 20 ° C. was measured, and 95% or more was marked with ⊚, 80% or more was marked with ◯, 60% or more was marked with Δ, and less than 60% was marked with x.
複層塗膜の塗膜外観評価
　得られた複層塗膜について、目視で、表面の凹凸を観察し、平滑性を評価した。
　平滑なものを○、鳥肌状のひどいものを×、その中間を△とした。 Evaluation of coating film appearance of multilayer coating film The obtained multilayer coating film was visually observed for surface irregularities to evaluate smoothness.
The smooth one was marked with O, the severe goose bump-like one was marked with X, and the middle was marked with Δ.
耐候性評価
　複層塗膜について、促進耐候性試験としてキセノンウェザーメーター（キセノン、スガ試験機製）を用いた。初期光沢との比較において光沢維持率が８５％以上で、色差（ΔＥ）が３以下である場合を○、汚染により上記条件を満たさない場合を×とした。 Weather resistance evaluation For the multilayer coating film, a xenon weather meter (xenon, manufactured by Suga Test Instruments Co., Ltd.) was used as an accelerated weather resistance test. In comparison with the initial gloss, the gloss retention rate is 85% or more and the color difference (ΔE) is 3 or less, and the case where the above conditions are not satisfied due to contamination is marked as x.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
　実施例で得られた複層塗膜はいずれも、塗膜外観、耐水性、耐薬品性、耐擦傷性、耐候性が優れることが確認された。
　比較例１は、トップコート用塗料組成物に含まれるポリイソシアネート化合物が、炭素数４～５の脂肪族ジイソシアネートのヌレート体ではない例である。この例では、耐薬品性（密着性）が劣ることが確認された。
　比較例２は、トップコート用塗料組成物がシランカップリング剤を含まない例である。この例では、耐薬品性（密着性）が劣ることが確認された。
　比較例３は、アンダーコート用塗料組成物の硬化塗膜のＴｇが８０℃以上である例である。この例では、複層塗膜の塗膜外観が劣ることが確認された。
　比較例４は、アンダーコート用塗料組成物がシランカップリング剤を含まない例である。この例では、耐薬品性（密着性）が劣ることが確認された。
　比較例５は、トップコート用塗料組成物およびアンダーコート用塗料組成物がいずれも、シランカップリング剤を含まない例である。この例では、塗膜外観、耐水性、耐薬品性が劣ることが確認された。
　比較例６は、トップコート用塗料組成物をアンダーコート用塗料組成物として用い、そしてアンダーコート用塗料組成物をトップコート用塗料組成物として用いた例である。この例では、耐薬品性および耐候性が劣ることが確認された。 It was confirmed that each of the multilayer coating films obtained in the examples had excellent coating film appearance, water resistance, chemical resistance, scratch resistance, and weather resistance.
Comparative Example 1 is an example in which the polyisocyanate compound contained in the coating composition for a top coat is not a nurate of an aliphatic diisocyanate having 4 to 5 carbon atoms. In this example, it was confirmed that the chemical resistance (adhesion) was inferior.
Comparative Example 2 is an example in which the topcoat coating composition does not contain a silane coupling agent. In this example, it was confirmed that the chemical resistance (adhesion) was inferior.
Comparative Example 3 is an example in which the cured coating film of the undercoat coating composition has a Tg of 80 ° C. or higher. In this example, it was confirmed that the coating film appearance of the multilayer coating film was inferior.
Comparative Example 4 is an example in which the undercoat coating composition does not contain a silane coupling agent. In this example, it was confirmed that the chemical resistance (adhesion) was inferior.
Comparative Example 5 is an example in which neither the coating composition for top coat nor the coating composition for undercoat contains a silane coupling agent. In this example, it was confirmed that the coating film appearance, water resistance and chemical resistance were poor.
Comparative Example 6 is an example in which the topcoat coating composition was used as the undercoat coating composition, and the undercoat coating composition was used as the topcoat coating composition. In this example, it was confirmed that the chemical resistance and weather resistance were poor.
　上記アンダーコート用塗料組成物および不連続金属薄膜トップコート用塗料組成物を用いて形成される複層塗膜は、耐薬品性（耐ハンドクリーム性、耐汁性等）、耐候性（汚染耐久性、耐水性など）、耐久性、耐擦傷性に優れるという利点がある。この複層塗膜は、自動車のフロント部、自動車のドアハンドル、車搭載通信機器、携帯電話、携帯情報端末機器（タブレットパソコン、モバイル機器および電子手帳など）、電磁波の受発信システムを有する各種家電製品および住宅設備などにおいて好適に用いることができる。 A multilayer coating film formed by using the above coating composition for undercoat and coating composition for discontinuous metal thin film topcoat has chemical resistance (hand cream resistance, juice resistance, etc.), weather resistance (contamination durability). Properties, water resistance, etc.), durability, and scratch resistance. This multi-layer coating film is used for automobile front parts, automobile door handles, vehicle-mounted communication devices, mobile phones, personal digital assistants (tablets, mobile devices, electronic notebooks, etc.), and various home appliances with electromagnetic wave transmission / reception systems. It can be suitably used in products and housing equipment.

Claims (12)

  1. 　水酸基含有樹脂（Ａ－１）、
    ポリイソシアネート化合物（Ｂ－１）、および
    シランカップリング剤（Ｃ－１）、
    を含む、不連続金属薄膜トップコート用塗料組成物であって、
    　前記ポリイソシアネート化合物（Ｂ－１）は、炭素数４～５の脂肪族ジイソシアネートのヌレート体を含む、
    不連続金属薄膜トップコート用塗料組成物。     Hydroxyl group-containing resin (A-1),
    A polyisocyanate compound (B-1), and a silane coupling agent (C-1),
    A coating composition for a discontinuous metal thin film top coat, comprising:
    The polyisocyanate compound (B-1) contains a nurate of an aliphatic diisocyanate having 4 to 5 carbon atoms,
    A coating composition for a discontinuous metal thin film top coat.
  2. 　前記水酸基含有樹脂（Ａ－１）の水酸基および前記ポリイソシアネート化合物（Ｂ－１）のイソシアネート基の当量比Ｅ１（ＮＣＯ基／ＯＨ基）は、１．０～３．０の範囲内である、
    請求項１記載の不連続金属薄膜トップコート用塗料組成物。     The equivalent ratio E1 (NCO group / OH group) of the hydroxyl group of the hydroxyl group-containing resin (A-1) and the isocyanate group of the polyisocyanate compound (B-1) is in the range of 1.0 to 3.0.
    The coating composition for a discontinuous metal thin film top coat according to claim 1.
  3. 　前記水酸基含有樹脂（Ａ－１）は、１級水酸基および２級水酸基の両方を有し、前記水酸基の比率は、１級水酸基／２級水酸基＝１０／９０～８０／２０の範囲内である、
    請求項１または２記載の不連続金属薄膜トップコート用塗料組成物。     The hydroxyl group-containing resin (A-1) has both a primary hydroxyl group and a secondary hydroxyl group, and the ratio of the hydroxyl groups is in the range of primary hydroxyl group / secondary hydroxyl group = 10/90 to 80/20. ,
    The coating composition for a discontinuous metal thin film top coat according to claim 1 or 2.
  4. 　前記不連続金属薄膜トップコート用塗料組成物の硬化塗膜のＴｇは、８０～１３０℃の範囲内である、
    請求項１～３いずれかに記載の不連続金属薄膜トップコート用塗料組成物。     The Tg of the cured coating film of the discontinuous metal thin film topcoat coating composition is in the range of 80 to 130 ° C.,
    The coating composition for a discontinuous metal thin film top coat according to any one of claims 1 to 3.
  5. 　前記シランカップリング剤（Ｃ－１）は、アミノ基含有シランカップリング剤、エポキシ基含有シランカップリング剤およびイソシアネート基含有シランカップリング剤からなる群から選択されるカップリング剤である、
    請求項１～４いずれかに記載の不連続金属薄膜トップコート用塗料組成物。     The silane coupling agent (C-1) is a coupling agent selected from the group consisting of an amino group-containing silane coupling agent, an epoxy group-containing silane coupling agent and an isocyanate group-containing silane coupling agent,
    The coating composition for a discontinuous metal thin film top coat according to any one of claims 1 to 4.
  6. 　水酸基含有樹脂（Ａ－２）、
    ポリイソシアネート化合物（Ｂ－２）、および
    シランカップリング剤（Ｃ－２）、
    を含む、不連続金属薄膜アンダーコート用塗料組成物であって、
    　前記不連続金属薄膜アンダーコート用塗料組成物の硬化塗膜のＴｇは、８０℃未満である、
    不連続金属薄膜アンダーコート用塗料組成物。     Hydroxyl group-containing resin (A-2),
    A polyisocyanate compound (B-2), and a silane coupling agent (C-2),
    A coating composition for a discontinuous metal thin film undercoat, comprising:
    Tg of the cured coating film of the discontinuous metal thin film undercoat coating composition is less than 80 ° C.,
    A coating composition for a discontinuous metal thin film undercoat.
  7. 　前記水酸基含有樹脂（Ａ－２）の水酸基および前記ポリイソシアネート化合物（Ｂ－２）のイソシアネート基の当量比Ｅ２（ＮＣＯ基／ＯＨ基）は、０．３～０．９５の範囲内である、
    請求項６記載の不連続金属薄膜アンダーコート用塗料組成物。     The equivalent ratio E2 (NCO group / OH group) of the hydroxyl group of the hydroxyl group-containing resin (A-2) and the isocyanate group of the polyisocyanate compound (B-2) is in the range of 0.3 to 0.95.
    The coating composition for a discontinuous metal thin film undercoat according to claim 6.
  8. 　前記シランカップリング剤（Ｃ－２）は、アミノ基含有シランカップリング剤、エポキシ基含有シランカップリング剤およびイソシアネート基含有シランカップリング剤からなる群から選択されるカップリング剤である、
    請求項６または７記載の不連続金属薄膜アンダーコート用塗料組成物。     The silane coupling agent (C-2) is a coupling agent selected from the group consisting of an amino group-containing silane coupling agent, an epoxy group-containing silane coupling agent, and an isocyanate group-containing silane coupling agent.
    The coating composition for a discontinuous metal thin film undercoat according to claim 6 or 7.
  9. 　請求項１～５いずれかに記載の不連続金属薄膜トップコート用塗料組成物、および、請求項６～８いずれかに記載の不連続金属薄膜アンダーコート用塗料組成物を含む、不連続金属薄膜含有複層塗膜形成用塗料セット。 A discontinuous metal thin film comprising the coating composition for a discontinuous metal thin film topcoat according to any one of claims 1 to 5 and the coating composition for a discontinuous metal thin film undercoat according to any one of claims 6 to 8. Containing multi-layer coating film forming paint set.
  10. 　前記不連続金属薄膜トップコート用塗料組成物における前記当量比Ｅ１（ＮＣＯ基／ＯＨ基）および前記不連続金属薄膜アンダーコート用塗料組成物における前記当量比Ｅ２（ＮＣＯ基／ＯＨ基）が、下記式
    Ｅ１／Ｅ２＝１．３～４
    を満たす、請求項９記載の不連続金属薄膜含有複層塗膜形成用塗料セット。     The equivalent ratio E1 (NCO group / OH group) in the coating composition for a discontinuous metal thin film topcoat and the equivalent ratio E2 (NCO group / OH group) in the coating composition for a discontinuous metal thin film undercoat are as follows. Formula E1 / E2 = 1.3-4
    The coating set for forming a multilayer coating film containing a discontinuous metal thin film according to claim 9, which satisfies the above condition.
  11. 　被塗物に、請求項６～８いずれかに記載の不連続金属薄膜アンダーコート用塗料組成物を塗装してアンダーコート層を設ける、アンダーコート層形成工程、
    　前記アンダーコート層の上に不連続金属薄膜を設ける、不連続金属薄膜形成工程、
    　前記不連続金属薄膜の上に、請求項１～５いずれかに記載の不連続金属薄膜トップコート用塗料組成物を塗装して、トップコート層を設ける、トップコート層形成工程、および
    前記アンダーコート層およびトップコート層を硬化させる、硬化工程、
    を包含する、不連続金属薄膜含有複層塗膜の形成方法であって、
    　前記不連続金属薄膜は、インジウム、スズ、クロムまたはこれらの合金を含む、
    不連続金属薄膜含有複層塗膜の形成方法。     An undercoat layer forming step of applying an undercoat layer by coating the coating composition for a discontinuous metal thin film undercoat according to any one of claims 6 to 8 on an article to be coated,
    Providing a discontinuous metal thin film on the undercoat layer, a discontinuous metal thin film forming step,
    A topcoat layer forming step of applying the coating composition for a discontinuous metal thin film topcoat according to any one of claims 1 to 5 on the discontinuous metal thin film to form a topcoat layer, and the undercoat. A curing step of curing the layer and the topcoat layer,
    A method of forming a discontinuous metal thin film-containing multilayer coating film, comprising:
    The discontinuous metal thin film contains indium, tin, chromium or an alloy thereof.
    A method for forming a multilayer coating film containing a discontinuous metal thin film.
  12. 　前記不連続金属薄膜トップコート用塗料組成物における当量比Ｅ１（ＮＣＯ基／ＯＨ基）および前記不連続金属薄膜アンダーコート用塗料組成物における当量比Ｅ２（ＮＣＯ基／ＯＨ基）が、下記式
    Ｅ１／Ｅ２＝１．３～４
    を満たす、請求項１１記載の形成方法。     An equivalent ratio E1 (NCO group / OH group) in the coating composition for a discontinuous metal thin film topcoat and an equivalent ratio E2 (NCO group / OH group) in the coating composition for a discontinuous metal thin film undercoat are represented by the following formula E1. /E2=1.3-4
    The forming method according to claim 11, which satisfies the above condition.
PCT/JP2019/042521 2018-10-31 2019-10-30 Topcoating composition for discontinuous metallic thin film, and undercoating composition for discontinuous metallic thin film WO2020090868A1 (en)

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JP2008126171A (en) * 2006-11-22 2008-06-05 Toyota Motor Corp Multilayer coating film, method of applying multilayer coating film and automobile coated with multilayer coating film
WO2009001818A1 (en) * 2007-06-26 2008-12-31 Fujikura Kasei Co., Ltd. Coating composition for metal thin film, and luster composite coating film produced from the coating composition
JP2009191097A (en) * 2008-02-12 2009-08-27 Fujikura Kasei Co Ltd Coating composition for thin metal film, and bright resin product using coating composition for thin metal film
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